CN106280199A - A kind of compositions of thermosetting resin and application thereof - Google Patents
A kind of compositions of thermosetting resin and application thereof 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
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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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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- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- 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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- B32—LAYERED PRODUCTS
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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
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- 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, including butadiene styrene resin, the unsaturated polyester butadiene of modified with polar, styrene, cross-linking agent, initiator, ceramic packing.The invention also discloses the application in prepreg, laminate, copper-clad laminate, printed circuit board of the above-mentioned compositions of thermosetting resin.Compositions of thermosetting resin of the present invention, it 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
Technical field
The present invention relates to copper-clad plate technical field, be specifically related to a kind of compositions of thermosetting resin, the invention still further relates to heat
The application in prepreg, copper-clad laminate, printed circuit board of the thermosetting resin compositions.
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.
Patent JP60011634B2, JP1993068484 disclose in a kind of polybutadiene formula and use maleimide to change
The thermostability of kind sheet material, but maleimide is with the phase tolerance between resin, and maleimide can increase the loss of sheet material.
Application No. 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 is not given
MA functional group percent grafting on modified strand, if percent grafting is excessive, can cause the polarity of composite to increase, and dielectric is normal
Number, dielectric loss increase.If functional group's percent grafting is too small, resin system can be caused too small with the peel strength between Copper Foil.
Additionally, this patent does not use in resin combination butadiene styrene resin, the poor heat resistance of sheet material.
Application No. 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
Thing maleic anhydride grafting ratio is too high, causes the polarity of composite to increase, and dielectric constant, dielectric loss increase.Additionally, this patent
Disclosed in MA 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: 2008.7.28, notification number: CN101328277A, the day for announcing:
2010.7.21) Chinese patent discloses the maleic anhydride modified polybutadiene of a kind of use, maleic anhydride modified molecular weight is more than
The butadiene of 50000 and cinnamic copolymer, this patent is also without the MA functional group grafting be given on modified strand
Rate, if percent grafting is excessive, can cause the polarity of composite to increase, and dielectric constant, dielectric loss increase；If functional group connects
Branch rate is too small, and resin system can be caused too small with the peel strength between Copper Foil.Additionally, the MA modification fourth two disclosed in this patent
Alkene and cinnamic molecular weight of copolymer, more than 50,000, are difficult to dissolve in a solvent, and subsequent technique is poor.
For problem above, the present invention propose one have heat-resist, that peel strength is high, dielectric loss is little etc. is excellent
The baseplate material of combination property.
Summary of the invention
It is an object of the invention to provide a kind of compositions of thermosetting resin, its have heat-resist, peel strength is high, dielectric
Little Dengs excellent comprehensive performance is lost, the performance requirement of high frequency sheet material can be met.
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 solution adopted in the present invention is, a kind of compositions of thermosetting resin, changes including butadiene styrene resin, polar group
The unsaturated polyester butadiene of property, styrene, cross-linking agent, initiator, ceramic packing.
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%.
Polybutadiene is modified with polar polybutadiene, and modified with polar polybutadiene is selected from ring
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%, the most excellent
Select 75～93wt%；Epoxide group percent grafting on modified with polar polybutadiene strand is between 5 to 10；Polar group
It is 10～50wt% that group's modified polybutadiene resin accounts for the percentage by weight of resin combination, preferably 15～40wt%, further
Preferably 20～30wt%.
Styrene accounts for the percentage by weight 1～30wt% of resin combination, preferably 5～25%, further preferred 10～
20wt%.
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 resin composition weight percentage ratio, and initiator is selected from a, a '-two (tert-butyl hydroperoxide
Between isopropylbenzene) benzene, cumyl peroxide, cumyl t-butyl peroxide, double (tertiary hexyl the peroxidating)-3,3,5-front three 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 the mixing of at least two.
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.
Ceramic packing is selected from powdered quartz, unformed silicon dioxide, spherical silica, titanium dioxide, nitrogen
Change boron, aluminium nitride, carborundum, aluminium oxide, Barium metatitanate., strontium titanates, magnesium titanate, calcium titanate, barium strontium titanate, calcium Barium metatitanate., 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 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, titanium
Any one or the mixture of at least two in acid barium rubidium, copper titanate, lead titanates-lead magnesio-niobate；
In the particle diameter of ceramic packing, angle value is 0.5～20uM, preferably 1～15uM, further preferred 4～10uM；
It is 0～90wt% that ceramic packing accounts for the percentage by weight of resin combination, preferably 40～85wt%, further preferably
60～80wt%.
Second technical scheme of the present invention is, above-mentioned compositions of thermosetting resin at prepreg, laminate, cover
Application in copper-clad laminate, 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.
Compositions of thermosetting resin of the present invention, including butadiene styrene resin, the unsaturated polyester butadiene of modified with polar, benzene second
Alkene, cross-linking agent, initiator, ceramic packing.
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%.
It is 45～80wt% that butadiene styrene resin accounts for the percentage by weight of resin combination, 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
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, 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, polybutadiene can be caused to be difficult in a solvent dissolve, subsequent technique is poor.If molecule
Amount less than 5000, can cause follow-up prepare sheet material during gummosis excessive, manufacturability is poor.
The contents of ethylene 60～99% of modified with polar polybutadiene, such as 60%, 65%, 70%, 75%,
80%, 85%, 90%, 92% or 95%, preferably 70～95wt%, preferably 70～95wt%, further preferred 75～93wt%.
Epoxide group percent grafting on modified with polar 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 modified with polar 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 1～30wt% that styrene accounts for the percentage by weight of resin combination, 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 more than 30%, and the fragility that can cause prepreg is big, and manufacturability is poor.If cinnamic content is less than 1%, does not has and change
The effect of kind sheet material thermostability.
Cross-linking agent percentage by weight is 3～40wt%；Cross-linking agent is selected from triallyl isocyanurate, poly-isocyanuric acid triolefin
Propyl ester, triallyl cyanurate, trimethacrylate acid, diallyl phthalate, divinylbenzene or polyfunctional
Any one or the mixing of at least two in 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 is selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, cumyl peroxide, tert-butyl hydroperoxide
Isopropylbenzene, 1, double (the tertiary hexyl peroxidating)-3 of 1-, 3,5-trimethyl-cyclohexanes, 2,5-dimethyl-2,5-bis-(t-butyl peroxy
Base) hex-3-alkynes, octanoic acid ter-butyl ester, any one or the mixing of at least two in peroxidized t-butyl perbenzoate.
This compositions of thermosetting resin also includes fire retardant, and (tetrabromo-benzene is adjacent selected from deca-BDE, ethyl-bis-for fire retardant
Dicarboximide), decabromodiphenylethane, three (2,6-3,5-dimethylphenyl) phosphine, 10-(2,5-dihydroxy phenyl)-9,10-two
Hydrogen-9-oxidation-10 phosphine phenanthrene-10-oxides, 2,6-bis-(2,6-3,5-dimethylphenyl) phosphino-benzene or 10-phenyl-9,10-dihydro-9-
Any one or the mixing of at least two in oxidation-10-phosphine phenanthrene-10-oxide.
Ceramic packing is selected from powdered quartz, unformed silicon dioxide, spherical silica, titanium dioxide, nitrogen
Change boron, aluminium nitride, carborundum, aluminium oxide, Barium metatitanate., strontium titanates, magnesium titanate, calcium titanate, barium strontium titanate, calcium Barium metatitanate., 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 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, titanium
Any one or the mixture of at least two in acid barium rubidium, copper titanate, lead titanates-lead magnesio-niobate.
In the particle diameter of ceramic packing, 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 ceramic packing accounts for the percentage by weight of resin combination, 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, different molecular weight, different contents of ethylene, the polybutadiene of different epoxy percent grafting can be prepared
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 1000g polybutadiene, 2.5L ethyl acetate 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 80 DEG C～95 DEG C, be slowly added in system containing 50g～
200g formic acid, 5g～42g Polyethylene Glycol, stirring reaction 2～4 hours after dropping, then by the hydrogen peroxide of 30g～215g
Being slowly dropped in 30min in four-hole bottle, reactant is slowly warmed up to 120 DEG C, continues reaction 3～5 hours at a constant temperature,
After reaction terminates, being poured out by product, add dehydrated alcohol precipitation, settle a period of time, sucking filtration, with sodium bicarbonate solution and distillation
Water washs at least 12 times, puts into 25 DEG C of baking oven vacuum drying 12h, obtains white solid product.
Different molecular weight, different contents of ethylene, different epoxy percent grafting polybutadiene as shown in table 1.
The epoxide modified polybutadiene of table 1
| Molecular weight | Contents of ethylene | Epoxy percent grafting | |
| 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, 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 2.
Table 2 MA modified polybutadiene
| Molecular weight | Contents of ethylene | MA percent grafting | |
| 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, 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 3.
Table 3 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-1000-5 | 1000 | 60% | 5% |
| PBS-1000 | 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 1-10 and the manufacture method of comparative example 1-5 copper-clad laminate: design parameter is as shown in table 4 and table 5.
Butadiene styrene resin, modified polybutadiene, cross-linking agent, styrene, 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 is shown in Table 4, table 5.
Material used in above-described embodiment and comparative example 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
Styrene: Xi'an weber power raises chemical industry
BPO: great river oils and fats Co., Ltd.
BIPB: great river oils and fats 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 Prunus persica f. compressa culminant star electronics.
Table 4 embodiment 1～8 formula and test result
Table 5 embodiment 9～10, comparative example 1～5 formula and test result
The method of testing of above characteristic is as follows::
1, glass transition temperature (Tg): be measured according to the DMA method of IPC-TM-650 2.4.24 defined.
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 4 and table 5, from the contrast of embodiment and comparative example it can be seen that what embodiment 1 was prepared to embodiment 10
Sheet material, the combination property such as its dielectric loss, peel strength, glass transition temperature is preferable, uses unmodified poly-in comparative example 1
Butadiene, the dielectric loss ratio of sheet material is relatively low, and the peel strength of sheet material is low；Comparative example 2 uses the polybutadiene of high percent grafting,
The peel strength of sheet material is high, but dielectric loss is high；Comparative example 3 uses the butadiene styrene resin that styrene-content is little, and the Tg of sheet material is low；
The cinnamic addition of comparative example 4 is less than 1%, and the Tg value of sheet material is low, comparative example 5 use butadiene styrene resin that contents of ethylene is little,
Butadiene resin, the Tg of sheet material is low.
Combining the above results to understand, the material of the present invention can reach heat-resist, peel strength is high, dielectric constant is low, Jie
Electrical loss is little waits excellent comprehensive performance, and 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 compositions of thermosetting resin, it is characterised in that include the unsaturated polybutadiene of butadiene styrene resin, modified with polar
Alkene, styrene, cross-linking agent, initiator, ceramic packing.
Compositions of thermosetting resin 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%；
The styrene-content of described butadiene styrene resin is 30～60%, preferably 35～55%, further preferred 40～50%；Described butylbenzene tree
It is 45～80wt% that fat accounts for the percentage by weight of resin combination, preferably 48～70wt%, further preferred 50～60wt%.
Compositions of thermosetting resin the most according to claim 1, it is characterised in that described polybutadiene is polar group
Group's modified polybutadiene resin, described modified with polar polybutadiene is selected from epoxide modified polybutadiene, Malaysia
Anhydride modified polybutadiene, acrylic acid modified polybutadiene, hydroxy-end capped polybutadiene, carboxy blocking
The modified polybutadiene of polybutadiene, amine any one or the mixing of at least two.
4. according to the compositions of thermosetting resin described in claim 1 or 3, it is characterised in that the poly-fourth of described modified with polar
The molecular weight of diene is 5000～50000, preferably 8000～40000, further preferred 11000～30000；Modified with polar
The contents of ethylene 60～99% of polybutadiene, preferably 70～95wt%, further preferred 75～93wt%；Modified with polar
Epoxide group percent grafting on polybutadiene strand is between 5 to 10；Modified with polar polybutadiene accounts for resin
The percentage by weight of compositions is 10～50wt%, preferably 15～40wt%, further preferred 20～30wt%.
Compositions of thermosetting resin the most according to claim 1, it is characterised in that described styrene accounts for resin combination
Percentage by weight 1～30wt%, preferably 5～25%, further preferred 10～20wt%.
Compositions of thermosetting resin the most according to claim 1, it is characterised in that described cross-linking agent accounts for resin combination
Percentage by weight is 3～40wt%；Described cross-linking agent is selected from triallyl isocyanurate, poly-triallyl isocyanurate, triolefin
In the acid of propyl ester cyanurate, trimethacrylate, diallyl phthalate, divinylbenzene or polyfunctional acrylate
Any one or the mixing of at least two.
Compositions of thermosetting resin the most according to claim 1, it is characterised in that described initiator accounts for resin combination weight
Amount percentage ratio is 1～7wt%, and described initiator is selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, peroxidating diisopropyl
Benzene, cumyl t-butyl peroxide, 1, double (the tertiary hexyl peroxidating)-3 of 1-, 3,5-trimethyl-cyclohexanes, 2,5-dimethyl-2,5-
Any one or at least two in two (t-butylperoxy) hex-3-alkynes, octanoic acid ter-butyl ester, peroxidized t-butyl perbenzoate
Mixing.
Compositions of thermosetting resin the most according to claim 1, it is characterised in that described ceramic packing is selected from crystal type two
Silicon oxide, unformed silicon dioxide, spherical silica, titanium dioxide, boron nitride, aluminium nitride, carborundum, aluminium oxide, titanium
Acid barium, 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, tantalum niobate
Potassium, strontium barium niobate, lead bariun niobate, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, Barium metatitanate. rubidium, copper titanate, lead titanates-lead magnesio-niobate
In any one or the mixture of at least two；
In the particle diameter of described ceramic packing, angle value is 0.5～20uM, preferably 1～15uM, further preferred 4～10uM；
It is 0～90wt% that described ceramic packing accounts for the percentage by weight of resin combination, preferably 40～85wt%, further preferably
60～80wt%.
Compositions of thermosetting resin the most according to claim 1, it is characterised in that this resin combination also includes fire-retardant
Agent, described fire retardant selected from deca-BDE, ethyl-bis-(tetrabromo phthalimide), decabromodiphenylethane, three (2,
6-3,5-dimethylphenyl) phosphine, 10-(2,5-dihydroxy phenyl)-9,10-dihydro-9-oxy-10 phosphine phenanthrene-10-oxide, 2,6-bis-
Any one in (2,6-3,5-dimethylphenyl) phosphino-benzene or 10-phenyl-9,10-dihydro-9-oxy-10-phosphine phenanthrene-10-oxide
Plant or the mixing of at least two.
10. according to the arbitrary described compositions of thermosetting resin of claim 1～9 in prepreg, laminate, copper foil covered pressure
Application in plate, printed circuit board.
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| CN107090065A (en) * | 2017-06-22 | 2017-08-25 | 陕西生益科技有限公司 | High frequency resin composition and its application in prepreg and metal-clad laminate |
| 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 |
| 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 |
| CN111378242A (en) * | 2018-12-29 | 2020-07-07 | 广东生益科技股份有限公司 | Resin composition, prepreg containing resin composition, dielectric substrate and printed circuit board |
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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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| 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 |
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| CN107090065A (en) * | 2017-06-22 | 2017-08-25 | 陕西生益科技有限公司 | High frequency resin composition and its application in prepreg and metal-clad laminate |
| 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 |
| CN111378242A (en) * | 2018-12-29 | 2020-07-07 | 广东生益科技股份有限公司 | Resin composition, prepreg containing resin composition, dielectric substrate and printed circuit board |
| 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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| CN106280199B (en) | 2019-05-28 |
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