CN106939019A - A kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board - Google Patents

A kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board Download PDF

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CN106939019A
CN106939019A CN201610008251.3A CN201610008251A CN106939019A CN 106939019 A CN106939019 A CN 106939019A CN 201610008251 A CN201610008251 A CN 201610008251A CN 106939019 A CN106939019 A CN 106939019A
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unsubstituted
substituted
alkyl
group
combination
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潘庆崇
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Guangdong Guang Shan New Materials Ltd By Share Ltd
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Guangdong Guang Shan New Materials Ltd By Share Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
    • C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
    • C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • 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
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • 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
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/041—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/02—Coating on the layer surface on fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • 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

Abstract

The present invention relates to a kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board.The phosphazene compound with carboxylate has the molecular structure shown in formula (I).The present invention obtains the phosphazene compound with carboxylate by using the M groups of specific composition, and its solidfied material has low-dielectric, good heat resistance and mechanical performance, is a kind of dielectric materials with larger economy and environmentally friendly friendly.

Description

A kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board
Technical field
The invention belongs to dielectric materials technical field, more particularly to a kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board.
Background technology
The various products used using mobile phone, computer, video camera, electronic game machine as the electronic product of representative, with family expenses that air-conditioning, refrigerator, television image, sound equipment articles for use etc. are representative, office electric equipment products and other field, for safety, significant portion of product requires that it possesses low-dielectric and heat resistance.
For electrical properties, the factor that need to mainly consider also includes the dielectric constant and dielectric loss of material.Generally, due to which the signal transfer rate of substrate and the square root of dielectric constant of baseplate material are inversely proportional, therefore the dielectric constant of baseplate material is generally the smaller the better；On the other hand, the loss that signal transmission is represented because dielectric loss is smaller is fewer, therefore the transmission quality that the less material of dielectric loss can be provided is also more good.
Therefore, the material with low-k and low-dielectric loss how is developed, and is applied to the manufacture of high frequency printed circuit board, is printed circuit board material field urgent problem to be solved at this stage.
The content of the invention
In view of this, one aspect of the present invention provides a kind of phosphazene compound, pre-impregnated sheet and composite metal substrate, and the phosphazene compound has low-dielectric, good heat resistance and mechanical performance, moreover, the phosphazene compound has the advantage of low cost.
To achieve these goals, present invention employs following technical scheme：
A kind of phosphazene compound, it has the molecular structure as shown in formula (I)：
In formula (I), R1Represent arbitrary organic group, R2For aliphatic group, R is the inertia nucleophilic group that is provided by nucleopilic reagent；M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2Or non-annularity polyphosphazene base M3In any one or its at least two combination；
A is the integer more than zero, such as 1,2,3,4,5,6,7, b is the integer more than or equal to zero, such as 0,1,2,3,4,5,6,7, c is the integer more than zero, such as 1,2,3,4,5,6,7, and 2 times of total number equal to number of phosphorus atoms on M groups for the substituent being connected with M groups.
In the present invention, R1Arbitrary organic group is represented, condition is that atom is no more than normal valency, and can produce stable compound." stable compound " is to refer to sufficiently strong separate from reactant mixture to effective purity strongly and be configured to compounds effective.
In the present invention, " the inertia nucleophilic group " refers to, a kind of functional group, it is without active group, it is not allowed to change places or reacted with the speed of a reality under conditions of conventional organic synthesis, and it is nucleopilic reagent and the remaining functional group reacted without common sense after chloro phosphazene compound nucleophilic substitution.
Preferably, in formula (I), R1For aliphatic group and/or aryl, further preferably any one in substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl or its at least two combination.
Preferably, R1For any one in unsubstituted straight chained alkyl or branched alkyl, unsubstituted cycloalkyl, unsubstituted aralkyl, unsubstituted alkylaryl, unsubstituted aryl or unsubstituted heteroaryl or at least two combination.
Preferably, R1Without reactive group that can be with epoxy resin reaction generation secondary hydroxyl groups.
Preferably, R2For any one in substituted or unsubstituted aralkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl or its at least two combination.
Nucleopilic reagent containing hydroxyl such as alcohols or aldehydes matter, such as methanol, ethanol, propyl alcohol, phenol or hydroquinones, now R is CH3O-、CH3CH2-O-、CH3CH2CH-O-, phenoxy group or para hydroxybenzene epoxide.
In the present invention, it is preferred to, the inertia nucleophilic group is that R is selected from-OR13、-C≡C-R18、R22-COO-、In any one or at least two combination；
R13For any one in substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted carbonate group, substituted or unsubstituted sulfonate group, substituted or unsubstituted phosphonate group, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl or at least two combination, R15、R16And R17It independently is any one in substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, R18For any one in substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl or at least two combination, R22For any one in substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl or at least two combination, R23And R24Independently be in substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl any one or at least two combination, R26And R27Independently be in substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl any one or at least two combination.
In foregoing description, substituted or unsubstituted straight chained alkyl or branched alkyl are preferably substituted or unsubstituted C1~C12 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11) straight chained alkyls or branched alkyl, it is preferred that C1~C8 straight chained alkyls or branched alkyl, it is methyl when carbon number is C1, when carbon number is C2, as ethyl.
The substituted or unsubstituted cycloalkyl is preferably the substituted or unsubstituted cycloalkyl that carbon number is C3~C12 (such as C4, C5, C6, C7, C8, C9, C10 or C11).
Substituted or unsubstituted aryl is preferably phenyl, benzyl, 1,2,3,4- tetralyls,Deng.The example of phenyl includes xenyl, terphenyl, benzyl, phenethyl or phenylpropyl etc..
Substituted or unsubstituted heteroaryl is five yuan or six membered heteroaryl.
Substituted or unsubstituted alkoxy is C1-C12 (such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 or C11) alkoxy.
Substituted or unsubstituted aralkyl is C7-C12 (such as C8, C9, C10 or C11) aralkyl.
Substituted or unsubstituted cycloalkyloxy is C3-C8 (such as C4, C5, C6, C7 or C8) cycloalkyloxy.
Substituted or unsubstituted aralkoxy is C7-C12 (such as C8, C9, C10 or C11) aralkoxy.
Substituted or unsubstituted alkyl-aryloxy is C7-C12 (such as C8, C9, C10 or C11) alkyl-aryloxy.
Preferably, the R is substituted or unsubstituted alkoxy or aryloxy.
The example of alkoxy includes, but are not limited to methoxyl group, ethyoxyl, isopropoxy, propoxyl group, butoxy and amoxy.Alkoxy grp can be replaced by substituents, such as alkenyl, alkynyl, halogen, hydroxyl, alkyl carbonyl oxy, aryl-carbonyl oxygen, alkoxy carbonyloxy group, aryloxy group carbonyloxy group, carboxylate, alkyl-carbonyl, aryl carbonyl, alkoxy carbonyl, amino carbonyl, alkyl amino-carbonyl, dialkyl amino carbonyl, alkylthiocarbonyl, alkoxy, phosphate, phosphonate radical is closed, phosphinic acids root is closed, amino (including alkyl amino, dialkyl amido, arylamino, ammonia diaryl base and alkyl aryl amino), acylamino- (including alkyl-carbonyl-amino, aryl-amino-carbonyl, carbamoyl and urea groups), amidino groups, imino group, sulfydryl, carbothioic acid ester, sulfuric ester, alkyl sulphinyl, sulfonic group, sulfamoyl, sulfonamido, nitromethyla, trifluoromethyl, cyano group, azido, heterocyclic radical, alkylaryl or aromatics or heteroaromatic group.The example of the alkoxy grp of halogen substitution includes, but are not limited to a fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy, a chloromethane epoxide, dichloro methoxyl group, trichloromethoxy.
The example of the aryloxy includes phenoxy group, benzyloxy, naphthoxy or biphenylyloxy, and the aryloxy can be replaced by alkyl etc..
Preferably, the phosphazene compound is any one in the phosphazene compound with following structure or at least two mixture：
A is that 4, b is that 0, c is 2, R1For ethyl, R2For ethyl, R is methoxyl group；
A is that 4, b is that 1, c is 1, R1For ethyl, R2For ethyl, R is methoxyl group；
Or
A is that 4, b is that 0, c is 2, R1For ethyl, R2For ethyl, R is phenoxy group.
Term " substituted " used in the present invention refers to that any one or more hydrogen atoms on specified atom are selected from the substituent substitution of designated groups, and condition is that the specified atom is no more than normal valency, and the result replaced is to produce stable compound.When substituent is oxo group or ketone group (i.e.=O), then 2 hydrogen atoms on atom are substituted.Ketone substituent is not present on aromatic rings." stable compound " is to refer to sufficiently strong separate from reactant mixture to effective purity strongly and be configured to compounds effective.
In the present invention, it is preferred to, M1Structure is：
M2Structure is：
Wherein, x is more than or equal to 4；
M3Structure is：
Wherein, y is more than or equal to 3.
Note, M1、M2In the expression of structural formula, there is symbolOnly one kind to " ring-type " structure is illustrated.M1、M2And M3InThe key connected on middle P atoms, which only represents substituent substitution in three, to be occurred on P atoms, is not to be construed as the expression of methyl.
Preferably, M represents the group for the phosphorus nitrogen skeleton being mainly made up of unsaturated phosphorus and nitrogen-atoms, i.e. phosphazenium groups, is specially：M includes at least 50wt% phosphonitrile base M of ring three1, at most 48wt% the phosphonitrile base M of ring more than four2And at most 48wt% non-annularity polyphosphazene base M3。
In the present invention, M1Content is at least 50wt%, i.e. M1Content can be 50wt~100wt%, M1For bulk composition.Work as M1When content is 100wt%, then M is not contained2And M3.The typical but non-limiting M of the present invention1Content can be 50wt%, 51wt%, 55wt%, 58wt%, 60wt%, 65wt%, 70wt%, 74wt%, 75wt%, 80wt%, 85wt%, 90wt%, 92wt%, 95wt%, 98wt% or 100wt%.
In the present invention, M2Content is at most 48wt%, that is, is referred to, M2Content can be 0~48wt%.Work as M2When content is 0wt%, that is, refers to, do not contain M2.The typical but non-limiting M of the present invention2Content can be 0wt%, 2wt%, 5wt%, 8wt%, 11wt%, 14wt%, 17wt%, 20wt%, 23wt%, 26wt%, 29wt%, 32wt%, 35wt%, 38wt%, 42wt%, 45wt% or 48wt%.
In the present invention, M3Content is at most 48wt%, that is, is referred to, M3Content can be 0~48wt%.Work as M3When content is 0wt%, that is, refers to, do not contain M3.The typical but non-limiting M of the present invention3Content can be 0wt%, 2wt%, 5wt%, 8wt%, 11wt%, 14wt%, 17wt%, 20wt%, 23wt%, 26wt%, 29wt%, 32wt%, 35wt%, 38wt%, 42wt%, 45wt% or 48wt%.
In the present invention, if M1Content is less than 50wt%, or M2More than 48wt%, then heat resistance, water resistance and mechanical performance can be damaged in use with the reacted product of epoxy resin.If M3Content is more than 48%, then would be possible in use with the reacted product of epoxy resin because viscosity is excessive cause it is inconvenient for use, and because of molecular weight the is excessive bad result such as make its performance suffer damage.
Another aspect of the present invention provides a kind of preparation method of the phosphazene compound with carboxylate, and the phosphazene compound prepared by this method has good heat resistance, good mechanical performance, and dielectric constant is low.
It is a kind of to prepare the above-mentioned method for stating phosphazene compound, obtained by phosphonitrile chloride and nucleopilic reagent progress nucleophilic substitution.
Nucleophilic displacement of fluorine can be prepared using method well known in the art, for example refer to " progress of polyphosphazene, Zhang Hongwei etc., material Leader 2010 year the 7th phase of volume 24 ".The instantiation of catalyst has the lewis bases such as the metal chlorides such as zinc chloride, magnesium chloride, aluminium chloride, boron trifluoride and its complex compound, NaOH.These catalyst can one or more be used in mixed way, the present invention in have no special regulation.Phosphonitrile chloride can be using most commonly used hexachlorocyclotriph,sphazene etc. of originating.To obtain the R bases in target product, can add simultaneously can provide the nucleopilic reagent of R bases, and such as R is alkoxy or phenoxy group.
In the reaction of nucleopilic reagent and phosphonitrile chloride, first it can be reacted using a kind of nucleopilic reagent with phosphonitrile chloride, chlorine in part substitution phosphonitrile chloride, is then reacted with another nucleopilic reagent and phosphonitrile chloride, to obtain the phosphazene compound of formula (I) structure again.And can be by controlling the material magnitude relation between material, to obtain the phosphazene compound containing a M group or containing multiple M groups in structure.
Further aspect of the present invention provides a kind of with good heat resistance, good mechanical performance, the composition epoxy resin of low-k.
The above-mentioned phosphazene compound with carboxylate is added in the composition epoxy resin, curing agent is used as.
Known epoxy resin can be used as the epoxy resin of composition epoxy resin, curing agent, other fillers.
The composition epoxy resin can also include other polyester in addition to the foregoing polyester containing phosphonitrile.
A kind of pre-impregnated sheet, it is impregnated with by the phosphazene compound with carboxylate described above or is coated on base material and formed.
Base material can be fiberglass substrate, polyester base material, polyimide base material, ceramic base material or carbon fiber base material etc..
Here, the concrete technology condition of its impregnation or coating is not particularly limited." bonding sheet " that " pre-impregnated sheet " is also well known to those skilled in the art.
The invention provides a kind of flexible copper-clad plate, Copper Foil of the flexible copper-clad plate comprising more than one pre-impregnated sheet of the present invention and the pre-impregnated sheet one or both sides being overlying on after overlapping.
A kind of composite metal substrate, it include more than one as above-mentioned pre-impregnated sheet carry out successively surface metal-clad it is overlapping, pressing form.
Here, the material of surface metal-clad is the alloy of aluminium, copper, iron and its any combination.
The instantiation of composite metal substrate has CEM-1 copper-clad plates, CEM-3 copper-clad plates, FR-4 copper-clad plates, FR-5 copper-clad plates, CEM-1 aluminium bases, CEM-3 aluminium bases, FR-4 aluminium bases or FR-5 aluminium bases.
A kind of wiring board, is formed in the Surface Machining circuit of above-mentioned composite metal substrate.
The raw material of composition epoxy resin forms the coating with good dielectric properties by being solidificated on composite metal substrate, wiring board can be improved, the extensive use of the industries such as machine, equipment, instrument, the instrument of wiring board is needed such as electronic industry, electric, Electric Industrial, communications and transportation, Aero-Space, toy industry.
Above-mentioned term " ××× base or group ", which refers to, sloughs remaining part after one or more hydrogen atoms or other atoms or atomic group in ××× molecular structure of compounds.
The present invention obtains the phosphazene compound with carboxylate by using the M groups of specific composition, enable the compound that there is good low-dielectric, its solidfied material has good heat resistance, mechanical performance and low dielectric constant and dielectric loss, is a kind of dielectric materials also with larger economy and environmentally friendly friendly.The dielectric constant (1GHz) for the copper-clad plate that the resin combination obtains is used for 3.0-3.1, dielectric loss (1GHz) is 0.004-0.006, Tg can reach 173 DEG C and more than, T- peel strengths can reach 1.93kg/mm2And more than, interlaminar strength can reach 1.65kg/mm2And more than, saturated water absorption can reach less than 0.34%.
Embodiment
Technical scheme is further illustrated with reference to embodiment.
Embodiment 1
The structural formula of phosphazene compound of the present embodiment with carboxylate is as follows：
Hexachlorocyclotriph,sphazene 1mol is put into three mouthfuls of 2000ml glass reactors with agitating device, acetone 200ml, sodium methoxide 4mol, ethylene glycol 2mol, while stirring, while logical nitrogen, it is warming up to 60 DEG C, 20% sodium hydroxide solution 620g is instilled with 60min, keep 60 DEG C of temperature, 15 hours of stirring reaction, after the completion of reaction, with inorganic constituents and moisture in the method removal system of physics, 3mL 98% concentrated sulfuric acid is added dropwise, and add acetic acid 2mol, in 40 DEG C of stirring reactions 2 hours, after reaction, with the impurity and moisture in physical method removal system, distill solvent in system, the ester equivalent for obtaining said structure is 240g/eq carboxylate A 1mol.
Proton nmr spectra sign is carried out to obtained compound A, it is as a result as follows：
1H NMR(CDCl3,500MHz):3.39 (hydrogen on m, 12H, methoxyl group), 2.01 (m, 6H, CH3 COO), 4.27 (m, 4H, COOCH2 ),3.81(m,4H,CH2CH2 O)。
The position of infrared spectrum characteristic peak：Ester carbonyl group 1730-1740cm-1, the C-O-C 1200cm of ester group-1, the characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P-N 874cm in phosphazene backbone-1, the characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P-N 874cm in phosphazene backbone-1, the absworption peak 2995.3cm of methyl ether-1, P-O-C key absworption peaks 1035cm-1, CH2- O absworption peak 2983cm-1。
Epoxide equivalent is added using above-mentioned carboxylate A 120g as curing agent as 200g/eq o-cresol formaldehyde epoxy resin 100g, curing accelerator pyridine 0.2g, composition epoxy resin is prepared.The standard copper-clad plate sample for meeting the standards such as GB, UL is made according to general copper-clad plate production process using the composition epoxy resin, a copper-clad plates are named as, the performance of a copper-clad plates is tested, its result is represented in table 1.
Embodiment 2
The structural formula of phosphazene compound of the present embodiment with carboxylate is as follows：
Hexachlorocyclotriph,sphazene 1mol is put into three mouthfuls of 2000ml glass reactors with agitating device, acetone 200ml, sodium methoxide 4mol, ethylene glycol 2mol, while stirring, while logical nitrogen, it is warming up to 60 DEG C, 20% sodium hydroxide solution 620g is instilled with 60min, keep 60 DEG C of temperature, 15 hours of stirring reaction, after the completion of reaction, with inorganic constituents and moisture in the method removal system of physics, 3mL 98% concentrated sulfuric acid is added dropwise, and add benzoic acid 2mol, in 40 DEG C of stirring reactions 2 hours, after reaction, with the impurity and moisture in physical method removal system, distill solvent in system, the ester equivalent for obtaining said structure is 300g/eq carboxylate B 1mol.
Proton nmr spectra sign is carried out to obtained compound B, it is as a result as follows：
1H NMR(CDCl3,500MHz):7.4-7.9 (m, 10H, benzene ring hydrogen), 4.5 (m, 4H, COOCH 2CH2),4.0(m,4H,COOCH2CH 2), 3.39 (hydrogen on s, 12H, methoxyl group).
The position of infrared spectrum characteristic peak：Ester carbonyl group 1730-1740cm-1, the C-O-C 1200cm of ester group-1, the characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P-N 874cm in phosphazene backbone-1, the characteristic absorption peak 1217cm of P=N keys in phosphazene backbone-1, P-N 874cm in phosphazene backbone-1, the absworption peak 2995.3cm of methyl ether-1, P-O-C key absworption peaks 1035cm-1, CH2- O absworption peak 2983cm-1。
Epoxide equivalent is added using above-mentioned carboxylate B 150g as curing agent as 200g/eq o-cresol formaldehyde epoxy resin 100g, curing accelerator pyridine 0.2g, composition epoxy resin is prepared.The standard copper-clad plate sample for meeting the standards such as GB, UL is made according to general copper-clad plate production process using the composition epoxy resin, b copper-clad plates are named as, the performance of b copper-clad plates is tested, its result is represented in table 1.
Embodiment 3
The structural formula of phosphazene compound of the present embodiment with carboxylate is as follows：
Hexachlorocyclotriph,sphazene 1mol is put into three mouthfuls of 2000ml glass reactors with agitating device, acetone 200ml, sodium methoxide 4mol, ethylene glycol 2mol, while stirring, while logical nitrogen, it is warming up to 60 DEG C, 20% sodium hydroxide solution 620g is instilled with 60min, keep 60 DEG C of temperature, 15 hours of stirring reaction, after the completion of reaction, with inorganic constituents and moisture in the method removal system of physics, 3mL 98% concentrated sulfuric acid is added dropwise, and add benzoic acid 1mol, in 40 DEG C of stirring reactions 3 hours, after reaction, with the impurity and moisture in physical method removal system, and hexachlorocyclotriph,sphazene 1mol is added in backward reactor, sodium methoxide 4mol, ethylene glycol 1mol, stirring reaction 10 hours, after the completion of reaction, with inorganic constituents and moisture in the method removal system of physics, 3mL 98% concentrated sulfuric acid is added dropwise, and add benzoic acid 1mol, in 40 DEG C of stirring reactions 3 hours, after reaction, with the impurity and moisture in physical method removal system, distill solvent in system, the ester equivalent for obtaining said structure is 460g/eq carboxylate C 1mol.
Proton nmr spectra sign is carried out to obtained compound C, it is as a result as follows：
1H NMR(CDCl3,500MHz):2.01 (m, 6H, CH3 COO), 4.27 (m, 4H, COOCH2 ),3.81(CH2CH2 O), 7.09 (hydrogen of O metas in m, 8H, POPh), 6.82 (hydrogen that O is aligned in m, 4H, POPh), 6.73 (hydrogen at O ortho positions in m, 8H, POPh).
The position of infrared spectrum characteristic peak：Ester carbonyl group 1730-1740cm-1, the C-O-C 1200cm of ester group-1。
Epoxide equivalent is added using above-mentioned carboxylate C 230g as curing agent as 200g/eq o-cresol formaldehyde epoxy resin 100g, curing accelerator pyridine 0.2g, composition epoxy resin is prepared.The standard copper-clad plate sample for meeting the standards such as GB, UL is made according to general copper-clad plate production process using the composition epoxy resin, c copper-clad plates are named as, the performance of c copper-clad plates is tested, its result is represented in table 1.
Comparative example 1
Epoxide equivalent is 200g/eq o-cresol formaldehyde epoxy resin 200g, add six phenoxy group phosphorus cyanogen 70gs and 0.2g of the phenolic hydroxyl equivalent for 105g/eq linear phenol-aldehyde resin curing agent 105g and as fire retardant pyridine, solution is dissolved into appropriate butanone, use normal glass cloth, according to conventional preparation method, the copper-clad plate d that resinous amount is 50% is obtained, the properties for covering copper d are represented in table 1.
Comparative example 2
Epoxide equivalent is 200g/eq o-cresol formaldehyde epoxy resin 200g, adding has such as the resin compound 220g of formula (1) structure, ester equivalent is 220g/eq and six phenoxy group phosphorus the cyanogen 70g and 0.2g as fire retardant pyridine, solution is dissolved into appropriate butanone, use normal glass cloth, according to conventional preparation method, the copper-clad plate e that resinous amount is 50% is obtained.The properties for covering copper e are represented in table 1.
Embodiment and the test result of comparative example are (in view of specific method of testing has been well known to those skilled in the art, method is no longer described in detail at this) as shown in table 1 below：
Table 1
As can be seen from Table 1, the resin combination that the present invention is prepared using the compound for containing the molecular structure shown in formula I as curing agent, so that being 3.0-3.1 by the dielectric constant (1GHz) of its copper-clad plate prepared, dielectric loss (1GHz) is 0.004-0.006, Tg can reach 173 DEG C and more than, T- peel strengths can reach 1.93kg/mm2And more than, interlaminar strength can reach 1.65kg/mm2And more than, saturated water absorption can reach less than 0.34%, hence it is evident that better than the performance of comparative example copper-clad plate.
Applicant states that the present invention illustrates phosphazene compound, pre-impregnated sheet, composite metal substrate and the wiring board of the present invention by above-described embodiment, but the invention is not limited in above-described embodiment, that is, does not mean that the present invention has to rely on above-described embodiment and could implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., within the scope of all falling within protection scope of the present invention and being open.

Claims (10)

1. a kind of phosphazene compound, it is characterised in that it has the molecular structure as shown in formula (I)：
In formula (I), R1Represent arbitrary organic group, R2For aliphatic group, R is to be carried by nucleopilic reagent The inertia nucleophilic group of confession；M is the phosphonitrile base M of ring three1, the phosphonitrile base M of ring more than four2Or non-annularity polyphosphazene Base M3In any one or its at least two combination；
A is integer more than zero, and b is the integer more than or equal to zero, and c is the integer more than zero, and and M The total number of the connected substituent of group is equal to 2 times of number of phosphorus atoms on M groups.
2. phosphazene compound as claimed in claim 1, it is characterised in that R1For aliphatic group and/or virtue Alkyl, further preferred substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkanes In base, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl Any one or its at least two combination；
Preferably, R1For unsubstituted straight chained alkyl or branched alkyl, unsubstituted cycloalkyl, unsubstituted In aralkyl, unsubstituted alkylaryl, unsubstituted aryl or unsubstituted heteroaryl any one or The combination of person at least two；
Preferably, R1Without reactive group that can be with epoxy resin reaction generation secondary hydroxyl groups；
Preferably, R2For substituted or unsubstituted aralkyl, substituted or unsubstituted alkylaryl, substitution or Any one in unsubstituted aryl or substituted or unsubstituted heteroaryl or its at least two combination；
Preferably, the inertia nucleophilic group is that R is selected from-OR13、-C≡C-R18、 R22-COO-、In any one or at least two combination；
R13For substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, take Generation or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, take Generation or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted carbonic ester Base, substituted or unsubstituted sulfonate group, substituted or unsubstituted phosphonate group, substituted or unsubstituted virtue In base or substituted or unsubstituted heteroaryl any one or at least two combination, R15、R16And R17 It independently is substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted cycloalkyl, takes Generation or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, take Generation or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted aryl or In substituted or unsubstituted heteroaryl any one or at least two combination, R18To replace or not taking The straight chained alkyl or branched alkyl in generation, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, Substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy, In substituted or unsubstituted alkyl-aryloxy, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl Any one or at least two combination, R22For substituted or unsubstituted straight chained alkyl or branched alkyl, Substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, take Generation or the fragrant oxygen of unsubstituted cycloalkyloxy, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl Any one in base, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl or at least two Combination, R23And R24It independently is substituted or unsubstituted straight chained alkyl or branched alkyl, substitution or not Substituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substitution do not take The cycloalkyloxy in generation, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substitution Or in unsubstituted aryl or substituted or unsubstituted heteroaryl any one or at least two combination, R26And R27It independently is substituted or unsubstituted straight chained alkyl or branched alkyl, substituted or unsubstituted ring Alkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted cycloalkanes Epoxide, substituted or unsubstituted aralkoxy, substituted or unsubstituted alkyl-aryloxy, substitution or unsubstituted Aryl or substituted or unsubstituted heteroaryl in any one or at least two combination；
Preferably, the phosphazene compound be the phosphazene compound with following structure in any one or At least two mixture：
A is 4, b It is 2, R for 0, c1For ethyl, R2For ethyl, R is methoxyl group；
A is 4, b It is 1, R for 1, c1For ethyl, R2For ethyl, R is methoxyl group；
Or
A is 4, b It is 2, R for 0, c1For ethyl, R2For ethyl, R is phenoxy group.
3. the phosphazene compound according to claim 1 or 2 with carboxylate, it is characterised in that M1 Structure is：
M2Structure is：
Wherein, x is more than or equal to 4；
M3Structure is：
Wherein, y is more than or equal to 3.
4. a kind of preparation method of the phosphazene compound with carboxylate as described in one of claim 1-3, its It is characterised by, obtained by phosphonitrile chloride and nucleopilic reagent progress nucleophilic substitution.
5. a kind of composition epoxy resin, it is characterised in that include the band described in one of claim 1-3 The phosphazene compound of carboxylate.
6. a kind of pre-impregnated sheet, it is characterised in that it is contained by composition epoxy resin as claimed in claim 5 Soak or be coated on base material and form.
7. pre-impregnated sheet as claimed in claim 6, it is characterised in that the base material be fiberglass substrate, Polyester base material, polyimide base material, ceramic base material or carbon fiber base material.
8. a kind of composite metal substrate, it is characterised in that it includes more than one such as claim 6 or 7 The pre-impregnated sheet carries out surface metal-clad, overlapping, pressing and formed successively；
Preferably, the material of the surface metal-clad is the alloy of aluminium, copper, iron and its any combination；
Preferably, the composite metal substrate is that CEM-1 copper-clad plates, CEM-3 copper-clad plates, FR-4 cover copper Plate, FR-5 copper-clad plates, CEM-1 aluminium bases, CEM-3 aluminium bases, FR-4 aluminium bases or FR-5 aluminium bases Plate.
9. a kind of flexible copper-clad plate, it is characterised in that the flexible copper-clad plate includes more than one such as right It is required that pre-impregnated sheet described in 6 or 7 and the Copper Foil for the pre-impregnated sheet one or both sides being overlying on after overlapping.
10. a kind of wiring board, it is characterised in that in the surface of the composite metal substrate described in claim 8 Processing line is formed.
CN201610008251.3A 2016-01-04 2016-01-04 A kind of phosphazene compound, pre-impregnated sheet, composite metal substrate and wiring board Pending CN106939019A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63241075A (en) * 1986-11-26 1988-10-06 Idemitsu Petrochem Co Ltd Reaction-curable coating material
EP0443626A2 (en) * 1990-02-23 1991-08-28 Idemitsu Petrochemical Co. Ltd. Electrophotographic photosensensitive member
JPH05286988A (en) * 1992-04-14 1993-11-02 Idemitsu Petrochem Co Ltd Curable phosphazene compound, its production and cured body thereof
JPH0782324A (en) * 1993-09-17 1995-03-28 Mitsui Toatsu Chem Inc Flame-retardant transparent resin
US6045975A (en) * 1990-04-16 2000-04-04 Fujitsu Limited Photosensitive, heat-resistant resin composition for forming patterns
CN105153234A (en) * 2014-06-13 2015-12-16 广东生益科技股份有限公司 Phenoxy cyclotriphosphazene active ester, halogen free resin composition and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63241075A (en) * 1986-11-26 1988-10-06 Idemitsu Petrochem Co Ltd Reaction-curable coating material
EP0443626A2 (en) * 1990-02-23 1991-08-28 Idemitsu Petrochemical Co. Ltd. Electrophotographic photosensensitive member
US6045975A (en) * 1990-04-16 2000-04-04 Fujitsu Limited Photosensitive, heat-resistant resin composition for forming patterns
JPH05286988A (en) * 1992-04-14 1993-11-02 Idemitsu Petrochem Co Ltd Curable phosphazene compound, its production and cured body thereof
JPH0782324A (en) * 1993-09-17 1995-03-28 Mitsui Toatsu Chem Inc Flame-retardant transparent resin
CN105153234A (en) * 2014-06-13 2015-12-16 广东生益科技股份有限公司 Phenoxy cyclotriphosphazene active ester, halogen free resin composition and application thereof

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Application publication date: 20170711