WO2018103276A1 - Composition de résine thermodurcissable - Google Patents

Composition de résine thermodurcissable Download PDF

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Publication number
WO2018103276A1
WO2018103276A1 PCT/CN2017/085676 CN2017085676W WO2018103276A1 WO 2018103276 A1 WO2018103276 A1 WO 2018103276A1 CN 2017085676 W CN2017085676 W CN 2017085676W WO 2018103276 A1 WO2018103276 A1 WO 2018103276A1
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Prior art keywords
resin composition
thermosetting resin
curing agent
resin
epoxy resin
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PCT/CN2017/085676
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English (en)
Chinese (zh)
Inventor
罗成
唐国坊
张江陵
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广东生益科技股份有限公司
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Publication of WO2018103276A1 publication Critical patent/WO2018103276A1/fr

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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
    • 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
    • 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.
  • DOPO-HQ is a reactive phosphorus-containing curing agent which can react with epoxy resin.
  • its reactive group is a phenolic hydroxyl group, it reacts with an epoxy resin to form a secondary hydroxyl group with a relatively large polarity.
  • the dielectric properties of the cured product are poor.
  • CN103965249A discloses a process for preparing an active ester of an alkyl group by using a phosphorus-containing phenanthrene and a use thereof, but the phosphorus-containing phenanthrene-linked alkyl group causes a slightly lower Tg when it is cured with an epoxy resin, so that it is on a high Tg copper clad plate. The use of this is limited.
  • a non-active ester compound is synthesized by using a phosphorus-containing phenanthrene derivative and glycerin, and the engineering material can be flame-retarded in an added form, which also does not contribute to the Tg of the reinforcing material.
  • the esterified dihydroxyphenylphosphaphenanthrene is used as a curing agent for epoxy resin, and does not generate a secondary hydroxyl group with a large polarity when reacted with an epoxy resin, so that the dielectric properties of the system are better.
  • it is a phosphorus-containing active curing agent. It is also used as a curing agent and has the effect of halogen-free flame retardant. It can be added in a small amount or without adding other flame retardants to make the sheet reach UL94 V-0. Halogen 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 laminate for printed circuit board produced using the resin composition has high glass transition temperature, excellent dielectric properties, high heat resistance and moist heat resistance, excellent peel strength, and good processability, and can be realized. Halogen-free flame retardant, reaching UL94 V-0.
  • 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 bishydroxyphenylphosphaphenanthrene, and optionally other curing agents can be obtained.
  • a composition obtained by appropriately mixing a halogen-free epoxy resin, an esterified bishydroxyphenylphosphaphenanthrene, and optionally other curing agents can be obtained.
  • the above purpose 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 bishydroxyphenylphosphaphenanthrene, and optionally other curing agents can be obtained.
  • the above purpose was obtained by appropriately mixing a halogen-free epoxy resin, an esterified bishydroxyphenylphosphaphenanthrene, and optionally other curing agents.
  • thermosetting resin composition comprising an epoxy resin and a curing agent, wherein the curing agent contains at least one esterified bishydroxyphenylphosphaphenanthrene.
  • thermosetting resin composition of the present invention is a halogen-free thermosetting resin composition which uses esterified dihydroxyphenylphosphaphenanthrene 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 good heat resistance and high Tg can be obtained; and the esterified dihydroxyphenylphosphonium is obtained.
  • the phenanthrene structure has high symmetry, and the active ester unit in the molecule does not generate a secondary hydroxyl group having a large polarity after reacting with the epoxy resin, and the disadvantage of poor dielectric properties due to the secondary hydroxyl group having a large polarity can be eliminated.
  • the dielectric property is excellent; the esterified dihydroxyphenylphosphaphenanthrene is an active ester, and the ester bond formed by the reaction with the epoxy has a low water absorption rate, thereby improving the disadvantage that the phosphorus-containing compound has poor moist heat resistance.
  • the esterified dihydroxyphenylphosphaphene can have a halogen-free flame retardant effect, and UL94 V-0 flame retardant can be achieved with little or no additional flame retardant.
  • the present invention utilizes the highly symmetrical esterified dihydroxyphenylphosphaphenanthrene ester ester group to significantly improve the glass transition temperature and heat resistance of the prepreg prepared using the resin composition and the laminate for printed circuit boards. 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. Each component will be described in detail below.
  • esterified bishydroxyphenylphosphaphenanthrene has the structural formula shown in formula (I):
  • n 1 is an integer from 1 to 20, such as 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20;
  • R 1 is selected from any one of the following groups:
  • Ar 1 is selected from any one of the following groups:
  • Ar 2 is selected from any one 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 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, an ethyl group or a propyl group. Any of a butyl group, a butyl group, an isopropyl group, an isobutyl group or a tert-butyl group.
  • esterified bishydroxyphenylphosphaphenanthene of the present invention may have the following structural formula:
  • the esterified bishydroxyphenylphosphaphene accounts for 20% to 50%, for example, 20%, 22%, 24%, 25 of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. %, 26%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48% or 50%, and the specific point value between the above values, limited by space and out 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 is no longer Exhaustive enumeration of specific point values included in the stated range.
  • the epoxy resin is a halogen-free epoxy resin, which means an epoxy resin having two or more epoxy groups in one molecule, and is selected from glycidyl ethers and glycidyl esters. Any one or a mixture of at least two of a glycidylamine, an alicyclic epoxy resin, an epoxidized olefin, a hyacinol epoxy resin or an imide epoxy resin.
  • 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 above epoxy resins are all halogen-free epoxy resins.
  • 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 a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group.
  • Y 1 and Y 2 are each independently selected from -CH 2 -, Any one of them, n 3 is an arbitrary integer of 1 to 10, for example, 1, 2, 3, 4 , 5, 6, 7, 8, 9, or 10, and R 4 is selected from a hydrogen atom and has a carbon number of 1 to 5 Any one of a linear alkyl group or a branched alkyl group; for example, it may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a t-butyl group or an isopentyl group. Any of them.
  • 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 13 is -CH 2 -, Any one or a mixture of at least two;
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 or R 12 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 prepolymer, 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 and conciseness, the present invention is no longer exhaustively enumerated. The specific point value included.
  • 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 0% to 20%, such as 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%, or 20%, and the specific point values between the above values are limited, and for the sake of brevity, the present invention will not exhaustively enumerate the specific point values included in the range.
  • thermosetting resin composition of the present invention the organic solid content is 100 parts by weight, and specifically comprises: esterified bishydroxyphenylphosphaphenanthene: 20-50 parts by weight; halogen-free epoxy resin: 30-60 weight Parts; 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 Effect of esterified bishydroxyphenylphosphaphenanthene and optionally cyanate resin and/or bismaleimide-triazine resin, SMA resin or phenolic resin, which does not contain fillers, accelerators and flame retardants Components such as agents.
  • 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 content of the organic halogen-free flame retardant is 0 to 15 parts by weight, that is, according to the esterified double Hydroxyphenyl phosphate
  • the sum of the addition amount of the phenanthrene, the epoxy resin, and the cyanate resin, the SMA resin, and the phenol resin to be added 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.
  • 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 addition of the curing accelerator is based on 100 parts by weight of the sum of the esterified bishydroxyphenylphosphaphenanthrene, epoxy resin, and possibly added cyanate resin, SMA resin, and phenol resin.
  • the amount 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 filler is added in an amount of 100 parts by weight based on 100 parts by weight of the combined amount of the esterified bishydroxyphenylphosphaphenanthrene, the epoxy resin, and the cyanate resin, the SMA resin, and the phenol resin which may be added. 5 to 300 parts by weight, preferably 5 to 200 parts by weight, more preferably 5 to 150 parts by weight.
  • the term “comprising” as used in the present invention 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 present invention The “contains” can 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, a lubricant, and the like. 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 reinforcing material is impregnated with the above halogen-free thermosetting resin composition at 100 to 250 ° C
  • the prepreg is obtained by baking 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 halogen-free 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 in the range of 0.07-0.1% Internal; high heat resistance; excellent heat and humidity resistance and good processability; excellent flame retardant efficiency, UL content of 1.5% can reach UL94 V-0.
  • P-AE esteerified bishydroxyphosphaphenanthrene
  • halogen-free epoxy resin and curing accelerator halogen-free flame retardant
  • filler filler
  • the solid content of the glue is controlled to be 65%.
  • the above glue is impregnated with a 2116 glass fiber cloth, and the appropriate thickness is controlled.
  • the prepreg is prepared by baking in an oven at 115 to 175 ° C for 2 to 15 minutes, and then several prepregs are stacked and stacked on both sides.
  • the upper 18 ⁇ RTF copper foil is made into a copper clad laminate under the conditions of a curing temperature of 170-250 ° C, a curing pressure of 25-60 kg/cm 2 and a curing time of 60-300 min.
  • Examples 1-20 and Comparative Examples 1-8 relate to materials and grade information as follows:
  • P-AE1 Self-made esterified modified bishydroxyphenylphosphine phenanthrene
  • P-AE2 Self-made esterified modified bishydroxyphenylphosphine phenanthrene
  • P-AE3 Self-made esterified modified bishydroxyphenylphosphine phenanthrene
  • P-AE4 Self-made esterified modified bishydroxyphenylphosphine phenanthrene
  • P-AE5 Self-made esterified modified bishydroxyphenylphosphine phenanthrene
  • ODOPB 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-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
  • SEB-0904PM60 Phosphorus phenolic, SHIN-A
  • SHN-1655TM65 Phosphorus-containing phenolic, SHIN-A
  • SPB-100 Otsuka Chemical, phosphazene flame retardant, phosphorus content 13.4%
  • EF40 SMA, styrene-maleic anhydride copolymer, Sartomer
  • EF60 SMA, styrene-maleic anhydride copolymer, Sartomer
  • EF80 SMA, styrene-maleic anhydride copolymer, Sartomer
  • Fused silica (average particle size 0.2 to 10 ⁇ m, purity 99% or more)
  • Tables 1-4 are the formulation compositions and physical property data of Examples 1 to 20, Table 5, Comparative Examples 1 to 8.
  • Example 6 Example 7
  • Example 8 Example 9
  • Example 10 P-AE2 20 20 20 20 50 CE01MO 50 CEO1PS 40 CY-40 30 PT-60S 20 10 HP-6000 50 NC-3000H 60 SKE-1 30 SKE-3 40 40 SPB-100 3 5 10 15 0 DMAP 0.01 0.08 0.1 1 0.3 Spherical silicon 100 25 25 25 5 P% 1.50% 1.73% 2.26% 2.74% 2.87% Tg(DMA)/°C 245 235 210 195 198 Dk (10GHz) 4.2 3.8 3.8 3.9 3.8 Df (10GHz) 0.0072 0.072 0.075 0.0078 0.008 Water absorption /% 0.05 0.07 0.07 0.07 0.1 PCT/6h OOO OOO OOO OOO T288/min >60 >60 >60 >60 >60 Difficult to burn V-0 V-0 V-0 V-0 V-0 V-0 V-0
  • Example 16 Example 17 Example 18 Example 19 Example 20 P-AE1 20 P-AE2 30 P-AE3 40 P-AE4 50 P-AE5 50 92741 10 SEB-0904PM60 10 SHN-1655TM65 5 20 2812 10 5 5 5 HP-7200HHH 45 HP-6000 50 HP-9900 55 NC-3000H 60 2E4MZ 0.1 0.1 0.1 0.1 0.1 Spherical silicon 25 25 25 25 25 P% 2.22% 2.72% 2.45% 2.31% 2.99% Tg(DMA)/°C 180 185 180 190 195 Dk (10GHz) 3.8 3.8 3.8 3.8 3.8 Df (10GHz) 0.008 0.0075 0.0075 0.0085 0.007 Water absorption /% 0.08 0.08 0.08 0.08 0.085
  • PCT/6h OOO OOO OOO OOO OOO T288/min >60 >60 >60 >60 >60 Difficult to burn V-0 V-0 V-0 V-0 V-0 V-0
  • ⁇ is a layered burst board
  • O is a layered burst board
  • T g Glass transition temperature
  • 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.
  • Comparative Example 1 and Example 4 the copper clad laminate prepared by using ODOBP and the halogen-free epoxy resin in Comparative Example 1 has poor dielectric properties, poor moist heat resistance, high water absorption, and low Tg; Comparative Example 2 and Examples 9 comparison, the copper clad laminate prepared by using ODOBP and cyanate resin and halogen-free epoxy resin in Comparative Example 2 has poor dielectric properties, high water absorption, poor moist heat resistance and low Tg; Comparative Example 3 and Example 13 In comparison, the copper clad laminate prepared by using ODOBP and SMA resin and halogen-free epoxy resin in Comparative Example 3 has poor dielectric properties, high water absorption, and poor heat and humidity resistance; Comparative Example 4 is compared with Example 17, in Comparative Example 4 The copper clad laminate prepared by using ODOBP and phenolic resin and halogen-free epoxy resin has poor dielectric properties, high water absorption, poor heat resistance and moist heat resistance, and low Tg; Comparative Example 5 is compared with Example 4, Comparative Example 5 The FR
  • Comparative Example 7 Comparative Example 9
  • Comparative Example 8 Comparative Example 9
  • the content of the esterified bishydroxyphenylphosphonium in Example 8 is lower than that in Example 9.
  • the prepreg and the printed circuit board laminate made of the halogen-free thermosetting resin composition provided by the present invention have a 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 flame retardant, reaching UL94 V-0.

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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)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une composition de résine thermodurcissable comprenant un dihydroxylphényl phosphaphénanthrène estérifié. La composition de résine thermodurcissable présente les avantages d'une bonne stabilité thermique, d'une résistance à la chaleur et à l'humidité, d'une ténacité, d'une faible constante diélectrique et d'une faible tangente de l'angle de perte diélectrique, une faible absorption d'eau, et d'un effet ignifuge sans halogène, etc., ainsi qu'une excellente aptitude au traitement. L'invention concerne également des utilisations de la composition de résine thermodurcissable dans une feuille de résine, une feuille métallique composite de résine, un préimprégné, un stratifié, un stratifié de placage de feuille métallique et une carte de circuit imprimé.
PCT/CN2017/085676 2016-12-05 2017-05-24 Composition de résine thermodurcissable WO2018103276A1 (fr)

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CN114605780A (zh) * 2020-12-09 2022-06-10 广东生益科技股份有限公司 一种热固性树脂组合物及包含其的预浸料、层压板、电路基板和印刷电路板

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