CN106280178A - A kind of resin combination and application thereof - Google Patents

A kind of resin combination and application thereof Download PDF

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Publication number
CN106280178A
CN106280178A CN201610769465.2A CN201610769465A CN106280178A CN 106280178 A CN106280178 A CN 106280178A CN 201610769465 A CN201610769465 A CN 201610769465A CN 106280178 A CN106280178 A CN 106280178A
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resin combination
resin
barium
niobate
further preferred
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CN106280178B (en
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殷卫峰
李莎
张记明
曾耀德
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SHAANXI SHENGYI SCI TECH Co Ltd
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SHAANXI SHENGYI SCI TECH Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Abstract

The invention discloses a kind of resin combination, including maleic anhydride modified polybutadiene less than 50000 of butadiene styrene resin, molecular weight, cross-linking agent, initiator.And disclose the application in prepreg, laminate, copper-clad laminate, printed circuit board of this resin combination.The resin combination that the present invention provides, has the excellent comprehensive performances such as heat-resist, peel strength is high, dielectric loss is little, can meet the performance requirement of high frequency sheet material.

Description

A kind of resin combination and application thereof
Technical field
The present invention relates to copper-clad plate field, be specifically related to a kind of resin combination, the invention still further relates to this resin combination Application in prepreg, laminate, copper-clad laminate, printed circuit board.
Background technology
In recent years, along with the development of communication apparatus high performance, multifunction and networking stepped on by computer, mobile phone, for High-speed transfer and process Large Copacity information, operation signal is carrying out high frequency, needs one to be applicable to high frequency signal transmission The high-performance electric insulant of characteristic.
In high-frequency circuit, signal of telecommunication transmission loss dielectric loss represents with conductor losses, radiation loss sum, telecommunications Number the highest then dielectric loss of frequency, conductor losses, radiation loss are the biggest.Owing to transmission loss makes signal of telecommunication decay, destroys telecommunications Number reliability, this loss is from high frequency circuit radiation simultaneously, is likely to result in electronic failure.Therefore must reduce dielectric to damage Consumption, conductor losses, radiation loss.It is known that the dielectric loss angle of the insulator of the dielectric loss of the signal of telecommunication and formation circuit Tangent and the product of signal frequency used are directly proportional.Therefore as insulator, can be by just selecting dielectric loss angle Cut little insulant, the increase of suppression dielectric loss.
Application No. JP53145891A (applying date: 1977.05.26, publication number: JP53145891A, publication date: 1978.12.19) patent discloses a kind of high-frequency copper-clad plate using maleic anhydride modified polybutadiene, but is not given Maleic anhydride functional groups percent grafting on modified strand, if percent grafting is excessive, can cause the polarity of composite to increase, Dielectric loss increases.If functional group's percent grafting is too small, resin system can be caused too small with the peel strength between Copper Foil.This Outward, this patent does not use butadiene styrene resin, the poor heat resistance of sheet material in resin combination.
Application No. JP57105347A (applying date: 1980.12.24, publication number: JP57105347A, publication date: 1982.06.30) patent discloses a kind of high-frequency copper-clad plate using maleic anhydride modified polybutadiene, but modified poly- Compound maleic anhydride grafting ratio is too high, causes the polarity of composite to increase, and dielectric loss increases.Additionally, disclosed in this patent Maleic anhydride modified polybutadiene molecular weight be 5 ten thousand to 20 ten thousand, be difficult in a solvent dissolve, subsequent technique is poor.
Application No. CN200810142665.0 (applying date: 2008.07.28, notification number: CN101328277A, bulletin Day: Chinese patent 2010.07.21) discloses a kind of use maleic anhydride modified polybutadiene, maleic anhydride modified molecular weight Butadiene more than 50000 and cinnamic copolymer, this patent is also without the maleic anhydride be given on modified strand Functional group's percent grafting, if percent grafting is excessive, can cause the polarity of composite to increase, and dielectric loss increases；If functional group Percent grafting is too small, and resin system can be caused too small with the peel strength between Copper Foil.Additionally, the maleic anhydride disclosed in this patent Modified butadiene and cinnamic molecular weight of copolymer, more than 50,000, are difficult to dissolve in a solvent, and subsequent technique is poor.
Summary of the invention
It is an object of the invention to provide a kind of resin combination, its have heat-resist, peel strength is high, dielectric constant The excellent comprehensive performances such as low, dielectric loss is little, can meet the performance requirement of high frequency sheet material.
It is a further object to provide a kind of above-mentioned composition in prepreg, laminate, copper-clad laminate, print Application in circuit board processed.
The technical solution adopted in the present invention is, a kind of resin combination, including butadiene styrene resin, molecular weight less than 50000 Maleic anhydride modified polybutadiene, cross-linking agent, initiator.
The feature of the present invention also resides in,
The molecular weight of butadiene styrene resin be less than 11000, the contents of ethylene of butadiene styrene resin is 60～99%, preferably 70～ 95wt%, further preferred 75～93wt%；The styrene-content of butadiene styrene resin is 30～60%, and preferably 35～55% enter one Step preferably 40～50%；It is 45～80wt% that butadiene styrene resin accounts for the percentage by weight of resin combination, and preferably 48～70wt% enter One step preferably 50～60wt%.
The molecular weight of maleic anhydride modified polybutadiene is 5000～50000, preferably 8000～40000, further preferably 11000～30000.
The contents of ethylene 60～99% of maleic anhydride modified polybutadiene, preferably 70～95wt%, preferably 70～ 95wt%, further preferred 75～93wt%；Polar group percent grafting on maleic anhydride modified polybutadiene strand is between 5 Between 10.
It is 10～50wt% that maleic anhydride modified polybutadiene accounts for the percentage by weight of resin combination, preferably 15～ 40wt%, further preferred 20～30wt%.
It is 3～40wt% that cross-linking agent accounts for the percentage by weight of resin combination；Cross-linking agent selected from triallyl isocyanurate, Poly-triallyl isocyanurate, triallyl cyanurate, trimethacrylate acid, diallyl phthalate, divinyl Any one or the mixing of at least two in base benzene or polyfunctional acrylate.
It is 1～7wt% that initiator accounts for the percentage by weight of resin combination；Initiator is selected from a, a '-two (t-butyl peroxy Isopropylbenzene between change) benzene, cumyl peroxide, cumyl t-butyl peroxide, double (tertiary hexyl the peroxidating)-3,3,5-three of 1,1- Hexahydrotoluene, 2,5-dimethyl-2,5-bis-(t-butylperoxy) hex-3-alkynes, octanoic acid ter-butyl ester, the tertiary fourth of perbenzoic acid Any one or the mixing of at least two in ester.
This resin combination also includes fire retardant, and fire retardant is selected from deca-BDE, ethyl-bis-(adjacent two formyls of tetrabromo-benzene Imines), decabromodiphenylethane, three (2,6-3,5-dimethylphenyl) phosphine, 10-(2,5-dihydroxy phenyl)-9,10-dihydro-9-oxy Change-10 phosphine phenanthrene-10-oxides, 2,6-bis-(2,6-3,5-dimethylphenyl) phosphino-benzene or 10-phenyl-9,10-dihydro-9-oxy- Any one or the mixing of at least two in 10-phosphine phenanthrene-10-oxide.
This resin combination also includes filler, and filler is selected from powdered quartz, unformed silicon dioxide, ball-type two Silicon oxide, titanium dioxide, boron nitride, aluminium nitride, carborundum, aluminium oxide, Barium metatitanate., strontium titanates, magnesium titanate, calcium titanate, metatitanic acid Strontium barium, calcium Barium metatitanate., lead titanates, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, hafnium oxide, Lead magnesio-niobate, barium magnesium niobate, Lithium metaniobate, potassium niobate, tantalic acid aluminum strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, titanium niobate barium, Any one or the mixing of at least two in bismuth tantalate strontium, bismuth titanates, Barium metatitanate. rubidium, copper titanate, lead titanates-lead magnesio-niobate Thing；
In the particle diameter of filler, angle value is 0.5～20uM, preferably 1～15uM, further preferred 4～10uM；
It is 0～90wt% that filler accounts for the percentage by weight of resin combination, preferably 40～85wt%, further preferred 60～ 80wt%.
Second technical scheme of the present invention is, above-mentioned resin combination is at prepreg, laminate, copper foil covered Application in pressing plate, printed circuit board.
Compared with prior art, there is advantages that
The resin combination that the present invention provides, it has the excellent combination such as heat-resist, peel strength is high, dielectric loss is little Performance, can meet the performance requirement of high frequency sheet material.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is described in detail.
Invention resin composition, including butadiene styrene resin, molecular weight less than 50000 maleic anhydride modified polybutadiene, Cross-linking agent, initiator.
The molecular weight of butadiene styrene resin is less than 11000, and the contents of ethylene of butadiene styrene resin is 60～99%, such as 60%, 65%, 70%, 75%, 80%, 85%, 90%, 92% or 95%, preferably 70～95wt%, further preferred 75～93wt%.
The styrene-content of butadiene styrene resin is 30～60%, such as 30%, 32%, 38%, 40%, 45%, 48%, 50%, 55% or 60%, preferably 35～55%, further preferred 40～50%.
Butadiene styrene resin accounts for the percentage by weight 45～80wt% of resin combination, such as 45%, 50%, 55%, 60%, 65%, 70%, 75%, 78% or 80%, preferably 48～70wt%, further preferred 50～60wt%.
The molecular weight of maleic anhydride modified polybutadiene is 5000～50000, such as 5000,8000,10000,15000, 20000,25000,30000,35000,40000,45000 or 50000, preferably 8000～40000, further preferred 11000～ 30000.If molecular weight is more than 50,000, maleic anhydride modified polybutadiene can be caused to be difficult in a solvent dissolve, subsequent technique Difference.If molecular weight less than 5000, can cause follow-up prepare sheet material during gummosis excessive, manufacturability is poor.
The contents of ethylene 60～99% of maleic anhydride modified polybutadiene, such as 60%, 65%, 70%, 75%, 80%, 85%, 90%, 92% or 95%, preferably 70～95wt%, preferably 70～95wt%, further preferred 75～93wt%；
Polar group percent grafting on maleic anhydride modified polybutadiene strand is between 5 to 10；If percent grafting More than 10, the polarity of composite can be caused to increase, dielectric loss increases；If functional group's percent grafting is less than 5, resin can be caused System is too small with the peel strength between Copper Foil.
It is 10～50wt% that maleic anhydride modified polybutadiene accounts for the percentage by weight of resin combination, such as 10%, 15%, 20%, 25%, 28%, 30%, 33%, 35%, 40%, 43%, 35% or 50%, preferably 15～40wt%, Further preferred 20～30wt%.
It is 3～40wt% that cross-linking agent accounts for the percentage by weight of resin combination；Cross-linking agent selected from triallyl isocyanurate, Poly-triallyl isocyanurate, triallyl cyanurate, trimethacrylate acid, diallyl phthalate, divinyl Any one or the mixing of at least two in base benzene or polyfunctional acrylate.
It is 1～7wt% that initiator accounts for the percentage by weight of resin combination, such as 1%, 1.3%, 1.5%, 1.7%, 2%, 2.3%, 2.5%, 3%, 3.5%, 4%, 5%, 6% or 7%, preferably 1.5～5%, further preferred 2～4wt%； Initiator selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, cumyl peroxide, cumyl t-butyl peroxide, 1,1-double (tertiary hexyl peroxidating)-3,3,5-trimethyl-cyclohexanes, 2,5-dimethyl-2,5-bis-(t-butylperoxy) hex-3- Any one or the mixing of at least two in alkynes, octanoic acid ter-butyl ester, peroxidized t-butyl perbenzoate.
This resin combination also includes fire retardant, and fire retardant is selected from deca-BDE, ethyl-bis-(adjacent two formyls of tetrabromo-benzene Imines), decabromodiphenylethane, three (2,6-3,5-dimethylphenyl) phosphine, 10-(2,5-dihydroxy phenyl)-9,10-dihydro-9-oxy Change-10 phosphine phenanthrene-10-oxides, 2,6-bis-(2,6-3,5-dimethylphenyl) phosphino-benzene or 10-phenyl-9,10-dihydro-9-oxy- Any one or the mixing of at least two in 10-phosphine phenanthrene-10-oxide.
This resin combination also includes filler, and filler is selected from powdered quartz, unformed silicon dioxide, ball-type two Silicon oxide, titanium dioxide, boron nitride, aluminium nitride, carborundum, aluminium oxide, Barium metatitanate., strontium titanates, magnesium titanate, calcium titanate, metatitanic acid Strontium barium, calcium Barium metatitanate., lead titanates, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, hafnium oxide, Lead magnesio-niobate, barium magnesium niobate, Lithium metaniobate, potassium niobate, tantalic acid aluminum strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, titanium niobate barium, Any one or the mixing of at least two in bismuth tantalate strontium, bismuth titanates, Barium metatitanate. rubidium, copper titanate, lead titanates-lead magnesio-niobate Thing；In the particle diameter of filler, angle value is 0.5～20uM, such as 0.5,1.0,2.0,4.0,6.0,10,12,15,20,25,28 or 30, Preferably 1～15uM, further preferred 4～10uM；
It is 0～90wt% that filler accounts for the percentage by weight of resin combination, such as 25%, 35%, 45%, 55%, 65%, 70%, 75%, 78%, 80%, 85% or 90%, preferably 40～85wt%, further preferred 60～80wt%.
According to information in the public domain, different molecular weight, different contents of ethylene, the poly-fourth of different maleic anhydride grafting ratio can be prepared Diene resin, as follows:
16L is dried hexamethylene, and 1600g is dried butadiene and puts into four mouthfuls of glass reaction bottles of 4L and (be dried place through overbaking Reason) in, it is passed through drying nitrogen protection, constant temperature 40 DEG C～80 DEG C, is then sequentially added into following catalytic component: 4ml～9ml tri- The hexane solution of [di-(2-ethylhexyl)phosphoric acid] ferrum (0.4mmol～0.9mmol), 16ml～36ml triisobutyl aluminium (8mmol) hexane solution, the hexane solution of 12ml～27ml triphenyl phosphate (1.2mmol～2.7mmol), 17mmol～ The tetrahydrofurfuryl alcohol ethylether of 38mmol, PMDETA 7mmol～17mmol, be warming up to 65 DEG C～90 DEG C, is polymerized 1～9 hour.So After add ethanol and terminate reaction and separate out glue sample, sucking filtration, with acetone extraction 12～18h, put into 25 DEG C of baking ovens vacuum drying 12h, Obtain white solid product polybutadiene.
By above-mentioned for 1000g polybutadiene, 300ml dimethylbenzene is put in four mouthfuls of glass reaction bottles of 4L, constant temperature 65 DEG C～75 DEG C, after polybutadiene is completely dissolved, be passed through drying nitrogen, be warming up to 85 DEG C～95 DEG C, be slowly added in system containing 165g～370g maleic anhydride, the xylene solution of 48g～110g acetanilide, stir 10min～25min after dropping, By the xylene solution containing 24g～56g BPO in 30min in be slowly dropped in four-hole bottle, reactant is slowly warmed up to 120 DEG C, continuing reaction 3～5 hours at a constant temperature, after reaction terminates, blood pressure lowering is distilled, and removes dimethylbenzene and unreacted maleic acid Acid anhydride, pours out product, adds dehydrated alcohol precipitation, settles a period of time, sucking filtration, with acetone extraction 12h～18h, put into 25 DEG C Baking oven vacuum drying 12h, obtains white solid product MA modified polybutadiene.
Different molecular weight, different contents of ethylene, different MA percent grafting butadiene resin as shown in table 1.
Table 1 MA modified polybutadiene
Molecular weight Contents of ethylene MA percent grafting
PB-5000 5000 60% 5
PB-7000 7000 85% 7
PB-10000 10000 90% 8
PB-50000 50000 99% 10
PB-5000-02 5000 60% 2
PB-5000 5000 60% 15
PB-5000 5000 30% 5
According to information in the public domain, the butadiene styrene resin of different molecular weight, different contents of ethylene can be prepared, specific as follows:
4L is dried hexamethylene, 0.05ml～0.48ml tetrahydrofurfuryl alcohol ethylether, puts into four mouthfuls of glass reaction bottle (warps of 4L Overbaking dried) in, it is passed through drying nitrogen protection, constant temperature 40 DEG C～60 DEG C, then in 60min, is simultaneously introduced following group Point: 25g～200g styrene (S), 30～the mix monomer of 210g butadiene (B), 0.4mol/L butyl lithium 0.02mL～ 0.1mL, is subsequently adding the cyclohexane solution of the 0.2mol/L mono-chlorine trimethyl silane of 1.0mL～16.65mL, reacts 30min, adds Enter isopropanol and terminate reaction precipitation glue sample, sucking filtration, use acetone extraction 12h, put into 25 DEG C of baking ovens vacuum drying 12h, obtain white Solid product.
Different molecular weight, different contents of ethylene, different styrene-content butadiene styrene resin as shown in table 2.
Table 2 butadiene styrene resin
Molecular weight Contents of ethylene Styrene-content
PBS-1000 1000 60% 30%
PBS-5000 5000 85% 40%
PBS-7000 7000 90% 50%
PBS-11000 11000 99% 60%
PBS-1000-05 1000 60% 5%
PBS-1000-30 1000 30% 30%
For the present invention is better described, it is simple to understand technical scheme, the present invention's is typical but non-limiting Embodiment is as follows:
Embodiment
Embodiment 1-8 and the manufacture method of comparative example 1-4 copper-clad laminate: design parameter is as shown in Table 3 and Table 4.
Butadiene styrene resin, maleic anhydride modified polybutadiene, cross-linking agent, initiator are dissolved in toluene, after fully dissolving, Add angle value, the filler of different quality mark in different-grain diameter, be the most at room temperature mixed to get glue.Use glass cloth impregnates Above-mentioned glue, then in the baking oven of 155 DEG C, baking is cured as B-stage for 5 minutes, and control obtains prepreg.
Then, the prepreg of making is placed between Copper Foil, is laminated in 210 DEG C and solidifies in press, obtaining solidfied material Rear Measuring Dielectric Constant, Tg, peel strength, DK, Df.Specific performance test result is shown in Table 3, table 4.
Material used in above-described embodiment and comparative example is specific as follows:
Triallyl isocyanurate: Nippon Kasei Chemical Company TAIC M-60
Poly-triallyl isocyanurate: Nippon Kasei Chemical Company
Triallyl cyanurate: Nippon Kasei Chemical Company
BPO: great river oils and fats Co., Ltd.
BIPB: great river oils and fats Co., Ltd.
DCP: Shanghai Fang Rui reaches chemical industry
Barium titanate/strontium titanate/barium strontium titanate: Shanghai allusion quotation raises science and technology
Lead titanates: Hubei Prunus persica f. compressa culminant star electronics.
Table 3 embodiment 1～8 formula and test result
Table 4 comparative example 1～4 formula and test result
The method of testing of above characteristic is as follows:
1, glass transition temperature (Tg): survey according to the D maleic anhydride method of IPC-TM-650 2.4.24 defined Fixed.
2, peel strength (PS): according to " after thermal stress " experiment condition in IPC-TM-650 2.4.8 method, tests sheet material Peel strength.
3, dielectric properties: SPDR (splite post dielectric resonator) method is tested, test condition For A state, 10GHz.
From table 3 and table 4, from the contrast of embodiment and comparative example it can be seen that what embodiment 1 was prepared to embodiment 8 Sheet material, the combination property such as its dielectric loss, dielectric constant, peel strength, glass transition temperature is preferable, uses in comparative example 1 The polybutadiene of low percent grafting, the dielectric loss ratio of sheet material is relatively low, but peel strength is little；Comparative example 2 uses high percent grafting Polybutadiene, the peel strength rate of exchange of sheet material are high, but dielectric loss is high；Comparative example 3 uses the butylbenzene that styrene-content is little Resin, the Tg of sheet material is low；Comparative example 4 uses butadiene styrene resin, the butadiene resin that contents of ethylene is little, and the Tg of sheet material is low.
Combining the above results to understand, invention resin composition can reach heat-resist, peel strength is high, dielectric loss is little Deng excellent comprehensive performance, performance has obtained bigger improvement, can meet the performance requirement of high dielectric material.
Above example, not imposes any restrictions the content of the compositions of the present invention, every technology according to the present invention Any trickle amendment, equivalent variations and the modification that above example is made by essence or compositions composition or content, all still falls within In the range of technical solution of the present invention.
Applicant states, by above-described embodiment, the present invention illustrates that the detailed of the present invention forms, but the present invention not office It is limited to above-mentioned detailed composition, does not i.e. mean that the present invention has to rely on above-mentioned detailed composition and could implement.Art Technical staff is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.

Claims (10)

1. a resin combination, it is characterised in that include maleic anhydride modified poly-less than 50000 of butadiene styrene resin, molecular weight Butadiene, cross-linking agent, initiator.
Resin combination the most according to claim 1, it is characterised in that the molecular weight of described butadiene styrene resin is less than 11000, The contents of ethylene of described butadiene styrene resin is 60～99%, preferably 70～95wt%, further preferred 75～93wt%；Described fourth The styrene-content of benzene resin is 30～60%, preferably 35～55%, further preferred 40～50%；Described butadiene styrene resin accounts for tree The percentage by weight of oil/fat composition is 45～80wt%, preferably 48～70wt%, further preferred 50～60wt%.
Resin combination the most according to claim 1, it is characterised in that the molecule of described maleic anhydride modified polybutadiene Amount is 5000～50000, preferably 8000～40000, further preferred 11000～30000.
Resin combination the most according to claim 1, it is characterised in that the ethylene of described maleic anhydride modified polybutadiene Base content 60～99%, preferably 70～95wt%, preferably 70～95wt%, further preferred 75～93wt%；Described maleic acid Polar group percent grafting on anhydride modification polybutadiene strand is between 5 to 10.
5. according to the arbitrary described resin combination of claim 1,3,4, it is characterised in that described maleic anhydride modified polybutadiene It is 10～50wt% that olefine resin accounts for the percentage by weight of resin combination, preferably 15～40wt%, further preferred 20～ 30wt%.
Resin combination the most according to claim 1, it is characterised in that described cross-linking agent accounts for the weight hundred of resin combination Proportion by subtraction is 3～40wt%；Described cross-linking agent is selected from triallyl isocyanurate, poly-triallyl isocyanurate, triallyl three Any in the acid of polycyanate ester, trimethacrylate, diallyl phthalate, divinylbenzene or polyfunctional acrylate A kind of or the mixing of at least two.
Resin combination the most according to claim 1, it is characterised in that described initiator accounts for the weight hundred of resin combination Proportion by subtraction is 1～7wt%；Described initiator selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, cumyl peroxide, Cumyl t-butyl peroxide, 1, double (the tertiary hexyl peroxidating)-3 of 1-, 3,5-trimethyl-cyclohexanes, 2,5-dimethyl-2,5-bis- Any one or at least two in (t-butylperoxy) hex-3-alkynes, octanoic acid ter-butyl ester, peroxidized t-butyl perbenzoate Mixing.
Resin combination the most according to claim 1, it is characterised in that this resin combination also includes fire retardant, described Fire retardant is selected from deca-BDE, ethyl-bis-(tetrabromo phthalimide), decabromodiphenylethane, three (2,6-dimethyl Phenyl) phosphine, 10-(2,5-dihydroxy phenyl)-9,10-dihydro-9-oxy-10 phosphine phenanthrene-10-oxide, 2,6-bis-(2,6-diformazan Base phenyl) in phosphino-benzene or 10-phenyl-9,10-dihydro-9-oxy-10-phosphine phenanthrene-10-oxide any one or at least The mixing of two kinds.
Resin combination the most according to claim 1, it is characterised in that this resin combination also includes filler, described in fill out Material is selected from powdered quartz, unformed silicon dioxide, spherical silica, titanium dioxide, boron nitride, aluminium nitride, carbon SiClx, aluminium oxide, Barium metatitanate., strontium titanates, magnesium titanate, calcium titanate, barium strontium titanate, calcium Barium metatitanate., lead titanates, lead zirconate titanate, zirconium Lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, hafnium oxide, lead magnesio-niobate, barium magnesium niobate, Lithium metaniobate, potassium niobate, Tantalic acid aluminum strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, Barium metatitanate. rubidium, copper titanate, Any one or the mixture of at least two in lead titanates-lead magnesio-niobate；
In the particle diameter of described filler, angle value is 0.5～20uM, preferably 1～15uM, further preferred 4～10uM；
It is 0～90wt% that described filler accounts for the percentage by weight of resin combination, preferably 40～85wt%, further preferred 60～ 80wt%.
10. the resin combination as described in as arbitrary in claim 1～9 is at prepreg, laminate, copper-clad laminate, printing electricity Application in the plate of road.
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Publication number Priority date Publication date Assignee Title
CN107964203A (en) * 2017-12-26 2018-04-27 浙江华正新材料股份有限公司 A kind of low dielectric prepreg composition, copper-clad plate and preparation method thereof
CN108752827A (en) * 2018-05-17 2018-11-06 常州中英科技股份有限公司 A kind of crosslinkable resin composition of high heat conduction and its prepreg and the heat curing type copper-clad plate of preparation
CN109467862A (en) * 2018-11-09 2019-03-15 陕西生益科技有限公司 A kind of high frequency resin composition and its application
CN113444471A (en) * 2021-07-20 2021-09-28 郴州功田电子陶瓷技术有限公司 Composition applied to multilayer high-frequency copper-clad plate bonding sheet and application thereof

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CN101328277A (en) * 2008-07-28 2008-12-24 广东生益科技股份有限公司 Composite material, high-frequency circuit board made thereof and making method
CN102161823A (en) * 2010-07-14 2011-08-24 广东生益科技股份有限公司 Composite material, high-frequency circuit substrate therefrom and manufacture method thereof

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US20020040104A1 (en) * 1998-11-02 2002-04-04 Gil Technologies Vinyl-terminated polybutadiene and butadiene-styrene copolymers containing urethane and/or ester residues, and the electrical laminates obtained therefrom
CN101328277A (en) * 2008-07-28 2008-12-24 广东生益科技股份有限公司 Composite material, high-frequency circuit board made thereof and making method
CN102161823A (en) * 2010-07-14 2011-08-24 广东生益科技股份有限公司 Composite material, high-frequency circuit substrate therefrom and manufacture method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107964203A (en) * 2017-12-26 2018-04-27 浙江华正新材料股份有限公司 A kind of low dielectric prepreg composition, copper-clad plate and preparation method thereof
CN107964203B (en) * 2017-12-26 2020-09-22 浙江华正新材料股份有限公司 Low-dielectric prepreg composition, copper-clad plate and manufacturing method thereof
CN108752827A (en) * 2018-05-17 2018-11-06 常州中英科技股份有限公司 A kind of crosslinkable resin composition of high heat conduction and its prepreg and the heat curing type copper-clad plate of preparation
CN108752827B (en) * 2018-05-17 2021-06-01 常州中英科技股份有限公司 High-thermal-conductivity crosslinkable resin composition, prepreg prepared from same and thermosetting copper-clad plate
CN109467862A (en) * 2018-11-09 2019-03-15 陕西生益科技有限公司 A kind of high frequency resin composition and its application
CN113444471A (en) * 2021-07-20 2021-09-28 郴州功田电子陶瓷技术有限公司 Composition applied to multilayer high-frequency copper-clad plate bonding sheet and application thereof

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