CN106221126B - A kind of compositions of thermosetting resin and prepreg and laminate using its making - Google Patents
A kind of compositions of thermosetting resin and prepreg and laminate using its making Download PDFInfo
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- CN106221126B CN106221126B CN201610749083.3A CN201610749083A CN106221126B CN 106221126 B CN106221126 B CN 106221126B CN 201610749083 A CN201610749083 A CN 201610749083A CN 106221126 B CN106221126 B CN 106221126B
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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
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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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
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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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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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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Abstract
The invention discloses a kind of compositions of thermosetting resin, with solid weight meter, including：(a) hydrocarbon resin：10 ~ 100 parts；(b) maleimide ester：20 ~ 100 parts；(c) initiator：0.1 ~ 8 part.Present invention employs the maleimide esters with multifunctional backbone and rigid imide ring, there is hydrocarbon resin flexible to form thermoset composition for cooperation, the two interacts, it is final that the compositions of thermosetting resin of the present invention and its printed circuit prepreg and laminate of preparation is made to have both excellent dielectric properties, heat resistance, cementability, anti-flammability, bending strength, toughness, the features such as peel strength is high, water absorption rate is low, and process industrial art performance is excellent.
Description
Technical field
The present invention relates to a kind of compositions of thermosetting resin and using prepreg and laminate that it makes, belong to electronics
Field of material technology.
Background technology
In recent years, as information processing and information transmit the continuous propulsion of high-speed high frequency technology, to tellite
Material proposes increasingly higher demands in terms of dielectric properties.In simple terms, i.e., tellite material need to have it is relatively low
Dielectric constant and dielectric loss tangent, when reducing high-speed transfer between the delay, distortion and loss and signal of signal
Interference.Accordingly, it is desired to provide a kind of compositions of thermosetting resin, the printed circuit made using this compositions of thermosetting resin
Plate material can show substantially low low-k and low-dielectric loss just in the signals transmission of high speed, high frequency
It cuts.
The excellent resin of dielectric properties in order to obtain, those skilled in the art to the good hydrocarbon resin of dielectric properties into
The resins such as a large amount of research, such as the copolymer of polybutadiene, butadiene and styrene are gone.Although it is a large amount of studies have shown that
Hydrocarbon resin is capable of providing good dielectric properties, but due to the flexibility of hydrocarbon resin, non-polar carbon chains structure, causes hydrocarbon
Rigidity is insufficient after resin solidification, intensity is low, poor heat resistance, the problems such as glass transition temperature is low, cementability is poor, in practical application
There are still many problems to need to solve.For example, being changed using hydrocarbon resin and allyl in Chinese invention patent CN10544841B
Property phenolic resin composition make printed circuit board, although improving the adhesive property of resin so that plank peel strength
It is improved, but still relatively low, and the heat resistance of system is low.Using hydrocarbon resin, alkene in Chinese patent CN104845363A
The bimaleimide resin composition that modified benzoxazine colophony and allyl are modified makes printed circuit board, improves
Heat resistance and peel strength, but because the bismaleimide that benzoxazine colophony and allyl that allyl is modified are modified
Polyimide resin can introduce a large amount of hydroxyl, damage the dielectric properties of system.
Therefore, a kind of compositions of thermosetting resin and prepreg and laminate using its making are developed, it is made to have both
Excellent heat resistance, intensity, hard and soft and dielectric properties, it is clear that there is positive realistic meaning.
Invention content
The goal of the invention of the present invention is to provide a kind of compositions of thermosetting resin and prepreg and layer using its making
Pressing plate.
To achieve the above object of the invention, the technical solution adopted by the present invention is：A kind of compositions of thermosetting resin, with solid
Weight meter, including：
(a) hydrocarbon resin：10 ~ 100 parts；
(b) maleimide ester：20 ~ 100 parts；
(c) initiator：0.1 ~ 8 part；
The structure of the maleimide ester is as follows：, wherein：
It is 2 ~ 20, y is 1 ~ 10 that n, which is 1 ~ 10, x,；
The one kind of Ar in following structural：
、、、、、、；
R is the alkyl that carbon atom number is less than or equal to 5, or is phenyl, aminomethyl phenyl, xenyl, n-propyl phenyl, isopropyl
Phenyl, tert-butyl-phenyl, ethenylphenyl, 4- maleimidophenyls, p-nitrophenyl.
Above, 2 and 2 or more dimaleoyl iminos and 2 and 2 are contained in a molecule of the maleimide ester
The above ester group.
The component（a）The content of hydrocarbon resin is specifically as follows：10 parts by weight, 15 parts by weight, 25 parts by weight, 40 weights
Measure part, 50 parts by weight, 80 parts by weight, 90 parts by weight or 100 parts by weight.
In above-mentioned technical proposal, the component（b）The content of maleimide ester is specifically as follows：20 parts by weight, 40 weights
Measure part, 50 parts by weight, 60 parts by weight, 80 parts by weight or 100 parts by weight.
In above-mentioned technical proposal, the component（c）The content of initiator is specifically as follows：0.1 parts by weight, 0.5 parts by weight,
1.0 parts by weight, 2.0 parts by weight, 3.0 parts by weight, 4.5 parts by weight, 6.0 parts by weight, 8.0 parts by weight.
Component（a）Hydrocarbon resin, component（b）The ratio of maleimide ester, can according to specific practical application and
Adjustment, when applying when requiring high specific field to mechanical performance, heat resistance and peel strength, can suitably increase component
（b）The ratio of maleimide ester；When applying in the specific field high to dielectric properties and toughness reguirements, can suitably increase
Component（a）The ratio of hydrocarbon resin.
The ratio x of x and y in the structure of the maleimide ester：The value of y can also according to specific practical application and
Adjustment can be 0.1,0.3,0.5,1,5,10,15,20 equivalences.When apply to the mechanical performance of laminate, plate heat resistance and
When peel strength requires high specific field, the ratio of increase x structural units can be passed through.The ratio for increasing x, can increase point
The amount of imide ring in minor structure, to be conducive to the raising of heat resistance and adhesive property.
R bases are that vinyl or ethenylphenyl or 4- maleimidophenyls etc. contain in the maleimide ester structure
There is the structure of unsaturated double-bond.When R bases are vinyl, in the molecular structure of the maleimide ester in said program further
Vinyl reactive functionality flexible is introduced, does not influence resin while increasing the crosslink density of resin system, improve heat resistance
The toughness of system.When R bases are ethenylphenyl or 4- maleimidophenyls, maleimide ester in said program
Rigid phenyl ring or maleimide ring are further introduced in molecular structure, can further increase the rigidity of resin system
And heat resistance.
The initiator be refer to the compound that free radical is resolved by thermal energy, can be used for cause alkenes, double vinyl monomers
Free radical polymerization and copolymerization, it can also be used to the crosslinking curing and high molecular crosslink of unsaturated polyester (UP) react.Described
Initiator can be azo-initiator, peroxide initiator, redox type initiators, one kind in preferably following initiator
Or it is several：Cumyl peroxide, di-t-butyl peroxide, peroxidized t-butyl perbenzoate, di-cyclohexylperoxy di-carbonate,
Isopropyl benzene hydroperoxide, azodiisobutyronitrile.
Preferably, R bases are vinyl, ethenylphenyl or 4- dimaleoyl imino benzene in the maleimide ester structure
Base.Contain unsaturated double-bond group i.e. in maleimide ester structure.
Preferably, the ratio of x and y is 5 in the maleimide ester structure：1~10：1.When the ratio of x and y is less than 5：1
When, the maleimide structure in Malaysia elder generation imines ester is less, and heat resistance and peel strength can all be affected；When the ratio of x and y
Value is more than 10：When 1, the maleimide structure in Malaysia elder generation imines ester is more, and toughness can be affected；When the ratio of x and y
Value is 5：1~10：1 heat resistance and toughness are attained by optimal.
Superior heat resistance, peel strength and mechanical performance in order to obtain, preferably a kind of thermosetting resin combination
Object, with solid weight meter, including：
(a) hydrocarbon resin：10 ~ 25 parts；
(b) maleimide ester：50 ~ 100 parts；
(c) initiator：0.1 ~ 8 part.
Superior dielectric properties, heat resistance, moisture pick-up properties in order to obtain, preferably a kind of compositions of thermosetting resin,
With solid weight meter, including：
(a) hydrocarbon resin：30 ~ 100 parts；
(b) maleimide ester：20 ~ 40 parts；
(c) initiator：0.1 ~ 8 part.
Preferably, the hydrocarbon resin be selected from butadiene styrene resin, polybutadiene, polyisobutene resin, polyprene,
Polystyrene, 2- methylated polystyrenes, 3- methylated polystyrenes, 4- methylated polystyrenes, 2,4- diisopropyls polystyrene, 2,
One or more of 4- diformazans base polystyrene, styrene-butadiene copolymer, styrene-isobutene copolymer；It is described
The number-average molecular weight of hydrocarbon resin is less than 11000 and its contents of ethylene is more than 60%.Preferably, hydrocarbon in above-mentioned technical proposal
The number-average molecular weight of resin is less than 7000, and is liquid at room temperature.Preferably, hydrocarbon resin is butylbenzene in above-mentioned technical proposal
One or more of resin, polybutadiene, polyisobutene resin.
Further include 1 ~ 100 part of component (d) with solid weight meter, the component (d) is selected from second in above-mentioned technical proposal
Alkenyl Noryl, allyl modifying benzoxazine resin, allyl modified bismaleimide, vinyl modified phenolic aldehyde tree
Fat, olefin copolymer, Petropols, epoxy resin, unsaturated polyester resin, one kind in mono-component polyurethane resin or arbitrary
Several mixtures.
In the component (d), allyl modifying benzoxazine resin can be allyl modified bisphenol A type benzoxazine,
Allyl modified bisphenol g types benzoxazine, allyl modified bisphenol S types benzoxazine, two amine type benzoxazine of bis-phenol, allyl
One kind in modified dicyclopentadiene phenolic benzoxazine or arbitrary several mixture.Preferably, the allyl is modified benzene
The adding proportion of Bing oxazine resins is 1 ~ 20 parts by weight.Adding suitable allyl modifying benzoxazine resin can be further excellent
Change heat resistance and adhesive property, but addition excessively can cause harmful effect to the dielectric properties and toughness of resin system.
In the component (d), allyl modified bismaleimide can be by allyl compound and maleimide
Resin prepolymer closes the prepolymer generated, and the allyl compound is selected from allyl ether compound, allyl phenoxy resin, allyl
One or more of base phenolic resin, diallyl bisphenol, diallyl bisphenol S；The maleimide resin is selected from 4,
4 '-diphenyl methane dimaleimide resins, 4,4 '-Diphenyl Ether Bismaleimide resins, 4,4 '-hexichol isopropyl spans come
One or more of imide resin, 4,4 '-diphenyl sulphone (DPS) bimaleimide resins.Preferably, the allyl is modified double
The number-average molecular weight of maleimide is 2000 ~ 5000g/mol.Adding suitable allyl modified bismaleimide can be into
One-step optimization heat resistance and adhesive property, but addition excessively can cause harmful effect to the dielectric properties of resin system.
In the component (d), the vinyl modified phenolic resin can be allyl modified maleimide base phenolic aldehyde
Dilute benzyl phenylate of resin, allyl phenol-formaldehyde resin modified, dicyclopentadiene-second etc..The allyl modified maleimide base
Phenolic resin is the resin having the following structure：
Or；
Wherein, it be 1 ~ 10, s is 1 ~ 10 that x, which is 2 ~ 20, y,.
In the component (d), Petropols can be alicyclic petroleum resin（eCPe）, aromatic petroleum resin（C9）、
Aliphatic/aromatic copolymerized petroleum resin（C5/C9）In one or any several mixture.Preferably, the oil
The molecular weight of resin is 1000 ~ 3000g/mol.Preferably, the adding proportion of the Petropols is 5 ~ 25 parts by weight.Addition is suitable
While the Petropols of amount can advanced optimize the dielectric properties and adhesive property of resin system, moreover it is possible to improve resin system
Mobile performance improve processing performance.
In the component (d), epoxy resin refers to the compound containing epoxy group, can be bisphenol A epoxide resin, bis-phenol
G epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol phenol
Formaldehyde epoxy resin, cresol novolak epoxy, triphenyl methane epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy
Resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate-based epoxy resin, aralkyl line style phenolic aldehyde ring
Oxygen resin, polyphenyl ether modified epoxy resin, alicyclic based epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type
A kind of or arbitrarily several mixture in epoxy resin.Epoxy resin is added to compositions of thermosetting resin of the present invention
In, epoxy group and component mainly in epoxy resin（b）Ester group reaction in maleimide ester.Add epoxy resin it
Afterwards, component（b）Maleimide ester plays the role of a bridge formation, component（b）Ester in maleimide ester molecular structure
Base and epoxy resin react, the dimaleoyl imino in structure and component（a）Double bond reaction in hydrocarbon resin, thus by epoxy
The advantages of resin and hydrocarbon resin, concentrates in a kind of resin combination.It, can be in the resin combination of addition epoxy resin
Further addition curing accelerator, the curing accelerator can be selected from dimethyl aminopyridine, tertiary amine and its salt, imidazoles,
Organic metal salt, triphenylphosphine are Ji Qi phosphonium salt etc..Preferably, epoxy resin is polyphenyl ether modified epoxy resin, mentioned here
Polyphenyl ether modified epoxy resin refers to the resin after the terminal epoxy by polyphenylene oxide.Preferably, the adding proportion of epoxy resin
For 10 ~ 50 parts by weight.The processing performance and mechanical performance of resin system can be advanced optimized by adding suitable epoxy resin.
In the component (d), unsaturated polyester resin or mono-component polyurethane resin, preferred adding proportion are 5 ~ 25 weights
Measure part.It adds suitable unsaturated polyester resin or mono-component polyurethane resin can optimize the adhesive property of resin system and tough
Property, but additive amount excessively can cause harmful effect to the heat resistance and dielectric properties of resin system.
Based on the above technical solution, the compositions of thermosetting resin further includes the component of 1 ~ 80 parts by weight（e）
Fire retardant.The fire retardant can be bromide fire retardant, phosphorus flame retardant, nitrogenated flame retardant, organic silicon fibre retardant, organic metal
Salt fire retardant, inorganic flame retardant etc..Wherein, bromide fire retardant can be deca-BDE, decabromodiphenylethane, bromination benzene second
Alkene or tetrabromo-phthalic diformamide.Phosphorus flame retardant can be Phos, phosphate compound, phosphinic acid compounds, phosphinic acids
Compound, phosphine oxide compound and the miscellaneous phenanthrene -10- oxides of -9 oxa- -10- phosphines of 9,10- dihydros, 10-（2,5 dihydroxy benzenes
Base）Miscellaneous phenanthrene -10- the oxides of -9 oxa- -10- phosphines of -9,10- dihydros, the miscellaneous -10- phosphines phenanthrene -10- of 10- phenyl -9,10- dihydro-9-oxies
Oxide, three（2,6 3,5-dimethylphenyls）The organophosphorus compounds such as phosphine, phosphine nitrile.Nitrogenated flame retardant can be triaizine compounds, cyanogen
Uric acid compound, isocyanide acid compound, phenthazine etc..Organic silicon fibre retardant can be organic silicone oil, organic silicon rubber, organosilicon
Resin etc..Organic metal fire retardant can be ferrocene, acetylacetone metal complex, organic metal carbonyls etc..Nothing
Machine fire retardant can be aluminium hydroxide, magnesium hydroxide, aluminium oxide, barium monoxide etc..The fire retardant added can be according to laminate
Concrete application field and select, to the application field that halogen requires, preferably non-halogen fire retardant, such as phosphorous or nitrogenous resistance
Fire agent.Preferably, when selecting phosphonium flame retardant, nitrogen can be formed with the nitrogen of maleimide ester in above-mentioned technical proposal
Phosphorus cooperative flame retardant improves flame retarding efficiency.Preferably, the fire retardant additive amount in above-mentioned compositions of thermosetting resin is 5 ~ 50 weight
Part.
Based on the above technical solution, the compositions of thermosetting resin further includes the component of 1 ~ 100 parts by weight（f）
Filler.The inorganic filler is selected from powdered quartz, fused silica, preparing spherical SiO 2, aluminium oxide, hydroxide
Aluminium, aluminium nitride, boron nitride, titanium dioxide, strontium titanates, barium titanate, barium sulfate, talcum powder, calcium silicates, calcium carbonate, mica, poly- four
One or more of vinyl fluoride, graphene filler, the grain size of above-mentioned inorganic filler are 0.3~20 micron, preferentially select 0.5~
5 microns.In resin combination inorganic filler can direct plunge into previously prepared filler dispersion liquid or be made lotion input tree
In oil/fat composition.Preferably, the inorganic filler additive amount in above-mentioned compositions of thermosetting resin is 10 ~ 50 parts by weight.
In above-mentioned compositions of thermosetting resin, it can also be added using silane coupling agent, pigment, emulsification according to practical feelings
One in the additives such as agent, dispersant, antioxidant, antistatic agent, heat stabilizer, ultra-violet absorber, colorant, lubricant
Kind is several.
Above-mentioned compositions of thermosetting resin can be used for manufacturing prepreg, laminate, printed circuit board, semiconductor close
Closure material, lamination adhering film, binder, resin cast material, conductive paste etc..
The prepreg made of above-mentioned resin combination is claimed in the present invention simultaneously, and above-mentioned resin combination is used
Glue is made in solvent dissolving, and then reinforcing material is immersed in above-mentioned glue；After impregnating after reinforcing material heat drying, i.e.,
The prepreg can be obtained.
The solvent is selected from acetone, butanone, toluene, methylisobutylketone, N, dinethylformamide, N, N- dimethyl second
One or more of amide, ethylene glycol monomethyl ether, propylene glycol monomethyl ether.Natural fiber, You Jihe can be used in the reinforcing material
At fiber, organic fabric or inorganic fabric.
The laminate made of above-mentioned resin combination is claimed in the present invention 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 in its single or double
Metal foil, hot forming, you can obtain the laminate.
The quantity of the prepreg is determined according to the laminate thickness of customer requirement, can use one or more.Institute
Metal foil is stated, can be copper foil, can also be aluminium foil, their thickness is not particularly limited.
Since above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1. present invention employs the maleimide ester with multifunctional backbone and rigid imide ring, cooperation has
Hydrocarbon resin flexible forms thermoset composition, and the two interacts, the heat resistance of maleimide ester improvement hydrocarbon resin,
Rigidity, the problem of intensity deficiency, hydrocarbon resin improves the problem of maleimide ester toughness deficiency, so that composition is simultaneous
Have excellent heat resistance, intensity, hard and soft；The final printed circuit for making compositions of thermosetting resin of the invention and its preparation
Excellent dielectric properties, heat resistance, intensity, hard and soft, peel strength height, percent thermal shrinkage are had both with prepreg and laminate
It is small, the features such as process industrial art performance is excellent, obtain unexpected technique effect；
2. the component that the present invention uses（b）Dimaleoyl imino and ester group in maleimide ester molecular structure improve
The adhesive property of the system of hydrocarbon resin improves the peel strength between laminate copper foil layer and resin layer, has no effect on simultaneously
The dielectric properties of resin system；In addition, component（b）The multifunctional backbone of maleimide ester and the acid imide of rigidity
Ring improves resistance to thermal energy, rigidity and the mechanical strength of resin system；The maleimide ester of backbone is conducive to improve component
（a）Hydrocarbon resin makes tacky characteristic after prepreg, while can also reduce component（a）Contraction after hydrocarbon resin solidification
Rate；
3. the component that the present invention uses（a）The non-polar conformations of hydrocarbon resin are that resin system contributes to excellent dielectricity
Can, carbon-chain structure flexible can improve the toughness of maleimide ester solidfied material.
Specific implementation mode
With reference to embodiment, the invention will be further described：
Synthesis example 1~7 is the synthesis of maleimide ester of the present invention, and embodiment 1~12 and comparative example 1~6 are the present invention
The preparation of the compositions of thermosetting resin of offer and evaluation of physical property.
Synthesis example 1
N- (4- hydroxy phenyls) maleimide is put into the flask for being equipped with thermometer, condenser pipe, blender
（190g, 1mol）, phenol（94g, 1mol, M94）And oxalic acid（10g）, after being mixed evenly, it is placed in 70 DEG C of water bath with thermostatic control
In；Then, under stiring, formalin was added dropwise into flask with 0.5 hour（The ratio of 150mL, phenol/aldehyde are 1/0.8）；It adds
After formaldehyde, the temperature and stirring condition that maintain 70 DEG C are reacted 15 hours；Then, with 400mL acetone by reaction product dissolved dilution,
Then again with 40% methanol aqueous solution precipitation reaction product；It repeats above dissolving-precipitation operation 3~5 times, is filtered, divided
From, be dried to obtain pure maleimide phenolic aldehyde（P-1）.
Take maleimide phenolic aldehyde made from the above method（P-1）100g and methyl isobutyl ketone solvent 500g are placed in flask
In be sufficiently mixed dissolving, will in reaction system depressurize lead to nitrogen, and by system temperature control at 65 DEG C；Then, 140g benzene is put into
Formyl chloride（1mol, M140.5）, then, with 3 hours into system be added dropwise 20% sodium hydroxide solution 210g, after being added dropwise,
Reaction 3 hours is maintained at 65 DEG C；After the completion of reaction, it is separated off water layer；Then it is added water into system again, stirring and washing,
It is separated off water layer；Repeat the above cleaning operation 3~5 times；Then it vacuumizes decompression to remove methyl iso-butyl ketone (MIBK), obtain as follows
The maleimide ester of structure（B-1）：；Wherein, Ar is：, R is phenyl；
Wherein, the ratio that n is 1 ~ 10, x and y is 1：1.
Synthesis example 2
With reference to the method for real synthesis example 1, the maleimide ester such as lower structure is made（B-2)：
；Wherein, Ar is, R
For phenyl；
Wherein, the ratio that n is 1 ~ 10, x and y is 0.5：1.
Synthesis example 3
With reference to the method for synthesis example 1, the maleimide ester such as lower structure is made（B-3)：
；Wherein, Ar is：, R is maleimide
Base phenyl；
Wherein, the ratio that n is 1 ~ 10, x and y is 0.1：1.
Synthesis example 4
With reference to the method for synthesis example 1, the maleimide ester such as lower structure is made（B-4)：；Its
In, Ar is, R is ethenylphenyl；
Wherein, the ratio that n is 1 ~ 10, x and y is 5：1.
Synthesis example 5
With reference to the method for synthesis example 1, the maleimide ester such as lower structure is made（B-5)：
；Wherein, Ar is, R is ethyl；
Wherein, the ratio that n is 1 ~ 10, x and y is 10：1.
Synthesis example 6
With reference to the method for synthesis example 1, the maleimide ester such as lower structure is made（B-6)：
；Wherein, Ar is, R is methyl；
Wherein, the ratio that n is 1 ~ 10, x and y is 20：1.
Synthesis example 7
With reference to the method for synthesis example 1, the maleimide ester such as lower structure is made（B-7)：
；Wherein, Ar is, R is dimaleoyl imino
Phenyl；
Wherein, the ratio that n is 1 ~ 10, x and y is 1：1.
Embodiment 1~12 and comparative example 1~6
Be formulated according to shown in Tables 1 and 2, by each component be uniformly mixed be made 65% resin solution, made using glass-fiber-fabric
It is impregnated with upper above-mentioned resin solution for reinforcing material, then heats the glass-fiber-fabric being impregnated with 3 ~ 10 minutes in 175 DEG C of baking oven
Printed circuit pre-preg material is made, laminate is then made under the following conditions, and its dielectricity is evaluated by following methods
The performances such as energy, heat resistance, adhesive property, toughness, intensity, are as a result shown in Tables 1 and 2.
<Laminate manufacturing conditions>
Base material：2116 glass-fiber-fabric of ordinary electronic grade；
The number of plies：8；
Plate thickness after molding：1.0mm；
Pre-preg semi-solid preparation condition：175℃/5min；
Condition of cure：150℃/60min+220℃/120min.
<The measurement of dielectric constant and dielectric loss tangent>Dielectric constant uses tablet according to IPC-TM-650 2.5.5.9
Method measures the dielectric constant under 10GHz, dielectric loss tangent：Flat band method is used according to IPC-TM-650 2.5.5.9, is measured
Dielectric loss factor under 10GHz.
<Peel strength>The adhesive property that compositions of thermosetting resin is characterized using the peel strength of laminate, according to
" after thermal stress " experiment condition in IPC-TM-6502.8 methods, tests the peel strength of metal cladding.
<Water absorption rate>It is measured according to the method for IPC-TM-6502.6.2.1.
<Thermally stratified layer time T-288>It is measured according to IPC-TM-6502.4.24.1 methods.
<Glass transition temperature>Show differential scanning calorimetry（DSC）, according to IPC-TM-650 2.4.25 defineds
DSC method is measured.
<Bending strength>Using universal testing machine test material bend loading effect under rupture or reach regulation it is curved
The maximum stress that can be born when square, maximum (normal) stress when this stress is bending, with MPa（Megapascal）For unit.
<Drop impact toughness>The toughness that laminate is characterized with this, using Apparatus for Impacting at low-temp, Apparatus for Impacting at low-temp height of the fall 45cm, under
Fall weight weight 1Kg.According to the good and bad of following Standard Judgement toughness：Cross shape of the drop hammer on laminate is more clear
It is clear, illustrate that the toughness of product is better；Cross shape is clear, illustrates good toughness, is denoted as character ◎；Cross shape is fuzzy, illustrates tough
Property is poor, is denoted as character Δ；Cross between it is clear with it is fuzzy between, be denoted as character.
<Anti-flammability>It is measured according to UL94 vertical combustions.
Table 1
Table 2
The footnote of Tables 1 and 2：
A-1：Butadiene styrene resin（Sartomer, Ricon 100）
A-2：Polybutadiene（Sartomer, Ricon 153H）
B-1：Maleimide ester obtained in synthesis example 1（B-1）
B-2：Maleimide ester obtained in synthesis example 2（B-2）
B-3：Maleimide ester obtained in synthesis example 3（B-3）
B-4：Maleimide ester obtained in synthesis example 4（B-4）
B-5：Maleimide ester obtained in synthesis example 5（B-5）
B-6：Maleimide ester obtained in synthesis example 6（B-6）
C：Initiator, cumyl peroxide
D-1：2,2- is bis-（4-（4- maleimidephenoxies）Phenyl）Propane（BMI-4000, Japan is big and is melted into）
D-2：Petropols (Eastman, C9Resin)
D-3：Allyl is modified Malaysia PN（Self-control）
D-4:Epoxy-modified polyphenylene oxide（Self-control）
E：Fire retardant, phenoxyphosphazene compound（Japanese big tomb chemistry, SPB-100）
F：Filler, ball-type silicon powder（Japan Electric chemistry, SFP-30M）
P-1：Maleimide phenolic aldehyde（Intermediate resin obtained in embodiment 1）
It was found from the result of Tables 1 and 2：
Embodiment 1 has better heat resistance, bending strength, stripping compared to the comparative example 1 that hydrocarbon resin is only used only
From intensity, process industrial art performance, lower dielectric properties are maintained.
Embodiment 1 has preferably resistance to compared to the comparative example 2 of the BOZ and hydrocarbon resin combination that use allyl to be modified
Hot property, dielectric properties and bending strength.
Embodiment 1 is bis- compared to 2,2- is used（4-（4- maleimidephenoxies）Phenyl）Propane and hydrocarbon resin combination
Comparative example 3, have better adhesive property, peel strength higher.
Embodiment 1 has more preferable compared to the comparative example 4 of the phenolic resin and hydrocarbon resin combination that use allyl to be modified
Heat resistance, dielectric properties and bending strength.
Embodiment 1 has better dielectric compared to the comparative example 5 for using maleimide phenolic aldehyde and hydrocarbon resin to combine
Performance.
Embodiment 1 has better dielectric properties, toughness compared to the comparative example for using pure polymaleimide ester.
Embodiment 1 has used the maleimide ester of greater proportion compared to embodiment 8, have better heat resistance,
Bending strength, peel strength, still, embodiment 8 have better dielectric properties.
Embodiment 1 is compared with embodiment 2, and the x structural units with greater proportion in molecular structure have superior resistance to
Hot heat resistance, bending strength, peel strength, still, embodiment 2 have better dielectric properties.Embodiment 6 and embodiment
5 compare, and x structural units are more in molecular structure, although the performances such as heat resistance, peel strength, bending strength are more preferable, its
Toughness relative deficiency.
Embodiment 1 is compared with embodiment 7, and the R substituent in molecular structure is the group containing double bond structure, is had more preferable
Heat resistance, bending strength, peel strength.
Embodiment 9 is compared with embodiment 1, and the allyl modified bismaleimide of part is added in composition, is had
Better peel strength, bending strength, heat resistance, but dielectric can decline unobvious.
Embodiment 10 is compared with embodiment 1, and the Petropols of part are added in composition, has better dielectricity
Energy.
Embodiment 11 is compared with embodiment 1, and allyl is added in composition and is modified More Malay phenolic resin, is had more preferable
Bending strength, heat resistance, but do not influence dielectric properties.
Embodiment 12 is compared with embodiment 1, and epoxy-modified polyphenylene oxide is added in composition, has superior dielectric
Performance.
Embodiment 1~12 has both excellent heat resistance, bending compared to the comparative example 1~6 that hydrocarbon resin is only used only
Intensity, peel strength, process industrial art performance maintain lower dielectric properties.
In conclusion compositions of thermosetting resin using the present invention and its printed circuit prepreg and layer of preparation
Pressing plate has both excellent dielectric properties, heat resistance, anti-flammability, bending strength, toughness, and peel strength is high, water absorption rate is low, adds
The features such as work processing performance is excellent.
Claims (10)
1. a kind of compositions of thermosetting resin, which is characterized in that with solid weight meter, including：
(a) hydrocarbon resin：10 ~ 100 parts；
(b) maleimide ester：20 ~ 100 parts；
(c) initiator：0.1 ~ 8 part；
The structure of the maleimide ester is as follows：, wherein：
It is 2 ~ 20, y is 1 ~ 10 that n, which is 1 ~ 10, x,；
The one kind of Ar in following structural：
、、、、、、；
R is the alkyl that carbon atom number is less than or equal to 5, or is phenyl, aminomethyl phenyl, xenyl, n-propyl phenyl, cumene
Base, tert-butyl-phenyl, ethenylphenyl, 4- maleimidophenyls, p-nitrophenyl.
2. compositions of thermosetting resin according to claim 1, it is characterised in that：R in the maleimide ester structure
Base is vinyl, ethenylphenyl or 4- maleimidophenyls.
3. compositions of thermosetting resin according to claim 1, it is characterised in that：X in the maleimide ester structure
Ratio with y is 5：1~10：1.
4. compositions of thermosetting resin according to claim 1, it is characterised in that：With solid weight meter, including：
(a) hydrocarbon resin：10 ~ 25 parts；
(b) maleimide ester：50 ~ 100 parts；
(c) initiator：0.1 ~ 8 part.
5. compositions of thermosetting resin according to claim 1, it is characterised in that：With solid weight meter, including：
(a) hydrocarbon resin：30 ~ 100 parts；
(b) maleimide ester：20 ~ 40 parts；
(c) initiator：0.1 ~ 8 part.
6. compositions of thermosetting resin according to claim 1, it is characterised in that：The hydrocarbon resin is selected from butylbenzene tree
Fat, polybutadiene, polyisobutene resin, polyprene, polystyrene, 2- methylated polystyrenes, 3- methyl polyphenyl second
Alkene, 4- methylated polystyrenes, 2,4- diisopropyls polystyrene, 2,4- diformazans base polystyrene, styrene butadiene copolymers
One or more of object, styrene-isobutene copolymer；The number-average molecular weight of the hydrocarbon resin be less than 11000 and its
Contents of ethylene is more than 60%.
7. compositions of thermosetting resin according to claim 6, it is characterised in that：The hydrocarbon resin is selected from butylbenzene tree
One or more of fat, polybutadiene, polyisobutene resin.
8. compositions of thermosetting resin according to claim 1, it is characterised in that：Further include 1 ~ 100 with solid weight meter
The component (d) of part, the component (d) are selected from vinyl modified polyphenylene oxide, allyl modifying benzoxazine resin, allyl and are modified
Bismaleimide, vinyl modified phenolic resin, olefin copolymer, Petropols, epoxy resin, unsaturated polyester resin,
One kind in mono-component polyurethane resin or arbitrary several mixture.
9. the prepreg that a kind of any one compositions of thermosetting resin using as described in claim 1 ~ 8 makes, special
Sign is：Glue is made in any one compositions of thermosetting resin solvent dissolving described in claim 1 ~ 8, then will be increased
Strong material is immersed in above-mentioned glue；After impregnating after reinforcing material heat drying, you can obtain the prepreg.
10. a kind of laminate made of compositions of thermosetting resin as described in claim 1, it is characterised in that：One
Metal foil is covered with by the single or double of the prepreg described in claim 9, or will at least 2 by claim 9 institute
After the prepreg superposition stated, it is covered with metal foil, hot forming in its single or double, you can obtain the laminate.
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| CN111072979B (en) * | 2019-12-30 | 2022-03-08 | 四川东材科技集团股份有限公司 | Modified hydrocarbon resin prepolymer, copper-clad plate and preparation method thereof |
| CN113121999B (en) * | 2019-12-31 | 2023-04-07 | 广东生益科技股份有限公司 | Resin composition, and prepreg, laminated board and printed circuit board using same |
| CN111978726B (en) * | 2020-07-28 | 2022-09-16 | 江南大学 | Thermosetting resin composition and preparation method and application thereof |
| CN114634713B (en) * | 2020-12-16 | 2023-07-14 | 广东生益科技股份有限公司 | Resin composition, prepreg and metal-clad laminate |
| CN113603848A (en) * | 2021-07-21 | 2021-11-05 | 四川东材科技集团股份有限公司 | Low-dielectric and high-heat-resistance benzoxazine resin containing hydrocarbon chain segment and imine ring and preparation method thereof |
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