WO2016141707A1 - 含磷阻燃组合物以及使用它的含磷聚苯醚树脂组合物、预浸料和层压板 - Google Patents
含磷阻燃组合物以及使用它的含磷聚苯醚树脂组合物、预浸料和层压板 Download PDFInfo
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- WO2016141707A1 WO2016141707A1 PCT/CN2015/090079 CN2015090079W WO2016141707A1 WO 2016141707 A1 WO2016141707 A1 WO 2016141707A1 CN 2015090079 W CN2015090079 W CN 2015090079W WO 2016141707 A1 WO2016141707 A1 WO 2016141707A1
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- carbon atoms
- polyphenylene ether
- ether 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
- 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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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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
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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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- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
Definitions
- the invention belongs to the technical field of copper clad laminates, and relates to a phosphorus-containing composition and a phosphorus-containing polyphenylene ether resin composition, a prepreg and a laminate using the same.
- the epoxy resin circuit board generally has a high dielectric constant and dielectric loss tangent (dielectric constant greater than 4, dielectric loss tangent is about 0.02), and high frequency characteristics are insufficient, which cannot meet the requirements of high frequency signal. Therefore, it is necessary to develop a resin excellent in dielectric properties, that is, a resin having a low dielectric constant and a dielectric loss tangent.
- Heat resistance has also been studied by many technicians as high-frequency high-speed materials. However, due to its high melting point and poor fluidity, it is subject to many restrictions. The melt viscosity of prepregs is large and cannot meet multi-layer printing. The manufacturing requirements of the circuit board. By lowering the molecular weight of the polyphenylene ether resin, it is possible to effectively lower the melting temperature and improve the fluidity, but this also sacrifices the heat resistance of the polyphenylene ether resin.
- CN1745142A uses a polyphenylene ether resin containing a vinyl phenyl group and a methylene phenyl group as a host resin, and uses a trialenyl isocyanurate as a crosslinking curing agent, and if necessary, an inorganic filler or a flame retardant.
- an olefin resin can be used as a compatibilizer, but the performance of the cured product is not mentioned. research.
- US2009/0247032 uses a vinyl bifunctional polyphenylene ether resin as the main body, and a cyanate ester having a naphthalene ring structure, a bisphenol A type cyanate, a brominated flame retardant and an inorganic filler to obtain a It has good fluidity and can obtain good peel strength, heat and humidity resistance and flame retardancy under the premise of ensuring good dielectric properties.
- WO2006/023371A1 provides a combination of a difunctionalized polyphenylene ether resin and an unsaturated olefin monomer, which can improve the fluidity and post-curing properties of the polyphenylene ether resin, but does not indicate a bifunctional polyphenylene ether resin.
- the performance advantage in the field of laminates, and the use of unsaturated olefin monomers are low molecular weight compounds, which are also easily volatilized at high temperatures and have poor processability.
- some materials containing phosphorus epoxy resin and phosphorus-containing phenolic resin can achieve good flame retardant effect, but in terms of dielectric properties. Poor performance and too much
- the introduction of ground phosphorus brings about deterioration of moisture and heat resistance, and cannot meet the reliability requirements of high-layer PCBs; the added type of phosphinate alone has poor flame retardant effect, especially in resin systems with lower carbon formation; Since the phosphazene compound has a relatively low melting point and strong plasticity, a large amount of addition causes a large decrease in heat resistance such as a decrease in the glass transition temperature, and at the same time, even when used alone, it is difficult to achieve flame retardancy V- even when added in a large amount. The level of 0. Similar problems exist with other phosphate compounds.
- the object of the present invention is a phosphorus-containing flame retardant composition which can achieve halogen-free flame retardant at a lower added amount, achieving UL 94V-0.
- Another object of the present invention is to provide a phosphorus-containing polyphenylene ether resin composition which can maintain good dielectric properties and heat resistance of a polyphenylene ether resin, and achieve halogen-free flame retardant, and the flame retardant reaches UL 94V- 0.
- Another object of the present invention is to provide a prepreg and a copper-clad laminate produced by using the above phosphorus-containing polyphenylene ether resin composition, which has good dielectric properties and heat resistance, and realizes halogen-free flame retardant. The flame retardant reaches UL 94V-0.
- a phosphorus-containing flame retardant composition comprising:
- R 1 is one of a C2 to C20 alkylene or an aromatic hydrocarbon.
- the content of the hypophosphite compound is, for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight or 45 parts by weight.
- the content of the polyphosphazene compound is, for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight or 45 parts by weight.
- the above phosphorus-containing composition as a flame retardant, a synergistic effect between the three phosphorus-containing compounds can be exerted, and a halogen-free flame retardant can be achieved with a small addition amount to a V-0 level.
- the component (A) DOPO derivative can be obtained by the following method, specifically: the reaction temperature of the compound DOPO and the diol under the action of a catalyst is 50-300 ° C, and the reaction time is 0.5. ⁇ 48 hours, the reaction is obtained, the specific reaction formula is as follows:
- n is an integer of 2 to 20.
- the above-mentioned reaction is obtained by dehydration condensation reaction with a glycol compound under the action of a catalyst through an active hydrogen atom of DOPO; wherein the molar charge ratio of DOPO and glycol is controlled 0.5 to 100, preferably 0.5 to 10, and still more preferably 0.5 to 5. If the molar ratio is too low, the DOPO conversion rate is low, and if the molar ratio is too high, the subsequent recovery of the diol is difficult.
- the catalyst is not particularly limited, and any catalyst which can promote the dehydration reaction and the Arbuzov reaction can be used.
- the optional catalysts are alkyl halides, alkali metals, alkaline earth metal halides, transition metals and their halogenated acids, acids, Arbuzov.
- the derivative of DOPO can be of the following structural formula:
- the component (B) hypophosphite compound has the following structure:
- M is a metal atom selected from the group consisting of sodium, calcium, magnesium, aluminum, arsenic, and zinc. Or any of the irons.
- M is preferably aluminum or sodium from the viewpoint of lowering its water absorption rate and increasing its phosphorus content, but M is more preferably further if it is further considered to minimize the influence of the phosphorus-containing composition addition on the dielectric properties after curing of the resin composition. aluminum.
- hypophosphite compound in the present invention is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl
- the component (C) described in the present invention is a polyphosphazene compound.
- Polyphosphazene compound is a kind of all-phosphorus nitrogen heterocyclic non-conjugated compound with excellent light stability and thermal stability, high limiting oxygen index, low smoke emission and good chemical resistance, water resistance and resistance. Solvent.
- the polyphosphazene compound in the present invention has the following structural formula:
- n is an integer from 3 to 100, such as 5, 10, 20, 30, 40, 50, 60, 70, 80 or 90.
- R is any one of a phenoxy group, an alkyl group having 1 to 10 carbon atoms, a vinylphenoxy group or an allylphenoxy group;
- q is an integer from 3 to 25, such as 4, 6, 7, 10, 13, 16, 19 or 22; and R is a phenoxy group, an alkyl group having 1 to 10 carbon atoms, a vinylphenoxy group or an alkene group; Any one of propylphenoxy groups.
- the present invention also provides a phosphorus-containing polyphenylene ether resin composition comprising the phosphorus-containing composition as described above and a terminally functionalized polyphenylene ether resin.
- the terminal functionalized polyphenylene ether resin is any one of a hydroxylated polyphenylene ether resin, an epoxidized polyphenylene ether resin, a vinylated polyphenylene ether resin or a cyanated polyphenylene ether resin.
- a and b are independently an integer of 1 to 30, for example, 2, 5, 8, 11, 14, 17, 20, 23, 26 or 29, and Z is a formula (3) or (4)
- Z is a formula (3) or (4)
- -(-OY-)- is a structure represented by the formula (5)
- -(-OXO-)- is a structure represented by the formula (6):
- A is an arylene group, a carbonyl group or an alkylene group having 1 to 10 (for example, 2, 3, 4, 5, 6, 7, 8, or 9) carbon atoms, and m is 0 to 10 ( An integer of, for example, 1 , 2 , 3 , 4, 5, 6, 7, 8, or 9), wherein R 1 , R 2 and R 3 are the same or different and are independently hydrogen or an alkyl group having 10 or less carbon atoms;
- R 4 is the same as or different from R 6 and independently represents a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group having 8 or less carbon atoms, and R 5 and R 7 are the same or different. And independently a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group having 8 or less carbon atoms;
- R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are the same or different and independently represent a hydrogen atom, a halogen atom or a carbon atom of 8 or less.
- R 16 is a hydrogen atom or an alkyl group having 1 to 10 (e.g., 2, 3, 4, 5, 6, 7, 8, or 9) carbon atoms.
- terminally functionalized polyphenylene ether resin is of the formula (7) or (8):
- R 1 to R 3 are the same or different and independently represent hydrogen or an alkyl group having 10 or less carbon atoms; and R 4 is the same as or different from R 6 and independently represents a hydrogen atom, a halogen atom, and a carbon atom; 8 or less alkyl or phenyl; R 5 and R 7 are the same or different and independently represent a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group having 8 or less carbon atoms; R 8 , R 9 and R 10 ; R 11 , R 12 , R 13 , R 14 and R 15 are the same or different and independently represent a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group having 8 or less carbon atoms; b is independently an integer of 1 to 30, for example, 2, 5, 8, 11, 14, 17, 20, 23, 26 or 29, and B is an alkylene group having 20 or less carbon atoms,
- R 4 is the same as or different from R 6 and independently represents a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; and R 5 is the same as or different from R 7 and is a halogen atom or a carbon.
- An alkyl group having 8 or less atoms or a phenyl group; and R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are the same or different and are a hydrogen atom, a halogen atom or a carbon atom.
- 8 or less alkyl or phenyl; a and b are independently an integer of 1 to 30;
- B is an alkylene group having 20 or less carbon atoms, and n is 0 or 1.
- terminal functionalized polyphenylene ether resin may also be a structure represented by the formulas (9) to (13):
- R 1 to R 3 are the same or different and are hydrogen or an alkyl group having 10 or less carbon atoms; and R 4 is the same as or different from R 6 and is a hydrogen atom, a halogen atom or an alkyl group having 8 or less carbon atoms; Or a phenyl group; R 5 and R 7 are the same or different and are a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 And R 15 are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; and a and b are independently an integer of 1 to 30.
- R 1 to R 3 are the same or different and are hydrogen or an alkyl group having 10 or less carbon atoms; and R 4 is the same as or different from R 6 and is a hydrogen atom, a halogen atom or an alkyl group having 8 or less carbon atoms; Or a phenyl group; R 5 and R 7 are the same or different and are a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 And R 15 are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; and a and b are independently an integer of 1 to 30.
- R 1 to R 3 are the same or different and are hydrogen or an alkyl group having 10 or less carbon atoms; and R 4 is the same as or different from R 6 and is a hydrogen atom, a halogen atom or an alkyl group having 8 or less carbon atoms; Or a phenyl group; R 5 and R 7 are the same or different and are a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 And R 15 are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; and a and b are independently an integer of 1 to 30.
- R 4 is the same as or different from R 6 and is a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; and R 5 is the same as or different from R 7 and is a halogen atom or a carbon atom; 8 or less alkyl or phenyl; R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are the same or different and are a hydrogen atom, a halogen atom or a carbon atom of 8 or less.
- Alkyl or phenyl; a and b are independently an integer from 1 to 30.
- R 4 is the same as or different from R 6 and is a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group; and R 5 is the same as or different from R 7 and is a halogen atom or a carbon atom; 8 or less alkyl or phenyl; R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are the same or different and are a hydrogen atom, a halogen atom or a carbon atom of 8 or less.
- Alkyl or phenyl; a and b are independently an integer from 1 to 30.
- the phosphorus-containing flame-retardant composition is added in an amount of 15 to 60 parts by weight, for example, 25 parts by weight based on 100 parts by weight of the terminal-functionalized polyphenylene ether resin.
- the amount of the flame retardant composition added is less than 15 parts by weight, the flame retardancy of the system is less than V-0, and when the amount is more than 60 parts, the cured polyphenylene ether resin composition can be sufficiently ensured. Good flame retardancy, but due to the large water absorption of the phosphorus-containing flame retardant composition, the heat resistance and dielectric properties of the system are greatly deteriorated.
- the phosphorus-containing polyphenylene ether resin composition further includes a crosslinking agent which is a polyolefin resin having an unsaturated double bond
- a crosslinking agent which is a polyolefin resin having an unsaturated double bond
- the polyolefin resin having an unsaturated double bond is Polybutadiene and its graft modified polymer such as maleic anhydride grafted polybutadiene polymer, acrylic modified butadiene polymer, butadiene-styrene copolymer, butadiene-benzene Ethylene-divinylbenzene copolymer or cyclic olefin copolymer Any one or a mixture of at least two.
- the polyolefin resin having an unsaturated double bond is added in an amount of 10 to 100 parts by weight, for example, 15 parts by weight, 20 parts by weight, 25 parts by weight, based on 100 parts by weight of the terminal functionalized polyphenylene ether resin. 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight, 90 parts by weight Parts or 95 parts by weight.
- the addition of an appropriate ratio of the olefin resin can further improve the dielectric properties of the fixed-line system such as Dk/Df, and further, the unsaturated double bond carried in the olefin resin can be further combined with the polyphenylene ether resin. Crosslinking and curing can further improve heat resistance.
- the amount added is less than 10 parts, the amount of unsaturated double bonds introduced into the olefin resin is too small to effectively crosslink, failing to improve heat resistance and dielectric properties; if the amount of olefin resin exceeds 100 In part, the rigidity of the olefin resin itself is too poor, and the coefficient of expansion is large, which causes a large decrease in heat resistance of the cured product.
- the terminal functionalized polyphenylene ether resin has a number average molecular weight of 500 to 5,000, preferably a number average molecular weight of 500 to 3,000, and more preferably a number average molecular weight of 800 to 2,500.
- a terminal functionalized polyphenylene ether resin having a number average molecular weight of more than 5,000 is used, solubility is deteriorated during processing, and it is impossible to perform sizing using a conventional laminate process, and heating is required to make a process in the process of copper clad laminate processing.
- the resin composition and the laminate material also have lower dielectric properties.
- the functionalized polyphenylene ether resin having a smaller number average molecular weight can better improve the compatibility with the crosslinking agent, that is, the molecular weight The smaller the mixing, the better the compatibility between the mixed components and the better the storage stability.
- the lower molecular weight provides better flow and facilitates better fillability during multilayer board processing.
- the phosphorus-containing polyphenylene ether resin composition further includes a co-crosslinking agent, and the co-crosslinking agent is
- the bismaleimide resin or/and the polyfunctional acrylate compound are preferably maleimide resins.
- the co-crosslinking agent is added in an amount of 5 to 50 parts by weight, for example, 7 parts by weight, 10 parts by weight, 13 parts by weight, 16 parts by weight, and 19 parts by weight based on 100 parts by weight of the terminal-functionalized polyphenylene ether resin. Parts, 22 parts by weight, 25 parts by weight, 28 parts by weight, 31 parts by weight, 35 parts by weight, 38 parts by weight, 41 parts by weight, 44 parts by weight or 47 parts by weight.
- the main purpose of the introduction of the co-crosslinking agent is to further improve the heat resistance of the cured product of the polyphenylene ether, since the maleimide resin can be functionalized with the terminal functionalized polyphenylene ether resin and the olefin resin.
- the saturated double bond undergoes a curing cross-linking reaction to form a cross-linked network structure composed of three, and the system has better heat resistance stability; if the amount of maleimide resin added is too small, the crosslink density is not improved. For the purpose of improving heat resistance, if the amount is too large, the crosslinking density of the system can be effectively increased, but the polarity of the structure of the maleimide itself is large, which causes a significant decrease in dielectric properties.
- the phosphorus-containing polyphenylene ether resin composition further includes an initiator.
- the initiator has a half-life temperature t 1/2 of not less than 100 ° C and is a peroxide radical initiator selected from the group consisting of dicumyl peroxide, tert-butyl peroxybenzoate, 2,5-di(2- Ethylhexanoyl peroxy)-2,5-dimethylhexane, di-(tert-butylperoxyisopropyl)benzene, peroxy(2,4-dichlorobenzoyl), 2,5- Dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butyl peroxy-2-ethylhexyl carbonate, 2,5-dimethyl-2,5-bis(tert-butyl Oxy)-3-hexyne, butyl 4,4-di(tert-butylperoxy)pentanoate, 1,1-
- the initiator in the polyphenylene ether resin composition of the present invention aims to improve the crosslinking curing effect.
- the terminal functionalized polyphenylene ether resin and the crosslinking agent can also be cured under heating and high temperature conditions, but laminated When the board is applied, the process conditions are difficult to meet the high temperature requirements, which makes the processing difficulty increase, and on the other hand, it is not conducive to the process efficiency and increase the production cost, so it is more advantageous to add the initiator.
- the initiator is added in an amount of 0.5 to 7 parts by weight, for example, 1.3 parts by weight, 1.6 parts by weight, 1.9 parts by weight, 2.2 parts by weight, 2.5 parts by weight, based on 100 parts by weight of the terminal functionalized polyphenylene ether resin. 3.1 parts by weight, 3.5 parts by weight, 3.9 parts by weight, 4.3 parts by weight, 4.7 parts by weight, 5 parts by weight, 5.4 parts by weight, 5.8 parts by weight, 6.2 parts by weight or 6.6 parts by weight.
- the phosphorus-containing polyphenylene ether resin composition further comprises a silane coupling agent, and the silane coupling agent is added in an amount of 0.1 to 10 by weight based on 100 parts by weight of the terminal-functionalized polyphenylene ether resin.
- a silane coupling agent for example, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, and 6 parts by weight 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight or 9.5 parts by weight.
- the kind of the coupling agent is not particularly limited.
- the coupling agent can further reduce the surface tension of the cured resin, further reduce the viscosity, and improve the fluidity of the resin composition.
- the addition of a coupling agent can effectively improve the bonding force between the resin and the filler, eliminate the interface between the two, and further reduce the water absorption rate of the cured product.
- the coupling agent may be a silane, a silane prepolymer or a titanate, and the silane coupling agent may be an epoxy silane coupling agent, an amino silane coupling agent, a phenylamino silane coupling agent, or a vinyl group.
- Silane coupling agent isocyanate-based silane coupling agent, acryl-based silane coupling agent, isobutylene silane coupling agent, styryl silane coupling agent, urea-based silane coupling agent, chloropropyl silane coupling agent, sulfur a silane coupling agent or a sulfurized silane coupling agent or the like.
- the phosphorus-containing polyphenylene ether resin composition further comprises a filler, the filler is an organic or inorganic filler, and the inorganic filler is selected from the group consisting of crystalline silica, fused silica, spherical silica, and hollow dioxide.
- the organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide or polyethersulfone powder.
- the shape, particle diameter and the like of the inorganic filler are also not particularly limited, and usually have a particle diameter of 0.01 to 50 ⁇ m, preferably 0.01 to 20 ⁇ m, more preferably 0.01 to 10 ⁇ m, and the inorganic filler having such a particle diameter range is more easily dispersed in the resin liquid. .
- the filler is added in an amount of 10 to 300 parts by weight, for example, 30 parts by weight, 60 parts by weight, 90 parts by weight, 120 parts by weight, 150 parts by weight, and 180 parts by weight based on 100 parts by weight of the terminal functionalized polyphenylene ether resin. Parts by weight, 210 parts by weight, 240 parts by weight or 270 parts by weight.
- the phosphorus-containing polyphenylene ether resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, or a lubricant. . These various additives may be used singly or in combination of two or more kinds.
- the present invention provides a prepreg prepared using the above-described phosphorus-containing polyphenylene ether resin composition, comprising a substrate and a phosphorus-containing polyphenylene ether resin composition as described above adhered to the substrate by impregnation and drying .
- the end group functionalized polyphenylene ether resin, the phosphorus containing composition, the optional crosslinking agent, optionally the co-crosslinking agent, the optional initiator, the optional coupling agent, and optionally the filler are first dissolved.
- a uniform glue is prepared in one or more organic solvents.
- the organic solvent is not particularly limited as long as it can dissolve the above components without affecting its reactivity; suitable solvents include: ketones such as methyl ethyl ketone, acetone, etc., ethers such as propylene glycol monomethyl ether, dibutyl ether, etc., esters Such as ethyl acetate, aromatics such as toluene, xylene, etc., halogenated hydrocarbons such as trichloroethane and the like. Each solvent may be used singly or in combination.
- Resin in glue The concentration of the solid matter can be appropriately changed depending on the kind and process in which the glue is impregnated into the substrate, for example, a suitable concentration thereof is 30 to 80%.
- the prepreg is obtained by impregnating the substrate with the glue prepared above, followed by heating and drying to remove the organic solvent and partially curing the resin composition in the substrate.
- the substrate is a woven or non-woven fabric made of organic fibers, carbon fibers or glass fibers; for a woven or non-woven fabric made of glass fibers, the main component comprises 50 to 80% by weight of SiO 2 . And a weight ratio of 0 to 30% of CaO, a weight ratio of 0 to 20% of Al 2 O 3 , a weight ratio of 5 to 25% of B 2 O 3 , and a weight ratio of 0 to 5% of MgO.
- the reinforcing material is preferably a braided fiber cloth, optionally E-Glass, T-Glass, NE-Glass, L-Glass, Q-Glass.
- the content of the resin used to impregnate the above substrate is preferably such that the content of the resin in the prepreg is 30% by mass or more. Since the dielectric constant of the substrate tends to be higher than that of the resin composition, in order to lower the dielectric constant of the laminate prepared from these prepregs, the content of the resin composition component in the prepreg is preferably higher than the above content.
- the present invention also provides a laminate comprising at least one laminated prepreg as described above.
- the present invention provides a copper-clad laminate produced using the above phosphorus-containing polyphenylene ether resin composition, comprising a plurality of laminated prepregs and copper laminated on one or both sides of the laminated prepreg. Foil.
- a multilayer printed wiring board can also be prepared by the following methods and steps: using a printed wiring board as an inner printed circuit board, surface-treating the copper foil thereon, and pressing according to requirements
- the prepreg of the present invention and the above-mentioned surface-treated printed wiring board stack are hot-pressed in a certain order, and the hot pressing conditions may be determined according to the composition ratio of the polyphenylene ether resin composition of the present invention, and there is no particular limited.
- the hot pressing conditions are preferably hot pressed for a period of time in a temperature range of 150 to 250 ° C and a pressure range of 1.0 MPa to 10.0 MPa.
- the laminate and the printed wiring board obtained by this method and the step have good high-frequency characteristics such as dielectric properties and the like, and also have good workability, heat resistance and moisture resistance.
- the copper foil used may be selected from an electrolytic copper foil or a rolled copper foil, and the surface roughness thereof is less than 5 ⁇ m. It can improve and improve the signal loss of laminate materials used in high frequency and high speed printed circuit boards.
- the copper foil used above can also be chemically treated with a silane coupling agent, and the coupling agent used is an epoxy silane coupling agent and a vinyl silane coupling.
- the present invention also provides a printed circuit board comprising at least one laminated prepreg as described above.
- the present invention has the following beneficial effects:
- the polyphenylene ether resin composition of the present invention is a low molecular weight functionalized polyphenylene ether resin composition, has good processability, maintains good dielectric properties and heat resistance of the polyphenylene ether resin, and adds a specific structure.
- the phosphorus-containing flame retardant component not only maintains the heat resistance, dielectric properties, and low water absorption of the original polyphenylene ether resin system, but also achieves halogen-free flame retardant, and the flame retardant reaches UL 94V-0 level.
- Synthetic method Referring to Synthesis Example 1, dichloromethane was replaced with dichloro-p-xylene to obtain DOPO derivative 2 of the formula (1) wherein R 1 was a phenyl group.
- the hypophosphite compound is:
- the polyphosphazene compound has the following structure:
- R is a methyl group, wherein n is an integer from 3 to 100.
- the hypophosphite compound is:
- the polyphosphazene compound has the following structure:
- R is an ethyl group, wherein n is an integer of from 3 to 100.
- the hypophosphite compound is:
- the polyphosphazene compound has the following structure:
- the hypophosphite compound is:
- the polyphosphazene compound has a mixture of both of the following structures:
- R is a methyl group, wherein n is an integer of 80;
- the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
- a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
- B-1000 as a crosslinking agent, 2.0 g of dicumyl peroxide as an initiator, 30 g of the phosphorus-containing composition of the mixing example 2 as a flame retardant, 0.8 g of a vinyl silane coupling agent and 80 g of silica (SC) -2050SQ)
- SC silica
- the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
- a copper foil having a thickness of 35 ⁇ m was attached to both sides of the eight prepregs prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
- Crosslinking agent 15 g of bismaleimide resin as co-curing agent, 3.0 g of dicumyl peroxide as initiator, 35 g of phosphorus-containing composition of mixing example 2 as flame retardant, 2 g of vinyl silane A coupling agent and 150 g of silica were used as a filler, and the above mixture was mixed in toluene and stirred to dissolve to obtain a uniform resin composition, that is, a gum solution.
- the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
- a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
- the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
- a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
- styrene-terminated polyphenylene ether resin OPE-2000 and 100 g of toluene as a solvent were mixed and dissolved to obtain a terminal-functionalized polyphenylene ether resin solution, and then 20 g of styrene-butadiene copolymer R100 was added as a crosslinking agent.
- the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
- a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
- a crosslinking agent 45 g of bismaleimide resin as a co-curing agent, 3.0 g of dicumyl peroxide as an initiator, and 35 g of the phosphorus-containing composition of the mixing example 4 as a flame retardant, treated with 200 g of vinylsilane Silica SC-2300SVJ as a filler, the above mixture is mixed in toluene, The mixture was stirred and dissolved to obtain a uniform resin composition, that is, a gum solution.
- the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
- a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
- a diene polymer Ricon 156MA17 as a crosslinking agent
- 25 g of a maleimide resin as a co-crosslinking agent
- 2.5 g of dicumyl peroxide as an initiator
- 35 g of a phosphorus-containing composition of the mixing example 3 as a flame retardant 300 g of vinylsilane-treated silica SC-2300SVJ was used as a filler, and the above mixture was mixed in toluene and stirred to dissolve to obtain a uniform resin composition, that is, a gum solution.
- the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
- a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
- the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg. 8 rise prepregs prepared above the overlap are attached to each side
- a copper foil having a thickness of 35 ⁇ m was heat-pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
- the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
- a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
- a coupling agent adding 2 g of dicumyl peroxide as an initiator, 45 g of ethyl-bis(tetrabromophthalimide) BT-93W, 0.8 g of an epoxy silane coupling agent and 80 g of silica as A filler, the above mixture was mixed in toluene, and stirred to dissolve to obtain a uniform resin composition, that is, a gum solution.
- the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
- a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
- the glue obtained by the above preparation was impregnated into an E-glass cloth, and dried by heating at 155 ° C for 3 to 10 minutes, and the solvent was completely evaporated to obtain a prepreg.
- a copper foil having a thickness of 35 ⁇ m was attached to both sides of the 8-up prepreg prepared above the overlap, and hot pressed at a temperature of 200 ° C and a pressure of 3.0 MPa for 90 minutes to obtain a double-sided copper-clad laminate.
- thermosetting composition composed of a polyphenylene ether resin, an olefin resin, and a bismaleimide resin can be cured to have excellent heat resistance and dielectric properties while satisfying the flame retardancy requirement of UL 94V-0.
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Abstract
Description
Claims (10)
- 一种含磷聚苯醚树脂组合物,其特征在于,其包含如权利要求1或2所述的含磷阻燃组合物和端基官能化聚苯醚树脂。
- 如权利要求3所述的树脂组合物,其特征在于,以所述端基官能化聚苯醚树脂为100重量份计,含磷阻燃组合物的添加量为15~60重量份,优选为20~50重量份,进一步优选为25~40重量份;优选地,所述端基官能化聚苯醚树脂为端羟基化聚苯醚树脂、环氧化聚苯醚树脂、乙烯基化聚苯醚树脂或氰基化聚苯醚树脂中的任意一种或者至少两种的混合物,优选为乙烯基化聚苯醚树脂或/和氰基化聚苯醚树脂,进一步优选为乙烯基化聚苯醚树脂;优选地,所述端基官能化聚苯醚树脂结构式如式(2)所示:式(2)中,a和b独立地为1~30的整数,Z为式(3)或(4)所示的结构,-(-O-Y-)-为式(5)所示的结构,-(-O-X-O-)-为式(6)所示的结构:式(4)中,A为亚芳香基、羰基或碳原子数为1~10的亚烷基,m为0~10的整数,R1、R2和R3相同或不同,独立地为氢或碳原子数10以下的烷基;式(5)中,R4与R6相同或不同,独立地为氢原子、卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基,R5与R7相同或不同,独立地为卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基;式(6)中,R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同,独立地为氢原子、卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基,B为碳原子数20以下的亚烃基、 n为0或1;R16为氢原子或碳原子数为1~10的烷基;优选地,所述端基官能化聚苯醚树脂为式(7)或(8)所示的结构:式(7)中,R1~R3相同或不同,独立地为氢或碳原子数10以下的烷基;R4与R6相同或不同,独立地为氢原子、卤素原子、碳原子数8以下的烷基或苯基;R5与R7相同或不同,独立地为卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基;R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同,独立地为氢原子、卤素原子、碳原子数8以下的烷基或碳原子数8以下的苯基;a和b独立地为1~30的整数,B为碳原子数20以下的亚烃基、n为0或者1,R16为氢原子或碳原子数为1~10的烷基;式(8)中,R4与R6相同或不同,独立地为氢原子、卤素原子、碳原子数8以下的烷基或苯基;R5与R7相同或不同,为卤素原子、碳原子数8以下的烷基或苯基;R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同,为氢原子、卤素原子、碳原子数8以下的烷基或苯基;a和b独立地为1~30的整数;B为碳原子数20以下的亚烃基,n为0或者1;优选地,所述端基官能化聚苯醚树脂为式(9)至(13)所示的结构:式(9)中,R1~R3相同或不同,为氢或碳原子数10以下的烷基;R4与R6相同或不同,为氢原子、卤素原子、碳原子数8以下的烷基或苯基;R5与R7相同或不同,为卤素原子、碳原子数8以下的烷基或苯基;R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同,为氢原子、卤素原子、碳原子数8以下的烷基或苯基;a和b独立地为1~30的整数;或,式(10)中,R1~R3相同或不同,为氢或碳原子数10以下的烷基;R4与R6相同或不同,为氢原子、卤素原子、碳原子数8以下的烷基或苯基;R5与R7相同或不同,为卤素原子、碳原子数8以下的烷基或苯基;R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同,为氢原子、卤素原子、碳原子数8以下的烷基或苯基;a和b独立地为1~30的整数;或,式(11)中,R1~R3相同或不同,为氢或碳原子数10以下的烷基;R4与R6相同或不同,为氢原子、卤素原子、碳原子数8以下的烷基或苯基;R5与R7 相同或不同,为卤素原子、碳原子数8以下的烷基或苯基;R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同,为氢原子、卤素原子、碳原子数8以下的烷基或苯基;a和b独立地为1~30的整数;或,式(12)中,R4与R6相同或不同,为氢原子、卤素原子、碳原子数8以下的烷基或苯基;R5与R7相同或不同,为卤素原子、碳原子数8以下的烷基或苯基;R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同,为氢原子、卤素原子、碳原子数8以下的烷基或苯基;a和b独立地为1~30的整数;或,式(13)中,R4与R6相同或不同,为氢原子、卤素原子、碳原子数8以下的烷基或苯基;R5与R7相同或不同,为卤素原子、碳原子数8以下的烷基或苯基;R8、R9、R10、R11、R12、R13、R14及R15之间相同或不同,为氢原子、卤素原子、碳原子数8以下的烷基或苯基;a和b独立地为1~30的整数。
- 如权利要求3-4之一所述的树脂组合物,其特征在于,所述含磷聚苯醚树脂组合物还包括交联剂;优选地,所述交联剂为带有不饱和双键的聚烯烃树脂,所述带有不饱和双键的聚烯烃树脂为聚丁二烯、马来酸酐改性聚丁二烯聚合物、丙烯酸改性聚丁 二烯聚合物、丁二烯-苯乙烯共聚物、丁二烯-苯乙烯-二乙烯基苯共聚物或环烯烃共聚物中的任意一种或者至少两种的混合物;优选地,以端基官能化聚苯醚树脂为100重量份计,所述带有不饱和双键的聚烯烃树脂的添加量为10~100重量份;优选地,所述端基官能化聚苯醚树脂的数均分子量为500~5000,优选数均分子量为500~3000,更优选数均分子量为800~2500;优选地,所述含磷聚苯醚树脂组合物还包括共交联剂;优选地,所述共交联剂为双马来酰亚胺树脂或/和多官能团丙烯酸酯化合物,优选为马来酰亚胺树脂;优选地,以端基官能化聚苯醚树脂为100重量份计,所述共交联剂的添加量为5~50重量份。
- 如权利要求3-5之一所述的树脂组合物,其特征在于,所述含磷聚苯醚树脂组合物还包括引发剂;优选地,所述引发剂的半衰期温度t1/2不小于100℃,为过氧化物自由基引发剂,选自过氧化二异丙苯、过氧化苯甲酸叔丁酯、2,5-二(2-乙基己酰过氧)-2,5-二甲基己烷、二-(叔丁基过氧异丙基)苯、过氧化(2,4-二氯苯甲酰)、2,5-二甲基-2,5-双(叔丁基过氧)己烷、过氧化-2-乙基己基碳酸叔丁酯、2,5-二甲基-2,5-双(叔丁基过氧)-3-己炔、4,4-二(叔丁基过氧化)戊酸丁酯、1,1-双(叔丁基过氧化)-3,3,5-三甲基环己烷、3,3,5,7,7-五甲基-1,2,4-三氧杂环庚烷、二叔丁基过氧化物或叔丁基过氧化异丙苯中的任意一种或者至少两种的混合物,优选过氧化二异丙苯;优选地,以端基官能化聚苯醚树脂为100重量份计,所述引发剂的添加量为0.5~7重量份;优选地,所述含磷聚苯醚树脂组合物还包括硅烷偶联剂,以端基官能化聚苯醚树脂为100重量份计,所述硅烷偶联剂的添加量为0.1~10重量份;优选地,所述含磷聚苯醚树脂组合物还包括填料,所述填料为有机或无机填料;优选地,所述无机填料选自结晶型二氧化硅、熔融二氧化硅、球形二氧化硅、空心二氧化硅、玻璃粉、氮化铝、氮化硼、碳化硅、氢氧化铝、二氧化钛、钛酸锶、钛酸钡、氧化铝、硫酸钡、滑石粉、硅酸钙、碳酸钙或云母中的任意一种或者至少两种的混合物;优选地,所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的任意一种或者至少两种的混合物;优选地,以端基官能化聚苯醚树脂为100重量份计,所述填料的添加量为10~300重量份。
- 一种预浸料,包括基材及通过含浸干燥后附着于基材上的如权利要求3-6之一所述的含磷聚苯醚树脂组合物。
- 一种层压板,包括至少一张叠合的如权利要求7所述的预浸料。
- 一种覆铜箔层压板,包括至少一张叠合的如权利要求7所述的预浸料及压覆于叠合后预浸料的一面或两面的铜箔;优选地,所述铜箔为电解铜箔或压延铜箔,所述铜箔为使用硅烷偶联剂进行化学处理,所用的偶联剂为环氧基硅烷偶联剂、乙烯基硅烷偶联剂或丙烯酸酯基硅烷偶联剂中的一种或至少两种的混合物,且其表面粗糙度小于5微米。
- 一种印制电路板,包括至少一张叠合的如权利要求7所述的预浸料。
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TWI612130B (zh) | 2018-01-21 |
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