CN106280199A - A kind of compositions of thermosetting resin and application thereof - Google Patents

A kind of compositions of thermosetting resin and application thereof Download PDF

Info

Publication number
CN106280199A
CN106280199A CN201610765448.1A CN201610765448A CN106280199A CN 106280199 A CN106280199 A CN 106280199A CN 201610765448 A CN201610765448 A CN 201610765448A CN 106280199 A CN106280199 A CN 106280199A
Authority
CN
China
Prior art keywords
polybutadiene
compositions
resin
modified
thermosetting resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610765448.1A
Other languages
Chinese (zh)
Other versions
CN106280199B (en
Inventor
殷卫峰
师剑英
张记明
李莎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHAANXI SHENGYI SCI TECH Co Ltd
Original Assignee
SHAANXI SHENGYI SCI TECH Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SHAANXI SHENGYI SCI TECH Co Ltd filed Critical SHAANXI SHENGYI SCI TECH Co Ltd
Priority to CN201610765448.1A priority Critical patent/CN106280199B/en
Publication of CN106280199A publication Critical patent/CN106280199A/en
Application granted granted Critical
Publication of CN106280199B publication Critical patent/CN106280199B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00Compositions 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
    • C08L53/02Compositions 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered 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
    • B32B15/08Layered 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
    • B32B15/082Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/20Layered products comprising a layer of metal comprising aluminium or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00Layered 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F287/00Macromolecular compounds obtained by polymerising monomers on to block polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04Polymers provided for in subclasses C08C or C08F
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/20Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/306Resistant to heat
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/08PCBs, i.e. printed circuit boards
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/014Additives containing two or more different additives of the same subgroup in C08K
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

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

A kind of compositions of thermosetting resin and application thereof
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.
CN201610765448.1A 2016-08-29 2016-08-29 A kind of compositions of thermosetting resin and its application Active CN106280199B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610765448.1A CN106280199B (en) 2016-08-29 2016-08-29 A kind of compositions of thermosetting resin and its application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610765448.1A CN106280199B (en) 2016-08-29 2016-08-29 A kind of compositions of thermosetting resin and its application

Publications (2)

Publication Number Publication Date
CN106280199A true CN106280199A (en) 2017-01-04
CN106280199B CN106280199B (en) 2019-05-28

Family

ID=57675047

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610765448.1A Active CN106280199B (en) 2016-08-29 2016-08-29 A kind of compositions of thermosetting resin and its application

Country Status (1)

Country Link
CN (1) CN106280199B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (3)

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

Patent Citations (3)

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

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
CN106280199B (en) 2019-05-28

Similar Documents

Publication Publication Date Title
CN106379006A (en) High frequency copper-clad plate
CN106280199A (en) A kind of compositions of thermosetting resin and application thereof
CN104725857B (en) A kind of resin combination and use its prepreg and laminate
CN106280179A (en) A kind of high frequency resin composition and application thereof
CN107964203B (en) Low-dielectric prepreg composition, copper-clad plate and manufacturing method thereof
CN106280178B (en) A kind of resin combination and its application
CN104725828B (en) A kind of resin combination and use its prepreg and laminate
CN103937156A (en) Thermosetting resin composition and method for manufacturing prepreg and laminated board by using thermosetting resin composition
CN107090065A (en) High frequency resin composition and its application in prepreg and metal-clad laminate
KR20080093920A (en) Prepreg, multilayer wiring board and electronic parts using same
WO2013029271A1 (en) Halogen-free resin composition and method for preparation of copper clad laminate with same
EP2595460A1 (en) Composite material and high frequency circuit substrate manufactured with the composite material and the manufacturing method thereof
CN106366477B (en) A kind of high frequency resin composition
JP5603470B2 (en) Composition for coverlay of flexible printed circuit board and method for producing the same
CN108250716A (en) Polyphenyl ether resin composition and its prepreg, the laminate and printed circuit board of a kind of polysiloxanes-allyl compound modification
CN107108820A (en) Resin combination, prepreg, metal-clad laminate and circuit board
CN111253888A (en) Circuit material and circuit board comprising same
CN106380715B (en) A kind of resin combination
CN108659501B (en) Polyphenylene ether resin composition
TW201124478A (en) Dielectric material formula and circuit board utilizing the same
CN109467862A (en) A kind of high frequency resin composition and its application
CN104356604A (en) Dielectric material composition as well as preparation method and application thereof
CN103214796A (en) Epoxy resin composition, preparation method of epoxy resin composition, and copper-clad plate prepared by epoxy resin composition
CN108192264A (en) A kind of resin combination for high frequency flexible circuit board
JPH04258658A (en) Flame-retardant thermosetting resin composition

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant