CN109694462B - Thermosetting resin composition, and prepreg, metal foil-clad laminate and printed circuit board using same - Google Patents

Thermosetting resin composition, and prepreg, metal foil-clad laminate and printed circuit board using same Download PDF

Info

Publication number
CN109694462B
CN109694462B CN201811606732.XA CN201811606732A CN109694462B CN 109694462 B CN109694462 B CN 109694462B CN 201811606732 A CN201811606732 A CN 201811606732A CN 109694462 B CN109694462 B CN 109694462B
Authority
CN
China
Prior art keywords
resin composition
thermosetting resin
phosphorus
epoxy resin
parts
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.)
Active
Application number
CN201811606732.XA
Other languages
Chinese (zh)
Other versions
CN109694462A (en
Inventor
游江
林伟
黄天辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shengyi Technology Co Ltd
Original Assignee
Shengyi Technology Co Ltd
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 Shengyi Technology Co Ltd filed Critical Shengyi Technology Co Ltd
Priority to CN201811606732.XA priority Critical patent/CN109694462B/en
Priority to PCT/CN2018/125306 priority patent/WO2020133335A1/en
Publication of CN109694462A publication Critical patent/CN109694462A/en
Application granted granted Critical
Publication of CN109694462B publication Critical patent/CN109694462B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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

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)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Epoxy Resins (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a thermosetting resin composition, and a prepreg, a metal foil-clad laminate and a printed circuit board using the thermosetting resin composition. The thermosetting resin composition comprises epoxy resin, phosphorus-containing bisphenol and an ester curing agent with a structure shown in a formula I. The invention adopts the ester curing agent with the structure shown in the formula I and the phosphorus-containing bisphenol to cure the epoxy resin in a synergistic manner, and uses the phosphorus-containing bisphenol as a main curing agent, so that a cured product has excellent dielectric property, high heat resistance and adhesive force, and halogen-free flame retardance can be realized at the same time. The prepared laminated board and the metal foil-clad laminated board have good heat resistance, moisture resistance, peeling strength, dielectric property and flame retardance.

Description

Thermosetting resin composition, and prepreg, metal foil-clad laminate and printed circuit board using same
Technical Field
The invention belongs to the technical field of printed circuit boards, and particularly relates to a thermosetting resin composition, and a prepreg, a metal foil-clad laminate and a printed circuit board using the thermosetting resin composition.
Background
With the increasing speed and multi-function of electronic product information processing, the application frequency is increasing, and the dielectric constant (Dk) and dielectric loss (Df) are required to be lower, so reducing Dk/Df has become a pursuing hot spot for substrate manufacturers. Meanwhile, under the global strong green and environmental protection trend, the development of the halogen-free flame-retardant copper-clad laminate becomes a hot spot in the industry, and various manufacturers of the copper-clad laminate push out their own halogen-free flame-retardant copper-clad laminates.
In order to realize low Dk/Df and halogen-free flame retardation at the same time, the curing agent with low Dk/Df and high phosphorus content is the most ideal choice. Through research, the phosphorus-containing bisphenol has higher phosphorus content and can realize halogen-free flame retardance; meanwhile, the phosphorus-containing bisphenol can be used as a curing agent of epoxy resin, and the generated cured product has higher glass transition temperature, excellent dielectric property, high heat resistance and high adhesive force. However, due to the phosphonate structure in the phosphorus-containing bisphenol structure, the water absorption of the cured product is very high, and the high water absorption not only causes the dielectric property of the board to be obviously deteriorated due to moisture absorption, but also may cause the board to be cracked due to heating after moisture absorption during PCB processing. Therefore, on the premise of ensuring excellent dielectric property, how to reduce the water absorption of a phosphorus-containing bisphenol system and improve the glass transition temperature of a cured product becomes a technical problem.
Benzoxazine resin is commonly used in the copper-clad plate industry to reduce the water absorption of a cured substance, but the dielectric property of the benzoxazine resin is poor, and the dielectric property of a phosphorus-containing bisphenol system is seriously deteriorated.
CN104761719A discloses a double-ended multifunctional active ester resin containing PPO main chain, which has the following structure:
Figure BDA0001923052730000021
wherein R1 is
Figure BDA0001923052730000022
R2 is
Figure BDA0001923052730000023
Substituted or unsubstituted Cl-C3 linear or branched alkyl, allyl, or isopropenyl; r3Is H, allyl or isoallyl; r4、R5、R6、R7Independently selected from H, substituted or unsubstituted C1-C3 linear or branched alkyl, allyl, isopropenyl propyl or-O-R8；R8Is a substituted or unsubstituted C1-C3 straight or branched alkyl group or a substituted or unsubstituted phenyl group, n1, n2 are positive integers greater than 0, and satisfy 4. ltoreq. n1+ n 2. ltoreq.25, n3, n4 are equal or different and are independently 1, 2 or 3.The prepreg, the laminated board and the copper-clad plate made of the thermosetting resin composition containing the active ester have excellent dielectric property, humidity resistance, heat resistance, extremely low water absorption and high bending strength. The two-end ester groups of the double-end multifunctional active ester can react with epoxy resin, but not all ester groups can be cured and crosslinked due to the influence of steric hindrance; the middle PPO backbone and R1 structure are free of reactive groups (R)1Is composed of
Figure BDA0001923052730000024
And p) or the cured crosslinking group is a double bond, and does not react with the epoxy resin at all. Therefore, the cross-linking density of the reaction between the double-end multifunctional active ester resin and the epoxy resin is not high, while the middle PPO main chain is a thermoplastic chain segment, so that the Coefficient of Thermal Expansion (CTE) is high, and the final cured product or plate has low glass transition temperature and high Coefficient of Thermal Expansion (CTE).
In the field, how to reduce the water absorption, the thermal expansion coefficient and the dielectric loss of the copper-clad plate while ensuring the copper-clad plate to have higher glass transition temperature is a problem to be solved in the field.
Disclosure of Invention
In view of the disadvantages of the prior art, an object of the present invention is to provide a thermosetting resin composition, and a prepreg, a metal foil-clad laminate and a printed circuit board using the same. The laminated board and the metal foil-clad laminated board prepared by the thermosetting resin composition have high glass transition temperature, low water absorption, low dielectric constant, low dielectric loss factor, high heat resistance and good flame retardance, processability and chemical resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a thermosetting resin composition, characterized in that the thermosetting resin composition comprises the following components: epoxy resin, phosphorus-containing bisphenol and ester curing agent;
the ester curing agent has a structure of formula I:
Figure BDA0001923052730000031
wherein R is1-R8Each independently selected from hydrogen atom, C1-C10Aliphatic hydrocarbon group, C3-C10Alicyclic hydrocarbon radicals or C6-C10Aromatic hydrocarbon group, and not all hydrogen atoms;
x is selected from-O-, -S-, -CH2-or-C (CH)3)2-one of the above;
y is selected from C1-C10Aliphatic hydrocarbon group, C3-C10Alicyclic hydrocarbon radicals or C6-C10One of aromatic hydrocarbon groups;
n is an integer of 1 to 10.
The invention adopts the ester curing agent with the structure shown in the formula I and the phosphorus-containing bisphenol to cure the epoxy resin in a synergistic manner, and uses the phosphorus-containing bisphenol as a main curing agent, so that a cured product has excellent dielectric property, high heat resistance and adhesive force, and halogen-free flame retardance can be realized at the same time. The prepreg and the laminated board for the printed circuit made of the resin composition have high glass transition temperature, low water absorption rate, low dielectric constant, low dielectric loss factor, high heat resistance and good flame retardance, processability and chemical resistance.
In the present invention, said C1-C10Aliphatic hydrocarbyl refers to aliphatic hydrocarbyl groups containing 1-10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10) carbon atoms; for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or the like can be mentioned.
Said C is3-C10By cycloaliphatic hydrocarbon radical is meant a fat containing from 3 to 10 (e.g. 3, 4, 5, 6, 7, 8, 9 or 10) carbon atomsA cyclic hydrocarbon group; for example, it may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or the like.
Said C is6-C10Aromatic hydrocarbon group means an aliphatic hydrocarbon group containing 6 to 10 (e.g., 6, 7, 8, 9 or 10) carbon atoms; for example, phenyl, benzyl, phenethyl, phenylpropyl, etc.
In formula I n may be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
As a preferred technical scheme of the invention, the thermosetting resin composition comprises the following components in parts by weight based on 100 parts by weight of the total weight of the epoxy resin, the phosphorus-containing bisphenol and the ester curing agent: 40-75 parts of epoxy resin, 15-40 parts of phosphorus-containing bisphenol and 5-25 parts of ester curing agent.
Unless otherwise specified, the term "ester curing agent" used herein refers to an ester curing agent having a structure of formula I.
In the present invention, 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 parts, 75 parts, etc.
The weight portion 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 parts, 40 parts and the like.
The weight portion of the ester curing agent can be 5, 6, 8, 10, 12, 13, 15, 16, 18, 20, 22, 23 or 25 parts.
According to the invention, the epoxy resin, the phosphorus-containing bisphenol and the ester curing agent are matched with each other at the specific ratio, so that the comprehensive performance of a cured product of the epoxy resin, the phosphorus-containing bisphenol and the laminated board prepared from the cured product can be further improved. If the addition amount of the epoxy resin is too small, the processability of a cured product and a laminated board is poor; if the amount of the epoxy resin added is too large, the glass transition temperature of the cured product and the laminate becomes low, and the dielectric properties become poor. If the addition amount of the phosphorus-containing bisphenol is too small, the toughness of a cured product and a laminated board is poor, and the flame retardance is insufficient; if the amount of the phosphorus-containing bisphenol added is too large, the glass transition temperature of the cured product and the laminate is low. If the amount of the ester curing agent added is too small, the effect of reducing the water absorption rate of the cured product or the laminate and increasing the glass transition temperature is not significant, and if the amount of the ester curing agent added is too large, the brittleness of the cured product and the laminate is large, and the processability is poor.
As a preferred technical scheme of the invention, the epoxy resin is halogen-free epoxy resin.
Preferably, the halogen-free epoxy resin is selected from one or a combination of at least two of bisphenol a type epoxy resin, bisphenol F type epoxy resin, o-cresol novolac epoxy resin, bisphenol a type novolac epoxy resin, triphenol type novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl type novolac epoxy resin, alkylbenzene type novolac epoxy resin or naphthol type novolac epoxy resin.
Preferably, the halogen-free epoxy resin has the structure of formula II:
Figure BDA0001923052730000051
wherein, X1、X2And X3Each independently is
Figure BDA0001923052730000052
R9Selected from hydrogen atoms, substituted or unsubstituted C1-C5Straight chain alkyl or substituted or unsubstituted C3-C5One of the branched alkyl groups;
Y1and Y2Each independently selected from a single bond, -CH2-、
Figure BDA0001923052730000053
Figure BDA0001923052730000061
One of (1), R10Selected from hydrogen atoms, substituted or unsubstituted C1-C5Straight chain alkyl or substituted or unsubstituted C3-C5One of the branched alkyl groups;
m is an integer of 1 to 10; for example, it may be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
In the present invention, said C1-C5Straight chain alkyl refers to straight chain alkyl groups containing 1 to 5 (e.g., 1, 2, 3, 4, or 5) carbon atoms; for example, methyl, ethyl, propyl, butyl or pentyl.
Said C is3-C5Branched alkyl refers to branched alkyl groups containing 3 to 5 (e.g., 3, 4, or 5) carbon atoms; for example, isopropyl, isobutyl, tert-butyl, isopentyl, etc. may be mentioned.
The halogen-free epoxy resin with the structure of the formula II has higher functionality and good dielectric property, and is beneficial to further improving the glass transition temperature of a cured product and reducing dielectric loss and water absorption.
As a preferred embodiment of the present invention, the phosphorus-containing bisphenol has the structure of formula III:
Figure BDA0001923052730000062
where k is an integer from 2 to 20 (e.g., 2, 3, 4, 5, 6, 7, 8, 9,10, 12, 15, 18, or 20, etc.), preferably from 3 to 10.
Preferably, the weight average molecular weight of the phosphorus-containing bisphenol is 1000-10000; for example, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 10000, etc. Preferably 1000-.
As a preferred embodiment of the present invention, the thermosetting resin composition further comprises a flame retardant.
Preferably, the flame retardant is a phosphorus-containing flame retardant.
Preferably, the phosphorus-containing flame retardant is added in an amount of 0 to 50 parts, for example, 0 part, 1 part, 2 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, etc., based on 100 parts of the total weight of the epoxy resin, the phosphorus-containing bisphenol and the ester curing agent; further preferably 0 to 30 parts.
Preferably, the phosphorus-containing flame retardant is selected from one or a combination of at least two 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-10-phosphaphenanthrene-10-oxide, a phenoxyphosphazene compound, a phosphate ester, a polyphosphate ester, a phosphonate ester, or a polyphosphonate ester.
In a preferred embodiment of the present invention, the thermosetting resin composition further comprises a curing accelerator to cure the resin composition and accelerate the curing speed of the resin composition.
Preferably, the addition amount of the curing accelerator is 0.05-1 part by taking the total weight parts of the epoxy resin, the phosphorus-containing bisphenol and the ester curing agent as 100 parts; for example, it may be 0.05 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part, etc.
Preferably, the curing accelerator is one or a combination of at least two of imidazole compounds, triphenylphosphine, dimethylaminopyridine, boron trifluoride monoethylamine or zinc octoate.
Preferably, 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.
As a preferred embodiment of the present invention, the 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 to improve thermal conductivity.
Preferably, the filler is added in an amount of 0 to 150 parts, for example, 0 part, 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, 150 parts, etc., based on 100 parts of the total weight of the epoxy resin, the phosphorus-containing bisphenol, and the ester curing agent; further preferably 0 to 100 parts.
Preferably, the filler is an organic filler and/or an inorganic filler.
Preferably, the inorganic filler is selected from one or a combination of at least two of silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.
Preferably, the organic filler is selected from one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide or polyether sulfone powder.
In the present invention, the filler is most preferably silica, and may be, for example, fused silica, crystalline silica, spherical silica, hollow silica or the like; the median particle diameter is 1 to 15 μm, and may be, for example, 1 μm, 2 μm, 3 μm, 5 μm, 6 μm, 8 μm, 10 μm, 12 μm, 13 μm or 15 μm; more preferably 1 to 10 μm. The filler having a particle size distribution within the above range has better dispersibility in the thermosetting resin composition.
In a second aspect, the present invention provides a resin glue solution, wherein the resin glue solution is obtained by dissolving or dispersing the thermosetting resin composition according to the first aspect in a solvent.
The solvent in the present invention is not particularly limited, and alcohols such as methanol, ethanol and butanol, alcohols such as ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol and butyl carbitol, ketones such as acetone, butanone, methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and ethoxyethyl acetate, and nitrogen-containing solvents such as N, N-dimethylformamide and N, N-dimethylacetamide can be used. The above solvents may be used alone or in combination of two or more. Ketones such as acetone, methyl ethyl ketone, and cyclohexanone are preferable. The addition amount of the solvent is selected by the skilled person according to the experience of the person in the art, so that the resin glue solution can reach the viscosity suitable for use.
The solvent is preferably Methyl Ethyl Ketone (MEK), and the solid content of the glue solution is preferably 60-70%.
In a third aspect, the present invention provides a prepreg comprising a reinforcing material, and the thermosetting resin composition provided by the first aspect of the present invention attached to the reinforcing material by impregnation drying.
In the present invention, the prepreg can be prepared by the following method:
and impregnating a reinforcing material with the resin glue solution of the thermosetting resin composition, and drying to obtain the prepreg.
Wherein, the reinforcing material is preferably glass cloth, and the impregnation amount of the glue solution is preferably 200-2The drying temperature is preferably 155 ℃ and the drying time is preferably 5-10 min.
In a fourth aspect, the present invention provides a laminate comprising one or at least two prepregs according to the third aspect of the present invention in stacked relationship.
In a fifth aspect, the present invention provides a metal foil clad laminate comprising one or at least two prepregs according to the third aspect of the present invention and a metal foil clad on one or both sides of the outer side of the prepreg.
The metal foil-clad laminate is prepared by bonding at least two prepregs together to form a laminate, then attaching metal foils to one side or two sides of the laminate, and finally heating, pressurizing and curing.
The heating and pressing operation can be performed by a laminating machine, and the laminating machine has the following requirements: firstly, the heating rate of lamination is controlled to be 1.5-2.5 ℃/min when the material temperature is 80-120 ℃; setting the laminating pressure, wherein the outer layer material temperature is 120 ℃ and 150 ℃, and full pressure is applied, and the full pressure is about 350 psi; and thirdly, controlling the material temperature to be 200 ℃ and preserving the heat for 90min during curing.
The metal foil may be a copper foil, a nickel foil, an aluminum foil, or a SUS foil (stainless steel foil), or the like.
In a sixth aspect, the present invention provides a printed circuit board comprising at least one prepreg as described above.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts the ester curing agent with the structure shown in the formula I and the phosphorus-containing bisphenol to cure the epoxy resin cooperatively, and uses the phosphorus-containing bisphenol as a main curing agent, so that the cured product has excellent dielectric property, high heat resistance, adhesive force and toughness, and simultaneously, the halogen-free flame retardance can be realized. Combined I-junctionThe ester curing agent does not generate polar groups such as secondary hydroxyl groups and the like in the curing process, can obviously improve the glass transition temperature of a cured product while ensuring excellent dielectric property, and the cured product contains a large amount of hydrophobic groups, so that the water absorption rate of the cured product can be greatly reduced, the problem of high water absorption rate of phosphorus-containing bisphenol due to high phosphorus content is solved, and the dielectric constant and the dielectric loss factor of the cured product are more stable. The laminated board prepared by the thermosetting resin composition has the glass transition temperature of 172-196 ℃, the thermal expansion coefficient of 2.1-2.8 percent, the water absorption of 0.20-0.32 percent, the dielectric constant (1GHz) of 3.48-3.71, the dielectric loss factor (1GHz) of 0.0071-0.0089, the dielectric constant after being wetted of 3.58-3.89, the dielectric loss factor after being wetted of 0.0078-0.0105, the delamination foaming time at 288 ℃ of more than 120s, the peel strength of 1.38-1.48N/mm, the drop hammer impact crack area of 192-325mm2The flame retardant property reaches V-0 level, and the flame retardant has good heat resistance, moisture resistance, peel strength, dielectric property and flame retardance.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The sources/preparation methods of the materials involved in the examples of the invention and the comparative examples are as follows:
(A) halogen-free epoxy resin
(A-1) Dicyclopentadiene novolac epoxy HP-7200H (trade name for Large Japanese ink);
(A-2) a biphenyl type novolac epoxy resin NC-3000 (trade name of Nippon Chemicals);
(A-3) naphthalene-containing epoxy resin HP-9900 (trade name for Dainippon ink).
(B) Phosphorus-containing curing agent
(B-1) phosphorus-containing bisphenol OL3001 (trade name of FRX Polymers, USA, phosphorus content 10.8%, weight average molecular weight 3000);
(B-2) phosphorus-containing bisphenol OL5000 (trade name of FRX Polymers, USA, phosphorus content 10%, weight average molecular weight 5000);
(B-3) phosphorus-containing phenol aldehyde XZ-92741 (trade name of DOW in the United states, phosphorus content 9%).
(C) Co-curing agent
(C-1a) an ester curing agent having the structure of formula I, wherein the structure is as follows:
Figure BDA0001923052730000111
wherein the average repeat unit n is 1.25;
the preparation method comprises the following steps:
a flask equipped with a thermometer, a dropping funnel and a stirrer was charged with 2mol (568.78g) of tetramethylbisphenol A and 1500g of tetrahydrofuran, and the mixture was stirred with nitrogen gas until it was completely dissolved. Then, 1mol (203.02g) of terephthaloyl chloride was added and dissolved by stirring, and then, 2mol (202.38g) of triethylamine (prepared as a 20% triethylamine/tetrahydrofuran solution) was slowly added dropwise (more than 0.5 hour) while controlling the system temperature to 20 ℃ or lower. Then, the reaction is continued for 2 to 3 hours at a temperature of 20 ℃. Then, 2mol (381.25g) of 2-naphthoyl chloride is added, the temperature of the system is controlled below 15 ℃, then 2mol (202.38g) of triethylamine (prepared into a 20% triethylamine/tetrahydrofuran solution for dropwise addition) is slowly added dropwise, and the stirring reaction is continued for 2-5 hours at the temperature below 15 ℃. And standing after the reaction is finished, filtering to remove triethylamine hydrochloride solid, carrying out reduced pressure distillation concentration on the solution, then adding methanol to separate out a resin product, filtering, washing with water until the pH value of a final water layer is 7, then washing with methanol, and drying to obtain a product. The ester equivalent of the prepared active ester resin is 252g/eq according to the feeding ratio.
(C-1b) an ester curing agent having the structure of formula I, wherein the structure is as follows:
Figure BDA0001923052730000112
wherein the average repeat unit n is 1.25;
the preparation method comprises the following steps:
a flask equipped with a thermometer, a dropping funnel and a stirrer was charged with 2mol (568.78g) of tetramethylbisphenol A and 1500g of tetrahydrofuran, and the mixture was stirred with nitrogen gas until it was completely dissolved. Then, 1mol (203.02g) of terephthaloyl chloride was added and dissolved by stirring, and then, 2mol (202.38g) of triethylamine (prepared as a 20% triethylamine/tetrahydrofuran solution) was slowly added dropwise (more than 0.5 hour) while controlling the system temperature to 20 ℃ or lower. Then, the reaction is continued for 2 to 3 hours at a temperature of 20 ℃. Then, 2mol (281.14g) of benzoyl chloride is added, the system temperature is controlled below 15 ℃, then 2mol (202.38g) of triethylamine (prepared into a 20% triethylamine/tetrahydrofuran solution for dropwise addition) is slowly added dropwise, and the stirring reaction is continued below 15 ℃ for 2-5 hours. And standing after the reaction is finished, filtering to remove triethylamine hydrochloride solid, carrying out reduced pressure distillation concentration on the solution, then adding methanol to separate out a resin product, filtering, washing with water until the pH value of a final water layer is 7, then washing with methanol, and drying to obtain a product. The ester equivalent of the prepared active ester resin is 226g/eq according to the feeding ratio.
(C-1C) an ester curing agent having the structure of formula I, wherein the structure is as follows:
Figure BDA0001923052730000121
wherein the average repeat unit n is 1.25;
the preparation method comprises the following steps:
a flask equipped with a thermometer, a dropping funnel and a stirrer was charged with 2mol (512.66g) of tetramethylbisphenol F and 1500g of tetrahydrofuran, and the mixture was stirred with nitrogen gas until it was completely dissolved. Then, 1mol (203.02g) of terephthaloyl chloride was added and dissolved by stirring, and then, 2mol (202.38g) of triethylamine (prepared as a 20% triethylamine/tetrahydrofuran solution) was slowly added dropwise (more than 0.5 hour) while controlling the system temperature to 20 ℃ or lower. Then, the reaction is continued for 2 to 3 hours at a temperature of 20 ℃. Then, 2mol (157g) of acetyl chloride is added, the temperature of the system is controlled below 15 ℃, then 2mol (202.38g) of triethylamine (prepared into a 20% triethylamine/tetrahydrofuran solution for dropwise addition) is slowly added dropwise, and the stirring reaction is continued below 15 ℃ for 2-5 hours. And standing after the reaction is finished, filtering to remove triethylamine hydrochloride solid, carrying out reduced pressure distillation concentration on the solution, then adding methanol to separate out a resin product, filtering, washing with water until the pH value of a final water layer is 7, then washing with methanol, and drying to obtain a product. The ester equivalent of the prepared active ester resin is 181g/eq according to the feeding ratio.
(C-2) an ester curing agent V-575 (trade name of NITIKA) having the following structure:
Figure BDA0001923052730000131
wherein the average repeat unit n is 1.25;
(C-3) Dicyclopentadienol-type active ester HPC-8000T65 (trade name of Dainippon ink);
(C-4) bisphenol A type cyanate ester prepolymer CE01PS (trade name, Yangzhou Tianji);
(C-5) Dicyclopentadiene-type benzoxazine LZ8260N70 (trade name HUNTSMAN).
(D) Additive flame retardant
The phenoxyphosphazene compound SPB-100 (trade name of Mitsubishi Japan).
(E) Curing accelerator
4-dimethylaminopyridine (trade name of Kyoho chemical Co., Ltd., Japan).
(F) Filler material
(F-1) spherical silicon micropowder (with average particle size of 1-10 μm and purity of more than 99%);
(F-2) alumina (average particle diameter of 1-10 μm, purity of 99% or more).
Examples 1 to 16
Examples 1 to 16 provide thermosetting resin composition glue solutions, prepregs and copper clad laminates using the same, the preparation methods are as follows:
(1) preparation of thermosetting resin composition glue solution:
preparing a solution with solid contents of 60%, 50% and 25% by using an MEK solvent through respectively preparing a phosphorus-containing curing agent (B), a co-curing agent (C) and a phenoxyphosphazene compound (D) SPB-100 into the solution, sequentially adding the solution into a 1000mL beaker, sequentially adding a halogen-free epoxy resin (A) and a filler (F), adding a proper amount of a curing accelerator (E), namely 4-dimethylaminopyridine, adjusting the Gelation Time (GT) to 200-300s, adding the MEK solvent to control the solid content to 65%, and continuously stirring for 2h for curing to obtain a thermosetting resin composition glue solution;
the kinds and amounts (in parts by weight) of the respective components are shown in tables 1 and 2.
(2) Preparation of prepreg:
6 pieces of 2116 glass cloth (manufacturer: Taiwan Hubei Co., Ltd.) were prepared, and the size: 320mm 380mm, coating the glue solution of the thermosetting resin composition on each glass cloth to make the glue solution infiltrate the glass cloth and stick resin on the two surfaces, then scraping the two surfaces of the infiltrated glass cloth through a rolling clamping shaft and removing part of the glue solution, and controlling the sum of the weight of the glass cloth and the resin composition after removing the solvent at 200-230g/m2And (3) obtaining the pre-impregnated glass cloth, and then putting the glass cloth into an oven at 155 ℃ for baking for 6-8min to obtain the pre-impregnated material.
(3) Manufacturing a copper-clad plate:
2 pieces of electrolytic copper foil (manufacturer: suzhou fuda) having a thickness of 35 μm and a size of 410mm were prepared, 6 pieces of the above prepreg were stacked while maintaining 4-angle alignment, and the prepared electrolytic copper foil was coated on each of the upper and lower surfaces of the stacked prepreg, which was placed in a laminator and laminated under the following conditions: firstly, the temperature rising rate of lamination is controlled to be 1.5-2.5 ℃/min when the material temperature is 80-120 ℃; setting the laminating pressure, wherein the outer layer material temperature is 120 ℃ and 150 ℃ and full pressure is applied, and the full pressure is 350 psi; and thirdly, controlling the material temperature to be 200 ℃ during curing, and preserving the heat for 90min to obtain the copper-clad plate.
Comparative example 1
Comparative example 1 differs from example 7 in the kind of the phosphorus-containing curing agent of component (B), which is specifically shown in Table 3 below.
Comparative examples 2 to 5
Comparative examples 2 to 5 are different from example 5 in the kind of the curing agent of the component (C), and are specifically shown in the following Table 3.
Comparative examples 6 to 9
Comparative examples 6 to 9 are different from example 16 in the kind of the curing agent of the component (C), and are specifically shown in the following Table 3.
The performance of the copper-clad plates provided by the above examples and comparative examples is tested, and the test standards/methods are as follows:
(a) glass transition temperature (Tg): the measurement was carried out by Differential Scanning Calorimetry (DSC) according to the DSC method defined by IPC-TM-6502.4.25.
(b) Coefficient of Thermal Expansion (CTE)
Measured according to the Z-directed CTE test method specified in IPC-TM-6502.4.24.
(c) Water absorption
After a sample of 100mm multiplied by 100mm is placed in a constant temperature and humidity box with the temperature of 85 ℃ and the humidity of 85 percent for treatment for 168 hours, the water absorption rate of the treated sample is tested.
(d) Dielectric constant and dielectric dissipation factor
The dielectric loss and dielectric dissipation factor at 1GHz were measured by IPC-TM-6502.5.5.5 according to the resonance method using a strip line.
(e) Dielectric constant, dielectric dissipation factor (after moisture)
After the sample is placed in a constant temperature and humidity box with the temperature of 85 ℃ and the humidity of 85 percent for treatment for 168 hours, the dielectric loss and the dielectric loss factor under 1GHz are measured according to IPC-TM-6502.5.5.5.
(f) Resistance to dip soldering
The delamination foaming time was observed according to IPC-TM-6502.4.13.1.
(g) Peel strength
The peel strength of the metal cap was tested according to the "post thermal stress" experimental conditions in the IPC-TM-6502.4.8 method.
(h) Area of drop hammer impact crack
Adopting a drop hammer impact tester for testing, wherein the test method comprises the following steps: the height of the drop weight was 1m, the weight of the drop weight was 0.75kg, the drop weight was released, and the plate crack area was measured. The fracture area of the plate can preliminarily reflect the toughness of the plate, and generally speaking, the smaller the fracture area is, the better the toughness of the plate is.
(i) Fire resistance property
Measured according to the UL94 vertical burning method.
The performance of the copper-clad plates provided by the above examples and comparative examples is shown in the following tables 1 to 3:
TABLE 1
Figure BDA0001923052730000161
Figure BDA0001923052730000171
TABLE 2
Figure BDA0001923052730000172
Figure BDA0001923052730000181
TABLE 3
Figure BDA0001923052730000191
Figure BDA0001923052730000201
From the physical property data of tables 1 to 3, it is found that: in examples 1-9, 5-25 parts of the ester curing agent with the structure of formula I and 15-40 parts of the phosphorus-containing bisphenol are compounded and cured with 40-75 parts of the halogen-free epoxy resin, and the prepared sheet material has high Tg, low CTE, low water absorption, excellent dielectric properties, high heat resistance, peel strength and excellent toughness, and can realize halogen-free flame retardant V-0 grade.
In example 10, 78 parts of dicyclopentadiene novolac epoxy resin HP-7200H is cured by compounding the ester curing agent with the structure of formula I and the phosphorus-containing bisphenol OL3001, and because the dosage of the dicyclopentadiene novolac epoxy resin HP-7200H exceeds the preferable dosage range, the reaction is incomplete, the Tg of the final board is reduced, the CTE and the water absorption are increased, the dielectric property is poor, and the heat resistance is not ideal.
In example 11, 38 parts of dicyclopentadiene novolac epoxy resin HP-7200H was cured by compounding the ester curing agent with the structure of formula I with the phosphorus-containing bisphenol OL3001, and the board had a higher Tg and a lower CTE, but due to insufficient epoxy resin and excessive curing agent, the final board had a higher water absorption, a poor dielectric property and an unsatisfactory heat resistance.
In example 12, the ester curing agent with the structure of formula I and 42 parts of phosphorus-containing bisphenol OL3001 are compounded to cure dicyclopentadiene novolac epoxy resin HP-7200H, and since the usage of the curing agent phosphorus-containing bisphenol OL3001 exceeds the preferable usage range, the final board has slightly low Tg and high water absorption, and the dielectric properties of the board after moisture absorption are seriously deteriorated.
In example 13, the dicyclopentadiene novolac epoxy resin HP-7200H is cured by compounding the ester curing agent having the structure of formula I with 8 parts of phosphorus-containing bisphenol OL3001, and because the addition amount of the curing agent phosphorus-containing bisphenol OL3001 is low, the epoxy resin is incompletely cured in an excessive manner, the CTE of the final board is relatively high, and the dielectric properties are general.
In example 14, 27 parts of the ester curing agent with the structure of formula I and the phosphorus-containing bisphenol OL3001 are compounded to cure the dicyclopentadiene novolac epoxy resin HP-7200H, so that the plate has high Tg, low CTE, low water absorption and excellent dielectric properties, but the fracture area of the drop hammer impact test for representing the toughness is too large, the plate has poor toughness, and the downstream PCB processing is not facilitated.
In example 15, 3 parts of the ester curing agent having the structure of formula I and the phosphorus-containing bisphenol OL3001 were used to cure dicyclopentadiene novolac epoxy resin HP-7200H, so that the final board had a low Tg, a high CTE and a high water absorption, and the dielectric properties of the board after moisture absorption were seriously deteriorated.
In example 16, the ester curing agent with the structure of formula I is compounded with the phosphorus-containing bisphenol OL3001 to cure the dicyclopentadiene novolac epoxy resin HP-7200H, no filler is added, the CTE and the water absorption of the board are increased, but the CTE and the water absorption of the board are still kept at a more ideal level, and meanwhile, the board has high Tg and excellent dielectric property, heat resistance and toughness.
As described above, compared with a general halogen-free laminate, the laminate prepared by using the thermosetting resin composition provided by the present invention has higher Tg, lower CTE, lower water absorption, and more excellent dielectric properties, peel strength, heat resistance, and toughness, and is suitable for high-speed application fields. In addition, the halogen content of the invention can reach the V-0 standard in a flame retardant test UL94 within the halogen-free standard requirement range of JPCA, and the invention has the effect of environmental protection.
In comparative example 1, the ester curing agent with the structure shown in formula I and the phosphorus-containing phenolic aldehyde XZ-92741 are compounded to cure the dicyclopentadiene novolac epoxy resin HP-7200H, and the phosphorus-containing phenolic aldehyde has too low reactivity, so that the final board has low Tg, high CTE and poor dielectric property and heat resistance.
In comparative example 2, the dicyclopentadiene novolac epoxy resin HP-7200H is cured by compounding the ester curing agent V-575 and the phosphorus-containing bisphenol OL3001, so that the sheet material has high Tg, low CTE, excellent heat resistance and excellent toughness, but the dielectric property is general, the water absorption rate is high, and the dielectric property of the sheet material after moisture absorption is poor.
In comparative example 3, the dicyclopentadiene phenol type active ester HPC-8000T65 and the phosphorus-containing bisphenol OL3001 are compounded and cured to obtain the dicyclopentadiene novolac epoxy resin HP-7200H, so that the final board has excellent dielectric properties, but the Tg is low, the water absorption rate is high, and the dielectric properties of the board after moisture absorption are seriously deteriorated.
In comparative example 4, the dicyclopentadiene novolac epoxy resin HP-7200H is cured by compounding the bisphenol A cyanate ester prepolymer CE01PS with the phosphorus-containing bisphenol OL3001, so that the plate has high Tg, low CTE, excellent dielectric properties and heat resistance, but high water absorption rate and poor dielectric properties after the plate absorbs moisture.
In comparative example 5, the dicyclopentadiene novolac epoxy resin HP-7200H is cured by compounding dicyclopentadiene benzoxazine LZ8260N70 with phosphorus-containing bisphenol OL3001, and the plate has low water absorption rate, excellent dielectric constant and heat resistance, but low Tg and high CTE and dielectric loss factor.
In comparative example 6, the dicyclopentadiene novolac epoxy resin HP-7200H is cured by compounding the ester curing agent V-575 and the phosphorus-containing bisphenol OL3001, no filler is added, the plate has high Tg, low CTE and excellent dielectric constant, but the water absorption is high, the dielectric property of the plate after moisture absorption is poor, and the heat resistance is not ideal.
In comparative example 7, dicyclopentadiene phenol type active ester HPC-8000T65 and phosphorus-containing bisphenol OL3001 were used to cure dicyclopentadiene novolac epoxy resin HP-7200H, no filler was added, and the final board had excellent dielectric properties, but low Tg, high CTE, high water absorption, and severe deterioration of the dielectric properties after moisture absorption.
In comparative example 8, the dicyclopentadiene novolac epoxy resin HP-7200H was cured by compounding the bisphenol A cyanate ester prepolymer CE01PS with the phosphorus-containing bisphenol OL3001 without adding any filler, so that the board had high Tg, low CTE, excellent dielectric properties and heat resistance, but high water absorption rate and poor dielectric properties after moisture absorption.
In comparative example 9, dicyclopentadiene benzoxazine LZ8260N70 and phosphorus-containing bisphenol OL3001 were used to cure dicyclopentadiene novolac epoxy resin HP-7200H without adding filler, and the plate had low water absorption and excellent dielectric constant, but the plate had low Tg, high CTE and dielectric loss factor, and unsatisfactory heat resistance.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (31)

1. A thermosetting resin composition characterized by comprising the following components: epoxy resin, phosphorus-containing bisphenol and ester curing agent;
the ester curing agent has a structure of formula I:
Figure FDA0002544139830000011
wherein R is1-R8Each independently selected from hydrogen atom, C1-C10Aliphatic hydrocarbon group, C3-C10Alicyclic hydrocarbon radicals or C6-C10Aromatic hydrocarbon group, and not all hydrogen atoms;
x is selected from-CH2-or-C (CH)3)2-；
Y is selected from C1-C10Aliphatic hydrocarbon group, C3-C10Alicyclic hydrocarbon radicals or C6-C10One of aromatic hydrocarbon groups;
n is an integer of 1 to 10;
wherein the thermosetting resin composition comprises the following components in parts by weight based on 100 parts by weight of the epoxy resin, the phosphorus-containing bisphenol and the ester curing agent: 40-75 parts of epoxy resin, 15-40 parts of phosphorus-containing bisphenol and 5-25 parts of ester curing agent.
2. The thermosetting resin composition of claim 1, wherein the epoxy resin is a halogen-free epoxy resin.
3. The thermosetting resin composition according to claim 2, wherein the halogen-free epoxy resin is selected from one or a combination of at least two of bisphenol a type epoxy resin, bisphenol F type epoxy resin, o-cresol novolac epoxy resin, bisphenol a type novolac epoxy resin, triphenol type novolac epoxy resin, dicyclopentadiene novolac epoxy resin, biphenyl type novolac epoxy resin, alkylbenzene type novolac epoxy resin, or naphthol type novolac epoxy resin.
4. The thermosetting resin composition of claim 3, wherein the halogen-free epoxy resin has the structure of formula II:
Figure FDA0002544139830000021
wherein, X1Is composed of
Figure FDA0002544139830000022
X2And X3Each independently is
Figure FDA0002544139830000023
Figure FDA0002544139830000024
R9Selected from hydrogen atoms, substituted or unsubstituted C1-C5Straight chain alkyl orSubstituted or unsubstituted C3-C5One of the branched alkyl radicals, Y1And Y2Each independently selected from a single bond, -CH2-、
Figure FDA0002544139830000025
Figure FDA0002544139830000026
One of (1), R10Selected from hydrogen atoms, substituted or unsubstituted C1-C5Straight chain alkyl or substituted or unsubstituted C3-C5One of the branched alkyl groups; m is an integer of 1 to 10.
5. The thermosetting resin composition of claim 1, wherein the phosphorus-containing bisphenol has a structure represented by formula III:
Figure FDA0002544139830000027
wherein k is an integer from 2 to 20.
6. The thermosetting resin composition claimed in claim 5, wherein k is an integer of 3 to 10.
7. The thermosetting resin composition of claim 1, wherein the phosphorus-containing bisphenol has a weight average molecular weight of 1000-10000 independently.
8. The thermosetting resin composition of claim 7, wherein the phosphorus-containing bisphenol has a weight average molecular weight of 1000-6500 independently.
9. The thermosetting resin composition of claim 8, wherein the phosphorus-containing bisphenol has a weight average molecular weight of 1000-4500 independently.
10. The thermosetting resin composition of claim 1, further comprising a flame retardant.
11. The thermosetting resin composition of claim 10, wherein the flame retardant is a phosphorus-containing flame retardant.
12. The thermosetting resin composition of claim 11, wherein the phosphorus-containing flame retardant is added in an amount of 0 to 50 parts based on 100 parts by weight of the total amount of the epoxy resin, the phosphorus-containing bisphenol, and the ester curing agent.
13. The thermosetting resin composition of claim 12, wherein the phosphorus-containing flame retardant is added in an amount of 0 to 30 parts.
14. The thermosetting resin composition of claim 11, wherein the phosphorus-containing flame retardant is one or a combination of at least two selected from 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-10-phosphaphenanthrene-10-oxide, a phenoxyphosphazene compound, a phosphate ester, a polyphosphate ester, a phosphonate ester, or a polyphosphonate ester.
15. The thermosetting resin composition of claim 1, further comprising a curing accelerator.
16. The thermosetting resin composition of claim 15, wherein the curing accelerator is added in an amount of 0.05 to 1 part based on 100 parts by weight of the total amount of the epoxy resin, the phosphorus-containing bisphenol, and the ester curing agent.
17. The thermosetting resin composition of claim 15, wherein the curing accelerator is one or a combination of at least two selected from the group consisting of imidazoles, triphenylphosphine, dimethylaminopyridine, boron trifluoride monoethylamine, and zinc octoate.
18. The thermosetting resin composition of claim 17, wherein the imidazole based compound is selected from one or a combination of at least two of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and 2-undecylimidazole.
19. The thermosetting resin composition of claim 1, further comprising a filler.
20. The thermosetting resin composition of claim 19, wherein the filler is added in an amount of 0 to 150 parts based on 100 parts by weight of the total amount of the epoxy resin, the phosphorus-containing bisphenol, and the ester curing agent.
21. The thermosetting resin composition of claim 20, wherein the filler is added in an amount of 0 to 100 parts.
22. The thermosetting resin composition of claim 19, wherein the filler is an organic filler and/or an inorganic filler.
23. The thermosetting resin composition of claim 22, wherein the inorganic filler is selected from one or a combination of at least two of silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.
24. The thermosetting resin composition of claim 22, wherein the organic filler is selected from one or a combination of at least two of polytetrafluoroethylene powder, polyphenylene sulfide, or polyethersulfone powder.
25. The thermosetting resin composition of claim 22, wherein the filler is silica and has a particle size median value of 1-15 μm.
26. The thermosetting resin composition of claim 25, wherein the particle size median value is 1-10 μ ι η.
27. A resin cement obtained by dissolving or dispersing the thermosetting resin composition according to any one of claims 1 to 26 in a solvent.
28. A prepreg comprising a reinforcing material and the thermosetting resin composition according to any one of claims 1 to 26 attached to the reinforcing material by impregnation drying.
29. A laminate comprising one or at least two superimposed prepregs according to claim 28.
30. A metal-clad laminate comprising one sheet or at least stacked sheets of the prepreg of claim 28 and a metal foil clad on one or both sides of the outside of the prepreg.
31. A printed circuit board comprising at least one prepreg according to claim 28.
CN201811606732.XA 2018-12-26 2018-12-26 Thermosetting resin composition, and prepreg, metal foil-clad laminate and printed circuit board using same Active CN109694462B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201811606732.XA CN109694462B (en) 2018-12-26 2018-12-26 Thermosetting resin composition, and prepreg, metal foil-clad laminate and printed circuit board using same
PCT/CN2018/125306 WO2020133335A1 (en) 2018-12-26 2018-12-29 Thermosetting resin composition, prepreg using same, metal foil-cladded laminate, and printed circuit board

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811606732.XA CN109694462B (en) 2018-12-26 2018-12-26 Thermosetting resin composition, and prepreg, metal foil-clad laminate and printed circuit board using same

Publications (2)

Publication Number Publication Date
CN109694462A CN109694462A (en) 2019-04-30
CN109694462B true CN109694462B (en) 2020-10-27

Family

ID=66232024

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811606732.XA Active CN109694462B (en) 2018-12-26 2018-12-26 Thermosetting resin composition, and prepreg, metal foil-clad laminate and printed circuit board using same

Country Status (2)

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

Family Cites Families (9)

* 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
CN105566621B (en) * 2014-11-11 2018-09-21 江苏雅克科技股份有限公司 Low dielectric phosphorous-containing polyester compound composition and its preparation method
CN105802128B (en) * 2014-12-29 2018-05-04 广东生益科技股份有限公司 A kind of halogen-free thermosetting resin composite and use its prepreg and laminate for printed circuits
CN105440263A (en) * 2015-12-15 2016-03-30 广东广山新材料有限公司 Epoxy resin curing agent, and preparation method and use thereof
CN105542128A (en) * 2015-12-15 2016-05-04 广东广山新材料有限公司 Curing agent for epoxy resin as well as preparation method and application thereof
CN105399927A (en) * 2015-12-15 2016-03-16 广东广山新材料有限公司 Epoxy resin curing agent and preparation method and application thereof
CN108164685B (en) * 2016-12-07 2019-08-27 广东生益科技股份有限公司 A kind of compositions of thermosetting resin
TWI620763B (en) * 2017-04-27 2018-04-11 Taiwan Union Technology Corporation Resin composition, and prepreg, metal-clad laminate and printed circuit board prepared using the same

Also Published As

Publication number Publication date
CN109694462A (en) 2019-04-30
WO2020133335A1 (en) 2020-07-02

Similar Documents

Publication Publication Date Title
EP3053963B1 (en) Halogen-free resin composition and uses thereof
KR101897426B1 (en) Halogen-free resin composition and prepreg and laminated prepared therefrom
KR101508083B1 (en) Halogen-free resin composition and method for fabricating halogen-free copper clad laminate using the same
CN108219371B (en) Epoxy resin composition, prepreg, laminate, and printed wiring board
EP2770025B1 (en) Halogen-free low-dielectric resin composition, and prepreg and copper foil laminate made by using same
CN109851997B (en) Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same
CN108485182B (en) High-frequency resin composition and prepreg and laminated board manufactured by using same
CN109651763B (en) Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same
TWI666248B (en) Maleimide resin composition, prepreg, laminate and printed circuit board
TWI716967B (en) Resin composition, prepreg, laminate, metal-clad laminate and printed circuit board
EP3412722B1 (en) Halogen-free thermosetting resin composition, prepreg containing same, laminate, and printed circuit board
CN109608828B (en) Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same
CN109535653B (en) Phosphorus-containing epoxy resin composition, and prepreg and laminated board prepared from same
TWI669340B (en) Halogen-free thermosetting resin composition and prepreg, laminate, metal foil-clad laminate, and printed circuit board using the same
CN108047647B (en) Halogen-free thermosetting resin composition, and prepreg, laminated board, metal foil-clad laminated board and printed circuit board using same
JP6163804B2 (en) Compatibilized resin production method, thermosetting resin composition, prepreg and laminate
CN109694462B (en) Thermosetting resin composition, and prepreg, metal foil-clad laminate and printed circuit board using same
CN114605779B (en) Thermosetting resin composition, prepreg comprising thermosetting resin composition, circuit substrate and printed circuit board
JP2013189578A (en) Compatibilization resin, and thermosetting resin composition, prepreg and laminated plate using the same
CN115819766B (en) Modified maleimide prepolymer, resin composition and application of resin composition
CN113121793B (en) Halogen-free thermosetting resin composition, and prepreg, laminated board and printed circuit board using same
JP6353633B2 (en) Compatibilizing resin, thermosetting resin composition, prepreg and laminate
CN113121957B (en) Halogen-free thermosetting resin composition, prepreg, laminated board and printed circuit board using same
CN118255969A (en) Thermosetting resin composition and prepreg, laminated board and printed circuit board using thermosetting resin composition
CN118256061A (en) Halogen-free thermosetting resin composition, laminated board and printed circuit board

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant