CN110330759B - Thermosetting resin composition and application thereof - Google Patents
Thermosetting resin composition and application thereof Download PDFInfo
- Publication number
- CN110330759B CN110330759B CN201910659226.5A CN201910659226A CN110330759B CN 110330759 B CN110330759 B CN 110330759B CN 201910659226 A CN201910659226 A CN 201910659226A CN 110330759 B CN110330759 B CN 110330759B
- Authority
- CN
- China
- Prior art keywords
- copolymer
- styrene
- resin composition
- parts
- thermosetting resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J153/02—Vinyl aromatic monomers and conjugated dienes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention relates to a thermosetting resin composition and application thereof, 30-70 parts of block copolymer rubber, 10-50 parts of unsaturated diene rubber, 5-30 parts of N-substituted maleimide copolymer, 10-50 parts of micromolecule cross-linking agent, flame retardant, filler and accelerator. Compared with the prior art, the N-substituted maleimide copolymer is introduced into a rubber system, so that the glass transition temperature and the peel strength of the material can be obviously improved, and the rubber material has the advantages of low dielectric loss, good heat resistance and the like.
Description
Technical Field
The invention relates to the technical field of high frequency and high speed, in particular to a thermosetting resin composition and application thereof.
Background
With the arrival of the 5G era, the terminal application and the network speed are continuously improved, the data transmission rate between devices has been increased from hundreds of Mbps to 20Gbps, the current industrial technology of the PCB is developed to a high-frequency, high-speed and high-density packaging method regardless of the soft board and the hard board, the requirements on materials and preparation methods are more and more stringent corresponding to the development trend of light, thin, portable and multifunctional products, the high-frequency transmission and low-loss materials can comprehensively replace transmission lines under the requirements of high-frequency, high-speed and miniaturization, wherein the most important material characteristic requirements are ultra-low dielectric property, high heat resistance and good flame retardance.
In a circuit for high-frequency signal transmission, an electric signal transmission loss is represented by the sum of a dielectric loss, a conductor loss, and a radiation loss. The higher the frequency of the electrical signal, the greater the dielectric loss, conductor loss, and radiation loss. Thus, an insulating material having a small dielectric loss tangent can be selected as an insulator for high-frequency signal transmission, thereby suppressing an increase in dielectric loss.
At present, as an insulating material for high frequency signal transmission, it is generally prepared by a teflon material or a hydrocarbon resin material, and the hydrocarbon material is widely used in the high frequency aspect due to the difficulty in processing the teflon material. Hydrocarbon resins prepared from block copolymer rubbers or unsaturated olefin resins and fillers have the disadvantages of low peel strength, poor heat resistance and low flexural strength, and the prepared bonding sheets may have sticking problems due to the rubber materials, which affects the production, storage and transportation of the bonding sheets. Therefore, there is a need for a high frequency substrate material having high heat resistance, high peel strength, low dielectric loss, and low expansion coefficient.
Disclosure of Invention
The present invention is directed to overcoming the above-mentioned drawbacks of the prior art and providing a thermosetting resin composition based on a hydrocarbon resin.
The purpose of the invention can be realized by the following technical scheme:
a thermosetting resin composition comprises the following components in parts by weight:
n-substituted maleimide copolymer
The N-substituted maleimide copolymer is copolymerized by the following monomers in molar part content: 30-60 parts of styrene monomer, 30-70 parts of N-substituted maleimide and 1-20 parts of unsaturated anhydride; the molecular formula of the copolymer of styrene, N-substituted maleimide and maleic anhydride is as follows:
wherein x, y and z are respectively the molar ratio of styrene monomer, N-substituted maleimide and unsaturated acid anhydride, and x, y and z are 0.3-0.6: 0.3-0.7: 0.01-0.2.
In the molecular formula of the N-substituted maleimide copolymer, R groups are methyl, ethyl, isopropyl, cyclohexyl, phenyl, benzyl, phenylethyl, phenyl vinyl, p-hydroxyphenyl, biphenyl and naphthyl ring groups; methyl, phenyl and phenyl vinyl are preferred, and the molecular formulas are respectively shown as follows:
a) n-methylmaleimide copolymer:
b) n-phenylmaleimide copolymer:
c) n-phenyl vinyl maleimide copolymer:
the N-substituted maleimide copolymer adopted by the invention is a copolymer (SMI) of styrene, N-substituted maleimide and maleic anhydride, can improve the compatibility between polar and non-polar resins, the styrene chain segment and rubber materials have good compatibility, and the maleimide and maleic anhydride chain segments can have good compatibility with polar resins, and can improve the interface strength, the peeling strength with metal foil and the bonding force with glass fiber bundles. The N-substituted maleimide copolymer has good heat resistance and excellent heat stability (no decomposition at 350 ℃), and when being mixed with hydrocarbon resin for use, the N-substituted maleimide copolymer is used as a heat-resistant modifier for the hydrocarbon material, and improves the glass transition temperature and the heat resistance of the sheet material.
Wherein, the content of the N-substituted maleimide copolymer is preferably 5 to 30 parts, if the N-substituted maleimide copolymer is added too little, the improvement of the heat resistance of the material is limited, and the peeling strength is lower; if too much N-substituted maleimide copolymer is added, the dielectric properties thereof will be increased and the water absorption will be increased significantly.
The molecular weight of the N-substituted maleimide copolymer is not particularly limited, and usually the number average molecular weight is preferably in the range of 2000 to 200000, and among them, more preferably in the range of 5000 to 50000, and the copolymer has a fast and good solubility in the resin composition, and also ensures reliable heat resistance and thermal stability of the material.
Block copolymer rubber
The block copolymer rubber is a linear triblock copolymer taking styrene as a terminal segment and polybutadiene and isoprene as middle segments, the number average molecular weight of the block copolymer rubber is 5000-150000, and the styrene segment accounts for 10-50% of the total mass of the block copolymer rubber.
The thermosetting resin composition contains a block copolymer rubber with larger molecular weight, the block copolymer is a linear triblock copolymer taking styrene as a terminal segment and polybutadiene and isoprene as a middle segment, and the block copolymer generally has no double bond structure and has lower reactivity. The block copolymer rubber has low polarity characteristics, can show extremely low dielectric constant and low dielectric loss required by high-frequency and high-speed materials, but is often poor in heat resistance of the materials and low in peel strength with metal foils. Good balance of properties can be achieved using such low polarity materials in combination with small amounts of polar materials such as polyphenylene ether, cyanate ester, maleimide and like resins. Therefore, the block copolymer rubber is one of the main components of the composition, and the selection of the ratio of the styrene segment to the butadiene segment is particularly important.
The block copolymer rubber is preferably styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene/isoprene-styrene (SBIS), hydrogenated styrene-butadiene-styrene (HSBS), hydrogenated styrene-isoprene-styrene (HSIS), hydrogenated styrene-butadiene/isoprene-styrene (HSBIS).
The number average molecular weight of the block copolymer rubber is preferably 5000-; when the molecular weight of the copolymer is more than 150000, the molecular weight of the block copolymer is too high, the solubility of the resin in a solvent is poor, the viscosity is too high, good processing production conditions are not provided, and the prepreg does not have good fluidity during lamination, which is not beneficial to the production of the substrate and the filling and flowing of the circuit board into the patterning characteristics of the adjacent layer.
The proportion of the styrene chain segment in the total mass of the block copolymer rubber is preferably 10-50%, and when the proportion of the styrene chain segment is less than 10%, the glass transition temperature of the material is too low; when the styrene chain segment is more than 50%, the peeling strength of the base material and the metal foil is low. When the mass proportion of the styrene chain segment in the block copolymer is 10-50%, the material has better balance of various properties such as dielectric property, glass transition temperature, peeling strength, heat resistance and the like.
Unsaturated diene rubber
The polymerization monomer of the unsaturated diene rubber comprises one or more of unmodified or modified group-containing butadiene or isoprene, wherein the modified group is selected from one or more of epoxy group, maleic anhydride, acrylate, hydroxyl or carboxyl; wherein the number average molecular weight of the diene rubber is 500 to 20000, and the unsaturated double bond structure accounts for 60 to 99% of the mass of the main chain of the diene rubber.
Specifically, the diene rubber is polybutadiene or polyisoprene containing a double bond structure in a side chain or a main chain; preferred are 1, 2-polybutadiene, cis-1, 4-polybutadiene, 1, 2-polyisoprene, cis-1, 4-polyisoprene.
More specifically, the unsaturated diene rubber is one or more selected from polybutadiene resin, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, divinylbenzene-butadiene copolymer, divinylbenzene-isoprene copolymer, styrene-butadiene-divinylbenzene copolymer or styrene-isoprene-divinylbenzene copolymer.
The number average molecular weight of the unsaturated diene rubber selected in the present invention is 500 to 20000, and more preferably 1000 to 10000. When the molecular weight of the unsaturated polymer resin is less than 500, the dielectric property reduction is not obviously improved, and when the molecular weight of the unsaturated polymer resin is more than 20000, the glass transition temperature and the peel strength of a resin system are deteriorated; the unsaturated double bond structure in the diene rubber accounts for 60-99% of the main chain mass of the diene rubber, and when the content of the unsaturated double bond is too low, the diene rubber has fewer groups which are subjected to crosslinking reaction with other thermosetting resins, low peel strength, low glass transition temperature and poor mechanical strength.
Wherein, the unsaturated diene rubber modified group is selected from one or more of epoxy group, maleic anhydride, (methyl) acrylate, hydroxyl or carboxyl; further preferred are maleic anhydride and (meth) acrylate-modified unsaturated butadiene-based polymers. The modified unsaturated diene rubber is advantageous for further improving the peel strength between the resin and the metal foil and the adhesive strength between resin interface layers.
Small molecule cross-linking agent
The resin composition also contains a micromolecular cross-linking agent which is mainly used for improving the cross-linking density of the block copolymer rubber, the unsaturated diene rubber and the N-substituted maleimide copolymer, increasing the compactness of a cross-linking network and improving the glass transition temperature and the heat resistance of the material.
The micromolecule crosslinking agent is preferably selected from one or more of triallyl isocyanurate, triallyl cyanurate, trimethallyl isocyanurate, trihydroxyethyl isocyanurate, tert-butyl styrene, diallyl isophthalate, diallyl phthalate, trimethylolpropane triacrylate or pentaerythritol tetraacrylate;
in addition, the invention patent also comprises a flame retardant, a filler and an accelerator.
Fire retardant
The flame retardant used in the present invention is preferably selected from one or a mixture of two of a bromine-containing flame retardant and a phosphorus-containing flame retardant, wherein the preferred bromine-containing flame retardant or phosphorus-containing flame retardant is not soluble in the resin system in order to adapt to a low dielectric resin system, and is usually selected from an additive bromine-containing flame retardant or phosphorus-containing flame retardant which is unreactive with polyphenylene ether resins and other resins and does not lower heat resistance and dielectric characteristics.
The additive bromine-containing flame retardant is preferably one or more of decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or decabromodiphenyl ether and ethylene bistetrabromophthalimide; the additive phosphorus-containing flame retardant is one or more selected from tris (2, 6-dimethylphenyl) phosphorus, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 6-bis (2, 6-dimethylphenyl) phosphaphenylbenzene or 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
Packing
The filler used in the present invention is not particularly limited, and may be one or more selected from the group consisting of aluminum nitride, aluminum borate, magnesium oxide, magnesium carbonate, boron nitride, crystalline silica, synthetic silica, hollow silica, spherical silica, fused silica, talc, alumina, barium sulfate, barium titanate, strontium titanate, calcium carbonate and titanium dioxide.
"Accelerator
In order to accelerate the reaction of the resin composition, enhance the crosslinking density, and increase the glass transition temperature and heat resistance, an accelerator (initiator) may be used to further accelerate the reaction.
The accelerator used in the present invention is preferably an organic peroxide free radical initiator selected from the group consisting of di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-3, 5, 5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1-di-tert-butylperoxy-3, 5, 5-trimethylcyclohexane, 1-di-tert-butylperoxycyclohexane, 2-di (tert-butylperoxy) butane, bis (4-tert-butylcyclohexyl) peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, diterbutyl hexanoate, dicumyl peroxide, cumyl peroxide, and mixtures thereof, One or more of bis (tert-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane, 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexyne, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-amyl hydroperoxide, tert-butyl cumyl peroxide, diisopropylbenzene hydroperoxide, tert-butyl peroxycarbonate-2-ethyl hexanoate, tert-butyl peroxycarbonate-2-ethylhexyl, 4-di (tert-butylperoxy) pentanoate, methyl ethyl ketone peroxide or cyclohexane peroxide.
The thermosetting resin composition of the present invention can be used for producing adhesive sheets, metal-clad laminates, and printed wiring boards.
Preparing a bonding sheet: the thermosetting resin composition is coated on the reinforcing fiber to form a prepreg; the reinforcing fiber can be organic fiber or inorganic fiber formed by weaving to form a reinforcing textile, preferably glass fiber woven fiber cloth, comprising E-glass, T-glass, NE-glass, L-glass and Q-glass.
Preparing a metal foil-clad laminate: the metal foil-clad laminate is formed by laminating one or at least two surfaces of the bonding sheets through hot pressing; the metal foil is preferably a copper foil, more preferably an electrolytic copper foil, and the surface roughness Rz thereof is preferably less than 5um, such as RTF copper foil, VLP copper foil, HVLP2 copper foil, which can further improve the signal loss problem of the high-frequency high-speed circuit board.
Preparing a printed circuit board: the printed wiring board comprises at least one of the adhesive sheet and the metal-clad laminate. The resin composition has good mechanical strength and toughness, good glass transition temperature, peeling strength and low dielectric property, so that the resin composition is suitable for processing high-multilayer printed circuit boards.
In the present invention, an N-substituted maleimide copolymer is used as a heat-resistant modifier and a compatibilizer for a rubber in a resin composition, the triblock copolymer contains an N-substituted maleimide structure and a maleic anhydride structure, the N-substituted maleimide copolymer is used in a resin base material of a vinyl-containing block copolymer rubber and an unsaturated diene rubber, the heat resistance of a vinyl segment is improved by the maleimide structure, the heat resistance of the resin base material is enhanced, and the polarity of the vinyl segment is also improved by the maleic anhydride structure.
Compared with the prior art, the invention has the following advantages:
(1) the N-substituted maleimide copolymer is adopted, so that the heat resistance of the resin base material is improved, the compatibility with inorganic materials and flame retardants is improved, and the interface peeling strength of the high resin base material and the metal foil is improved;
(2) the selection of the unsaturated diene rubber in the resin base material is optimized, and the liquid polybutadiene with a high-content unsaturated double bond structure is adopted, so that the electrical insulation property, the peeling strength and the glass transition temperature of the resin composition are further improved.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
A thermosetting resin composition comprises the following components in parts by weight: 30-70 parts of block copolymer rubber, 10-50 parts of unsaturated diene rubber, 5-30 parts of N-substituted maleimide copolymer, 10-30 parts of micromolecule cross-linking agent, flame retardant, filler and accelerator.
N-substituted maleimide copolymers
N-substituted maleimide copolymer
The N-substituted maleimide copolymer is copolymerized by the following monomers in molar part content: 30-60 parts of styrene monomer, 30-70 parts of N-substituted maleimide and 1-20 parts of unsaturated anhydride; the molecular formula of the copolymer of styrene, N-substituted maleimide and maleic anhydride is as follows:
wherein x, y and z are respectively the molar ratio of styrene monomer, N-substituted maleimide and unsaturated acid anhydride, and x, y and z are 0.3-0.6: 0.3-0.7: 0.01-0.2.
In the molecular formula of the N-substituted maleimide copolymer, R groups are methyl, ethyl, isopropyl, cyclohexyl, phenyl, benzyl, phenylethyl, phenyl vinyl, p-hydroxyphenyl, biphenyl and naphthyl ring groups; methyl, phenyl and phenyl vinyl are preferred, and the molecular formulas are respectively shown as follows:
a) n-methylmaleimide copolymer:
b) n-phenylmaleimide copolymer:
c) n-phenyl vinyl maleimide copolymer:
block copolymer rubber
The block copolymer rubber is a linear triblock copolymer taking styrene as a terminal segment and polybutadiene and isoprene as middle segments, the number average molecular weight of the block copolymer rubber is 5000-150000, and the styrene segment accounts for 10-50% of the total mass of the block copolymer rubber.
The thermosetting resin composition in the embodiment of the invention contains a block copolymer rubber with a larger molecular weight, the block copolymer is a linear triblock copolymer taking styrene as a terminal segment and polybutadiene and isoprene as a middle segment, and the block copolymer generally has no double bond structure and has lower reactivity. The block copolymer rubber has low polarity characteristics, can show extremely low dielectric constant and low dielectric loss required by high-frequency and high-speed materials, but is often poor in heat resistance of the materials and low in peel strength with metal foils. Good balance of properties can be achieved using such low polarity materials in combination with small amounts of polar materials such as polyphenylene ether, cyanate ester, maleimide and like resins. Therefore, the block copolymer rubber is one of the main components of the composition, and the selection of the ratio of the styrene segment to the butadiene segment is particularly important.
The block copolymer rubber is preferably styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene/isoprene-styrene (SBIS), hydrogenated styrene-butadiene-styrene (HSBS), hydrogenated styrene-isoprene-styrene (HSIS), hydrogenated styrene-butadiene/isoprene-styrene (HSBIS).
Unsaturated diene rubber
The polymerization monomer of the unsaturated diene rubber comprises one or more of butadiene or isoprene which is not modified or contains a modified group, wherein the modified group is one or more of epoxy group, maleic anhydride, acrylate, hydroxyl or carboxyl, and preferably unsaturated butadiene polymers modified by maleic anhydride and (methyl) acrylate; wherein the unsaturated diene rubber has a number average molecular weight of 1000 to 10000, and a 1, 4-cis double bond structure accounts for 60 to 95% of the total mass of the unsaturated diene rubber.
Specifically, the diene rubber is polybutadiene or polyisoprene containing a double bond structure in a side chain or a main chain; preferred are 1, 2-polybutadiene, cis-1, 4-polybutadiene, 1, 2-polyisoprene, cis-1, 4-polyisoprene.
More specifically, the unsaturated diene rubber is exemplified by one or more of polybutadiene resin, polyisoprene, a styrene-butadiene copolymer, a styrene-isoprene copolymer, a divinylbenzene-butadiene copolymer, a divinylbenzene-isoprene copolymer, a styrene-butadiene-divinylbenzene copolymer or a styrene-isoprene-divinylbenzene copolymer.
Small molecule cross-linking agent
The micromolecule crosslinking agent is preferably selected from one or more of triallyl isocyanurate, triallyl cyanurate, trimethallyl isocyanurate, trihydroxyethyl isocyanurate, tert-butyl styrene, diallyl isophthalate, diallyl phthalate, trimethylolpropane triacrylate or pentaerythritol tetraacrylate;
in addition, the invention also comprises a flame retardant, a filler and an accelerator, wherein the flame retardant, the filler and the accelerator are selected conventionally.
Fire retardant
The flame retardant used in the present invention is preferably selected from one or a mixture of two of a bromine-containing flame retardant and a phosphorus-containing flame retardant, wherein the preferred bromine-containing flame retardant or phosphorus-containing flame retardant is not soluble in the resin system in order to adapt to a low dielectric resin system, and is usually selected from an additive bromine-containing flame retardant or phosphorus-containing flame retardant which is unreactive with polyphenylene ether resins and other resins and does not lower heat resistance and dielectric characteristics.
The additive bromine-containing flame retardant is preferably one or more of decabromodiphenyl ether, decabromodiphenyl ethane, brominated styrene or decabromodiphenyl ether and ethylene bistetrabromophthalimide; the additive phosphorus-containing flame retardant is one or more selected from tris (2, 6-dimethylphenyl) phosphorus, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2, 6-bis (2, 6-dimethylphenyl) phosphaphenylbenzene or 10-phenyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
Packing
The filler used in the present invention is not particularly limited, and may be one or more selected from the group consisting of aluminum nitride, aluminum borate, magnesium oxide, magnesium carbonate, boron nitride, crystalline silica, synthetic silica, hollow silica, spherical silica, fused silica, talc, alumina, barium sulfate, barium titanate, strontium titanate, calcium carbonate and titanium dioxide.
"Accelerator
In order to accelerate the reaction of the resin composition, enhance the crosslinking density, and increase the glass transition temperature and heat resistance, an accelerator (initiator) may be used to further accelerate the reaction.
The accelerator used in the present invention is preferably an organic peroxide free radical initiator selected from the group consisting of di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-3, 5, 5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1-di-tert-butylperoxy-3, 5, 5-trimethylcyclohexane, 1-di-tert-butylperoxycyclohexane, 2-di (tert-butylperoxy) butane, bis (4-tert-butylcyclohexyl) peroxydicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, diterbutyl hexanoate, dicumyl peroxide, cumyl peroxide, and mixtures thereof, One or more of bis (tert-butylperoxyisopropyl) benzene, 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane, 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexyne, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tert-amyl hydroperoxide, tert-butyl cumyl peroxide, diisopropylbenzene hydroperoxide, tert-butyl peroxycarbonate-2-ethyl hexanoate, tert-butyl peroxycarbonate-2-ethylhexyl, 4-di (tert-butylperoxy) pentanoate, methyl ethyl ketone peroxide or cyclohexane peroxide.
The thermosetting resin composition of the present invention can be used for producing adhesive sheets, metal-clad laminates, and printed wiring boards.
Preparation of adhesive sheet
The thermosetting resin composition is coated on the reinforcing fiber to form a prepreg; the reinforcing fiber can be organic fiber or inorganic fiber formed by weaving to form a reinforcing textile, preferably glass fiber woven fiber cloth, comprising E-glass, T-glass, NE-glass, L-glass and Q-glass.
Preparation of Metal foil-clad laminate
The metal foil-clad laminate is formed by laminating one or at least two surfaces of the bonding sheets through hot pressing; the metal foil is preferably a copper foil, more preferably an electrolytic copper foil, and the surface roughness Rz thereof is preferably less than 5um, such as RTF copper foil, VLP copper foil, HVLP2 copper foil, which can further improve the signal loss problem of the high-frequency high-speed circuit board.
Preparation of printed Circuit Board
The printed wiring board comprises at least one of the adhesive sheet and the metal-clad laminate. The resin composition has good mechanical strength and toughness, good glass transition temperature, peeling strength and low dielectric property, so that the resin composition is suitable for processing high-multilayer printed circuit boards.
The method for producing a thermosetting resin composition of the present embodiment includes the steps of:
(1) preparing materials according to a formula;
(2) dissolving the block copolymer rubber, the unsaturated diene rubber and the N-substituted maleimide copolymer in a solvent, adding a cross-linking agent, and performing dispersion treatment to obtain the thermosetting resin composition.
Further, if the composition formula contains a flame retardant, an inorganic filler and an accelerator, the step (2) is to dissolve the block copolymer rubber, the unsaturated diene rubber and the N-substituted maleimide copolymer in a solvent, add the flame retardant, the inorganic filler and the accelerator, stir uniformly, and obtain the low dielectric resin composition after dispersion treatment.
The performance test is carried out on the prepared copper-clad plate, and the test method comprises the following steps:
glass transition temperature (Tg): the measurement was carried out by using a DMA instrument test according to the DMA test method specified in IPC-TM-6502.4.24.4.
Z-axis Coefficient of Thermal Expansion (CTE) was measured using a TMA instrument according to the TMA test method specified by IPC-TM-6502.4.24.
Copper foil Peel Strength (PS): measured using Shimadzu tensile machine according to the test method specified by IPC-TM-6502.4.8.
Dielectric constant (Dk) and dielectric loss factor (Df): dielectric constant and dielectric dissipation factor test methods were determined according to the test methods specified in IPC-TM-6502.5.5.9.
Autoclave cooking experiment (PCT): the laminates were autoclaved at 120 ℃ and tested according to the test method specified in IPC-TM-6502.6.16.
288 ℃ delamination time (T288) determined using TMA instrumentation according to the test method specified by IPC-TM-6502.4.24.1.
Flame retardancy: the test was carried out according to the flammability method of materials as specified in UL-94.
Water absorption: the water absorption of the laminate was measured according to the test method for water absorption of laminates as specified in IPC-TM-6502.6.2.1.
Resin fluidity: the fluidity of the resin was measured by Shimadzu capillary rheometer, and a 2g resin powder slug was extruded from a small hole at a certain pressure and evaluated according to the path of the resin flowing out of the rheometer. The longer the flow stroke, the better the resin fluidity.
Heat resistance: refers to the property of a substance that can maintain its excellent physical and mechanical properties under the condition of being heated.
Compatibility of the resin system: and (3) observing the microscopic uniformity of the cured resin under SEM by taking the cross section of the base material, wherein if the resin agglomeration phenomenon occurs, the resin is incompatible.
The following is a specific embodiment of the present invention.
Examples 1 to 13
A thermosetting resin composition comprises the following components in parts by weight: the sources and choices of the components in the block copolymer rubber, the unsaturated diene rubber, the N-substituted maleimide copolymer, the small molecule cross-linking agent, the flame retardant, the filler and the accelerator are shown in Table 1, and the contents of the components are shown in Table 2.
TABLE 1 sources of feed Components in examples 1-13 and comparative examples 1-3
TABLE 2 component proportion data for examples 1-13 and comparative examples 1-3
TABLE 2 compositional ratio data for examples 1 to 13 and comparative examples 1 to 3 (Table continuation)
TABLE 3 compositional proportions data for examples 1 to 13 and comparative examples 1 to 3 (Table continuation)
TABLE 4 compositional ratio data for examples 1 to 13 and comparative examples 1 to 3 (Table continuation)
Example 11
A thermosetting resin composition comprises the following components in parts by weight: the rubber comprises block copolymer rubber, unsaturated diene rubber, N-substituted maleimide copolymer, a small molecular cross-linking agent, a flame retardant, a filler and an accelerator, wherein the content of each component is shown in Table 2.
Wherein, the adopted filler is high Dk filler (Dk >10), which leads to the improvement of dielectric loss.
Example 12
A thermosetting resin composition comprises the following components in parts by weight: the rubber comprises block copolymer rubber, unsaturated diene rubber, N-substituted maleimide copolymer, a small molecular cross-linking agent, a flame retardant, a filler and an accelerator, wherein the content of each component is shown in Table 2.
The block copolymer rubber is a linear triblock copolymer taking styrene as a terminal segment and polybutadiene and isoprene as middle segments, the number average molecular weight of the block copolymer rubber is 5000, and the content of the styrene segment is 10%; the unsaturated diene rubber is styrene-isoprene copolymer and divinylbenzene-isoprene copolymer, wherein the 1, 4-cis double bond structure accounts for 60%, and the number average molecular weight is 1000; the monomer of the N-substituted maleimide copolymer is styrene, N-phenylmaleimide and unsaturated anhydride, wherein the mole fraction of the styrene is 30 parts, the mole fraction of the unsaturated anhydride is 1 part, the mole fraction of the N-substituted maleimide is 30 parts, the micromolecule crosslinking agent is a mixture of triallyl isocyanurate, triallyl cyanurate, trimethallyl isocyanurate and trihydroxyethyl isocyanurate, the flame retardant is a bromine-containing flame retardant, the filler is spherical silica micropowder, the filler is a low Dk material, and the accelerator is a peroxide accelerator.
Example 13
A thermosetting resin composition comprises the following components in parts by weight: the rubber comprises block copolymer rubber, unsaturated diene rubber, N-substituted maleimide copolymer, a small molecular cross-linking agent, a flame retardant, a filler and an accelerator, wherein the content of each component is shown in Table 2.
The block copolymer rubber is a linear triblock copolymer taking styrene as a terminal segment and polybutadiene and isoprene as middle segments, the number average molecular weight of the block copolymer rubber is 15000, and the content of the styrene segment is 50%; the unsaturated diene rubber is styrene-isoprene copolymer and divinylbenzene-isoprene copolymer, wherein the 1, 4-cis double bond structure accounts for 95%, and the number average molecular weight is 10000; the monomer of the N-substituted maleimide copolymer is styrene, N-phenyl maleimide and unsaturated acid anhydride, wherein the mole fraction of the styrene is 60 parts, the mole fraction of the unsaturated acid anhydride is 20 parts, the mole fraction of the N-substituted maleimide is 70 parts, the micromolecule cross-linking agent is a mixture of tert-butyl styrene, diallyl isophthalate, diallyl phthalate, trimethylolpropane triacrylate or pentaerythritol tetraacrylate, the flame retardant is a bromine-containing flame retardant, the filler is spherical silicon micropowder, the filler is a low Dk material, and the accelerator is a peroxide accelerator.
Comparative example 1
Comparative example 1 is a resin composition comprising an unsaturated diene rubber, an N-substituted maleimide copolymer, a small molecule crosslinking agent, a flame retardant, a filler and an accelerator, the contents and selection of which are shown in Table 2.
The main difference between comparative example 1 and the examples is that no block copolymer rubber was added in the comparative example, and it can be seen from the test data in table 1 that the glass transition temperature of the resin composition in comparative example 1 is 135 ℃, which is much lower than that of the resin composition in any of the examples of the present invention, and further, the peel strength of the copper foil is low, indicating that the mechanical properties are not good, and the delamination time at 288 ℃ is short, indicating that the thermal stability is poor. Therefore, the addition of the block copolymer rubber to the resin base material is advantageous for improving the heat resistance and peel strength of the resin composition.
Comparative example 2
Comparative example 2 is a resin composition whose raw material composition includes a block copolymer rubber, an unsaturated diene rubber, BDM type maleimide, a small molecule crosslinking agent, a flame retardant, a filler and an accelerator, and the contents and selections of the respective components are shown in table 2.
Comparative example 2 is different from examples mainly in that the N-substituted maleimide copolymer is replaced with BDM type maleimide, and as can be seen from the test data in table 1, the glass transition temperature of the resin composition in comparative example 2 is 165 ℃, which is lower than that of the resin composition in any of the examples of the present invention, and the resin composition has high dielectric loss, high energy consumption, poor resin flowability and poor heat resistance, indicating that the addition of the N-substituted maleimide copolymer can reduce the heat resistance and peel strength of the resin composition.
Comparative example 3
Comparative example 3 is a resin composition, the raw material composition of which includes block copolymer rubber, unsaturated diene rubber, styrene, maleic anhydride copolymer, small molecule cross-linking agent, flame retardant, filler and accelerator, and the content and selection of each component are shown in table 2.
The main difference between comparative example 3 and the examples is that, in place of the N-substituted maleimide copolymer, styrene and maleic anhydride copolymer is used, and it can be seen from the test data in table 1 that the compatibility of the resin composition in comparative example 3 is poor, and in addition, the peel strength of the resin composition is extremely low, and the delamination time at 288 ℃ is very short, therefore, the addition of the N-substituted maleimide copolymer is very important, and the synergy between the maleimide structure and the maleic anhydride structure and the resin substrate is beneficial to improving the mechanical properties and dielectric properties of the resin composition.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (8)
1. The thermosetting resin composition is characterized by comprising the following components in parts by weight:
5-30 parts of N-substituted maleimide copolymer,
30-70 parts of block copolymer rubber,
10 to 50 parts of an unsaturated diene rubber,
10-30 parts of a small molecular crosslinking agent;
the molecular general formula of the N-substituted maleimide copolymer is as follows:
in the formula, R groups are methyl, ethyl, isopropyl, cyclohexyl, phenyl, benzyl, phenylethyl, phenyl vinyl, p-hydroxyphenyl, biphenyl and naphthalene ring groups;
the block copolymer rubber is a linear triblock copolymer taking styrene as a terminal segment and polybutadiene or isoprene as a middle segment, the number average molecular weight of the block copolymer rubber is 5000-150000, and the styrene segment accounts for 10-50% of the total mass of the block copolymer rubber.
2. The thermosetting resin composition as claimed in claim 1, wherein the N-substituted maleimide copolymer is copolymerized from the following monomers in molar parts: 30-60 parts of styrene monomer, 30-70 parts of N-substituted maleimide and 1-20 parts of unsaturated anhydride.
3. The thermosetting resin composition of claim 1, wherein in the molecular formula of the N-substituted maleimide copolymer, x, y and z are molar ratios of the styrene monomer, the N-substituted maleimide and the unsaturated acid anhydride, respectively, and x: y: z = 0.3-0.6: 0.3-0.7: 0.01-0.2.
4. The thermosetting resin composition as claimed in claim 1, wherein the polymerized monomer of the unsaturated diene rubber comprises one or more of butadiene or isoprene which is not modified or contains a modified group, and the modified group is one or more of epoxy group, maleic anhydride, acrylate, hydroxyl group or carboxyl group; wherein the number average molecular weight of the diene rubber is 500 to 20000, and the unsaturated double bond structure accounts for 60 to 99% of the mass of the main chain of the diene rubber.
5. The thermosetting resin composition as claimed in claim 4, wherein the unsaturated diene rubber is one or more selected from polybutadiene resin, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, divinylbenzene-butadiene copolymer, divinylbenzene-isoprene copolymer, styrene-butadiene-divinylbenzene copolymer and styrene-isoprene-divinylbenzene copolymer.
6. The thermosetting resin composition of claim 1, wherein the small molecule cross-linking agent is selected from one or more of triallyl isocyanurate, triallyl cyanurate, trimethylallylisocyanurate, trimethylallylcyanurate, trishydroxyethyl isocyanurate, t-butyl styrene, diallyl isophthalate, diallyl phthalate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate.
7. The thermosetting resin composition of claim 1, further comprising a flame retardant, a filler and an accelerator.
8. Use of the thermosetting resin composition claimed in claim 1 for producing adhesive sheets, metal-clad laminates and printed wiring boards.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910659226.5A CN110330759B (en) | 2019-07-22 | 2019-07-22 | Thermosetting resin composition and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910659226.5A CN110330759B (en) | 2019-07-22 | 2019-07-22 | Thermosetting resin composition and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110330759A CN110330759A (en) | 2019-10-15 |
| CN110330759B true CN110330759B (en) | 2022-01-11 |
Family
ID=68146981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910659226.5A Active CN110330759B (en) | 2019-07-22 | 2019-07-22 | Thermosetting resin composition and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110330759B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2613819A (en) * | 2021-12-15 | 2023-06-21 | Univ Stellenbosch | Terpolymers for lipid nanodisc formation |
| CN116200077B (en) * | 2023-03-13 | 2023-11-03 | 黄山晖瑞新材料科技有限公司 | Anticorrosion waterproof coating based on various main chain saturated resins and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5223568A (en) * | 1987-05-14 | 1993-06-29 | Rogers Corporation | Process for forming hard shaped molded article of a cross-linked liquid polybutadiene or polyisoprene resin and a butadiene or isoprene containing solid polymer and resulting articles |
| JP2007154010A (en) * | 2005-12-02 | 2007-06-21 | Kuraray Co Ltd | Thermoplastic elastomer composition for diene rubber adhesion |
| CN108329676A (en) * | 2017-01-20 | 2018-07-27 | 台燿科技股份有限公司 | Resin composition, and prepreg, metal foil laminate and printed wiring board produced using the same |
| CN109504062A (en) * | 2018-11-22 | 2019-03-22 | 南亚塑胶工业股份有限公司 | A kind of compositions of thermosetting resin |
-
2019
- 2019-07-22 CN CN201910659226.5A patent/CN110330759B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5223568A (en) * | 1987-05-14 | 1993-06-29 | Rogers Corporation | Process for forming hard shaped molded article of a cross-linked liquid polybutadiene or polyisoprene resin and a butadiene or isoprene containing solid polymer and resulting articles |
| JP2007154010A (en) * | 2005-12-02 | 2007-06-21 | Kuraray Co Ltd | Thermoplastic elastomer composition for diene rubber adhesion |
| CN108329676A (en) * | 2017-01-20 | 2018-07-27 | 台燿科技股份有限公司 | Resin composition, and prepreg, metal foil laminate and printed wiring board produced using the same |
| CN109504062A (en) * | 2018-11-22 | 2019-03-22 | 南亚塑胶工业股份有限公司 | A kind of compositions of thermosetting resin |
Non-Patent Citations (1)
| Title |
|---|
| 关于苯乙烯-马来酸酐-马来酰亚胺衍生物在覆铜板中的应用研究;马建;《第十八届中国覆铜板技术•市场研讨会论文集》;20171130;157-158,160-161 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110330759A (en) | 2019-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7170136B2 (en) | High frequency resin composition and use thereof | |
| JP5093059B2 (en) | Resin composition, prepreg, laminate and printed circuit board | |
| JP7117498B2 (en) | Thermosetting resin composition, resin sheet, resin-coated metal foil, metal-clad laminate, and printed wiring board | |
| KR101716990B1 (en) | Polyphenyl ether resin composite and prepreg and copper clad laminate made of polyphenyl ether resin composite | |
| KR101321235B1 (en) | Thermocurable resin composition comprising semi-ipn-type complex, and varnish, prepreg and metal-clad laminate sheet using the same | |
| US10584222B2 (en) | Resin composition and pre-preg and laminate using the composition | |
| CN111635626B (en) | Resin composition, prepreg, laminated sheet, preparation method of prepreg, preparation method of laminated sheet and application of laminated sheet | |
| JP5303852B2 (en) | Semi-IPN type composite resin composition and varnish, prepreg and metal-clad laminate using the same | |
| TWI704185B (en) | Resin composition, prepreg for printed circuit and metal-clad laminate | |
| CN111285980A (en) | Halogen-free low dielectric resin composition, prepreg, metal foil laminate and printed wiring board using the same | |
| CN110655775A (en) | Resin composition, and prepreg, laminated board and printed wiring board provided with same | |
| JP2011225639A (en) | Thermosetting resin composition, and resin varnish, prepreg and metal-clad laminate using the same | |
| CN110330759B (en) | Thermosetting resin composition and application thereof | |
| JP2022022090A (en) | Resin composition for high-frequency substrates, and metal laminate board | |
| CN114231014A (en) | Resin composition for preparing heat-conducting high-frequency copper-clad plate adhesive and preparation method thereof | |
| JP5374891B2 (en) | Process for producing resin varnish containing semi-IPN type thermosetting resin, resin varnish for printed wiring board, prepreg and metal-clad laminate | |
| JP5303853B2 (en) | Thermosetting resin composition of IPN type composite and varnish, prepreg and metal-clad laminate using the same | |
| TWI782579B (en) | A resin composition and its products | |
| JP4255759B2 (en) | Polyphenylene ether resin composition, prepreg containing the same, laminate, copper-clad laminate and printed wiring board | |
| CN114106267A (en) | Thermosetting resin composition containing styrene compound, preparation method and application thereof | |
| CN113121981B (en) | Resin composition, prepreg and insulating plate using same | |
| TW202214809A (en) | Adhesive composition, adhesive sheet, multilayer body and printed wiring board | |
| JP2004231781A (en) | Curable polyphenylene ether-based resin material | |
| TWI763402B (en) | A kind of thermosetting resin composition and its application | |
| WO2022244726A1 (en) | Resin composition, prepreg using same, film provided with resin, metal foil provided with resin, metal-clad laminate, and wiring 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 |