CN108250675B - Phosphorus-containing active ester, halogen-free composition thereof and copper-clad substrate - Google Patents

Phosphorus-containing active ester, halogen-free composition thereof and copper-clad substrate Download PDF

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CN108250675B
CN108250675B CN201611238071.0A CN201611238071A CN108250675B CN 108250675 B CN108250675 B CN 108250675B CN 201611238071 A CN201611238071 A CN 201611238071A CN 108250675 B CN108250675 B CN 108250675B
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halogen
resin composition
component
composition according
weight
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CN108250675A (en
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曾宪平
徐浩晟
何烈相
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B15/00—Layered products comprising a layer of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • 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
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/6574—Esters of oxyacids of phosphorus
    • 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
    • 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
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
    • 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'
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • 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
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • 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
    • 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
    • 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
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    • B32B2262/101—Glass fibres
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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Abstract

The invention provides phosphorus-containing active ester, a halogen-free resin composition thereof, and a prepreg and a laminated board using the same. The halogen-free resin composition comprises: (A) a thermosetting resin; (B) a phosphorus-containing active ester resin. The prepreg and the laminated board made of the halogen-free resin composition have low dielectric loss factors and can realize halogen-free flame retardance.

Description

Phosphorus-containing active ester, halogen-free composition thereof and copper-clad substrate
Technical Field
The invention belongs to the technical field of copper-clad plates, and particularly relates to phosphorus-containing active ester, a halogen-free resin composition thereof, and a prepreg, a laminated board and a printed circuit board using the phosphorus-containing active ester.
Background
With the development of electronic components toward miniaturization, light weight, thinness, high performance, and multi-functionalization, high-frequency and high-speed signal transmission is accompanied. This requires that the electronic material have low dielectric constant and low dielectric loss ratios, which are related to the structure of the material, while low dielectric constant, low dielectric loss resins generally have: large free volume, low polarizability, low water absorption, low dielectric constant structure, and the like. In addition, on 1/7/2006, two environmental protection instructions of the european union, namely an instruction on scrapping electrical and electronic equipment and an instruction on limiting the use of certain hazardous substances in electrical and electronic equipment, are officially implemented, the development of the halogen-free flame-retardant copper-clad laminate becomes a hot spot in the industry, and manufacturers of the copper-clad laminates have made efforts to develop their own halogen-free flame-retardant copper-clad laminates.
The phosphorus-containing compound is introduced into the resin matrix of the copper-clad plate, so that the halogen-free flame-retardant copper-clad plate becomes a main technical route of halogen-free flame retardant. The phosphorus flame retardant widely adopted in the field of copper-clad plates at present is mainly divided into a reaction type flame retardant and an additive type flame retardant. The reaction type is mainly DOPO compounds, mainly phosphorus-containing epoxy resin and phosphorus-containing phenolic resin, and the phosphorus content is 2-10%. However, in practical application, the DOPO compound has the characteristics of high water absorption rate, poor dielectric property and poor wet heat resistance of the plate. The additive type is mainly phosphazene and phosphonate compounds, the flame retardant efficiency of the additive type flame retardant is low, and the flame retardant requirement can be met by adding more flame retardant. Meanwhile, due to the low melting point (generally lower than 150 ℃), the high-melting-point aluminum alloy is easy to migrate to the surface of a plate in the processing process of the laminated plate, and the performance of the plate is influenced.
Disclosure of Invention
Aiming at the problems of the prior art, the invention aims to provide a novel phosphorus-containing active ester, and the phosphorus-containing active ester is introduced into thermosetting resin to prepare a halogen-free resin composition, and a prepreg and a laminated board using the halogen-free resin composition.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a phosphorus-containing active ester, which comprises a component with a structure shown as a formula (I):
Figure GDA0002784363100000021
wherein R is
Figure GDA0002784363100000022
R1Is composed of
Figure GDA0002784363100000023
m represents the average degree of polymerization, m is any number between 0.25 and 3, such as 0.25, 0.5, 1, 1.2, 1.8, 2.05, 2.8 or 3, and the specific values therebetween are not exhaustive for the purpose of brevity and clarity.
The invention also aims to provide a halogen-free resin composition, which comprises the following components:
(A) a thermosetting resin;
(B) a phosphorus-containing active ester resin;
the phosphorus-containing active ester resin has a structure shown in a formula (I):
Figure GDA0002784363100000031
wherein R is
Figure GDA0002784363100000032
R1Is composed of
Figure GDA0002784363100000033
m represents the average degree of polymerization, m is any number between 0.25 and 3, such as 0.25, 0.5, 1, 1.2, 1.8, 2.05, 2.8 or 3, and the specific values therebetween are not exhaustive for the purpose of brevity and clarity.
The invention introduces the phosphorus-containing structure active ester into the thermosetting resin, and does not generate secondary hydroxyl by utilizing the reaction of the active ester and the epoxy resin and the like; the halogen-free flame retardant material can meet the halogen-free flame retardant requirement, and can improve the electrical property of the system (reduce dielectric loss factor) so as to realize the non-halogenation of the high-frequency high-speed substrate material.
According to the present invention, the thermosetting resin is any one of or a mixture of at least two of epoxy resin, benzoxazine resin, cyanate ester resin, unsaturated polyester resin, vinyl resin, bismaleimide resin, BT resin, phenolic resin, polyurethane resin, thermosetting polyimide, aryl acetylene resin or furan resin, wherein a typical but non-limiting mixture is: epoxy and benzoxazine resins, cyanate ester resins and unsaturated polyester resins, vinyl resins and bismaleimide resins.
In the present invention, the epoxy resin is any one of or a mixture of at least two of bisphenol a type epoxy resin, bisphenol F type epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin or naphthol epoxy resin, wherein a typical but non-limiting mixture is: bisphenol a-type epoxy resins and bisphenol F-type epoxy resins, bisphenol F-type epoxy resins and dicyclopentadiene epoxy resins, biphenyl epoxy resins and naphthol epoxy resins.
Preferably, the epoxy resin is a diphenol epoxy resin or/and a DCPD novolac epoxy resin, which has both heat resistance and dielectric property and low water absorption.
In the present invention, the ratio of the epoxy equivalent of the epoxy resin to the ester equivalent of the phosphorus-containing active ester resin is 1 (0.9-1.1), such as 1:0.9, 1:0.95, 1:1, 1:1.05 or 1:1.1, and the specific values between the above values are not exhaustive, and for brevity, the specific values included in the range are preferably 1 (0.95-1.05).
In the present invention, the halogen-free resin composition may further include a curing accelerator, component (C), which cures the resin and accelerates the curing speed of the resin.
Preferably, the curing accelerator is added in an amount of 0.05 to 1 part by weight, for example, 0.05 part by weight, 0.08 part by weight, 0.1 part by weight, 0.15 part by weight, 0.2 part by weight, 0.25 part by weight, 0.3 part by weight, 0.35 part by weight, 0.4 part by weight, 0.45 part by weight, 0.5 part by weight, 0.55 part by weight, 0.6 part by weight, 0.65 part by weight, 0.7 part by weight, 0.75 part by weight, 0.8 part by weight, 0.85 part by weight, 0.9 part by weight, or 1 part by weight, based on 100 parts by weight of the sum of the addition amounts of the component (a) and the component (B), and specific point values between the above-mentioned values are not listed in the present invention for the sake of brevity and the range is not listed in specific point values.
Preferably, the curing accelerator is any one of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl-4-ethylimidazole or 2-phenylimidazole or a mixture of at least two of them, wherein a typical but non-limiting mixture is: 4-dimethylaminopyridine and 2-methylimidazole, 2-methylimidazole and 2-methyl-4-ethylimidazole, 2-methyl-4-ethylimidazole and 2-phenylimidazole.
In the present invention, the halogen-free resin composition may further comprise component (D) a flame retardant compound, which is a halogen-free flame retardant.
Preferably, the flame retardant compound is added in an amount of 0 to 50 parts by weight, for example, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 parts by weight, based on 100 parts by weight of the sum of the addition amounts of the component (a), the component (B) and the component (C), and specific point values between the above values are not exhaustive, and the invention is not limited to the specific point values included in the ranges for brevity and conciseness.
Preferably, the flame retardant compound is any one or a mixture of at least two of phosphorus-containing phenolic resin, phosphorus-containing bismaleimide, phosphinate, aryl phosphate type compound, nitrogen-phosphorus intumescent flame retardant, phosphazene type flame retardant or organic polymer flame retardant, wherein a typical but non-limiting mixture is: phosphorus-containing phenolic resin, phosphorus-containing bismaleimide, phosphinate, a nitrogen-phosphorus intumescent flame retardant and a phosphazene flame retardant.
Preferably, the halogen-free resin composition may further include a filler of component (E), the filler being organic or/and inorganic, which is mainly used to adjust some physical property effects of the composition, such as lowering of Coefficient of Thermal Expansion (CTE), lowering of water absorption, increasing of thermal conductivity, and the like.
Preferably, the filler is added in an amount of 0 to 100 parts by weight, preferably 0 to 50 parts by weight, based on 100 parts by weight of the sum of the addition amounts of component (a), component (B), component (C) and component (D). The filler is added in an amount of, for example, 0.5 parts by weight, 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, or 100 parts by weight, and specific point values between the above-mentioned values are not exhaustive, and the invention is not limited to the specific point values included in the ranges for brevity.
Preferably, the inorganic filler is any one or a mixture of at least two of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, or glass fiber powder, wherein a typical but non-limiting mixture is: a mixture of fused silica and crystalline silica, a mixture of spherical silica and hollow silica, a mixture of aluminum hydroxide and alumina, a mixture of talc powder and aluminum nitride, a mixture of boron nitride and silicon carbide, a mixture of barium sulfate and barium titanate, a mixture of strontium titanate and calcium carbonate, a mixture of calcium silicate, mica and glass fiber powder, a mixture of fused silica, crystalline silica and spherical silica, a mixture of hollow silica, aluminum hydroxide and alumina, a mixture of talc, aluminum nitride and boron nitride, a mixture of silicon carbide, barium sulfate and barium titanate, a mixture of strontium titanate, calcium carbonate, calcium silicate, mica and glass fiber powder.
Preferably, the organic filler is any one of polytetrafluoroethylene powder, polyphenylene sulfide or polyether sulfone powder or a mixture of at least two of them, wherein a typical but non-limiting mixture is: the composite material comprises a mixture of polytetrafluoroethylene powder and polyphenylene sulfide, a mixture of polyether sulfone powder and polytetrafluoroethylene powder, a mixture of polyphenylene sulfide and polyether sulfone powder and a mixture of polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
Preferably, the filler is silicon dioxide, the particle size median value of the filler is 1-15 μm, and the particle size median value of the filler is preferably 1-10 μm.
The term "comprising" as used herein means that it may comprise, in addition to the components, other components which impart different properties to the halogen-free resin composition. In addition, the term "comprising" as used herein may be replaced by "being" or "consisting of … …" as closed.
For example, the halogen-free 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, a lubricant, and the like. These various additives may be used alone or in combination of two or more.
The preparation method of the halogen-free resin composition is a conventional technical means in the field, and the specific method comprises the following steps: firstly, adding the solid matter, then adding the liquid solvent, stirring until the solid matter is completely dissolved, then adding the liquid resin and the accelerator, and continuously stirring uniformly.
The solvent in the present invention is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol and butanol, ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol and butyl carbitol, ketones such as acetone, butanone, methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and ethoxyethyl acetate; nitrogen-containing solvents such as N, N-dimethylformamide and N, N-dimethylacetamide. The above solvents may be used alone or in combination of two or more. Ketones such as acetone, methyl ethyl ketone, and cyclohexanone are preferable. The addition amount of the solvent is selected by the skilled person according to the experience of the person in the art, so that the resin glue solution can reach the viscosity suitable for use.
The present invention also provides a prepreg comprising a reinforcing material and the above halogen-free resin composition attached thereto by impregnation and drying.
Exemplary reinforcing materials are non-woven fabrics and/or other fabrics, such as natural fibers, organic synthetic fibers, and inorganic fibers.
The glue solution is used for infiltrating reinforcing materials such as glass cloth and other fabrics or organic fabrics, and the impregnated reinforcing materials are heated and dried in an oven at 155 ℃ for 5-10 minutes to obtain the prepreg.
It is a fourth object of the present invention to provide a laminate comprising at least one sheet of prepreg as described above.
The laminate of the present invention includes a laminate made by bonding one or more sheets of prepreg together by heating and pressing, and a metal foil bonded to one or both sides of the laminate. The laminated board is prepared by curing in a hot press, the curing temperature is 150-250 ℃, and the curing pressure is 10-60 kg/cm2. The metal foil is copper foil, nickel foil, aluminum foil, SUS foil, etc., and the material is not limited.
The fifth purpose of the invention is to provide a printed circuit board, which comprises at least one prepreg.
Compared with the prior art, the invention has the following beneficial effects:
(1) by introducing the novel active ester containing the phosphorus structure into the thermosetting resin and utilizing the reaction of the active ester with the epoxy resin and the like, secondary hydroxyl is not generated, so that the halogen-free flame retardant requirement can be met, the electrical property of the system can be improved (the dielectric loss factor is reduced), and the high-frequency high-speed substrate material is possible to be free of halogenation;
(2) the prepreg, the laminated board and the metal foil-clad laminated board manufactured by using the halogen-free resin composition have low dielectric loss factors, the Df value of the prepreg, the laminated board and the metal foil-clad laminated board is between 0.0076 and 0.0097, and halogen-free flame retardance is realized and reaches UL 94V-0.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
While the following is a detailed description of the embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and alterations without departing from the principle of the embodiments of the present invention, and such modifications and alterations are also considered as the protection scope of the embodiments of the present invention.
The following examples are intended to illustrate the invention in more detail. The embodiments of the present invention are not limited to the following specific examples. The present invention can be modified and implemented as appropriate without changing the scope of the claims.
Synthesis example 1
Heating 0.3mol of DOPO to 160 ℃ to melt, adding 0.1mol of 4, 4' -dihydroxybenzophenone into the molten DOPO, generating water in the reaction process, and evaporating the generated water under reduced pressure to promote the forward movement of the reaction. After reacting for 4h, cooling to 100 ℃, adding 100ml of toluene, dissolving excessive DOPO in the toluene, precipitating the product as white powder, filtering to obtain a product, washing and purifying by tetrahydrofuran to obtain 2DOPO-2 PhOH.
628.5g (1mol) of 2DOPO-2PhOH and 816g of methyl isobutyl ketone (MIBK) were put into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, and the inside of the system was replaced with nitrogen gas under reduced pressure to dissolve the compounds. Then 182.7g (0.9mol) of terephthaloyl chloride is added to react for 2 hours, and the temperature in the system is controlled below 60 ℃; then, 114g (1.2mol) of phenol was added to the system, and the reaction was continued for 1 hour; 189g of 20% sodium hydroxide aqueous solution is slowly dropped under the condition of introducing nitrogen; stirring was continued for 1h under these conditions. After the reaction was completed, the aqueous layer was removed by static liquid separation. Water was added to the MIBK phase in which the reaction product was dissolved, followed by stirring and mixing, and by static liquid separation, the aqueous layer was removed. The above procedure was repeated until the pH of the aqueous layer reached about 7.0. Then, water was removed by a decanter, followed by distilling off MIBK under reduced pressure to give a phosphorus-containing active ester resin A1.
Synthesis example 2
Heating 0.3mol of DOPO to 160 ℃ to melt, adding 0.1mol of 4, 4' -dihydroxybenzophenone into the molten DOPO, generating water in the reaction process, and evaporating the generated water under reduced pressure to promote the forward movement of the reaction. After reacting for 4h, cooling to 100 ℃, adding 100ml of toluene, dissolving excessive DOPO in the toluene, precipitating the product as white powder, filtering to obtain a product, washing and purifying by tetrahydrofuran to obtain 2DOPO-2 PhOH.
628.5g (1mol) of 2DOPO-2PhOH and 816g of methyl isobutyl ketone (MIBK) were put into a flask equipped with a thermometer, a dropping funnel, a condenser, a fractionating tube and a stirrer, and the inside of the system was replaced with nitrogen gas under reduced pressure to dissolve the compounds. Then 182.7g (0.9mol) of terephthaloyl chloride is added to react for 2 hours, and the temperature in the system is controlled below 60 ℃; then, 172.8g (1.2mol) of naphthol is added into the system, and the reaction is continued for 1 hour; 189g of 20% sodium hydroxide aqueous solution is slowly dropped under the condition of introducing nitrogen; stirring was continued for 1 hour under these conditions. After the reaction was completed, the aqueous layer was removed by static liquid separation. Water was added to the MIBK phase in which the reaction product was dissolved, followed by stirring and mixing, and by static liquid separation, the aqueous layer was removed. The above procedure was repeated until the pH of the aqueous layer reached about 7.0. Then, water was removed by a decanter, followed by distilling off MIBK under reduced pressure to give a phosphorus-containing active ester resin A2.
In the tables, the materials listed in tables 1-2 are as follows, based on the weight of the solid components:
627: bisphenol A novolac epoxy resin (American Hexion trade name)
7200-3H: dicyclopentadiene type novolac epoxy resin (trade name of Japanese DIC)
NC-3000H: biphenyl type novolac epoxy resin (Japan chemical trade name)
HP 8000: dicyclopentadiene type active ester (trade name of Japanese DIC)
CE-01 PS: bisphenol A cyanate ester (Yangzhou Tianqi brand name)
Filling: spherical silicon powder DQ1040 (trade name of Jiangsu Lirui)
Flame retardant: DOPO structural flame retardant XP-7866 (Yabao brand name)
A1: synthesis of phosphorus-containing structural active ester described in example 1
A2: synthesis of phosphorus-containing active ester of example 2
DMAP: 4-dimethylaminopyridine, accelerator (trade name of Guangrong Chemicals)
Example 1
Adding 627 of 60 parts by weight into a container, adding A1 active ester of equivalent weight, continuously stirring, adding a proper amount of 4-dimethylaminopyridine as a curing accelerator, continuously stirring uniformly, and finally adjusting the solid content of the liquid to 60-80% by using a solvent to prepare a glue solution. And (3) impregnating the glue solution with glass fiber cloth to obtain the glue solution. And (3) soaking the glue solution by using glass fiber cloth, controlling the thickness to be proper, and drying to remove the solvent to obtain the prepreg. And overlapping a plurality of prepared prepregs, respectively pressing and covering a copper foil on two sides of each prepreg, and putting the prepregs into a hot press to cure to prepare the epoxy resin copper-clad laminate. The physical property data are shown in Table 1.
Examples 2 to 9
The preparation process is the same as that of example 1, and the formula composition and the physical index thereof are shown in tables 1-2.
Comparative examples 1 to 6
The preparation process was the same as in example 1, and the formulation composition and physical properties thereof are shown in Table 2.
TABLE 1
Figure GDA0002784363100000101
Figure GDA0002784363100000111
TABLE 2
Substance(s) Example 8 Example 9 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6
NC-3000H 60 60 60 60 60 60 60 60
A1 20 20
A2
HP8000 1eq 1eq 1eq 20 20 20
CE-01PS 20 20 20 20 20
Filler material 20 20 20
Flame retardant 15 15 15 15
DMAP 0.05 0.05 0.07 0.08 0.07 0.08 0.05 0.08
Tg(DSC)/℃ 187 190 155 148 150 182 175 178
Dk(10GHz) 3.98 4.05 3.95 3.96 4.02 4.02 4.08 4.06
Df(10GHz) 0.078 0.076 0.0095 0.0010 0.0098 0.0086 0.0089 0.0087
Flame retardant property 94V-0 94V-0 94V-2 94V-0 94V-0 94V-2 94V-0 94V-0
The test method of the above characteristics is as follows:
(1) glass transition temperature (Tg): the measurement was carried out by Differential Scanning Calorimetry (DSC) according to the DSC method defined by IPC-TM-6502.4.25.
(2) Dielectric constant and dielectric dissipation factor: the test was carried out according to the method specified in IPC-TM-6502.5.5.9, the test frequency being 10 GHz.
(3) Flame retardancy: the method is carried out according to the UL94 standard method.
Physical property analysis:
as can be seen from the examples 1-9 in tables 1-2, after the phosphorus-containing active ester curing agent is introduced, the system has a low dielectric loss factor and can meet the UL 94V-0 flame retardant requirement; from example 7, it can be seen that the system has a lower dielectric dissipation factor after the incorporation of the silica filler; from examples 8 and 9, it can be seen that the ternary system has a lower dielectric loss factor and a higher glass transition temperature due to the introduction of the cyclic DOPO structure with a large free volume and symmetry.
As can be seen from comparative example 1 and comparative example 2 in Table 2, the system has a lower dielectric dissipation factor but cannot meet the flame retardant requirement of UL94 after the dicyclopentadiene type active curing agent is introduced, and the dielectric dissipation factor is slightly increased even though the flame retardant is added to meet the flame retardant requirement of UL 94; compared with comparative examples 1 and 2, the flame retardant of the UL 94V-0 grade flame retardant has the advantages that the system has lower dielectric loss factor and higher glass transition temperature due to the introduction of the symmetrical annular DOPO structure with large free volume.
As is clear from comparison between comparative example 3 and example 7 and comparison between comparative example 5 and example 8 in Table 2, when the phosphorus-containing active ester curing agent of the present invention was replaced by a mixture of a DOPO structure flame retardant and a dicyclopentadiene type active ester, the system was inferior in heat resistance and dielectric properties; as can be seen from comparative example 4, the introduction of cyanate ester can reduce the dielectric loss factor of the system, but still can not meet the flame retardant requirement of UL 94V-0 grade; it is understood from comparative examples 5 and 6 that the introduction of the flame retardant can improve the flame retardant property, but the dielectric dissipation factor is increased, and even though the dielectric dissipation factor of the system is decreased by the addition of the filler, the dielectric dissipation factor is still higher than that of the systems of examples 8 and 9.
As described above, the circuit substrate material made of the halogen-free composition of the present invention has a low dielectric dissipation factor and can realize halogen-free flame retardancy, compared to general laminates.
The above description is only a preferred embodiment of the present invention, and it will be obvious to those skilled in the art that various other changes and modifications may be made according to the technical solution and the technical idea of the present invention, and all such changes and modifications should fall within the scope of the claims of the present invention.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (18)

1. A halogen-free resin composition for reducing dielectric loss factor is characterized by comprising the following components:
(A) an epoxy resin;
(B) a phosphorus-containing active ester resin;
the phosphorus-containing active ester resin has a structure shown in a formula (I):
Figure FDA0002559263470000011
wherein R is
Figure FDA0002559263470000012
R1Is composed of
Figure FDA0002559263470000013
m represents an average polymerization degree, and m is an arbitrary number between 0.25 and 3;
the ratio of the epoxy equivalent of the epoxy resin to the ester equivalent of the phosphorus-containing active ester resin is 1 (1-1.1);
the epoxy resin is diphenol aldehyde epoxy resin;
the halogen-free resin composition does not contain phenolic resin.
2. The halogen-free resin composition according to claim 1, further comprising a curing accelerator as component (C).
3. The halogen-free resin composition according to claim 2, wherein the curing accelerator is added in an amount of 0.05 to 1 part by weight based on 100 parts by weight of the sum of the amounts of the component (A) and the component (B).
4. The halogen-free resin composition according to claim 2, wherein the curing accelerator is any one or a mixture of at least two of 4-dimethylaminopyridine, 2-methylimidazole, 2-methyl-4-ethylimidazole and 2-phenylimidazole.
5. The halogen-free resin composition according to claim 1, wherein the halogen-free resin composition further comprises component (D) a flame retardant compound.
6. The halogen-free resin composition according to claim 5, wherein the flame retardant compound is added in an amount of 0 to 50 parts by weight based on 100 parts by weight of the sum of the amounts of the component (A), the component (B) and the component (C).
7. The halogen-free resin composition according to claim 5, wherein the flame retardant compound is any one or a mixture of at least two of phosphorus-containing phenolic resin, phosphorus-containing bismaleimide, phosphinate, aryl phosphate type compound, nitrogen-phosphorus intumescent flame retardant, phosphazene type flame retardant, or organic polymer flame retardant.
8. The halogen-free resin composition according to claim 1, wherein the halogen-free resin composition further comprises a filler of component (E).
9. Halogen-free resin composition according to claim 8, wherein the filler is an organic or/and inorganic filler.
10. The halogen-free resin composition according to claim 8, wherein the filler is added in an amount of 0 to 100 parts by weight and not 0 based on 100 parts by weight of the sum of the addition amounts of the component (A), the component (B), the component (C) and the component (D).
11. The halogen-free resin composition according to claim 10, wherein the filler is added in an amount of 0 to 50 parts by weight and not 0 based on 100 parts by weight of the sum of the addition amounts of the component (A), the component (B), the component (C) and the component (D).
12. The halogen-free resin composition according to claim 9, wherein the inorganic filler is any one or a mixture of at least two of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, or glass fiber powder.
13. The halogen-free resin composition according to claim 9, wherein the organic filler is any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyether sulfone powder.
14. The halogen-free resin composition according to claim 8, wherein the filler is silica, and the median particle size of the filler is 1 to 15 μm.
15. The halogen-free resin composition according to claim 14, wherein the silica has a median particle size of 1 to 10 μm.
16. A prepreg comprising a reinforcing material and the halogen-free resin composition according to any one of claims 1 to 15 attached thereto by impregnation drying.
17. A laminate comprising at least one prepreg according to claim 16.
18. A printed circuit board comprising at least one prepreg according to claim 16.
CN201611238071.0A 2016-12-28 2016-12-28 Phosphorus-containing active ester, halogen-free composition thereof and copper-clad substrate Expired - Fee Related CN108250675B (en)

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