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WO2018098908A1 - Composition de résine thermodurcissable - Google Patents

Composition de résine thermodurcissable Download PDF

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Publication number
WO2018098908A1
WO2018098908A1 PCT/CN2017/074298 CN2017074298W WO2018098908A1 WO 2018098908 A1 WO2018098908 A1 WO 2018098908A1 CN 2017074298 W CN2017074298 W CN 2017074298W WO 2018098908 A1 WO2018098908 A1 WO 2018098908A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
thermosetting resin
curing agent
epoxy resin
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2017/074298
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English (en)
Chinese (zh)
Inventor
罗成
唐国坊
许永静
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Shengyi Technology Co Ltd
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Shengyi Technology Co Ltd
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Publication date
Application filed by Shengyi Technology Co Ltd filed Critical Shengyi Technology Co Ltd
Publication of WO2018098908A1 publication Critical patent/WO2018098908A1/fr
Anticipated expiration legal-status Critical
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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
    • C08G59/18—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
    • C08G59/423—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof containing an atom other than oxygen belonging to a functional groups to C08G59/42, carbon and hydrogen
    • 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
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

  • the present invention relates to the field of polymer materials, and in particular to a thermosetting resin composition and a prepreg and printed circuit board using the same.
  • phosphorus-based flame retardants widely used in the field of copper clad laminates are mainly classified into two types: reactive type and additive type.
  • the reaction type is mainly a DOPO compound, and the phosphorus-containing epoxy resin and the phosphorus-containing phenolic resin are mainly used, and the phosphorus content is between 2% and 10%.
  • DOPO-based compounds have a large water absorption rate and poor dielectric properties, and the sheet has poor heat and humidity resistance.
  • the addition type is mainly a phosphazene and a phosphonate compound, and the added flame retardant has a low flame retardancy efficiency, and it is necessary to add more amount to achieve the flame retardant requirement.
  • due to its lower melting point generally lower than 150 ° C, it is easy to migrate to the surface of the sheet during the processing of the laminate, which affects the performance of the sheet.
  • the dicarboxyarylhydrocarbylphosphine oxide is a reactive phosphorus-containing curing agent capable of curing with an epoxy resin, but since its reactive group is a carboxyl group, it reacts with the epoxy resin to form a second polarity. Hydroxyl groups result in poor dielectric properties of the cured product. And the carboxyl group has strong reaction activity, and the process control is too difficult.
  • CN103384674A a polyphosphonate or/and a phosphonate-carbonate copolymer having a hydroxyl group and an epoxy composition are used, the active group of which is a phenolic hydroxyl group, and the problem of poor dielectric properties is also present.
  • CN103694642A discloses the use of epoxy resins, cyanate ester compounds or/and cyanate ester prepolymers, polyphosphonates or/and phosphonate-carbonate copolymers to prepare dielectric properties and good heat and humidity resistance.
  • Halogen UL94 V-0 is flame retardant, but its peel strength, interlayer adhesion and bending strength are low.
  • a phosphorus-containing active ester that is, an esterified modified dicarboxyarylhydrocarbylphosphine oxide
  • the dielectric property of the system is better, and at the same time, it is a phosphorus-containing active ester curing agent, and has the effect of halogen-free flame retardant while being used as a curing agent, and has high flame retardant efficiency, and requires little or no addition. Adding other flame retardants can achieve a UL94 V-0 halogen-free flame retardant effect.
  • one of the objects of the present invention is to provide a thermosetting resin composition, and a prepreg and a laminate for printed circuit board using the same.
  • the printed circuit board laminate produced by using the resin composition has high glass transition temperature, excellent dielectric properties, high heat resistance and moist heat resistance, and good processability, and can realize halogen-free flame retardant.
  • UL94 V-0 The printed circuit board laminate produced by using the resin composition has high glass transition temperature, excellent dielectric properties, high heat resistance and moist heat resistance, and good processability, and can realize halogen-free flame retardant.
  • the present inventors conducted intensive studies to achieve the above object, and as a result, found that a composition obtained by appropriately mixing a halogen-free epoxy resin, an esterified modified dicarboxyarylhydrocarbylphosphine oxide, and optionally other curing agents, The above purpose can be achieved.
  • thermosetting resin composition comprising an epoxy resin and an epoxy resin curing agent, wherein the curing agent contains at least one esterified modified dicarboxyarylhydrocarbylphosphine oxide.
  • thermosetting resin composition of the present invention contains a phosphorus-containing active ester, that is, an esterified modified dicarboxyarylhydrocarbylphosphine oxide as a curing agent for an epoxy resin.
  • the active ester group as a reactive group has a high content, and can be cured with an epoxy resin to obtain a cured product having a high crosslinking density, and a material having high heat resistance and high Tg can be obtained; and the esterified modified dicarboxy aromatic group can be obtained.
  • the hydrocarbyl phosphine oxide structure has high symmetry, and the reactive ester unit in the molecule does not generate a secondary hydroxyl group having a large polarity after reacting with the epoxy resin, and the dielectric property of the secondary hydroxyl group having a large polarity can be eliminated.
  • excellent dielectric properties the esterified modified dicarboxyarylhydrocarbylphosphine oxide is an active ester, and the ester bond formed by the reaction with the epoxy resin has a low water absorption rate, which improves the wet heat resistance of the phosphorus-containing compound Shortcomings.
  • esterified modified dicarboxyarylhydrocarbylphosphine oxide can have a halogen-free flame retardant effect, and has high flame retardant efficiency, and can achieve UL94 V-0 flame retardant with little or no additional flame retardant.
  • the present invention utilizes an active ester group of a highly symmetric esterified modified dicarboxyarylhydrocarbylphosphine oxide to significantly increase the glass transition temperature of a prepreg prepared using the resin composition and a laminate for a printed circuit.
  • Heat resistance and it has excellent dielectric properties, low water absorption, good heat and humidity resistance, and good processability, and achieves halogen-free flame retardant, reaching UL94 V-0.
  • esterified modified dicarboxyarylhydrocarbylphosphine oxide has a structural formula of the formula (I):
  • n 1 is an integer of 1 to 20, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20;
  • R 1 is any one of a phenyl group, a naphthyl group, and a linear or branched alkyl group having 1 to 4 carbon atoms; and a linear or branched alkyl group having 1 to 4 carbon atoms may be, for example, a Any one of a group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a t-butyl group;
  • Ar 1 and Ar 2 are each independently selected from any one of the following groups:
  • X is selected from any of the following groups:
  • n 2 is an integer from 0 to 5, such as 0, 1, 2 , 3, 4 or 5;
  • n 3 is an integer from 0 to 7, such as 0, 1, 2, 3, 4, 5, 6 or 7;
  • R 2 is any one of an allyl group and a linear or branched alkyl group having 1 to 4 carbon atoms; and a linear or branched alkyl group having 1 to 4 carbon atoms may be, for example, a methyl group. Either ethyl, propyl, butyl, isopropyl, isobutyl or tert-butyl.
  • esterification-modified dicarboxyarylhydrocarbylphosphine oxide in the present invention may have the following structural formula:
  • the esterification-modified dicarboxyarylhydrocarbylphosphine oxide accounts for 20% to 50%, for example, 20%, 22%, 24% of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. , 25%, 26%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48% or 50%, and the specific value between the above values, limited by space and For the sake of brevity, the present invention is no longer exhaustive of the specific point values included in the scope.
  • the epoxy resin accounts for 30% to 60%, for example, 30%, 32%, 34%, 35%, 36%, 38% of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. , 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58% or 60%, and the specific point value between the above values, limited by space and for the sake of concise consideration, the present invention does not The specific point values included in the range are exhausted.
  • the present invention preferably employs a halogen-free epoxy resin, which is an epoxy resin having two or more epoxy groups in one molecule, and may be specifically selected from glycidyl ethers and shrinkage.
  • a halogen-free epoxy resin which is an epoxy resin having two or more epoxy groups in one molecule, and may be specifically selected from glycidyl ethers and shrinkage.
  • the glycidyl ethers include bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, and trisphenol novolac epoxy resin. Any one or a mixture of at least two of a dicyclopentadiene novolac epoxy resin, a biphenyl type novolac epoxy resin, an alkylbenzene type novolac epoxy resin or a naphthol type novolac epoxy resin.
  • the glycidyl ether is selected from the group consisting of epoxy resins having the following structure:
  • Z 1 , Z 2 and Z 3 are each independently selected from R 3 is selected from the group consisting of a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group; for example, it may be a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group. Any one of a benzyl group, an isopropyl group, an isobutyl group, a t-butyl group or an isopentyl group;
  • Y 1 and Y 2 are each independently selected from -CH 2 -, Any one of R 4 is selected from a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group; for example, it may be a methyl group, an ethyl group or a C group. Any one of a butyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a t-butyl group or an isopentyl group;
  • n 4 is any integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
  • the glycidylamine is selected from the group consisting of triglycidyl-p-aminophenol, triglycidyl trimer isocyanate, tetraglycidyldiaminodimethylenebenzene, tetraglycidyl-4, 4' -diaminodiphenylmethane, tetraglycidyl-3,4'-diaminodiphenyl ether, tetraglycidyl-4,4'-diaminodiphenyl ether or tetraglycidyl-1,3- Any one or a mixture of at least two of diaminomethylcyclohexane.
  • the halogen-free thermosetting resin composition of the present invention employs the halogen-free epoxy resin having the specific molecular structure described above, which has high functionality and good dielectric properties, and has a high Tg of cured product and low water absorption.
  • the curing agent may further comprise a cyanate resin and/or a bismaleimide-triazine resin; wherein the cyanate resin has the following structure:
  • R 5 is -CH 2 -, Any one or a mixture of at least two;
  • R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 are each independently selected from a hydrogen atom, a substituted or unsubstituted carbonaceous Any one of a linear alkyl group or a branched alkyl group having 1 to 4 may be, for example, any one of a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a t-butyl group.
  • the cyanate resin is selected from the group consisting of 2,2-bis(4-cyanooxyphenyl)propane, bis(4-cyanooxyphenyl)ethane, bis(3,5-dimethyl- 4-cyanooxyphenyl)methane, 2,2-bis(4-cyanooxyphenyl)-1,1,1,3,3,3-hexafluoropropane, ⁇ , ⁇ '-bis(4- Cyanooxyphenyl)-m-isopropylbenzene, cyclopentadiene cyanate, phenol novolac cyanate, cresol novolac cyanate, 2,2-bis(4-cyanooxybenzene) Propane pre Polymer, bis(4-cyanooxyphenyl)ethane prepolymer, bis(3,5-dimethyl-4-cyanooxyphenyl)methane prepolymer, 2,2-bis(4- Cyanooxyphenyl)-1,1,1,3,3,3-hexafluoropropane
  • the cyanate resin and/or bismaleimide-triazine resin accounts for 0% to 50%, for example 0%, of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition.
  • the curing agent may further comprise an SMA resin;
  • the SMA resin means a styrene-maleic anhydride resin which can be obtained by copolymerization of styrene and maleic anhydride in a ratio of from 1:1 to 8:1.
  • the SMA resin accounts for 0% to 40%, for example, 0%, 2%, 4%, 5%, 8%, 10%, of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. 12%, 14%, 15%, 17%, 20%, 22%, 25%, 30%, 32%, 35%, 37%, 39% or 40%, and the specific value between the above values is limited For the sake of brevity, the present invention is no longer exhaustive of the specific point values included in the scope.
  • the curing agent may further comprise a phenolic resin;
  • the phenolic resin is a phosphorus-containing or phosphorus-free phenolic resin, which is a phenolic resin well known in the art, and is not particularly limited in the present invention.
  • the phenolic resin accounts for an epoxy resin and a curing agent in the thermosetting resin composition.
  • 0% to 20% of the total weight such as 0%, 2%, 4%, 5%, 8%, 10%, 12%, 14%, 15%, 17% or 20%, and the specific between the above values
  • Point values limited to length and for the sake of brevity, the present invention is no longer exhaustive of the specific point values included in the ranges.
  • thermosetting resin composition according to the present invention, the organic solid content is 100 parts by weight, and specifically comprises: esterified modified dicarboxyaryl hydrocarbon phosphine oxide: 20 to 50 parts by weight; halogen-free epoxy resin: 30 to 60 parts by weight; cyanate resin and/or bismaleimide-triazine resin: 0 to 50 parts by weight; SMA resin: 0 to 40 parts by weight; phenol resin: 0 to 20 parts by weight.
  • total weight of the epoxy resin and the curing agent in the thermosetting resin composition means the total weight of the components participating in the crosslinking polymerization reaction, wherein the curing agent means curing the epoxy resin Functional esterified modified dicarboxyarylhydrocarbylphosphine oxide and optionally cyanate resin and/or bismaleimide-triazine resin, SMA resin or phenolic resin, which does not contain fillers, accelerators and Flame retardant and other components.
  • thermosetting resin composition of the present invention may further comprise an organic halogen-free flame retardant, and the organic halogen-free flame retardant may specifically be selected from the group consisting of phosphorus-containing flame retardants.
  • the phosphorus-containing flame retardant may be selected from the group consisting of tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa- Any one or a mixture of at least two of 10-phosphaphenanthrene-10-oxide, phenoxyphosphazene compound, phosphate, polyphosphate, polyphosphonate or phosphonate-carbonate copolymer.
  • the total amount of the epoxy resin and the curing agent in the thermosetting resin composition is 100 parts by weight, and the organic halogen-free flame retardant is added in an amount of 0 to 15 parts by weight, that is, modified according to esterification.
  • the sum of the addition amount of the dicarboxylic acid-based hydrocarbon phosphine oxide, the epoxy resin and the possibly added cyanate resin, the SMA resin, and the phenol resin is 100 parts by weight, and the organic halogen-free flame retardant is added in an amount of 0 to 15 parts by weight, for example, 1 part by weight, 3 parts by weight, 5 parts by weight, 6 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 Part by weight, 12 parts by weight, 13 parts by weight or 15 parts by weight, and the specific point values between the above values are limited to the extent and for the sake of brevity, the present invention is not exhaustively enumerated.
  • the halogen-free thermosetting resin composition of the present invention may further comprise a curing accelerator.
  • the curing accelerator comprises an organic metal salt and any one or at least two selected from the group consisting of an imidazole compound, a derivative of an imidazole compound, a piperidine compound, a pyridine compound, a Lewis acid or a triphenylphosphine.
  • an imidazole compound a derivative of an imidazole compound
  • a piperidine compound a pyridine compound
  • a Lewis acid or a triphenylphosphine.
  • the organometallic salt in the curing accelerator comprises any one of a metal octoate, a metal isooctanoate, a metal acetylacetonate, a metal naphthenate, a metal salicylate or a metal stearate. Or a mixture of at least two, wherein the metal is selected from any one or a mixture of at least two of zinc, copper, iron, tin, cobalt or aluminum.
  • the imidazole compound is any one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole or a mixture of at least two .
  • the piperidine compound is 2,3-diaminopiperidine, 2,5-diaminopiperidine, 2,6-diaminopiperidine, 2-amino-3-methylpiperidine, 2- Any one of amino-4-methylpiperidine, 2-amino-3-nitropiperidine, 2-amino-5-nitropiperidine or 2-amino-4,4-dimethylpiperidine or a mixture of at least two.
  • the pyridine compound is any one or a mixture of at least two of 4-dimethylaminopyridine, 2-aminopyridine, 3-aminopyridine or 4-aminopyridine.
  • the curing accelerator is based on 100 parts by weight of the sum of the esterification-modified dicarboxyarylhydrocarbylphosphine oxide, epoxy resin, and possibly added cyanate resin, SMA resin, and phenol resin.
  • the amount added is 0.01 to 1 part by weight, for example, 0.01 parts by weight, 0.025 parts by weight, 0.05 parts by weight, 0.07 parts by weight, 0.085 parts by weight, 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 0.9 parts by weight. Or 1 part by weight, preferably 0.025 to 0.85 parts by weight.
  • the halogen-free thermosetting resin composition of the present invention may further comprise a filler.
  • the filler is selected from the group consisting of organic or inorganic fillers, preferably inorganic fillers, further preferably surface treated inorganic fillers, most preferably surface treated silica.
  • the surface treated surface treatment agent is selected from any one or a mixture of at least two of a silane coupling agent, a silicone oligomer or a titanate coupling agent.
  • the surface treatment agent is used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, more preferably 0.75 to 2 parts by weight, based on 100 parts by weight of the inorganic filler.
  • the inorganic filler is selected from any one or a mixture of at least two of a non-metal oxide, a metal nitride, a non-metal nitride, an inorganic hydrate, an inorganic salt, a metal hydrate or an inorganic phosphorus, preferably molten.
  • the organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide or polyethersulfone powder.
  • the filler has a median particle diameter of from 0.01 to 50 ⁇ m, preferably from 0.01 to 20 ⁇ m, further preferably from 0.1 to 10 ⁇ m.
  • the addition of the filler is carried out in an amount of 100 parts by weight of the addition amount of the esterified modified dicarboxyarylhydrocarbylphosphine oxide, epoxy resin, and possibly added cyanate resin, SMA resin, and phenol resin.
  • the amount is 5 to 300 parts by weight, preferably 5 to 200 parts by weight, and more preferably 5 to 150 parts by weight.
  • composition means that it may include other components in addition to the components, and these other components impart different characteristics to the halogen-free thermosetting resin composition.
  • the "comprising” described in the present invention may also be replaced by a closed “for” or “consisting of”.
  • the halogen-free thermosetting resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, or a lubricant. Agents, etc. These additives may be used singly or in combination of two or more.
  • the preparation method of the halogen-free thermosetting resin composition of the present invention is a conventional technical means in the art, which is: firstly, the solid matter is put in, then the liquid solvent is added, and the mixture is stirred until the solid matter is completely dissolved, and then the liquid resin is added. Accelerator, continue to stir evenly.
  • 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, cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and ethoxyethyl acetate a nitrogen-containing solvent such as N,N-dimethylformamide or N,N-dimethylacetamide.
  • the above solvents may be used singly or in combination of two or more. Preference is given to ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone and cyclohexanone.
  • the amount of the solvent to be added is selected by those skilled in the art based on his own experience, so that the resin glue can reach a viscosity suitable for use.
  • the prepreg of the present invention comprises a reinforcing material and a halogen-free thermosetting resin composition as described above which is impregnated and adhered to the reinforcing material after drying, and the reinforcing material to be used is not particularly limited and may be an organic fiber, an inorganic fiber woven fabric or Non-woven fabric.
  • the organic fiber may be selected from aramid nonwoven fabric, and the inorganic fiber woven fabric may be E-glass fabric, D-glass fabric, S-glass fabric, T-glass fabric, NE-glass fabric. Or quartz cloth.
  • the thickness of the reinforcing material is not particularly limited, and the thickness of the woven fabric and the nonwoven fabric is preferably 0.01 to 0.2 mm, and preferably the fiber-opening treatment and the silane coupling agent are considered.
  • the surface treatment in order to provide good water resistance and heat resistance, the silane coupling agent is preferably any one or at least two of an epoxy silane coupling agent, an amino silane coupling agent or a vinyl silane coupling agent. kind of mixture.
  • the prepreg is obtained by impregnating the above-mentioned halogen-free thermosetting resin composition by baking at 100 to 250 ° C for 1 to 15 minutes.
  • the laminate for printed circuit of the present invention comprises a laminate prepared by bonding together one or two or more prepregs by heat and pressure, and a metal foil bonded to one or both sides of the laminate. .
  • the laminate is obtained by curing in a hot press at a curing temperature of 150 to 250 ° C and a curing pressure of 10 to 60 kg/cm 2 .
  • the metal foil is copper foil, nickel foil, aluminum foil, SUS foil, etc., and the material thereof is not limited.
  • the present invention has at least the following beneficial effects:
  • the prepreg and the printed circuit board made of the thermosetting resin composition provided by the invention have a glass transition temperature of up to 245 ° C; excellent dielectric properties, and the water absorption rate is controlled within a range of 0.05 to 0.10%; It has high heat resistance, excellent heat and humidity resistance and good processability; excellent flame retardant efficiency, and the phosphorus content of 1.0% can achieve UL94 V-0 halogen-free flame retardant effect.
  • the above phosphine oxide active ester, halogen-free epoxy resin, curing accelerator, halogen-free flame retardant, filler are uniformly mixed in a solvent in a certain ratio, and the solid content of the glue is controlled to be 65%, and the glue is impregnated with 2116 glass fiber cloth.
  • the copper-clad laminate is prepared at a temperature of 170 to 250 ° C, a curing pressure of 25 to 60 kg/cm 2 , and a curing time of 60 to 300 minutes.
  • Examples 1 to 10 and Comparative Examples 1 to 7 relate to materials and brand information as follows:
  • n 1 5;
  • BCPPO bis(4-carboxyphenyl)phenylphosphine oxide
  • CE01PS Jiangsu Tianqi, bisphenol A type cyanate resin
  • CE01MO Jiangsu Tianqi, bisphenol A type cyanate resin
  • HP-7200HHH DIC, DCPD type epoxy resin, epoxy equivalent 288
  • HP-7200H-75M DIC, DCPD type epoxy resin, epoxy equivalent 280
  • HP-9900 DIC, naphthol type epoxy resin, epoxy equivalent 274
  • DOW92741 Phosphorus-containing phenolic, Dow Chemical
  • SPB-100 Otsuka Chemical, phosphazene flame retardant, phosphorus content 13.4%
  • Fused silica (average particle size 1 to 10 ⁇ m, purity 99% or more)
  • Table 1 shows the formulation compositions and physical property data of Examples 1 to 10, Table 2 Comparative Examples 1 to 7.
  • ⁇ is a layered burst board
  • O is a layered burst board
  • Glass transition temperature (Tg) Measured according to the DMA test method specified in IPC-TM-650 2.4.24 using a DMA test.
  • PCT heat and humidity resistance
  • T288 Determined by TMA instrument according to the T300 test method specified in IPC-TM-650 2.4.24.1.
  • the FRX3001 had poor reactivity and low OH-content, and it was impossible to form a copper clad laminate;
  • Comparative Example 4 and Comparing Example 2 the copper clad laminate prepared by using FRX3001 and cyanate resin co-cured halogen-free epoxy resin in Comparative Example 4 has poor dielectric properties, low Tg, poor heat and humidity resistance, and poor flame retardancy;
  • Comparative Example 6-7 when Comparative Example 6-7 was compared with Example 6, it was found that when the content of Comparative Example 6 was lower than that of the esterification-modified dicarboxyarylhydrocarbylphosphine oxide in Example 6, the curing agent was insufficient.
  • the sheet material was formed, and the content of the copper carboxylate prepared by using the esterification-modified dicarboxyaryl hydrocarbon phosphine oxide in Comparative Example 7 was higher than that in Comparative Example 7, the dielectric properties were poor, water absorption, heat resistance, and Poor heat and humidity resistance.
  • the pressure plate has a glass transition temperature of up to 245 ° C; excellent dielectric properties, water absorption is controlled in the range of 0.05 to 0.10%; high heat resistance, excellent heat and humidity resistance and good processability; excellent resistance
  • the fuel efficiency, phosphorus content of 1.0% can achieve UL94 V-0 halogen-free flame retardant effect.
  • the prepreg and the printed circuit board made of the halogen-free thermosetting resin composition provided by the present invention have high glass transition temperature and excellent dielectric properties as compared with a general laminate. Low water absorption, high heat resistance, excellent heat and humidity resistance and good processability, and can achieve halogen-free resistance Combustion, UL94 V-0 halogen-free flame retardant.

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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)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)

Abstract

L'invention concerne une composition de résine thermodurcissable comprenant un ester actif contenant du phosphore, la composition de résine thermodurcissable présentant les avantages d'une bonne stabilité thermique, d'une résistance à l'humidité et à la chaleur, d'une faible constante diélectrique et d'une tangente de perte diélectrique, d'une faible absorption d'eau, d'un effet ignifuge sans halogène, etc., et elle présente une excellente aptitude au traitement. L'invention concerne également une utilisation de la composition de résine thermodurcissable dans une feuille de résine, une feuille métallique composite de résine, un préimprégné, un stratifié, un stratifié de feuille métallique et une carte de circuit imprimé.
PCT/CN2017/074298 2016-11-30 2017-02-21 Composition de résine thermodurcissable Ceased WO2018098908A1 (fr)

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CN109852004B (zh) * 2019-01-04 2022-03-04 恩莱登（北京）工业技术有限公司 环氧树脂基体组合物、环氧树脂基体及其制备方法
CN111205423A (zh) * 2020-02-28 2020-05-29 杭摩新材料(嘉兴)有限公司 阻燃型酚醛树脂及其制备方法和用途

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