WO2020133335A1 - 一种热固性树脂组合物及使用其的预浸料、覆金属箔层压板和印制电路板 - Google Patents

一种热固性树脂组合物及使用其的预浸料、覆金属箔层压板和印制电路板 Download PDF

Info

Publication number
WO2020133335A1
WO2020133335A1 PCT/CN2018/125306 CN2018125306W WO2020133335A1 WO 2020133335 A1 WO2020133335 A1 WO 2020133335A1 CN 2018125306 W CN2018125306 W CN 2018125306W WO 2020133335 A1 WO2020133335 A1 WO 2020133335A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy resin
parts
phosphorus
resin composition
curing agent
Prior art date
Application number
PCT/CN2018/125306
Other languages
English (en)
French (fr)
Inventor
游江
林伟
黄天辉
Original Assignee
广东生益科技股份有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 广东生益科技股份有限公司 filed Critical 广东生益科技股份有限公司
Publication of WO2020133335A1 publication Critical patent/WO2020133335A1/zh

Links

Classifications

    • 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
    • C08G59/62—Alcohols or phenols
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

Definitions

  • the invention belongs to the technical field of printed circuit boards, and particularly relates to a thermosetting resin composition and a prepreg, metal foil-clad laminate and printed circuit board using the same.
  • phosphorus-containing bisphenol not only has a high phosphorus content, but also can achieve halogen-free flame retardation; at the same time, the phosphorus-containing bisphenol can also be used as a curing agent for epoxy resin, and the resulting cured product has a higher glass transition temperature, Excellent dielectric properties, high heat resistance and high adhesion.
  • the water absorption rate of the cured product is very high.
  • the high water absorption rate will not only cause the dielectric properties of the plate to deteriorate significantly due to moisture absorption, but also may cause the substrate to absorb due to PCB processing. After the tide was heated and burst. Therefore, on the premise of ensuring excellent dielectric properties, how to reduce the water absorption rate of the phosphorus-containing bisphenol system and increase the glass transition temperature of the cured product has become a technical problem.
  • benzoxazine resins are commonly used to reduce the water absorption of cured products.
  • the dielectric properties of benzoxazine resins are poor, which will seriously deteriorate the dielectric properties of phosphorus-containing bisphenol systems.
  • CN104761719A discloses a bifunctional polyfunctional active ester resin containing a PPO backbone, which has the structure shown below: Where R1 is R2 is Substituted or unsubstituted C1-C3 linear or branched alkyl, allyl or isoallyl; R 3 is H, allyl or isoallyl; R 4 , R 5 , R 6 , R 7 is independently selected from H, substituted or unsubstituted C1-C3 linear or branched alkyl, allyl, isoallyl or -OR 8 ; R 8 is substituted or unsubstituted C1-C3 straight Alkyl or branched alkyl or substituted or unsubstituted phenyl, n1, n2 are positive integers greater than 0, and satisfy 4 ⁇ n1+n2 ⁇ 25, n3, n4 are equal or unequal, independently 1, 2 or 3.
  • the prepregs, laminates, and copper clad laminates made from the thermosetting resin composition containing the active ester have excellent dielectric properties, moisture and heat resistance, heat resistance, and extremely low water absorption and high bending strength.
  • the ester groups at both ends of the bifunctional polyfunctional active ester can react with epoxy resin. However, due to the influence of steric hindrance, not all ester groups can undergo curing crosslinking; the middle PPO main chain and R1 structure have no reaction Group (R 1 is When) or curing crosslinking group is a double bond, and will not react with epoxy resin at all.
  • the cross-linking density of the bifunctional polyfunctional active ester resin and epoxy resin is not high, while the middle PPO main chain is a thermoplastic segment, the coefficient of thermal expansion (CTE) is high, and the glass transition temperature of the final cured product or sheet Low, high coefficient of thermal expansion (CTE).
  • the object of the present invention is to provide a thermosetting resin composition and a prepreg, metal foil-clad laminate and printed circuit board using the same.
  • the laminate and the metal foil-clad laminate prepared by using the thermosetting resin composition have high glass transition temperature, low water absorption rate, low dielectric constant, low dielectric loss factor, high heat resistance, good flame retardancy, and processing Performance and chemical resistance.
  • the present invention uses the following technical solutions:
  • the present invention provides a thermosetting resin composition, wherein the thermosetting resin composition includes the following components: an epoxy resin, a phosphorus-containing bisphenol, and an ester curing agent;
  • the ester curing agent has the structure of formula I:
  • R 1 -R 8 are each independently selected from one of a hydrogen atom, a C 1 -C 10 aliphatic hydrocarbon group, a C 3 -C 10 alicyclic hydrocarbon group, or a C 6 -C 10 aromatic hydrocarbon group, and not all are A hydrogen atom;
  • X is selected from one of -O-, -S-, -CH 2 -or -C(CH 3 ) 2 -;
  • Y is selected from one of C 1 -C 10 aliphatic hydrocarbon groups, C 3 -C 10 alicyclic hydrocarbon groups or C 6 -C 10 aromatic hydrocarbon groups;
  • n is an integer of 1-10.
  • the present invention adopts an ester curing agent having the structure of Formula I and phosphorus-containing bisphenol to cure epoxy resin synergistically, and uses phosphorus-containing bisphenol as the main curing agent, which gives the cured product excellent dielectric properties, high heat resistance and adhesion At the same time, it can also achieve halogen-free flame retardancy.
  • the ester curing agent of formula I structure it does not generate polar groups such as secondary hydroxyl groups during the curing process, which can significantly improve the cured product while ensuring excellent dielectric properties.
  • the glass transition temperature, and the cured product contains a large number of hydrophobic groups, can greatly reduce the water absorption rate of the cured product, making the cured product dielectric constant and dielectric loss factor more stable.
  • the prepreg and printed circuit board made with the resin composition have high glass transition temperature, low water absorption, low dielectric constant, low dielectric loss factor, high heat resistance and good flame retardancy , Processing performance and chemical resistance.
  • the C 1 -C 10 aliphatic hydrocarbon group refers to containing 1-10 (for example, 1, 2, 3, 4, 5, 6, 6, 7, 8, 9 or 10) aliphatic hydrocarbon group of carbon atom; for example, it may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl and the like.
  • the C 3 -C 10 alicyclic hydrocarbon group refers to an alicyclic group containing 3 to 10 (eg, 3, 4, 5, 6, 7, 8, 8, 9 or 10) carbon atoms Hydrocarbon group; for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • the C 6 -C 10 aromatic hydrocarbon group refers to an aliphatic hydrocarbon group containing 6-10 (for example 6, 7, 8, 9, or 10) carbon atoms; for example, it may be phenyl, benzyl , Phenethyl or phenylpropyl, etc.
  • n may be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
  • the thermosetting resin composition includes: 40-75 parts of epoxy resin, 15-40 parts phosphorus-containing bisphenol and 5-25 parts ester curing agent.
  • ester curing agent in the present invention refers to an ester curing agent having the structure of Formula I.
  • the weight parts of the epoxy resin may be 40 parts, 42 parts, 45 parts, 48 parts, 50 parts, 52 parts, 55 parts, 58 parts, 60 parts, 62 parts, 65 parts, 68 parts , 70 copies, 75 copies, etc.
  • the weight parts of the phosphorus-containing bisphenol can be 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 23 parts, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 33 parts, 35 parts , 38 or 40 copies.
  • the weight parts of the ester curing agent may be 5, 6, 8, 10, 12, 13, 15, 15, 18, 20, 22, 23, or 25 parts Wait.
  • the epoxy resin, the phosphorus-containing bisphenol and the ester curing agent are mixed with each other at the above-mentioned specific ratio to further improve the comprehensive performance of the cured product and the laminate prepared therefrom. If the amount of epoxy resin added is too small, the processability of the cured product and the laminate will be poor; if the amount of epoxy resin added too much, it will lead to a low glass transition temperature of the cured product and the laminate. Poor electrical performance. If the amount of phosphorus-containing bisphenol is too small, the toughness of the cured product and the laminate is poor, and the flame retardancy is insufficient; if the amount of phosphorus-containing bisphenol is too large, the glass transition temperature of the cured product and the laminate is low.
  • the addition amount of the ester curing agent is too small, the effect of reducing the water absorption of the cured product or laminate and increasing the glass transition temperature is not obvious. If the addition amount of the ester curing agent is too large, This leads to greater brittleness of the cured product and laminate, and poor processing performance.
  • the epoxy resin is a halogen-free epoxy resin.
  • the halogen-free epoxy resin is selected from bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, triphenol novolac ring Oxygen resin, dicyclopentadiene novolac epoxy resin, biphenyl novolac epoxy resin, alkylbenzene novolac epoxy resin or naphthol novolac epoxy resin, or a combination of at least two of them.
  • the halogen-free epoxy resin has the structure of formula II:
  • X 1 , X 2 and X 3 are each independently R 9 is selected from a hydrogen atom, a substituted or unsubstituted C 1 -C 5 linear alkyl group or a substituted or unsubstituted C 3 -C 5 branched alkyl group;
  • Y 1 and Y 2 are each independently selected from a single bond, -CH 2 -,
  • One of R 10 is selected from a hydrogen atom, a substituted or unsubstituted C 1 -C 5 linear alkyl group or a substituted or unsubstituted C 3 -C 5 branched alkyl group;
  • n is an integer of 1-10; for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.
  • the C 1 -C 5 straight-chain alkyl group refers to a straight-chain alkyl group containing 1 to 5 (eg 1, 2, 3, 4 or 5) carbon atoms; for example, it may be Methyl, ethyl, propyl, butyl or pentyl.
  • the C 3 -C 5 branched alkyl group refers to a branched alkyl group containing 3-5 (eg 3, 4 or 5) carbon atoms; for example, it may be isopropyl, isobutyl, tert-butyl Base or isoamyl, etc.
  • the halogen-free epoxy resin having the structure of Formula II has higher functionality and good dielectric properties, which helps to further increase the glass transition temperature of the cured product, and reduce dielectric loss and water absorption.
  • the phosphorus-containing bisphenol has the structure of formula III:
  • k is an integer of 2-20 (for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 18 or 20, etc.), preferably an integer of 3-10.
  • the weight average molecular weight of the phosphorus-containing bisphenol is 1000-10000; for example, it may be 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, or 10000. It is preferably 1000-6500, and more preferably 1000-4500.
  • thermosetting resin composition further includes a flame retardant.
  • the flame retardant is a phosphorus-containing flame retardant.
  • the added amount of the phosphorus-containing flame retardant is 0-50 parts, for example, 0 parts , 1, 2, 5, 8, 10, 12, 15, 18, 20, 22, 25, 28, 30, 35, 40, 45, or 50 Parts etc.; further preferably 0-30 parts.
  • the phosphorus-containing flame retardant is selected from tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa -10-phosphinophenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa-10- One or a combination of at least two of phosphaphenanthrene-10-oxide, phenoxyphosphazene compound, phosphate, polyphosphate, phosphonate or polyphosphonate.
  • thermosetting resin composition further includes a curing accelerator to cure the resin composition and accelerate the curing speed of the resin composition.
  • the addition amount of the curing accelerator is 0.05-1 part; for example, it may be 0.05 parts, 0.1 Parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts or 1 part, etc.
  • the curing accelerator is selected from one or a combination of at least two of imidazole compounds, triphenylphosphine, dimethylaminopyridine, boron trifluoride monoethylamine, or zinc octoate.
  • the imidazole compound is selected from one or a combination of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole .
  • thermosetting resin composition further includes a filler to further reduce the coefficient of thermal expansion (CTE) and water absorption of the cured product and the laminate, and improve the thermal conductivity.
  • CTE coefficient of thermal expansion
  • the addition amount of the filler is 0-150 parts, for example, 0 parts, 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts , 110 parts, 120 parts, 130 parts, 140 parts or 150 parts, etc.; further preferably 0-100 parts.
  • the filler is an organic filler and/or an inorganic filler.
  • the inorganic filler is selected from silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, silicic acid One or a combination of at least two of calcium, mica, and glass fiber powder.
  • the organic filler is selected from one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide or polyethersulfone powder.
  • the filler is most preferably silica, which may be, for example, fused silica, crystalline silica, spherical silica or hollow silica; the median particle size is 1-15 ⁇ m, For example, it may be 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 5 ⁇ m, 6 ⁇ m, 8 ⁇ m, 10 ⁇ m, 12 ⁇ m, 13 ⁇ m or 15 ⁇ m, etc.; further preferably 1-10 ⁇ m.
  • the filler having a particle size distribution within the above range has better dispersibility in the thermosetting resin composition.
  • the present invention provides a resin glue obtained by dissolving or dispersing the thermosetting resin composition as described in the first aspect in a solvent.
  • the solvent in the present invention is not particularly limited, and alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol, butyl carbitol, etc. can be used.
  • Alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol, butyl carbitol, etc.
  • 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
  • N, N-di Nitrogen-containing solvents such as methylformamide and N,N-dimethylacetamide.
  • the above solvents can be used alone or in combination of two or more. Ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, and cyclohexanone are preferred.
  • the added amount of the solvent is selected by those skilled in the art according to their own experience, so that the resin glue solution can reach a viscosity suitable for use.
  • the solvent is preferably methyl ethyl ketone (MEK), and the solid content of the glue solution is preferably 60-70%.
  • MEK methyl ethyl ketone
  • the present invention provides a prepreg including a reinforcing material, and the thermosetting resin composition provided in the first aspect of the present invention adhered to the reinforcing material after being impregnated and dried.
  • the resin material is used to impregnate the reinforcing material with the thermosetting resin composition, and the prepreg is obtained after drying.
  • the reinforcing material is preferably glass cloth
  • the glue impregnation amount is preferably 200-230 g/m 2
  • the drying temperature is preferably 155° C.
  • the time is preferably 5-10 min.
  • the invention provides a laminate comprising one or at least two superposed prepregs provided in the third aspect of the invention.
  • the present invention provides a metal-clad laminate comprising one or at least two superposed prepregs provided in the third aspect of the present invention and one or both sides covered on the outside of the prepreg Metal foil.
  • the metal foil-clad laminate is prepared by bonding at least two prepregs together to form a laminate, and then affixing metal foil on one or both sides of the laminate, and finally heating and pressure curing.
  • the heating and pressing operation can be carried out by a laminator, and the lamination must meet the following requirements: 1
  • the temperature increase rate of lamination should be controlled at 1.5-2.5°C/min when the material temperature is 80-120°C; 2 Lamination Pressure setting, the outer layer material temperature is applied full pressure at 120-150 °C, the full pressure is about 350psi; 3
  • When curing control the material temperature at 200 °C, and keep it warm for 90 minutes.
  • the metal foil may be copper foil, nickel foil, aluminum foil, SUS foil (stainless steel foil), or the like.
  • the present invention provides a printed circuit board including at least one prepreg as described above.
  • the present invention has the following beneficial effects:
  • the present invention adopts an ester curing agent having a structure of Formula I and a phosphorus-containing bisphenol to cure an epoxy resin synergistically, and uses a phosphorus-containing bisphenol as a main curing agent, which imparts excellent dielectric properties, high heat resistance, and adhesion Strength and toughness, while also achieving halogen-free flame retardancy.
  • the ester curing agent of formula I structure does not generate polar groups such as secondary hydroxyl groups during the curing process, which can significantly increase the glass transition temperature of the cured product while ensuring excellent dielectric properties, and the cured product contains a large amount of The hydrophobic group can greatly reduce the water absorption rate of the cured product, make up for the problem of high water absorption caused by the high phosphorus content of the phosphorus-containing bisphenol, and make the cured product dielectric constant and dielectric loss factor more stable.
  • the laminate prepared by using the thermosetting resin composition has a glass transition temperature of 172-196°C, a thermal expansion coefficient of 2.1%-2.8%, a water absorption rate of 0.20%-0.32%, and a dielectric constant (1 GHz) of 3.48-3.71 ,
  • the dielectric loss factor (1GHz) is 0.0071-0.0089
  • the dielectric constant after wet is 3.58-3.89
  • the dielectric loss factor after wet is 0.0078-0.0105
  • the peel strength is 1.38-1.48 N/mm
  • the drop hammer impact crack area is 192-325mm 2
  • the flame resistance is V-0, and it has good heat resistance, moisture resistance, peel strength, dielectric properties and flame retardancy.
  • B-1 Phosphorus-containing bisphenol OL3001 (US FRX Polymers trade name, phosphorus content 10.8%, weight average molecular weight 3000);
  • B-2 Phosphorus-containing bisphenol OL5000 (US FRX Polymers trade name, phosphorus content 10%, weight average molecular weight 5000);
  • the average repeating unit n is 1.25;
  • the preparation method is as follows:
  • the solution was distilled and concentrated under reduced pressure, and then methanol was added to precipitate the resin product, which was filtered, washed with water until the pH value of the final water layer was 7, and then washed with methanol , And then dried to obtain the product.
  • the ester equivalent of the prepared active ester resin was 252 g/eq according to the charging ratio.
  • the average repeating unit n is 1.25;
  • the preparation method is as follows:
  • the solution was distilled and concentrated under reduced pressure, and then methanol was added to precipitate the resin product, which was filtered, washed with water until the pH value of the final water layer was 7, and then washed with methanol , And then dried to obtain the product.
  • the ester equivalent of the prepared active ester resin was 226 g/eq according to the charging ratio.
  • the average repeating unit n is 1.25;
  • the preparation method is as follows:
  • reaction is continued to be stirred for 2 to 3 hours below 20°C.
  • the stirring reaction is continued for 2 to 5 hours. After the reaction was completed, it was allowed to stand, and the solid of triethylamine hydrochloride was removed by filtration.
  • the solution was distilled and concentrated under reduced pressure, and then methanol was added to precipitate the resin product, which was filtered, washed with water until the pH value of the final water layer was 7, and then washed with methanol , And then dried to obtain the product.
  • the ester equivalent of the prepared active ester resin was 181 g/eq according to the charging ratio.
  • the average repeating unit n is 1.25;
  • Phenoxyphosphazene compound SPB-100 Japanese Mitsubishi trade name
  • Examples 1-16 provide a thermosetting resin composition glue, a prepreg and a copper clad laminate using the same, the preparation method is as follows:
  • MEK solvent to prepare components (B) phosphorus-containing curing agent, (C) co-curing agent and (D) phenoxyphosphazene compound SPB-100 into solid solutions of 60%, 50% and 25%, respectively. Add it to a 1000mL beaker in sequence, then add (A) halogen-free epoxy resin and (F) filler, add an appropriate amount of (E) curing accelerator 4-dimethylaminopyridine, and adjust the gelation time (GT) to 200- 300s, add MEK solvent to control the solid content to 65%, continue to stir for 2h to ripen, to obtain the thermosetting resin composition glue;
  • Comparative Example 1 The difference between Comparative Example 1 and Example 7 is that the type (B) of the phosphorus-containing curing agent is different, as shown in Table 3 below.
  • Comparative Examples 2-5 and Example 5 The difference between Comparative Examples 2-5 and Example 5 is that the type of component (C) curing agent is different, as shown in Table 3 below.
  • Comparative Examples 6-9 and Example 16 lies in the type of component (C) curing agent, as shown in Table 3 below.
  • test standards/methods are as follows:
  • Tg Glass transition temperature: measured according to the differential scanning calorimetry (DSC) method according to the DSC method specified in IPC-TM-650 2.4.25.
  • the dielectric loss and the dielectric loss factor at 1 GHz were measured according to IPC-TM-650 2.5.5.5.
  • the dielectric loss and dielectric loss factor at 1 GHz are measured according to IPC-TM-650 2.5.5.5.
  • the drop weight impact test machine is used for testing.
  • the test method the drop weight height is 1 m, the drop weight is 0.75 kg, the drop weight is released, and the crack area of the plate is tested.
  • the size of the crack area of the plate can initially reflect the toughness of the plate. Generally speaking, the smaller the crack area, the better the toughness of the plate.
  • Example 1-9 uses 5-25 parts of an ester curing agent having the structure of Formula I and 15-40 parts of phosphorus-containing bisphenol to cure 40-75 parts of halogen-free epoxy resin,
  • the resulting board has high Tg, low CTE, low water absorption, excellent dielectric properties, high heat resistance and peel strength, and excellent toughness, while achieving halogen-free flame retardant V-0 level.
  • Example 10 an ester curing agent having the structure of Formula I and phosphorus-containing bisphenol OL3001 were used to cure 78 parts of dicyclopentadiene novolac epoxy resin HP-7200H, due to the amount of dicyclopentadiene novolac epoxy resin HP-7200H Exceeding the preferred dosage range leads to incomplete reaction, the final sheet Tg is reduced, CTE and water absorption are increased, the dielectric properties are poor and the heat resistance is not ideal.
  • Example 11 38 parts of dicyclopentadiene novolac epoxy resin HP-7200H was cured by compounding an ester curing agent with the structure of Formula I with phosphorus-containing bisphenol OL3001.
  • the sheet has a higher Tg and a lower CTE, but due to Insufficient epoxy resin and excessive curing agent will result in higher water absorption rate, poorer dielectric properties and less ideal heat resistance.
  • Example 12 an ester curing agent having the structure of Formula I and 42 parts of phosphorus-containing bisphenol OL3001 composite cured dicyclopentadiene novolac epoxy resin HP-7200H were used, because the amount of curing agent phosphorus-containing bisphenol OL3001 exceeded the preferred amount range
  • the final sheet Tg is slightly lower and the water absorption rate is high, and the dielectric properties of the sheet deteriorate seriously after moisture absorption.
  • Example 13 an ester curing agent having the structure of Formula I and 8 parts of phosphorus-containing bisphenol OL3001 are used to cure dicyclopentadiene novolac epoxy resin HP-7200H. Since the curing agent contains a low amount of phosphorus-containing bisphenol OL3001, the ring The over-curing of the oxygen resin is incomplete, and the final sheet CTE is high and the dielectric properties are average.
  • Example 14 27 parts of an ester curing agent having the structure of Formula I and a phosphorus-containing bisphenol OL3001 composite cured dicyclopentadiene novolac epoxy resin HP-7200H are used.
  • the sheet has high Tg, low CTE, low water absorption and excellent Dielectric properties, but the crack area of the drop weight impact test used to characterize toughness is too large, and the toughness of the sheet is poor, which is not conducive to downstream PCB processing.
  • Example 15 3 parts of an ester curing agent having the structure of Formula I and a phosphorus-containing bisphenol OL3001 composite cured dicyclopentadiene novolac epoxy resin HP-7200H were used.
  • the final sheet had a low Tg, a high CTE, and a high water absorption rate. After the tide, the dielectric properties of the sheet deteriorated seriously.
  • Example 16 an ester curing agent having the structure of Formula I and a phosphorus-containing bisphenol OL3001 composite cured dicyclopentadiene novolac epoxy resin HP-7200H are used, without adding fillers, the CTE and water absorption of the sheet have increased, but It is still maintained at an ideal level, and the sheet has high Tg, excellent dielectric properties, heat resistance and toughness.
  • the laminate prepared using the thermosetting resin composition provided by the present invention has higher Tg, lower CTE, lower water absorption, and more excellent dielectric properties compared to the general halogen-free laminate And peel strength, heat resistance, toughness, suitable for high-speed applications.
  • the halogen content of the present invention can reach the V-0 standard in the flame retardant test UL94 within the range required by the JPCA halogen-free standard, and has the effect of environmental protection.
  • Comparative Example 2 an ester curing agent V-575 and a phosphorus-containing bisphenol OL3001 composite cured dicyclopentadiene phenol epoxy resin HP-7200H were used.
  • the sheet has high Tg, low CTE, excellent heat resistance and toughness, but The electrical properties are general, the water absorption rate is high and the dielectric properties of the sheet after moisture absorption are poor.
  • Comparative Example 4 bisphenol A type cyanate prepolymer CE01PS and phosphorus-containing bisphenol OL3001 composite cured dicyclopentadiene phenol epoxy resin HP-7200H were used.
  • the sheet has high Tg, low CTE, excellent dielectric properties and Heat resistance, but high water absorption and poor dielectric properties after moisture absorption.
  • Comparative Example 6 an ester curing agent V-575 and a phosphorus-containing bisphenol OL3001 composite cured dicyclopentadiene novolac epoxy resin HP-7200H were used without fillers.
  • the sheet has high Tg, low CTE and excellent dielectric constant. However, the water absorption rate is high and the dielectric properties of the sheet after moisture absorption are poor, and the heat resistance is also not ideal.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Epoxy Resins (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

本发明提供了一种热固性树脂组合物及使用其的预浸料、覆金属箔层压板和印制电路板。热固性树脂组合物包括环氧树脂、含磷双酚和具有式I结构的酯类固化剂。本发明采用具有式I结构的酯类固化剂与含磷双酚协同固化环氧树脂，用含磷双酚为主固化剂，赋予了固化物优异的介电性能、高耐热性和粘合力，同时还能实现无卤阻燃，结合式I结构的酯类固化剂，使得在固化过程中不产生二次羟基等极性基团，可在保证介电性能优异的同时明显提高固化物玻璃化转变温度，且固化产物中含有大量疏水基团，能大幅降低固化物吸水率，使得固化物介电常数和介电损耗因子更加稳定。制备的层压板和覆金属箔层压板具有良好的耐热性、耐湿性、剥离强度、介电性能和阻燃性。

Description

一种热固性树脂组合物及使用其的预浸料、覆金属箔层压板和印制电路板 技术领域
本发明属于印制电路板技术领域，具体涉及一种热固性树脂组合物及使用其的预浸料、覆金属箔层压板和印制电路板。
背景技术
随着电子产品信息处理的高速化和多功能化，应用频率不断提高，要求介电常数(Dk)和介电损耗值(Df)越来越低，因此降低Dk/Df已成为基板业者的追逐热点。同时在全球强化“绿色”“环保”的大趋势下，无卤阻燃型覆铜箔层压板的开发成为业界的热点，各覆铜箔层压板厂家都纷纷推出自己的无卤阻燃覆铜箔层压板。
为了同时实现低Dk/Df和无卤阻燃，采用高磷含量的低Dk/Df固化剂是最理想的选择。经研究，含磷双酚不仅磷含量较高，能实现无卤阻燃；同时该含磷双酚还可以用作环氧树脂的固化剂，生成的固化物有着较高的玻璃化转变温度、优异的介电性能、高耐热性以及高粘合力。但由于该含磷双酚结构中含膦酸酯结构，固化物吸水率非常高，高吸水率不仅会造成板材介电性能因吸潮而明显恶化，还可能会导致基板在PCB加工时因吸潮后受热而爆板。因此在保证优异的介电性能的前提下，如何降低含磷双酚体系的吸水率并提高固化物玻璃化转变温度成为一个技术难题。
覆铜板业内常用苯并噁嗪树脂来降低固化物吸水率，然而苯并噁嗪树脂的介电性能较差，会严重恶化含磷双酚体系的介电性能。
CN104761719A公开了一种含有PPO主链的双端基多官能活性酯树脂，其具 有下所示的结构：
Figure PCTCN2018125306-appb-000001
其中R1为
Figure PCTCN2018125306-appb-000002
R2为
Figure PCTCN2018125306-appb-000003
取代或未取代的C1-C3直链烷基或支链烷基、烯丙基或异烯丙基；R 3为H、烯丙基或异烯丙基；R 4、R 5、R 6、R 7独立选自H、取代或未取代的C1-C3直链烷基或支链烷基、烯丙基、异烯丙基或-O-R 8；R 8为取代或未取代的C1-C3直链烷基或支链烷基或取代或未取代的苯基，n1、n2为大于0的正整数，且满足4≤n1+n2≤25，n3、n4相等或不等，独立地为1、2或3。由含有该活性酯的热固性树脂组合物制作的预浸料、层压板及覆铜板，具有优良的介电性能、耐湿热性、耐热性和极低的吸水率以及较高的弯曲强度。该双端基多官能活性酯两端酯基可与环氧树脂发生反应，然而由于空间位阻的影响，并不是所有酯基都能发生固化交联；中间的PPO主链和R1结构没有反应基团(R 1为
Figure PCTCN2018125306-appb-000004
时)或固化交联基团为双键，与环氧树脂根本不会发生反应。因此该双端基多官能活性酯树脂与环氧树脂反应的交联密度不高，而中间的PPO主链是热塑性链段，热膨胀系数(CTE)高，最终固化物或板材的玻璃化转变温度较低、热膨胀系数(CTE)高。
在本领域中，如何在保证覆铜板具有较高玻璃化转变温度的同时，降低其吸水率、热膨胀系数和介电损耗是本领域亟待解决的问题。
发明内容
针对现有技术存在的不足，本发明的目的在于提供一种热固性树脂组合物及使用其的预浸料、覆金属箔层压板和印制电路板。采用该热固性树脂组合物 制备的层压板和覆金属箔层压板具有高玻璃化转变温度、低吸水率、低介电常数、低介电损耗因数、高耐热性以及良好的阻燃性、加工性能和耐化学性。
为达此目的，本发明采用以下技术方案：
第一方面，本发明提供一种热固性树脂组合物，其特征在于，所述热固性树脂组合物包括如下组分：环氧树脂、含磷双酚和酯类固化剂；
所述酯类固化剂具有式I结构：
Figure PCTCN2018125306-appb-000005
其中，R 1-R 8各自独立地选自氢原子、C 1-C 10脂肪族烃基、C 3-C 10脂环族烃基或C 6-C 10芳香族烃基中的一种，且不全为氢原子；
X选自-O-、-S-、-CH 2-或-C(CH 3) 2-中的一种；
Y选自C 1-C 10脂肪族烃基、C 3-C 10脂环族烃基或C 6-C 10芳香族烃基中的一种；
n为1-10的整数。
本发明采用具有式I结构的酯类固化剂与含磷双酚协同固化环氧树脂，用含磷双酚为主固化剂，赋予了固化物优异的介电性能、高耐热性和粘合力，同时还能实现无卤阻燃，结合式I结构的酯类固化剂，使得在固化过程中不产生二次羟基等极性基团，可在保证介电性能优异的同时明显提高固化物玻璃化转变温度，且固化产物中含有大量疏水基团，能大幅降低固化物吸水率，使得固化物介电常数和介电损耗因子更加稳定。使用该树脂组合物制成的预浸料、印制电路用层压板具有高玻璃化转变温度、低吸水率、低介电常数、低介电损耗 因素、高耐热性以及良好的阻燃性、加工性能和耐化学性。
本发明中，所述C 1-C 10脂肪族烃基是指含1-10个(例如1个、2个、3个、4个、5个、6个、7个、8个、9个或10个)碳原子的脂肪族烃基；例如可以是甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基或癸基等。
所述C 3-C 10脂环族烃基是指含3-10个(例如3个、4个、5个、6个、7个、8个、9个或10个)碳原子的脂环族烃基；例如可以是环丙基、环丁基、环戊基或环己基等。
所述C 6-C 10芳香族烃基是指含6-10个(例如6个、7个、8个、9个或10个)碳原子的脂肪族烃基；例如可以是苯基、苯甲基、苯乙基或苯丙基等。
式I中n可以是1、2、3、4、5、6、7、8、9或10。
作为本发明的优选技术方案，以所述环氧树脂、含磷双酚和酯类固化剂的总重量份数为100份计，所述热固性树脂组合物包括：40-75份环氧树脂、15-40份含磷双酚和5-25份酯类固化剂。
如无特殊说明，本发明中所述“酯类固化剂”均是指具有式I结构的酯类固化剂。
本发明中，所述环氧树脂的重量份数可以是40份、42份、45份、48份、50份、52份、55份、58份、60份、62份、65份、68份、70份、75份等。
所述含磷双酚的重量份数可以是15份、16份、18份、20份、22份、23份、25份、26份、28份、30份、32份、33份、35份、38份或40份等。
所述酯类固化剂的重量份数可以是5份、6份、8份、10份、12份、13份、15份、16份、18份、20份、22份、23份或25份等。
本发明通过环氧树脂、含磷双酚和酯类固化剂在上述特定的比例下相互配合，能够进一步提升其固化物和由其制备的层压板的综合性能。若环氧树脂的 添加量过少，会导致固化物和层压板的加工性能较差；若环氧树脂的添加量过多，则会导致固化物和层压板的玻璃化转变温度较低，介电性能较差。若含磷双酚的添加量过少，则固化物和层压板的韧性较差、阻燃不足；若含磷双酚的添加量过多，则固化物和层压板的玻璃化转变温度低。若所述酯类固化剂的添加量过少，则对于降低固化产物或层压板的吸水率和提高玻璃化转变温度的效果不明显，若所述酯类固化剂的添加量过多，则会导致固化产物和层压板的脆性较大，加工性能差。
作为本发明的优选技术方案，所述环氧树脂为无卤环氧树脂。
优选地，所述无卤环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂、邻甲酚酚醛环氧树脂、双酚A型酚醛环氧树脂、三酚型酚醛环氧树脂、双环戊二烯酚醛环氧树脂、联苯型酚醛环氧树脂、烷基苯型酚醛环氧树脂或萘酚型酚醛环氧树脂中的一种或至少两种的组合。
优选地，所述无卤环氧树脂具有式II结构：
Figure PCTCN2018125306-appb-000006
其中，X 1、X 2和X 3各自独立地为
Figure PCTCN2018125306-appb-000007
R 9选自氢原子、取代或未取代的C 1-C 5直链烷基或者取代或未取代的C 3-C 5支链烷基中的一种；
Y 1和Y 2各自独立地选自单键、-CH 2-、
Figure PCTCN2018125306-appb-000008
Figure PCTCN2018125306-appb-000009
中的一种，R 10选自氢原子、取代或未取代的C 1-C 5直链烷基或者取代或未取代的C 3-C 5支链烷基中的一种；
m为1-10的整数；例如可以是1、2、3、4、5、6、7、8、9或10。
本发明中，所述C 1-C 5直链烷基是指含有1-5个(例如1个、2个、3个、4个或5个)碳原子的直链烷基；例如可以是甲基、乙基、丙基、丁基或戊基。
所述C 3-C 5支链烷基是指含有3-5个(例如3个、4个或5个)碳原子的支链烷基；例如可以是异丙基、异丁基、叔丁基或异戊基等。
具有式II结构的无卤环氧树脂具有较高的官能度和良好的介电性能，有助于进一步提高固化产物的玻璃化转变温度，降低介电损耗和吸水率。
作为本发明的优选技术方案，所述含磷双酚具有式III结构：
Figure PCTCN2018125306-appb-000010
其中k为2-20的整数(例如2、3、4、5、6、7、8、9、10、12、15、18或20等)，优选3-10的整数。
优选地，所述含磷双酚的重均分子量为1000-10000；例如可以是1000、2000、3000、4000、5000、6000、7000、8000或10000等。优选为1000-6500，更优选为1000-4500。
作为本发明的优选技术方案，所述热固性树脂组合物还包括阻燃剂。
优选地，所述阻燃剂为含磷阻燃剂。
优选地，以所述环氧树脂、含磷双酚和酯类固化剂的总重量份数为100份计，所述含磷阻燃剂的添加量为0-50份，例如可以是0份、1份、2份、5份、8份、10份、12份、15份、18份、20份、22份、25份、28份、30份、35份、40份、45份或50份等；进一步优选为0-30份。
优选地，所述含磷阻燃剂选自三(2，6-二甲基苯基)膦、10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、2，6-二(2，6-二甲基苯基)膦基苯、10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基磷腈化合物、磷酸酯、聚磷酸酯、膦酸酯或聚膦酸酯中的一种或至少两种的组合。
作为本发明的优选技术方案，所述热固性树脂组合物还包括固化促进剂，使树脂组合物固化并加快树脂组合物的固化速度。
优选地，以所述环氧树脂、含磷双酚和酯类固化剂的总重量份数为100份计，所述固化促进剂的添加量为0.05-1份；例如可以是0.05份、0.1份、0.2份、0.3份、0.4份、0.5份、0.6份、0.7份、0.8份、0.9份或1份等。
优选地，所述固化促进剂选自咪唑类化合物、三苯基膦、二甲氨基吡啶、三氟化硼单乙胺或辛酸锌中的一种或至少两种的组合。
优选地，所述咪唑类化合物选自2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或2-十一烷基咪唑中的一种或至少两种的组合。
作为本发明的优选技术方案，所述热固性树脂组合物还包括填料，以进一步降低固化产物和层压板的热膨胀系数(CTE)和吸水率，提高热导率。
优选地，以所述环氧树脂、含磷双酚和酯类固化剂的总重量份数为100份计，所述填料的添加量为0-150份，例如可以是0份、1份、2份、5份、8份、10份、15份、20份、25份、30份、35份、40份、45份、50份、60份、70 份、80份、90份、100份、110份、120份、130份、140份或150份等；进一步优选为0-100份。
优选地，所述填料为有机填料和/或无机填料。
优选地，所述无机填料选自二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙、云母、玻璃纤维粉中的一种或至少两种的组合。
优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的一种或至少两种的组合。
本发明中，所述填料最优选为二氧化硅，例如可以是熔融二氧化硅、结晶型二氧化硅、球型二氧化硅或空心二氧化硅等；粒径中度值为1-15μm，例如可以是1μm、2μm、3μm、5μm、6μm、8μm、10μm、12μm、13μm或15μm等；进一步优选为1-10μm。粒径分布在上述范围内的填料在热固性树脂组合物中具有更好的分散性。
第二方面，本发明提供一种树脂胶液，所述树脂胶液是将如第一方面所述的热固性树脂组合物溶解或分散在溶剂中得到。
作为本发明中的溶剂，没有特别的限定，可以选用甲醇、乙醇、丁醇等醇类，乙基溶纤剂、丁基溶纤剂、乙二醇甲醚、卡必醇、丁基卡必醇等，丙酮、丁酮、甲基乙基甲酮、环己酮等酮类，甲苯、二甲苯等芳香烃类，醋酸乙酯、乙氧基乙基乙酸酯等酯类，N，N-二甲基甲酰胺、N，N-二甲基乙酰胺等含氮类溶剂。以上溶剂可单独使用，也可两种或两种以上混合使用。优选丙酮、丁酮、甲基乙基甲酮、环己酮等酮类。所述溶剂的添加量由本领域技术人员根据自己经验来选择，使得树脂胶液达到适合使用的粘度即可。
所述溶剂优选为丁酮(MEK)，所述胶液的固含量优选为60-70％。
第三方面，本发明提供一种预浸料，包括增强材料，和通过含浸干燥后附着在所述增强材料上的本发明第一方面提供的热固性树脂组合物。
本发明中，可以采用如下方法制备预浸料：
利用所述热固性树脂组合物的树脂胶液含浸增强材料，干燥后得到预浸料。
其中，所述增强材料优选为玻璃布，胶液含浸量优选为200-230g/m 2，所述干燥的温度优选为155℃，时间优选为5-10min。
第四方面，本发明提供一种层压板，包括一张或至少两张叠合的本发明第三方面提供的预浸料。
第五方面，本发明提供一种覆金属箔层压板，包括一张或至少两张叠合的本发明第三方面提供的预浸料和覆于所述预浸料外侧的一侧或两侧的金属箔。
所述覆金属箔层压板是通过先将至少两张预浸料粘合在一起形成层压板，然后再在层压板一侧或两侧贴覆金属箔，最后加热加压固化的方法制备得到。
所述加热加压的操作可以通过层压机进行，层压须满足以下要求：①层压的升温速率通常在料温80-120℃时应控制在1.5-2.5℃/min；②层压的压力设置，外层料温在120-150℃施加满压，满压压力为350psi左右；③固化时，控制料温在200℃，并保温90min。
所述金属箔可以是铜箔、镍箔、铝箔或SUS箔(不锈钢箔)等。
第六方面，本发明提供一种印制电路板，所述印制电路板包括至少一张如上所述的预浸料。
与现有技术相比，本发明具有以下有益效果：
本发明采用具有式I结构的酯类固化剂与含磷双酚协同固化环氧树脂，用含磷双酚为主固化剂，赋予了固化物优异的介电性能、高耐热性、粘合力和韧性，同时还能实现无卤阻燃。结合式I结构的酯类固化剂，使得在固化过程中 不产生二次羟基等极性基团，可在保证介电性能优异的同时明显提高固化物玻璃化转变温度，且固化产物中含有大量疏水基团，能大幅降低固化物吸水率，弥补含磷双酚因磷含量高带来吸水率高的问题，使得固化物介电常数和介电损耗因子更加稳定。采用该热固性树脂组合物制备得到的层压板的玻璃化转变温度为172-196℃，热膨胀系数为2.1％-2.8％，吸水率为0.20％-0.32％，介电常数(1GHz)为3.48-3.71，介电损耗因子(1GHz)为0.0071-0.0089，潮湿后介电常数为3.58-3.89，潮湿后介电损耗因子为0.0078-0.0105，288℃分层起泡时间＞120s，剥离强度为1.38-1.48N/mm，落锤冲击裂痕面积为192-325mm 2，难燃烧性达到V-0级，具有良好的耐热性、耐湿性、剥离强度、介电性能和阻燃性。
具体实施方式
下面通过具体实施例来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
本发明实施例和对比例中涉及的材料的来源/制备方法如下：
(A)无卤环氧树脂
(A-1)双环戊二烯酚醛环氧树脂HP-7200H(大日本油墨商品名)；
(A-2)联苯型酚醛环氧树脂NC-3000(日本化药商品名)；
(A-3)含萘环氧树脂HP-9900(大日本油墨商品名)。
(B)含磷固化剂
(B-1)含磷双酚OL3001(美国FRX Polymers商品名，磷含量10.8％，重均分子量为3000)；
(B-2)含磷双酚OL5000(美国FRX Polymers商品名，磷含量10％，重均分子量为5000)；
(B-3)含磷酚醛XZ-92741(美国DOW商品名，磷含量9％)。
(C)共固化剂
(C-1a)具有式I结构的酯类固化剂，其结构为：
Figure PCTCN2018125306-appb-000011
其中平均重复单元n为1.25；
其制备方法如下：
在安装有温度计、滴液漏斗、搅拌器的烧瓶中投入2mol(568.78g)四甲基双酚A和1500g四氢呋喃，通入氮气，搅拌至完全溶解。接着，投入1mol(203.02g)对苯二甲酰氯搅拌溶解，然后，将体系温度控制在20℃以下，缓慢滴加(大于0.5小时)2mol(202.38g)三乙胺(配制成20％的三乙胺/四氢呋喃溶液滴加)。接着，在20℃以下继续搅拌反应2～3小时。接着，投入2mol(381.25g)2-萘甲酰氯，将体系温度控制在15℃以下，然后缓慢滴加2mol(202.38g)三乙胺(配制成20％的三乙胺/四氢呋喃溶液滴加)，在15℃以下继续搅拌反应2～5小时。反应完成后静置，过滤除去三乙胺盐酸盐固体，溶液中进行减压蒸馏浓缩，然后再加入甲醇析出树脂产物，过滤，用水洗至最终水层的pH值为7，再用甲醇洗涤，然后干燥得产物。所制备的活性酯树脂的酯当量根据投料比为252g/eq。
(C-1b)具有式I结构的酯类固化剂，其结构为：
Figure PCTCN2018125306-appb-000012
其中平均重复单元n为1.25；
其制备方法如下：
在安装有温度计、滴液漏斗、搅拌器的烧瓶中投入2mol(568.78g)四甲基双酚A和1500g四氢呋喃，通入氮气，搅拌至完全溶解。接着，投入1mol(203.02g)对苯二甲酰氯搅拌溶解，然后，将体系温度控制在20℃以下，缓慢滴加(大于0.5小时)2mol(202.38g)三乙胺(配制成20％的三乙胺/四氢呋喃溶液滴加)。接着，在20℃以下继续搅拌反应2～3小时。接着，投入2mol(281.14g)苯甲酰氯，将体系温度控制在15℃以下，然后缓慢滴加2mol(202.38g)三乙胺(配制成20％的三乙胺/四氢呋喃溶液滴加)，在15℃以下继续搅拌反应2～5小时。反应完成后静置，过滤除去三乙胺盐酸盐固体，溶液中进行减压蒸馏浓缩，然后再加入甲醇析出树脂产物，过滤，用水洗至最终水层的pH值为7，再用甲醇洗涤，然后干燥得产物。所制备的活性酯树脂的酯当量根据投料比为226g/eq。
(C-1c)具有式I结构的酯类固化剂，其结构为：
Figure PCTCN2018125306-appb-000013
其中平均重复单元n为1.25；
其制备方法如下：
在安装有温度计、滴液漏斗、搅拌器的烧瓶中投入2mol(512.66g)四甲基双酚F和1500g四氢呋喃，通入氮气，搅拌至完全溶解。接着，投入1mol(203.02g)对苯二甲酰氯搅拌溶解，然后，将体系温度控制在20℃以下，缓慢滴加(大于0.5小时)2mol(202.38g)三乙胺(配制成20％的三乙胺/四氢呋喃溶液滴加)。接着，在20℃以下继续搅拌反应2～3小时。接着，投入2mol(157g)乙酰氯，将体系温度控制在15℃以下，然后缓慢滴加2mol(202.38g) 三乙胺(配制成20％的三乙胺/四氢呋喃溶液滴加)，在15℃以下继续搅拌反应2～5小时。反应完成后静置，过滤除去三乙胺盐酸盐固体，溶液中进行减压蒸馏浓缩，然后再加入甲醇析出树脂产物，过滤，用水洗至最终水层的pH值为7，再用甲醇洗涤，然后干燥得产物。所制备的活性酯树脂的酯当量根据投料比为181g/eq。
(C-2)一种酯类固化剂V-575(日本UNITIKA商品名)，结构如下：
Figure PCTCN2018125306-appb-000014
其中平均重复单元n为1.25；
(C-3)双环戊二烯酚型活性酯HPC-8000T65(大日本油墨商品名)；
(C-4)双酚A型氰酸酯预聚物CE01PS(扬州天启商品名)；
(C-5)双环戊二烯型苯并噁嗪LZ 8260N70(HUNTSMAN商品名)。
(D)添加型阻燃剂
苯氧基磷腈化合物SPB-100(日本三菱商品名)。
(E)固化促进剂
4-二甲氨基吡啶(日本广荣化学商品名)。
(F)填料
(F-1)球型硅微粉(平均粒径为1-10μm，纯度99％以上)；
(F-2)氧化铝(平均粒径为1-10μm，纯度99％以上)。
实施例1-16
实施例1-16提供热固性树脂组合物胶液、使用其的预浸料和覆铜板，制备方法如下：
(1)热固性树脂组合物胶液的制备：
用MEK溶剂将组分(B)含磷固化剂、(C)共固化剂和(D)苯氧基磷腈化合物SPB-100分别配制成固含量为60％、50％和25％的溶液，依次加入到1000mL烧杯中，再依次加入(A)无卤环氧树脂和(F)填料，加入适量(E)固化促进剂4-二甲氨基吡啶，调节凝胶化时间(GT)至200-300s，加入MEK溶剂将固体含量控制为65％，继续搅拌2h熟化，得到热固性树脂组合物胶液；
其中，各组分的种类和用量(以重量份数计)如表1、表2所示。
(2)预浸料的制备：
准备好6张2116玻璃布(生产厂家：台湾休贝尔公司)，尺寸：320mm*380mm，先将上述热固性树脂组合物胶液涂在每张玻璃布上，使胶液浸润玻璃布且在两表面粘上树脂，然后将浸润后的玻璃布通过辊压的夹轴将两表面刮平并去掉部分胶液，将玻璃布和去除溶剂后的树脂组合物重量之和控制在200-230g/m 2，得到预浸好的玻璃布，之后将其放入155℃烘箱中烘烤6-8min，得到预浸料。
(3)覆铜板的制作：
准备2张厚度为35μm、尺寸为410mm*410mm的电解铜箔(生产厂家：苏州福田)，将6张上述预浸料叠起来，保持4角对齐，并在叠好的预浸料上下表面各覆一张已准备好的电解铜箔，放入层压机，并按如下条件进行层压：①层压的升温速率在料温80-120℃时应控制在1.5-2.5℃/min；②层压的压力设置，外层料温在120-150℃施加满压，满压压力为350psi；③固化时，控制料温在200℃，并保温90min，得到覆铜板。
比较例1
比较例1与实施例7的区别在于，组份(B)含磷固化剂的种类不同，具体 如下表3所示。
比较例2-5
比较例2-5与实施例5的区别在于，组分(C)固化剂的种类不同，具体如下表3所示。
比较例6-9
比较例6-9与实施例16的区别在于，组分(C)固化剂的种类不同，具体如下表3所示。
分别对上述实施例和对比例提供的覆铜板的性能进行测试，测试标准/方法如下：
(a)玻璃化转变温度(Tg)：根据差示扫描量热法(DSC)，按照IPC-TM-650 2.4.25所规定的DSC方法进行测定。
(b)热膨胀系数(CTE)
按照IPC-TM-650 2.4.24所规定的Z向CTE测试方法测定。
(c)吸水性
将100mm×100mm样品置于温度85℃、湿度85％的恒温恒湿箱中处理168h后，测试处理后样品的吸水率。
(d)介电常数、介电损耗因子
根据使用条状线的共振法，按照IPC-TM-650 2.5.5.5测定1GHz下的介电损耗、介电损耗因子。
(e)介电常数、介电损耗因子(潮湿后)
将样品置于温度85℃、湿度85％的恒温恒湿箱中处理168h后，再按照IPC-TM-650 2.5.5.5测定1GHz下的介电损耗、介电损耗因子。
(f)耐浸焊性
按照IPC-TM-650 2.4.13.1观察分层起泡时间。
(g)剥离强度
按照IPC-TM-650 2.4.8方法中的“热应力后”的实验条件，测试金属盖层的剥离强度。
(h)落锤冲击裂痕面积
采用落锤冲击试验机测试，测试方法：落锤高度为1m，落锤重量为0.75kg，释放落锤，测试板材裂痕面积。板材裂痕面积大小可初步反映出板材的韧性优劣，一般说来，裂痕面积越小表明板材韧性越好。
(i)难燃烧性
依据UL 94垂直燃烧法测定。
上述各实施例和比较例提供的覆铜板的性能如下表1-3所示：
表1
Figure PCTCN2018125306-appb-000015
Figure PCTCN2018125306-appb-000016
表2
Figure PCTCN2018125306-appb-000017
Figure PCTCN2018125306-appb-000018
表3
Figure PCTCN2018125306-appb-000019
Figure PCTCN2018125306-appb-000020
从表1-3的物性数据可知：实施例1-9使用5-25份具有式I结构的酯类固化剂与15-40份含磷双酚复合固化40-75份无卤环氧树脂，所制得的板材有着高Tg、低CTE、低吸水率、优异的介电性能、高耐热性和剥离强度以及优异的韧性，同时还能实现无卤阻燃V-0级。
实施例10中使用具有式I结构的酯类固化剂与含磷双酚OL3001复合固化78份双环戊二烯酚醛环氧树脂HP-7200H，由于双环戊二烯酚醛环氧树脂HP-7200H的用量超出优选用量范围，导致反应不完全，最终板材Tg有所降低、CTE和吸水率都有所升高、介电性能较差且耐热性不够理想。
实施例11中使用具有式I结构的酯类固化剂与含磷双酚OL3001复合固化38份双环戊二烯酚醛环氧树脂HP-7200H，板材有着较高的Tg和较低的CTE，但由于环氧树脂不足、固化剂过量，最终板材吸水率较高、介电性能较差且耐热性不够理想。
实施例12中使用具有式I结构的酯类固化剂与42份含磷双酚OL3001复合固化双环戊二烯酚醛环氧树脂HP-7200H，由于固化剂含磷双酚OL3001的用量超出优选用量范围，最终板材Tg稍低且吸水率高，吸潮后板材介电性能恶化严重。
实施例13中使用具有式I结构的酯类固化剂与8份含磷双酚OL3001复合 固化双环戊二烯酚醛环氧树脂HP-7200H，由于固化剂含磷双酚OL3001添加量较低，环氧树脂过量固化不完全，最终板材CTE偏高且介电性能一般。
实施例14中使用27份具有式I结构的酯类固化剂与含磷双酚OL3001复合固化双环戊二烯酚醛环氧树脂HP-7200H，板材有着高Tg、低CTE、低吸水率和优异的介电性能，但用来表征韧性的落锤冲击测试裂痕面积过大，板材韧性差，不利于下游的PCB加工。
实施例15中使用3份具有式I结构的酯类固化剂与含磷双酚OL3001复合固化双环戊二烯酚醛环氧树脂HP-7200H，最终板材Tg偏低、CTE高且吸水率高，吸潮后板材介电性能恶化严重。
实施例16中使用具有式I结构的酯类固化剂与含磷双酚OL3001复合固化双环戊二烯酚醛环氧树脂HP-7200H，不添加填料，板材的CTE和吸水率有所升高，但仍保持在较理想的水平，同时板材有着高Tg、优异的介电性能、耐热性以及韧性。
如上所述，与一般的无卤层压板相比，使用本发明提供的热固性树脂组合物制备的层压板具有更高的Tg、更低的CTE、更低的吸水率、更优异的介电性能以及剥离强度、耐热性、韧性，适用于高速应用领域。另外本发明卤素含量在JPCA无卤标准要求范围内能达到难燃性试验UL94中的V-0标准，有环保的功效。
比较例1中具有式I结构的酯类固化剂与含磷酚醛XZ-92741复合固化双环戊二烯酚醛环氧树脂HP-7200H，由于含磷酚醛反应活性太低，最终板材Tg低、CTE高且介电性能和耐热性差。
比较例2中使用酯类固化剂V-575与含磷双酚OL3001复合固化双环戊二烯酚醛环氧树脂HP-7200H，板材有着高Tg、低CTE、优异的耐热性和韧性， 但介电性能一般，吸水率较高且板材吸潮后的介电性能较差。
比较例3中使用双环戊二烯酚型活性酯HPC-8000T65与含磷双酚OL3001复合固化双环戊二烯酚醛环氧树脂HP-7200H，最终板材有着优异的介电性能，但Tg偏低、吸水率高且吸潮后板材介电性能恶化严重。
比较例4中使用双酚A型氰酸酯预聚物CE01PS与含磷双酚OL3001复合固化双环戊二烯酚醛环氧树脂HP-7200H，板材有着高Tg、低CTE、优异的介电性能和耐热性，但吸水率高且板材吸潮后的介电性能较差。
比较例5中使用双环戊二烯型苯并噁嗪LZ 8260N70与含磷双酚OL3001复合固化双环戊二烯酚醛环氧树脂HP-7200H，板材有着低吸水率、优异的介电常数和耐热性，但Tg偏低、CTE和介电损耗因子高。
比较例6中使用酯类固化剂V-575与含磷双酚OL3001复合固化双环戊二烯酚醛环氧树脂HP-7200H，不添加填料，板材有着高Tg、低CTE和优异的介电常数，但吸水率高且板材吸潮后的介电性能较差，耐热性也不理想。
比较例7中使用双环戊二烯酚型活性酯HPC-8000T65与含磷双酚OL3001复合固化双环戊二烯酚醛环氧树脂HP-7200H，不添加填料，最终板材有着优异的介电性能，但Tg低、CTE高、吸水率高且吸潮后板材介电性能恶化严重。
比较例8中使用双酚A型氰酸酯预聚物CE01PS与含磷双酚OL3001复合固化双环戊二烯酚醛环氧树脂HP-7200H，不添加填料，板材有着高Tg、低CTE、优异的介电性能和耐热性，但吸水率高且板材吸潮后的介电性能较差。
比较例9中使用双环戊二烯型苯并噁嗪LZ 8260N70与含磷双酚OL3001复合固化双环戊二烯酚醛环氧树脂HP-7200H，不添加填料，板材有着低吸水率和优异的介电常数，但板材Tg偏低、CTE和介电损耗因子较高，且耐热性不理想。
申请人声明，以上所述仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，所属技术领域的技术人员应该明了，任何属于本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种热固性树脂组合物，其特征在于，所述热固性树脂组合物包括如下组分：环氧树脂、含磷双酚和酯类固化剂；
    所述酯类固化剂具有式I结构：
    Figure PCTCN2018125306-appb-100001
    其中，R 1-R 8各自独立地选自氢原子、C 1-C 10脂肪族烃基、C 3-C 10脂环族烃基或C 6-C 10芳香族烃基中的一种，且不全为氢原子；
    X选自-O-、-S-、-CH 2-或-C(CH 3) 2-中的一种；
    Y选自C 1-C 10脂肪族烃基、C 3-C 10脂环族烃基或C 6-C 10芳香族烃基中的一种；
    n为1-10的整数。
  2. 根据权利要求1所述的热固性树脂组合物，其特征在于，以所述环氧树脂、含磷双酚和酯类固化剂的总重量份数为100份计，所述热固性树脂组合物包括：40-75份环氧树脂、15-40份含磷双酚和5-25份酯类固化剂。
  3. 根据权利要求1或2所述的热固性树脂组合物，其特征在于，所述环氧树脂为无卤环氧树脂；
    优选地，所述无卤环氧树脂选自双酚A型环氧树脂、双酚F型环氧树脂、邻甲酚酚醛环氧树脂、双酚A型酚醛环氧树脂、三酚型酚醛环氧树脂、双环戊二烯酚醛环氧树脂、联苯型酚醛环氧树脂、烷基苯型酚醛环氧树脂或萘酚型酚醛环氧树脂中的一种或至少两种的组合；
    优选地，所述无卤环氧树脂具有式II结构：
    Figure PCTCN2018125306-appb-100002
    其中，X 1、X 2和X 3各自独立地为
    Figure PCTCN2018125306-appb-100003
    R 9选自氢原子、取代或未取代的C 1-C 5直链烷基或者取代或未取代的C 3-C 5支链烷基中的一种，Y 1和Y 2各自独立地选自单键、-CH 2-、
    Figure PCTCN2018125306-appb-100004
    Figure PCTCN2018125306-appb-100005
    中的一种，R 10选自氢原子、取代或未取代的C 1-C 5直链烷基或者取代或未取代的C 3-C 5支链烷基中的一种；m为1-10的整数。
  4. 根据权利要求1-3任一项所述的热固性树脂组合物，其特征在于，所述含磷双酚具有式III所示结构：
    Figure PCTCN2018125306-appb-100006
    其中k为2-20的整数，优选3-10的整数；
    优选地，所述含磷双酚的重均分子量独立地为1000-10000，优选为1000-6500，更优选为1000-4500。
  5. 根据权利要求1-4任一项所述的热固性树脂组合物，其特征在于，所述 热固性树脂组合物还包括阻燃剂；
    优选地，所述阻燃剂为含磷阻燃剂；
    优选地，以所述环氧树脂、含磷双酚和酯类固化剂的总重量份数为100份计，所述含磷阻燃剂的添加量为0-50份，进一步优选为0-30份；
    优选地，所述含磷阻燃剂选自三(2，6-二甲基苯基)膦、10-(2，5-二羟基苯基)-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、2，6-二(2，6-二甲基苯基)膦基苯、10-苯基-9，10-二氢-9-氧杂-10-膦菲-10-氧化物、苯氧基磷腈化合物、磷酸酯、聚磷酸酯、膦酸酯或聚膦酸酯中的一种或至少两种的组合；
    优选地，所述热固性树脂组合物还包括固化促进剂；
    优选地，以所述环氧树脂、含磷双酚和酯类固化剂的总重量份数为100份计，所述固化促进剂的添加量为0.05-1份；
    优选地，所述固化促进剂选自咪唑类化合物、三苯基膦、二甲氨基吡啶、三氟化硼单乙胺或辛酸锌中的一种或至少两种的组合；
    优选地，所述咪唑类化合物选自2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑或2-十一烷基咪唑中的一种或至少两种的组合；
    优选地，所述热固性树脂组合物还包括填料；
    优选地，以所述环氧树脂、含磷双酚和酯类固化剂的总重量份数为100份计，所述填料的添加量为0-150份，进一步优选为0-100份；
    优选地，所述填料为有机填料和/或无机填料；
    优选地，所述无机填料选自二氧化硅、氢氧化铝、氧化铝、滑石粉、氮化铝、氮化硼、碳化硅、硫酸钡、钛酸钡、钛酸锶、碳酸钙、硅酸钙、云母、玻璃纤维粉中的一种或至少两种的组合；
    优选地，所述有机填料选自聚四氟乙烯粉末、聚苯硫醚或聚醚砜粉末中的 一种或至少两种的组合；
    优选地，所述填料为二氧化硅，粒径中度值为1-15μm，进一步优选为1-10μm。
  6. 一种树脂胶液，其特征在于，所述树脂胶液是将如权利要求1-5中任一项所述的热固性树脂组合物溶解或分散在溶剂中得到。
  7. 一种预浸料，其特征在于，所述预浸料包括增强材料，和通过含浸干燥后附着在所述增强材料上的如权利要求1-5任一项所述的热固性树脂组合物。
  8. 一种层压板，其特征在于，所述层压板包括一张或至少两张叠合的如权利要求7所述的预浸料。
  9. 一种覆金属箔层压板，其特征在于，所述覆金属箔层压板包括一张或至少两张叠合的如权利要求7所述的预浸料和覆于所述预浸料外侧的一侧或两侧的金属箔。
  10. 一种印制电路板，其特征在于，所述印制电路板包括至少一张如权利要求7所述的预浸料。
PCT/CN2018/125306 2018-12-26 2018-12-29 一种热固性树脂组合物及使用其的预浸料、覆金属箔层压板和印制电路板 WO2020133335A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811606732.XA CN109694462B (zh) 2018-12-26 2018-12-26 一种热固性树脂组合物及使用其的预浸料、覆金属箔层压板和印制电路板
CN201811606732.X 2018-12-26

Publications (1)

Publication Number Publication Date
WO2020133335A1 true WO2020133335A1 (zh) 2020-07-02

Family

ID=66232024

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/125306 WO2020133335A1 (zh) 2018-12-26 2018-12-29 一种热固性树脂组合物及使用其的预浸料、覆金属箔层压板和印制电路板

Country Status (2)

Country Link
CN (1) CN109694462B (zh)
WO (1) WO2020133335A1 (zh)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105802128A (zh) * 2014-12-29 2016-07-27 广东生益科技股份有限公司 一种无卤热固性树脂组合物及使用它的预浸料和印制电路用层压板
CN108164685A (zh) * 2016-12-07 2018-06-15 广东生益科技股份有限公司 一种热固性树脂组合物
CN108794978A (zh) * 2017-04-27 2018-11-13 台燿科技股份有限公司 树脂组成物、及使用该树脂组成物所制得的预浸渍片、金属箔积层板及印刷电路板

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8143331B2 (en) * 2007-02-07 2012-03-27 Air Products And Chemicals, Inc. Alkylated polyalkyleneamines and uses thereof
US8288591B2 (en) * 2008-11-20 2012-10-16 Designer Molecules, Inc. Curing agents for epoxy resins
CN106750226B (zh) * 2014-11-11 2019-01-08 江苏雅克科技股份有限公司 含磷聚酯化合物组成及含磷阻燃环氧树脂固化物的制备方法
CN105542128A (zh) * 2015-12-15 2016-05-04 广东广山新材料有限公司 一种环氧树脂固化剂及其制备方法和用途
CN105440263A (zh) * 2015-12-15 2016-03-30 广东广山新材料有限公司 一种环氧树脂固化剂及其制备方法和用途
CN105399927A (zh) * 2015-12-15 2016-03-16 广东广山新材料有限公司 一种环氧树脂固化剂及其制备方法和用途

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105802128A (zh) * 2014-12-29 2016-07-27 广东生益科技股份有限公司 一种无卤热固性树脂组合物及使用它的预浸料和印制电路用层压板
CN108164685A (zh) * 2016-12-07 2018-06-15 广东生益科技股份有限公司 一种热固性树脂组合物
CN108794978A (zh) * 2017-04-27 2018-11-13 台燿科技股份有限公司 树脂组成物、及使用该树脂组成物所制得的预浸渍片、金属箔积层板及印刷电路板

Also Published As

Publication number Publication date
CN109694462B (zh) 2020-10-27
CN109694462A (zh) 2019-04-30

Similar Documents

Publication Publication Date Title
CN107254144B (zh) 树脂组合物和使用其的预浸料以及层压板
TWI532784B (zh) A halogen-free resin composition and use thereof
CN108219371B (zh) 环氧树脂组合物、预浸料、层压板和印刷电路板
CN108485182B (zh) 一种高频树脂组合物及使用其制作的半固化片和层压板
US9215803B2 (en) Epoxy resin composition and pre-preg, support-provided resin film, metallic foil clad laminate plate and multilayer printed circuit board utilizing said composition
CN110218415B (zh) 树脂组合物、预浸料、层压板、覆金属箔层压板以及印刷线路板
CN109851997B (zh) 一种热固性树脂组合物及使用其的预浸料、层压板和覆金属箔层压板
WO2018120564A1 (zh) 一种含磷活性酯及其无卤组合物与覆铜箔基板
CN109651763B (zh) 一种热固性树脂组合物及使用其的预浸料、层压板和覆金属箔层压板
CN110204862B (zh) 树脂组合物、预浸料、层压板、覆金属箔层压板以及印刷线路板
WO2016074288A1 (zh) 一种热固性树脂组合物及用其制作的预浸料与层压板
TWI666248B (zh) 馬來醯亞胺樹脂組合物、預浸料、層壓板和印刷電路板
TWI706997B (zh) 無鹵阻燃熱固性樹脂組合物、印刷電路用預浸料及覆金屬層壓板
WO2018120587A1 (zh) 一种无卤热固性树脂组合物及含有它的预浸料、层压板和印制电路板
WO2018120614A1 (zh) 一种含磷活性酯及其无卤组合物与覆铜箔基板
EP3412722B1 (en) Halogen-free thermosetting resin composition, prepreg containing same, laminate, and printed circuit board
WO2019127391A1 (zh) 马来酰亚胺树脂组合物、预浸料、层压板和印刷电路板
TW202222890A (zh) 一種熱固性樹脂組成物及包含其的預浸料、層壓板和高頻電路基板
CN109608828B (zh) 一种热固性树脂组合物及使用其的预浸料、层压板和覆金属箔层压板
CN114605767A (zh) 一种热固性树脂组合物及其应用
CN114230794B (zh) 改性双马来酰亚胺预聚物及树脂组合物、应用
CN114605779B (zh) 一种热固性树脂组合物及包含其的预浸料、电路基板和印刷电路板
CN109694462B (zh) 一种热固性树脂组合物及使用其的预浸料、覆金属箔层压板和印制电路板
CN109970952B (zh) 氰酸酯树脂组合物及其用途
JP2016153497A (ja) エポキシ樹脂組成物、このエポキシ樹脂組成物を用いたプリプレグ、支持体付き樹脂フィルム、金属箔張り積層板及び多層プリント配線板

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18945128

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18945128

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 18945128

Country of ref document: EP

Kind code of ref document: A1