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WO2015101232A1 - Composition de résine époxy sans halogène et son utilisation - Google Patents
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WO2015101232A1 - Composition de résine époxy sans halogène et son utilisation - Google Patents

Composition de résine époxy sans halogène et son utilisation Download PDF

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Publication number
WO2015101232A1
WO2015101232A1 PCT/CN2014/095203 CN2014095203W WO2015101232A1 WO 2015101232 A1 WO2015101232 A1 WO 2015101232A1 CN 2014095203 W CN2014095203 W CN 2014095203W WO 2015101232 A1 WO2015101232 A1 WO 2015101232A1
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Prior art keywords
epoxy resin
halogen
resin composition
free epoxy
weight
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Ceased
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PCT/CN2014/095203
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English (en)
Chinese (zh)
Inventor
吴奕辉
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Publication of WO2015101232A1 publication Critical patent/WO2015101232A1/fr
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Classifications

    • 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
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4246—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof polymers with carboxylic terminal groups
    • C08G59/4261—Macromolecular compounds obtained by reactions involving only unsaturated carbon-to-carbon bindings
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
    • 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
    • C08G59/68—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 catalysts used
    • C08G59/686—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 catalysts used containing nitrogen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • 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
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O
    • 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
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers

Definitions

  • the present invention relates to a halogen-free epoxy resin composition and use thereof, and in particular to a halogen-free epoxy resin composition and a resin glue, prepreg, laminate and copper-clad laminate prepared therefrom.
  • the traditional copper-clad laminate for printed circuit is mainly made of brominated epoxy resin, and the flame-retardant function of the plate is realized by bromine.
  • carcinogens such as dioxins and dibenzofurans have been detected in the combustion products of electrical and electronic equipment wastes containing halogens such as bromine and chlorine, and halogen-containing products may release highly toxic substances during combustion. Hydrogen halide.
  • the EU's two environmental protection directives, the Waste Electrical and Electronic Equipment Directive and the Directive on the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment were officially implemented.
  • the first approach is to use phosphorus-containing epoxy resin as the main resin, and then dicyandiamide or phenolic resin.
  • a curing agent adding a certain amount of inorganic filler such as aluminum hydroxide, using dicyandiamide as a curing agent for the phosphorus-containing epoxy resin, the sheet has poor heat resistance and high water absorption; and the phenolic resin is used as a curing agent for the phosphorus-containing epoxy resin.
  • the appearance of the prepreg is poor, the brittleness of the sheet is large, and the workability is poor.
  • benzoxazine resin As the main resin, add appropriate amount of phosphorus-containing epoxy resin or phosphorus-containing, nitrogen-containing curing agent, and then add appropriate amount of organic or inorganic filler, benzoxazine resin has good Heat resistance and low water absorption, but the brittleness is large and the processing properties of the sheet are poor.
  • the fluororesin represented by polytetrafluoroethylene has been used for the substrate material for processing high frequency signals due to its low dielectric constant and dielectric loss tangent, but polytetrafluoroethylene is a highly inert thermoplastic material. It is difficult and costly.
  • researchers in the field have conducted various studies on an insulating material which is easy to varnish with an organic solvent, has a molding process, has a low curing temperature, is easy to handle, has a low dielectric constant of a non-fluorine type, and has a low dielectric loss tangent.
  • Styrene maleic anhydride cured epoxy resin curable polyolefin, isocyanate resin, curable polyphenylene ether, allyl modified polyphenylene ether, vinyl modified polyphenylene ether, polyvinyl benzyl Ether resins, divinylbenzene or divinylnaphthalene-modified polyetherimides, liquid crystal resins, and the like are proposed.
  • These low dielectric constant and low dielectric loss tangent resin compositions are designed to be thermosetting resins because they must be able to withstand electronic component manufacturing processes such as solder reflow and wire bonding.
  • US6509414 uses styrene maleic anhydride as a curing agent, and selects tetrabromobisphenol A (TBBPA), tetrabromobisphenol A diglycidyl ether (TBBPADGE), etc. as a second curing agent to cure a thermosetting resin such as an epoxy resin.
  • TBPA tetrabromobisphenol A
  • TBBPADGE tetrabromobisphenol A diglycidyl ether
  • thermosetting resin such as an epoxy resin.
  • good resistance to humidity and heat, high glass transition temperature due to the use of bromine as a flame retardant in the co-crosslinking agent, the entire system is a halogen-containing system, which has been unable to meet the growing demand for halogen-free.
  • WO 03/048251 uses styrene maleic anhydride as a curing agent, with a bismaleimide resin and an appropriate amount of epoxy to achieve a high glass transition temperature and good electrical properties. However, the entire system still uses bromine resistance. The fuel is flame retardant.
  • styrene maleic anhydride is used as curing agent
  • benzoxazine is selected as the second curing agent
  • epoxy and a certain amount of phosphorus-containing flame retardant the halogen-free copper-clad board is realized, and Good dielectric properties, however, due to the inherent brittleness of benzoxazine, the drill bit is severely worn, the processing is difficult, and the wet heat resistance is unstable.
  • CN 201010184744.5 The use of styrene maleic anhydride as a curing agent, with a certain amount of halogen-free epoxy resin and poly(phenyl phenyl phenyl) phenyl phenyl ester as a flame retardant, achieves better dielectric properties, and at the same time achieves Halogen-free, however, due to the characteristics of styrene maleic anhydride as a single curing agent, its resistance to moist heat is poor.
  • one of the objects of the present invention is to provide a halogen-free epoxy resin composition
  • a halogen-free epoxy resin composition comprising a copolymer of styrene and maleic anhydride as a first curing agent and a phosphorus-containing compound as a second curing agent.
  • the agent can provide good dielectric properties required for high-frequency high-speed circuit substrates, has good processability, is simple in process operation, and has good moist heat resistance.
  • a halogen-free epoxy resin composition comprising, by weight of an organic solid, comprising:
  • the component (A) halogen-free epoxy resin is an epoxy resin having a benzene ring or a thick benzene structure.
  • the epoxy resin having a benzene ring or a thick benzene structure is in a biphenyl type epoxy resin, a fluorene type epoxy resin or a naphthol type epoxy resin. Any one or a mixture of at least two.
  • the mixture is, for example, a mixture of a biphenyl type epoxy resin and a fluorene type epoxy resin, a mixture of a naphthol type epoxy resin and a biphenyl type epoxy resin, a bismuth type epoxy resin and a naphthol type epoxy resin.
  • the mixture a mixture of a biphenyl type epoxy resin, a fluorene type epoxy resin, and a naphthol type epoxy resin, preferably a naphthol type epoxy resin, more preferably any one of the naphthol type epoxy resins having the following structural formula; Or a mixture of at least two:
  • n and n are each independently 1 or 2
  • q is an integer of 1 to 10
  • R is H or a substituted or unsubstituted C1-C5 alkyl group.
  • the q is, for example, 2, 3, 4, 5, 6, 7, 8, or 9.
  • the epoxy resin of the rigid structure of thick benzene has a large proportion of aromatic rings in the structure, and the flame retardancy is good.
  • the content of the component (B) styrene and maleic anhydride copolymer (SMA) is 50 to 300 parts by weight, for example, 60 parts by weight based on 100 parts by weight of the halogen-free epoxy resin. 70 parts by weight, 80 parts by weight, 100 parts by weight, 120 parts by weight, 140 parts by weight, 160 parts by weight, 180 parts by weight, 200 parts by weight, 240 parts by weight, 260 parts by weight, 270 parts by weight, 280 parts by weight or 290 Parts by weight.
  • the addition of SMA improves the electrical properties of the halogen-free epoxy resin composition and its articles.
  • the SMA may be used singly or in combination, and the amount of use is preferably 50 to 300 parts by weight. If the amount is too small, the dielectric properties of the sheet are lowered, and if too much, the heat and humidity resistance of the sheet is improved, preferably 100 to 200 parts by weight. .
  • the styrene and maleic anhydride copolymer has the following structural formula:
  • n 1 1 : 1, 2 : 1, 3 : 1, 4 : 1, 6 : 1 or 8 : 1.
  • the weight average molecular weight of the styrene and maleic anhydride copolymer is from 1300 to 50,000, and the styrene and maleic anhydride copolymers may, for example, be commercially available SMA1000, SMA2000, SMA. EF-30, SMA EF-40, SMA EF-60, SMA EF-80, etc.
  • the content of the component (C) phosphorus-containing compound is 1.0 to 20 parts by weight, for example, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, based on 100 parts by weight of the halogen-free epoxy resin. Parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight Or 19 parts by weight.
  • This level is advantageous for increasing the heat and humidity resistance required for the composition to be made. Since the system contains a copolymer of styrene and maleic anhydride, the composition has poor heat and humidity resistance.
  • the amount of phosphorus-containing compound is too small, and the phosphorus-containing compound cannot form an effective synergistic curing with the copolymer of styrene and maleic anhydride, and the wet heat resistance of the composition cannot be effectively improved. If the amount is too large, the water absorption becomes large, which is also disadvantageous to the resin.
  • the composition has an improved resistance to moist heat.
  • the component (C) phosphorus-containing compound is not limited, and any phosphorus-containing compound can be used in the present invention, and the phosphorus-containing compound can be produced according to a method well known to those skilled in the art, for example, CN1960997.
  • the phosphorus-containing compound of the component (C) as the second curing agent is selected from the group consisting of phosphorus-containing compounds having the following structural formula:
  • the phenolic hydroxyl group in the phosphorus-containing compound may undergo a ring-opening crosslinking reaction with the epoxy and co-cure the epoxy with the acid anhydride.
  • the halogen-free epoxy resin composition further comprises a component (D) phosphorus-containing flame retardant for improving the cured resin and the copper-clad thereof Flame retardant properties of foil laminates.
  • the phosphorus-containing flame retardant is any one of a phosphate ester, a phenoxyphosphazene compound or a phosphine phenanthrene and a derivative thereof, or a mixture of at least two .
  • the phosphorus-containing flame retardant is preferably not reduced in dielectric constant, and the phosphorus-containing flame retardant is preferably a phenoxyphosphazene compound or/and a phosphate ester, etc., which may be independently or according to a synergistic flame retardant effect with a naphthol epoxy resin or Mixed use.
  • the amount of the flame retardant of the present invention can be appropriately added according to the flame retardant condition of the composition, so that the flame retardant grade of the composition is V-0, and if the amount is too much, the flame retardant effect is excessive, and the amount is too small. Flame retardant effect decline.
  • the optional halogen-free flame retardants are SPB-100, PX-200, PX-202, FR-700, OP-930, OP-935, but are not limited to the above selection.
  • the halogen-free epoxy resin composition further comprises a component (E) curing accelerator.
  • the curing accelerator is any accelerator known to accelerate the curing speed of the thermosetting resin, preferably any one of an imidazole compound, a tertiary amine compound or a quaternary amine compound or a mixture of at least two, and further preferably 2-methylimidazole Any one or a mixture of at least two of 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole or benzyldimethylamine, further preferably 2-ethyl- 4-methylimidazole.
  • the (E) curing accelerator is added in an amount of 0.001 to 1%, for example, 0.005%, 0.01%, 0.05%, based on the total weight of the halogen-free epoxy resin composition. 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9%, preferably 0.05% to 0.5%.
  • the halogen-free epoxy resin composition further comprises a component (F) filler based on the technical solution provided by the present invention.
  • the addition of fillers is mainly used to adjust some physical properties of the composition, such as lowering the coefficient of thermal expansion (CTE), increasing the thermal conductivity, and the like.
  • CTE coefficient of thermal expansion
  • the mixing amount of the filler can be appropriately added according to the desired technical effect. When the amount is increased, the CTE is lowered, but the workability of the composition is deteriorated. On the contrary, the CTE is large, but the processability of the composition is good.
  • the filler is an organic or inorganic filler based on the technical solution provided by the present invention.
  • the inorganic filler is selected from the group consisting of crystalline silica, fused silica, spherical silica, hollow silica, glass powder, aluminum nitride, and nitrided. Any one or a mixture of at least two of boron, silicon carbide, aluminum hydroxide, titanium dioxide, barium titanate, barium titanate, alumina, barium sulfate, talc, calcium silicate, calcium carbonate or mica.
  • the organic filler is selected from any one of a polytetrafluoroethylene powder, a polyphenylene sulfide or a polyethersulfone powder or a mixture of at least two.
  • An exemplary halogen-free epoxy resin composition based on parts by weight of the organic solids, comprising:
  • An exemplary halogen-free epoxy resin composition based on parts by weight of the organic solids, comprising:
  • the molecular structure of styrene and maleic anhydride copolymer is
  • An exemplary halogen-free epoxy resin composition based on parts by weight of the organic solids, comprising:
  • the molecular structure of styrene and maleic anhydride copolymer is
  • a phosphorus-containing compound as a second curing agent is contained in an amount of 1.0 to 20 parts by weight based on 100 parts by weight of the halogen-free epoxy resin, and the phosphorus-containing compound has the following structural formula:
  • the phosphorus content of the halogen-free epoxy resin composition is controlled to be 1 to 5% by weight based on 100% by weight of the total weight of the halogen-free epoxy resin composition.
  • the nitrogen content is controlled at 1 to 5% by weight, such as 1.3% by weight, 1.6% by weight, 2% by weight, 2.3% by weight, 2.6% by weight, 3% by weight, 3.3% by weight, 3.6% by weight, 4% by weight, 4.3% by weight or 4.7% by weight.
  • the phosphorus content and the nitrogen content are too low to achieve a good flame retardant effect, and if the phosphorus content and the nitrogen content are too high, the water absorption becomes large, which is disadvantageous to the improvement of the moist heat resistance of the resin composition
  • the halogen content of the halogen-free epoxy resin composition is controlled to be less than 0.09% by weight based on 100% by weight of the total weight of the halogen-free epoxy resin composition.
  • the halogen-free epoxy resin composition may further contain various additives, and specific examples thereof include a flame retardant, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, or Lubricants, etc. These various additives may be used singly or in combination of two or more kinds.
  • the halogen-free epoxy resin, the copolymer of styrene and maleic anhydride, the phosphorus-containing compound, and the phosphorus-containing compound may be blended, stirred, and mixed by a known method. Flame retardants and curing accelerators, as well as various additives, are prepared.
  • a second object of the present invention is to provide a resin glue which is a halogen-free epoxy tree as described above.
  • the lipid composition is obtained by dissolving or dispersing in a solvent.
  • the solvent in the present invention is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, and butyl.
  • Ethers such as carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and mesitylene; An ester such as ethyl acetate or ethyl acetate; a nitrogen-containing solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methyl-2-pyrrolidone. These solvents may be used alone or in combination of two or more.
  • aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, and acetone, methyl ethyl ketone, methyl ethyl ketone, and methyl group.
  • a ketone flux such as butyl ketone or cyclohexanone is used in combination.
  • the amount of the solvent to be used can be selected by a person skilled in the art according to his own experience, so that the obtained resin glue can reach a viscosity suitable for use.
  • An emulsifier may be added during the process of dissolving or dispersing the halogen-free epoxy resin composition as described above in a solvent. By dispersing by an emulsifier, the filler or the like can be uniformly dispersed in the glue.
  • a third object of the present invention is to provide a prepreg comprising a reinforcing material and a halogen-free epoxy resin composition as described above adhered to the reinforcing material by impregnation and drying.
  • the prepreg has good dielectric properties, good processability, simple process operation, and good moist heat resistance.
  • An exemplary method of preparing the prepreg of the present invention is:
  • the epoxy resin composition of the present invention is made into a certain concentration of a glue, and the prepreg is obtained by impregnating the reinforcing material and then drying at a certain temperature to remove the solvent and curing the resin composition.
  • the reinforcing material is a reinforcing material disclosed in the prior art, such as a fiberglass cloth or the like.
  • a fourth object of the present invention is to provide a laminate comprising at least one prepreg as described above.
  • a fifth object of the present invention is to provide a copper clad laminate comprising at least one laminated prepreg as described above and laminated on one side of the laminated prepreg Or copper on both sides Foil.
  • the copper clad laminate has good dielectric properties, good processability, simple process operation, and good moist heat resistance.
  • An exemplary copper-clad laminate of the present invention is prepared by laminating one or more of the prepregs described above in a certain order, and respectively pressing the copper foil on the prepreg which is superposed on each other. One or both sides of the material are solidified in a hot press to obtain a copper clad laminate having a curing temperature of 150 to 250 ° C and a curing pressure of 25 to 60 kg/cm 2 .
  • the present invention has the following beneficial effects:
  • the halogen-free epoxy resin composition of the present invention has a styrene maleic anhydride copolymer as a curing agent and a phosphorus-containing compound as a second curing agent, and exhibits excellent dielectric properties after curing the epoxy resin with styrene maleic anhydride.
  • the utility model also has the phosphorus-containing compound as the second curing agent, effectively improves the moisture-heat resistance of the halogen-free epoxy resin composition, fully utilizes the synergistic curing effect of the styrene and the maleic anhydride copolymer and the phosphorus-containing compound, and overcomes the styrene.
  • the problem of poor heat and humidity resistance inherent in maleic anhydride alone curing epoxy; 2Prepreg and copper clad laminate prepared by using the above halogen-free epoxy resin composition of the invention has good dielectric properties and good processability The process is simple and easy to operate, and has good moist heat resistance; 3 the invention is matched with the flame retardant property of the halogen-free epoxy resin having a benzene ring or a thick benzene structure and the phosphorus-containing flame retardant, and the flame retardant requirement is met at the same time
  • the halogen content is below 0.09%, thereby achieving the effect of environmental protection.
  • A1 NC-7700L, naphthol type novolac epoxy resin (Japanese medicine);
  • EPR627MEK80 bisphenol A type multifunctional epoxy resin (Mitu Chemical);
  • A3 NPEP-204, DOPO modified o-cresol novolac epoxy resin (Taiwan South Asia);
  • SMAEF-40 a copolymer of styrene and maleic anhydride (American sartomer);
  • Comparative example 1 Comparative example 2 Comparative example 3 A1 0 0 0 A2 0 0 A3 100 100 100 B 15 80 80 C1 0 0 30 C2 0 150 150 D1 0 50 50 D2 40 0 0 E Moderate amount Moderate amount Moderate amount F 15 20 20 Glass transition temperature (Tg, °C) 156 181 178 Dielectric constant, 1 GHz 4.39 4.0 4.0 Dielectric loss, 1 GHz 0.011 0.006 0.006 Heat and humidity resistance 0/5 0/5 2/5 Drilling wear ⁇ x x Flame retardancy V-0 V-0 V-0 Halogen content, % 0.03 0.03 0.03 0.03
  • the epoxy resin composition is made into a certain concentration of a glue, and the prepreg is obtained by impregnating the reinforcing material and then drying at a certain temperature to remove the solvent and curing the resin composition. Then, one or more sheets of the prepreg described above are stacked in a certain order, and the copper foil is respectively pressed on both sides of the prepreg which are superposed on each other, and solidified in a hot press to obtain a copper-clad foil.
  • the laminate has a curing temperature of 150 to 250 ° C and a curing pressure of 25 to 60 kg/cm 2 .
  • the copper-clad laminate produced above was measured for dielectric constant and dielectric loss factor, glass transition temperature and moist heat resistance, drilling wear resistance, flame retardant type, and the like.
  • Tg Glass transition temperature
  • Dielectric constant and dielectric loss factor The dielectric constant and the dielectric loss factor at 1 GHz were measured in accordance with IPC-TM-6502.5.5.5 according to the resonance method using a strip line.
  • halogen content of the copper-clad laminate was measured by an oxygen cylinder combustion method and an ion chromatography method in accordance with JPCA-ES-01-2002 "Halogen-free copper-clad laminate test method".
  • the composition has good moist heat resistance and good dielectric properties, and no benzene ring structure is selected.
  • a halogen epoxy resin the composition has a certain deficiency in flame retardancy, and by using a halogen-free epoxy resin with a thick benzene structure, the composition reaches a flame retardant V-0 and a halogen content of 0.09% or less. Reach environmental protection.
  • Comparative Example 1 has poor heat and humidity resistance
  • Comparative Example 2 The heat and humidity resistance is poor, and the drilling wear is poor.
  • the copper-clad laminate produced by the resin of the invention has good moist heat resistance and processing properties, and also has excellent high-frequency dielectric properties, and can satisfy the halogen-free high-frequency high-speed field for printed circuit boards. Requirements.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de résine époxy sans halogène et un pré-imprégné et un laminé plaqué de cuivre fabriqué en utilisant ladite composition. La composition de résine époxy comprend les constituants suivants: (A) une résine époxy sans halogène; (B) un copolymère de styrène-anhydride maléique (SAM) agissant comme premier agent de durcissement; (C) un composé contenant du phosphore agissant comme second agent de durcissement. Un pré-imprégné et un laminé plaqué de cuivre fabriqué en utilisant la composition de résine époxy sans halogène ont de bonnes propriétés diélectriques, une bonne aptitude à la transformation, des opérations de procédé simples, et une bonne résistance à la chaleur et à l'humidité.
PCT/CN2014/095203 2013-12-31 2014-12-26 Composition de résine époxy sans halogène et son utilisation Ceased WO2015101232A1 (fr)

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