CN106280199B - A kind of compositions of thermosetting resin and its application - Google Patents
A kind of compositions of thermosetting resin and its application Download PDFInfo
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- 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
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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- B32B2307/00—Properties of the layers or laminate
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B2307/306—Resistant to heat
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- B32B2457/00—Electrical equipment
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Abstract
The invention discloses a kind of compositions of thermosetting resin, unsaturated polybutadiene, styrene, crosslinking agent, initiator, ceramic packing including butadiene styrene resin, modified with polar.The invention also discloses application of the above-mentioned compositions of thermosetting resin in prepreg, laminate, copper-clad laminate, printed circuit board.Compositions of thermosetting resin of the present invention can satisfy the performance requirement of high frequency plate with the excellent comprehensive performances such as heat-resist, peel strength is high, dielectric loss is small.
Description
Technical field
The present invention relates to technical field of copper clad laminate, and in particular to a kind of compositions of thermosetting resin, the invention further relates to heat
Application of the thermosetting resin composition in prepreg, copper-clad laminate, printed circuit board.
Background technique
In recent years, as computer, mobile phone step on communication apparatus high performance, multifunction and the development of networking, it is
High-speed transfer and processing large capacity information, operation signal are carrying out high frequency, need a kind of to be suitable for high frequency signal transmission
The high-performance electric insulating materials of characteristic.
In high-frequency circuit, electric signal transmission loss dielectric loss is indicated with the sum of conductor losses, radiation loss, telecommunications
Number more high then dielectric loss of frequency, conductor losses, radiation loss are bigger.Since transmission loss makes electric signal decaying, destruction telecommunications
Number reliability, while the loss may cause electronic failure from high frequency circuit radiation.Therefore it must reduce dielectric damage
Consumption, conductor losses, radiation loss.It is well known that the dielectric loss angle of the insulator of the dielectric loss of electric signal and formation circuit
The product of tangent and used signal frequency is directly proportional.Therefore it is used as insulator, it can be by selection dielectric loss angle just
Small insulating materials is cut, the increase of dielectric loss is inhibited.
Patent JP60011634B2, JP1993068484, which discloses, to be changed in a kind of polybutadiene formula using maleimide
The heat resistance of kind plate, but maleimide is with the phase tolerance between resin, and maleimide will increase the loss of plate.
Application No. is JP19770061619 (applying date: 1977.5.26, notification number: JP53145891A, the day for announcing:
1978.12.19 patent) discloses a kind of high-frequency copper-clad plate using maleic anhydride modified polybutadiene, but does not provide
MA functional group grafting rate on modified strand, if grafting rate is excessive, the polarity that will lead to composite material increases, and dielectric is normal
Number, dielectric loss increase.If functional group's grafting rate is too small, it is too small with the peel strength between copper foil to will lead to resin system.
In addition, without using butadiene styrene resin, the poor heat resistance of plate in resin combination in this patent.
Application No. is JP19800183423 (applying date: 1980.12.24, notification number: JP57105347A, the day for announcing:
1982.6.30 patent) discloses a kind of high-frequency copper-clad plate using maleic anhydride modified polybutadiene, but modified post-polymerization
Object maleic anhydride grafting ratio is excessively high, causes the polarity of composite material to increase, dielectric constant, dielectric loss increase.In addition, this patent
Disclosed in MA modified polybutadiene molecular weight be 5 ten thousand to 20 ten thousand, be difficult to dissolve in a solvent, subsequent technique is poor.
Application No. is CN200810142665.0 (applying date: 2008.7.28, notification number: CN101328277A, the day for announcing:
2010.7.21 Chinese patent) discloses a kind of maleic anhydride modified polybutadiene of use, maleic anhydride modified molecular weight is greater than
50000 butadiene and the copolymer of styrene, this patent are grafted also without the MA functional group provided on modified strand
Rate, if grafting rate is excessive, the polarity that will lead to composite material increases, and dielectric constant, dielectric loss increase；If functional group connects
Branch rate is too small, and it is too small with the peel strength between copper foil to will lead to resin system.In addition, MA disclosed in this patent is modified fourth two
The molecular weight of copolymer of alkene and styrene is greater than 50,000, is difficult to dissolve in a solvent, subsequent technique is poor.
In view of the above problems, the invention proposes one kind, to have that heat-resist, peel strength is high, dielectric loss is small etc. excellent
The baseplate material of comprehensive performance.
Summary of the invention
The object of the present invention is to provide a kind of compositions of thermosetting resin, with heat-resist, peel strength is high, dielectric
Small Deng excellent comprehensive performances are lost, can satisfy the performance requirement of high frequency plate.
It is a further object to provide a kind of above-mentioned compositions of thermosetting resin in prepreg, copper foil covered pressure
Application in plate, printed circuit board.
The technical scheme adopted by the invention is that a kind of compositions of thermosetting resin, including butadiene styrene resin, polar group change
Unsaturated polybutadiene, the styrene, crosslinking agent, initiator, ceramic packing of property.
The features of the present invention also characterized in that
The molecular weight of butadiene styrene resin 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%, preferably 35~55%, into one
Step preferably 40~50%.Butadiene styrene resin account for resin combination weight percent be 45~80wt%, preferably 48~70wt%, into
One step preferably 50~60wt%.
Polybutadiene is modified with polar polybutadiene, and modified with polar polybutadiene is selected from ring
It is oxygen modified polybutadiene resin, maleic anhydride modified polybutadiene, acrylic acid modified polybutadiene, hydroxy-end capped
The modified polybutadiene of polybutadiene, the polybutadiene of carboxy blocking, amine any one or at least two
Mixing.
The molecular weight of modified with polar polybutadiene is 5000~50000, preferably 8000~40000, further preferably
11000~30000；The contents of ethylene 60~99% of modified with polar polybutadiene, preferably 70~95wt% are further excellent
Select 75~93wt%；Epoxy group grafting rate on modified with polar polybutadiene strand is between 5 to 10；Polar group
Group's modified polybutadiene resin accounts for the weight percent of resin combination for 10~50wt%, preferably 15~40wt%, further
It is preferred that 20~30wt%.
Styrene accounts for 1~30wt% of weight percent of resin combination, preferably 5~25%, further preferred 10~
20wt%.
The weight percent that crosslinking agent accounts for resin combination is 3~40wt%；Crosslinking agent be selected from triallyl isocyanurate,
Poly- triallyl isocyanurate, triallyl cyanurate, trimethacrylate acid, diallyl phthalate, divinyl
In base benzene or polyfunctional acrylate any one or at least two mixing.
It is 1~7wt% that initiator, which accounts for resin composition weight percentage, and initiator is selected from a, (tert-butyl hydroperoxide of a '-two
Between isopropylbenzene) benzene, cumyl peroxide, cumyl t-butyl peroxide, bis- (the tert-hexyl peroxide) -3,3,5- front threes of 1,1-
Butylcyclohexane, 2,5- dimethyl -2,5- bis- (t-butylperoxy) hex- 3- alkynes, octanoic acid ter-butyl ester, peroxidized t-butyl perbenzoate
In any one or at least two mixing.
The resin combination further includes fire retardant, and fire retardant is selected from bis- (tetrabromo-benzene two formyls of neighbour of deca-BDE, ethyl-
Imines), decabromodiphenylethane, three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxy
Change -10 phosphine phenanthrene -10- oxides, (2,6- 3,5-dimethylphenyl) the phosphino- benzene of 2,6- bis- or 10- phenyl -9,10- dihydro-9-oxy -
In 10- phosphine phenanthrene -10- oxide any one or at least two mixing.
Ceramic packing is selected from crystalline sillica, unformed silica, spherical silica, titanium dioxide, nitrogen
Change boron, aluminium nitride, silicon carbide, aluminium oxide, barium titanate, strontium titanates, magnesium titanate, calcium titanate, barium strontium titanate, calcium barium titanate, metatitanic acid
Lead, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, hafnium oxide, lead magnesio-niobate, barium magnesium niobate,
Lithium niobate, potassium niobate, tantalic acid aluminium strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, titanium
Sour barium rubidium, copper titanate, in lead titanates-lead magnesio-niobate any one or at least two mixture；
Angle value is 0.5~20uM, preferably 1~15uM, further preferred 4~10uM in the partial size of ceramic packing；
Ceramic packing accounts for the weight percent of resin combination for 0~90wt%, preferably 40~85wt%, further preferably
60~80wt%.
Second technical solution of the present invention be, above-mentioned compositions of thermosetting resin in prepreg, laminate, cover
Application in copper-clad laminate, printed circuit board.
Compared with prior art, the invention has the following beneficial effects:
Resin combination provided by the invention, with the excellent combinations such as heat-resist, peel strength is high, dielectric loss is small
Performance can satisfy the performance requirement of high frequency plate.
Specific embodiment
The present invention is described in detail With reference to embodiment.
Compositions of thermosetting resin of the present invention, including butadiene styrene resin, the unsaturated polybutadiene of modified with polar, benzene second
Alkene, crosslinking agent, initiator, ceramic packing.
The molecular weight of butadiene styrene resin less than 11000, 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 be 30~60%, such as 30%, 32%, 38%, 40%, 45%, 48%,
50%, 55% or 60%, preferably 35~55%, further preferred 40~50%.
Butadiene styrene resin account for resin combination weight percent be 45~80wt%, such as 45%, 50%, 55%, 60%,
65%, 70%, 75%, 78% or 80%, preferably 48~70wt%, further preferred 50~60wt%.
Polybutadiene is modified with polar polybutadiene, and modified with polar polybutadiene is selected from ring
It is oxygen modified polybutadiene resin, maleic anhydride modified polybutadiene, acrylic acid modified polybutadiene, hydroxy-end capped
The modified polybutadiene of polybutadiene, the polybutadiene of carboxy blocking, amine any one or at least two
Mixing.
The molecular weight of modified with polar polybutadiene be 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 greater than 50,000, it will lead to polybutadiene and be difficult to dissolve in a solvent, subsequent technique is poor.If molecule
Amount less than 5000, will lead to it is subsequent prepare plate during gummosis it is excessive, craftsmanship is poor.
The contents of ethylene 60~99% of modified with polar polybutadiene, for example, 60%, 65%, 70%, 75%,
80%, 85%, 90%, 92% or 95%, preferably 70~95wt%, preferably 70~95wt%, further preferred 75~93wt%.
Epoxy group grafting rate on modified with polar polybutadiene strand is between 5 to 10；If grafting rate
Greater than 10, the polarity that will lead to composite material increases, and dielectric loss increases；If functional group's grafting rate will lead to resin less than 5
System is too small with the peel strength between copper foil.
The weight percent that modified with polar polybutadiene accounts for resin combination is 10~50wt%, such as
10%, 15%, 20%, 25%, 28%, 30%, 33%, 35%, 40%, 43%, 35% or 50%, preferably 15~40wt%,
Further preferred 20~30wt%.
Styrene account for resin combination weight percent be 1~30wt%, such as 1%, 3%, 5%, 10%, 13%,
15%, 17%, 20%, 23%, 25%, 27% or 30%, preferably 5~25%, further preferred 10~20wt%.If benzene second
Alkene content is greater than 30%, and the brittleness that will lead to prepreg is big, and craftsmanship is poor.If the content of styrene does not have and changes less than 1%
The effect of kind plate heat resistance.
Crosslinking agent weight percent is 3~40wt%；Crosslinking agent is selected from triallyl isocyanurate, poly- isocyanuric acid triolefin
Propyl ester, triallyl cyanurate, trimethacrylate acid, diallyl phthalate, divinylbenzene or polyfunctional
In acrylate any one or at least two mixing.
Initiator account for resin combination weight percent be 1~7wt%, 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 is selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, cumyl peroxide, tert-butyl hydroperoxide
Bis- (tert-hexyl peroxide) -3 isopropylbenzene, 1,1-, 3,5- trimethyl-cyclohexanes, 2,5- dimethyl -2,5-, bis- (t-butyl peroxy
Base) hex- 3- alkynes, octanoic acid ter-butyl ester, in peroxidized t-butyl perbenzoate any one or at least two mixing.
The compositions of thermosetting resin further includes fire retardant, and fire retardant is selected from bis- (the tetrabromo-benzene neighbours of deca-BDE, ethyl-
Dicarboximide), decabromodiphenylethane, three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,10- two
Hydrogen -9- aoxidizes -10 phosphine phenanthrene -10- oxides, (2,6- 3,5-dimethylphenyl) the phosphino- benzene of 2,6- bis- or 10- phenyl -9,10- dihydro -9-
In oxidation -10- phosphine phenanthrene -10- oxide any one or at least two mixing.
Ceramic packing is selected from crystalline sillica, unformed silica, spherical silica, titanium dioxide, nitrogen
Change boron, aluminium nitride, silicon carbide, aluminium oxide, barium titanate, strontium titanates, magnesium titanate, calcium titanate, barium strontium titanate, calcium barium titanate, metatitanic acid
Lead, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, hafnium oxide, lead magnesio-niobate, barium magnesium niobate,
Lithium niobate, potassium niobate, tantalic acid aluminium strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, titanium
Sour barium rubidium, copper titanate, in lead titanates-lead magnesio-niobate any one or at least two mixture.
In the partial size of ceramic packing angle value be 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；
Ceramic packing account for resin combination weight percent be 0~90wt%, such as 0%, 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, the polybutadiene of different molecular weight, different contents of ethylene, different epoxy grafting rates can be prepared
Resin, it is as follows.
By the dry hexamethylene of 16L, the dry butadiene of 1600g is put into four mouthfuls of glass reaction bottles of 4L (at overbaking drying
Reason) in, it is passed through drying nitrogen protection, 40 DEG C~80 DEG C of constant temperature, then sequentially adds following catalytic component: 4ml~9ml tri-
The hexane solution, 16ml~36ml triisobutyl aluminium of [di-(2-ethylhexyl)phosphoric acid] iron (0.4mmol~0.9mmol)
The hexane solution of (8mmol), the hexane solution of 12ml~27ml triphenyl phosphate (1.2mmol~2.7mmol), 17mmol~
Tetrahydrofurfuryl alcohol ethylether, the PMDETA 7mmol~17mmol of 38mmol is warming up to 65 DEG C~90 DEG C, polymerize 1~9 hour.So
After add ethyl alcohol and terminate reaction glue sample is precipitated, filter, with 12~18h of acetone extraction, be put into 25 DEG C of baking ovens vacuum drying 12h,
Obtain white solid product polybutadiene.
By 1000g polybutadiene, 2.5L ethyl acetate is put into four mouthfuls of glass reaction bottles of 4L, and 65 DEG C~75 DEG C of constant temperature,
After polybutadiene is completely dissolved, it is passed through drying nitrogen, is warming up to 80 DEG C~95 DEG C, be slowly added into system containing 50g~
200g formic acid, 5g~42g polyethylene glycol are stirred to react 2~4 hours, then by the hydrogen peroxide of 30g~215g after being added dropwise
It being slowly dropped in four-hole bottle in 30min, reactant is slowly warming up to 120 DEG C, and the reaction was continued at a constant temperature 3~5 hours,
After reaction, product is poured out, dehydrated alcohol precipitating is added, sedimentation a period of time, filters, with sodium bicarbonate solution and distillation
Water washing at least 12 times, 25 DEG C of baking oven vacuum drying 12h are put into, white solid product is obtained.
Different molecular weight, different contents of ethylene, the polybutadiene of different epoxy grafting rates are as shown in table 1.
The epoxy-modified polybutadiene of table 1
| Molecular weight | Contents of ethylene | Epoxy grafting rate | |
| PB-5000 (epoxy) | 5000 | 60% | 5 |
| PB-10000 (epoxy) | 10000 | 90% | 8 |
| PB-5000-30 (epoxy) | 5000 | 30% | 5 |
| PB-5000-02 (epoxy) | 5000 | 60% | 2 |
According to information in the public domain, the poly- fourth of different molecular weight, different contents of ethylene, different maleic anhydride grafting ratios can be prepared
Diene resin, it is as follows.
By the dry hexamethylene of 16L, the dry butadiene of 1600g is put into four mouthfuls of glass reaction bottles of 4L (at overbaking drying
Reason) in, it is passed through drying nitrogen protection, 40 DEG C~80 DEG C of constant temperature, then sequentially adds following catalytic component: 4ml~9ml tri-
The hexane solution, 16ml~36ml triisobutyl aluminium of [di-(2-ethylhexyl)phosphoric acid] iron (0.4mmol~0.9mmol)
The hexane solution of (8mmol), the hexane solution of 12ml~27ml triphenyl phosphate (1.2mmol~2.7mmol), 17mmol~
Tetrahydrofurfuryl alcohol ethylether, the PMDETA 7mmol~17mmol of 38mmol is warming up to 65 DEG C~90 DEG C, polymerize 1~9 hour.So
After add ethyl alcohol and terminate reaction glue sample is precipitated, filter, with 12~18h of acetone extraction, be put into 25 DEG C of baking ovens vacuum drying 12h,
Obtain white solid product polybutadiene.
By the above-mentioned polybutadiene of 1000g, 300ml dimethylbenzene is put into 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 into system containing
165g~370g maleic anhydride, the xylene solution of 48g~110g antifebrin stir 10min~25min after being added dropwise,
By the xylene solution containing 24g~56g BPO in 30min in be slowly dropped in four-hole bottle, reactant is slowly warming up to
120 DEG C, the reaction was continued at a constant temperature 3~5 hours, and after reaction, decompression distillation removes dimethylbenzene and unreacted maleic acid
Acid anhydride pours out product, and dehydrated alcohol precipitating is added, sedimentation a period of time, filters, with acetone extraction 12h~18h, is put into 25 DEG C
Baking oven is dried in vacuo 12h, obtains white solid product MA modified polybutadiene.
Different molecular weight, different contents of ethylene, the butadiene resin of difference MA grafting rate are as shown in table 2.
2 MA modified polybutadiene of table
| Molecular weight | Contents of ethylene | MA grafting rate | |
| PB-5000(MA) | 5000 | 60% | 5 |
| PB-7000(MA) | 7000 | 85% | 7 |
| PB-50000(MA) | 50000 | 99% | 10 |
| PB-5000-15(MA) | 5000 | 60% | 15 |
According to information in the public domain, the butadiene styrene resin of different molecular weight, different contents of ethylene can be prepared, it is specific as follows.
By 4L dry hexamethylene, 0.05ml~0.48ml tetrahydrofurfuryl alcohol ethylether, it is put into four mouthfuls of glass reaction bottles (warp of 4L
Overbaking is dried) in, it is passed through drying nitrogen protection, 40 DEG C~60 DEG C of constant temperature, is then added simultaneously with the following group in 60min
Point: 25g~200g styrene (S), the mix monomer of 30~210g butadiene (B), 0.4mol/L butyl lithium 0.02mL~
Then the cyclohexane solution of the mono- chlorine trimethyl silane of 0.2mol/L of 1.0mL~16.65mL is added in 0.1mL, react 30min, add
Enter isopropanol and terminate reaction precipitation glue sample, filter, with acetone extraction 12h, is put into 25 DEG C of baking ovens vacuum drying 12h, obtains white
Solid product.
Different molecular weight, different contents of ethylene, the butadiene styrene resin of different styrene-contents are as shown in table 3.
3 butadiene styrene resin of table
| 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-1000-5 | 1000 | 60% | 5% |
| PBS-1000 | 1000 | 30% | 30% |
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, of the invention is typical but non-limiting
Embodiment is as follows:
Embodiment
The production method of embodiment 1-10 and comparative example 1-5 copper-clad laminate: design parameter is as shown in table 4 and table 5.
Butadiene styrene resin, modified polybutadiene, crosslinking agent, styrene, initiator are dissolved in toluene, after completely dissolution,
The filler of angle value, different quality containing in different-grain diameter is added, is then mixed to get glue at room temperature.It is impregnated using glass cloth
Then above-mentioned glue toasts in 155 DEG C of baking oven and is cured as within 5 minutes B-stage, control obtains prepreg.
Then, the prepreg of production is placed between copper foil, is laminated and solidifies in 210 DEG C in press, obtains solidfied material
Measuring Dielectric Constant afterwards, Tg, peel strength, DK, Df.Specific performance is shown in Table 4, table 5.
Used material is specific as follows in above-described embodiment and comparative example example:
Triallyl isocyanurate: Nippon Kasei Chemical Company TAIC M-60
Poly- triallyl isocyanurate: Nippon Kasei Chemical Company
Triallyl cyanurate: Nippon Kasei Chemical Company
Styrene: Xi'an weber power Yang Huagong
BPO: great river grease Co., Ltd.
BIPB: great river grease Co., Ltd.
DCP:99% purity, Mike woods Chemical Company
Barium titanate/strontium titanate/barium strontium titanate: Shanghai allusion quotation raises science and technology
Lead titanates: Hubei flat peach culminant star electronics.
4 Examples 1 to 8 formula of table and test result
5 embodiment 9~10 of table, the Comparative Examples 1 to 5 formula and test result
The test method of the above characteristic is as follows::
1, it glass transition temperature (Tg): is measured according to the DMA method of IPC-TM-650 2.4.24 defined.
2, peel strength (PS): according to experiment condition " after thermal stress " in IPC-TM-650 2.4.8 method, plate is tested
Peel strength.
3, dielectric properties: SPDR (splite post dielectric resonator) method is tested, test condition
For A state, 10GHz.
By table 4 and table 5 it is found that being prepared to embodiment 10 from embodiment 1 it can be seen from the comparison of embodiment and comparative example
Plate, the comprehensive performances such as dielectric loss, peel strength, glass transition temperature are preferable, using unmodified poly- in comparative example 1
The dielectric loss of butadiene, plate is relatively low, and the peel strength of plate is low；The polybutadiene of high grafting rate is used in comparative example 2,
The peel strength of plate is high, but dielectric loss is high；The butadiene styrene resin small using styrene-content of comparative example 3, the Tg of plate are low；
For the additive amount of 4 styrene of comparative example less than 1%, the Tg value of plate is low, the small butadiene styrene resin of the use contents of ethylene of comparative example 5,
The Tg of butadiene resin, plate is low.
Heat-resist, peel strength is high, dielectric constant is low it is found that material of the invention can achieve for comprehensive the above results, is situated between
The small equal excellent comprehensive performances of electrical loss, performance have obtained biggish improvement, can satisfy the performance requirement of high dielectric material.
Above embodiments not impose any restrictions the content of composition of the invention, all technologies according to the present invention
Essence or composition composition or content any subtle modifications, equivalent variations and modifications to the above embodiments, still fall within
In the range of technical solution of the present invention.
The Applicant declares that the present invention is explained by the above embodiments detailed composition of the invention, but the present invention not office
It is limited to above-mentioned detailed composition, that is, does not mean that the present invention must rely on above-mentioned detailed composition and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (25)
1. a kind of compositions of thermosetting resin, which is characterized in that the unsaturated polybutadiene including butadiene styrene resin, modified with polar
Alkene, styrene, crosslinking agent, initiator, ceramic packing；
For the molecular weight of the butadiene styrene resin less than 11000, the contents of ethylene of the butadiene styrene resin is 60~99wt%；The fourth
The styrene-content of benzene resin is 30~60wt%；The butadiene styrene resin account for resin combination weight percent be 45~
80wt%；
The molecular weight of the unsaturated polybutadiene of the modified with polar is 5000~50000；The insatiable hunger of modified with polar
With 60~99wt% of contents of ethylene of polybutadiene；Epoxy group on the unsaturated polybutadiene strand of modified with polar
Group's grafting rate is between 5 to 10；The unsaturated polybutadiene of modified with polar accounts for the weight percent of resin combination
Than for 10~50wt%；
The styrene accounts for 1~30wt% of weight percent of resin combination.
2. compositions of thermosetting resin according to claim 1, which is characterized in that the contents of ethylene of the butadiene styrene resin
For 70~95wt%.
3. compositions of thermosetting resin according to claim 2, which is characterized in that the contents of ethylene of the butadiene styrene resin
For 75~93wt%.
4. compositions of thermosetting resin according to claim 1, which is characterized in that the styrene-content of the butadiene styrene resin
For 35~55wt%.
5. compositions of thermosetting resin according to claim 4, which is characterized in that the styrene-content of the butadiene styrene resin
For 40~50wt%.
6. compositions of thermosetting resin according to claim 1, which is characterized in that the butadiene styrene resin accounts for resin combination
Weight percent be 48~70wt%.
7. compositions of thermosetting resin according to claim 6, which is characterized in that the butadiene styrene resin accounts for resin combination
Weight percent be 50~60wt%.
8. compositions of thermosetting resin according to claim 1, which is characterized in that the unsaturation of the modified with polar
The molecular weight of polybutadiene is 8000~40000.
9. compositions of thermosetting resin according to claim 8, which is characterized in that the unsaturation of the modified with polar
The molecular weight of polybutadiene is 11000~30000.
10. compositions of thermosetting resin according to claim 1, which is characterized in that the insatiable hunger of the modified with polar
With 70~95wt% of contents of ethylene of polybutadiene.
11. compositions of thermosetting resin according to claim 10, which is characterized in that the insatiable hunger of the modified with polar
With 75~93wt% of contents of ethylene of polybutadiene.
12. compositions of thermosetting resin according to claim 1, which is characterized in that the insatiable hunger of the modified with polar
The weight percent for accounting for resin combination with polybutadiene is 15~40wt%.
13. compositions of thermosetting resin according to claim 12, which is characterized in that the insatiable hunger of the modified with polar
The weight percent for accounting for resin combination with polybutadiene is 20~30wt%.
14. compositions of thermosetting resin according to claim 1, which is characterized in that the styrene accounts for resin combination
Weight percent 5~25%.
15. compositions of thermosetting resin according to claim 14, which is characterized in that the styrene accounts for resin combination
10~20wt% of weight percent.
16. compositions of thermosetting resin according to claim 1, which is characterized in that the insatiable hunger of the modified with polar
Epoxy-modified polybutadiene, maleic anhydride modified polybutadiene, acrylic acid modified poly- is selected from polybutadiene
The modified polybutadiene of butadiene resin, hydroxy-end capped polybutadiene, the polybutadiene of carboxy blocking, amine
Any one or at least two mixing.
17. compositions of thermosetting resin according to claim 1, which is characterized in that the crosslinking agent accounts for resin combination
Weight percent be 3~40wt%；The crosslinking agent is selected from triallyl isocyanurate, poly- triallyl isocyanurate, three
Any one in allyl ester cyanurate, diallyl phthalate, divinylbenzene or polyfunctional acrylate
Or at least two mixing.
18. compositions of thermosetting resin according to claim 1, which is characterized in that the initiator accounts for resin combination
Weight percent is 1~7wt%, and the initiator is selected from a, and a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, peroxidating two are different
Bis- (tert-hexyl peroxide) -3 propyl benzene, cumyl t-butyl peroxide, 1,1-, 3,5- trimethyl-cyclohexanes, dimethyl -2 2,5-,
In 5- bis- (t-butylperoxy) hex- 3- alkynes, peroxidized t-butyl perbenzoate any one or at least two mixing.
19. compositions of thermosetting resin according to claim 1, which is characterized in that the ceramic packing is selected from crystal type
Silica, unformed silica, spherical silica, titanium dioxide, boron nitride, aluminium nitride, silicon carbide, aluminium oxide,
Barium titanate, strontium titanates, magnesium titanate, calcium titanate, barium strontium titanate, calcium barium titanate, lead titanates, lead zirconate titanate, zirconium lanthanium titanate lead, metatitanic acid
Lanthanum barium, zirconia titanate barium, hafnium oxide, lead magnesio-niobate, barium magnesium niobate, lithium niobate, potassium niobate, tantalic acid aluminium strontium, potassium tantallum niobate (KTH), niobic acid
Strontium barium, lead bariun niobate, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, barium titanate rubidium, copper titanate, appointing in lead titanates-lead magnesio-niobate
It anticipates a kind of or at least two mixtures；
Angle value is 0.5~20uM in the partial size of the ceramic packing；
The weight percent that the ceramic packing accounts for resin combination is 0~90wt%.
20. compositions of thermosetting resin according to claim 19, which is characterized in that the partial size moderate of the ceramic packing
Value is 1~15uM.
21. compositions of thermosetting resin according to claim 20, which is characterized in that the partial size moderate of the ceramic packing
Value is 4~10uM.
22. compositions of thermosetting resin according to claim 19, which is characterized in that the ceramic packing accounts for resin combination
The weight percent of object is 40~85wt%.
23. compositions of thermosetting resin according to claim 22, which is characterized in that the ceramic packing accounts for resin combination
The weight percent of object is 60~80wt%.
24. compositions of thermosetting resin according to claim 1, which is characterized in that the resin combination further includes fire-retardant
Agent, the fire retardant be selected from deca-BDE, ethyl-bis- (tetrabromo phthalimides), decabromodiphenylethane, three (2,
6- 3,5-dimethylphenyl) phosphine, -10 phosphine phenanthrene -10- oxide of 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxy, 2,6- bis-
It is any one in (2,6- 3,5-dimethylphenyl) phosphino- benzene or 10- phenyl -9,10- dihydro-9-oxy -10- phosphine phenanthrene -10- oxide
Kind or at least two mixing.
25. any compositions of thermosetting resin is in prepreg, copper-clad laminate, printing according to claim 1~24
Application in circuit board.
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| CN109385018A (en) * | 2017-08-04 | 2019-02-26 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin and prepreg and metal-clad laminate using its production |
| CN111378242B (en) * | 2018-12-29 | 2022-10-18 | 广东生益科技股份有限公司 | Resin composition, prepreg containing resin composition, dielectric substrate and printed circuit board |
| CN110922705A (en) * | 2019-12-13 | 2020-03-27 | 陕西易莱德新材料科技有限公司 | High-heat-resistance conductive composite material and preparation method 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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| 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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