CN109535653B - Phosphorus-containing epoxy resin composition, and prepreg and laminated board prepared from same - Google Patents
Phosphorus-containing epoxy resin composition, and prepreg and laminated board prepared from same Download PDFInfo
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- CN109535653B CN109535653B CN201811392536.7A CN201811392536A CN109535653B CN 109535653 B CN109535653 B CN 109535653B CN 201811392536 A CN201811392536 A CN 201811392536A CN 109535653 B CN109535653 B CN 109535653B
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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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
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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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
-
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
- B32B2307/7265—Non-permeable
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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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2471/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention discloses a phosphorus-containing epoxy resin composition, which comprises the following components in parts by weight: (A) phosphorus compound modified epoxy resin: 100 parts of (A); (B) curing accelerator: 0-5 parts; (C) cyanate ester resin: 5-80 parts; (D) polyphenylene ether resin: 5-70 parts; (E) filling: 0 to 100 parts. The phosphorus-containing epoxy resin composition has the characteristics of halogen-free flame retardance, high humidity and heat resistance, low water absorption, high flame retardance, high peel strength and good dielectric property; the prepreg and the laminated board prepared from the resin composition have the characteristics of halogen-free flame retardance, high humidity resistance, low water absorption, high flame retardance, high peel strength and good dielectric property, and can be used as printed circuit boards for electronic instruments.
Description
Technical Field
The invention relates to a phosphorus-containing epoxy resin composition, and a prepreg and a laminated board prepared from the phosphorus-containing epoxy resin composition, and belongs to the technical field of electronic materials.
Background
In the prior art, the traditional brominated flame retardant such as brominated epoxy resin, tetrabromobisphenol A and the like has excellent flame retardance and relatively low price, and is always the main flame retardant of the common FR-4 copper-clad plate. However, with the improvement of the quality of life and safety awareness of people, the safety requirements of people on electronic products at the sides are higher and higher. Bromine-containing flame retardants generate hydrogen bromide, which is an irritant and corrosive toxic gas such as dioxin and polybrominated dibenzofuran during combustion, and thus harm the health of people and cause pollution. In addition, the bond energy of the carbon-bromine bond in the bromine-containing flame retardant is weaker, so that the thermal decomposition temperature is lower, and the application of the bromine-containing flame retardant in a high-performance copper-clad plate is obviously insufficient. At present, the development direction of the flame retardant tends to be non-halogenated increasingly, and manufacturers of flame retardant materials in various countries begin to apply the flame retardant to be brominated in high polymers in a strict attitude, and the halogen-free flame retardant, especially the phosphorus flame retardant, gradually becomes the mainstream. Among them, DOPO (9, 10-Dihydro-9-oxa-10-phosphaphenthrene-10-oxide) is the most important, and after the printed circuit board is in high frequency, good flame retardant property and dielectric property can be obtained. However, because the DOPO ring has hydrolysis problem under high temperature, high humidity or alkaline condition, the phosphoric acid generated by hydrolysis will corrode copper wires, for example, P-O-C bond in phosphorus-containing epoxy resin or phosphorus-containing flame retardant is hydrolyzed to form P-OH bond, and the residual acid or acid generated after hydrolysis will corrode metal surface or metal wire to generate metal ion migration, which will affect the electrical performance of circuit board or packaged circuit board.
Chinese patent application CN101357999 discloses an epoxy resin containing DPO structure, and compared with an epoxy resin containing DOPO structure, the DPO epoxy resin has better humidity resistance, but in practical application, it is found that: the DPO epoxy resin has low peel strength, relatively poor flame retardance and slightly poor dielectric property, and can not meet the requirements of high-performance copper-clad plates.
On the other hand, all additive flame retardants in the prior art are physically blended in a resin system and cannot react with the resin, so that the resin system has high water absorption rate and poor heat resistance.
In addition, the polyphenylene oxide adopted in the prior art is a high-performance resin, and due to good symmetry of molecular chains, small intermolecular force and high aryl proportion, the polyphenylene oxide has excellent dielectric properties, namely low dielectric constant and dielectric loss, and can well meet the requirements of high-frequency application on the dielectric properties of materials. Meanwhile, the polyphenyl ether also has higher glass transition temperature, low water absorption rate, excellent impact resistance and the like, and has wide application prospect in high-frequency laminated plate materials. However, polyphenylene ether resins with large molecular weight (> 10000g/mol) have problems of poor solubility, poor compatibility with epoxy resins, high melt viscosity, and the like, and the prepared laminates have phenomena of insufficient heat resistance, low adhesiveness, poor dimensional stability, and the like, thereby seriously affecting the use reliability. Chinese patent 20111015600.5 discloses a thermosetting resin composition containing a low molecular weight polyphenylene ether resin containing phosphorus, an epoxy resin and a cyanate ester resin, and a laminated board with excellent low dielectric constant and dielectric loss is prepared by using the thermosetting resin composition, but the peeling strength is low (less than or equal to 1.0N/mm), and the manufacturing process requirements of high-performance electronic substrate materials cannot be met.
In view of the above problems, it is obvious that the development of a phosphorus-containing epoxy resin composition having halogen-free flame retardancy, high moisture and heat resistance, low water absorption, high flame retardancy, high peel strength and good dielectric properties, and a prepreg and a laminate using the same have positive practical significance.
Disclosure of Invention
The invention aims to provide a phosphorus-containing epoxy resin composition, and a semi-cured sheet and a laminated board prepared by using the same.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: a phosphorus-containing epoxy resin composition comprises the following components in parts by weight:
(A) phosphorus compound modified epoxy resin: 100 parts of (A);
(B) curing accelerator: 0-5 parts;
(C) cyanate ester resin: 5-80 parts;
(D) polyphenylene ether resin: 5-70 parts;
(E) filling: 0-100 parts;
the phosphorus compound modified epoxy resin is selected from any one or more of the following structures (I), (II) and (III):
wherein: r is
In the general formula of R, n is an integer of 1-8; r1、R2、R3The same or different, each being an alkyl group having 1 to 5 carbon atoms; EPOXY is selected from one of bisphenol A EPOXY resin, bisphenol F EPOXY resin, o-cresol novolac EPOXY resin, bisphenol A novolac EPOXY resin, phenol novolac EPOXY resin, trifunctional phenol type EPOXY resin, tetraphenylethane EPOXY resin, biphenyl type EPOXY resin, naphthalene ring type EPOXY resin, dicyclopentadiene type EPOXY resin, isocyanate type EPOXY resin, aralkyl novolac type EPOXY resin, alicyclic EPOXY resin, glycidyl amine type EPOXY resin and glycidyl ester type EPOXY resin.
Preferably, EPOXY is bisphenol A EPOXY resin, bisphenol F EPOXY resin, biphenyl type EPOXY resin, naphthalene ring type EPOXY resin, or dicyclopentadiene type EPOXY resin. More preferably, EPOXY is a biphenyl type EPOXY resin, a naphthalene ring type EPOXY resin or a dicyclopentadiene type EPOXY resin.
In the general formula of R, n is an integer of 1-8, for example, n is 2, 3, 4, 5, 6 or 7.
Preferably, R1、R2、R3Likewise, both are methyl, ethyl or propyl.
In the above technical solution, more preferably, the R group is
Preferably, the phosphorus content of the phosphorus compound modified epoxy resin is 0.1-10% by weight. The phosphorus content may be 0.5%, 0.8%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 9.5%. Preferably 1.0 to 5.0%.
Preferably, the number average molecular weight of the phosphorus compound modified epoxy resin is 200-2000 g/mol, and the epoxy equivalent is 100-1000 g/eq.
The number average molecular weight of the phosphorus compound modified epoxy resin is 300g/mol, 400g/mol, 500g/mol, 700g/mol, 1000g/mol, 1200g/mol, 1300g/mol, 1500g/mol, 1600g/mol, 1700g/mol, 1800g/mol and 1900 g/mol. Preferably 400 to 1600 g/mol.
The epoxy equivalent is 120g/eq, 160g/eq, 180g/eq, 200g/eq, 300g/eq, 400g/eq, 500g/eq, 600g/eq, 700g/eq, 800g/eq, 850g/eq, 900g/eq, 950g/eq, 970g/eq, 980g/eq, 990 g/eq. Preferably 200 to 800 g/eq.
In the above technical scheme, the cyanate ester resin is selected from one or more of bisphenol a type cyanate ester, bisphenol F type cyanate ester, dicyclopentadiene type cyanate ester, phenolic type cyanate ester, tetramethyl bisphenol F type cyanate ester, bisphenol M type cyanate ester, bisphenol E type cyanate ester, phosphorus-containing cyanate ester, and prepolymers of the above cyanate esters. Preferably, the amount of cyanate ester may be 6 parts, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 79 parts.
In the above technical scheme, the polyphenylene ether is polyphenylene ether or modified polyphenylene ether thereof having the following structure:
wherein m and n are adjusted to ensure that the molecular weight of the polyphenylene ether resin is within the range of 500-5000 g/mol;
x is-O-R-O-, R is S1, S2, S3, S4, S5 or S6,
S1：
S2：
S3：
S4：
S5：
S6：
the modified polyphenyl ether is selected from one or more of allyl modified polyphenyl ether, styrene modified polyphenyl ether, acrylate modified polyphenyl ether and vinyl benzyl modified polyphenyl ether, and the content of the modified polyphenyl ether is 5-70 parts by 100 parts of phosphorus compound modified epoxy resin in the component (A).
Preferably, the amount of polyphenylene ether may be 6 parts, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 69 parts.
In the above-mentioned embodiment, the resin composition further contains at least one of an epoxy resin, a modified or unmodified bismaleimide resin, and a silane resin other than the component (a).
The epoxy resin except the component (A) is selected from any one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, phenol novolac epoxy resin, trifunctional phenol epoxy resin, tetraphenylethane epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl novolac epoxy resin, alicyclic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin and phosphorus-containing epoxy resin. In the invention, the other epoxy resin accounts for 1-150% of the weight of the epoxy resin of the component (A).
The modified bismaleimide resin is allyl modified bismaleimide resin, amino modified bismaleimide resin or cyanate ester modified bismaleimide resin (BT resin), wherein the allyl modified bismaleimide resin is preferred; preferably, the number average molecular weight of the allyl modified bismaleimide is 2000-5000 g/mol, and the content is as follows: based on 100 parts of the component (A), the component (A) contains 1-50 parts.
In the above technical solution, the filler is selected from an organic filler or an inorganic filler;
the inorganic filler is selected from one or more of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talcum powder, boehmite, zinc borate, clay, mica, kaolin aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate and glass fiber powder;
the organic filler is selected from one or more of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyether sulfone powder.
Preferably, the particle size median value of the filler is 1-15 micrometers, and preferably, the median value of the filler is 1-10 micrometers. Most preferably, the filler is surface treated silica.
Preferably, the filler of the present invention is added in an amount of 0 to 100 parts by weight based on 100 parts by weight of the organic solid, and includes 0 part by weight, preferably 1 part by weight, 5 parts by weight, 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, 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, 95 parts by weight, 100 parts by weight.
In the technical scheme, the curing accelerator is selected from one or more of imidazole compounds and organic metal salts;
the imidazole compound is selected from one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole and 1-cyanoethyl-2-methylimidazole.
The organic metal salt is selected from one or more of cobalt acetylacetonate, copper acetylacetonate, iron acetylacetonate, zinc octoate, cobalt naphthenate and zinc naphthenate.
Preferably, the curing accelerator is contained in an amount of 0 to 5 parts by weight, including 0 part by weight, based on 100 parts by weight of the organic solid, and may be 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 or 5.0 parts by weight.
The invention also discloses a prepreg made of the phosphorus-containing epoxy 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. For example, the prepreg can be prepared by impregnating the glue solution with glass fiber cloth and then baking the glass fiber cloth at 80-170 ℃ for 1-10 minutes.
The solvent is selected from one or more of acetone, butanone, methyl isobutyl ketone, N-dimethylformamide, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, toluene and xylene.
In the above-mentioned embodiment, the 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 coloring agent, a lubricant, and the like. These various additives may be used alone or in combination of two or more.
The invention also discloses a laminated board, wherein a metal foil is coated on one or two sides of one prepreg, or after at least 2 prepregs are stacked, the metal foil is coated on one or two sides of the prepreg, and the laminated board can be obtained by hot press forming. For example, the sheet can be obtained by pressing the sheet at a pressure of 0.2 to 5MPa and a temperature of 180 to 250 ℃ for 2 to 4 hours.
Preferably, the metal foil is copper, aluminum, magnesium, nickel, iron, and alloys or composite metal foils of these metals. The copper foil used for the laminate is particularly preferably an electrolytic copper foil.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the invention develops a novel phosphorus-containing epoxy resin composition, adopts phosphorus compound modified epoxy resin with a very special structure, and can realize the synergistic flame retardance of P, N and Si of the epoxy resin, thereby greatly reducing the usage amount of phosphorus elements, further reducing the water absorption of a system and improving the flame retardance efficiency of the system; with the reduction of the P content in the system, the system can realize low water absorption rate, which also leads to more excellent dielectric property of the system;
2. in the epoxy resin composition, because the isocyanate group is introduced into the structure of the phosphorus compound in the phosphorus compound modified epoxy resin, the peel strength of the modified epoxy resin can be improved to a certain extent;
3. in the epoxy resin composition, because the phosphorus compound in the phosphorus compound modified epoxy resin contains silicon-oxygen bonds, a silicon-oxygen bond net structure can be formed in the curing process of the epoxy resin, so that the movement of the whole cured epoxy resin is limited, and the Tg of the modified epoxy resin is improved to a certain extent; thereby improving the heat resistance of the system;
4. experiments show that the phosphorus-containing epoxy resin composition has the characteristics of halogen-free flame retardance, high humidity and heat resistance, low water absorption, high flame retardance, high peel strength and good dielectric property; the prepreg and the laminated board prepared by using the resin composition have the characteristics of halogen-free flame retardance, high humidity and heat resistance, low water absorption rate, high flame retardance, high peel strength and good dielectric property, and can be used as a printed wiring board for electronic instruments;
5. the invention adopts the phosphorus compound modified epoxy resin as a main body and adopts the cyanate resin and the polyphenylene ether resin as the composite curing agent, thereby effectively improving the humidity resistance and the heat resistance of the cyanate resin and the dielectric property of a system, simultaneously improving the peeling strength of the system, obtaining unexpected effects and obtaining the prepreg and the laminated board with excellent performance.
Detailed Description
The invention is further described below with reference to the following examples:
synthesis example 1:
20.2g of DPO (structural formula 4), 20.5g of 3-isocyanate propyl trimethoxy silane, 70g of dichloromethane and 0.2g of triethylamine are added into a four-port reaction kettle provided with a stirring condensing device and nitrogen, the temperature is increased to 110 ℃, the reaction is carried out for 8 hours, and the dichloromethane is removed by reduced pressure distillation, so as to obtain powder DPO-3-isocyanate propyl trimethoxy silane.
Synthesis example 2:
31g of DPO-HQ (structural formula 5), 41g of 3-isocyanate propyl trimethoxy silane, 100g of xylene and 0.25g of triethylamine are added into a four-port reaction kettle provided with stirring and condensing equipment and nitrogen, the temperature is raised to 140 ℃, the reaction is carried out for 6 hours, and the xylene is removed by reduced pressure distillation, so as to obtain powder DPO-HQ-3-isocyanate propyl trimethoxy silane.
Synthesis example 3:
adding 36g of DPO-NQ (structural formula 6), 41g of 3-isocyanatopropyl trimethoxy silane, 100g of toluene and 0.3g of triethylamine into a four-port reaction kettle provided with a stirring condensing device and nitrogen, heating to 180 ℃, reacting for 7 hours, and removing the toluene by reduced pressure distillation to obtain powder DPO-NQ-3-isocyanatopropyl trimethoxy silane.
Synthesis example 4:
40g of DPO-3-isocyanatopropyltrimethoxysilane powder obtained in Synthesis example 1, 100g of biphenyl type epoxy resin (NC-3000, Japan chemical), 100g of dichloromethane and 0.3g of tributylamine were added to a four-port reaction vessel equipped with a stirring and condensing device and nitrogen, the temperature was raised to 130 ℃ for 6 hours, and dichloromethane was distilled off under reduced pressure to obtain a phosphide-modified epoxy resin having a phosphorus content of 2.18%.
Synthesis example 5:
45g of DPO-3-isocyanatopropyltrimethoxysilane powder obtained in Synthesis example 1, 100g of DCPD type epoxy resin (XD-1000, Japan chemical), 100g of dichloromethane and 0.3g of tributylamine were added into a four-port reaction vessel equipped with a stirring and condensing device and nitrogen, the temperature was raised to 140 ℃, reaction was carried out for 4 hours, and dichloromethane was removed by distillation under reduced pressure to obtain phosphide-modified epoxy resin having a phosphorus content of 2.36%.
Synthesis example 6:
85g of DPO-HQ-3-isocyanatopropyltrimethoxysilane powder obtained in Synthesis example 2, 100g of biphenyl type epoxy resin (NC-3000, Japan chemical), 130g of xylene and 0.4g of tributylamine were added into a four-port reaction vessel equipped with a stirring and condensing device and nitrogen, the temperature was raised to 150 ℃, reaction was carried out for 7 hours, and xylene was removed by distillation under reduced pressure to obtain a phosphide-modified epoxy resin having a phosphorus content of 1.98%.
Synthesis example 7:
90g of DPO-HQ-3-isocyanatopropyl trimethoxysilane powder obtained in synthesis example 2, 100g of o-cresol formaldehyde epoxy resin (N-695, Japan DIC), 130g of xylene and 0.4g of tributylamine are added into a four-port reaction kettle provided with stirring and condensing equipment and nitrogen, the temperature is raised to 155 ℃, the reaction is carried out for 3 hours, and the xylene is removed by reduced pressure distillation to obtain phosphide modified epoxy resin with the phosphorus content of 2.04 percent.
Synthesis example 8:
110g of DPO-NQ-3-isocyanatopropyltrimethoxysilane powder obtained in Synthesis example 3, 100g of bisphenol A type epoxy resin (NPEL-128, south Asia, Taiwan), 180g of toluene and 0.5g of tributylamine were added into a four-port reaction kettle equipped with a stirring and condensing device and nitrogen, the temperature was raised to 175 ℃, the reaction was carried out for 6 hours, and the toluene was removed by distillation under reduced pressure to obtain phosphide-modified epoxy resin with a phosphorus content of 2.11%.
Synthesis example 9:
90g of DPO-NQ-3-isocyanatopropyltrimethoxysilane powder obtained in Synthesis example 3, 100g of biphenyl type epoxy resin (NC-3000, Japan chemical), 180g of toluene and 0.5g of tributylamine were added into a four-port reaction vessel equipped with a stirring and condensing device and nitrogen, the temperature was raised to 170 ℃, the reaction was carried out for 4 hours, and the toluene was removed by distillation under reduced pressure to obtain a phosphide-modified epoxy resin having a phosphorus content of 1.91%.
Example 1:
70g of the modified epoxy resin obtained in Synthesis example 4 was added with 20g of bisphenol A cyanate ester resin (BA-3000S, Lonza), 10g of polyphenylene ether resin (having the structure of formula IV, R ═ S2), 0.2g of 2-ethyl-4-methylimidazole, 0.2g of zinc naphthenate and an appropriate amount of methyl ethyl ketone solvent, and stirred and mixed uniformly to obtain a dope.
The glue solution is dipped and coated on E glass fiber cloth (2116, single weight 104 g/m)2) And drying in an oven at 160 ℃ for 5min to obtain the prepreg.
And placing a metal copper foil on each of the upper and lower prepregs, and placing the prepregs in a vacuum hot press for pressing to obtain the laminated board. The specific pressing process is pressing under 1.5Mpa and 220 deg.C for 2 hr.
The laminate properties obtained are shown in table 1.
Example 2:
60g of the modified epoxy resin obtained in Synthesis example 5 was added with 15g of dicyclopentadiene cyanate ester resin (CY-3, Jiangdu Malayu Kogyo Co., Ltd.), 25g of polyphenylene ether resin (having the structure shown in formula IV, wherein R is S1), 0.1g of 2-methylimidazole, 0.2g of zinc naphthenate and an appropriate amount of methyl ethyl ketone solvent, and stirred and mixed uniformly to obtain a glue solution.
The preparation methods of the prepreg and the laminated board are the same as those of example 1.
The laminate properties obtained are shown in table 1.
Example 3:
65g of the modified epoxy resin obtained in Synthesis example 6 was added with 20g of bisphenol E type cyanate ester resin (CY-9, Jiangdu malt chemical Co., Ltd.), 15g of polyphenylene ether resin (having the structure of formula IV, R ═ S2), 0.3g of 2-ethyl-4-methylimidazole, 0.1g of cobalt acetylacetonate and an appropriate amount of methyl ethyl ketone solvent, and stirred and mixed uniformly to obtain a cement.
The preparation methods of the prepreg and the laminated board are the same as those of example 1.
The laminate properties obtained are shown in table 1.
Example 4:
60g of the modified epoxy resin obtained in Synthesis example 7 was added with 20g of novolac cyanate ester resin (CY-5, Jiangdu malt chemical Co., Ltd.), 20g of polyphenylene ether resin (having the structure of formula IV, R ═ S2), 15g of fused silica, 0.4g of 2-phenylimidazole, 0.2g of cobalt acetylacetonate and an appropriate amount of methyl ethyl ketone solvent, and stirred and mixed uniformly to obtain a liquid cement.
The preparation methods of the prepreg and the laminated board are the same as those of example 1.
The laminate properties obtained are shown in table 1.
Example 5:
65g of the modified epoxy resin obtained in Synthesis example 8 was added with 25g of bisphenol E type cyanate ester resin (CY-5, Jiangdu malt chemical Co., Ltd.), 10g of polyphenylene ether resin (having the structure of formula IV, R ═ S1), 15g of fused silica, 0.4g of 2-phenylimidazole, 0.3g of cobalt acetylacetonate and an appropriate amount of methyl ethyl ketone solvent, and stirred and mixed uniformly to obtain a liquid cement.
The preparation methods of the prepreg and the laminated board are the same as those of example 1.
The laminate properties obtained are shown in table 1.
Example 6:
60g of the modified epoxy resin obtained in Synthesis example 9 was added with 20g of novolac cyanate ester resin (CY-9, Jiangdu malt chemical Co., Ltd.), 20g of polyphenylene ether resin (having a structure represented by formula IV, R ═ S1), 0.3g of 2-ethyl-4-methylimidazole, 0.2g of zinc octoate and an appropriate amount of methyl ethyl ketone solvent, and stirred and mixed uniformly to obtain a glue solution.
The preparation methods of the prepreg and the laminated board are the same as those of example 1.
The laminate properties obtained are shown in table 1.
Comparative example 1:
70g of the modified epoxy resin obtained in Synthesis example 4 was added to 70g of methyl ethyl ketone, and the mixture was stirred to completely dissolve the resin. After the solution was completely dissolved, 30g of phenol novolac (PSM-4357, Nippon chemical), 0.2g of 2-ethyl-4-methylimidazole and a suitable amount of butanone solvent were added and mixed to obtain a dope.
The prepreg and the copper clad laminate were prepared in the same manner as in example 1.
The properties of the copper-clad laminate obtained are shown in Table 1.
Comparative example 2:
108.6g of phosphorus-containing epoxy resin of DOPO type (XZ92530, Olin, USA) was stirred to be completely dissolved. After the solution was completely dissolved, 24g of phenol novolac (PSM-4357, Nippon chemical), 0.2g of 2-ethyl-4-methylimidazole and a suitable amount of butanone solvent were added and mixed well to obtain a glue solution.
The prepreg and the copper clad laminate were prepared in the same manner as in example 1.
The properties of the copper-clad laminate obtained are shown in Table 1.
Comparative example 3:
40g of the modified epoxy resin obtained in Synthesis example 4 was added with 40g of bisphenol A cyanate ester resin (BA-3000S, Lonza), 20g of polyphenylene ether resin (having the structure of formula IV, R ═ S2), 0.2g of 2-ethyl-4-methylimidazole, 0.2g of zinc naphthenate and an appropriate amount of methyl ethyl ketone solvent, and stirred and mixed uniformly to obtain a dope.
The prepreg and the copper clad laminate were prepared in the same manner as in example 1.
The properties of the copper-clad laminate obtained are shown in Table 1.
TABLE 1 Properties of copper-clad laminates obtained in different examples
Note: the relevant test data cells in the table are based on laminate samples with RC-50%.
The test methods for the properties in the table are as follows:
(1) flame resistance (flame retardancy): measured according to the UL94 method.
(2) Water absorption (%): water absorption in the A state was measured according to the method specified in IPC-TM-6502.6.2.1.
(3) Dielectric constant: the dielectric constant at 1GHz was measured by the plate method according to IPC-TM-6502.5.5.9.
(4) Dielectric loss tangent: the dielectric dissipation factor at 1GHz was measured by the plate method according to IPC-TM-6502.5.5.9.
(5) Glass transition temperature (Tg,. degree.C.): the measurement was carried out by Differential Scanning Calorimetry (DSC) method in accordance with the DSC method defined by IPC-TM-6502.4.25.
(6) Peel strength (PS, N/mm): 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.
(7) Tin immersion heat resistance after moist heat treatment: 3 samples of 10cm X10 cm, 0.80mm in thickness and having both sides free of metal foil were dried at 100 ℃ for 2 hours, and then treated at 121 ℃ under 2 atmospheres in a Pressure Cooker test (Pressure Cooker test) machine for 1 hour, and then dipped in tin at 288 ℃ for 20 seconds, and visually observed for the presence or absence of delamination. If there are 0, 1, 2, 3 blocks in the 3 blocks, the layering phenomena are respectively recorded as 0/3, 1/3, 2/3, 3/3.
As can be seen from Table 1, the epoxy resin modified by DPO-3-isocyanatopropyltrimethoxysilane cured by the phenol-formaldehyde novolac resin in the comparative example 1 has improved flame retardance, water absorption, wet heat resistance and dielectric property compared with the epoxy resin modified by DOPO cured by the phenol-formaldehyde novolac resin in the comparative example 2, but has larger difference compared with the examples, which shows that the performance of the phosphorus-containing epoxy resin is deteriorated by the phenol-formaldehyde novolac resin as a curing agent; comparative example 2 the dielectric properties of the DOPO modified epoxy resin cured by the phenolic novolac resin are significantly inferior to those of the examples and comparative example 1; comparative example 3 modified epoxy resin synthesized by curing a large amount of cyanate ester resin and a small amount of PPO resin has quite excellent dielectric properties, but has poor wet heat resistance; the embodiment of the invention has the characteristics of high flame retardance, low dielectric constant, low dielectric loss tangent, low water absorption, high heat resistance, excellent humidity resistance and good adhesion with copper foil. The invention has excellent peeling strength mainly because the phosphorus-containing epoxy resin contains isocyanate group and has good bonding effect between the N atom on the group and the copper foil, thereby improving the peeling strength of the system and overcoming the defect of comprising polyphenyl ether as a composite curing agent.
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 (10)
1. The phosphorus-containing epoxy resin composition is characterized by comprising the following components in parts by weight:
(A) phosphorus compound modified epoxy resin: 100 parts of (A);
(B) curing accelerator: 0-5 parts;
(C) cyanate ester resin: 5-80 parts;
(D) polyphenylene ether resin: 5-70 parts;
(E) filling: 0-100 parts;
the phosphorus compound modified epoxy resin is selected from any one or more of the following structures (I), (II) and (III):
(I)
(II)
(III)
wherein: r is
In the general formula of R, n is an integer of 1-8; r1、R2、R3The same or different, each being an alkyl group having 1 to 5 carbon atoms; EPOXY is selected from one of bisphenol A EPOXY resin, bisphenol F EPOXY resin, o-cresol novolac EPOXY resin, bisphenol A novolac EPOXY resin, phenol novolac EPOXY resin, trifunctional phenol type EPOXY resin, tetraphenylethane EPOXY resin, biphenyl type EPOXY resin, naphthalene ring type EPOXY resin, dicyclopentadiene type EPOXY resin, isocyanate type EPOXY resin, aralkyl novolac type EPOXY resin, alicyclic EPOXY resin, glycidyl amine type EPOXY resin and glycidyl ester type EPOXY resin.
2. The phosphorus-containing epoxy resin composition according to claim 1, wherein: the phosphorus content of the phosphorus compound modified epoxy resin is 0.1-10% by weight.
3. The phosphorus-containing epoxy resin composition according to claim 1, wherein: the number average molecular weight of the phosphorus compound modified epoxy resin is 200-2000 g/mol, and the epoxy equivalent is 100-1000 g/eq.
4. The phosphorus-containing epoxy resin composition according to claim 1, wherein: the cyanate resin is selected from one or more of bisphenol A cyanate, bisphenol F cyanate, dicyclopentadiene cyanate, phenolic cyanate, tetramethyl bisphenol F cyanate, bisphenol M cyanate, bisphenol E cyanate, phosphorus cyanate and prepolymers of the cyanate.
5. The phosphorus-containing epoxy resin composition according to claim 1, wherein: the number average molecular weight of the polyphenylene ether resin is 500-5000 g/mol, and the hydroxyl equivalent weight is 250-2500 g/eq.
6. The phosphorus-containing epoxy resin composition according to claim 1, wherein: the filler is selected from organic filler or inorganic filler;
the inorganic filler is selected from one or more of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talcum powder, boehmite, zinc borate, clay, mica, kaolin, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate and glass fiber powder;
the organic filler is selected from one or more of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyether sulfone powder.
7. The phosphorus-containing epoxy resin composition according to claim 1, wherein: the curing accelerator is selected from one or more of imidazole compounds and organic metal salts;
the imidazole compound is selected from one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole and 1-cyanoethyl-2-methylimidazole.
8. A prepreg manufactured by using the phosphorus-containing epoxy resin composition as claimed in any one of claims 1 to 7, wherein: dissolving any one of the resin compositions of claims 1-7 with a solvent to prepare a glue solution, then dipping the reinforcing material in the glue solution, and heating and drying the dipped reinforcing material to obtain the prepreg.
9. 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 8, or by laminating at least 2 prepregs according to claim 8, coating a metal foil on one side or both sides, and hot press forming.
10. The laminate of claim 9, wherein: the metal foil is copper, aluminum, magnesium, nickel, iron and alloy or composite metal foil of the metals.
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