CN110527037B - Halogen-free polyphenyl ether resin composition and prepreg and laminated board manufactured by using same - Google Patents
Halogen-free polyphenyl ether resin composition and prepreg and laminated board manufactured by using same Download PDFInfo
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- CN110527037B CN110527037B CN201910921153.2A CN201910921153A CN110527037B CN 110527037 B CN110527037 B CN 110527037B CN 201910921153 A CN201910921153 A CN 201910921153A CN 110527037 B CN110527037 B CN 110527037B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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
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- 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
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- 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
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- 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
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Abstract
The invention discloses a halogen-free polyphenyl ether resin composition which comprises the following components: (a) polyphenylene ether resin containing carbon-carbon unsaturated bond: 100 parts of (A); (b) phosphorus-containing compounds containing carbon-carbon unsaturated bonds: 5-60 parts; (c) initiator: 0 to 10 parts. According to the invention, the phosphorus-containing compound containing carbon-carbon unsaturated bonds plays a role of a cross-linking agent in the polyphenyl ether and the carbon-carbon unsaturated bond-containing compound, so that the polyphenyl ether and the carbon-carbon unsaturated bond-containing compound can be well and uniformly compatible with each other, a lower dielectric constant and a lower dielectric loss value are obtained, and experimental data prove that: the resin composition of the present invention and the laminate prepared therefrom may satisfy the current 5G product.
Description
Technical Field
The invention relates to a halogen-free polyphenyl ether resin composition, and a prepreg and a laminated board prepared from the halogen-free polyphenyl ether resin composition, and belongs to the technical field of electronic materials.
Background
With the upgrading of technology, the consumer electronics markets such as automobile markets and smart phones have new requirements on PCBs, and after the 5G commercial market appears in 2018, the requirements on the dielectric property of PCB substrates are one step higher, and the high-frequency high-speed copper-clad plate is one of indispensable electronic substrates in the 5G era. In short, the PCB substrate material needs to have a low dielectric constant and dielectric loss tangent to reduce the delay, distortion and loss of signals during high-speed transmission and the interference between signals. Accordingly, it is desirable to provide a thermosetting resin composition which can exhibit a sufficiently low dielectric constant and dielectric loss tangent (i.e., the lower the dielectric constant and dielectric loss tangent, the better) in a printed circuit board material manufactured by using the thermosetting resin composition during signal transmission at a high speed and a high frequency.
In order to meet the requirement of high dielectric property, a hydrocarbon resin system is generally selected in the prior art, but the problems of poor flame retardant property, low glass transition temperature, insufficient rigidity and the like are brought, so that when a high-performance substrate for high frequency and high speed is prepared, in order to solve the problems of flame retardant property, rigidity and the like, other components such as bismaleimide resin, benzoxazine resin or common DOPO structure phosphorus-containing flame retardant are also added into a resin composition, but the dielectric constant of the finally obtained substrate material still cannot well meet the requirement of the high-frequency and high-speed substrate.
Japanese patent JP2019023263 and JP2019044031 disclose that by adding a phosphorus-containing flame retardant (such as phosphazenes) which is incompatible with polyphenylene ether and crosslinking property into a resin composition containing polyphenylene ether resin and a carbon-carbon unsaturated crosslinking agent, the technical scheme can obtain halogen-free flame retardance and reduce the dielectric constant and dielectric loss of a cured product to a certain extent, but phosphorus atoms in the incompatible phosphorus-containing flame retardant cannot be well introduced into a high-molecular network structure, so that the humidity and heat resistance of the cured product are influenced, and the overall crosslinking density is reduced, so that the heat resistance of the cured product is influenced. Furthermore, the compatibility of the polyphenylene ether resin and the crosslinking agent is also affected by the immiscible phosphorus-containing flame retardant.
In view of the above, it is obvious that the development of a high-frequency resin composition with high glass transition temperature, high toughness, low dielectric constant and dielectric loss tangent and excellent flame retardance has positive practical significance in meeting the requirements of high-performance printed circuit boards such as high-frequency, high-speed and high-density interconnections.
Disclosure of Invention
The invention aims to provide a high-frequency resin composition which can meet the requirements of high-performance printed circuit boards such as high-frequency high-speed and high-density interconnection and the like.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a halogen-free polyphenyl ether resin composition comprises the following components in percentage by weight of solid:
(a) polyphenylene ether resin containing carbon-carbon unsaturated bond: 100 parts of (A);
(b) phosphorus-containing compounds containing carbon-carbon unsaturated bonds: 5-60 parts;
(c) initiator: 0-10 parts;
the phosphorus-containing compound containing carbon-carbon unsaturated bonds is selected from at least one compound in the following structure:
as described above, the phosphorus-containing compound containing carbon-carbon unsaturated bonds has 13 chemical structural formulas, wherein 6 phosphorus-containing compounds containing sulfur structures, namely sulfur-containing carbon-carbon unsaturated bonds, are contained.
Preferably, the phosphorus-containing compound containing carbon-carbon unsaturated bonds is a sulfur-containing phosphorus-containing compound containing carbon-carbon unsaturated bonds, or is a combination of the sulfur-containing phosphorus-containing compound containing carbon-carbon unsaturated bonds and other phosphorus-containing compounds containing carbon-carbon unsaturated bonds. Namely: the phosphorus-containing compound containing a carbon-carbon unsaturated bond is preferably one or more of the above 6 chemical structural formulas containing a sulfur structure, or may be a combination of the 6 chemical structural formulas containing a sulfur structure (one or more of them may be selected) and other chemical structural formulas not containing a sulfur structure.
More preferably, the phosphorus-containing compound containing carbon-carbon unsaturated bonds is a composition of a sulfur-containing phosphorus-containing compound containing carbon-carbon unsaturated bonds and other phosphorus-containing compounds containing carbon-carbon unsaturated bonds, and the mass ratio of the phosphorus-containing compound containing carbon-carbon unsaturated bonds to the other phosphorus-containing compounds is 100: 0-100: 100, and preferably 100: 10-100: 60.
The initiator is the prior art, and can be selected from azo initiators, peroxy initiators and redox initiators, and preferably one or more of the following initiators: dicumyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, dicyclohexyl peroxydicarbonate, cumene hydroperoxide and azobisisobutyronitrile.
Hereinbefore, the content of the phosphorus compound having a carbon-carbon unsaturated bond of the component (b) is 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 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 parts, 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 parts, 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 parts, preferably 10 to 40 parts, based on 100 parts by weight of the polyphenylene ether resin having a carbon-carbon unsaturated bond of the component (a).
Preferably, the polyphenylene ether resin containing carbon-carbon unsaturated bonds is selected from at least one of vinyl modified polyphenylene ether resin, acrylate modified polyphenylene ether resin, allyl modified polyphenylene ether resin and maleimide modified polyphenylene ether resin, and the number average molecular weight of the vinyl modified polyphenylene ether resin and the number average molecular weight of the acrylate modified polyphenylene ether resin are both less than 6000. More preferably 1000 to 3000.
Preferably, the vinyl modified polyphenylene ether resin is selected from one or more compounds shown in the following structural formulas (1) and (2):
-Y2-O-structure is:
wherein R is26、R28Identical or different, each being a halogen atom, an alkyl group or a phenyl group, R25、R27Are respectively selected from hydrogen atom, halogen atom, alkyl or phenyl;
m and n represent integers of 0-30 respectively and cannot be 0 at the same time;
the acrylate modified polyphenyl ether resin is selected from one or more compounds shown in the following structural formula (3):
Still more preferably, the vinyl-modified polyphenylene ether resin is selected from the following structures:
in the above technical scheme, the halogen-free polyphenylene ether resin composition further comprises a crosslinking assistant, wherein the crosslinking assistant is one or more selected from maleimide compounds, hydrocarbon resins, benzoxazines containing carbon-carbon unsaturated bonds, phenolic resins containing carbon-carbon unsaturated bonds, cyanate esters containing carbon-carbon unsaturated bonds, and polyimides containing carbon-carbon unsaturated bonds. Preferably, the crosslinking assistant is selected from hydrocarbon resins.
The content of the crosslinking assistant is 1 to 80 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the polyphenylene ether resin containing carbon-carbon unsaturated bonds of component (a).
The resin composition preferably comprises the following components in percentage by weight of solid:
(a) polyphenylene ether resin containing carbon-carbon unsaturated bond: 100 parts of (A);
(b) phosphorus-containing compounds containing carbon-carbon unsaturated bonds: 10-40 parts;
(c) initiator: 0.1-3 parts;
(d) hydrocarbon resin: 15-40 parts.
In the above technical solution, the hydrocarbon resin is selected from one or more of polybutadiene, polypentadiene, polystyrene, polybutadiene-styrene copolymer, styrene-butadiene-styrene copolymer, polypentadiene-styrene copolymer, styrene-pentadiene-styrene copolymer, diphenylethylene ethane, diphenylethylene methane, diphenylethylene hexane, triallyl isocyanate, and prepolymers thereof.
Preferably, the hydrocarbon resin is selected from one or more of styrene-butadiene-styrene copolymer (SBS), stilbene ethane (BVPE), stilbene methane (BVPM), stilbene hexane (BVPH) and triallyl isocyanate (TAIC).
In the above technical solution, the resin composition further includes a filler, and it is understood that the resin composition may or may not include the filler.
When the filler is contained in the resin composition, the filler is included in an amount of 0 to 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 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight, or 200 parts by weight, based on 100 parts by weight of the resin composition; preferably, the filler content is 10 to 100 parts by weight, more preferably 30 to 70 parts by weight.
Specifically, the filler is an organic filler or an inorganic filler, wherein the inorganic filler is selected from one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
More preferably, the inorganic filler is at least one selected from the group consisting of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder. Preferably, the filler is silica, more preferably, surface-treated spherical silica. Specifically, the surface treatment agent is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent.
Preferably, the filler has a particle size median value of 1 to 15 microns, for example 1 micron, 2 microns, 5 microns, 8 microns, 10 microns, 11 microns, 12 microns, 13 microns, 14 microns or 15 microns. More preferably, the filler has a median particle size value of 1 to 10 microns.
In a further improvement of the present invention, the resin composition further comprises an elastomer, the elastomer is a low modulus component, and is at least one selected from the group consisting of polybutadienes, styrenes, olefins, polyurethanes, polyesters, polyamines, acrylates and silicones, preferably a low modulus component containing a reactive group, and the reactive group may be an epoxy group, a hydroxyl group, an amino group, an acid anhydride group, a carboxyl group or a vinyl group, and more preferably an epoxy-modified polybutadiene, an acid anhydride-modified polybutadiene, a styrene-butadiene copolymer, a styrene-propylene copolymer or a styrene-acrylic copolymer. The elastomer is present in an amount of 5 to 20 parts based on 100 parts resin solids.
According to different requirements of final products, the resin composition further comprises 0-5 parts of other auxiliary agents. The other auxiliary agents comprise a coupling agent, a dispersing agent and a dye. The coupling agent is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent; the dispersant is amino silane compound having amino group and having hydrolytic group or hydroxyl group such as gamma-aminopropyltriethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltrimethoxysilane, epoxy silane compound having epoxy group and having hydrolytic group or hydroxyl group such as 3-acryloxypropyltrimethoxysilane, vinyl silane compound having vinyl group and having hydrolytic group or hydroxyl group such as gamma-methacryloxypropyltrimethoxysilane, and cationic silane coupling agent, and the dispersant can be Disperbyk-110, 111, 118, 180, 161, 2009, BYK-W996, W9010, W903 (all product names) manufactured by BYK; the dye is fluorescent dye and black dye, wherein the fluorescent dye is pyrazoline and the like, and the black dye is carbon black (liquid or powder), pyridine complex, azo complex, aniline black, black talcum powder, cobalt chromium metal oxide, azine, phthalocyanine and the like.
The invention also discloses a prepreg prepared by the resin composition, the resin composition is dissolved by a solvent to prepare a glue solution, then the reinforcing material is soaked in the glue solution, and the soaked reinforcing material is heated and dried to obtain the prepreg.
Wherein the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric; preferably, the reinforcing material is glass fiber cloth, and open fiber cloth or flat cloth is preferably used in the glass fiber cloth. In addition, when the reinforcing material is a glass cloth, the glass cloth generally needs to be chemically treated to improve the interface between the resin composition and the glass cloth. The main method of the chemical treatment is a coupling agent treatment. The coupling agent used is preferably an epoxy silane, an aminosilane or the like to provide good water resistance and heat resistance.
The preparation method of the prepreg comprises the following steps: and (2) soaking the reinforcing material in the resin composition glue solution, then baking the soaked reinforcing material for 1-10min at the temperature of 50-170 ℃, and drying to obtain the prepreg.
The invention also discloses an interlayer insulating film prepared by adopting the resin composition, the resin composition is dissolved by a solvent to prepare a glue solution, then the glue solution is coated on a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the interlayer insulating film.
The preparation method of the interlayer insulating film comprises the following steps: and adding the resin composition into a solvent, dissolving to prepare a glue solution, coating the glue solution on a carrier film, heating and drying the carrier film coated with the glue solution, and forming an insulating resin layer by using the glue solution to obtain the interlayer insulating film. The solvent is selected from one or more of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether and propylene glycol methyl ether. The carrier film may be a polyethylene terephthalate (PET) film, a release film, a copper foil, an aluminum foil, or the like, and is preferably a PET film. The above heating and drying conditions are baking at 50-170 deg.C for 1-10 min.
Further, one side of the interlayer insulating film, which faces away from the carrier film, is covered with a protective film to protect the insulating resin layer. The material of the protective film is the same as that of the carrier film, but of course, the material is not limited thereto.
The invention also discloses a laminated board, wherein a metal foil is coated on one side or two sides of one prepreg, or after at least 2 prepregs are stacked, a metal foil is coated on one side or two sides of the prepreg, and the laminated board is obtained by hot press forming.
The preparation steps of the laminated board are as follows: and covering a metal foil on one or two sides of one prepreg, or covering a metal foil on one or two sides of at least 2 prepregs after laminating, and performing hot press forming to obtain the metal foil laminated board. The pressing conditions of the above laminate were: pressing for 2-4 hours under the pressure of 0.2-2 MPa and the temperature of 180-250 ℃.
Specifically, the number of prepregs may be determined according to the thickness of a desired laminate, and one or more prepregs may be used.
The metal foil can be copper foil or aluminum foil, and the material is not limited; the thickness of the metal foil is also not particularly limited, and may be, for example, 5 micrometers, 8 micrometers, 12 micrometers, 18 micrometers, 35 micrometers, or 70 micrometers.
The invention also provides a printed wiring board which comprises at least one prepreg or at least one insulating film.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. according to the invention, the phosphorus-containing compound containing carbon-carbon unsaturated bonds plays a role of a cross-linking agent in the polyphenyl ether and the carbon-carbon unsaturated bond-containing compound, so that the polyphenyl ether and the carbon-carbon unsaturated bond-containing compound can be well and uniformly compatible with each other, a lower dielectric constant and a lower dielectric loss value are obtained, and experimental data prove that: the resin composition of the invention and the laminate prepared therefrom can meet the current 5G product;
2. the three components with carbon-carbon unsaturated bonds have equivalent reaction activity, so that the reaction of the system can be consistent, and a uniform phase is formed; meanwhile, the selected phosphorus-containing compound has a special structure: the middle phosphorus and nitrogen are annular, so that the problem of easy moisture absorption of phosphorus-containing resin is avoided, and electronic conjugation can be generated, so that the final product has excellent dielectric property and moist heat resistance, and the stability of the dielectric property of the product can be maintained at high frequency;
3. the phosphorus-containing compound containing carbon-carbon unsaturated bonds takes part in the reaction to form a cross-linked interpenetrating network structure, so that the problems of phase separation, low flame retardant efficiency and the like caused by an additive type or other phosphorus-containing flame retardants which cannot perform free radical polymerization are solved;
4. the invention adopts the sulfur-containing phosphorus-containing compound containing carbon-carbon unsaturated bonds, not only has the synergistic flame-retardant effect of phosphorus and sulfur, but also can improve the caking property of a system, and experiments prove that: the peel strength of laminates made from the resin composition of the present invention is much higher than other sulfur-free phosphorus-containing compounds containing carbon-carbon unsaturated bonds.
Detailed Description
The invention is further described below with reference to the following examples:
examples
A halogen-free polyphenylene ether resin composition has a formula shown in the following table 1:
TABLE 1
The details of the above components are shown in table 2 below:
TABLE 2
The synthesis method of the phosphorus-containing compound A comprises the following steps: the method is characterized in that hexachlorocyclotriphosphazene, 3-allylphenol and phenol are used as main raw materials, and a novel cyclotriphosphazene compound containing an allyl structure is synthesized through two-step nucleophilic substitution reaction by adopting a step-by-step dropwise adding method.
The synthesis method of the phosphorus-containing compound B comprises the following steps:
adding polyphenylene ether, triallyl isocyanate, a phosphorus-containing compound, an initiator, a proper amount of inorganic filler and a solvent into a glue mixing kettle, uniformly stirring the mixture until the solid content is 55-70%, curing the mixture for 4-8 hours to prepare a resin composition glue solution, and then soaking a reinforcing material into the resin composition glue solution; and then baking the impregnated reinforcing material at the temperature of 155-175 ℃ for 3-7 min, and drying to form a prepreg.
The manufacturing method of the laminated board prepared by the prepreg comprises the following steps:
1) stacking 8 prepregs on the surface of the substrate,
2) copper foils are coated on the two sides of the prepreg,
3) hot press forming, the lamination of the copper clad laminate needs to meet the following requirements: (1) heating rate of lamination: generally, the heating rate is controlled to be 0.8-5.0 ℃/min when the material temperature is 30-160 ℃; (2) pressure setting of lamination: when the temperature of the outer layer material is 70-110 ℃, full pressure is required to be applied, and the full pressure is about 300 psi; (3) and during curing, controlling the material temperature to be over 195 ℃ and preserving the temperature for at least 90 min.
Table 3 is a performance test performed on examples one to five and comparative examples one to three, with the following results:
TABLE 3
As can be seen from the above table, the glass transition temperature, the moist heat resistance, the dielectric properties and the toughness of the first and second examples are much better than those of the second comparative example; further, it can be seen from the comparison among the third, fourth and fifth examples and the third comparative example that: the laminated board prepared by the invention has good moist heat resistance, excellent dielectric property and high glass transition temperature, and particularly has excellent reliability in the moist heat resistance.
The resin composition has high humidity resistance, high glass transition temperature, low dielectric constant and dielectric loss tangent value, and can meet the requirements of high-performance printed circuit boards such as high-frequency, high-speed and high-density interconnection.
With respect to the adhesion: referring to examples one, four and five, compared with other examples and comparative examples, the phosphorus-containing compound containing sulfur and carbon-carbon unsaturated bonds has the synergistic flame retardant effect of phosphorus and sulfur, and more importantly, the adhesion of the system can be improved, namely, the peeling strength of the system is greatly advanced. The peel strength of the laminate made from the resin composition of the present invention was much higher.
The test methods for each property in table 3 are as follows:
(1) compatibility of each component of the glue solution: visual inspection was carried out.
(2) Glass transition temperature (Tg): according to differential scanning calorimetry, the measurement was carried out by the DSC method specified by IPC-TM-6502.4.25.
(3) Peel Strength (PS): the peel strength of the metal cap was tested according to the "post thermal stress" experimental conditions in the IPC-TM-6502.4.8 method.
(4) Tin immersion heat resistance: A50X 50mm sample with copper on both sides was immersed in solder at 288 ℃ and the time for delamination of the bubbles was recorded.
(5) Tin immersion heat resistance after moisture treatment: 25 pieces of 100X 100mm substrate samples were held in a pressure cooker at 121 ℃ and 105Kpa for 3hr, and then immersed in a solder bath at 288 ℃ for 2min to observe whether or not delamination and bubbling occurred in the samples.
(6) Thermal decomposition temperature Td: the measurement was carried out according to the IPC-TM-6502.4.26 method.
(7) Dielectric constant: the dielectric constant at 1GHz was measured by the plate method according to IPC-TM-6502.5.5.9.
(8) Dielectric loss tangent: the dielectric dissipation factor at 1GHz was measured by the plate method according to IPC-TM-6502.5.5.9.
(9) Thermal stratification time T-300: the measurement was carried out according to the IPC-TM-6502.4.24 method.
(10) Flame resistance (flame retardancy): measured according to the UL94 method.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. The halogen-free polyphenyl ether resin composition is characterized by comprising the following components in percentage by weight of solid:
(a) polyphenylene ether resin containing carbon-carbon unsaturated bond: 100 parts of (A);
(b) phosphorus-containing compounds containing carbon-carbon unsaturated bonds: 5-60 parts;
(c) initiator: 0-10 parts;
the phosphorus-containing compound containing carbon-carbon unsaturated bonds is a sulfur-containing phosphorus-containing compound containing carbon-carbon unsaturated bonds, or is a composition of the sulfur-containing phosphorus-containing compound containing carbon-carbon unsaturated bonds and other phosphorus-containing compounds containing carbon-carbon unsaturated bonds;
the sulfur-containing carbon-carbon unsaturated bond-containing phosphorus-containing compound is selected from at least one compound in the following structure:
the other phosphorus-containing compound containing carbon-carbon unsaturated bonds is selected from at least one compound in the following structure:
2. the resin composition according to claim 1, characterized in that: the polyphenyl ether resin containing carbon-carbon unsaturated bonds is selected from at least one of vinyl modified polyphenyl ether resin, acrylate modified polyphenyl ether resin, allyl modified polyphenyl ether resin and maleimide modified polyphenyl ether resin;
the number average molecular weight of the vinyl modified polyphenyl ether resin and the number average molecular weight of the acrylate modified polyphenyl ether resin are both less than 6000.
3. The resin composition according to claim 2, characterized in that: the vinyl modified polyphenyl ether resin is selected from one or more compounds shown in the following structural formulas (1) and (2):
-Y2-O-structure is:
wherein R is26、R28Identical or different, each being a halogen atom, an alkyl group or a phenyl group, R25、R27Are respectively selected from hydrogen atom, halogen atom, alkyl or phenyl;
m and n represent integers of 0-30 respectively and cannot be 0 at the same time;
the acrylate modified polyphenyl ether resin is selected from one or more compounds shown in the following structural formula (3):
4. The resin composition according to claim 1, characterized in that: the halogen-free polyphenyl ether resin composition also comprises a crosslinking assistant, wherein the crosslinking assistant is selected from one or more of maleimide compounds, hydrocarbon resins, benzoxazines containing carbon-carbon unsaturated bonds, phenolic resins containing carbon-carbon unsaturated bonds, cyanate esters containing carbon-carbon unsaturated bonds and polyimides containing carbon-carbon unsaturated bonds.
5. The resin composition according to claim 1, characterized in that: the solid weight ratio of the components is as follows:
(a) polyphenylene ether resin containing carbon-carbon unsaturated bond: 100 parts of (A);
(b) phosphorus-containing compounds containing carbon-carbon unsaturated bonds: 10-40 parts;
(c) initiator: 0.1-3 parts;
(d) hydrocarbon resin: 15-40 parts.
6. The resin composition according to claim 4 or 5, characterized in that: the hydrocarbon resin is selected from one or more of polybutadiene, polypentadiene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, pentadiene-styrene copolymer and styrene-pentadiene-styrene copolymer.
7. A prepreg produced using the resin composition according to any one of claims 1 to 6, characterized in that: dissolving the resin composition with a solvent to prepare a glue solution, then soaking the reinforcing material in the glue solution, and heating and drying the soaked reinforcing material to obtain the prepreg.
8. A laminate, characterized by: the laminate can be obtained by coating a metal foil on one side or both sides of a prepreg according to claim 7, or by laminating at least 2 prepregs according to claim 7, coating a metal foil on one side or both sides, and hot press forming.
9. An interlayer insulation film produced by using the resin composition according to any one of claims 1 to 6, wherein the resin composition is dissolved in a solvent to prepare a glue solution, the glue solution is applied to a carrier film, and the carrier film coated with the glue solution is heated and dried to obtain the interlayer insulation film.
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| 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 |
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| 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 |
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| 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 |
| 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 |
| CN111635626B (en) * | 2020-06-30 | 2021-09-07 | 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 |
| 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 |
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6835785B2 (en) * | 2002-01-28 | 2004-12-28 | Mitsubishi Gas Chemical Company, Inc. | Polyphenylene ether oligomer compound, derivatives thereof and use thereof |
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| 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 |
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