CN109943072A - A kind of compositions of thermosetting resin - Google Patents
A kind of compositions of thermosetting resin Download PDFInfo
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- CN109943072A CN109943072A CN201910141818.8A CN201910141818A CN109943072A CN 109943072 A CN109943072 A CN 109943072A CN 201910141818 A CN201910141818 A CN 201910141818A CN 109943072 A CN109943072 A CN 109943072A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C08K5/00—Use of organic ingredients
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- 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
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- 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
- C08L51/085—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 on to polysiloxanes
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Abstract
The present invention relates to a kind of compositions of thermosetting resin, raw material composition includes biphenyl type maleimide resin, carbodiimides, core-shell structure rubber toughening agent and thermosetting resin.Wherein, the carbodiimides is cyclic structure, number-average molecular weight 200-5000g/mol；The thermosetting resin includes cyanate ester resin or benzoxazine resin.Compared with prior art, the present invention has excellent heat resistance, stability, damp and hot reliability, dielectric properties, can be applied to production prepreg and laminate.
Description
Technical field
The present invention relates to thermosetting material technical fields, more particularly, to a kind of compositions of thermosetting resin.
Background technique
The present invention relates to a kind of resin combination and the prepreg made using this resin combination, laminate and
Copper-clad plate, with the rapid development of electronic technology, the high performance of electronic electric equipment and miniaturization are rapidly developing, and
With the promotion of power, calorific value also greatly improves the electronic component of installation.In this context, electronic component is intensive
Change and minimizes, it is higher to being proposed on the heat resistance of the circuit substrate of Metal Substrate, moisture-proof thermal insulation and environmental reliability
It is required that.
Insulating resin layer used in metal-base circuit board, usually resin combination pass through the thermosetting for solidifying and obtaining
Property resin material.Although maleimide is a kind of high performance resin with excellent heat resistance well known in the industry, due to general
Logical maleimide can not sufficiently solidify with other resins, and secondary curing can occur under the high temperature conditions, cause scantling steady
It is qualitative poor, and the water absorption rate of maleimide material is higher and cause the damp and hot reliability of material poor, so that in high multilayer
The problems such as performance failure, plate bursting occurs in the application such as wiring board or high-density interconnected circuit board.
In order to improve maleimide resin system damp and hot reliability, patent JPH02218751A and
CN104910621B individually discloses a kind of resin combination, and the resin combination is by cyanate ester resin and carbodiimides chemical combination
Object composition.Since the dielectric properties of material after ethylene rhodanate resin curing and thermal stability are not as good as maleimide resin, to electricity
Performance And Reliability requires to be limited on higher application product, it is therefore desirable to adjust resin system composition to obtain more preferably
Performance.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of thermosetting resin groups
Close object.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of compositions of thermosetting resin, raw material composition include the composition of following parts by weight content:
Basic components of the invention are biphenyl type maleimide resin, carbodiimides, thermosetting resin and nucleocapsid knot
Structure rubber toughening agent；Resin combination further includes fire retardant, filler, curing accelerator.Compared to traditional epoxy resin,
High performance resin material, for example, maleimide resin, cyanate ester resin, benzoxazine resin show more preferably mechanical property,
Hot property and dielectric properties etc..
By carbodiimides and high performance resin material in the compositions of thermosetting resin, such as maleimide resin,
Cyanate ester resin, benzoxazine resin combination, the introducing of carbodiimides promote the solidification of thermosetting resin, can get low suction
Water rate, high heat resistance reduce laminate plate bursting risk.Made in resin combination using the core shell rubbers of specific structure simultaneously
For toughener, being introduced into resin system as micro-and nano-particles not only will not have an impact material performance itself, moreover it is possible to drop
Low-dielectric energy improves peel strength, resists stress rupture.
Also, compared to the polycarbodiimide compound and cyanate resin composition announced in CN104910621
Composition, the present invention use cyclic annular carbodiimides, biphenyl type maleimide resin and cyanate ester resin or benzoxazine resin
Both thermosetting resins are as composition.Due to after ethylene rhodanate resin curing the dielectric properties of material and thermal stability not as good as horse
Bismaleimide resin and benzoxazine resin are limited on to electrical property and the higher application product of reliability requirement, because
This present invention is formed to cope with higher demand, using maleimide with cyanate ester resin or benzoxazine resin system to obtain
Obtain more preferably performance.
The carbodiimides is cyclic structure, number-average molecular weight 200-5000g/mol；Structure is shown in formula I:
In Formulas I, X is selected from made of one of aromatic series base, fatty group, alicyclic group or more than one any combination
Chemical structure.
The present invention selects the cyclic structure of carbodiimides, and selected ring-type carbodiimides structure is cyclic formula knot
Structure, contains 1 and the above carbodiimide groups (- C=N=C-) in molecular formula, and with arlydene, alkylidene, cycloalkylidene
One of or more than one any combination and form closed loop configuration.
X is selected from one of aromatic series base, fatty group, alicyclic group or more than one combination, wherein aromatic series base
It can enumerate for example: phenylene, biphenylene, naphthylene, anthrylene；Fatty group can enumerate such as methylene, ethylidene, Asia third
Base, isopropylidene, butylidene；Alicyclic group can enumerate such as cyclopropylidene, sub- cyclobutyl, cyclopentylene, cyclohexylidene.
Aromatic series base that X is selected from, fatty group, alicyclic group can have substituent group, and substituent group can enumerate such as halogen
Plain group, alkyl, alkoxy, aryl, aryloxy group, naphthenic base, acyl group.
For electric material, the durability of resin material can be various with temperature, ultraviolet light, oxygen etc.
Condition and change, wherein humidity, rain and moisture condensation etc. on the reliability of electronic material its influence greatly, use carbonization two
Imines can effectively inhibit material penalty caused by recurring structure destruction in hygrothermal environment as anti-hydrolysis agent.
But know that carbodiimide monomer or straight chain carbodiimide compound may generate when with resin reaction
The isocyanates gas of poison.For isocyanates gas because of the difference of its chemical structure, extremely low concentration exposes that there is also to skin, eye to the open air
The irritation of eyeball, respiratory tract etc. is a kind of to the defined gas of operating environment feasible value progress of production scene.Therefore, exist
It is the carbodiimide compound with cyclic structure used in compositions of thermosetting resin, completely will not when with resin reaction
Toxic isocyanates gas is generated, is not also restricted by operating environment in production scene, safe manufacture can be carried out and made
With.In addition, the Cyclic carbodiimide compound itself is compared to usual carbodiimide compound in production, storage and transport
Better reflect advantage.Meanwhile cyclic carbodimide can not reduce each resin as previous carbodiimide compound
It is suitable for the wide range of areas such as plastics, electric, rubber in the case where performance.
Cyclic annular carbodiimides can be by than traditional carbodiimides monomer or carbodiimides linear chain structure compound
Higher hydrolytic Resistance and heat-resisting quantity are realized with the addition of less dosage.Cyclic annular carbodiimides usually have 300 DEG C with
On heat resistance, therefore, the resin material of formation can have higher resistance to thermal decomposition temperature.In addition it is also possible to as adjusting
The viscosity of resin combination or enable its harden crosslinking agent come using.
Although cyclic annular carbodiimides with than common carbodiimides monomer have higher boiling point, in order to avoid
The gaseous volatilization that may occur in high temperature curing process, the number-average molecular weight of cyclic annular carbodiimides is preferably 200g/mol
More than, further preferably 500g/mol or more.In view of the dissolubility of cyclic annular carbodiimides in a solvent, and and resin
The number-average molecular weight upper limit of the consistency problem of other resin components in composition, cyclic annular carbodiimides is preferably 5000g/
Mol is hereinafter, further preferably 3500g/mol or less.
The thermosetting resin is cyanate ester resin.
The cyanate ester resin is selected from bisphenol A dicyanate, polyphenol cyanate, oligomeric (3- methylene -1,5- phenylene cyanogen
Acid esters), 4,4 '-di-2-ethylhexylphosphine oxides (2,6- 3,5-dimethylphenyl cyanate), 4,4 '-ethylidenediphenyl dicyanates, hexafluoro bisphenol-a
Bis- (4- cyanate) phenyl-propanes of dicyanate, 2,2-, 1,1- bis- (4- cyanatephenyl methane), it is bis- (4- cyanic acid ester group -3,
5- 3,5-dimethylphenyl) methane, bis- (4- cyanatephenyl -1- (methyl the ethylidene)) benzene of 1,3-, bis- (4- cyanatephenyls)
Thioether, bis- (4- cyanatephenyl) ethers, the multifunctional cyanate ester resin as derived from phenol novolacs or by cresol novolac tree
The mixture of one or more of multifunctional cyanate ester resin derived from rouge.
A kind of substitution resin of the cyanate ester resin as conventional curing material epoxy resin has good reactivity, Gu
Material has higher crosslink density, high glass-transition temperature, low-shrinkage and excellent heat resistance and dielectricity after change
Energy.Maleimide resin co-curing in cyanate ester resin and resin combination forms BT resin (maleimide-triazine
Resin) material, there are the performances such as good dielectric properties, heat resistance, low water absorption, resistance to CAF, especially in high-fire resistance and excellent
Good balance is obtained between good dielectric properties.
In cyanate ester resin and maleimide resin solidification process, it may occur that the triazine cyclization of cyanate, span
Come imido Diene-addition reaction and the copolyreaction of cyanate (or triazine ring) and bismaleimide.Non-catalytic
Under the conditions of, these types reaction at relatively high temperatures, could occur at generally higher than 150 DEG C, will result in the gel of resin in this way
Time is longer, and solidification is incomplete.When in resin combination there are when carbodiimides structure, the introducing of carbodiimide compound
The solidification for promoting maleimide and cyanate or benzoxazine resin, is conducive to the complete reaction of thermoset material.
As the concrete example of cyanate system curing agent, PT30 and the PT60 (phenol novolac of such as Lonza corporation can be enumerated
Type multifunctional cyanate ester resin), ULL-950S (multifunctional cyanate ester resin), BA230, BA3000S, BA230S75 (bisphenol-A two
Part or all of cyanate carries out triazine and forms tripolymer).
The thermosetting resin can also be benzoxazine resin.
The benzoxazine resin can be bisphenol A-type benzoxazine, bisphenol-f type benzoxazine, bisphenol S type benzo and dislike
One of piperazine, two amine type benzoxazine of bis-phenol, dicyclopentadiene phenolic benzoxazine or its modified benzoxazine are any several
The mixture of kind.
A part using benzoxazine resin as resin combination, since benzoxazine resin is as a kind of novel
Thermoset material has good processing technology, wider process window in solidification, does not discharge small-molecule substance and cut and consolidate
Dimensional contraction rate is almost nil when change, and in dimensional stability, benzoxazine resin is compared to maleimide resin and cyanic acid
Ester has more advantage.In addition, using benzoxazine resin in resin combination, cyanate ester resin can be advanced optimized as thermosetting
Property material wet-hot aging performance and adhesive property, while can material fragility, improve toughness, make it have good processability
Can, but add excessively can dielectric properties to resin system and toughness cause adverse effect.
The core-shell structure rubber toughening agent is cross-linked polymer particle, and average grain diameter is 20nm-5 μm；The nucleocapsid
Structure rubber toughener includes shell portion and core portion；The core portion of the core shell rubbers is selected from diene polymer, organosiloxane system
The shell portion of polymer, the core shell rubbers toughener is selected from styrenic and (methyl) acrylic ester polymer, shell
Portion is the chemical structure with high glass-transition temperature.
The core portion of the core shell rubbers is selected from diene polymer, organosiloxane system rubber, and diene polymer can be lifted
Example polybutadiene, poly- hexadiene, polyisoprene, dicyclopentadiene, organosiloxane based polymer can illustrate poly dimethyl silicon
Oxygen alkane, polymethy ethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane；The nucleocapsid
The shell portion of rubber toughening agent is selected from styrenic and (methyl) acrylic ester polymer, and styrenic can be lifted
Example polystyrene, poly alpha methylstyrene, polydivinylbenezene, (methyl) acrylic ester polymer can illustrate polyacrylic acid first
Ester, polyacrylic acid propyl ester, butyl polyacrylate, the different monooctyl ester of polyacrylic acid, polymethyl methacrylate, gathers polyethyl acrylate
Ethyl methacrylate, polybutyl methacrylate.
Using Core-shell rubber particles as toughener in resin combination, rubber micro-and nano-particles as addition type auxiliary agent,
Its cross-linked structure does not dissolve in resin system, can play the role of adjusting resin system viscosity.Due to maleimide resin,
Bulk composition of the cyanate ester resin as resin combination can be such that resin adhesive liquid and the viscosity of prepreg reduces, thus difficult
With production.Therefore, Core-shell rubber particles are introduced into resin system, adjust resin system viscosity, improved processing technology, disappear
Except because of one property of product appearance defect or uneven thickness caused by viscosity problem.
In addition, doing toughener using Core-shell rubber particles, material fragility can not only be improved, toughness is improved, due to nucleocapsid rubber
Micelle is scattered among the continuous phase structure of entire resin, can not only reduce dielectric properties, is improved peel strength, is answered in the external world
Power also can play a buffer role in when destroying.
The present invention is defined the average grain diameter of used Core-shell rubber particles, when Core-shell rubber particles are too small
When, it is difficult to it is evenly dispersed in resin system, agglomeration occurs.And when Core-shell rubber particles are excessive, material appearance can become
Difference, material property can also deteriorate.Therefore, the average grain diameter of the Core-shell rubber particles is 20nm-5 μm, further preferably
For 100-500nm.
The biphenyl type maleimide resin is the biphenyl type maleimide resin with Formula II structure, and number is equal
Molecular weight is 500-5000g/mol；
In Formula II, n is the arbitrary integer in 1~10.
It is middle compared to the prior art to use maleimide tree using biphenyl type maleimide resin (biphenyl type BMI)
Rouge is usually phenyl type bismaleimide or phenyl type polyfunctionality maleimide, for example, by the Malaysia acyl being unsubstituted
Imines, N-phenylmaleimide, N- (o-methyl-phenyl)-maleimide, N- (aminomethyl phenyl)-maleimide, N-
(p-methylphenyl)-maleimide, N- cyclohexyl maleimide, dimaleoyl imino phenol, dimaleoyl imino benzo
Cyclobutane, phosphorous maleimide, phosphate maleimide, oxosilane base maleimide, N- (THP trtrahydropyranyl-oxygroup
Phenyl) maleimide and 2, group composed by 6- xylyl maleimide, the biphenyl type BMI composition in the present invention
Resin base material illustrate better performance in metal-stripping intensity and heat resistance, flame resistance and reliability.Though conventional BMI
So there is preferable heat resistance and thermomechanical property, but it is not high with the peel strength of metal, and dielectric properties are poor, water absorption rate compared with
Greatly, final material is had adverse effect on.There are biggish promotion, material using the peel strength of biphenyl type BMI and metal
Water absorption rate it is lower, so as to improve the humidity resistance of product, and biphenyl type structure have compared to phenyl type BMI it is more excellent
Heat resistance and dielectric properties, be suitable for high-order copper-clad plate Material Field.
Component of the invention further includes fire retardant and inorganic filler.
The inorganic filler be selected from aluminium nitride, aluminium borate, magnesia, magnesium carbonate, cubic boron nitride, crystalline silica,
Synthetic silica, hollow silica, preparing spherical SiO 2, fused silica, talcum powder, aluminium oxide, barium sulfate, metatitanic acid
One or more of mixtures of barium, strontium titanates, calcium carbonate, titanium dioxide etc..
The fire retardant is selected from the mixture of one of brominated flame-retardant or phosphonium flame retardant or both；
The brominated flame-retardant is in deca-BDE, decabromodiphenylethane, brominated styrene or deca-BDE
One or more of mixtures；
The phosphonium flame retardant is selected from three (2,6- 3,5-dimethylphenyl) phosphorus, 10 (2,5- dihydroxy phenyl) -9,10- dihydros -
9- oxa- -10- phosphorus phenanthrene -10- oxide, (2,6- 3,5-dimethylphenyl) the phosphorus base benzene of 2,6- bis- or 10- phenyl -9,10- dihydro-9-oxy
The mixture of one or more of miscellaneous -10- phosphorus phenanthrene -10- oxide.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
A kind of compositions of thermosetting resin, basic raw material composition includes (A) biphenyl type maleimide resin (biphenyl
Type BMI), (B) carbodiimides, (C) core-shell structure rubber toughening agent and (D) thermosetting resin.Wherein each component in raw material
Parts by weight content are as follows: 10-70 parts of biphenyl type maleimide resin, 5-20 parts of carbodiimides；Core-shell structure rubber toughening agent
1-10 parts；20-80 parts of thermosetting resin.
The following are the specific choices of each component:
Biphenyl type maleimide resin (biphenyl type BMI):
Biphenyl type maleimide resin is the biphenyl type maleimide resin with Formula II structure, number-average molecular weight
For 500-5000g/mol；
In Formula II, n is the arbitrary integer in 1~10.
Using biphenyl type maleimide resin (biphenyl BMI), the maleimide resin of use in the prior art is logical
It is often phenyl type bismaleimide or phenyl type polyfunctionality maleimide, and present invention employs biphenyl type maleimides
Polyimide resin, compared to traditional BMI being made of phenyl, for example, by the maleimide, the N- benzyl maleimide that are unsubstituted
Amine, N- (o-methyl-phenyl)-maleimide, N- (aminomethyl phenyl)-maleimide, N- (p-methylphenyl)-Malaysia acyl
Imines, N- cyclohexyl maleimide, dimaleoyl imino phenol, dimaleoyl imino benzocyclobutene, phosphorous maleimide
Amine, phosphate maleimide, oxosilane base maleimide, N- (THP trtrahydropyranyl-phenyl) maleimide and 2,
Group composed by 6- xylyl maleimide, the present invention in biphenyl type BMI composition resin base material in metal-stripping
Better performance is illustrated in intensity and heat resistance, flame resistance and reliability.Although conventional BMI have preferable heat resistance and
Thermomechanical property, but it is not high with the peel strength of metal, and dielectric properties are poor, and water absorption rate is larger, generate to final material
Detrimental effect.There is biggish promotion using the peel strength of biphenyl type BMI and metal, the water absorption rate of material is lower, to change
The humidity resistance of kind product, and biphenyl type structure has more excellent heat resistance and dielectric properties compared to phenyl type BMI,
Suitable for high-order copper-clad plate Material Field.
Carbodiimides:
Carbodiimides is cyclic structure, number-average molecular weight 200-5000g/mol；Structure is shown in formula I:
In Formulas I, X is selected from made of one of aromatic series base, fatty group, alicyclic group or more than one any combination
Chemical structure.
Selected ring-type carbodiimides structure is cyclic formula structure, contains 1 or more two Asia of carbonization in molecular formula
Amine groups (- C=N=C-), and formed with one of arlydene, alkylidene, cycloalkylidene or more than one any combination
Closed loop configuration.
X is selected from one of aromatic series base, fatty group, alicyclic group or more than one combination, wherein aromatic series base
It can enumerate for example: phenylene, biphenylene, naphthylene, anthrylene；Fatty group can enumerate such as methylene, ethylidene, Asia third
Base, isopropylidene, butylidene；Alicyclic group can enumerate such as cyclopropylidene, sub- cyclobutyl, cyclopentylene, cyclohexylidene.
Aromatic series base that X is selected from, fatty group, alicyclic group can have substituent group, and substituent group can enumerate such as halogen
Plain group, alkyl, alkoxy, aryl, aryloxy group, naphthenic base, acyl group.
For electric material, the durability of resin material can be various with temperature, ultraviolet light, oxygen etc.
Condition and change, wherein humidity, rain and moisture condensation etc. on the reliability of electronic material its influence greatly, use carbonization two
Imines can effectively inhibit material penalty caused by recurring structure destruction in hygrothermal environment as anti-hydrolysis agent.
But know that carbodiimide monomer or straight chain carbodiimide compound may generate when with resin reaction
The isocyanates gas of poison.For isocyanates gas because of the difference of its chemical structure, extremely low concentration exposes that there is also to skin, eye to the open air
The irritation of eyeball, respiratory tract etc. is a kind of to the defined gas of operating environment feasible value progress of production scene.Therefore, exist
It is the carbodiimide compound with cyclic structure used in compositions of thermosetting resin, completely will not when with resin reaction
Toxic isocyanates gas is generated, is not also restricted by operating environment in production scene, safe manufacture can be carried out and made
With.In addition, the Cyclic carbodiimide compound itself is compared to usual carbodiimide compound in production, storage and transport
Better reflect advantage.Meanwhile cyclic carbodimide can not reduce each resin as previous carbodiimide compound
It is suitable for the wide range of areas such as plastics, electric, rubber in the case where performance.
Cyclic annular carbodiimides can be by than traditional carbodiimides monomer or carbodiimides linear chain structure compound
Higher hydrolytic Resistance and heat-resisting quantity are realized with the addition of less dosage.Cyclic annular carbodiimides usually have 300 DEG C with
On heat resistance, therefore, the resin material of formation can have higher resistance to thermal decomposition temperature.In addition it is also possible to as adjusting
The viscosity of resin combination or enable its harden crosslinking agent come using.
Although cyclic annular carbodiimides with than common carbodiimides monomer have higher boiling point, in order to avoid
The gaseous volatilization that may occur in high temperature curing process, the number-average molecular weight of cyclic annular carbodiimides is preferably 200g/mol
More than, further preferably 500g/mol or more.In view of the dissolubility of cyclic annular carbodiimides in a solvent, and and resin
The number-average molecular weight upper limit of the consistency problem of other resin components in composition, cyclic annular carbodiimides is preferably 5000g/
Mol is hereinafter, further preferably 3500g/mol or less.
Core-shell structure rubber toughening agent:
The core-shell structure rubber toughening agent is cross-linked polymer particle, and average grain diameter is 20nm-5 μm；The nucleocapsid
Structure rubber toughener includes shell portion and core portion；The core portion of the core shell rubbers is selected from diene polymer, organosiloxane system
The shell portion of polymer, the core shell rubbers toughener is selected from styrenic and (methyl) acrylic ester polymer, shell
Portion is the chemical structure with high glass-transition temperature.
The core portion of the core shell rubbers is selected from diene polymer, organosiloxane system rubber, and diene polymer can be lifted
Example polybutadiene, poly- hexadiene, polyisoprene, dicyclopentadiene, organosiloxane based polymer can illustrate poly dimethyl silicon
Oxygen alkane, polymethy ethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane；The nucleocapsid
The shell portion of rubber toughening agent is selected from styrenic and (methyl) acrylic ester polymer, and styrenic can be lifted
Example polystyrene, poly alpha methylstyrene, polydivinylbenezene, (methyl) acrylic ester polymer can illustrate polyacrylic acid first
Ester, polyacrylic acid propyl ester, butyl polyacrylate, the different monooctyl ester of polyacrylic acid, polymethyl methacrylate, gathers polyethyl acrylate
Ethyl methacrylate, polybutyl methacrylate.
Using Core-shell rubber particles as toughener in resin combination, rubber micro-and nano-particles as addition type auxiliary agent,
Its cross-linked structure does not dissolve in resin system, can play the role of adjusting resin system viscosity.Due to maleimide resin,
Bulk composition of the cyanate ester resin as resin combination can be such that resin adhesive liquid and the viscosity of prepreg reduces, thus difficult
With production.Therefore, Core-shell rubber particles are introduced into resin system, adjust resin system viscosity, improved processing technology, disappear
Except because of one property of product appearance defect or uneven thickness caused by viscosity problem.
In addition, doing toughener using Core-shell rubber particles, material fragility can not only be improved, toughness is improved, due to nucleocapsid rubber
Micelle is scattered among the continuous phase structure of entire resin, can not only reduce dielectric properties, is improved peel strength, is answered in the external world
Power also can play a buffer role in when destroying.
The present invention is defined the average grain diameter of used Core-shell rubber particles, when Core-shell rubber particles are too small
When, it is difficult to it is evenly dispersed in resin system, agglomeration occurs.And when Core-shell rubber particles are excessive, material appearance can become
Difference, material property can also deteriorate.Therefore, the average grain diameter of the Core-shell rubber particles is 20nm-5 μm, further preferably
For 100-500nm.
Thermosetting resin:
The thermosetting resin includes cyanate ester resin or benzoxazine resin.
The cyanate ester resin is selected from bisphenol A dicyanate, polyphenol cyanate, oligomeric (3- methylene -1,5- phenylene cyanogen
Acid esters), 4,4 '-di-2-ethylhexylphosphine oxides (2,6- 3,5-dimethylphenyl cyanate), 4,4 '-ethylidenediphenyl dicyanates, hexafluoro bisphenol-a
Bis- (4- cyanate) phenyl-propanes of dicyanate, 2,2-, 1,1- bis- (4- cyanatephenyl methane), it is bis- (4- cyanic acid ester group -3,
5- 3,5-dimethylphenyl) methane, bis- (4- cyanatephenyl -1- (methyl the ethylidene)) benzene of 1,3-, bis- (4- cyanatephenyls)
Thioether, bis- (4- cyanatephenyl) ethers, the multifunctional cyanate ester resin as derived from phenol novolacs or by cresol novolac tree
The mixture of one or more of multifunctional cyanate ester resin derived from rouge.
Replace epoxy resin as curing agent using cyanate ester resin or benzoxazine resin, cyanate ester resin is as tradition
A kind of substitution resin of curing materials epoxy resin has good reactivity, and material has higher crosslink density after solidification,
High glass-transition temperature, low-shrinkage and excellent heat resistance and dielectric properties.In cyanate ester resin and resin combination
Maleimide resin co-curing, formed BT resin (maleimide-cyanate resin) material, have good dielectricity
The performances such as energy, heat resistance, low water absorption, resistance to CAF especially obtain between high-fire resistance and excellent dielectric performance good flat
Weighing apparatus.
In cyanate ester resin and maleimide resin solidification process, it may occur that the triazine cyclization of cyanate, span
Come imido Diene-addition reaction and the copolyreaction of cyanate (or triazine ring) and bismaleimide.Non-catalytic
Under the conditions of, these types reaction at relatively high temperatures, could occur at generally higher than 150 DEG C, will result in the gel of resin in this way
Time is longer, and solidification is incomplete.When in resin combination there are when carbodiimides structure, the introducing of carbodiimide compound
The solidification for promoting maleimide and cyanate or benzoxazine resin, is conducive to the complete reaction of thermoset material.
As the concrete example of cyanate system curing agent, PT30 and the PT60 (phenol novolac of such as Lonza corporation can be enumerated
Type multifunctional cyanate ester resin), ULL-950S (multifunctional cyanate ester resin), BA230, BA3000S, BA230S75 (bisphenol-A two
Part or all of cyanate carries out triazine and forms tripolymer).
The benzoxazine resin can be bisphenol A-type benzoxazine, bisphenol-f type benzoxazine, bisphenol S type benzo and dislike
One of piperazine, two amine type benzoxazine of bis-phenol, dicyclopentadiene phenolic benzoxazine or its modified benzoxazine are any several
The mixture of kind.
A part using benzoxazine resin as resin combination, since benzoxazine resin is as a kind of novel
Thermoset material has good processing technology, wider process window in solidification, does not discharge small-molecule substance and cut and consolidate
Dimensional contraction rate is almost nil when change, and in dimensional stability, benzoxazine resin is compared to maleimide resin and cyanic acid
Ester has more advantage.In addition, using benzoxazine resin in resin combination, cyanate ester resin can be advanced optimized as thermosetting
Property material wet-hot aging performance and adhesive property, while can material fragility, improve toughness, make it have good processability
Can, but add excessively can dielectric properties to resin system and toughness cause adverse effect.
As needed, part epoxy can be replaced as curing agent using cyanate ester resin or benzoxazine resin,
I.e. thermosetting resin is cyanate ester resin or the mixture of benzoxazine resin and epoxy resin.
Component of the invention further includes fire retardant and inorganic filler.
Inorganic filler:
The inorganic filler be selected from aluminium nitride, aluminium borate, magnesia, magnesium carbonate, cubic boron nitride, crystalline silica,
Synthetic silica, hollow silica, preparing spherical SiO 2, fused silica, talcum powder, aluminium oxide, barium sulfate, metatitanic acid
One or more of mixtures of barium, strontium titanates, calcium carbonate, titanium dioxide etc..
Fire retardant:
The fire retardant is selected from the mixture of one of brominated flame-retardant or phosphonium flame retardant or both；
The brominated flame-retardant is in deca-BDE, decabromodiphenylethane, brominated styrene or deca-BDE
One or more of mixtures；
The phosphonium flame retardant is selected from three (2,6- 3,5-dimethylphenyl) phosphorus, 10 (2,5- dihydroxy phenyl) -9,10- dihydros -
9- oxa- -10- phosphorus phenanthrene -10- oxide, (2,6- 3,5-dimethylphenyl) the phosphorus base benzene of 2,6- bis- or 10- phenyl -9,10- dihydro-9-oxy
The mixture of one or more of miscellaneous -10- phosphorus phenanthrene -10- oxide.
As needed, compositions of thermosetting resin of the invention can also add other additives, such as imidazoles promote
Agent, specially 2-methylimidazole, -4 methylimidazole of 2- ethyl, 1,2- methylimidazole, 2- phenylimidazole, -4 methyl miaow of 2- phenyl
Azoles, 2-methylimidazole quinoline, 2- benzylimidazoline, 1- cyano ethyl -2- undecyl imidazole, 1- cyano ethyl -2- phenylimidazole
Deng it is one or more；Such as organic cobalt complex such as acetylacetone cobalt (II), acetylacetone cobalt (III), acetylacetone copper (II)
The one of the Organic-iron complexes such as organozinc complexes, the ferric acetyl acetonades (III) such as equal organic copper complex, zinc acetylacetonate (II)
Kind is a variety of；Such as organic metal salt, it can be specially the one or more of zinc octoate, tin octoate, zinc stearate etc..
Basic components of the invention are biphenyl type maleimide resin, carbodiimides, thermosetting resin and nucleocapsid knot
Structure rubber toughening agent；Resin combination further includes fire retardant, filler, curing accelerator.Compared to traditional epoxy resin,
High performance resin material, for example, maleimide resin, cyanate ester resin, benzoxazine resin show more preferably mechanical property,
Hot property and dielectric properties etc..
Compared with prior art, the copper coated foil plate that the compositions of thermosetting resin that the present invention obtains is prepared as adhesive,
Tg>270℃(DMA)；Z axis CTE < 1.5%；In terms of heat resistance: Td > 380 DEG C, T288 > 60min；In terms of electrical property: dielectric is normal
Number Dk < 3.9 (10GHz)；Dielectric loss Df < 0.0057 (10GHz)；Peel strength of copper foil > 1.0N/mm；It is provided additionally with very low
Water absorption rate and good machining property, and fire-retardant reach UL94V-0 grades.With excellent heat resistance, stability, wet
Thermal reliability, dielectric properties；It can be applied to production prepreg and laminate.
The test method of thermoset composition in the present embodiment are as follows:
Glass transition temperature (Tg): DMA instrument test is used, according to the DMA of IPC-TM-650 2.4.24.4 defined
Test method is measured.
Z axis thermal expansion coefficient (CTE): using TMA instrument test, surveys according to the TMA of IPC-TM-650 2.4.24 defined
Method for testing measurement.
288 DEG C of layering pyrolysis times (T288): TMA instrument test is used, according to IPC-TM-650 2.4.24.1 defined
Test method measurement.
Peel strength of copper foil (PS): being tested using Shimadzu puller system, according to the test of IPC-TM-650 2.4.8 defined
Method measurement.
Dielectric constant (Dk) and dielectric loss factor (Df): dielectric constant and dielectric loss factor test method are according to IPC-
The test method of TM-650 2.5.5.9 defined measures.
Pressure cooker gluten substitute (PCT): laminate is in 120 DEG C of progress thermophilic digestion experiments, according to IPC-TM-650
2.6.16 the test method of defined measures.
Anti-flammability: test grading is carried out according to the material combustion method of UL-94 defined.
Water absorption rate: it is measured according to the laminate water absorption rate test method of IPC-TM-650 2.6.2.1 defined.
Resin Flow: being measured Resin Flow by Shimadzu capillary rheometer, and 2g resin-oatmeal briquetting is with one
Constant-pressure squeezes out resin from aperture, is assessed according to the stroke that resin flows out in rheometer.It is longer to flow out stroke, tree
Membranous lipid fluidity is better.
Dimensional stability: the prepreg of 10 layers of 500mm*500mm of overlapping quick pressing in press, 180 DEG C after 2 hours
When the difference of the thickness of taking-up test plate each position, maximum gauge and minimum thickness is less than 5%, the dimensional stability of material is considered as
Well.
Following embodiment illustrates applicable cases of the invention:
Embodiment 1~11
A kind of compositions of thermosetting resin, basic raw material composition includes (A) biphenyl type maleimide resin (biphenyl
Type BMI), (B) carbodiimides, (C) core-shell structure rubber toughening agent and (D) thermosetting resin.Component is used in the present embodiment
Product name and concrete composition be shown in Table 1.In order to preferably illustrate the present invention, it is made using the component and proportion of such as the following table 2
The compositions of thermosetting resin.
The marque and composition parameter of each component in 1 the present embodiment of table
The raw material of 2 embodiment 1~11 of table and comparative example 1~5 composition
The raw material of 2 embodiment 1~11 of table and comparative example 1~5 forms (Continued)
The raw material of 2 embodiment 1~11 of table and comparative example 1~5 forms (Continued)
Embodiment 12~13
A kind of compositions of thermosetting resin, basic raw material composition includes (A) biphenyl type maleimide resin (biphenyl
Type BMI), (B) carbodiimides, (C) core-shell structure rubber toughening agent and (D) thermosetting resin.In order to preferably illustrate this hair
It is bright, which is made using the component and proportion of such as the following table 3.In the present embodiment, (A) biphenyl type maleimide
The number-average molecular weight of polyimide resin is 500g/mol；(B) number-average molecular weight of carbodiimides is 200g/mol；(C) core-shell structure
Rubber toughening agent is cross-linked polymer particle, average grain diameter 20nm；Core-shell structure rubber toughening agent includes shell portion and core portion；
Core portion is selected from diene polymer, and shell portion is selected from styrenic；(D) thermosetting resin is commercially available cyanate ester resin；
Fire retardant is the mixture of deca-BDE, decabromodiphenylethane, brominated styrene and deca-BDE；Inorganic filler is dioxy
SiClx；Promotor is imidazoles promotor.
Embodiment 14~15
A kind of compositions of thermosetting resin, basic raw material composition includes (A) biphenyl type maleimide resin (biphenyl
Type BMI), (B) carbodiimides, (C) core-shell structure rubber toughening agent and (D) thermosetting resin.In order to preferably illustrate this hair
It is bright, which is made using the component and proportion of such as the following table 3.In the present embodiment, (A) biphenyl type maleimide
The number-average molecular weight of polyimide resin is 5000g/mol；(B) number-average molecular weight of carbodiimides is 5000g/mol；(C) nucleocapsid knot
Structure rubber toughening agent is cross-linked polymer particle, and average grain diameter is 5 μm；Core-shell structure rubber toughening agent includes shell portion and core
Portion；Core portion is selected from styrenic, and shell portion is selected from (methyl) acrylic ester polymer；(D) thermosetting resin is commercially available
Cyanate ester resin；Fire retardant is the mixture of deca-BDE, decabromodiphenylethane, brominated styrene and deca-BDE；
Inorganic filler is silica；Promotor is imidazoles promotor.
The raw material of 3 embodiment 12~14 of table forms
Comparative example 1
A kind of compositions of thermosetting resin, basic raw material composition includes the bis- (Malaysias 3- ethyl -5- methyl -4- (A2)
Imide benzene) methane (i.e. phenyl BMI), (A3) phenylmethane maleimide；(B) carbodiimides, (C) core-shell structure rubber
Glue toughener and (D) thermosetting resin, specific raw material composition are shown in Table 2.
Comparative example 2
A kind of compositions of thermosetting resin, basic raw material composition includes (A) biphenyl type maleimide resin (biphenyl
Type BMI), (C) core-shell structure rubber toughening agent and (D) thermosetting resin, the difference with embodiment is sub- without (B) carbonization two
Amine；Specific raw material composition is shown in Table 2.
Comparative example 3
A kind of compositions of thermosetting resin, basic raw material composition includes (A) biphenyl type maleimide resin (biphenyl
Type BMI), (B) carbodiimides and (D) thermosetting resin, the difference with embodiment is rubber toughened without (C) core-shell structure
Agent；Specific raw material composition is shown in Table 2.
Comparative example 4
A kind of compositions of thermosetting resin, basic raw material composition includes (A) biphenyl type maleimide resin (biphenyl
Type BMI), (B) carbodiimides and (D) thermosetting resin, the difference with embodiment is rubber toughened without (C) core-shell structure
Agent；Specific raw material composition is shown in Table 2.
Comparative example 5
A kind of compositions of thermosetting resin, basic raw material composition includes the bis- (Malaysias 3- ethyl -5- methyl -4- (A2)
Imide benzene) methane (i.e. phenyl BMI) and (D) thermosetting resin, the difference with embodiment is without (B) carbodiimides
(C) core-shell structure rubber toughening agent；Specific raw material composition is shown in Table 2.
The property of compositions of thermosetting resin in embodiment and comparative example is tested, comparative example and comparative example
1, all using phenyl BMI in comparative example 1, measuring its Z axis CTE is 1.75%, greater than the thermosetting resin in any embodiment
Composition Z axis CTE value, and PS value is lower, illustrates that biphenyl type BMI has preferable dimensionally stable compared to conventional type phenyl BMI
Property, lower thermal expansion coefficient, and be significantly improved with the peel strength of copper foil, dielectric properties are relative to conventional BMI
Also advantage is had more.
Comparative example and comparative example 2, since comparative example 2 is free of carbodiimides, the thermosetting resin group in comparative example 2
Closing object Z axis CTE is 1.72%, and the water absorption rate of material is higher, and plate bursting occurs in 60min for T288 test, illustrates carbon
The presence for changing diimine promotes the solidification of resin combination, hence it is evident that reduces the water absorption rate of material, exists to reduce material
A possibility that plate bursting occurs in hot environment, improves the thermal stability of material, and furthermore carbodiimides is to improvement material
Mobility also has clear improvement.
Comparative example and comparative example 3 and comparative example 4, since comparative example 3 and comparative example 4 are rubber toughened without core-shell structure
Agent, peel strength of copper foil value in comparative example is lower to show that core-shell tougheners are added among material as micro-and nano-particles, can
Promote interface peel intensity；And comparative example 3 and comparative example 4 fail to test by 3 hours PCT, and dimensional stability is big
In 5%, poor dimensional stability shows that this core shell rubbers are obviously improved as dimensional stability of the toughener to system, is situated between
Electrical property is also improved.
Comparative example and comparative example 5, since comparative example 5 increases without biphenyl type BMI, carbodiimides and core shell rubbers
Tough dose, only conventional BMI is combined with thermosetting resin, and the mechanical property, heat resistance and dielectric properties in comparative example are compared to reality
Apply that example is poor, the thermal stability of material, size reliability and Resin Flow are bad.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (10)
1. a kind of compositions of thermosetting resin, which is characterized in that its raw material composition includes the composition of following parts by weight content:
2. a kind of compositions of thermosetting resin according to claim 1, which is characterized in that the carbodiimides is ring-type
Structure, number-average molecular weight 200-5000g/mol；Structure is shown in formula I:
In Formulas I, X is selected from chemistry made of one of aromatic series base, fatty group, alicyclic group or more than one any combination
Structure.
3. a kind of compositions of thermosetting resin according to claim 1, which is characterized in that the thermosetting resin is cyanic acid
Ester resin or benzoxazine resin.
4. a kind of compositions of thermosetting resin according to claim 3, which is characterized in that the cyanate ester resin is selected from double
Phenol A dicyanate, polyphenol cyanate, oligomeric (3- methylene -1,5- phenylenecyanate), 4,4 '-di-2-ethylhexylphosphine oxides (2,6- diformazan
Base phenylcyanate), 4,4 '-ethylidenediphenyl dicyanates, hexafluoro bisphenol-a dicyanate, bis- (4- cyanate) benzene of 2,2-
Base propane, 1,1- bis- (4- cyanatephenyl methane), bis- (4- cyanic acid ester group -3,5- 3,5-dimethylphenyl) methane, the bis- (4- of 1,3-
Cyanatephenyl -1- (methyl ethylidene)) benzene, bis- (4- cyanatephenyl) thioethers, bis- (4- cyanatephenyl) ethers, by
In multifunctional cyanate ester resin or the multifunctional cyanate ester resin as derived from cresol novolac resin derived from phenol novolacs
One or more of mixtures.
5. a kind of compositions of thermosetting resin according to claim 1, which is characterized in that the benzoxazine resin is selected from
Bisphenol A-type benzoxazine, bisphenol-f type benzoxazine, bisphenol S type benzoxazine, two amine type benzoxazine of bis-phenol, dicyclopentadiene
One of phenolic benzoxazine or its modified benzoxazine or any several mixture.
6. a kind of compositions of thermosetting resin according to claim 1, which is characterized in that the core-shell structure is rubber toughened
Agent is cross-linked polymer particle, and average grain diameter is 20nm-5 μm；The core-shell structure rubber toughening agent includes shell portion and core portion；
The core portion of the core shell rubbers is selected from diene polymer or organosiloxane based polymer, the shell of the core shell rubbers toughener
Portion is selected from styrenic and (methyl) acrylic ester polymer.
7. a kind of compositions of thermosetting resin according to claim 1, which is characterized in that the biphenyl type maleimide
Polyimide resin is the biphenyl type maleimide resin with Formula II structure, number-average molecular weight 500-5000g/mol；
In Formula II, n is the arbitrary integer in 1~10.
8. a kind of compositions of thermosetting resin according to claim 1, which is characterized in that further include fire retardant and inorganic fill out
Material.
9. a kind of compositions of thermosetting resin according to claim 8, which is characterized in that the inorganic filler is selected from nitridation
Aluminium, aluminium borate, magnesia, magnesium carbonate, cubic boron nitride, crystalline silica, synthetic silica, hollow silica, ball
Shape silica, fused silica, talcum powder, aluminium oxide, barium sulfate, barium titanate, strontium titanates, calcium carbonate, titanium dioxide
One or more of mixtures.
10. a kind of compositions of thermosetting resin according to claim 8, which is characterized in that the fire retardant is selected from brominated
The mixture of one of fire retardant or phosphonium flame retardant or both；
The brominated flame-retardant is selected from one of deca-BDE, decabromodiphenylethane, brominated styrene or deca-BDE
Or several mixture；
The phosphonium flame retardant is selected from three (2,6- 3,5-dimethylphenyl) phosphorus, 10 (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxies
Miscellaneous -10- phosphorus phenanthrene -10- oxide, (2,6- 3,5-dimethylphenyl) the phosphorus base benzene of 2,6- bis- or 10- phenyl -9,10- dihydro-9-oxy it is miscellaneous -
The mixture of one or more of 10- phosphorus phenanthrene -10- oxide.
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| JP2021528891A JP7170137B2 (en) | 2019-02-26 | 2019-12-30 | Thermosetting resin composition |
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| WO2023145473A1 (en) * | 2022-01-28 | 2023-08-03 | パナソニックＩｐマネジメント株式会社 | Resin composition, prepreg, resin-equipped film, resin-equipped metal foil, metal-cladded laminated board, and printed wiring board |
| CN115124958B (en) * | 2022-08-23 | 2023-08-15 | 绵阳惠利电子材料有限公司 | Matte high-temperature-resistant and damp-heat-resistant double-component epoxy compound and preparation method thereof |
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| KR20210087072A (en) | 2021-07-09 |
| JP7170137B2 (en) | 2022-11-11 |
| JP2022508174A (en) | 2022-01-19 |
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