CN112266572B - Resin composition, prepreg, laminate, and circuit board - Google Patents

Resin composition, prepreg, laminate, and circuit board Download PDF

Info

Publication number
CN112266572B
CN112266572B CN202011177408.8A CN202011177408A CN112266572B CN 112266572 B CN112266572 B CN 112266572B CN 202011177408 A CN202011177408 A CN 202011177408A CN 112266572 B CN112266572 B CN 112266572B
Authority
CN
China
Prior art keywords
resin composition
composition according
resin
structural formula
benzoxazine
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
CN202011177408.8A
Other languages
Chinese (zh)
Other versions
CN112266572A (en
Inventor
杨宋
马建
熊峰
崔春梅
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.)
Suzhou Shengyi Technology Co Ltd
Original Assignee
Suzhou 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 Suzhou Shengyi Technology Co Ltd filed Critical Suzhou Shengyi Technology Co Ltd
Priority to CN202011177408.8A priority Critical patent/CN112266572B/en
Publication of CN112266572A publication Critical patent/CN112266572A/en
Application granted granted Critical
Publication of CN112266572B publication Critical patent/CN112266572B/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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Abstract

The invention provides a resin composition, which comprises a phosphorus-containing double bond-containing benzoxazine resin, can lead a condensate to have more excellent low dielectric constant, low dielectric loss, halogen-free flame retardance and wet heat resistance, and has higher glass transition temperature; the invention also provides a prepreg, a laminated board and a circuit substrate prepared by using the resin composition.

Description

Resin composition, prepreg, laminate, and circuit board
Technical Field
The invention relates to the technical field of electronic materials, in particular to a resin composition, a prepreg prepared from the resin composition, a laminated board and a circuit substrate.
Background
In the prior art, a halogen flame retardant is generally adopted in a laminated board for a circuit substrate to achieve the aim of flame retardance, however, the halogen flame retardant generates highly corrosive halogenated gas in the combustion process, and the document reports that the halogen flame retardant can generate cancerogens such as dioxin, dibenzofuran and the like during high-temperature pyrolysis and combustion. Since the official practice of the instructions on scrapped electrical and electronic equipment and the instructions on restricting the use of harmful substances in electrical and electronic equipment issued by the European Union, the development of laminates for halogen-free flame retardant circuit substrates has become an important point in the industry.
At present, a phosphorus-containing compound is used for replacing the prior brominated flame retardant in a common method in the industry, but the product of the phosphorus-containing compound has the common problems of insufficient tin immersion heat resistance, easiness in moisture absorption, insufficient tin immersion heat resistance after moisture treatment and the like.
With the recent increase in the speed and frequency of information processing and information transmission, there has been a demand for a laminate for a circuit board to have higher dielectric properties. In short, the laminate material needs to have a low dielectric constant and dielectric loss to reduce delay, distortion and loss of signals at high speed transmission, and interference between signals. However, epoxy resins have high dielectric constants and dielectric losses, and it is difficult to satisfy the application in high frequency.
Benzoxazine is a benzoxazine intermediate obtained by carrying out cyclization reaction on primary amine, phenol and aldehyde on the basis of the traditional method for preparing phenolic resin, and the benzoxazine is subjected to ring opening under the condition of heating or a catalyst to generate a novel thermosetting resin with a net structure, wherein a cured product of the novel thermosetting resin has higher glass transition temperature, and the decomposition of the cured product is less than 1% when the thermal decomposition temperature is up to 350 ℃, and in addition, the benzoxazine has better flame retardance because of containing nitrogen element. Benzoxazines do not exhibit sufficient flame retardant effects and require the addition of additives such as bromine, phosphorus or chlorine compounds. These additives affect the workability of the copper clad laminate and have poor oxidation stability and physical properties at high temperatures.
In view of the above, it is necessary to provide a novel resin composition, a prepreg, a laminate, and a circuit substrate prepared therefrom to solve the above-described problems.
Disclosure of Invention
The invention aims to provide a resin composition capable of meeting the requirements of no halogenation and high frequency at the same time, a prepreg, a laminated board and a circuit substrate prepared from the resin composition. The prepreg, the laminated board and the circuit substrate have more excellent low dielectric constant, low dielectric loss, halogen-free flame retardance and wet heat resistance, and have higher glass transition temperature.
In order to achieve the aim of the invention, the invention adopts the following technical scheme: a resin composition comprising, by weight:
crosslinking agent: 1-80 parts;
benzoxazine resin: 5-80 parts;
the benzoxazine resin comprises at least one of the following structural formulas:
Figure SMS_1
structural formula (1);
Figure SMS_2
structural formula (2);
Figure SMS_3
structural formula (3);
Figure SMS_4
structural formula (4);
Figure SMS_5
structural formula (5);
wherein R is 1 、R 2 、R 3 、R 4 Are identical or different and are each selected from hydrogen, methyl, ethyl, propyl or tert-butyl; r is methyl, ethyl, phenyl, vinyl, allyl, styryl, phenylallyl,
Figure SMS_6
、
Figure SMS_7
Or->
Figure SMS_8
At least one R group in each structural formula is a group containing an unsaturated double bond; x is phenyl, methyl or ethyl.
Further, the crosslinking agent has an unsaturated double bond; the cross-linking agent is at least one of polybutadiene, modified polybutadiene, polypentadiene, modified polypentadiene, polyisoprene, modified polyisoprene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleated diene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer, maleated styrene-butadiene copolymer, cyclopentadiene, modified cyclopentadiene, dicyclopentadiene, modified dicyclopentadiene, styrene-pentadiene copolymer, styrene-polypentadiene copolymer, butadiene-cyclopentadiene copolymer, ethylene-cyclopentadiene copolymer, norbornene polymer, modified norbornene polymer, divinylbenzene, bis (vinylbenzyl) ether, bis (vinylphenyl) ethane, divinylbenzene, double bond-containing polyphenylene ether, maleimide, double bond-containing cyanate ester, and double bond-containing phenolic resin.
Further, the resin composition includes 10 to 60 parts by weight of a benzoxazine resin, 5 to 70 parts by weight of maleimide.
Further, the resin composition further comprises a crosslinking aid; the cross-linking auxiliary agent is at least one of triallyl isocyanate monomer, triallyl isocyanate monomer prepolymer, butadiene monomer, styrene monomer, pentadiene monomer, norbornene monomer or cyclopentadiene monomer.
Further, the resin composition comprises 20 to 60 parts by weight of a benzoxazine resin, 5 to 60 parts by weight of a double bond-containing polyphenylene ether, and 5 to 60 parts by weight of a triallyl isocyanate monomer.
Further, the benzoxazine resin further comprises a benzoxazine resin except for structural formulas (1) to (5); the benzoxazine resin other than the structural formulas (1) to (5) is at least one of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin or bisphenol E type benzoxazine resin.
Further, based on 100 parts by weight of the benzoxazine resin, the content of the benzoxazine resin shown in the structural formula (1) to the structural formula (5) is 10-100 parts by weight, and the content of the benzoxazine resin except the structural formula (1) to the structural formula (5) is 1-40 parts by weight.
Further, the resin composition further comprises a flame retardant, and/or an initiator, and/or a catalyst, and/or a filler, and/or an auxiliary agent, wherein the auxiliary agent comprises at least one of a coupling agent, a dispersing agent and a dye.
In order to achieve the above object, the present invention further provides a prepreg, which is formed by immersing a reinforcing material in the glue solution of the resin composition and then heating and drying the reinforcing material.
In order to achieve the above object, the present invention also provides a laminate, which is formed by hot-pressing at least one side of one prepreg or at least two cured sheets laminated with each other with a metal foil.
In order to achieve the above object, the present invention also provides a circuit substrate comprising at least one prepreg as described above, or at least one laminate as described above.
Compared with the prior art, the invention has the following advantages:
in the resin composition of the invention, by adopting the benzoxazine resin containing phosphorus and olefin groups to be matched with the cross-linking agent, namely, double bonds in the benzoxazine resin react with the cross-linking agent, the resin composition which simultaneously meets the requirements of no halogenation and high frequency can be obtained, and a cured product with higher cross-linking density can be obtained, and the cured product has excellent low dielectric constant, low dielectric loss, no halogen flame retardance and moist heat resistance; on the other hand, the phosphorus-containing olefin-based benzoxazine resin contains nitrogen, phosphorus and phosphorus-nitrogen, and is synergistic in flame retardance, so that the flame retardance efficiency of a system is greatly improved, phosphorus groups can be well introduced into a cured product, and the dielectric property and the water absorption rate of the cured product are further improved on the basis of improving the heat resistance and the flame retardance of the cured product; meanwhile, the benzoxazine resin containing phosphorus and olefin groups has a large number of hydrogen bonds, so that the problems of poor cohesiveness, poor toughness and the like caused by fewer polar groups can be avoided, and the cohesiveness and toughness of a cured product are obviously improved.
Particularly, when the cross-linking agent is maleimide, the phosphorus-containing olefin-containing benzoxazine resin is matched with the maleimide, so that the flame retardant resin has more excellent toughness, heat resistance, flame retardance and dielectric property.
Detailed Description
The following description is given of specific embodiments of the present invention, and it should be noted that, for those skilled in the art, it is possible to make several improvements and modifications without departing from the principle of the embodiments of the present invention, and these improvements and modifications are also considered as the protection scope of the embodiments of the present invention.
The terms "comprising", "including" and "containing" in this specification mean that other components which are capable of imparting different properties to the resin composition may be contained in addition to the components.
In the present specification, "based on 100 parts by weight of the resin composition" means that the total amount of components excluding the crosslinking assistant, flame retardant, initiator, catalyst, filler, and assistant is 100 parts by weight.
The present invention provides a resin composition comprising, by weight:
crosslinking agent: 1-80 parts;
benzoxazine resin: 5-80 parts;
the benzoxazine resin comprises at least one of the following structural formulas:
Figure SMS_9
structural formula (1);
Figure SMS_10
structural formula (2);
Figure SMS_11
structural formula (3);
Figure SMS_12
structural formula (4);
Figure SMS_13
structural formula (5);
wherein R in structural formulas (1) to (3) 1 、R 2 、R 3 、R 4 Independent of each other, i.e. R 1 、R 2 、R 3 、R 4 Is the same or different, and R is 1 、R 2 、R 3 、R 4 Respectively selected from hydrogen, methyl, ethyl, propyl or tert-butyl; r is methyl, ethyl, phenyl, vinyl, allyl, styryl, phenylallyl,
Figure SMS_14
、/>
Figure SMS_15
Or->
Figure SMS_16
At least one R group in each structural formula is a group containing an unsaturated double bond; x is phenyl, methyl or ethyl.
The absence of epoxy resin in the resin composition of the present invention can provide the final cured product with more excellent dielectric properties.
Specifically, in one embodiment, R in structural formulae (1) to (3) 1 、R 2 、R 3 、R 4 And are the same and are each selected from hydrogen or methyl.
Further, the R group is selected from styryl, phenylallyl,
Figure SMS_17
Or->
Figure SMS_18
。
Further, the X group is phenyl or methyl.
Further, the benzoxazine resin further comprises a benzoxazine resin except for structural formulas (1) to (5).
In one embodiment, the benzoxazine resin other than the structural formula (1) to structural formula (5) is at least one of bisphenol a type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin, or bisphenol E type benzoxazine resin; of course, this is not a limitation.
Specifically, the benzoxazine resin shown in the structural formula (1) to the structural formula (5) accounts for 10-100 parts by weight based on 100 parts by weight of the benzoxazine resin.
The above-mentioned "the content of the benzoxazine resin shown in the structural formula (1) to structural formula (5) is 10-100 parts by weight" means the content of the benzoxazine resin shown in the structural formula (1) to structural formula (5) contained in the benzoxazine resin. That is, in the embodiment in which only the benzoxazine resin represented by the structural formula (1) is included in the benzoxazine resin, "the content of the benzoxazine resin represented by the structural formula (1) to the structural formula (5) is 10 to 100 parts by weight", that is, the content of the benzoxazine resin represented by the structural formula (1) is 10 to 100 parts by weight; in the embodiment in which the benzoxazine resin only includes the benzoxazine resin shown in the structural formula (1) and the structural formula (2), the "the content of the benzoxazine resin shown in the structural formula (1) to the structural formula (5) is 10-100 parts by weight", that is, the content of the benzoxazine resin shown in the structural formula (1) and the structural formula (2) is 10-100 parts by weight, and so on, the description thereof is omitted.
Specifically, the content of the benzoxazine resin other than the structural formula (1) to the structural formula (5) is 1-40 parts by weight based on 100 parts by weight of the benzoxazine resin.
Further, the crosslinking agent has an unsaturated double bond to enhance the reactivity of the crosslinking agent with the double bond in the benzoxazine resin.
Specifically, the crosslinking agent is at least one of polybutadiene, modified polybutadiene, polypentadiene, modified polypentadiene, polyisoprene, modified polyisoprene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleated diene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer, maleated styrene-butadiene copolymer, cyclopentadiene, modified cyclopentadiene, dicyclopentadiene, modified dicyclopentadiene, styrene-pentadiene copolymer, styrene-polypentadiene copolymer, butadiene-cyclopentadiene copolymer, ethylene-cyclopentadiene copolymer, norbornene polymer, modified norbornene polymer, divinylbenzene, bis (vinylbenzyl) ether, bis (vinylphenyl) ethane, divinylbenzene, double bond-containing polyphenylene ether, maleimide, double bond-containing cyanate ester, double bond-containing phenolic resin.
Preferably, the cross-linking agent is polybutadiene, wherein the content of 1, 2-vinyl is more than 45%, and the reactivity of the cross-linking agent with double bonds in the benzoxazine resin is further improved.
Further preferably, the crosslinking agent is polyphenylene ether containing double bonds, which is not limited to this.
Further, the double bond-containing polyphenyl ether has at least one of the following structures:
Figure SMS_19
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure SMS_20
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure SMS_21
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure SMS_22
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure SMS_23
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure SMS_24
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure SMS_25
in the structural formula, a and b are the same or different, a and b are integers of 1-10, and n is an integer of 0-5 (including 0);
Figure SMS_26
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure SMS_27
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure SMS_28
in the structural formula, a and b are the same or different, and a and b are integers of 1-10;
Figure SMS_29
in the structural formula, a and b are the same or different, a and b are integers of 1-10, and n is an integer of 1-5;
still more preferably, the crosslinking agent is maleimide.
In a specific embodiment wherein the crosslinking agent is maleimide, the resin composition comprises 10 to 60 parts by weight of the benzoxazine resin, 5 to 70 parts by weight of maleimide.
The maleimide refers specifically to a compound having at least one maleimide group in its molecular structure.
Preferably, the maleimide is at least one of the following structures:
Figure SMS_30
；
Figure SMS_31
；
Figure SMS_32
；
Figure SMS_33
wherein R2 is hydrogen, methyl or ethyl, R1 is methylene, ethylene or +.>
Figure SMS_34
；
Figure SMS_35
；
Figure SMS_36
Wherein n is an integer of 1 to 10;
Figure SMS_37
wherein n is an integer of 1 to 10;
Figure SMS_38
wherein n is an integer of 1 to 10;
Figure SMS_39
wherein n is an integer of 1 to 10.
Further, the resin composition further comprises 0.1 parts to 10 parts of a crosslinking auxiliary agent based on 100 parts of the resin composition.
Specifically, the crosslinking auxiliary agent is at least one of triallyl isocyanate monomer, triallyl isocyanate monomer prepolymer, butadiene monomer, styrene monomer, pentadiene monomer, norbornene monomer or cyclopentadiene monomer.
In a specific embodiment where the resin composition includes a crosslinking aid, the resin composition includes 20 to 60 parts by weight of a benzoxazine resin, 5 to 60 parts by weight of a double bond-containing polyphenylene ether, and 5 to 60 parts by weight of a triallyl isocyanate monomer.
Further, the resin composition further includes 5 parts to 40 parts of a flame retardant based on 100 parts of the resin composition to improve flame retardancy of a finally formed cured product.
The cured product in the present invention is understood to be a prepreg, an insulating film, a laminate, a circuit board, or the like.
Specifically, the flame retardant is selected from the group consisting of phosphorus-containing phenolic resins, phosphazenes or modified phosphazenes, phosphates, melamine cyanurate, polyorganosiloxanes, DOPO-HQ, DOPO-NQ,
Figure SMS_40
(m is an integer of 1 to 5),
Figure SMS_41
Or DPO.
Wherein, structural formula of DOPO is:
Figure SMS_42
；
the structural formula of DOPO-HQ is as follows:
Figure SMS_43
；
the structural formula of DOPO-NQ is as follows:
Figure SMS_44
；
the said
Figure SMS_45
The structural formula is as follows: />
Figure SMS_46
；
The said
Figure SMS_47
Is of the formula->
Figure SMS_48
。
Further, the flame retardant is preferably a phosphorus-containing compound, the phosphorus-containing compound is preferably an additive-type phosphorus-containing compound, and specifically, the additive-type phosphorus-containing compound can be phosphazene, such as the trademark SPB-100; or modified phosphazenes such as BP-PZ, PP-PZ, SPCN-100, SPV-100 and SPB-100L; or choose to use
Figure SMS_49
The method comprises the steps of carrying out a first treatment on the surface of the Or choose to use
Figure SMS_50
。
Further, based on 100 parts of the resin composition, the resin composition further comprises 0.1 to 5 parts of an initiator, wherein the initiator is used for opening double bonds in the benzoxazine and the crosslinking agent so as to increase the reactivity of the double bonds in the benzoxazine and the crosslinking agent, obtain a tighter crosslinked network structure and improve the heat resistance of a cured product.
Specifically, the initiator is a free radical initiator and is selected from at least one of dicumyl peroxide, or 2, 5-dimethyl-2, 5-bis (tertiary butyl peroxy) hexane, or tertiary butyl isopropyl peroxide, or di-tertiary butyl peroxide, or alpha, alpha' -bis (tertiary butyl peroxy) dicumyl and 2, 5-dimethyl-2, 5-bis (tertiary butyl peroxy) hexyne-3.
Further, the resin composition further contains 0.01 to 2 parts of a catalyst based on 100 parts of the resin composition. The catalyst is at least one selected from 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole and 1-cyanoethyl-2-methylimidazole.
Further, the resin composition further comprises 20 parts to 100 parts of a filler per 100 parts of the resin composition, and it is understood that the filler may be contained or not contained in the resin composition.
Specifically, the filler is at least one of an organic filler or an inorganic filler.
The inorganic filler is selected from one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus.
Preferably, the inorganic filler is at least one selected from fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.
Further, the filler is silica, especially spherical silica subjected to surface treatment, is easier to disperse, can prevent agglomeration, and meanwhile, the spherical silica subjected to surface treatment is low in thermal expansion coefficient, so that warping of a final product can be prevented.
Specifically, the surface treatment agent for treating the spherical silica is a silane coupling agent, such as an epoxy silane coupling agent or an aminosilane coupling agent.
The organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
In addition, the median particle size of the filler is 1 to 15. Mu.m, for example 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm or 15 μm, and the specific values between the above values, are limited in space and in the interest of brevity, the invention is not intended to be exhaustive of the specific values included in the ranges.
Preferably, the particle size of the filler has a median value of 1-10 mu m, so that the filler is easier to disperse and better in anti-agglomeration effect.
Further, the resin composition may further comprise an auxiliary agent according to the different requirements of the final product of the present invention, and it is understood that the resin composition may or may not comprise an auxiliary agent according to the different requirements of the final product, or a suitable auxiliary agent may be selected according to the requirements.
In the embodiment in which the resin composition contains an auxiliary agent, the content of the auxiliary agent is 0-5 parts by weight based on 100 parts by weight of the resin composition.
Specifically, the other auxiliary agents comprise a coupling agent, a dispersing agent and a dye. The coupling agent is a silane coupling agent, such as an epoxy silane coupling agent or an amino silane coupling agent; the dispersant may be an amino silane compound having an amino group and having a hydrolyzable group or a hydroxyl group, such as γ -aminopropyl triethoxysilane, N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, an epoxy silane compound having an epoxy group and having a hydrolyzable group or a hydroxyl group, such as 3-acryloxypropyl trimethoxysilane, a vinyl silane compound having a vinyl group and having a hydrolyzable group or a hydroxyl group, such as γ -methacryloxypropyl trimethoxysilane, or a cationic silane coupling agent, and for example, the dispersant may be Disperbyk-110, 111, 118, 180, 161, 2009, BYK-W996, W9010, W903 manufactured by BYK, the aforementioned code numbers being all the product names; the dye is a fluorescent dye and a black dye, wherein the fluorescent dye is pyrazoline and the like, and the black dye is liquid or powder carbon black, pyridine complex, azo complex, nigrosine, black talcum powder, cobalt chromium metal oxide, azine or phthalocyanine and the like.
It will be appreciated that the resin composition further comprises an appropriate amount of an organic solvent, and the above components of the resin composition and the organic solvent are mixed to form a resin composition glue solution for use.
Specifically, the organic solvent may be selected from one or a combination of any several of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene, xylene and cyclohexane.
The amount of the organic solvent to be used in the present invention is not particularly limited. The amount of the solvent to be added is selected by one skilled in the art according to his own experience, as long as the resulting resin composition dope can be brought to a viscosity suitable for use.
Further, the invention also provides a prepreg which comprises a reinforcing material and any one of the resin compositions attached to the surface of the reinforcing material.
Specifically, the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric; preferably, the reinforcing material is a glass fiber cloth, and a split cloth or a flat cloth is preferably used in the glass fiber cloth.
In addition, when the reinforcing material is a glass fiber cloth, the glass fiber cloth generally needs to be chemically treated to improve the bonding between the resin composition and the interface of the glass fiber cloth. The main method of the chemical treatment is treatment of a coupling agent, and the coupling agent is preferably epoxy silane or amino silane, etc. to provide good water resistance and heat resistance.
The preparation method of the prepreg comprises the following steps: and (3) dipping the reinforcing material in the resin composition glue solution, then baking the dipped reinforcing material for 1-10 min at 50-170 ℃ and drying to obtain the prepreg.
Further, the invention also provides a laminated board which comprises at least one prepreg and a metal foil formed on at least one surface of the prepreg.
In an embodiment in which the laminate comprises at least two prepregs as described above, the at least two prepregs are stacked and bonded together by heating and pressurizing, and then a metal foil is bonded on one or both sides of the bonded prepregs by heating and pressurizing to form the laminate.
Specifically, the laminate was prepared as follows: and coating metal foil on one side or two sides of one prepreg, or coating metal foil on one side or two sides of at least 2 prepregs after superposing, and performing hot press forming to obtain the laminated board.
The pressing conditions of the laminated board are as follows: pressing for 2-4 hours under the pressure of 0.2-2 MPa and the temperature of 180-250 ℃.
Specifically, the number of prepregs is determined according to the thickness of the laminate as required.
The metal foil can be copper foil or aluminum foil, and the material of the metal foil is not limited; the thickness of the metal foil is not particularly limited as long as it is set according to specific needs, and may be, for example, 5 μm, 8 μm, 12 μm, 18 μm, 35 μm or 70 μm.
Further, the invention also provides a circuit substrate, which comprises at least one prepreg or at least one laminated board.
The preparation method of the circuit substrate can adopt the existing technology, and is not repeated here.
The following describes the present invention in detail with reference to specific examples; of course, it is to be understood that the embodiments of the invention are not limited to these embodiments.
Examples 1-5 and comparative examples 1-3:
the components and contents of the resin compositions of examples 1 to 5 and comparative examples 1 to 3 are shown in Table 1 below:
TABLE 1
Figure SMS_51
Wherein, the structural formula of the benzoxazine A in the table 1 is:
Figure SMS_52
。
the reaction mechanism for preparing the benzoxazine A is as follows:
Figure SMS_53
Figure SMS_54
。
the structural formula of benzoxazine B in table 1 above is:
Figure SMS_55
。
the reaction mechanism for preparing the benzoxazine B is as follows:
Figure SMS_56
Figure SMS_57
。
the structural formula of the benzoxazine C in table 1 above is:
Figure SMS_58
。
the reaction mechanism for preparing the benzoxazine C is as follows:
Figure SMS_59
Figure SMS_60
。
the structural formula of the benzoxazine D in table 1 above is:
Figure SMS_61
。
it can be seen that the benzoxazines a, B, C belong to the benzoxazine resins shown in the above structural formula (2). The benzoxazine D does not belong to the benzoxazine resins represented by the structural formulae (1) to (5).
In addition, the other component information than benzoxazine a, benzoxazine B, benzoxazine C, benzoxazine D referred to in table 1 above is shown in table 2 below:
TABLE 2
Figure SMS_62
The preparation methods of the resin compositions of examples 1 to 5 and comparative examples 1 to 3 employ conventional preparation methods, specifically: the benzoxazine A, the benzoxazine B, the benzoxazine C, the benzoxazine D, the bisphenol A-type benzoxazine, polybutadiene, polyphenyl ether, maleimide, phosphate, filler, initiator and catalyst are mixed with a proper amount of organic solvent according to the components and the corresponding contents in the table 1, and are emulsified by adopting a high-speed emulsifier, so that a resin composition glue solution with 65% of solid content is obtained after the uniform dispersion and mixing, wherein the solid content is 65% by weight.
The obtained resin composition solutions of examples 1 to 5 and comparative examples 1 to 3 were respectively impregnated and coated on E glass cloth (2116, weight 104g/m 2 ) Prepregs with 50% resin content in examples 1-5 and comparative examples 1-2 were prepared, respectively, by drying in an oven at 145 ℃ for 6 min.
Preparation for performance evaluation sample laminates were evaluated:
(1) Preparation of Metal foil clad laminate
Prepregs with 50% resin content prepared in examples 1-5 and comparative examples 1-2 were each put one metal foil up and down, and placed in a vacuum hot press to be pressed to obtain metal foil laminates, respectively. The specific pressing process is to press for 2 hours at the temperature of 220 ℃ under the pressure of 1.5 MPa.
The performance evaluation method comprises the following steps:
(1) Dielectric constant (Dk)/dielectric loss (Df): a network analyzer (SPDR) method;
(2) Glass transition temperature (Tg): the Dynamic Mechanical Analysis (DMA) instrument is adopted for testing, and can be used for analyzing whether the system has phase separation, and generally, two or more Tg's show that the system has poor compatibility and phase separation.
(3) Flame retardancy: the UL94V method was used.
(4) Wet heat resistance (PCT): 3 metal foil-clad laminates of 10cm X10 cm and 0.80mm thickness with metal foil removed on both sides were dried at 100℃for 2 hours, then treated with a autoclave retort test (Pressure Cooker test) machine at 121℃for 3 hours under 2 atmospheres, and then tin-immersed in a tin oven at 288℃for 20 seconds, and visually inspected for delamination. The layering phenomenon of the blocks 0,1,2 and 3 in the 3 blocks is respectively marked as 0/3,1/3,2/3 and 3/3.
The properties of the metal foil-clad laminates obtained using the prepregs in examples 1 to 5 and comparative examples 1 to 3, respectively, are shown in table 3 below.
TABLE 3 Table 3
Figure SMS_63
As is clear from Table 3, the laminate obtained by using the resin composition of the present invention has more excellent low dielectric constant, low dielectric loss, halogen-free flame retardance, wet heat resistance and higher glass transition temperature.
In particular, as is clear from the parallel comparison of example 1 and comparative example 1, example 1 has more excellent low dielectric constant, low dielectric loss, halogen-free flame retardance, wet heat resistance, and higher glass transition temperature than comparative example 1; as can be seen from the parallel comparison of example 3 and comparative example 2, example 3 has more excellent low dielectric constant, low dielectric loss, halogen-free flame retardance, wet heat resistance and higher glass transition temperature than comparative example 2; as is clear from the parallel comparison between example 4 and comparative example 3, example 4 has a lower dielectric constant, lower dielectric loss, halogen-free flame retardancy, wet heat resistance, and a higher glass transition temperature than comparative example 3.
It should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is for clarity only, and that the skilled artisan should recognize that the embodiments may be combined as appropriate to form other embodiments that will be understood by those skilled in the art.
The above list of detailed descriptions is only specific to practical embodiments of the present invention, and they are not intended to limit the scope of the present invention, and all equivalent embodiments or modifications that do not depart from the spirit of the present invention should be included in the scope of the present invention.

Claims (26)

1. A resin composition comprising, by weight:
crosslinking agent: 1-80 parts of cross-linking agent with unsaturated double bond;
benzoxazine resin: 5-80 parts;
the benzoxazine resin comprises at least one of the following structural formulas:
Figure QLYQS_1
structural formula (1);
Figure QLYQS_2
structural formula (2);
Figure QLYQS_3
structural formula (3);
wherein R is 1 、R 2 、R 3 、R 4 Are identical or different and are each selected from hydrogen, methyl, ethyl, propyl or tert-butyl; r is methyl, ethyl, phenyl, vinyl, allyl, styryl, phenylallyl,
Figure QLYQS_4
、/>
Figure QLYQS_5
Or->
Figure QLYQS_6
At least one R group in each structural formula is a group containing an unsaturated double bond; x is phenyl, methyl or ethyl;
and/or, the benzoxazine resin is selected from at least one of the following structural formulas:
Figure QLYQS_7
structural formula (4);
Figure QLYQS_8
structural formula (5);
wherein R is methyl, ethyl, phenyl, vinyl, allyl, styryl, phenylallyl,
Figure QLYQS_9
、
Figure QLYQS_10
Or->
Figure QLYQS_11
At least one R group in each structural formula is a group containing an unsaturated double bond; x is phenyl, methyl or ethyl.
2. The resin composition according to claim 1, wherein: the cross-linking agent is at least one of polybutadiene, modified polybutadiene, polypentadiene, modified polypentadiene, polyisoprene, modified polyisoprene, polystyrene, butadiene-styrene copolymer, styrene-butadiene-styrene copolymer, hydrogenated diene-butadiene-styrene copolymer, maleated diene-butadiene-styrene copolymer, styrene-isoprene-styrene copolymer, styrene-butadiene-divinylbenzene copolymer, maleated styrene-butadiene copolymer, cyclopentadiene, modified cyclopentadiene, dicyclopentadiene, modified dicyclopentadiene, styrene-pentadiene copolymer, styrene-polypentadiene copolymer, butadiene-cyclopentadiene copolymer, ethylene-cyclopentadiene copolymer, norbornene polymer, modified norbornene polymer, divinylbenzene, bis (vinylbenzyl) ether, bis (vinylphenyl) ethane, divinylbenzene, double bond-containing polyphenylene ether, maleimide, double bond-containing cyanate ester, and double bond-containing phenolic resin.
3. The resin composition according to claim 1, wherein: comprises the following components in parts by weight:
benzoxazine resin: 10-60 parts;
maleimide: 5-70 parts.
4. The resin composition according to claim 1, wherein: the resin composition further includes a crosslinking aid.
5. The resin composition according to claim 4, wherein: the cross-linking auxiliary agent is at least one of triallyl isocyanate monomer, triallyl isocyanate monomer prepolymer, butadiene monomer, styrene monomer, pentadiene monomer, norbornene monomer or cyclopentadiene monomer.
6. The resin composition according to claim 4, wherein: comprises the following components in parts by weight:
benzoxazine resin: 20-60 parts;
polyphenylene ether containing double bonds: 5-60 parts;
triallyl isocyanate monomer: 5-60 parts.
7. The resin composition according to claim 1, wherein: the benzoxazine resin further comprises benzoxazine resins except structural formulas (1) - (5).
8. The resin composition according to claim 7, wherein: the benzoxazine resin other than the structural formulas (1) to (5) is at least one of bisphenol A type benzoxazine resin, bisphenol F type benzoxazine resin, bisphenol S type benzoxazine resin or bisphenol E type benzoxazine resin.
9. The resin composition according to claim 7, wherein: and the content of the benzoxazine resin shown in the structural formula (1) to the structural formula (5) is 10-100 parts by weight based on 100 parts by weight of the benzoxazine resin.
10. The resin composition according to claim 7, wherein: the benzoxazine resin except the structural formula (1) to the structural formula (5) has the content of 1-40 parts by weight.
11. The resin composition according to claim 1, wherein: the resin composition further includes a flame retardant.
12. The resin composition according to claim 11, wherein: the flame retardant is selected from phosphorus-containing phenolic resin, phosphazene or modified phosphazene, phosphate, melamine cyanurate, polyorganosiloxane, DOPO-HQ, DOPO-NQ,
Figure QLYQS_12
、/>
Figure QLYQS_13
Or at least one of DPO; wherein m is an integer of 1 to 5.
13. The resin composition according to claim 1, wherein: the resin composition further includes an initiator.
14. The resin composition according to claim 13, wherein: the initiator is a free radical initiator; the initiator is at least one selected from dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (tertiary butyl peroxy) hexane, tertiary butyl isopropyl phenyl peroxide, di-tertiary butyl peroxide, alpha' -bis (tertiary butyl peroxy) dicumyl peroxide and 2, 5-dimethyl-2, 5-bis (tertiary butyl peroxy) hexyne-3.
15. The resin composition according to claim 1, wherein: the resin composition further includes a catalyst.
16. The resin composition according to claim 15, wherein: the catalyst comprises at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-isopropylimidazole, 2-phenyl-4-methylimidazole, 2-dodecylimidazole and 1-cyanoethyl-2-methylimidazole.
17. The resin composition according to claim 1, wherein: the resin composition further includes a filler.
18. The resin composition according to claim 17, wherein: the filler is an organic filler; the organic filler is at least one selected from polytetrafluoroethylene powder, polyphenylene sulfide and polyether sulfone powder.
19. The resin composition according to claim 17, wherein: the filler is an inorganic filler; the inorganic filler is selected from one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus.
20. The resin composition according to claim 19, wherein: the inorganic filler is at least one selected from fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, aluminum oxide, talcum powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica and glass fiber powder.
21. The resin composition according to claim 20, wherein: the filler is spherical silica surface-treated with a silane coupling agent.
22. The resin composition according to claim 17, wherein: the particle size median of the filler is 1-15 μm.
23. The resin composition according to claim 1, wherein: the resin composition further comprises an auxiliary agent, wherein the auxiliary agent comprises at least one of a coupling agent, a dispersing agent and a dye.
24. A prepreg, characterized in that: a prepreg formed by impregnating a reinforcing material with a glue solution of the resin composition according to any one of claims 1 to 23 and then drying by heating.
25. A laminate, characterized in that: a laminated board is formed by coating at least one side of a prepreg or at least two prepregs which are laminated with metal foil in a hot pressing mode, wherein the prepreg is the prepreg according to claim 24.
26. A circuit substrate, characterized in that: comprising at least one prepreg according to claim 24 or at least one laminate according to claim 25.
CN202011177408.8A 2020-10-29 2020-10-29 Resin composition, prepreg, laminate, and circuit board Active CN112266572B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011177408.8A CN112266572B (en) 2020-10-29 2020-10-29 Resin composition, prepreg, laminate, and circuit board

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011177408.8A CN112266572B (en) 2020-10-29 2020-10-29 Resin composition, prepreg, laminate, and circuit board

Publications (2)

Publication Number Publication Date
CN112266572A CN112266572A (en) 2021-01-26
CN112266572B true CN112266572B (en) 2023-07-14

Family

ID=74344432

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011177408.8A Active CN112266572B (en) 2020-10-29 2020-10-29 Resin composition, prepreg, laminate, and circuit board

Country Status (1)

Country Link
CN (1) CN112266572B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115340651A (en) * 2022-08-30 2022-11-15 济南大学 Norbornene-nitrile-siloxane type benzoxazine resin and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1306041A (en) * 2000-01-17 2001-08-01 住友电木株式会社 Fire resistance resin compsns. and presoaking material and laminated products using same
JP2009120667A (en) * 2007-11-13 2009-06-04 Showa Highpolymer Co Ltd Thermosetting resin composition, and cured material and laminated plate produced by using the same
CN103119049A (en) * 2010-09-22 2013-05-22 宇部兴产株式会社 Organic phosphorus compound and method for producing same
CN106700424A (en) * 2016-12-30 2017-05-24 浙江华正新材料股份有限公司 Low-loss resin composition, prepreg and laminated board

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001271070A (en) * 2000-03-27 2001-10-02 Asahi Kasei Corp Flame retardant
CN101684191B (en) * 2009-08-27 2012-03-07 广东生益科技股份有限公司 Halogen-less high frequency resin composition, and prepreg and laminate manufacturing by using same
CN103435812B (en) * 2013-08-21 2015-08-19 广东生益科技股份有限公司 A kind of benzoxazine intermediate and preparation method thereof
CN103788580B (en) * 2014-01-27 2016-08-17 苏州生益科技有限公司 A kind of Halogen benzoxazine resin compositions and the prepreg using it to make and laminate
CN104845363B (en) * 2014-02-14 2017-04-05 广东生益科技股份有限公司 A kind of halogen-free resin composition and application thereof
CN109776611A (en) * 2019-02-23 2019-05-21 河南大学 A kind of phosphorous, silicon benzoxazine monomer and preparation method thereof
CN111117154B (en) * 2019-12-31 2022-10-18 广东生益科技股份有限公司 Flame-retardant thermosetting resin composition, and prepreg, laminated board and printed circuit board manufactured from same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1306041A (en) * 2000-01-17 2001-08-01 住友电木株式会社 Fire resistance resin compsns. and presoaking material and laminated products using same
JP2009120667A (en) * 2007-11-13 2009-06-04 Showa Highpolymer Co Ltd Thermosetting resin composition, and cured material and laminated plate produced by using the same
CN103119049A (en) * 2010-09-22 2013-05-22 宇部兴产株式会社 Organic phosphorus compound and method for producing same
CN106700424A (en) * 2016-12-30 2017-05-24 浙江华正新材料股份有限公司 Low-loss resin composition, prepreg and laminated board

Also Published As

Publication number Publication date
CN112266572A (en) 2021-01-26

Similar Documents

Publication Publication Date Title
CN112204105B (en) Resin composition, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board
EP2407503B1 (en) Thermosetting resin composition of semi-ipn composite, and varnish, prepreg and metal clad laminated board using the same
CN110655775B (en) Resin composition, and prepreg, laminated board and printed wiring board provided with same
CN111635626B (en) Resin composition, prepreg, laminated sheet, preparation method of prepreg, preparation method of laminated sheet and application of laminated sheet
CN108219371B (en) Epoxy resin composition, prepreg, laminate, and printed wiring board
CN114058181B (en) Resin composition, preparation method and application thereof
CN110885428B (en) Halogen-free thermosetting resin composition, prepreg using same, laminated board and printed circuit board
CN110527037B (en) Halogen-free polyphenyl ether resin composition and prepreg and laminated board manufactured by using same
TWI704185B (en) Resin composition, prepreg for printed circuit and metal-clad laminate
CN110845853B (en) Resin composition, and prepreg, laminated board, insulating board, circuit board and coverlay film comprising same
CN112280245B (en) Resin composition, prepreg, metal foil-clad laminate, and circuit board
TWI650361B (en) Thermosetting resin composition, prepreg prepared by the same, metal foil-clad laminate and high frequency circuit board
JP2016538363A (en) Curable composition for forming interpenetrating polymer networks
CN112266572B (en) Resin composition, prepreg, laminate, and circuit board
CN113088061A (en) Thermosetting resin composition, and prepreg, laminated board and metal foil-clad laminated board using same
CN112679936B (en) Thermosetting resin composition, resin glue solution containing thermosetting resin composition, prepreg, laminated board, copper-clad plate and printed circuit board
CN110950901B (en) Silicone resin, method for producing the same, resin composition, prepreg, laminated board, insulating board, circuit board, and coverlay film
CN112236464B (en) Resin composition, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board
CN110922764B (en) Silicon-containing resin composition and prepreg and laminated board manufactured by using same
CN110615876B (en) Halogen-free polyphenyl ether resin composition and prepreg and laminated board manufactured by using same
CN114634713B (en) Resin composition, prepreg and metal-clad laminate
CN113121981B (en) Resin composition, prepreg and insulating plate using same
CN116410594A (en) Resin composition, prepreg and metal foil-clad laminate
CN110643131B (en) Resin composition, and prepreg, laminated board and printed wiring board provided with same
CN114685929B (en) Thermosetting resin composition and application thereof

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