CN109535388B - 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 PDF

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CN109535388B
CN109535388B CN201811393894.XA CN201811393894A CN109535388B CN 109535388 B CN109535388 B CN 109535388B CN 201811393894 A CN201811393894 A CN 201811393894A CN 109535388 B CN109535388 B CN 109535388B
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epoxy resin
phosphorus
parts
curing agent
resin composition
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CN109535388A (en
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马建
陈诚
崔春梅
何继亮
黄荣辉
杨宋
储正振
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Suzhou Shengyi Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • B32B15/092—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 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
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)

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 agent: 1-100 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

Phosphorus-containing epoxy resin composition, and prepreg and laminated board prepared from same
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, the DOPO ring has high water absorption rate under high temperature, high humidity or alkaline conditions, which affects the dielectric property and the humidity resistance of the circuit board.
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 view of the above problems, it is obvious that the development of a phosphorus-containing epoxy resin composition with halogen-free flame retardance, high moisture and heat resistance, low water absorption, high flame retardance, high peel strength and good dielectric properties, and a prepreg and a laminated board made of the composition have positive practical significance.
Disclosure of Invention
The invention aims to provide a phosphorus-containing epoxy resin composition, and a prepreg 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 agent: 1-100 parts;
the phosphorus compound modified epoxy resin is selected from any one or more of the following structures (I), (II) and (III):
Figure BDA0001874679550000021
wherein: r is
Figure BDA0001874679550000022
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.
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.
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 above technical solution, more preferably, the R group is
Figure BDA0001874679550000023
Preferably, the amount of the curing agent may be 2 parts, 5 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, 80 parts, 85 parts, 90 parts, 95 parts, 97 parts, 98 parts, 99 parts.
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 technical scheme, the curing agent is selected from one or more of amine curing agent, anhydride curing agent, active ester curing agent, phenol curing agent, carboxylic acid, siloxane containing hydroxyl and polysiloxane. The curing agent may also be other compounds containing groups reactive with epoxide groups, such as cyanate ester resins, PPO resins.
In the technical scheme, the amine curing agent is selected from one or more of dicyandiamide, diaminodiphenyl sulfone, diaminodiphenyl ether and diaminodiphenylmethane; preferably dicyandiamide or diaminodiphenyl sulfone;
the anhydride curing agent is selected from one or more of phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, maleimide tung oil anhydride and styrene-maleic anhydride; preferably styrene-maleic anhydride;
the phenolic curing agent is selected from one or more of phenolic resin, benzoxazine resin, bisphenol, monophenol, polyhydric phenol and benzenediol; preferably a phenolic resin.
In the above technical scheme, the amount of the curing agent is determined according to the equivalent of reactive hydrogen in the curing agent and the epoxy equivalent of the epoxy resin. The ratio of the reactive hydrogen equivalent in the curing agent to the epoxy equivalent of the epoxy resin is 0.1-5.
Preferred several schemes are 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) amine curing agent: 2-20 parts.
Or,
(A) phosphorus compound modified epoxy resin: 100 parts of (A);
(B) acid anhydride curing agent: 20-100 parts.
Or,
(A) phosphorus compound modified epoxy resin: 100 parts of (A);
(B) active ester curing agent: 10 to 100 parts.
Or,
(A) phosphorus compound modified epoxy resin: 100 parts of (A);
(B) phenolic aldehyde curing agent: 10-50 parts.
The structure of the phosphorus compound modified epoxy resin is the same as that of the prior technical scheme.
Further comprising at least one of an epoxy resin other than the component (A), a modified or unmodified bismaleimide resin.
The epoxy resin except the component (A) is any one or more selected from 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 ring epoxy resin, dicyclopentadiene epoxy resin, isocyanate epoxy resin, aralkyl novolac epoxy resin, alicyclic epoxy resin, glycidylamine epoxy resin, glycidylester 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 in 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, the number average molecular weight of the allyl modified bismaleimide resin is preferably 2000-5000 g/mol, and the content of the allyl modified bismaleimide resin is 1-50 parts by 100 parts of the component (A).
The invention also discloses a prepreg prepared from the phosphorus-containing epoxy resin composition, which is prepared by adding 0-100 parts of filler and 0-5 parts of curing accelerator by weight of the phosphorus-containing epoxy resin composition 100 parts, dissolving the mixture with a solvent to prepare a glue solution, then soaking a reinforcing material in the glue solution, and heating and drying the soaked reinforcing material. For example, the glue solution can be impregnated by glass fiber cloth, and then the prepreg can be prepared by baking the glass fiber cloth at 80-170 ℃ for 1-10 minutes.
Preferably, 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;
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.
Preferably, the particle size median value of the filler is 1-15 micrometers, and preferably, the particle size 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 above technical scheme, the curing accelerator is selected from one or more of imidazole compounds and organic metal salts. Imidazole compounds are preferred. 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.
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 colorant, 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 side or two sides of one prepreg, or after at least 2 prepregs are stacked, the metal foil is coated on one side or two sides of the prepreg, and the laminated board is obtained by hot press forming. For example, the sheet can be obtained by pressing at a pressure of 0.2 to 2MPa 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 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.
Detailed Description
The invention is further described below with reference to the following examples:
Figure BDA0001874679550000071
synthesis example 1:
21.6g of DOPO (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 stirring and condensing equipment 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 the powder DOPO-3-isocyanate propyl trimethoxy silane.
Synthesis example 2:
324g of DOPO-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 a stirring condensing device 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 the powder DOPO-HQ-3-isocyanate propyl trimethoxy silane.
Synthesis example 3:
374g of DOPO-NQ (structural formula 6), 41g of 3-isocyanate propyl trimethoxy silane, 100g of toluene and 0.3g of triethylamine are added into a four-port reaction kettle provided with a stirring condensing device and nitrogen, the temperature is increased to 180 ℃, the reaction is carried out for 7 hours, and the toluene is removed by reduced pressure distillation, so as to obtain the powder DOPO-NQ-3-isocyanate propyl trimethoxy silane.
Synthesis example 4:
50g of DOPO-3-isocyanatopropyl-trimethoxysilane powder obtained in Synthesis example 1, 100g of biphenyl type epoxy resin (NC-3000, Japan chemical), 100g of methylene chloride 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 methylene chloride was distilled off under reduced pressure to obtain a phosphide-modified epoxy resin having a phosphorus content of 2.45%.
Synthesis example 5:
45g of DOPO-3-isocyanatopropyl-trimethoxysilane 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 ℃ for 4 hours, and dichloromethane was removed by distillation under reduced pressure to obtain a phosphide-modified epoxy resin having a phosphorus content of 2.28%.
Synthesis example 6:
110g of DOPO-HQ-3-isocyanatopropyl-trimethoxysilane 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 ℃, the 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 2.21%.
Synthesis example 7:
115g of DOPO-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, so that phosphide modified epoxy resin is obtained, wherein the phosphorus content is 2.26%.
Synthesis example 8:
120g of DOPO-NQ-3-isocyanatopropyl trimethoxysilane powder obtained in synthesis example 3, 100g of bisphenol A type epoxy resin (NPEL-128, south Taiwan Asia), 180g of toluene and 0.5g of tributylamine are added into a four-port reaction kettle provided with stirring and condensing equipment and nitrogen, the temperature is raised to 175 ℃, the reaction is carried out for 6 hours, and the toluene is removed by reduced pressure distillation, so that phosphide modified epoxy resin with the phosphorus content of 2.16 percent is obtained.
Synthesis example 9:
110g of DOPO-NQ-3-isocyanatopropyl-trimethoxysilane 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 phosphide-modified epoxy resin with a phosphorus content of 2.07%.
Example 1:
85g of the phosphide-modified epoxy resin obtained in Synthesis example 4 was added with 15g of phenol novolac (PSM-4357, Japan Dowang chemical Co., Ltd.), 0.2g of 2-ethyl-4-methylimidazole and an appropriate amount of methyl ethyl ketone solvent, and the mixture was stirred and mixed to obtain a liquid cement.
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 for 2 hours under the pressure of 1.5Mpa and the temperature of 220 ℃.
The laminate properties obtained are shown in table 1.
Example 2:
96g of phosphide-modified epoxy resin obtained in Synthesis example 5 was added with 4g of Dicyandiamide (DICY), 0.1g of 2-methylimidazole and an appropriate amount of methyl ethyl ketone solvent, and the mixture was 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 3:
90g of the phosphide-modified epoxy resin obtained in Synthesis example 6 was added with 10g of phenol novolac resin (PSM-4357, Japan Protoque chemical Co., Ltd.), 0.3g of 2-ethyl-4-methylimidazole and an appropriate amount of methyl ethyl ketone solvent, and the mixture was stirred and mixed 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 4:
92g of phosphide-modified epoxy resin obtained in Synthesis example 7 was added with 8g of diaminodiphenyl sulfone (DDS), 15g of fused silica, 0.4g of 2-phenylimidazole and an appropriate amount of butanone solvent, and the mixture was 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:
96.5g of the phosphide-modified epoxy resin obtained in Synthesis example 8 was added with 3.5g of Dicyandiamide (DICY), 15g of fused silica, 0.4g of 2-phenylimidazole and an appropriate amount of methyl ethyl ketone solvent, and the mixture was 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:
90g of the phosphide-modified epoxy resin obtained in Synthesis example 9 was added with 10g of phenol novolac resin (PSM-4357, Japan Protoque chemical Co., Ltd.), 0.3g of 2-ethyl-4-methylimidazole and an appropriate amount of methyl ethyl ketone solvent, and the mixture was stirred and mixed 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.
Comparative example 1:
108.6g of DOPO type phosphorus-containing epoxy resin (XZ92530, Olin, USA) is 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 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.
The laminate properties obtained are shown in table 1.
TABLE 1 Properties of laminates obtained with different examples
Figure BDA0001874679550000111
Note: the relevant test data in the table are based on a laminate sample 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 the 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, comparative example 1, in which DOPO-modified epoxy resin was cured with novolak resin, was inferior in flame retardancy, water absorption, wet heat resistance, dielectric properties and peel strength to those of the examples; 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 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 agent: 1-100 parts;
the phosphorus compound modified epoxy resin is selected from any one or more of the following structures (I), (II) and (III):
(I)
Figure FDA0002622888650000011
(II)
Figure FDA0002622888650000012
(III)
Figure FDA0002622888650000013
wherein: r is
Figure FDA0002622888650000014
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 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 resinOne of a resin, an aralkyl novolac epoxy resin, an alicyclic epoxy resin, a glycidylamine epoxy resin, and a glycidylester 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 curing agent is selected from one or more of amine curing agent, anhydride curing agent, active ester curing agent, phenol curing agent, carboxylic acid, siloxane containing hydroxyl and polysiloxane.
5. The phosphorus-containing epoxy resin composition according to claim 4, wherein: the amine curing agent is selected from one or more of dicyandiamide, diaminodiphenyl sulfone, diaminodiphenyl ether and diaminodiphenylmethane;
the anhydride curing agent is selected from one or more of phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, maleimide tung oil anhydride and styrene-maleic anhydride;
the phenolic curing agent is selected from one or more of phenolic resin, benzoxazine resin, bisphenol, monophenol, polyhydric phenol and benzenediol.
6. A prepreg produced using the phosphorus-containing epoxy resin composition according to claim 1, wherein: adding 0-100 parts of filler and 0-5 parts of curing accelerator by 100 parts by weight of the phosphorus-containing epoxy resin composition, dissolving the filler and the curing accelerator by using a solvent to prepare a glue solution, then soaking a reinforcing material in the glue solution, and heating and drying the soaked reinforcing material to obtain the prepreg.
7. The prepreg according to claim 6, characterized in that: 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;
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.
8. The prepreg according to claim 6, characterized in that: 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.
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 6, or by laminating at least 2 prepregs according to claim 6, 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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