KR102523921B1 - High-frequency resin composition and its application - Google Patents

Abstract

The present invention relates to a high frequency resin composition and its application, wherein the high frequency resin composition includes 25 to 50 parts of a modified polyphenyl ether resin, 15 to 40 parts of a block copolymer rubber, 10 to 50 parts of an unsaturated diene rubber, and N-substituted maleimide. It consists of 5 to 30 parts of copolymer, 10 to 30 parts of low molecular crosslinking agent, flame retardant, filler and accelerator. Compared with the prior art, the present invention has the advantages of significantly improving the glass transition temperature and peel strength of the material by introducing the N-substituted maleimide copolymer into the rubber system, as well as having a small dielectric loss and excellent heat resistance.

Description

High-frequency resin composition and its application

The present invention relates to the field of high-frequency and high-speed technology, and particularly to a high-frequency resin composition and its applications.

With the advent of the 5G era, terminal applications and network speeds continue to increase, and data transmission speeds between devices have already increased from hundreds of Mbps to 20Gbps. Currently, the PCB industry technology, regardless of soft board and hard board, is developing in the direction of high-frequency, high-speed and high-density packaging methods. In response to the product development trend toward light, thin, portable and multi-functional, The requirements for manufacturing methods are also becoming increasingly stringent. According to the requirements of high frequency, high speed and miniaturization, high frequency transmission and low loss materials will completely replace transmission lines, among which the most important material properties require ultra-low dielectric properties, high heat resistance and excellent flame retardancy.

In a high frequency signal transmission circuit, electrical signal transmission loss is expressed as the sum of dielectric loss, conductor loss and radiation loss. The higher the frequency of the electrical signal, the greater the dielectric loss, conductor loss and radiation loss. Therefore, as an insulator for high-frequency signal transmission, an insulating material having a low dielectric loss factor can be selected in order to suppress an increase in dielectric loss.

Currently, insulating materials for transmitting high-frequency signals are generally made of polytetrafluoroethylene (PTFE) materials or hydrocarbon resin materials, and since PTFE materials are difficult to process, hydrocarbon materials are widely used in the high-frequency field. Hydrocarbon resins made of block copolymer rubber or unsaturated olefin resins and fillers have disadvantages such as low peel strength, poor heat resistance, and low bending strength, and the manufactured adhesive sheet may have adhesive problems due to the rubber material. Therefore, it affects the production, storage and transportation of adhesive sheets. Therefore, it is necessary to develop a high-frequency substrate material having high heat resistance, high peel strength, low dielectric loss, and low expansion coefficient.

An object of the present invention is to provide a high-frequency resin composition based on a hydrocarbon resin to overcome the problems existing in the prior art.

The object of the present invention can be realized through the following technical solutions.

The high-frequency resin composition is a component of the weight part content,

25 to 50 parts of modified polyphenyl ether resin;

15 to 40 parts of block copolymer rubber;

10 to 50 parts of unsaturated diene rubber;

5 to 30 parts of N-substituted maleimide copolymer;

It contains 10 to 50 parts of a low molecular crosslinking agent.

<N-substituted maleimide copolymer>

The N-substituted maleimide copolymer is composed by copolymerization of 30 to 60 parts of styrene monomer, 30 to 70 parts of N-substituted maleimide, and 1 to 20 parts of unsaturated acid anhydride in terms of molar content, and styrene, N-substituted maleimide , The molecular formula of the maleic anhydride copolymer is shown below.

In the formula, x, y, z are the molar ratio of styrene monomer, N-substituted maleimide, and unsaturated acid anhydride, respectively, and x:y:z = 0.3 to 0.6: 0.3 to 0.7: 0.01 to 0.2.

The R group in the molecular formula of the N-substituted maleimide copolymer is preferably a methyl, ethyl, isopropyl, cyclohexyl, phenyl, benzyl, phenylethyl, phenylvinyl, p-hydroxyphenyl, biphenyl, naphthalene ring group, Among them, methyl, phenyl, and phenylvinyl are preferable, and the molecular formulas are respectively as follows.

) N-methyl maleimide copolymer:

b) N-phenyl maleimide copolymer:

c) N-phenyl vinyl maleimide copolymer:

The N-substituted maleimide copolymer used in the present invention is a copolymer (SMI) of styrene, N-substituted maleimide, and maleic anhydride, and can improve compatibility between polar and non-polar resins, and the styrene segment is a rubber It has excellent compatibility with materials, and maleimide and maleic anhydride segments have excellent compatibility with polar resins, and at the same time can improve interfacial strength, improve peel strength with metal foil and bonding strength with glass fiber bundles. can make it The N-substituted maleimide copolymer has excellent heat resistance and excellent thermal stability (does not decompose at 350 ° C), and when used in combination with hydrocarbon resins, it is used as a heat-resistant modifier for hydrocarbon materials to improve the glass transition temperature and heat resistance of sheet materials. let it

Here, the content of the N-substituted maleimide copolymer is preferably 5 to 30 parts, and if the added N-substituted maleimide copolymer is too small, the improvement in heat resistance of the material is relatively limited, and the peel strength is poor. relatively low If too much of the added N-substituted maleimide copolymer is added, the dielectric performance is increased to some extent and the water absorption rate is also significantly increased.

The molecular weight of the N-substituted maleimide copolymer is not particularly limited, and the preferred range of the general number average molecular weight may be 2000 to 200000, where the most preferred range is 5000 to 50000, and has rapid and excellent solubility in resin compositions; At the same time, it is possible to ensure the reliable heat resistance and thermal stability of the material.

<Block Copolymer Rubber>

The block copolymer rubber is a linear triblock copolymer having styrene as an end segment and polybutadiene and isoprene as a middle segment, a number average molecular weight of 5000 to 150000, and a styrene segment of the total mass of the block copolymer rubber It accounts for 10 to 50%.

The thermosetting resin composition includes a block copolymer rubber having a relatively high molecular weight, and the block copolymer is a linear triblock copolymer having styrene as a terminal segment and polybutadiene or isoprene as a middle segment. In general, it does not have a double bond structure and has relatively low reactivity. The block copolymer rubber has low polarity characteristics and can exhibit very low dielectric constant and low dielectric loss required for high-frequency and high-speed materials, but the material often has poor heat resistance and relatively low peel strength with metal foil. When these low polar materials are used with small amounts of polar materials such as resins such as polyphenyl ethers, cyanate esters and maleimides, a good balance of performance can be obtained. Therefore, the block copolymer rubber is one of the main components of the composition, and the selection of the ratio between the styrene segment and 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 to 150000, and when the copolymer molecular weight is less than 5000, the material itself is too soft and cannot exert a clear reinforcement effect on the resin substrate, and the semi-cured sheet is easily A sticking problem occurs. When the copolymer molecular weight exceeds 150000, the block copolymer molecular weight is too high, the resin has poor solubility in the solvent, the viscosity is too high, and the processing and production conditions are not good, and the semi-cured sheet has good fluidity when pressed. This is detrimental to the production of the substrate and the filling of the circuit board and the patterning features to flow into the adjacent layer.

The ratio of the styrene segment to the total mass of the block copolymer rubber is preferably 10 to 50%, and when the ratio of the styrene segment is less than 10%, the glass transition temperature of the material is too low. When the ratio of the styrene segment exceeds 50%, the peel strength between the substrate and the metal foil is lowered. When the mass ratio of the styrene segments in the block copolymer is 10 to 50%, for example, each performance such as dielectric performance, glass transition temperature, peel strength, heat resistance and the like has excellent balance.

<Unsaturated diene rubber>

The polymerized monomer of the unsaturated diene-based rubber includes at least one of unmodified or modified group-containing butadiene or isoprene, and the modifying group is at least one selected from epoxy, maleic anhydride, acrylate, hydroxy group, or carboxyl group. . Here, 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 main chain mass of the diene rubber.

Specifically, the diene rubber is polybutadiene or polyisoprene containing a side chain or a double bond structure in the main chain, preferably 1,2-polybutadiene, cis-1,4-polybutadiene, 1,2- polyisoprene, cis-1,4-polyisoprene.

More specifically, the unsaturated diene-based rubber is polybutadiene resin, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, divinylbenzene-butadiene copolymer, divinylbenzene-isoprene copolymer, styrene-butadiene-di It is one or more types selected from a vinylbenzene copolymer or a 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 molecular weight. When the molecular weight of the unsaturated polymer resin is less than 500, there is no significant improvement in dielectric performance reduction, and when the molecular weight of the unsaturated polymer resin exceeds 20000, the glass transition temperature and peel strength of the resin system are lowered. The unsaturated double bond structure in the diene rubber accounts for 60 to 99% of the main chain mass of the diene rubber, and if the unsaturated double bond content is too low, there are too few groups causing crosslinking reactions with other thermosetting resins, and the peel strength is low. , the glass transition temperature is low, and the mechanical strength is not good.

Here, the unsaturated diene-based rubber modifying group is at least one selected from an epoxy group, maleic anhydride, (methyl) acrylate, hydroxyl group or carboxyl group, more preferably unsaturated butadiene modified with maleic anhydride or (methyl) acrylate. It is a polymer based The modified unsaturated diene-based rubber is advantageous in further improving the peel strength between the resin and the metal foil and the bonding strength between the resin interface layer.

<Modified polyphenyl ether resin>

The modified polyphenyl ether resin is prepared by modifying the terminal group of the polyphenyl ether resin with a vinyl group or a methacrylate group, and the number average molecular weight of the modified polyphenyl ether resin is preferably 500 to 10,000.

The diene rubber having an unsaturated double bond structure can be combined with the modified polyphenyl ether resin to further reduce the dielectric constant and dielectric loss of the material, and at the same time improve the adhesive strength between the resin and the copper foil, and improve the bonding strength between the resin interface and the metal layer. Reliability can be improved.

The number average molecular weight of the modified polyphenyl ether is preferably 500 to 10000, more preferably 1000 to 5000. When the molecular weight is less than 500, there are too many reactive vinyl groups, making it difficult to obtain relatively low dielectric properties, and the reaction rate is too fast to control. When the molecular weight exceeds 10000, the melt viscosity of the polyphenyl ether resin is too high, the compatibility with other resins is low, and the produced material easily deteriorates in appearance.

The modified polyphenyl ether is polyphenyl ether modified by a vinyl group or end-capped by methacrylate, and Sabic SA-9000, which is a modified polyphenyl ether resin end-capped by methacrylate, is exemplified, , and also Mitsubishi Chemical OPE-2ST, which is a modified polyphenylether resin end-capped with a phenyl vinyl group.

<Low Molecular Crosslinking Agent>

The resin composition further comprises a low-molecular cross-linking agent, the low-molecular cross-linking agent mainly improves the cross-linking density of the block copolymer rubber, the unsaturated diene rubber and the N-substituted maleimide copolymer, improves the compactness of the cross-linked network, and improves the glass transition temperature of the material. and used to improve heat resistance.

The low molecular weight crosslinking agent is preferably triallyl isocyanurate, triallyl cyanurate, trimethylallyl isocyanurate, trimethylallyl cyanurate, trihydroxyethyl isocyanurate, tert-butyl styrene, diallyl isophthalate , diallyl phthalate, trimethanol propane triacrylate, or pentaerythritol tetraacrylate.

In addition, this patent further includes flame retardants, fillers and accelerators.

<Flame retardant>

The flame retardant used in the present invention is preferably one or a mixture of two selected from bromine-containing flame retardants and phosphorus-containing flame retardants, and in order to adapt to a low dielectric resin system, all of the bromine-containing flame retardants or phosphorus-containing flame retardants are in the resin system. It is preferably insoluble and is generally selected from addition-type bromine-based flame retardants or phosphorus-based flame retardants that do not have reactivity with polyphenyl ether resins and other resins and do not reduce heat resistance and dielectric properties.

The addition-type bromine-containing flame retardant of the present invention is at least one selected from decabromodiphenyl oxide, decabromodiphenylethane, brominated styrene or decabromodiphenyl oxide, and ethylenebistetrabromophthalimide. Added phosphorus-containing flame retardants include tris(2,6-dimethylphenyl)phosphorus, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphophenanthrene-10- oxide, at least one selected from 2,6-bis(2,6-dimethylphenyl)phosphorylbenzene or 10-phenyl-9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide am.

<filler>

The filler used in the present invention is not particularly limited, and aluminum nitride, aluminum borate, magnesium oxide, magnesium carbonate, boron nitride, crystalline silica, synthetic silica, hollow silica, spherical silica, fused silica, talcum powder, alumina, barium sulfate, and at least one selected from barium titanate, strontium titanate, calcium carbonate, and tertania.

<Accelerator>

In order to accelerate the reaction of the resin composition, increase the crosslinking density, and improve the glass transition temperature and heat resistance, the reaction may be further accelerated by using an accelerator (initiator).

The accelerator used in the present invention is preferably an organic peroxide radical initiator, di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxyneodecanoate, tert-butyl peroxyneo Decanoate, tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-3,5,5-trimethyl hexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzo Eight, 1,1-di-tert-butyl peroxy-3,5,5-trimethyl cyclohexane, 1,1-di-tert-butyl peroxy cyclohexane, 2,2-di(tert-butyl peroxy) Butane, bis(4-tert-butyl cyclohexyl)peroxy dicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, dipentahexyl peroxide, dicumyl peroxide, bis(t-butylperoxyisopropyl) Benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne, diisopropylbenzene hydroperoxide, Isopropylbenzene hydroperoxide, t-amyl hydroperoxide, t-butyl hydroperoxide, t-butylcumylperoxide, diisopropylbenzene hydroperoxide, peroxycarbonate-t-butyl-2-ethylhexanoate , t-butyl peroxy 2-ethylhexyl carbonate, n-butyl 4,4-di(t-butyl peroxy) valerate, methyl ethyl ketone peroxide, and cyclohexane peroxide.

The high-frequency resin composition of the present invention can be used to manufacture adhesive sheets, metal-clad laminates, and printed circuit boards.

Manufacture of adhesive sheet: In the present invention, a high frequency resin composition is applied to reinforcing fibers to form a semi-cured sheet. The reinforcing fiber may be a reinforcing fabric formed by weaving organic or inorganic fibers, preferably a fiber cloth woven with glass fibers, and E-glass, T-glass, NE-glass, L-glass and Q-glass. include

Manufacture of metal-clad laminate: The metal-clad laminate is manufactured by laminating one or at least two metal foils using the pressure-sensitive adhesive sheet and bonding them by thermal compression. The metal foil is preferably copper foil, more preferably electrolytic copper foil, and the surface roughness (Rz) thereof is preferably less than 5 μm. For example, it may be RTF copper foil, VLP copper foil, HVLP copper foil, or HVLP2 copper foil, The signal loss problem of the high-speed circuit board can be further improved.

Manufacture of printed circuit board: A printed circuit board includes at least one sheet of the adhesive sheet or the metal clad laminate. Since the resin composition of the present invention has excellent mechanical strength and toughness, excellent glass transition temperature, peel strength and low dielectric performance, it is suitable for processing for the manufacture of multilayer printed circuit boards.

In the present invention, an N-substituted maleimide-based copolymer is used as a rubber heat-resistant modifier and a compatibilizer in a resin composition, and an N-substituted maleimide structure and maleic anhydride are included in the triblock copolymer, and an N-substituted maleimide copolymer is included. The mid-based copolymer was used for a resin base material of a vinyl group-containing block copolymer rubber and an unsaturated diene rubber, and the maleimide structure was used to improve the heat resistance of the vinyl segment and enhance the heat resistance performance of the resin base material. In addition, the maleic anhydride structure also enhances the polarity of the vinyl segment.

Compared with the prior art, the present invention has the following advantages.

(1) By using an N-substituted maleimide copolymer, the heat resistance of the resin substrate is improved, the compatibility with the inorganic material and the flame retardant is improved, and the interfacial peel strength between the high resin substrate and the metal foil is improved. When the resin composition of the present invention is used as an insulator, it has excellent dielectric and mechanical performance.

(2) Optimize the selection of unsaturated diene rubber in the resin base material, and use a high content of unsaturated double bond liquid polybutadiene to further improve the electrical insulation properties, peel strength and glass transition temperature of the resin composition.

(3) A modified polyphenyl ether resin is added to the resin substrate to further improve the heat resistance and copper foil peel strength of the high-frequency resin composition.

Hereinafter, the present invention will be described in detail in combination with specific examples. The following examples are only intended to help those skilled in the art to fully understand the present invention, and do not limit the present invention in any form. It should be pointed out that those skilled in the art may make some changes and modifications without departing from the spirit of the present invention. All of these changes and modifications fall within the protection scope of the present invention.

The high-frequency resin composition includes 15 to 40 parts of block copolymer rubber, 25 to 50 parts of modified polyphenyl ether resin, 10 to 50 parts of unsaturated diene rubber, and 5 to 30 parts of N-substituted maleimide copolymer. ，Includes 10 to 50 parts of low molecular crosslinking agent, flame retardant, filler and accelerator.

<N-substituted maleimide copolymer>

The N-substituted maleimide copolymer is composed by copolymerization of 30 to 60 parts of styrene monomer, 30 to 70 parts of N-substituted maleimide, and 1 to 20 parts of unsaturated acid anhydride in terms of molar content, and styrene, N-substituted maleimide , The molecular formula of the maleic anhydride copolymer is shown below.

In the formula, x, y, z are the molar ratio of styrene monomer, N-substituted maleimide, and unsaturated acid anhydride, respectively, and x:y:z = 0.3 to 0.6: 0.3 to 0.7: 0.01 to 0.2.

The R group in the molecular formula of the N-substituted maleimide copolymer is methyl, ethyl, isopropyl, cyclohexyl, phenyl, benzyl, phenylethyl, phenylvinyl, p-hydroxyphenyl, biphenyl, or naphthalene ring group, preferably They are methyl, phenyl, and phenylvinyl, and the molecular formulas are respectively as follows.

a) N-methyl maleimide copolymer:

b) N-phenyl maleimide copolymer:

c) N-phenylvinyl maleimide copolymer:

<Block Copolymer Rubber>

The high-frequency resin composition includes a block copolymer rubber having a relatively high molecular weight, and the block copolymer rubber is a linear triblock copolymer having styrene as an end segment and polybutadiene and isoprene as a middle segment, and has a number average molecular weight of 5000. to 150,000, and the styrene segment accounts for 10 to 50% of the total mass of the block copolymer rubber. These block copolymers generally do not have a double bond structure and have relatively low reactivity. In the embodiment of the present invention, 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), and hydrogenated styrene-butadiene/isoprene-styrene (HSBIS).

<Unsaturated diene rubber>

The polymerized monomer of the unsaturated diene-based rubber in the resin composition includes at least one of unmodified or modified group-containing butadiene or isoprene, and the diene-based rubber includes polybutadiene containing a side chain or a double bond structure in the main chain, It is polyisoprene, Preferably they are 1,2-polybutadiene, cis-1,4-polybutadiene, 1,2-polyisoprene, and cis-1,4-polyisoprene.

Here, the unsaturated diene-based rubber modifying group is at least one selected from an epoxy group, maleic anhydride, (methyl) acrylate, hydroxyl group or carboxyl group, more preferably unsaturated butadiene modified with maleic anhydride or (methyl) acrylate. It is a polymer based The modified unsaturated diene-based rubber is advantageous in further improving the peel strength between the resin and the metal foil and the bonding strength between the resin interface layer.

Optional examples of the unsaturated diene rubber include polybutadiene resin, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, divinylbenzene-butadiene copolymer, divinylbenzene-isoprene copolymer, styrene-butadiene-divinylbenzene It is at least one of a copolymer or a styrene-isoprene-divinylbenzene copolymer.

<Modified polyphenyl ether resin>

The modified polyphenyl ether resin is prepared by modifying the terminal group of the polyphenyl ether resin with a vinyl group or a methacrylate group, and its molecular weight can be selected from 500 to 10,000.

<Low Molecular Crosslinking Agent>

Selective examples of the low molecular weight crosslinking agent are triallyl isocyanurate, triallyl cyanurate, trimethylallyl isocyanurate, trimethylallyl cyanurate, trihydroxyethyl isocyanurate, tert-butyl styrene, diallyl isophthalate , diallyl phthalate, trimethylolpropane triacrylate, or pentaerythritol tetraacrylate.

In addition, this embodiment patent further includes a flame retardant, a filler and an accelerator.

<Flame retardant>

The flame retardant used in this embodiment is preferably one or a mixture of two selected from bromine-containing flame retardants and phosphorus-containing flame retardants, and in order to adapt to the low dielectric resin system, the bromine-containing flame retardants or phosphorus-containing flame retardants are all resin systems. It is preferably selected from bromine-based flame retardants and phosphorus-based flame retardants that are not reactive with polyphenyl ether resins and other resins and do not reduce heat resistance and user characteristics.

The addition-type bromine-containing flame retardant of the present invention is preferably at least one selected from decabromodiphenyl oxide, decabromodiphenylethane, brominated styrene or decabromodiphenyl oxide, and ethylenebistetrabromophthalimide. Added phosphorus-containing flame retardants include tris(2,6-dimethylphenyl)phosphorus, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9-oxa-10-phosphophenanthrene-10- oxide, at least one selected from 2,6-bis(2,6-dimethylphenyl)phosphorylbenzene or 10-phenyl-9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide am.

<filler>

The filler used in the present invention is not particularly limited, and aluminum nitride, aluminum borate, magnesium oxide, magnesium carbonate, boron nitride, crystalline silica, synthetic silica, hollow silica, spherical silica, fused silica, talcum powder, alumina, barium sulfate, It is one or more types selected from barium titanate, strontium titanate, calcium carbonate, and titania.

<Accelerator>

In order to accelerate the reaction of the resin composition, increase the crosslinking density, and improve the glass transition temperature and heat resistance, the reaction may be further accelerated by using an accelerator (initiator).

The accelerator used in the present invention is preferably an organic peroxide radical initiator, di-tert-butyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, cumyl peroxyneodecanoate, tert-butyl peroxyneo Decanoate, tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-3,5,5-trimethyl hexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzo Eight, 1,1-di-tert-butyl peroxy-3,5,5-trimethyl cyclohexane, 1,1-di-tert-butyl peroxy cyclohexane, 2,2-di(tert-butyl peroxy) Butane, bis(4-tert-butyl cyclohexyl)peroxy dicarbonate, hexadecyl peroxydicarbonate, tetradecyl peroxydicarbonate, dipentahexyl peroxide, dicumyl peroxide, bis(t-butylperoxyisopropyl) Benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne, diisopropylbenzene hydroperoxide, Isopropylbenzene hydroperoxide, t-amyl hydroperoxide, t-butyl hydroperoxide, t-butylcumylperoxide, diisopropylbenzene hydroperoxide, peroxycarbonate-t-butyl-2-ethylhexanoate , t-butyl peroxy-2-ethylhexyl carbonate, n-butyl 4,4-di(t-butyl peroxy) valerate, methyl ethyl ketone peroxide, and cyclohexane peroxide.

The high-frequency resin composition of the present invention can be used to manufacture adhesive sheets, metal-clad laminates, and printed circuit boards.

Manufacture of pressure-sensitive adhesive sheet: In this embodiment, a high-frequency resin composition is applied to reinforcing fibers to form a semi-cured sheet. The reinforcing fiber may be a reinforcing fabric formed by weaving organic or inorganic fibers, preferably a fiber cloth woven of glass fibers, and E-glass, T-glass, NE-glass, L-glass and Q-glass. include

Manufacture of metal-clad laminate: The metal-clad laminate is manufactured by laminating one or at least two metal foils using the pressure-sensitive adhesive sheet and bonding them by thermal compression. The metal foil is preferably copper foil, more preferably electrolytic copper foil, and the surface roughness (Rz) thereof is preferably less than 5 μm. For example, it may be RTF copper foil, VLP copper foil, HVLP copper foil, or HVLP2 copper foil, The signal loss problem of the high-speed circuit board can be further improved.

Manufacture of printed circuit board: A printed circuit board includes at least one sheet of the adhesive sheet or the metal clad laminate. The resin composition of this embodiment has excellent mechanical strength and toughness, excellent glass transition temperature, peel strength, and low dielectric performance, and is thus suitable for processing for the manufacture of multilayer printed circuit boards.

The manufacturing method of the high-frequency resin composition according to this embodiment,

(1) preparing materials according to the blending method;

(2) dissolving the block copolymer rubber, the unsaturated diene rubber and the N-substituted maleimide copolymer in a solvent, adding a crosslinking agent, and dispersing to obtain a high frequency resin composition.

Additionally, if a flame retardant, an inorganic filler and an accelerator are included in the composition formulation method, in step (2), the block copolymer rubber, the unsaturated diene rubber and the N-substituted maleimide copolymer are dissolved in a solvent, and the flame retardant, the inorganic filler and the accelerator are dissolved. is added, stirred uniformly, and subjected to dispersion treatment to obtain a low dielectric resin composition.

A performance test is performed on the manufactured copper clad laminate, but the test method is as follows.

Glass transition temperature (Tg): Tested using a DMA instrument, measured according to the DMA test method specified in IPC-TM-650 2.4.24.4.

Z-axis coefficient of thermal expansion (CTE): tested using a TMA instrument, measured according to the TMA test method specified in IPC-TM-650 2.4.24.

Copper peel strength (PS): tested using a Shimadzu tensile machine, measured according to the test method specified in IPC-TM-650 2.4.8.

Dielectric constant (Dk) and dielectric dissipation factor (Df): The dielectric constant and dissipation factor were measured according to the test methods specified in IPC-TM-650 2.5.5.9.

High-pressure cooker cooking experiment (PCT): A high-temperature cooking experiment was conducted at 120 ° C. for the laminate, and measured according to the test method specified in IPC-TM-650 2.6.16.

Layering time at 288° C. (T288): Tested using a TMA instrument, measured according to the test method specified in IPC-TM-650 2.4.24.1.

Flame retardant: Tested and graded according to the material combustibility method specified in UL-94.

Water absorption: measured according to the laminated sheet water absorption test method specified in IPC-TM-650 2.6.2.1.

Resin fluidity: The resin fluidity was measured by a Shimadzu capillary rheometer, for a 2 g resin powder press ingot, the resin was extruded from a small hole at a constant pressure, and evaluated according to the stroke of the resin flowing out of the rheometer. The longer the outflow stroke, the better the resin fluidity.

Heat resistance: Refers to the property that a material can still maintain its excellent physical and mechanical performance even under the condition of receiving heat.

Resin system compatibility: Take a cross section of the substrate and observe the fine uniformity of the cured resin in SEM, if resin agglomeration occurs, it indicates that the resin is not compatible.

Specific implementation conditions of the present invention are as follows.

The high-frequency resin composition includes a modified polyphenyl ether resin, a block copolymer rubber, an unsaturated diene-based rubber, an N-substituted maleimide copolymer, a low molecular weight crosslinking agent, a flame retardant, a filler and an accelerator, as components by weight. The source and selection of each component is as shown in Table 1, and the content of each component is as shown in Table 2.

Table 1: Sources of raw material components of Examples 1 to 13 and Comparative Examples 1 to 3

ingredient company product name (A) modified polyphenyl ether SA-9000 A1 Sabic SA-9000 (B) block copolymer rubber SEBS B1 Kraton G1648 SBS B2 Kraton D1118K (C) unsaturated diene rubber liquid polybutadiene C1 Japanese Soda B-2000 Butadiene-styrene-divinylbenzene terpolymer C2 Cray Valley Ricon257 Maleic anhydride polybutadiene-styrene copolymer C3 Cray Valley Ricon184MA6 Maleic anhydride modified polybutadiene C4 Evonik MA75 (D) N-substituted maleimide copolymer Copolymer of styrene, N-phenyl maleimide and maleic anhydride D1 DENKA MS-NB Copolymer of styrene, N-phenylvinyl maleimide and maleic anhydride D2 self-manufactured SMI BDM type maleimide D3 Japanese KI SMA EF30 Copolymer of styrene and maleic anhydride D4 Cray Valley BMI-H (E) low molecular weight crosslinking agent E1 Japanese Kasei TAIC (F) flame retardant Bromine-containing flame retardant F1 Albemarle HP-8010 Halogen-free flame retardant F2 Otsuka chemical SPDO-100 (G) inorganic filler spherical silica powder G1 DENKA FB-3Y hollow filler G2 3M IM16K High Dk filler G3

) 충전제JINYI(

) filler TiO ₂ /BaTiO ₄ (H) Accelerator H1 Arkema 25B Evaluation results evaluation index test method unit Compatibility (O: means excellent compatibility, X: means not compatible) Tg (glass transition temperature) DMA ℃ TG (coefficient of thermal expansion before glass transition temperature) TMA (Z axis) % PS (copper foil peel strength) HVLP N/cm Dk (dielectric constant) 10 GHz Dielectric Loss (Dk) 10 GHz PCT (Saturated Steam Test) 3hr T288 (288℃ slice time) min flame retardant UL-94 absorption rate % resin fluidity mm heat resistance 5% Td ℃

Table 2: Component blending ratio data of Examples 1 to 13 and Comparative Examples 1 to 3

ingredient Example 1 Example 2 Example 3 Example 4 (A) modified polyphenyl ether SA-9000 A1 40 40 40 40 (B) block copolymer rubber SEBS B1 30 30 30 15 SBS B2 (C) unsaturated diene rubber liquid polybutadiene C1 30 30 30 40 Butadiene-styrene-divinylbenzene terpolymer C2 Maleic anhydride polybutadiene-styrene copolymer C3 Maleic anhydride modified polybutadiene C4 (D) N-substituted maleimide copolymer Copolymer of styrene, N-phenyl maleimide and maleic anhydride D1 5 15 30 15 Copolymer of styrene, N-phenylvinyl maleimide and maleic anhydride D2 BDM type maleimide D3 Copolymer of styrene and maleic anhydride D4 (E) small molecules
cross-linking agent E1 15 15 15 20 (F) flame retardant Bromine-containing flame retardant F1 30 30 30 30 Halogen-free flame retardant F2 (G) inorganic filler spherical silica powder G1 150 150 150 150 hollow filler G2 High Dk filler G3 (H) Accelerator H1 0.7 0.7 0.7 0.7 Evaluation results evaluation index Compatibility (O: means excellent compatibility, X: means not compatible) O O O O Tg (glass transition temperature) 201 207 215 211 TG (coefficient of thermal expansion before glass transition temperature) 2.5 2.3 2.2 2.7 PS (copper foil peel strength) 0.74 0.77 0.77 0.78 Dk (dielectric constant) 3.06 3.13 3.22 3.18 Dielectric Loss (Dk) 0.0025 0.0027 0.0029 0.0028 PCT (Saturated Steam Test) O O O O T288 (288℃ slice time) >60 >60 >60 >60 flame retardant V0 V0 V0 V0 absorption rate 0.03 0.04 0.05 0.05 resin fluidity 13 15 15 15 heat resistance 413 425 435 418

Table 3: Component blending ratio data of Examples 1 to 13 and Comparative Examples 1 to 3 (followed by the table above)

ingredient Example 5 Example 6 Example 7 Example 8 (A) modified polyphenyl ether SA-9000 A1 40 40 40 40 (B) block
copolymer rubber SEBS B1 30 30 30 SBS B2 30 (C) unsaturated diene rubber liquid polybutadiene C1 30 Butadiene-styrene-divinylbenzene terpolymer C2 30 Copolymer of maleic anhydride polybutadiene-styrene C3 30 Maleic anhydride modified polybutadiene C4 30 (D) N-substituted maleimide copolymer Copolymer of styrene, N-phenyl maleimide and maleic anhydride D1 15 15 15 Copolymer of styrene, N-phenylvinyl maleimide and maleic anhydride D2 15 BDM type maleimide D3 Copolymer of styrene and maleic anhydride D4 (E) small molecules
cross-linking agent E1 15 15 15 15 (F) flame retardant Bromine-containing flame retardant F1 30 30 30 30 Halogen-free flame retardant F2 (G) inorganic filler spherical silica powder G1 150 150 150 150 hollow filler G2 High Dk filler G3 (H) Accelerator H1 0.7 0.7 0.7 0.7 Evaluation results evaluation index Compatibility (O: means excellent compatibility, X: means not compatible) O O O O Tg (glass transition temperature) 195 212 205 201 TG (coefficient of thermal expansion before glass transition temperature) 2.9 2.3 2.3 2.4 PS (copper foil peel strength) 0.79 0.73 0.77 0.76 Dk (dielectric constant) 3.21 2.95 3.33 3.28 Dielectric Loss (Dk) 0.0029 0.0025 0.0033 0.0032 PCT (Saturated Steam Test) O O O O T288 (288℃ slice time) >60 >60 >60 >60 flame retardant V0 V0 V0 V0 absorption rate 0.04 0.04 0.05 0.05 resin fluidity 15 15 15 15 heat resistance 422 432 427 425

Table 4: Component blending ratio data of Examples 1 to 13 and Comparative Examples 1 to 3 (followed by the table above)

ingredient Example 9 Example 10 Example 11 Example 12 (A) modified polyphenyl ether SA-9000 A1 40 40 40 25 (B) block copolymer rubber SEBS B1 30 30 30 15 SBS B2 (C) unsaturated
diene rubber liquid polybutadiene C1 30 30 30 10 Butadiene-styrene-divinylbenzene terpolymer C2 Maleic anhydride polybutadiene-styrene copolymer C3 Maleic anhydride modified polybutadiene C4 (D) N-substituted maleimide copolymer Copolymer of styrene, N-phenyl maleimide and maleic anhydride D1 15 15 15 5 Copolymer of styrene, N-phenylvinyl maleimide and maleic anhydride D2 BDM type maleimide D3 Copolymer of styrene and maleic anhydride D4 (E) small molecules
cross-linking agent E1 15 15 15 10 (F) flame retardant Bromine-containing flame retardant F1 30 30 Halogen-free flame retardant F2 30 30 (G) inorganic filler spherical silica powder G1 150 100 150 hollow filler G2 30 High Dk filler G3 150 (H) Accelerator H1 0.7 0.7 0.7 0.7 Evaluation results evaluation index Compatibility (O: means excellent compatibility, X: means not compatible) O O O O Tg (glass transition temperature) 202 205 210 201 TG (coefficient of thermal expansion before glass transition temperature) 2.6 2.2 2.1 2.5 PS (copper foil peel strength) 0.75 0.71 0.73 0.74 Dk (dielectric constant) 2.18 2.98 12 2.16 Dielectric Loss (Dk) 0.0029 0.0031 0.0042 0.0030 PCT (Saturated Steam Test) O O O O T288 (288℃ slice time) >60 >60 >60 >60 flame retardant V0 V0 V0 V0 absorption rate 0.04 0.04 0.04 0.04 resin fluidity 15 15 15 15 heat resistance 415 420 428 416

Table 5: Component blending ratio data of Examples 1 to 13 and Comparative Examples 1 to 3 (followed by the table above)

ingredient Example 13 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) modified polyphenyl ether SA-9000 A1 40 40 40 (B) block copolymer rubber SEBS B1 30 30 SBS B2 (C) unsaturated
diene rubber liquid polybutadiene C1 30 30 30 Butadiene-styrene-divinylbenzene terpolymer C2 Maleic anhydride polybutadiene-styrene copolymer C3 Maleic anhydride modified polybutadiene C4 (D) N-substituted maleimide copolymer Copolymer of styrene, N-phenyl maleimide and maleic anhydride D1 15 Copolymer of styrene, N-phenylvinyl maleimide and maleic anhydride D2 BDM type maleimide D3 15 Copolymer of styrene and maleic anhydride D4 15 (E) small molecules
cross-linking agent E1 15 15 15 (F) flame retardant Bromine-containing flame retardant F1 30 30 30 Halogen-free flame retardant F2 (G) inorganic filler spherical silica powder G1 150 150 150 hollow filler G2 High Dk filler G3 (H) Accelerator H1 0.7 0.7 0.7 Evaluation results evaluation index Compatibility (O: means excellent compatibility, X: means not compatible) O O X Tg (glass transition temperature) 185 205 TG (coefficient of thermal expansion before glass transition temperature) 2.8 2.6 PS (copper foil peel strength) 0.55 0.70 0.53 Dk (dielectric constant) 3.25 3.42 Dielectric Loss (Dk) 0.0032 0.0035 PCT (Saturated Steam Test) O O X T288 (288℃ slice time) 32 >60 28 flame retardant V0 V0 V0 absorption rate 0.07 0.05 resin fluidity 15 8 heat resistance 422 405

Example 11

The high-frequency resin composition includes a modified polyphenyl ether resin, a block copolymer rubber, an unsaturated diene rubber, an N-substituted maleimide copolymer, a low molecular weight crosslinking agent, a flame retardant, a filler and an accelerator, as components in parts by weight, wherein each The content of the components is as shown in Table 2.

The filler used here is a high Dk filler (Dk > 10), and its dielectric loss is high.

Example 12

The high-frequency resin composition includes a modified polyphenyl ether resin, a block copolymer rubber, an unsaturated diene rubber, an N-substituted maleimide copolymer, a low molecular weight crosslinking agent, a flame retardant, a filler and a filler, as components in parts by weight, wherein, The content of each component is as shown in Table 2.

The modified polyphenyl ether resin is prepared by modifying the polyphenyl ether end group with a vinyl group, and the block copolymer rubber is a linear triblock copolymer having styrene as the terminal segment and polybutadiene and isoprene as the middle segment, and the block copolymer The number average molecular weight of the composite rubber is 5000, and the content of the styrene segment is 10%. The unsaturated diene rubber is a styrene-isoprene copolymer and a divinylbenzene-butadiene copolymer, of which the 1,4-cis double bond structure accounts for 60%, and the number average molecular weight of the unsaturated diene rubber is 1000. The monomers of the N-substituted maleimide copolymer are styrene, N-phenyl maleimide, and an unsaturated acid anhydride, of which the mole part of styrene is 30 parts, the mole part of the unsaturated acid anhydride is 1 part, and the mole part of the N-substituted maleimide is It is 30 copies. The low-molecular crosslinking agent uses a mixture of triallyl isocyanurate, triallyl cyanurate, trimethylallyl isocyanurate, trimethylallyl cyanurate, and trihydroxyethyl isocyanurate, and the flame retardant is a bromine-containing flame retardant, The filler uses spherical silica powder, which is a low Dk material, and the accelerator is a peroxide-based accelerator.

Example 13

The high-frequency resin composition includes a block copolymer rubber, an unsaturated diene-based rubber, an N-substituted maleimide copolymer, a low molecular weight crosslinking agent, a flame retardant, a filler, and an accelerator, as components in parts by weight, wherein the contents of each component are listed in the table As shown in 2.

The modified polyphenyl ether resin is prepared by modifying the terminal group of the polyphenyl ether resin with a vinyl group, and the block copolymer rubber is a linear triblock copolymer having styrene as an end segment and polybutadiene and isoprene as a middle segment, 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 a styrene-isoprene copolymer and a divinylbenzene-butadiene copolymer, of which the 1,4-cis double bond structure accounts for 95%, and the number average molecular weight of the unsaturated diene rubber is 10000. The monomers of the N-substituted maleimide copolymer are styrene, N-phenyl maleimide, and an unsaturated acid anhydride, of which the molar part of styrene is 60 parts, the molar part of the unsaturated acid anhydride is 20 parts, and the molar part of the N-substituted maleimide is It is 70 copies. A mixture of tert-butyl styrene, diallyl isophthalate, diallyl phthalate, trimethylolpropane triacrylate or pentaerythritol tetraacrylate is used as the low molecular crosslinking agent, a flame retardant containing bromine is used as the filler, and spherical silica powder is used as the filler. And, it is a low Dk material, and the accelerator is a peroxide-based accelerator.

Comparative Example 1

Comparative Example 1 is a resin composition, the raw material composition of which includes a modified polyphenyl ether resin, an unsaturated diene rubber, an N-substituted maleimide copolymer, a low molecular weight crosslinking agent, a flame retardant, a filler and an accelerator, and the content and selection of specific components is as shown in Table 2.

The main difference between Comparative Example 1 and Example is that no block copolymer rubber is added in Comparative Example, and as can be seen from the test data in Table 1, the glass transition temperature of the resin composition in Comparative Example 1 is 185 ° C, well below the glass transition temperature of the resin composition according to any one embodiment of the present invention. In addition, the peel strength of the copper foil of Comparative Example 1 is relatively low, indicating poor mechanical performance, and the layering time at 288 ° C. is relatively short, which means that the thermal stability of Comparative Example 1 is low. Therefore, adding a block copolymer rubber to the resin substrate is advantageous for improving the heat resistance and peel strength of the resin composition.

Comparative Example 2

Comparative Example 2 is a resin composition, the raw material composition of which includes a modified polyphenyl ether resin, a block copolymer rubber, an unsaturated diene rubber, a BDM type maleimide, a low molecular weight crosslinking agent, a flame retardant, a filler and an accelerator, and the specific content of each component and selection are as shown in Table 2.

The main difference between Comparative Example 2 and Example is that the N-substituted maleimide copolymer was replaced by using 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 205° C., which is lower than the glass transition temperature of the resin composition according to any one embodiment of the present invention. In addition, its dielectric loss is relatively high, energy consumption is high, resin fluidity is poor, and heat resistance is poor, which means that the heat resistance and peel strength of the resin composition may be reduced when the N-substituted maleimide copolymer is added. do.

Comparative Example 3

Comparative Example 3 is a resin composition, the raw material composition of which includes a modified polyphenyl ether resin, a block copolymer rubber, an unsaturated diene rubber, styrene, a maleic anhydride copolymer, a low molecular weight crosslinking agent, a flame retardant, a filler and an accelerator, and each specific The content and selection of components are as shown in Table 2.

The main difference between Comparative Example 3 and Example is that the N-substituted maleimide copolymer was replaced by using a styrene-maleic anhydride copolymer, and as can be seen from the test data in Table 1, the resin composition in Comparative Example 3 Compatibility is not good. In addition, the peel strength of the resin composition is very low, and the layering time at 288°C is very short. Therefore, the addition of the N-substituted maleimide copolymer is very important, and the synergistic effect between the maleimide structure and maleic anhydride structure and the resin substrate is advantageous for improving the mechanical performance and dielectric performance of the resin composition.

Above, specific embodiments of the present invention have been described. It should be understood that the present invention is not limited to the above specific implementation manner, and various variations or modifications may be made by those skilled in the art within the scope of the claims, and these changes and modifications do not affect the actual content of the present invention.

Claims (10)

Including the components of the following parts by weight,
20 to 50 parts of modified polyphenyl ether resin;
15 to 40 parts of block copolymer rubber;
10 to 50 parts of unsaturated diene rubber;
5 to 30 parts of an N-substituted maleimide copolymer, and
10 to 30 parts of a low molecular weight crosslinking agent;
The N-substituted maleimide copolymer is constituted by copolymerization of monomers of 30 to 70 parts of N-substituted maleimide, 30 to 60 parts of vinyl monomer, and 1 to 20 parts of unsaturated acid anhydride in molar content. High frequency resin composition. According to claim 1,
The molecular formula of the N-substituted maleimide copolymer is,

ego,
In the molecular formula, x, y, z are the molar ratios of styrene monomer, N-substituted maleimide, and unsaturated acid anhydride, respectively, and x: y: z = 0.3 to 0.6: 0.3 to 0.7: 0.01 to 0.2, and the R group is methyl , ethyl, isopropyl, cyclohexyl, phenyl, benzyl, phenylethyl, phenylvinyl, p-hydroxyphenyl, biphenyl, naphthalene ring, a high-frequency resin composition. According to claim 1,
The block copolymer rubber is a linear triblock copolymer having styrene as an end segment and polybutadiene and isoprene as a middle segment, a number average molecular weight of 5000 to 150000, and a styrene segment of the total mass of the block copolymer rubber Occupying 10% to 50%, a high-frequency resin composition. According to claim 1,
The polymerized monomer of the unsaturated diene-based rubber includes at least one of unmodified or modified group-containing butadiene or isoprene, and the modifying group is at least one selected from epoxy, maleic anhydride, acrylate, hydroxy group, or carboxyl group, , The number average molecular weight of the diene-based rubber is 500 to 20000, and the unsaturated double bond structure accounts for 60% to 99% of the main chain mass of the diene-based rubber, a high-frequency resin composition. According to claim 4,
The unsaturated diene rubber is polybutadiene resin, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, divinylbenzene-butadiene copolymer, divinylbenzene-isoprene copolymer, styrene-butadiene-divinylbenzene copolymer or at least one selected from styrene-isoprene-divinylbenzene copolymers. According to claim 1,
The modified polyphenyl ether resin is prepared by modifying the terminal group of the polyphenyl ether resin with a vinyl group or a methacrylate group, and the number average molecular weight of the modified polyphenyl ether resin is 500 to 10000, the high frequency resin composition. According to claim 1,
The low molecular weight crosslinking agent is triallyl isocyanurate, triallyl cyanurate, trimethylallyl isocyanurate, trimethylallyl cyanurate, trihydroxyethyl isocyanurate, tert-butyl styrene, diallyl isophthalate, di A high frequency resin composition comprising at least one selected from allyl phthalate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate. According to claim 1,
A high frequency resin composition further comprising a flame retardant, a filler and an accelerator.
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