CN106751524A - A kind of halogen-free thermosetting resin composite and the prepreg containing it, laminate and printed circuit board - Google Patents
A kind of halogen-free thermosetting resin composite and the prepreg containing it, laminate and printed circuit board Download PDFInfo
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- CN106751524A CN106751524A CN201611236980.0A CN201611236980A CN106751524A CN 106751524 A CN106751524 A CN 106751524A CN 201611236980 A CN201611236980 A CN 201611236980A CN 106751524 A CN106751524 A CN 106751524A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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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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- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/26—Di-epoxy compounds heterocyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
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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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use 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 C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
A kind of prepreg the invention provides halogen-free thermosetting resin composite and containing it, laminate and printed circuit board.The halogen-free thermosetting resin composite, it contains following three kinds of materials as necessary component, by organic solid content based on 100 weight portions, wherein：(A) halogen-free epoxy resin：35 65 weight portions；(B) polyphosphonates：10 35 weight portions；(C) cyanate：10 30 weight portions.Halogen-free thermosetting resin composite provided by the present invention and the prepreg containing it, laminate and printed circuit board, with high glass-transition temperature, excellent dielectric properties, high-peeling strength, high-fire resistance, low water absorption and good process processability, and halogen-free flameproof can be realized, reach UL94 V 0.
Description
Technical field
The present invention relates to copper-clad plate technical field, more particularly to a kind of halogen-free thermosetting resin composite and pre- containing it
Leaching material, laminate and printed circuit board.
Background technology
The high speed and multifunction processed with electronic product information, applying frequency are improved constantly, and 3-6GHz will turn into
Main flow, baseplate material is no longer to play the part of the mechanical support role under traditional sense, and will turn into PCB and end together with electronic building brick
End manufacturer designer lifts an important channel of properties of product.Because Dk high can make signal transmission speed slack-off, Df high can make
Signal section is converted into heat energy loss in baseplate material, thus reduce that Dk/Df turned into substrate dealer chase focus.Herein
Under background, the excellent cyanate ester resin of dielectric properties is into one of focus for getting most of the attention.But cyanate ester resin is due to its own
Limitation, the big poor in processability of fragility, and fire resistance is undesirable.
CN105968321A disclose the epoxy resin of Han oxazolidine ketone rings, its manufacture method, composition epoxy resin,
Its solidfied material and its application its solidfied material and its application.The epoxy resin of its Han oxazolidine ketone ring structure for disclosing has high resistance to
Hot, high-adhesion, excellent fire resistance and processability, but the dielectric constant of its resin combination and dielectric loss are equal
Typically.
The present invention does not generate secondary with the curing agent of epoxy resin that polyphosphonates are above-mentioned Han oxazolidines ketone ring, reaction
Hydroxyl, realizes while excellent dielectric properties, high-adhesion, excellent processability and higher glass transition temperature is kept
Halogen-free flameproof；Cyanate ester resin is added, solidfied material glass transition temperature (Tg) and heat resistance can be not only greatly improved, also
Solidfied material dielectric constant and dielectric loss value can further be reduced.In the present invention, the epoxy and poly- phosphine of Han oxazolidine ketone rings
The excellent caking property and processability that acid esters has can make up the weakness such as the big, poor in processability of cyanate system fragility；Additionally, poly-
Phosphonate ester phosphorus content is high, and has Yu the nitrogen in the nitrogen and cyanate in the epoxy resin of Han oxazolidone ring structures
Effect of phosphorus nitrogen cooperative flame retardant, solves the problems, such as that cyanate is fire-retardant poor, while phosphorus nitrogen cooperative flame retardant can reduce solidification
Thing anti-flammability reaches phosphorus content needed for UL94 V-0 and reduces water absorption rate, reduces the several of laminate work in-process moisture absorption plate bursting
Rate.
The content of the invention
Based on this, an object of the present invention is to provide a kind of halogen-free thermosetting resin composite.Use Halogen heat
Prepreg, laminate and the printed circuit board that thermosetting resin composition makes have high glass-transition temperature, excellent dielectric
Performance, high-peeling strength, high-fire resistance, low water absorption and good technique processability, and halogen-free flameproof can be realized, reach
UL94 V-0。
Inventor to achieve the above object, has carried out in-depth study repeatedly, as a result finds：By will be comprising with specific
The halogen-free epoxy resin of structure, polyphosphonates, cyanate and other optionally appropriate halogen-free thermosettings being obtained by mixing of material
Resin combination, can reach above-mentioned purpose.
To achieve these goals, present invention employs following technical scheme：
A kind of halogen-free thermosetting resin composite, it contains following three kinds of materials as necessary component, with organic solid content
Based on 100 weight portions, wherein：
(A) halogen-free epoxy resin：35-65 weight portions；
(B) polyphosphonates：10-35 weight portions；
(C) cyanate：10-30 weight portions.
It is matrix resin that the present invention use the halogen-free epoxy resin of ad hoc structure, its molecular structure symmetrically, and containing there is oxazole
Alkanone ring structure, the advantages of possess high-fire resistance, high-adhesion, high glass-transition temperature and good anti-flammability；Additionally, its
Also there are good dielectric properties；With polyphosphonates as curing agent, secondary hydroxyl is not generated with epoxy resin reaction, keeping
Halogen-free flameproof is realized while excellent dielectric properties, high-adhesion and higher glass transition temperature, and assigns solidfied material
Excellent processability；Cyanate ester resin is added, solidfied material glass transition temperature (Tg) and heat resistance can be not only greatly improved,
Can also further reduce solidfied material dielectric constant and dielectric loss value.Additionally, the epoxy and poly- phosphine of Han oxazolidine ketone ring structures
The excellent caking property and processability that acid esters has can make up the weakness such as the cyanate big poor in processability of system fragility；Polyphosphonates
Phosphorus content is high, and containing the nitrogen in epoxy resin of oxazolidone ring structure and the nitrogen in cyanate with this has phosphorus nitrogen
Effect of cooperative flame retardant, solves the problems, such as that cyanate is fire-retardant poor, at the same phosphorus nitrogen cooperative flame retardant can to reduce solidfied material fire-retardant
Property reach phosphorus content needed for UL94 V-0 and reduce water absorption rate, reduce laminate work in-process moisture absorption plate bursting probability.
The present invention in addition to the respective advantage of above-mentioned three kinds of components is made full use of, also by the synergy between it, most
Played to big degree the advantage of each component, so as to get solidfied material have high glass-transition temperature, excellent dielectric properties,
High-peeling strength, high-fire resistance, low water absorption and good process processability, and halogen-free flameproof can be realized, reach UL94 V-0.
Component (A) in the present invention, i.e. halogen-free epoxy resin, can provide resin and its laminate institute being made after solidifying
Heat resistance, caking property, fire resistance, dielectric properties and the mechanical property for needing.
According to the present invention, the halogen-free epoxy resin, it has the structure represented by following formula (I)：
In formula (I), X is represented with least one alkyl, the aryl of carbon number 6-10 and the carbon number 6-10's for being selected from carbon number 1-4
The cycloalkylidene of the ring element number 5-8 of the substitution base of aralkyl；The naphthenic ring for constituting these cycloalkylidenes is pentamethylene ring, hexamethylene
The anyone of ring, cycloheptane ring or cyclooctane ring, preferably pentamethylene ring or cyclohexane ring.
Replace to have on the naphthenic ring and replace base described at least one.For example, the alkyl of carbon number 1-4 can enumerate methyl, second
Base, propyl group, normal-butyl, isopropyl, isobutyl group, sec-butyl, tert-butyl group etc.；The aryl of carbon number 6-10 can enumerate phenyl, naphthyl, benzyl
Base, tolyl, ortho-xylene base etc., but be not limited to these bases, in the case where there is multiple, can it is each identical can also
It is different.From the viewpoint of the physical property such as the cementability from the easiness and plywood for obtaining, preferred substitution base is methyl or benzene
Base.
In formula (I), R separately represents hydrogen atom, the alkyl of carbon number 1-8, the alkoxy of carbon number 1-8, carbon number 5-8
The aralkoxy of cycloalkyl, the aryl of carbon number 6-10, the aralkyl of carbon number 6-10, the aryloxy group of carbon number 6-10 or carbon number 6-10.
For example, the alkyl of carbon number 1-8 can enumerate methyl, ethyl, propyl group, isopropyl, normal-butyl, the tert-butyl group, hexyl etc., carbon number 5-8's
Cycloalkyl can enumerate cyclohexyl etc., and the aryl or aralkyl of carbon number 6-10 can enumerate phenyl, naphthyl, benzyl, phenethyl, 1- phenyl
Ethyl etc., the aryloxy group or aralkoxy of carbon number 6-10 can enumerate phenoxy group, naphthoxy, benzyloxy, naphthylmethoxy etc., but simultaneously
Be not limited to these bases, each can it is identical can also be different.The things such as the heat resistance from the easiness for obtaining and when being made solidfied material
From the viewpoint of property, preferred R is hydrogen atom, 1- phenylethyls or methyl.
The position of substitution of R can be for ortho position, the optional position of meta, preferably for the carbon atom being bonded with X
It is ortho position.
In formula (I), Y is to remove two residues of NCO from polyisocyanate compounds, and expression can have substitution
Structure represented by the functional group more than divalent of base, preferably formula (1a)-formula (1k).It is the poly- isocyanide from more than 3 functions in Y
In the case of the base that ester compound is produced, can have base, the base containing amino-formate bond of Han oxazolidine ketone rings etc. to make
It is substitution base.
Preferably, halogen-free epoxy resin of the present invention has the structure represented by following formula (II)s：
In formula (II), Z represents divalent base, and the 5mol%-100mol% in Z is the divalent base represented by following formula (a)；Y tables
Show the residue that NCO is removed from diisocyanate cpd；G represents glycidyl；N represents repeat number, and average value is
1-5；
In formula (a), X is represented with least one alkyl, the aryl of carbon number 6-10 and the carbon number 6-10's for being selected from carbon number 1-4
The cycloalkylidene of the ring element number 5-8 of the substitution base of aralkyl；R separately represents hydrogen atom, the alkyl of carbon number 1-8, carbon number
The alkoxy of 1-8, the cycloalkyl of carbon number 5-8, the aryl of carbon number 6-10, the aralkyl of carbon number 6-10, the aryloxy group of carbon number 6-10
Or the aralkoxy of carbon number 6-10.
In formula (a), Xs and R of the X and R respectively with formula (I) are synonymous.
In the present invention, the halogen-free epoxy resin weight average molecular weight be 1000-8000, such as 1000,1500,2000,
2500th, between 3000,3500,4000,4500,5000,5500,6000,6500,7000,7500 or 8000, and above-mentioned numerical value
Specific point value, as space is limited and for concise consideration, the present invention specific point value that no longer scope described in exclusive list includes.
Preferably, the halogen-free epoxy resin epoxide equivalent is 200g/eq.-550g/eq., such as 200g/eq., 220g/
eq.、240g/eq.、260g/eq.、280g/eq.、300g/eq.、320g/eq.、340g/eq.、360g/eq.、380g/eq.、
400g/eq., 420g/eq., 440g/eq., 460g/eq., 480g/eq., 500g/eq., 520g/eq., 540g/eq. or
Specific point value between 550g/eq., and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer limit row
Lift the specific point value that the scope includes.
By organic solid content based on 100 weight portions, the addition of component (A) halogen-free epoxy resin is 35-65 weight
Part, such as 35 weight portions, 36 weight portions, 38 weight portions, 40 weight portions, 42 weight portions, 44 weight portions, 46 weight portions, 48 weight
Part, 50 weight portions, 52 weight portions, 54 weight portions, 56 weight portions, 58 weight portions, 60 weight portions, 62 weight portions, 64 weight portions or
Specific point value between 65 weight portions, and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer limit row
Lift the specific point value that the scope includes.
Component (B) in the present invention, as polyphosphonates, impart solidfied material fire resistance, excellent dielectric properties, height
Caking property and good processability.
By organic solid content based on 100 weight portions, the addition of component (B) polyphosphonates is 10-35 weight portions, example
Such as 10 weight portions, 12 weight portions, 14 weight portions, 16 weight portions, 18 weight portions, 20 weight portions, 22 weight portions, 24 weight portions, 26
It is specific between weight portion, 28 weight portions, 30 weight portions, 32 weight portions, 34 weight portions or 35 weight portions, and above-mentioned numerical value
Value, as space is limited and for concise consideration, the present invention specific point value that no longer scope described in exclusive list includes.
According to the present invention, component (B) polyphosphonates have following structural formula：
Wherein Ar is aryl, described-O-Ar-O-selected from resorcinol active group, hydroquinones active group, double
Phenol A active groups, Bisphenol F active group, 4,4 ＇-biphenol, phenolphthalein active group, 4,4 ＇-thio diphenol active group, 4,
Any one in 4 ＇-sulphonyl diphenol active group or 3,3,5- trimethylcyclohexyl biphenols；Q is the substitution or not of C1-C20
Substituted straight chained alkyl, the substituted or unsubstituted branched alkyl of C1-C20, the substituted or unsubstituted linear alkene of C2-C20
Base, the substituted or unsubstituted branched-chain alkene base of C2-C20, the substituted or unsubstituted straight-chain alkyl-sub of C2-C20, C2-C20
Substituted or unsubstituted branched alkylidene, the substituted or unsubstituted cycloalkyl of C5-C20 or the substituted or unsubstituted virtues of C6-C20
Base；M is the arbitrary integer of 1-75.
In the present invention, the weight average molecular weight of the polyphosphonates is 1000-50000, such as 1000,1500,2000,
2500、3000、3500、4000、4500、5000、5500、6000、6500、7000、7500、8000、10000、15000、
18000th, it is specific between 20000,22000,25000,30000,35000,40000,45000 or 50000, and above-mentioned numerical value
Point value, as space is limited and for concise consideration, the present invention specific point value that no longer scope described in exclusive list includes, preferably
1000-10000, more preferably 1000-4500.
Preferably, the polyphosphonates structural formula is as follows：
Wherein q is the arbitrary integer of 2-20, such as between 2,4,6,8,10,12,15,18 or 20, and above-mentioned numerical value
Specific point value, as space is limited and for concise consideration, the present invention specific point value that no longer scope described in exclusive list includes is excellent
Select the arbitrary integer that q is 3-10.
Heretofore described component (C) cyanate ester resin, assigns solidfied material high glass-transition temperature, heat resistance and excellent
Dielectric properties etc..
By organic solid content based on 100 weight portions, the addition of component (C) cyanate is 10-30 weight portions, for example
10 weight portions, 12 weight portions, 14 weight portions, 16 weight portions, 18 weight portions, 20 weight portions, 22 weight portions, 24 weight portions, 26 weights
Amount part, the specific point value between 28 weight portions or 30 weight portions, and above-mentioned numerical value, as space is limited and for concise consideration,
The present invention specific point value that no longer scope described in exclusive list includes.
In the present invention, described component (C) cyanate ester resin has no particular limits, and contains at least selected from molecular structure
Two cyanate ester resins or cyanate prepolymer of cyanic acid ester group, preferably are selected from bisphenol A cyanate ester resin, bisphenol-f type cyanate
Resin, tetramethyl bisphenol F cyanate resin, bis-phenol M types cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol E-type cyanic acid
Ester resin, bis-phenol p-type cyanate ester resin, novolac type cyanate ester resin, cresol novolak type cyanate ester resin, naphthol type cyanic acid
Ester resin, Naphthol phenolic cyanate ester resin, dicyclopentadiene type ethylene rhodanate resin, phenolphthalein type cyanate ester resin, aralkyl-type
Cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, bisphenol A cyanate ester prepolymer, bisphenol-f type cyanate prepolymer, four
Methyl bisphenol F types cyanate prepolymer, bis-phenol M types cyanate prepolymer, bisphenol S type cyanate prepolymer, bisphenol E-type cyanate
Prepolymer, bis-phenol p-type cyanate prepolymer, novolac type cyanate prepolymer, cresol novolak type cyanate prepolymer, naphthols
Type cyanate prepolymer, naphthol novolac type cyanate prepolymer, dicyclopentadiene type ethylene rhodanate prepolymer, phenolphthalein type cyanate are pre-
Any one in polymers, aralkyl-type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer or at least two
The mixture of mixture, the mixture such as bisphenol A cyanate ester resin and bisphenol-f type cyanate ester resin, tetramethyl Bisphenol F
The mixture of type cyanate ester resin and bis-phenol M type cyanate ester resins, bisphenol S type cyanate ester resin and bisphenol E-type cyanate resin
Mixture, the mixture of bis-phenol p-type cyanate ester resin and novolac type cyanate ester resin, cresol novolak type cyanate ester resin
With the mixture of Naphthol phenolic cyanate ester resin, the mixing of dicyclopentadiene type ethylene rhodanate resin and phenolphthalein type cyanate ester resin
Thing, the mixture of aralkyl-type cyanate ester resin, aralkyl Novolac Cyanate Ester Resins and bisphenol A cyanate ester prepolymer is double
The mixture of phenol F types cyanate prepolymer, tetramethyl bisphenol-f type cyanate prepolymer and bis-phenol M type cyanate prepolymers, bis-phenol
The mixture of S types cyanate prepolymer, bisphenol E-type cyanate prepolymer and bis-phenol p-type cyanate prepolymer, novolac type cyanogen
Acid esters prepolymer, cresol novolak type cyanate prepolymer, naphthol novolac type cyanate prepolymer and dicyclopentadiene type ethylene rhodanate
The mixture of prepolymer, phenolphthalein type cyanate prepolymer, aralkyl-type cyanate prepolymer and aralkyl Novolac Cyanate Eater Resin are pre-
The mixture of polymers.
In order to improve heat resistance, the anti-flammability of cyanate resin composition, the further preferably linear phenol of the cyanate ester resin
Aldehyde type cyanate ester resin, naphthol type cyanate ester resin, Naphthol phenolic cyanate ester resin, phenolphthalein type cyanate ester resin, aralkyl
Type cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, novolac type cyanate prepolymer, naphthol type cyanate pre-polymerization
Thing, naphthol novolac type cyanate prepolymer, phenolphthalein type cyanate prepolymer, aralkyl-type cyanate prepolymer or aralkyl phenolic aldehyde
In type cyanate prepolymer any one or at least two mixture, particularly preferred novolac type cyanate ester resin,
Naphthol phenolic cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, novolac type cyanate prepolymer, naphthol novolac type
In cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer any one or at least two mixture.Cyanate
Resin can be used alone, it is also possible to be used in mixed way as needed.
If it is desired, heretofore described halogen-free thermosetting resin composite can also include other phosphonium flame retardants.It is excellent
Selection of land, the phosphonium flame retardant is three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,10- dihydro-9-oxies
Miscellaneous -10- phosphines phenanthrene -10- oxides, 2,6- bis- (2,6- 3,5-dimethylphenyls) phosphino- benzene, 10- phenyl -9,10- dihydro-9-oxies be miscellaneous -
Any one in 10- phosphine phenanthrene -10- oxides, phenoxy phosphazene compound, phosphate, polyphosphate or at least two
Mixture.
Preferably, heretofore described halogen-free thermosetting resin composite can also include filler, be mainly used to adjustment group
Some physical property effects of compound, such as reduce thermal coefficient of expansion (CTE), reduce water absorption rate and improve thermal conductivity, with organic solid
Based on 100 weight portions, the addition of described filler is 0-200 weight portions to thing.
Preferably, described filler is selected from organic filler or inorganic filler, preferably inorganic filler, further preferably by surface
The inorganic filler for the treatment of, most preferably surface treated silica.
Preferably, the surface conditioning agent of the surface treatment is selected from silane coupler, silicone oligomer or titanate esters idol
Connection agent in any one or at least two mixture.
Preferably, counted with inorganic filler quality as 100%, the consumption of the surface conditioning agent is 0.1-5.0%, preferably
0.5-3.0%, further preferred 0.75-2.0%.
Preferably, the inorganic filler is selected from nonmetal oxide, metal nitride, non-metal nitride, inorganic hydration
In thing, inorganic salts, metal hydrate or Phos any one or at least two mixture, preferred molten titanium dioxide
Silicon, powdered quartz, spherical silica, hollow silicon dioxide, aluminium hydroxide, aluminum oxide, talcum powder, aluminium nitride, nitrogen
Change in boron, carborundum, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates, mica or glass fiber powder any one or
The mixture of person at least two.The mixture of the mixture such as fused silica and powdered quartz, ball-type two
The mixture of the mixture of the mixture of silica and hollow silicon dioxide, aluminium hydroxide and aluminum oxide, talcum powder and aluminium nitride,
The mixture of the mixture of boron nitride and carborundum, barium sulfate and barium titanate, the mixture of strontium titanates, calcium carbonate and calcium silicates,
The mixture of mica, glass fiber powder, fused silica and powdered quartz, spherical silica, hollow titanium dioxide
The mixture of silicon, aluminium hydroxide and aluminum oxide, the mixing of talcum powder, aluminium nitride, boron nitride, carborundum, barium sulfate and barium titanate
Thing, the mixture of strontium titanates, calcium carbonate, calcium silicates, mica and glass fiber powder.
Preferably, the organic filler is selected from any one in polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder
Kind or at least two mixture.The mixture of the mixture such as polytetrafluorethylepowder powder and polyphenylene sulfide, polytetrafluoro
The mixture of the mixture of ethylene powder and polyether sulfone powder, polyphenylene sulfide and polyether sulfone powder, polytetrafluorethylepowder powder, polyphenyl
The mixture of thioether and polyether sulfone powder.
Preferably, optimal filler is silica, and angle value is 1-15 μm in the particle diameter of filler, and the middle angle value of preferred filler is
1-10 μm, the filler positioned at this particle diameter section has good dispersiveness.
Preferably, by organic solid content based on 100 weight portions, the addition of filler of the present invention is preferably 0-100 weights
Amount part, such as 1 weight portion, 5 weight portions, 10 weight portions, 15 weight portions, 20 weight portions, 25 weight portions, 30 weight portions, 35 weight
Part, 40 weight portions, 45 weight portions, 50 weight portions, 55 weight portions, 60 weight portions, 65 weight portions, 70 weight portions, 75 weight portions, 80
Specific point value between weight portion, 85 weight portions, 90 weight portions, 95 weight portions or 100 weight portions, and above-mentioned numerical value, is limited to
Length and the consideration for simplicity, the present invention specific point value that no longer scope described in exclusive list includes.
If it is desired, heretofore described halogen-free thermosetting resin composite can also include curing accelerator, make resin
Solidify and accelerate resin solidification speed.The curing accelerator is not particularly limited, as long as cyanate, cyanate and ring can be catalyzed
The curing reaction of oxygen tree fat, can be selected from organometalate compound, such as copper, zinc, cobalt, nickel, iron, imidazolium compounds and its
In derivative, piperidines or tertiary amine any one or at least two mixture.Exemplary solidification promotes
Agent is selected from 2-methylimidazole, 2- phenylimidazoles, 2-ethyl-4-methylimidazole, tri-n-butylamine, triphenyl phosphorus, boron trifluoride complexing
It is any in thing, sad slaine, acetyl acetone salt, metal naphthenate, salicylic acid metal salt or Metallic stearates
It is a kind of or at least two mixture, the mixture of the mixture such as Metallic stearates and salicylic acid metal salt, ring
The mixture of the mixture of alkanoic acid slaine and acetyl acetone salt, sad slaine and boron trifluoride complex, triphenyl
The mixture of the mixture of phosphorus and tri-n-butylamine, 2-ethyl-4-methylimidazole and 2- phenylimidazoles, sad slaine and three positive fourths
The mixture of amine, the mixture of 2-ethyl-4-methylimidazole, tri-n-butylamine and 2- phenylimidazoles, wherein, the metal is selected from
In zinc, copper, iron, tin, cobalt or aluminium any one or at least two mixture.
It is 100 weight portion meters, the addition of the curing accelerator with the gross weight of component (A), component (B) and component (C)
It is 0.01-1 weight portions, such as 0.02 weight portion, 0.2 weight portion, 0.3 weight portion, 0.5 weight portion, 0.7 weight portion, 0.9 weight
Part, the specific point value between 0.95 weight portion, and above-mentioned numerical value, as space is limited and for concise consideration, the present invention is no longer
The specific point value that scope described in exclusive list includes, preferably 0.05-0.85 weight portions, further preferred 0.1-0.8 weight portions.
" organic solid content is based on 100 weight portions " of the present invention refer to halogen-free thermosetting resin composite of the present invention
The solid content of middle organic component adds up to 100 weight portions.The parts by weight of organic solid content are resin, curing agent and fire-retardant
The solid content parts by weight sum of agent, described filler and curing accelerator are not counted in organic solid content, in the present invention, described nothing
Halogen epoxy resin, polyphosphonates, cyanate, the solid content of fire retardant are counted in organic solid content of the present invention.
"comprising" of the present invention, it is intended that it can also include other components, these other components in addition to the component
Assign the halogen-free thermosetting resin composite different characteristics.In addition, "comprising" of the present invention, can also replace
For enclosed " being " or " by ... constitute ".
For example, the halogen-free thermosetting resin composite can also contain various additives, as concrete example, can enumerate
Antioxidant, heat stabilizer, antistatic additive, ultra-violet absorber, pigment, colouring agent or lubricant etc..These various additives can
To be used alone, it is also possible to which two kinds two or more are used in mixed way.
The customary preparation methods of the glue of halogen-free thermosetting resin composite of the present invention are：First solid content is put into, then
After adding liquid solvent, stirring to be completely dissolved to solid content, liquid resin and curing accelerator are added, continue to stir i.e.
Can, finally adjust solution solids content with solvent and glue is made to 65%-75%.
A kind of prepreg, including reinforcing material and by be impregnated with dry after adhere to halogen-free thermosetting as described above thereon
Resin combination.
Prepreg of the invention is used obtained in above-mentioned halogen-free thermosetting resin composite heat drying, is used
Base-material is adhesive-bonded fabric or other fabrics, such as natural fiber, organic synthetic fibers and inorfil.
The reinforcing materials such as glass cloth are impregnated with using above-mentioned glue, the reinforcing material that will be impregnated with adds in 155 DEG C of baking oven
It is made prepreg within heated drying 5-10 minutes.
A kind of laminate, it includes at least 1 prepreg as described above.
A kind of metal-clad laminate, it includes at least 1 prepreg as described above for overlapping and covers in overlapping
The metal foil of prepreg one or both sides, may be heated press molding and is obtained.That is, metal-clad laminate bag of the invention
Include by heating and the laminate for making the prepreg of or more than be bonded together and be made that pressurizes, and be bonded in layer
Metal foils more than pressing plate one or both sides.
Exemplary metal-clad laminate is the gold for using above-mentioned prepreg 1 and 2 0.5 ounce (18 μ m thick)
Category paper tinsel is superimposed together, and is laminated by hot press, so as to be pressed into the laminate of two-sided clad with metal foil.Described lamination must meet
It is claimed below：1. the heating rate that is laminated should be generally controlled in 1.5-2.5 DEG C/min in 80-120 DEG C of material temperature；2. the pressure being laminated
Power is set, and outer layer material temperature applies full pressure at 120-150 DEG C, and full pressure pressure is 350psi or so；When 3. solidifying, control material temperature exists
200 DEG C, and it is incubated 90min-120min.Described metal foil is Copper Foil, nickel foil, aluminium foil and SUS paper tinsels etc., and its material is not limited.
A kind of printed circuit board, it includes at least 1 prepreg as described above.
Compared with the prior art, the present invention has the advantages that：
It is matrix resin that the present invention uses the halogen-free epoxy resin of ad hoc structure, and the halogen-free epoxy resin structural symmetry is high
And Han oxazolidine ketone ring structures, coordinating polyphosphonates and cyanate co-curing, said composition has played individual group to greatest extent
The advantage divided, balances the advantage and shortcoming of each component, as the epoxy and polyphosphonates by Han oxazolidine ketone ring structures have
The excellent caking property and processability having can make up the weakness such as the cyanate big poor in processability of system fragility；Polyphosphonates and asphalt mixtures modified by epoxy resin
Fat reaction does not generate secondary hydroxyl so as to dielectric properties are excellent, and because polyphosphonates and halogen-free epoxy resin do not contain in itself with
And reaction does not generate polar group, it is to avoid because polar group catalysis polyisocyanate reactant causes the problems such as chemically reacting uncontrollable；
Cyanate can improve glass transition temperature and further reduce solidfied material dielectric constant and dielectric loss again simultaneously；Additionally,
The epoxy resin and cyanate of the Han oxazolidine ketone ring structures contain N element, have cooperative flame retardant to imitate with the P element of polyphosphonates
Really, solidfied material anti-flammability can be reduced to reach phosphorus content needed for UL94 V-0 and reduce water absorption rate, laminate work in-process is reduced
The probability of moisture absorption plate bursting.
To sum up, the prepreg and laminate being made using the halogen-free thermosetting resin composite have high glass transition temperature
Degree, can reach 205 DEG C, excellent dielectric properties, and, in 3.75-4.08, dielectric loss value can as little as 0.0070, tool for its dielectric constant
There are high-peeling strength, high-fire resistance, low water absorption, its water absorption rate can as little as 0.05%, and good process processability, and can be real
Existing halogen-free flameproof, reaches UL94 V-0.
Specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in understanding the present invention, is not construed as to concrete restriction of the invention.
Its glass transition temperature, dielectric constant, Jie are tested for the laminate for printed circuits (4 prepregs) being made
The performances such as electrical loss factor, peel strength, heat resistance, water imbibition, anti-flammability, following examples are further described and retouched
State.
The preparation method of the copper-clad plate employed in the present invention is：
By halogen-free epoxy resin, polyphosphonates, cyanate, phosphonium flame retardant and curing accelerator, filler by certain ratio
Example is well mixed in solvent, and it is 65% to control glue solid content, and above-mentioned glue is impregnated with 2116 glass-fiber-fabrics, and control is suitable thick
Degree, then toasts 2-15min in 115-175 DEG C of baking oven and is made prepreg, then stacks several prepregs, at it
The stacked on 18 μ RTF Copper Foils in both sides, are 170-250 DEG C in solidification temperature, and solidifying pressure is 25-60kg/cm2, hardening time is 60-
Copper-clad plate is made under the conditions of 300min.
It is hereby that embodiment of the present invention detailed description is as follows, but the present invention is not limited to scope of embodiments.Hereinafter without spy
Bright, its part representative " weight portion ", its % representatives " weight % " are not mentionleted alone.
The material and trade mark information that embodiment and comparative example are related to are as follows：
(A) halogen-free epoxy resin
(A-1) halogen-free epoxy resin with formula (I)
(A-1 ＇) has the halogen-free epoxy resin of formula (II)
(A-2) dicyclopentadiene type epoxy resin HP-7200H (big Japanese ink trade name)
(A-3) HP-9500 of epoxy containing naphthalene nucleus (big Japanese ink trade name)
(B) curing agent
(B-1) polyphosphonates OL3001 (U.S. FRX trade names)
(B-2) styrene maleic anhydride copolymer EF40 (Sartomer trade name)
(B-3) active ester HPC-8000-65T (big Japanese ink trade name)
(C) cyanate：CE01PS (Yangzhou apocalypse trade name)
(D) fire retardant：Phosphorus-containing phenolic aldehyde XZ-92741 (U.S. DOW trade names)
(E) accelerator：Zinc Isoocatanoate BICAT Z (leading chemistry)
(F) filler
(F-1) ball-type melting silicon powder (average grain diameter is 1 to 10 μm, purity more than 99%)
(F-2) polytetrafluorethylepowder powder (average grain diameter is 1 to 10 μm, purity more than 99%)
Formula composition and its physical data as in following table being respectively embodiment and comparative example.
Table 1
Table 2
Table 3
The method of testing of above characteristic is as follows：
(a) glass transition temperature (Tg)：According to differential scanning calorimetry (DSC), according to IPC-TM-6502.4.25 institutes
The DSC method of regulation is measured.
(b) dielectric constant, dielectric loss factors：The dielectric determined according to IPC-TM-650 2.5.5.13 under 10GHz is damaged
Consumption, dielectric loss factors.
(c) peel strength：According to the experiment condition of " after thermal stress " in IPC-TM-650 2.4.8 methods, metal is tested
The peel strength of cap rock.
(d) water imbibition：It is measured according to IPC-TM-650 2.6.2.1 methods.
E () is resistance to dip solderability：According to IPC-TM-650 2.4.13.1 observation layering cream times.
(f) difficult to burn：Determined according to the vertical combustions of UL 94.
Knowable to the physical data of table 1~3, compared with Example 3, dicyclopentadiene type epoxy tree is used in comparative example 1
When fat solidifies with polyphosphonates, cyanate, obtained sheet material Tg is high and dielectric properties are excellent, but peel strength is relatively low and fire-retardant
Can only achieve V-1 grades；When being solidified with polyphosphonates, cyanate using naphthalene-ring containing epoxy resin in comparative example 2, made covers
Copper coin Tg and peel strength is high and heat resistance and anti-flammability preferably, but dielectric constant and dielectric loss are also higher；Make in comparative example 3
When individually being solidified with the epoxy with formula (I) structure and polyphosphonates, obtained sheet material Tg is relatively low, and dielectric properties are general, and
Heat resistance is poor；When individually being solidified using the epoxy with formula (I) structure and cyanate in comparative example 4, obtained sheet material Tg
Height, but dielectric loss is general, and poor flame retardant properties, can only achieve V-2 grades；The epoxy with formula (I) structure is used in comparative example 5
When solidifying with styrene maleic anhydride copolymer, cyanate, obtained sheet material Tg and peel strength are very low, and fire resistance is not
Foot, can only achieve V-2 grades；It is obtained when being solidified with active ester, cyanate using the epoxy with formula (I) structure in comparative example 6
Sheet material Tg and peel strength is high, dielectric properties are excellent, but poor flame retardant properties, V-2 grades is can only achieve, if adding in addition fire-retardant
Agent, may result in the deterioration of other performances.
To sum up, the prepreg and laminate being made using halogen-free thermosetting resin composite of the invention have high-vitrification
Transition temperature, can reach 205 DEG C, excellent dielectric properties, and, in 3.75-4.08, dielectric loss value can be as little as its dielectric constant
0.0070, with high-peeling strength, high-fire resistance, low water absorption, water absorption rate can as little as 0.05%, and good process processing
Property, and halogen-free flameproof can be realized, UL94 V-0 are reached, with excellent combination property.
The above, only presently preferred embodiments of the present invention, for the person of ordinary skill of the art, can basis
Technical scheme and technology design make other various corresponding changes and deformation, and all these changes and deformation are all
The scope of the claims in the present invention should be belonged to.
Claims (10)
1. a kind of halogen-free thermosetting resin composite, it is characterised in that containing following three kinds of materials as necessary component, with organic
Solid content based on 100 weight portions, wherein：
(A) halogen-free epoxy resin：35-65 weight portions；
(B) polyphosphonates：10-35 weight portions；
(C) cyanate：10-30 weight portions；
The halogen-free epoxy resin has the structure represented by following formula (I)：
In formula (I), X represents the aralkyl selected from the alkyl, the aryl of carbon number 6-10 and carbon number 6-10 of carbon number 1-4 with least one
The cycloalkylidene of the ring element number 5-8 of the substitution base of base；R separately represents hydrogen atom, the alkyl of carbon number 1-8, carbon number 1-8
Alkoxy, the cycloalkyl of carbon number 5-8, the aryl of carbon number 6-10, the aralkyl of carbon number 6-10, the aryloxy group or carbon number of carbon number 6-10
The aralkoxy of 6-10；Y is represented from polyisocyanate compounds and is removed two residues of NCO.
2. halogen-free thermosetting resin composite as claimed in claim 1, it is characterised in that under the halogen-free epoxy resin has
State the structure represented by formula (II)：
In formula (II), Z represents divalent base, and the 5mol%-100mol% in Z is the divalent base represented by following formula (a)；Y is represented certainly
Diisocyanate cpd removes the residue of NCO；G represents glycidyl；N represents repeat number, and average value is 1-5；
In formula (a), X represents the aralkyl selected from the alkyl, the aryl of carbon number 6-10 and carbon number 6-10 of carbon number 1-4 with least one
The cycloalkylidene of the ring element number 5-8 of the substitution base of base；R separately represents hydrogen atom, the alkyl of carbon number 1-8, carbon number 1-8
Alkoxy, the cycloalkyl of carbon number 5-8, the aryl of carbon number 6-10, the aralkyl of carbon number 6-10, the aryloxy group or carbon number of carbon number 6-10
The aralkoxy of 6-10；
Preferably, the weight average molecular weight of the epoxy resin is 1000-8000, and epoxide equivalent is 200g/eq.-550g/eq..
3. halogen-free thermosetting resin composite as claimed in claim 1 or 2, it is characterised in that the polyphosphonates structural formula
It is as follows：
Wherein, Ar is aryl, described-O-Ar-O-be selected from resorcinol active group, hydroquinones active group, bisphenol-A
Active group, Bisphenol F active group, 4,4 ＇-biphenol, phenolphthalein active group, 4,4 ＇-thio diphenol active group, 4,4 ＇-sulphur
Any one in acyl diphenol active group or 3,3,5- trimethylcyclohexyl biphenols；Q is the substitution or unsubstituted of C1-C20
Straight chained alkyl, the substituted or unsubstituted branched alkyl of C1-C20, the substituted or unsubstituted linear alkene base of C2-C20,
The substituted or unsubstituted branched-chain alkene base of C2-C20, the substituted or unsubstituted straight-chain alkyl-sub of C2-C20, C2-C20 take
Generation or unsubstituted branched alkylidene, the substituted or unsubstituted cycloalkyl of C5-C20 or the substituted or unsubstituted virtues of C6-C20
Base；M is the arbitrary integer of 1-75；
Preferably, the weight average molecular weight of the polyphosphonates be 1000-50000, preferably 1000-10000, further preferably
1000-4500；
Preferably, the polyphosphonates structural formula is as follows：
Wherein q is the arbitrary integer of 2-20, and preferably q is the arbitrary integer of 3-10.
4. the halogen-free thermosetting resin composite as described in one of claim 1-3, it is characterised in that the cyanate is bis-phenol
It is A types cyanate ester resin, bisphenol-f type cyanate ester resin, tetramethyl bisphenol F cyanate resin, bis-phenol M types cyanate ester resin, double
Phenol S types cyanate ester resin, bisphenol E-type cyanate resin, bis-phenol p-type cyanate ester resin, novolac type cyanate ester resin, cresols
Novolac Cyanate Ester Resins, naphthol type cyanate ester resin, Naphthol phenolic cyanate ester resin, dicyclopentadiene type ethylene rhodanate tree
Fat, phenolphthalein type cyanate ester resin, aralkyl-type cyanate ester resin, aralkyl Novolac Cyanate Ester Resins, bisphenol A cyanate ester are pre-
Polymers, bisphenol-f type cyanate prepolymer, tetramethyl bisphenol-f type cyanate prepolymer, bis-phenol M types cyanate prepolymer, bisphenol S
Type cyanate prepolymer, bisphenol E-type cyanate prepolymer, bis-phenol p-type cyanate prepolymer, novolac type cyanate pre-polymerization
Thing, cresol novolak type cyanate prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate prepolymer, bicyclic penta 2
Ene-type cyanate prepolymer, phenolphthalein type cyanate prepolymer, aralkyl-type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin
In prepolymer any one or at least two mixture, preferably novolac type cyanate ester resin, naphthol type cyanate
Resin, Naphthol phenolic cyanate ester resin, phenolphthalein type cyanate ester resin, aralkyl-type cyanate ester resin, aralkyl phenol aldehyde type cyanogen
Acid ester resin, novolac type cyanate prepolymer, naphthol type cyanate prepolymer, naphthol novolac type cyanate prepolymer, phenol
In phthalein type cyanate prepolymer, aralkyl-type cyanate prepolymer or aralkyl Novolac Cyanate Eater Resin prepolymer any one or
The mixture of person at least two, further preferred novolac type cyanate ester resin, Naphthol phenolic cyanate ester resin, aralkyl
Novolac Cyanate Ester Resins, novolac type cyanate prepolymer, naphthol novolac type cyanate prepolymer or aralkyl phenol aldehyde type
In cyanate prepolymer any one or at least two mixture.
5. the halogen-free thermosetting resin composite as described in one of claim 1-4, it is characterised in that the halogen-free thermosetting tree
Oil/fat composition also includes other phosphonium flame retardants；
Preferably, the phosphonium flame retardant is three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy phenyl) -9,10- bis-
Hydrogen -9- oxa- -10- phosphine phenanthrene -10- oxides, 2,6- bis- (2,6- 3,5-dimethylphenyls) phosphino- benzene, 10- phenyl -9,10- dihydros -9-
In oxa- -10- phosphine phenanthrene -10- oxides, phenoxy phosphazene compound, phosphate or polyphosphate any one or at least
Two kinds of mixture.
6. the halogen-free thermosetting resin composite as described in one of claim 1-5, it is characterised in that the halogen-free thermosetting tree
Oil/fat composition also includes filler；
Preferably, by organic solid content based on 100 weight portions, the addition of described filler is 0-200 weight portions；
Preferably, described filler is selected from organic filler or inorganic filler, preferably inorganic filler, further preferably by surface treatment
Inorganic filler, most preferably surface treated silica；
Preferably, the surface conditioning agent of the surface treatment is in silane coupler, silicone oligomer or titanate coupling agent
Any one or at least two mixture；
Preferably, counted with inorganic filler quality as 100%, the consumption of the surface conditioning agent is 0.1-5.0%, preferably 0.5-
3.0%, further preferred 0.75-2.0%；
Preferably, the inorganic filler is nonmetal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic
In salt, metal hydrate or Phos any one or at least two mixture, preferred molten silica, crystal type
Silica, spherical silica, hollow silicon dioxide, aluminium hydroxide, aluminum oxide, talcum powder, aluminium nitride, boron nitride, carbonization
Any one in silicon, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates, mica or glass fiber powder or at least two
The mixture planted；
Preferably, the organic filler be polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder in any one or
At least two mixture；
Preferably, angle value is 1-15 μm, preferably 1-10 μm in the particle diameter of described filler.
7. the halogen-free thermosetting resin composite as described in one of claim 1-6, it is characterised in that the halogen-free thermosetting tree
Oil/fat composition also includes curing accelerator；
Preferably, the curing accelerator is organometalate compound, imidazolium compounds and its derivative, piperidines
Or in tertiary amine any one or at least two mixture；
Preferably, the curing accelerator be 2-methylimidazole, 2- phenylimidazoles, 2-ethyl-4-methylimidazole, tri-n-butylamine,
Triphenyl phosphorus, boron trifluoride complex, sad slaine, acetyl acetone salt, metal naphthenate, salicylic acid metal salt or
In Metallic stearates any one or at least two mixture, wherein, the metal be zinc, copper, iron, tin, cobalt or
In aluminium any one or at least two mixture；
Preferably, it is 100 weight portion meters, the addition of the curing accelerator with the total amount of component (A), component (B) and component (C)
It is 0.01-1 weight portions to measure, preferably 0.05-0.85 weight portions, further preferred 0.1-0.8 weight portions.
8. a kind of prepreg, including reinforcing material and by be impregnated with dry after adhere to thereon as described in one of claim 1-7
Halogen-free thermosetting resin composite.
9. a kind of laminate, it includes at least 1 prepreg as claimed in claim 8.
10. a kind of printed circuit board, it includes at least 1 prepreg as claimed in claim 8.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611236980.0A CN106751524A (en) | 2016-12-28 | 2016-12-28 | A kind of halogen-free thermosetting resin composite and the prepreg containing it, laminate and printed circuit board |
| PCT/CN2017/084315 WO2018120587A1 (en) | 2016-12-28 | 2017-05-15 | Halogen-free thermosetting resin composition and prepreg, laminate and printed circuit board containing same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611236980.0A CN106751524A (en) | 2016-12-28 | 2016-12-28 | A kind of halogen-free thermosetting resin composite and the prepreg containing it, laminate and printed circuit board |
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| CN106751524A true CN106751524A (en) | 2017-05-31 |
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| CN201611236980.0A Pending CN106751524A (en) | 2016-12-28 | 2016-12-28 | A kind of halogen-free thermosetting resin composite and the prepreg containing it, laminate and printed circuit board |
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| CN (1) | CN106751524A (en) |
| WO (1) | WO2018120587A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107298857A (en) * | 2017-07-20 | 2017-10-27 | 苏州益可泰电子材料有限公司 | A kind of halogen-free flame-resistant electronic material and preparation method thereof |
| CN107353640A (en) * | 2017-07-20 | 2017-11-17 | 苏州益可泰电子材料有限公司 | A kind of Halogen high dielectric property electronic material and preparation method thereof |
| WO2019062359A1 (en) * | 2017-09-29 | 2019-04-04 | 联茂电子股份有限公司 | Polymer matrix composite as well as prepreg and printed circuit board using same |
| GB2568995A (en) * | 2017-09-29 | 2019-06-05 | Iteq Corp | Polymer matrix composite as well as prepreg and printed circuit board using same. |
| CN114106517A (en) * | 2021-10-25 | 2022-03-01 | 航天特种材料及工艺技术研究所 | High-strength high-toughness flame-retardant epoxy resin and preparation method thereof |
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| GB2568995A (en) * | 2017-09-29 | 2019-06-05 | Iteq Corp | Polymer matrix composite as well as prepreg and printed circuit board using same. |
| GB2568995B (en) * | 2017-09-29 | 2022-07-13 | Iteq Corp | Polymer matrix composite, prepreg and printed circuit board thereof |
| CN114106517A (en) * | 2021-10-25 | 2022-03-01 | 航天特种材料及工艺技术研究所 | High-strength high-toughness flame-retardant epoxy resin and preparation method thereof |
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| WO2018120587A1 (en) | 2018-07-05 |
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