CN106749952A - Resin combination and the prepreg, laminate and the interlayer dielectric that are made using it - Google Patents

Resin combination and the prepreg, laminate and the interlayer dielectric that are made using it Download PDF

Info

Publication number
CN106749952A
CN106749952A CN201611052927.5A CN201611052927A CN106749952A CN 106749952 A CN106749952 A CN 106749952A CN 201611052927 A CN201611052927 A CN 201611052927A CN 106749952 A CN106749952 A CN 106749952A
Authority
CN
China
Prior art keywords
resin
parts
resin combination
crosspolymer
agent
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
CN201611052927.5A
Other languages
Chinese (zh)
Other versions
CN106749952B (en
Inventor
崔春梅
谌香秀
肖升高
陈诚
罗鹏辉
杨宋
何继亮
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.)
Suzhou Shengyi Technology Co Ltd
Original Assignee
Suzhou Shengyi Technology 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 Suzhou Shengyi Technology Co Ltd filed Critical Suzhou Shengyi Technology Co Ltd
Priority to CN201611052927.5A priority Critical patent/CN106749952B/en
Publication of CN106749952A publication Critical patent/CN106749952A/en
Application granted granted Critical
Publication of CN106749952B publication Critical patent/CN106749952B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • C08F283/045—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides on to unsaturated polycarbonamides, polyesteramides or polyimides
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of resin combination, with solid weight meter, including：(a) maleimide resin：10 ~ 80 parts；The agent of (b) crosspolymer：10 ~ 80 parts；(c) initiator：0.01 ~ 5 part；(d) inorganic filler：0 ~ 60 part；(e) fire retardant：0 ~ 30 part；Present invention employs crosspolymer agent, on the basis of providing excellent dielectric properties for maleimide resin, the caking property that further solves the hydrocarbon resins such as the polybutadiene of prior art is bad, thermal expansivity is poor, heat-resisting not enough and poor compatibility with other resins the problems such as.

Description

Resin combination and the prepreg, laminate and the interlayer dielectric that are made using it
Technical field
Prepreg, laminate and the interlayer dielectric made the present invention relates to a kind of resin combination and using it, category In technical field of electronic materials.
Background technology
In recent years, information terminal machine and Internet Router, optic communication headed by PC, server etc. is led to Letter machine processes the information of Large Copacity with a high speed, and the high speed of electric signal, high frequency are advanced, therefore improves transmission speed It is the emphasis that high-speed high frequency product is paid close attention to the integrality of holding signal.And printed circuit board material is to high speed signal integrality Influence is mainly reflected on loss of signal, including reflection, Kelvin effect and dielectric loss.Especially in recent years, with semiconductor With the miniaturization of package substrate, slimming, when part installs encapsulation assembling, there is the difference of the coefficient of thermal expansion because of chip and substrate And the warpage for producing becomes big problem, thus it requires low-thermal-expansion.
Regarding to the issue above, all it is in the prior art loading by increasing inorganic filler, however, people in the art Member, it is known that high amount of inorganic filler can cause the insulating reliability caused by moisture absorption reduces, resin-wiring layer it is closely sealed not enough, press The problems such as cob webbing processed.
On the other hand, polybutadiene is used as thermoplastic resin, with excellent dielectric properties (low dielectric constant and low Loss angle tangent), therefore, using polybutadiene it is ideal chose in high-frequency high-performance printed wiring board field.However, using During find, there is problems with polybutadiene：(1) viscosity of prepreg (prepreg) is high, is unfavorable for storing and uses； (2) and thermosetting resin poor compatibility, occur being separated in lamination process, and oozed out from laminate, so as to cause to gather The superior dielectric performance of butadiene can not be fully demonstrated and the heat resistance of sheet material, rigidity and caking property degradation.
In order to solve the problems, such as the use of polybutadiene, polyphenyl ether modified poly- fourth is employed in Japan Patent JP2014101398 Diene, improves resin combination consistency problem, therefore substantial amounts of inorganic filler can be added in resin combination, improves The rigidity and hot expansibility of sheet material, but the addition of substantial amounts of inorganic filler has had a strong impact on the caking property of sheet material and follow-up The drill processability of PCB.The liquid of amino modified of the molecular end with vinyl has been used to gather in United States Patent (USP) US6569943 Butadiene resin, adds the monomer Dowspray 9 of substantial amounts of low-molecular-weight as curing agent and diluent, impregnated glass fiber The circuit substrate that cloth is fabricated to, although dielectric properties are fine, but because resin system is at normal temperatures liquid, it is impossible to it is fabricated to Tack-free prepreg, thus sheet material it is compressing when, it is difficult with that general prepreg is folded to foretell technique, technique behaviour Make comparisons difficulty.The resin containing unmodified polybutadiene and polymaleimide is disclosed in Japan Patent JP2008133454 Composition, can improve dielectric properties, caking property and the heat of solidfied material because of use polymaleimide resin in the technical scheme Dilatancy, but because using being produced in unmodified polybutadiene, with polymaleimide resin hybrid process, compatibility is bad to ask Topic, influences the combination property of sheet material.
Therefore, a kind of resin combination is developed, and prepreg, laminate and the interlayer dielectric made using it, It is set to have excellent dielectric properties, heat resistance, intensity, toughness, low-thermal-expansion rate and high-adhesion concurrently, it is clear that with positive Realistic meaning.
The content of the invention
Goal of the invention of the invention is to provide a kind of resin combination and the prepreg, laminate and the layer that are made using it Between dielectric film.
To achieve the above object of the invention, the technical solution adopted by the present invention is：A kind of resin combination, with solid weight Meter, including：
(a) maleimide resin：10~80 parts；
The agent of (b) crosspolymer：10~80 parts；
(c) initiator：0.01~5 part；
(d) inorganic filler：0~60 part；
(e) fire retardant：0~30 part；
The structural formula of the crosspolymer agent is：Wherein：
N is 1~10 integer,
R1, R2, R3, R4, R5, R6It is identical or different, it is respectively selected from-H、-CH3、-CH2-CH3、-CH2- CH2-CH3、-O-R7、And wherein at least one group is
Wherein, R7、R8、R9、R10It is identical or different, it is respectively selected from-CH3、-CH2-CH3、-CH2-CH2-CH3、
Above, the content of crosspolymer agent is, for example, 10 weight portions, 20 weight portions, 25 weight portions, 30 weight portions, 35 weights Amount part, 40 weight portions, 45 weight portions, 50 weight portions, 55 weight portions, 60 weight portions, 65 weight portions, 70 weight portions, 75 weight portions, 80 weight portions.Preferably 40~60 weight portions.
Preferably, in the structural formula of crosspolymer agent, n is 1~5 integer.
Preferably, the maleimide resin is modified bismaleimide resin；The modified bismaleimide Resin is selected from pi-allyl modified bismaleimide resin or its prepolymer, amine modified bismaleimide resin or its pre-polymerization Thing, Si modification bimaleimide resin or its prepolymer, epoxide modified bimaleimide resin or its prepolymer, cyanic acid In ester-bimaleimide resin or its prepolymer (BT resins), benzoxazine-bimaleimide resin or its prepolymer extremely Few one kind.In above-mentioned technical proposal, the content of the maleimide resin is, for example, 10 weight portions, 20 weight portions, 25 weight Part, 30 weight portions, 35 weight portions, 40 weight portions, 45 weight portions, 50 weight portions, 55 weight portions, 60 weight portions, 65 weight portions, 70 Weight portion, 75 weight portions, 80 weight portions.Preferably 20~40 weight portions.
Preferably, in mol, the content of element silicon is 5~30% in the crosspolymer agent.It is preferred that 10~23%.
The present invention is crosslinked anti-using maleimide resin and crosspolymer agent as main body in the presence of initiator Should, decomposition of initiator goes out living radical, and maleimide resin and crosspolymer agent is double in the presence of living radical Key contains the cross-linked network solidfied material of siloxy according to the mechanism generation of radical polymerization.Except above-mentioned freedom in resin combination Beyond base polymerisation, also there is the self-polymeric reaction of crosspolymer agent, generation siloxy content polymer higher, so as to enter Step improve silicone content in the heat resistance of solidfied material, thermal expansivity and caking property, but resin system it is too high if, with other resins Compatibility poor simultaneously has a strong impact on the water absorption rate of solidfied material, while reducing glass transition temperature.
When in resin combination using compatibility poor component, maleimide resin and crosspolymer in the present invention Agent is used in mixed way with other resins or filler again after can preparing prepolymer, and the reactivity of the prepolymer is 10~90%, excellent Elect 40~60% as.
Preferably, with solid weight meter, including：
(a) maleimide resin：50~80 parts；
The agent of (b) crosspolymer：10~40 parts；
(c) initiator：0.01~5 part；
(d) inorganic filler：20~40 parts；
(e) fire retardant：5~20 parts.
Preferably, with solid weight meter, including：
(a) maleimide resin：10~50 parts
The agent of (b) crosspolymer：50~70 parts；
(c) initiator：0.01~5 part；
(d) inorganic filler：20~40 parts；
(e) fire retardant：5~20 parts.
Preferably, the structural formula of the crosspolymer agent is selected from following 10 structural formulas：
Wherein, n is 1~10 integer.
It refers to the compound that free radical is resolved into by heat energy that the initiator is, can be used to trigger alkenes, double vinyl monomers Radical polymerization and copolymerization, it can also be used to unsaturated polyester (UP) crosslinking curing and high molecular crosslink reaction.
In above-mentioned technical proposal, the initiator is selected from benzoyl peroxide, lauroyl peroxide, peroxidating neopentanoic acid uncle Own ester, toluoyl base peroxide, double butyl peroxy cumenes, double (4- tert-butylcyclohexyls) peroxy dicarbonates In one or more.The content of initiator is preferably 0.05~5 weight portion.
The fire retardant is brominated flame-retardant, phosphonium flame retardant or nitrogenated flame retardant.The brominated flame-retardant is selected from ten bromines The double formyls of tetrabromo-phthalic two of diphenyl ether, TDE, octa-BDE, pentabromotoluene, HBCD, ethylene are sub- The double tetrabromo acid imides of amine, brominated polycarbonate, brominated Polystyrene, bromination triazine, the phenyl-pentabromide of ethylene two, ethylene, ten tetrabromos two At least one in phenoxy group benzene, double (tribromophenoxy) ethane, tetrabromobisphenol A；The phosphonium flame retardant is selected from three (2,6- bis- Aminomethyl phenyl) phosphine, 10- (2, the 5- dihydroxy phenyl)-miscellaneous -10- phosphines phenanthrene -10- oxides of 9,10- dihydro-9-oxies, 2,6- bis- (2, 6- 3,5-dimethylphenyls) phosphino- benzene or the miscellaneous -10- phosphines phenanthrene -10- oxides of 10- phenyl -910- dihydro-9-oxies, phosphonitrile, phenoxy group phosphine Cyanogen compound, phosphate, polyphosphoric acid melamine, aluminium metaphosphate, triphenyl phosphate, bis-phenol biphenyl phosphate, APP, Phosphonitrile compound, even phosphorus-nitrogen compound, bisphenol-A double (diphenyl phosphoester), three (2,6 3,5-dimethylphenyl) phosphines, resorcinols At least one in double [two (2,6- 3,5-dimethylphenyls) phosphates]；The nitrogenous flame ratardant is selected from triaizine compounds, cyanuric acid It is a kind of in compound, isocyanide acid compound, phenthazine；The content of fire retardant is preferably 10~50 weight portions.
In above-mentioned technical proposal, the inorganic filler be selected from containing silica (molten state or non-melt state and Porous), Aluminum oxide, magnesia, magnesium hydroxide, calcium carbonate, aluminium nitride, boron nitride, aluminium hydroxide, aluminum silicon carbide, carborundum, sodium carbonate, Titanium dioxide, zinc oxide, zirconium oxide, quartz, diamond dust, class diamond dust, glass dust, graphite, magnesium carbonate, potassium titanate, ceramics are fine Dimension, mica, boehmite (boehmite, ALOOH), zinc molybdate, ammonium molybdate, Firebrake ZB, calcium phosphate, calcium silicates, calcium carbonate, calcining Talcum, talcum, silicon nitride, section burn at least one of kaolin, clay, magnesium sulfate, barium sulfate, strontium titanates, barium titanate；With solid 100 parts of meters of weight, the content of inorganic filler is preferably 10~30%.
The shape of above-mentioned inorganic filler is not particularly limited, can for spherical, tabular, needle-like, horn shape or unformed shape or Its mixing shape.Above-mentioned inorganic filler can be surface-treated using silane coupler, improve the dispersion in resin combination Property.When in use above-mentioned inorganic filler can direct plunge into previously prepared filler dispersion liquid or be made lotion input resin combination In thing.
In above-mentioned technical proposal, the resin combination still further comprises the component (f) of 1~100 weight portion：Ben Bing Evil One kind or any several mixture in piperazine resin, cyanate ester resin, epoxy resin.
Component (the f) benzoxazine colophony can be bisphenol A-type benzoxazine, bisphenol-f type benzoxazine, bisphenol S type One kind in benzoxazine, the amine type benzoxazine of bis-phenol two, dicyclopentadiene phenolic benzoxazine or its modified benzoxazine or Any several mixture.Preferably, the adding proportion of component (the f) benzoxazine colophony is 1~20 weight portion.Addition is suitable Component (the f) benzoxazine colophony of amount can further optimize heat resistance and adhesive property, but addition excessively can be to resin The dielectric properties and toughness of system have undesirable effect.
Component (f) epoxy resin refers to the compound containing epoxy radicals, can be bisphenol A epoxide resin, Bisphenol F ring Oxygen tree fat, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac Epoxy resin, cresol novolak epoxy, triphenyl methane epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy tree Fat, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate-based epoxy resin, aralkyl novolak type epoxy Resin, polyphenyl ether modified epoxy resin, alicyclic based epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type ring A kind of or arbitrarily several mixture in oxygen tree fat, while curing agent and curing accelerator can be coordinated.
Component (f) cyanate ester resin refers to the compound containing cyanic acid ester group in structure, can be bisphenol A cyanate ester Resin, Bisphenol F cyanate ester resin, bis-phenol M cyanate ester resins, dicyclopentadiene type ethylene rhodanate resin, o-cresol aldehyde type epoxy One or more in resin, phenol type cyanate ester resin, Cyanate Ester Resin Modified with Polyphenylene Oxide.Preferably, component (f) cyanogen The adding proportion of acid ester resin is 20~50 weight portions.Component (f) cyanate ester resin for adding the ratio can further optimize The heat resistance of resin system, cementability and dielectric properties, addition can excessively cause the decline of the wet-hot aging performance of resin system.
Preferably, a kind of resin combination, with solid weight meter, including：
(a) maleimide resin：50~80 parts；
The agent of (b) crosspolymer：10~40 parts；
(c) initiator：0.01~5 part；
(d) inorganic filler：10~60 parts；
(e) fire retardant：10~30 parts；
(f) cyanate：5~20 parts.
The present invention is claimed the prepreg made using above-mentioned resin combination simultaneously, and above-mentioned resin combination is used Solvent dissolving is made glue, and then reinforcing material is immersed in above-mentioned glue；After impregnating after reinforcing material heat drying, i.e., Can obtain the prepreg.The heat drying condition is to be toasted 1~10 minute at 50~170 DEG C.
Described solvent is selected from acetone, butanone, toluene, methylisobutylketone, N, dinethylformamide, N, N- dimethyl second One or more in acid amides, EGME, propylene glycol monomethyl ether.
Described reinforcing material can use natural fiber, organic synthetic fibers, organic fabric or inorganic fabric, such as D glass Glass, E glass, NE glass, S glass and T glass.Here the thickness to glass-fiber-fabric is not particularly limited, but for production thickness The laminate of 0.01~0.02mm, generally uses fibrillation cloth, flat fabric.Additionally, being tied with the interface of glass-fiber-fabric to improve resin Close, glass-fiber-fabric is typically necessary and is chemically treated, and main method is coupling agent treatment, coupling agent used such as epoxy silane, ammonia Base silane.
The present invention is claimed the laminate made using above-mentioned resin combination simultaneously, at one by above-mentioned semi-solid preparation The single or double of piece is covered with metal foil, or will at least 2 be superimposed by above-mentioned prepreg after, be covered with its single or double Metal foil, hot forming, you can obtain the laminate.The hot forming condition be 0.2~2MPa pressure and 180~ Suppressed 2~4 hours at a temperature of 250 DEG C.
The quantity of the prepreg is the laminate thickness according to customer requirement to be determined, can use one or more.Institute Metal foil is stated, can be Copper Foil, or aluminium foil, their thickness is not particularly limited.
The present invention is claimed a kind of interlayer dielectric simultaneously, adds solvent dissolving to be made glue using above-mentioned resin combination Liquid, will coat the glue in carrier film, by after the carrier film heat drying for coating glue, you can obtain the layer insulation Film.The heat drying condition is to be toasted 1~10 minute at 50~170 DEG C.Described solvent be selected from acetone, butanone, toluene, One kind in methylisobutylketone, N, dinethylformamide, N, N- dimethylacetylamide, EGME, propylene glycol monomethyl ether or It is several.
In above-mentioned technical proposal, the carrier film can be polyethylene terephthalate (PET) film, mould release membrance, Copper Foil, aluminium Paper tinsel etc., carrier film is preferably PET film.In order to protect interlayer dielectric, in its another side covering protection film, the diaphragm can be with Material identical with carrier film.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1. present invention employs crosspolymer agent, on the basis of providing excellent dielectric properties for maleimide resin, The caking property that further solves the hydrocarbon resin such as polybutadiene in the prior art is bad, thermal expansivity is poor, it is heat-resisting not enough and The problems such as with the poor compatibility of other resins；Finally so that resin combination of the invention and use the resin combination system Into prepreg, laminate and insulating film material there is relatively low dielectric constant and dielectric loss tangent value, stripping higher From intensity, glass transition temperature higher, relatively low thermal expansivity, relatively low water absorption rate, excellent toughness and excellent Manufacturability, while solving hydrocarbon resin and thermosetting resin solidification and the technical problem being separated in resin combination, obtains Unexpected technique effect；
2. carbon-carbon double bond, solidification are included in maleimide resin and crosspolymer agent in resin combination of the invention In course of reaction under the action of heat, decomposition of initiator goes out living radical, each component resin in the presence of living radical Double bond according to the mechanism generation crosslinking of radical polymerization macromolecule polyalcohol, Si-O molecular flexibilities in its polymer compared with Good (because Si-O keys bond angle is big, easily rotating freely), therefore the toughness of maleimide resin can be improved；
3. in resin combination of the invention, when crosspolymer agent slightly has unnecessary, occur in unnecessary crosspolymer agent Self-polymeric reaction, generation siloxy content polymer higher, so as to further improve the heat resistance of solidfied material, rigidity and bonding Property；And when maleimide resin slightly has unnecessary, unnecessary maleimide resin can also be with other resins (such as cyanate Resin) there is curing reaction, so as to further improve the heat resistance and dielectric properties of solidfied material.
Specific embodiment
With reference to embodiment, the invention will be further described：
A kind of resin combination, is obtained using the component and proportioning of following Tables 1 and 2：(table 1 is real
Example 1 to 8 is applied, table 2 is comparative example 1 to 6)
Table 1
Table 2
Note：The concrete structure transitivity parameter of each component is as follows in tables 1 and 2：
Maleimide 1：Structural formula is as follows：
Wherein R1It is methylene, R2And R3It is methyl.
Maleimide 2：Structural formula is as follows：
Wherein R1It is-O-, R2And R3It is methyl.
Crosspolymer agent 1：SiO-1, import, structural formula is
Crosspolymer agent 2：SiO-2, import, structural formula is
Crosspolymer agent 3：SiO-3, import, structural formula is
Crosspolymer agent 4：SiO-4, import, structural formula is
Crosspolymer agent 5：SiO-5, import, structural formula is
N is 1~3 integer in said structure.
Hydrocarbon resin 1：Polybutadiene；
Hydrocarbon resin 2：Epoxidized polybutadiene：
Initiator：Benzoyl peroxide；
Fire retardant：Deca-BDE；
Inorganic filler：Silica；
Cyanate：Bisphenol A cyanate ester.
Glue is blended：All components in formula are configured to the thermosetting that solid content is 60% by the formula in table Resin combination composition glue liquid.Then, prepreg and laminate are made under the following conditions：
Base material：Ordinary electronic 2116 glass-fiber-fabrics of level；Pre-preg semi-solid preparation condition：170℃/5min；The number of plies：8；Shaping back plate Material thickness：1.0mm；Condition of cure：150℃/60min+220℃/150min.
The method of testing of each performance is as follows in table 1 and 2, and the test result of each performance is shown in Tables 1 and 2：
Glass transition temperature (Tg)：According to differential scanning calorimetry, according to IPC-TM-650 2.4.25 defineds DSC method is measured.
Compatibility：Whether each component is layered, separates out in observation compositions of thermosetting resin glue, if not being layered, analysing Occur, as then showing group partition inter-capacitive preferably, being represented with " good ".
Peel strength (PS)：According to " after the thermal stress " experiment condition in IPC-TM-650 2.4.8 methods, metal is tested The peel strength of cap rock.
Dielectric constant：Flat band method is used according to IPC-TM-650 2.5.5.9, the dielectric constant under 10GHz is determined.
Dielectric loss tangent：Use flat band method according to IPC-TM-650 2.5.5.9, determine dielectric loss under 10GHz because Son.
Wicking heat resistance (T-288)：Using the two sides band copper sample of 50 × 50mm, in the scolding tin of 288 DEG C of immersion, sample is recorded The time of product layering foaming.
Thermal coefficient of expansion Z axis CTE (TMA)：It is measured according to IPC-TM-6502.4.24. methods.
Drop impact toughness (laminate fragility)：Use Apparatus for Impacting at low-temp, Apparatus for Impacting at low-temp height of the fall 45cm, whereabouts weight weight 1kg。
The good and bad judge of toughness：Cross is clear, illustrates that the toughness of product is better, is represented with character ◎；Cross mould Paste, illustrates that the poor toughness of product, fragility are big, is represented with character ◇.
Flame resistance (flame retardancy)：Determined according to UL94 methods.
From Table 1 and Table 2, embodiment 1-8 is using the resin combination of inventive formulation, using embodiment 1-8's Caking property, heat resistance, CTE and toughness after the laminate solidification that the obtained resin combination of formula is made significantly compare comparative example Middle polybutadiene and epoxidized polybutadiene it is excellent, not only to stripping when particularly adding more crosspolymer agent in embodiment 6 It is smaller from intensity and resin compatible influence, obtain excellent dielectric properties, heat resistance and CTE.In addition, being contained using 100 parts of silicon Understood in the comparative example 6 of amount crosspolymer agent 5 higher, glass transition temperature and heat resistance are decreased obviously, because working as The water absorption rate of solidfied material significantly rises when silicone content is higher in resin combination, causes the heat resistance and Tg of integrally curing thing tight Decline again.
It should be understood that, although the present specification is described in terms of embodiments, but not each implementation method only includes one Individual independent technical scheme, this narrating mode of specification is only that for clarity, those skilled in the art will should say Used as an entirety, technical scheme in each implementation method can also be through appropriately combined, and forming those skilled in the art can for bright book With the other embodiment for understanding.
Those listed above is a series of to be described in detail only for feasibility implementation method of the invention specifically Bright, they simultaneously are not used to limit the scope of the invention, all equivalent implementations made without departing from skill spirit of the present invention Or change should be included within the scope of the present invention.

Claims (10)

1. a kind of resin combination, it is characterised in that with solid weight meter, including：
(a) maleimide resin：10~80 parts；
The agent of (b) crosspolymer：10~80 parts；
(c) initiator：0.01~5 part；
(d) inorganic filler：0~60 part；
(e) fire retardant：0~30 part；
The structural formula of the crosspolymer agent is：Wherein：
N is 1~10 integer,
R1, R2, R3, R4, R5, R6It is identical or different, it is respectively selected from-H、-CH3、-CH2-CH3、-CH2-CH2- CH3、And wherein at least one group is
Wherein, R7、R8、R9、R10It is identical or different, it is respectively selected from-CH3、-CH2-CH3、-CH2-CH2-CH3、
2. resin combination according to claim 1, it is characterised in that：In mol, silicon unit in the crosspolymer agent The content of element is 5~30%.
3. resin combination according to claim 1, it is characterised in that：The structural formula of the maleimide resin is：
Wherein, R1It is selected from R2And R3It is identical or different, it is respectively selected from hydrogen-based, H3C- or C2H5-。
4. resin combination according to claim 1, it is characterised in that with solid weight meter, including：
(a) maleimide resin：50~80 parts；
The agent of (b) crosspolymer：10~40 parts；
(c) initiator：0.01~5 part；
(d) inorganic filler：20~40 parts；
(e) fire retardant：5~20 parts.
5. resin combination according to claim 1, it is characterised in that with solid weight meter, including：
(a) maleimide resin：10~50 parts
The agent of (b) crosspolymer：50~70 parts；
(c) initiator：0.01~5 part；
(d) inorganic filler：20~40 parts；
(e) fire retardant：5~20 parts.
6. resin combination according to claim 1, it is characterised in that：The structural formula of the crosspolymer agent is selected from following One in 10 structural formulas：
Wherein, n is 1~10 integer.
7. resin combination according to claim 1, it is characterised in that：The initiator is selected from benzoyl peroxide, mistake Oxidation lauroyl, the tertiary own ester of peroxidating neopentanoic acid, toluoyl base peroxide, double butyl peroxy cumenes, double (uncles 4- Butylcyclohexyl) one or more in peroxy dicarbonate.
8. a kind of prepreg that any one resin combination using as described in claim 1~7 makes, its feature exists In：Any one compositions of thermosetting resin solvent dissolving described in claim 1~7 is made glue, then will enhancing Material is immersed in above-mentioned glue；After impregnating after reinforcing material heat drying, you can obtain the prepreg.
9. the laminate that a kind of use resin combination as claimed in claim 1 makes, it is characterised in that：At one by right It is required that the single or double of the prepreg described in 8 is covered with metal foil, or it is solid as half described in claim 8 by least 2 After changing piece superposition, metal foil, hot forming are covered with its single or double, you can obtain the laminate.
10. the interlayer dielectric that a kind of use resin combination as claimed in claim 1 makes, it is characterised in that：By right It is required that any one the compositions of thermosetting resin solvent dissolving described in 1~7 is made glue, then applies on a carrier film and be covered with Glue is stated, by after the carrier film heat drying for coating glue, you can obtain the interlayer dielectric.
CN201611052927.5A 2016-11-25 2016-11-25 Resin combination and prepreg, laminate and the interlayer dielectric made using it Active CN106749952B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611052927.5A CN106749952B (en) 2016-11-25 2016-11-25 Resin combination and prepreg, laminate and the interlayer dielectric made using it

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611052927.5A CN106749952B (en) 2016-11-25 2016-11-25 Resin combination and prepreg, laminate and the interlayer dielectric made using it

Publications (2)

Publication Number Publication Date
CN106749952A true CN106749952A (en) 2017-05-31
CN106749952B CN106749952B (en) 2019-03-05

Family

ID=58911255

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611052927.5A Active CN106749952B (en) 2016-11-25 2016-11-25 Resin combination and prepreg, laminate and the interlayer dielectric made using it

Country Status (1)

Country Link
CN (1) CN106749952B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109825081A (en) * 2019-01-30 2019-05-31 广东生益科技股份有限公司 A kind of compositions of thermosetting resin, the prepreg comprising it and metal-clad laminate and printed circuit board
CN111909642A (en) * 2020-08-13 2020-11-10 常州市贝美家居科技有限公司 Melamine formaldehyde resin adhesive, calcium silicate composite floor and production process
CN112266612A (en) * 2020-10-29 2021-01-26 苏州生益科技有限公司 Resin composition, and preparation method and application thereof
CN114561170A (en) * 2022-03-28 2022-05-31 深圳市纽菲斯新材料科技有限公司 Insulating adhesive film and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5753523A (en) * 1980-09-18 1982-03-30 Toshiba Corp Epoxy resin composition
JP2004189790A (en) * 2002-12-09 2004-07-08 Hitachi Chem Co Ltd Resin paste composition and semiconductor device using the same
CN101692756A (en) * 2008-01-15 2010-04-07 日立化成工业株式会社 Prepreg and its application products for low thermal expansion and low dielectric tangent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5753523A (en) * 1980-09-18 1982-03-30 Toshiba Corp Epoxy resin composition
JP2004189790A (en) * 2002-12-09 2004-07-08 Hitachi Chem Co Ltd Resin paste composition and semiconductor device using the same
CN101692756A (en) * 2008-01-15 2010-04-07 日立化成工业株式会社 Prepreg and its application products for low thermal expansion and low dielectric tangent

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109825081A (en) * 2019-01-30 2019-05-31 广东生益科技股份有限公司 A kind of compositions of thermosetting resin, the prepreg comprising it and metal-clad laminate and printed circuit board
CN109825081B (en) * 2019-01-30 2021-06-04 广东生益科技股份有限公司 Thermosetting resin composition, prepreg containing thermosetting resin composition, metal foil-clad laminate and printed circuit board
US11975507B2 (en) 2019-01-30 2024-05-07 Shengyi Technology Co., Ltd. Thermosetting resin composition, prepreg containing same, metal foil-clad laminate and printed circuit board
CN111909642A (en) * 2020-08-13 2020-11-10 常州市贝美家居科技有限公司 Melamine formaldehyde resin adhesive, calcium silicate composite floor and production process
CN112266612A (en) * 2020-10-29 2021-01-26 苏州生益科技有限公司 Resin composition, and preparation method and application thereof
CN114561170A (en) * 2022-03-28 2022-05-31 深圳市纽菲斯新材料科技有限公司 Insulating adhesive film and preparation method and application thereof
CN114561170B (en) * 2022-03-28 2023-08-08 深圳市纽菲斯新材料科技有限公司 Insulating adhesive film and preparation method and application thereof

Also Published As

Publication number Publication date
CN106749952B (en) 2019-03-05

Similar Documents

Publication Publication Date Title
CN104845363B (en) A kind of halogen-free resin composition and application thereof
CN104371273B (en) Halogen-free resin composition and prepreg and laminate prepared therefrom
CN106633671B (en) A kind of resin combination and its application
CN105860436B (en) Resin combination, prepreg and plywood
CN104448702B (en) Halogen-free resin composition as well as prepreg and laminated board made of halogen-free resin composition
CN106632993B (en) A kind of resin combination and its application
CN106749952B (en) Resin combination and prepreg, laminate and the interlayer dielectric made using it
CN104845366B (en) A kind of halogen-free resin composition and application thereof
WO2001042360A1 (en) Flame-retardant epoxy resin composition and laminate made with the same
CN106543686B (en) A kind of resin combination and prepreg, laminate and interlayer dielectric using its making
CN106832226A (en) A kind of halogen-free epoxy resin composition and the prepreg containing it, laminate and printed circuit board
CN106700424B (en) A kind of low-loss resin combination, prepreg and laminate
WO2013056426A1 (en) Halogen-free low-dielectric resin composition, and prepreg and copper foil laminate made by using same
CN105348742B (en) Compositions of thermosetting resin, prepreg and the laminate of the benzoxazine colophony containing melamine-type
CN106221126B (en) A kind of compositions of thermosetting resin and prepreg and laminate using its making
CN104927353A (en) Inflaming-retarding halogen-free and phosphorus-free resin composition and use thereof and preparation method applying to half-curing piece, laminated board and copper-clad plate
TWI716967B (en) Resin composition, prepreg, laminate, metal-clad laminate and printed circuit board
CN104974469B (en) A kind of resin combination and the prepreg and laminate using its making
CN103980704A (en) Halogen-free resin composition for high-frequency and high-speed substrate as well as prepreg and laminated plate
KR20120079986A (en) Resin composition and prepreg and printed wiring board using the same
CN107033517A (en) A kind of prepolymer of modified polybutadiene and its preparation method and application
CN108047718A (en) Maleimide resin composition, prepreg, laminate and printed circuit board (PCB)
TW201617395A (en) Thermosetting resin composition and prepreg and laminate prepared therefrom
CN106349643B (en) A kind of compositions of thermosetting resin and prepreg and laminate using its making
CN107406577A (en) Resin combination, prepreg, clad with metal foil plywood, resin sheet and printed circuit board (PCB)

Legal Events

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