CN106380715B - A kind of resin combination - Google Patents
A kind of resin combination Download PDFInfo
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- CN106380715B CN106380715B CN201610769395.0A CN201610769395A CN106380715B CN 106380715 B CN106380715 B CN 106380715B CN 201610769395 A CN201610769395 A CN 201610769395A CN 106380715 B CN106380715 B CN 106380715B
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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
- 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
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- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/08—Impregnating
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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
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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
- C08L2312/00—Crosslinking
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Abstract
The invention discloses a kind of resin combination, epoxy-modified unsaturated polybutadiene, crosslinking agent, initiator including butadiene styrene resin, molecular weight less than 50000.The invention also discloses application of the resin combination in prepreg, laminate, copper-clad laminate, printed circuit board.Invention resin composition 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 copper-clad plate fields, and in particular to a kind of resin combination, the invention further relates to the resin combinations
Application in prepreg, laminate, 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.
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 epoxy-modified polybutadiene of use, maleic anhydride modified molecular weight is greater than
50000 butadiene and the copolymer of styrene, this patent do not provide the epoxy-modified range on modified strand, such as
Fruit epoxide group quantity is excessive, and the polarity that will lead to composite material increases, and dielectric constant, dielectric loss increase；If epoxy group
Group's quantity 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
The molecular weight of copolymer of diene and styrene is greater than 50,000, is difficult to dissolve in a solvent, subsequent technique is poor.
In view of the above problems, having the invention proposes one kind, heat-resist, peel strength is high, dielectric constant is low, dielectric
The baseplate material of small equal excellent comprehensive performances is lost.
Summary of the invention
The object of the present invention is to provide a kind of resin combinations, with heat-resist, peel strength is high, dielectric loss is small
Equal excellent comprehensive performances, can satisfy the performance requirement of high frequency plate.
It is a further object to provide a kind of resin combinations in prepreg, laminate, copper-clad laminate, print
Application in circuit board processed.
The technical scheme adopted by the invention is that a kind of resin combination, including butadiene styrene resin, molecular weight are less than 50000
Epoxy-modified unsaturated polybutadiene, crosslinking agent, initiator.
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%.
The molecular weight of epoxy-modified polybutadiene is 5000~50000, preferably 8000~40000, further preferred 11000
~30000.
The contents of ethylene 60~99% of epoxy-modified polybutadiene, preferably 70~95wt%, preferably 70~95wt%, into
One step preferably 75~93wt%；Epoxy group grafting rate on epoxy-modified polybutadiene strand is between 5 to 10.
Epoxy-modified polybutadiene account for resin combination weight percent be 10~50wt%, preferably 15~
40wt%, further preferred 20~30wt%.
Crosslinking agent account for resin combination weight percent be 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.
The weight percent that initiator accounts for the resin combination is 1~7wt%, and initiator is selected from a, (tert-butyl of a '-two
Isopropylbenzene between peroxidating) benzene, cumyl peroxide, cumyl t-butyl peroxide, bis- (tert-hexyl peroxide) -3,3 1,1-,
5- trimethyl-cyclohexane, 2,5- dimethyl -2,5- bis- (t-butylperoxy) hex- 3- alkynes, octanoic acid ter-butyl ester, perbenzoic acid
The tert-butyl ester, three second class amine and its esters, level Four amine salt compound, 2,4,6- tri- (dimethylamino methylamine) phenol, benzyl dimethylamine,
Imidazoles, three amylic phenol acid amides, single or multiple phenolic compounds, boron trifluoride and its organic matter complex, phosphoric acid or phosphorous acid three
In phenyl ester any one or at least two mixing.
Resin combination further includes fire retardant, and fire retardant is selected from bis- (tetrabromo-benzene two formyls of the neighbour Asias of deca-BDE, ethyl-
Amine), decabromodiphenylethane, three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxy -
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 -10- phosphine
In phenanthrene -10- oxide any one or at least two mixing.
Resin combination further includes filler, and filler is selected from crystalline sillica, unformed silica, ball-type dioxy
SiClx, titanium dioxide, boron nitride, aluminium nitride, silicon carbide, aluminium oxide, barium titanate, strontium titanates, magnesium titanate, calcium titanate, strontium titanates
Barium, calcium barium titanate, lead titanates, lead zirconate titanate, zirconium lanthanium titanate lead, lanthanium titanate barium, zirconia titanate barium, titanium dioxide, hafnium oxide, niobium
Magnesium lead plumbate, barium magnesium niobate, lithium niobate, potassium niobate, tantalic acid aluminium strontium, potassium tantallum niobate (KTH), strontium barium niobate, lead bariun niobate, titanium niobate barium, tantalum
Sour bismuth strontium, bismuth titanates, barium titanate rubidium, copper titanate, in lead titanates-lead magnesio-niobate any one or at least two mixing
Object；
Angle value is 0.5~20uM, preferably 1~15uM, further preferred 4~10uM in the partial size of filler；
Filler accounts for the weight percent of the resin combination for 0~90wt%, preferably 40~85wt%, further preferably
60~80wt%.
Second technical solution of the present invention be, above-mentioned resin combination is in prepreg, laminate, copper foil covered
Application in pressing plate, 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.
Invention resin composition, the epoxy-modified unsaturated polybutadiene including butadiene styrene resin, molecular weight less than 50000
Alkene, crosslinking agent, initiator.
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%.
The molecular weight of epoxy-modified 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 epoxy-modified polybutadiene and be difficult to dissolve in a solvent, subsequent technique is poor.
If molecular weight less than 5000, will lead to, subsequent gummosis during preparing plate is excessive, and craftsmanship is poor.
The contents of ethylene 60~99% of epoxy-modified 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 epoxy-modified polybutadiene strand is between 5 to 10；If grafting rate is 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 system less than 5
It is too small with the peel strength between copper foil.
Epoxy-modified polybutadiene account for resin composition weight percentage be 10~50wt%, such as 10%, 15%,
20%, 25%, 28%, 30%, 33%, 35%, 40%, 43%, 35% or 50%, preferably 15~40wt%, further preferably
20~30wt%.
Crosslinking agent account for resin combination weight percent be 3~40wt%, such as 3%, 5%, 15%, 20%, 22%,
25%, 28%, 30%, 33%, 35%, 38% or 40%, preferably 10~38wt%, further preferred 20~35wt%.Crosslinking
Agent is selected from triallyl isocyanurate, poly- triallyl isocyanurate, triallyl cyanurate, trimethacrylate acid, neighbour
In dially phthalate, divinylbenzene or polyfunctional 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%.Draw
Send out agent be selected from a, a '-two (isopropylbenzene between tert-butyl hydroperoxide) benzene, cumyl peroxide, cumyl t-butyl peroxide, 1,
Bis- (tert-hexyl peroxide) -3 1-, 3,5- trimethyl-cyclohexanes, 2,5- dimethyl -2,5- bis- (t-butylperoxy) hex- 3- alkynes,
Octanoic acid ter-butyl ester, peroxidized t-butyl perbenzoate, three second class amine and its esters, level Four amine salt compound, 2,4,6- tri- (dimethylamine
Base methylamine) phenol, benzyl dimethylamine, imidazoles, three amylic phenol acid amides, single or multiple phenolic compounds, boron trifluoride and its organic matter
Complex, in phosphoric acid or triphenyl phosphite 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.
The resin combination further includes filler, and filler is selected from crystalline sillica, unformed silica, ball-type two
Silica, titanium dioxide, boron nitride, aluminium nitride, silicon carbide, aluminium oxide, barium titanate, strontium titanates, magnesium titanate, calcium titanate, metatitanic acid
Strontium barium, calcium barium titanate, 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 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, barium titanate rubidium, copper titanate, in lead titanates-lead magnesio-niobate any one or at least two mixing
Object.
Angle value is 0.5~20uM in the partial size of filler, 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；
Filler account for resin combination weight percent be 0~90wt%, such as 0%, 10%, 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 | 5000 | 60% | 5 |
| PB-7000 | 7000 | 85% | 7 |
| PB-10000 | 10000 | 90% | 8 |
| PB-50000 | 50000 | 99% | 10 |
| PB-5000-2 | 5000 | 60% | 2 |
| PB-5000-15 | 5000 | 60% | 15 |
| PB-5000-30 | 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, 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 2.
2 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-1000-05 | 1000 | 60% | 5% |
| PBS-1000-30 | 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 1-8 and comparative example 1-4 copper-clad laminate: design parameter is as shown in Table 3 and Table 4.
Butadiene styrene resin, epoxy-modified polybutadiene, crosslinking agent, initiator are dissolved in toluene, after completely dissolution, are added
The filler of angle value, different quality containing, is then mixed to get glue at room temperature in different-grain diameter.It is impregnated using glass cloth above-mentioned
Then 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 3, table 4.
Used material is specific as follows in above-described embodiment and comparative example:
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 grease Co., Ltd.
BIPB: great river grease 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 flat peach culminant star electronics.
3 Examples 1 to 8 formula of table and test result
4 comparative example 1~4 of table 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 3 and table 4 it is found that being prepared to embodiment 8 from embodiment 1 it can be seen from the comparison of embodiment and comparative example
Plate, the comprehensive performances such as dielectric loss, dielectric constant, peel strength, glass transition temperature are preferable, use in comparative example 1
The dielectric loss of the polybutadiene of low grafting rate, plate is relatively low, but peel strength is low；High grafting rate is used in comparative example 2
Polybutadiene, the peel strength of plate is high, but the dielectric loss of plate is high；The fourth small using styrene-content of comparative example 3
The Tg of benzene resin, plate is low；For comparative example 4 using the small butadiene styrene resin of contents of ethylene, butadiene resin, the Tg of 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 (24)
1. a kind of resin combination, which is characterized in that including butadiene styrene resin, epoxy-modified unsaturated polybutadiene, crosslinking agent, draw
Send out agent；
60~99wt% of contents of ethylene of the epoxy-modified unsaturated polybutadiene；The epoxy-modified unsaturated polybutadiene
Epoxy group grafting rate on alkene strand is between 5 to 10；
The molecular weight of the epoxy-modified unsaturated polybutadiene is 5000~50000.
2. resin combination according to claim 1, which is characterized in that the second of the epoxy-modified unsaturated polybutadiene
70~95wt% of amount vinyl content.
3. resin combination according to claim 2, which is characterized in that the second of the epoxy-modified unsaturated polybutadiene
75~93wt% of amount vinyl content.
4. resin combination according to claim 1, which is characterized in that the molecular weight of the butadiene styrene resin less than 11000,
The contents of ethylene of the butadiene styrene resin is 60~99wt%；The styrene-content of the butadiene styrene resin is 30~60wt%；Institute
Stating butadiene styrene resin and accounting for the weight percent of resin combination is 45~80wt%.
5. resin combination according to claim 4, which is characterized in that the contents of ethylene of the butadiene styrene resin be 70~
95wt%.
6. resin combination according to claim 5, which is characterized in that the contents of ethylene of the butadiene styrene resin be 75~
93wt%.
7. resin combination according to claim 4, which is characterized in that the styrene-content of the butadiene styrene resin be 35~
55wt%.
8. resin combination according to claim 7, which is characterized in that the styrene-content of the butadiene styrene resin be 40~
50wt%.
9. resin combination according to claim 4, which is characterized in that the butadiene styrene resin accounts for the weight of resin combination
Percentage is 48~70wt%.
10. resin combination according to claim 9, which is characterized in that the butadiene styrene resin accounts for the weight of resin combination
Amount percentage is 50~60wt%.
11. resin combination according to claim 10, which is characterized in that the epoxy-modified unsaturated polybutadiene
Molecular weight is 8000~40000.
12. resin combination according to claim 11, which is characterized in that the epoxy-modified unsaturated polybutadiene
Molecular weight is 11000~30000.
13. resin combination according to claim 1, which is characterized in that the epoxy-modified unsaturated polybutadiene tree
The weight percent that rouge accounts for resin combination is 10~50wt%.
14. resin combination according to claim 13, which is characterized in that the epoxy-modified unsaturated polybutadiene tree
The weight percent that rouge accounts for resin combination is preferably 15~40wt%.
15. resin combination according to claim 14, which is characterized in that the epoxy-modified unsaturated polybutadiene tree
The weight percent that rouge accounts for resin combination is preferably 20~30wt%.
16. resin combination according to claim 1, which is characterized in that the crosslinking agent accounts for the weight of resin combination
Percentage is 3~40wt%, and the crosslinking agent is selected from triallyl isocyanurate, poly- triallyl isocyanurate, triallyl
In cyanurate, diallyl phthalate, divinylbenzene or polyfunctional acrylate any one or extremely
Few two kinds of mixing.
17. resin combination according to claim 1, which is characterized in that the initiator accounts for the 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-,
5- bis- (t-butylperoxy) hex- 3- alkynes, peroxidized t-butyl perbenzoate, triethylamine and its esters, level Four amine salt compound,
Benzyl dimethylamine, imidazoles, three amylic phenol acid amides, single or multiple phenolic compounds, boron trifluoride and its organic matter complex, phosphoric acid
Or in triphenyl phosphite any one or at least two mixing.
18. resin combination according to claim 1, which is characterized in that the resin combination further includes fire retardant, fire-retardant
Agent is selected from deca-BDE, ethyl-bis- (tetrabromo phthalimides), decabromodiphenylethane, three (2,6- dimethyl benzenes
Base) phosphine, -10 phosphine phenanthrene -10- oxide of 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxy, (the 2,6- dimethyl of 2,6- bis-
Phenyl) in phosphino- benzene or 10- phenyl -9,10- dihydro-9-oxy -10- phosphine phenanthrene -10- oxide any one or at least two
The mixing of kind.
19. resin combination according to claim 1, which is characterized in that the resin combination further includes filler, filler choosing
From crystalline sillica, 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, lanthanium titanate barium, zirconia titanate barium, hafnium oxide, lead magnesio-niobate, barium magnesium niobate, lithium niobate, potassium niobate, tantalic acid aluminium strontium, tantalum niobate
Potassium, strontium barium niobate, lead bariun niobate, titanium niobate barium, bismuth tantalate strontium, bismuth titanates, barium titanate rubidium, copper titanate, lead titanates-lead magnesio-niobate
In any one or at least two mixture；
Angle value is 0.5~20uM in the partial size of the filler；
The weight percent that the filler accounts for the resin combination is 0~90wt%.
20. resin combination according to claim 19, which is characterized in that in the partial size of the filler angle value be 1~
15uM。
21. resin combination according to claim 20, which is characterized in that in the partial size of the filler angle value be 4~
10uM。
22. resin combination according to claim 19, which is characterized in that the filler accounts for the weight of the resin combination
Amount percentage is 40~85wt%.
23. resin combination according to claim 22, which is characterized in that the filler accounts for the weight of the resin combination
Amount percentage is 60~80wt%.
24. the resin combination as described in claim 1~23 is any is in prepreg, copper-clad laminate, printed circuit board
Application.
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| CN106380715B true CN106380715B (en) | 2019-05-28 |
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| TWI785710B (en) * | 2021-08-02 | 2022-12-01 | 南亞塑膠工業股份有限公司 | Rubber resin material with high dielectric constant and metal substrate with high dielectric constant |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| 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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