CN108164684B

CN108164684B - A kind of compositions of thermosetting resin

Info

Publication number: CN108164684B
Application number: CN201611114924.XA
Authority: CN
Inventors: 罗成; 唐国坊; 张江陵
Original assignee: Shengyi Technology Co Ltd
Current assignee: Shengyi Technology Co Ltd
Priority date: 2016-12-07
Filing date: 2016-12-07
Publication date: 2019-08-27
Anticipated expiration: 2036-12-07
Also published as: CN108164684A

Abstract

The present invention provides a kind of compositions of thermosetting resin, it includes ester terminated phosphorous polymers, the compositions of thermosetting resin has many advantages, such as good thermal stability, humidity resistance, toughness, dielectric constant and dielectric loss angle tangent is low, water absorption rate is low and high halogen-free flameproof efficiency, and has excellent technique processability；The present invention also provides application of the compositions of thermosetting resin in resin sheet, resin laminated metal foil, prepreg, laminate, metal-clad laminate and printed wiring board.

Description

A kind of compositions of thermosetting resin

Technical field

The present invention relates to technical field of polymer materials more particularly to a kind of compositions of thermosetting resin and use the pre- of it Leaching material and laminate for printed circuits.

Background technique

Traditional on July 1st, 2006, two parts of environmental protection instructions " about electric/electronic device instruction is scrapped " of European Union and " about In the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment " formally implement, the exploitation of halogen-free flameproof copper-clad laminate As the hot spot of industry, each copper-clad laminate producer all releases the halogen-free flameproof copper-clad laminate of oneself one after another.

Phosphorus-containing compound is introduced in the resin matrix of copper-clad plate, becomes the main technological route of copper-clad plate halogen-free flameproof. The phosphorus flame retardant being widely used on copper-clad plate field at present is broadly divided into response type and two kinds of addition type.Response type is mainly DOPO class compound, based on phosphorous epoxy resin, phosphorus containing phenolic resin, phosphorus content is between 2~10%.However, actually answering With middle discovery, DOPO class compound has biggish water absorption rate and poor dielectric properties and plate humidity resistance poor.Addition type The flame retarding efficiency of predominantly phosphonitrile and phosphonate ester compound, additive flame retardant is lower, and needing to add more amounts could reach To flame-retardancy requirements.It is easy to migrate to plate in laminate process simultaneously because of its lower fusing point (generally below 150 DEG C) Surface influences plate property.

In addition, for copper clad foil substrate material, in order to meet the performance of PCB processing performance and terminal electronic product It is required that, it is necessary to have good dielectric properties, heat resistance and mechanical performance, while should also have good technique processing special Property, high peel strength, excellent humidity resistance.

DOPO-HQ is the phosphorus curing agent of reactivity, can be cured and react with epoxy resin, but due to its activity Group is phenolic hydroxyl group, and the biggish secondary hydroxyl of polarity can be generated after reacting with epoxy resin, leads to the dielectric properties of solidfied material It is poor.The preparation method and its purposes of the active ester with the connection alkyl containing phospho hetero phenanthrene are disclosed in CN103965249A, but contain phospha Phenanthrene connection alkyl causes it slightly lower with Tg when epoxy resin cure, is restricted its utilization on High Tg CCL. It is disclosed in CN105669760A and inactive ester type compound is synthesized using phenanthrene derivative containing phospha and glycerine, it can be to add The form added is fire-retardant to engineering material progress, does not contribute the Tg of reinforcing material equally.It is mentioned in CN103694642A with poly- Preparation copper-clad plate is blended in phosphonate ester or/and phosphonate ester-carbonic ester and epoxy resin, cyanate ester resin.Polyphosphonates in this system Or/and phosphonate ester-carbonic ester has negative effect to the heat resistance of system as additive flame retardant, and because of its phosphorus content Lower, flame retarding efficiency is low.

Summary of the invention

It is formed the study found that can be used as epoxy resin with ester terminated phosphorous polymer with its curing agent through inventor Curing system addition fire retardant, but its higher fusing point and higher phosphorus content, the phosphonic acids relative to common addition type Ester fire retardant has unrivaled advantage.Based on the above feature, without adding or only needing to add other fire retardants on a small quantity Plate is set to achieve the effect that UL94V-0 halogen-free flameproof.

Based on this, one of the objects of the present invention is to provide a kind of compositions of thermosetting resin, and use its preimpregnation Material and laminate for printed circuits.There is high glass transition temperature using the laminate for printed circuits that the resin combination makes Degree, excellent dielectric properties, high-fire resistance and good technique processability, and it is able to achieve halogen-free flameproof, reach UL94V-0.

The present inventor to achieve the above object, has carried out in-depth study repeatedly, as a result, it has been found that: by halogen-free epoxy resin, SMA resin and ester terminated phosphorous polymer and the composition that optionally other curing agent properly mix, can reach Above-mentioned purpose.

That is, the present invention adopts the following technical scheme: a kind of compositions of thermosetting resin, it includes epoxy resin, curing agent And ester terminated phosphorous polymer, wherein curing agent includes at least SMA resin.

Compositions of thermosetting resin of the invention is halogen-free thermosetting resin composite, with ester terminated phosphorous polymerization Halogen-free flame retardants of the object as the curing system of epoxy resin.Its phosphorus content is high, fusing point is high, is added in epoxy curing systems, Available heat-resist, Tg high bittern-free flame-proof material need to only add or can without additionally adding other fire retardants on a small quantity It is fire-retardant to reach UL94V-0.

The present invention is using high content of phosphorus, dystectic ester terminated phosphorous polymer as the fire-retardant of epoxy curing systems Agent can significantly improve the anti-flammability of the prepreg and laminate for printed circuits that make using the resin combination, and The glass transition temperature and heat resistance of plate will not be reduced, and makes it have good technique processability, and realize halogen-free flameproof, is reached To UL94V-0.Each component is described in detail below.

According to the present invention, the ester terminated phosphorous polymer, shown in structural formula such as formula (I):

Wherein, n₁For 1~20 integer, for example, 1,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18, 19 or 20；

Wherein, R₁For any one in phenyl, naphthalene, xenyl, the linear or branched alkyl group containing carbon number 1~4；Wherein Linear or branched alkyl group containing carbon number 1~4 for example can be methyl, ethyl, propyl, butyl, isopropyl, isobutyl group or tert-butyl In any one；

Wherein, Ar₁For In any one；

Wherein, Ar₂ForIn any one；

Wherein, n₂For 0~5 integer, such as 0,1,2,3,4 or 5；n₃For 0~7 integer, such as 0,1,2,3,4,5,6 Or 7；

Wherein, R₂For any one in the linear or branched alkyl group containing carbon number 1~4；The straight chain containing carbon number 1~4 Or branched alkyl for example can be any one in methyl, ethyl, propyl, butyl, isopropyl, isobutyl group or tert-butyl.

Heretofore described ester terminated phosphorous polymer, structural formula can be such as flowering structure:

Wherein, n₁For 1~20 integer.

According to the present invention, the ester terminated phosphorous polymer account for epoxy resin in the compositions of thermosetting resin, The 10%~35% of curing agent and ester terminated phosphorous polymer total weight, for example, 10%, 12%, 14%, 15%, 16%, the specific point value between 18%, 20%, 22%, 25%, 28%, 30%, 32% or 35% and above-mentioned numerical value, is limited to Length and for concise consideration, the specific point value that range described in the present invention no longer exclusive list includes.

According to the present invention, the epoxy resin accounts for epoxy resin, curing agent and ester in the compositions of thermosetting resin Base sealing end phosphorous polymer total weight 30%~55%, such as 30%, 32%, 34%, 35%, 36%, 38%, 40%, 42%, the specific point value between 45%, 48%, 50%, 52% or 55% and above-mentioned numerical value, as space is limited and for simplicity The considerations of, specific point value that range described in the present invention no longer exclusive list includes.

In the present invention, the epoxy resin is halogen-free epoxy resin, refer in 1 molecule tool there are two or two with The epoxy resin of upper epoxy group is selected from glycidol ethers, glycidol esters, glycidol amine, alicyclic epoxy tree In rouge, epoxidation of olefins class, glycolylurea epoxide resin or acid imide epoxy resin any one or at least two mixture.

Preferably, the glycidol ethers include bisphenol A type epoxy resin, bisphenol f type epoxy resin, o-cresol phenolic aldehyde Epoxy resin, bisphenol A-type novolac epoxy resin, three phenolic novolac epoxy resins, dicyclopentadiene novolac epoxy resin, biphenyl type Any one in novolac epoxy resin, alkyl benzene-type novolac epoxy resin or naphthol type novolac epoxy resin or at least two Mixture.Above-mentioned epoxy resin is the epoxy resin of Halogen.

Preferably, the glycidol ethers are selected from the epoxy resin having the following structure:

Wherein, Z₁、Z₂And Z₃It is each independently selected fromR₃For hydrogen atom, replace or Any one in unsubstituted straight chained alkyl or branched alkyl containing carbon number 1~5.

Y₁And Y₂It is each independently selected from-CH₂-、 In any one, n₄It is 1~10 Arbitrary integer, such as 1,2,3,4,5,6,7,8,9 or 10, R₄Straight chained alkyl or branch selected from hydrogen atom, containing carbon number 1~5 Any one in alkyl；Such as it can be methyl, ethyl, propyl, butyl, amyl, isopropyl, isobutyl group, tert-butyl or different Any one in amyl.

Preferably, it is different to be selected from triglycidyl group-p- amino-phenol, triglycidyl group trimerization for the glycidol amine Cyanate, four glycidyl group diamino dimethylene benzene, two amido diphenyl-methane of four glycidyl group -4,4`-, four shrinks are sweet Oil base -3,4`- diaminodiphenyl ether, four glycidyl group -4,4`- diaminodiphenyl ether or four glycidyl group -1,3- diamino In ylmethyl hexamethylene any one or at least two mixture.

Halogen-free thermosetting resin composite of the invention uses the halogen-free epoxy resin of above-mentioned specific molecular structure, has Higher degree of functionality and good dielectric properties, solidfied material Tg higher, water absorption rate are low.

According to the present invention, the SMA resin can be copolymerized using by styrene and maleic anhydride in the ratio of 1:1~8:1 It obtains, preferably has the following structure:

The wherein integer that a is 1~8, such as 1,2,3,4,5,6,7 or 8；B be 5~40 integer, such as 5,8,10,12, 15,18,25,28,30,35 or 40.

According to the present invention, the SMA resin accounts for epoxy resin, curing agent and ester group in the compositions of thermosetting resin The 35%~60% of the phosphorous polymer total weight of sealing end, for example, 35%, 37%, 38%, 40%, 42%, 45%, 48%, 50%, the specific point value between 52%, 55%, 57%, 58% or 60% and above-mentioned numerical value, as space is limited and for simplicity The considerations of, specific point value that range described in the present invention no longer exclusive list includes.

According to the present invention, the curing agent can also include cyanate ester resin and/or bismaleimide-triazine resin； Wherein, the cyanate ester resin has the following structure:

Wherein, R₁₃For-CH₂-、 In any one or at least two mixture；R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁Or R₁₂It is each independently selected from hydrogen atom, takes Any one in generation or unsubstituted straight chained alkyl or branched alkyl containing carbon number 1~4, such as can be methyl, ethyl, third Any one in base, butyl, isopropyl, isobutyl group or tert-butyl.

Preferably, the cyanate ester resin is selected from bis- (the 4- cyanato- phenyl) propane of 2,2-, bis- (4- cyanato- phenyl) second Alkane, bis- (3,5- dimethyl -4- cyanato- phenyl) methane, bis- (4- cyanato- the phenyl) -1,1,1,3,3,3- hexafluoropropane of 2,2-, Bis- (4- cyanato- the phenyl)-diisopropyl benzenes of α, α '-, Cyclopeutadiene type cyanate, phenol novolak type cyanate, cresol novolac Bis- (4- cyanato- phenyl) the propane prepolymers of type cyanate, 2,2-, bis- (4- cyanato- phenyl) ethane prepolymers, bis- (3,5- bis- Methyl -4- cyanato- phenyl) methane prepolymer, bis- (4- cyanato- the phenyl) -1,1,1,3,3,3- hexafluoropropane prepolymers of 2,2-, Bis- (4- cyanato- the phenyl)-diisopropyl benzene prepolymers, dicyclopentadiene type ethylene rhodanate prepolymer, phenol novolak type of α, α '- In cyanate prepolymer or cresol novolak type cyanate prepolymer any one or at least two mixture, preferably 2,2- Bis- (4- cyanato- phenyl) propane, α, bis- (4- cyanato- the phenyl)-diisopropyl benzenes of α ' -, bis- (3,5- dimethyl -4- cyanogen oxygen Base phenyl) methane, 2,2- bis- (4- cyanato- phenyl) propane prepolymers, α, bis- (4- cyanato- the phenyl)-diisopropyl benzenes of α '- In prepolymer or bis- (3,5- dimethyl -4- cyanato- phenyl) methane prepolymers any one or at least two mixture.

According to the present invention, the cyanate ester resin and/or bismaleimide-triazine resin account for the thermosetting resin group Close 0%~20% of epoxy resin and curing agent total weight in object, for example, 0%, 2%, 4%, 5%, 8%, 10%, 12%, 14%, the specific point value between 15%, 17% or 20% and above-mentioned numerical value, as space is limited and for concise consideration, this hair The specific point value that range described in bright no longer exclusive list includes.

According to the present invention, the curing agent can also include phenolic resin；The phenolic resin is phosphorous or not phosphorous Phenolic resin, is phenolic resin well known in the art, and the present invention does not do particular determination.

According to the present invention, the phenolic resin accounts for epoxy resin and curing agent total weight in the compositions of thermosetting resin 0%~20%, such as 0%, 2%, 4%, 5%, 8%, 10%, 12%, 14%, 15%, 17% or 20% and above-mentioned number Specific point value between value, as space is limited and for concise consideration, the tool that range described in the present invention no longer exclusive list includes Body point value.

Heretofore described compositions of thermosetting resin, organic solid content specifically include based on 100 parts by weight: Halogen Epoxy resin: 30~55 parts by weight；35~60 parts by weight of SMA resin；Ester terminated phosphorous polymer: 10~35 parts by weight； Cyanate ester resin and/or bismaleimide-triazine resin: 0~20 parts by weight；Phenolic resin: 0~20 parts by weight.

" epoxy resin in the compositions of thermosetting resin, curing agent and ester terminated mentioned in the present invention In phosphorous polymer total weight ", curing agent refers to the SMA resin for playing the role of cured epoxy resin and optionally cyanate resin Rouge and/or bismaleimide-triazine resin and phenolic resin.

Compositions of thermosetting resin of the invention can also include phosphonium flame retardant.

According to the present invention, the phosphonium flame retardant can be selected from three (2,6- 3,5-dimethylphenyl) phosphines, 10- (2,5- dihydroxy Phenyl) miscellaneous -10- phosphine phenanthrene -10- oxide of -9,10- dihydro-9-oxy, 2,6- bis- (2,6- 3,5-dimethylphenyl) phosphino- benzene, 10- benzene Miscellaneous -10- phosphine phenanthrene -10- the oxide of base -9,10- dihydro-9-oxy, phenoxy phosphazene compound, phosphate, polyphosphate, polyphosphonic acid In ester or phosphonate ester-carbonate copolymer any one or at least two mixture.

Halogen-free thermosetting resin composite of the invention can also further include curing accelerator.

Preferably, the curing accelerator includes organic metal salt and selected from glyoxaline compound, glyoxaline compound In derivative, piperidines, pyridine compounds and their, lewis acid or triphenylphosphine any one or at least two it is mixed Close object.

Preferably, the organic metal salt in the curing accelerator includes sad metal salt, isooctyl acid metal salt, levulinic In ketone metal salt, metal naphthenate, salicylic acid metal salt or Metallic stearates any one or at least two mixing Object, wherein the metal in zinc, copper, iron, tin, cobalt or aluminium any one or at least two mixture.

Preferably, the glyoxaline compound is 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole or 2- In undecyl imidazole any one or at least two mixture.

Preferably, the piperidines are 2,3- diamino phenylpiperidines, 2,5- diamino phenylpiperidines, 2,6- diamino piperazine Pyridine, 2- amino -3- methyl piperidine, 2- amino -4- methyl piperidine, 2- amino -3- nitro piperidines, 2- amino -5- nitro piperidines or In 2- amino -4,4- lupetidine any one or at least two mixture.

Preferably, the pyridine compounds and their is 4-dimethylaminopyridine, 2-aminopyridine, 3- aminopyridine or 4- amino Any one in pyridine or at least two mixtures.

Preferably, with ester terminated phosphorous polymer, epoxy resin and SMA resin and the cyanate resin that may be added The sum of rouge, additive amount of phenolic resin are 100 parts by weight meters, and the additive amount of the curing accelerator is 0.01~1 parts by weight, example Such as 0.01 parts by weight, 0.025 parts by weight, 0.05 parts by weight, 0.07 parts by weight, 0.085 parts by weight, 0.1 parts by weight, 0.3 weight Part, 0.5 parts by weight, 0.8 parts by weight, 0.9 parts by weight or 1 parts by weight, preferably 0.025~0.85 parts by weight.

Halogen-free thermosetting resin composite of the invention can also further include filler.

Preferably, the filler is selected from organic filler or inorganic filler, preferably inorganic filler, further preferably by surface The inorganic filler of processing, most preferably surface treated silica.

Preferably, it is even to be selected from silane coupling agent, silicone oligomer or titanate esters for the surface treating agent of the surface treatment Join agent in any one or at least two mixture.

Preferably, in terms of by inorganic filler for 100 parts by weight, the dosage of the surface treating agent is 0.1~5 parts by weight, excellent Select 0.5~3 parts by weight, more preferable 0.75~2 parts by weight.

Preferably, the inorganic filler is selected from nonmetal oxide, metal nitride, non-metal nitride, inorganic hydration In object, inorganic salts, metal hydrate or Phos any one or at least two mixture, preferred molten silica, Crystalline sillica, spherical silica, hollow silicon dioxide, aluminium hydroxide, aluminium oxide, talcum powder, aluminium nitride, nitridation In boron, silicon carbide, barium sulfate, barium titanate, strontium titanates, calcium carbonate, calcium silicates or mica any one or at least two it is mixed Close object.

Preferably, the organic filler is any one in polytetrafluorethylepowder powder, polyphenylene sulfide or polyether sulfone powder Kind or at least two mixture.

Preferably, the median of the filler be 0.01~50 μm, preferably 0.01~20 μm, further preferred 0.1~ 10μm。

Preferably, with ester terminated phosphorous polymer, epoxy resin and SMA resin and the cyanate resin that may be added Rouge, phenolic resin the sum of additive amount be 100 parts by weight meters, the additive amount of the filler is 5~300 parts by weight, preferably 5~ 200 parts by weight, further preferred 5~150 parts by weight.

"comprising" of the present invention, it is intended that it can also include other components, these other components especially except described group Assign the halogen-free thermosetting resin composite different characteristics.In addition to this, "comprising" of the present invention can also replace For enclosed " for " or " by ... form ".

For example, the halogen-free thermosetting resin composite can also contain various additives, as concrete example, can enumerate Antioxidant, heat stabilizer, antistatic agent, ultraviolet absorbing agent, pigment, colorant or lubricant etc..These additives can be single It solely uses, two or more can also be used in mixed way.

The preparation method of halogen-free thermosetting resin composite of the invention is ordinary skill in the art means, specific side Method are as follows: first solid content is put into, is then added liquid solvent, after stirring is completely dissolved to solid content, add liquid resin and Promotor continues to stir evenly.

As the solvent in the present invention, there is no particular limitation, as concrete example, can enumerate methanol, ethyl alcohol, butanol Equal alcohols, the ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol, butyl carbitol, acetone, butanone, first The ketones such as methyl ethyl ketone methyl ketone, cyclohexanone；The arenes such as toluene, dimethylbenzene；The esters such as ethyl acetate, ethoxyethyl acetate Class；The nitrogen-containing solvents such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide.The above solvent can be used alone, can also be two kinds Or it two or more is used in mixed way.It is preferred that the ketones such as acetone, butanone, methyl ethyl ketone, cyclohexanone.The additive amount of the solvent by Those skilled in the art select according to oneself experience, so that resin adhesive liquid reaches the viscosity for being suitble to use.

Prepreg of the invention include reinforcing material and impregnation it is dry after be attached to nothing as described above on reinforcing material Halogen compositions of thermosetting resin, used reinforcing material are limited without special, can be organic fiber, inorfil woven cloth Or non-woven fabrics.The organic fiber can choose aramid nonwoven, the inorfil woven cloth can for E- glass-fiber-fabric, D- glass-fiber-fabric, S- glass-fiber-fabric, T glass-fiber-fabric, NE- glass-fiber-fabric or quartz fabric.The thickness of the reinforcing material is not particularly limited, and is in Laminate has the considerations of good dimensional stability, the woven cloth and nonwoven thickness preferably 0.01~0.2mm, and preferably It is surface-treated by fibrillation processing and silane coupling agent, it is described silane coupled in order to provide good water resistance and heat resistance Agent is preferably any one or at least two in epoxy silane coupling agent, amino silicane coupling agent or vinyl silicane coupling agent Mixture.By reinforcing material by being impregnated with above-mentioned halogen-free thermosetting resin composite, under the conditions of 100~250 DEG C, baking Obtain the prepreg within 1~15 minute.

Laminate for printed circuits of the invention includes by being heated and pressurizeed, making the prepreg of a piece of or two panels or more viscous It is combined and manufactured laminate, and is bonded in the metal foil of laminate one or both sides or more.The laminate is Solidify in hot press and be made, solidification temperature is 150~250 DEG C, and solidifying pressure is 10~60kg/cm².The metal foil is Copper foil, nickel foil, aluminium foil and SUS foil etc., material is unlimited.

Compared with prior art, the present invention at least has the advantages that

The present invention is using high content of phosphorus, dystectic ester terminated phosphorous polymer as the fire-retardant of epoxy curing systems Agent can significantly improve the flame retarding efficiency of the prepreg and laminate for printed circuits that make using the resin combination, and And the glass transition temperature and heat resistance of plate will not be reduced, using made of halogen-free thermosetting resin composite provided by the invention Prepreg and laminate for printed circuits, with up to 245 DEG C of glass transition temperature；Excellent dielectric properties, water absorption rate Control is within the scope of 0.06-0.09%；High-fire resistance；Excellent humidity resistance and good technique processability；Excellent is fire-retardant Efficiency can reach UL94V-0.

Specific embodiment

The technical scheme of the invention is further explained by means of specific implementation.

As described below is the specific embodiment of the embodiment of the present invention, it is noted that for the common skill of the art For art personnel, without departing from the principles of the embodiments of the present invention, several improvements and modifications can also be made, these improvement Also it is considered as the protection scope of the embodiment of the present invention with retouching.

Divide multiple embodiments that the embodiment of the present invention is further detailed below.The embodiment of the present invention be not limited to Under specific embodiment.Do not changing in the scope of the claims, appropriate can change implementation.

1, the synthesis of phosphorous polymer P-AE1

By 320g ODOPB and 185g diphenylphosphoryl dichloro and 1.11g calcium chloride be added equipped with blender, condensing reflux pipe, It is stirred in the four-necked bottle of thermometer, while being passed through nitrogen, be then warming up to 160 DEG C, react 1.5h at this temperature.It then will be anti- It answers temperature to rise to 230 DEG C, and reacts 5h at this temperature.Then room temperature is reduced the temperature to, and methylene chloride dissolution tree is added Rouge, then 13.7g chlorobenzoyl chloride is added to reaction system, 1.5h is reacted at this temperature.Then 5% sodium carbonate liquor is added, and It is vigorously stirred, filters, washes, dries, obtain product, number P-AE1.

Wherein n₁=20

2, the synthesis of phosphorous polymer P-AE2

By 370g 10- (2,5- dihydroxy naphthalene) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxide, 175g phenyl Phosphinylidyne dichloro and 1.11g calcium chloride stir in the four-necked bottle that blender, condensing reflux pipe, thermometer are housed, while being passed through nitrogen Then gas is warming up to 160 DEG C, reacts 1.5h at this temperature.Then 230 DEG C are warming up to, and reacts 5h under logical condition of nitrogen gas. It is then cooled to room temperature, and methylene chloride, which is added, dissolves resin, then 2,4,6- trimethylbenzene of 36.6g is added to reaction system Phenol equally reacts 2h at this temperature.Then 5% sodium carbonate liquor is added, and is vigorously stirred, filters, wash, dry, obtain Product, number P-AE2.

Wherein n₁=10

3, the synthesis of phosphorous polymer P-AE3

By 370g 10- (2,5- dihydroxy naphthalene) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxide, 195.6g naphthalene Base phosphinylidyne dichloro and 1.11g calcium chloride stir in the four-necked bottle that blender, condensing reflux pipe, thermometer are housed, and are passed through simultaneously Then nitrogen is warming up to 160 DEG C, reacts 2h at this temperature.Under logical condition of nitrogen gas, 230 DEG C are warming up to, and at this temperature React 5h.It is then cooled to room temperature, and methylene chloride is added and dissolves resin.78.7g is added to tert-butyl to reaction system again Chlorobenzoyl chloride equally reacts 2h at this temperature.Then 5% sodium carbonate liquor is added, and is vigorously stirred, filters, wash, do It is dry, obtain product, number P-AE3.

Wherein n₁=5

4, the synthesis of phosphorous polymer P-AE4

By 320g ODOPB, 93.1g methyl phosphinylidyne dichloro and 1.11g calcium chloride in equipped with blender, condensing reflux pipe, temperature It spends in the four-necked bottle of meter and stirs, while being passed through nitrogen, be then warming up to 160 DEG C, react 1h at this temperature.In logical condition of nitrogen gas Under, 230 DEG C are warming up to, and react 5h at this temperature.It is then cooled to room temperature, methylene chloride is added, dissolves resin, then to 92.76g is added to methyl benzoyl chloride in reaction system, reacts 1h at this temperature.Then 5% sodium carbonate liquor is added, and acute Strong stirring, filtering, washing, drying, obtains product, number P-AE4.

Wherein n₁=3

5, the synthesis of phosphorous polymer P-AE5

By 370g 10- (2,5- dihydroxy naphthalene) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxide, 79.8g methyl Phosphinylidyne dichloro and 1.11g calcium chloride stir in the four-necked bottle that blender, condensing reflux pipe, thermometer are housed, while being passed through nitrogen Then gas is warming up to 160 DEG C, reacts 1h at this temperature.Under logical condition of nitrogen gas, 230 DEG C are warming up to, and anti-at this temperature Answer 5h.It is then cooled to room temperature, and methylene chloride is added and dissolves resin, then 152.5g 2- naphthalene formyl is added to reaction system Chlorine equally reacts 1h at this temperature.Product is cooled to room temperature, 5% sodium carbonate liquor is then added, and is vigorously stirred, mistake Filter, washing, drying, obtain product, number P-AE5.

Wherein n₁=1

By ester terminated phosphorous polymer P-AE, halogen-free epoxy resin, curing agent and curing accelerator, halogen-free flameproof Agent, filler are uniformly mixed in solvent by a certain percentage, and control glue solid content is 65%, impregnate above-mentioned glue with 2116 glass-fiber-fabrics Liquid controls suitable thickness, then toasts 2~15min in 115~175 DEG C of baking oven and prepreg is made, then presoak several Material stacks, and is 170~250 DEG C in solidification temperature, solidifying pressure is 25~60kg/ in the stacked on 18 μ RTF copper foil in its two sides cm², curing time be 60~300min under the conditions of copper-clad plate is made.

Embodiment 1~14 and comparative example 1~8 are related to material and trade mark information is as follows:

(A) phosphorous polymer P-AE fire retardant is made by oneself

P-AE1: self-control phosphorous polymer P-AE1 fire retardant

Wherein n₁=20.

P-AE2: self-control phosphorous polymer P-AE2 fire retardant

Wherein n₁=10.

P-AE3: self-control phosphorous polymer P-AE3 fire retardant

Wherein n₁=5.

P-AE4: self-control phosphorous polymer P-AE4 fire retardant

Wherein n₁=3.

P-AE5: self-control phosphorous polymer P-AE5 fire retardant

Wherein n₁=1.

ODOPB:10- (2,5- dihydroxy phenyl) -10- hydrogen -9- oxa- -10- phospho hetero phenanthrene -10- oxide

FRX-3001:

(B) epoxy resin

HP-7200HHH:DIC, DCPD type epoxy resin, epoxide equivalent 288

HP-7200H-75M:DIC, DCPD type epoxy resin, epoxide equivalent 280

HP-6000:DIC, epoxy resin, epoxide equivalent 250

HP-9900:DIC, naphthol type epoxy resin, epoxide equivalent 274

NC-3000H: Japanese chemical drug, biphenyl epoxy resin, epoxide equivalent 294

SKE-1: Shang Kete, special epoxy resin, epoxide equivalent 120

SKE-3: Shang Kete, special epoxy resin, epoxide equivalent 120

(C) SMA resin

EF1000:SMA, styrene-maleic anhydride copolymer, Sartomer

EF40:SMA, styrene-maleic anhydride copolymer, Sartomer

EF60:SMA, styrene-maleic anhydride copolymer, Sartomer

EF80:SMA, styrene-maleic anhydride copolymer, Sartomer

(D) cyanate

CY-40: Wuqiao resin factory, DCPD type cyanate ester resin

PT60S:LONCZ, Novolac Cyanate Ester Resins

CE01PS: Jiangsu apocalypse, bisphenol A cyanate ester resin

CE01MO: Jiangsu apocalypse, bisphenol A cyanate ester resin

(E) phenolic resin

DOW92741: phosphorus-containing phenolic aldehyde, DOW Chemical

SEB-0904PM60: phosphorus-containing phenolic aldehyde, SHIN-A

SHN-1655TM65: phosphorus-containing phenolic aldehyde, SHIN-A

2812: linear phenolic resin, MOMENTIVE (South Korea)

(F) phosphonium flame retardant

SPB-100: big tomb chemistry, phosphine nitrile fire retardant, phosphorus content 13.4%

(G) promotor

2E4MZ:2- ethyl -4-methylimidazole, four countries' chemical conversion

DMAP:4- dimethylamino naphthyridine, wide Rong Huaxue

BICAT Z: zinc Isoocatanoate, The Shepherd Chemical Company

(H) filler

Fused silica (average grain diameter is 0.2 to 10 μm, 99% or more purity)

Table 1-3 is embodiment 1~14, the formula composition and its physical data of 4 comparative example 1~8 of table.

Table 1

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4	Embodiment 5
						P-AE1					10
P-AE2		20
						P-AE3	35
P-AE4			10	10
						P-AE5			10
EF1000	35				35
						EF40			40
EF60		50
						EF80				60
HP-9900					55
						NC-3000H		30	40	30
SKE-1	30
						SPB-100				10	10
2E4MZ
						DMAP	0.01	0.05	0.1	0.2	0.5
Ball silicon	0	25	25	25	300
						P%	3.49%	2.31%	2.10%	2.37%	2.44%
Tg(DMA)/℃	185	190	185	190	185
						Dk(10GHz)	4	4	3.9	3.8	4.2
Df(10GHz)	0.008	0.0075	0.0075	0.0075	0.0071
						Water imbibition/%	0.08	0.07	0.07	0.07	0.05
PCT/6h	OOO	OOO	OOO	OOO	OOO
						T288/min	> 60	> 60	> 60	> 60	> 60
Difficult to burn	V-0	V-0	V-0	V-0	V-0

Table 2

Table 3

Table 4

PCT/6h performance map target supplementary explanation: × to be layered plate bursting, O is not stratified plate bursting.

The test method of the above characteristic is as follows:

(1) glass transition temperature (Tg): being tested using DMA, is surveyed according to the DMA of IPC-TM-650 2.4.24 defined Method for testing is measured.

(2) it dielectric constant and dielectric loss factor: is tested according to SPDR method.

(3) humidity resistance (PCT) is evaluated: after the copper foil on copper-clad plate surface is etched, evaluating substrate；By substrate placement force In pot, after being handled 6 hours under the conditions of 120 DEG C, 105KPa, it is immersed in 288 DEG C of tin furnace, is recorded when substrate de-lamination plate bursting The corresponding time；It can terminate to evaluate when substrate also does not occur blistering or being layered in tin furnace more than 5min.

(4) T288: TMA instrument is used, is measured according to the T300 test method of IPC-TM-650 2.4.24.1 defined.

(5) it water imbibition: is measured according to the water imbibition test method of IPC-TM-650 2.6.2.1 defined.

(6) it anti-flammability: is carried out according to 94 standard method of UL.

It can be seen that the following from the data comparison of table 1-4:

Comparative example 1 and embodiment 3 compare, using made by ODOPB, SMA resin and halogen-free epoxy resin in comparative example 1 Copper-clad plate dielectric properties are poor, heat resistance and humidity resistance are poor, water absorption rate is high and poor fire；Comparative example 2 and embodiment 7 Compare, low using copper-clad plate Tg made by ODOPB, SMA resin and cyanate ester resin and halogen-free epoxy resin in comparative example 2, Water absorption rate height, heat resistance and humidity resistance are poor, and poor fire；Comparative example 3 and embodiment 12 compare, and make in comparative example 3 The height of the copper-clad plate water absorption rate made by ODOPB, SMA resin and phenolic resin and halogen-free epoxy resin, heat resistance and wet-heat resisting Property is poor；Comparative example 4 and embodiment 3 compare, using made by FRX3001 and SMA resin and halogen-free epoxy resin in comparative example 4 Copper-clad plate dielectric properties are poor, water absorption rate is high, heat resistance and humidity resistance are poor, and Tg is low, and poor fire；Comparative example 5 and reality It applies example 7 to compare, covers copper using made by FRX3001, SMA resin and cyanate ester resin and halogen-free epoxy resin in comparative example 5 Plate Tg is low, water absorption rate is high, heat resistance and humidity resistance are poor, and poor fire；Comparative example 6 and embodiment 12 compare, comparison Copper-clad plate water absorption rate made by FRX3001, SMA resin and phenolic resin and halogen-free epoxy resin is high in example 6, heat resistance and resistance to Humid is poor.

In addition, comparative example 7 and embodiment 5 are compared it is found that using content lower than in embodiment 5 in comparative example 7 When ester terminated phosphorous polymer, made by copper-clad plate dielectric properties it is poor；Comparative example 8 and embodiment 1 are compared Compared with it is found that in comparative example 8 using content be higher than embodiment 1 in ester terminated phosphorous polymer when, made by cover copper Plate Tg is low, heat resistance and humidity resistance are poor.

By the above results as can be seen that by the way that ODOPB and FRX to be replaced with to ester terminated phosphorous polymerization of the invention Object, and prepreg and laminate for printed circuits made of SMA resin and halogen-free epoxy resin etc. have up to 245 DEG C Glass transition temperature；Excellent dielectric properties, water absorption rate control within the scope of 0.06-0.09%；High-fire resistance；Excellent is resistance to Humid and good technique processability；Excellent flame retarding efficiency can reach UL94 V-0.

As described above, compared with general laminate, made of halogen-free thermosetting resin composite provided by the present invention Prepreg and laminate for printed circuits have high glass-transition temperature, excellent dielectric properties, low water absorption, high heat resistance Property, excellent humidity resistance and good technique processability, and it is able to achieve halogen-free flameproof, reach UL94 V-0.

The above, only presently preferred embodiments of the present invention for those of ordinary skill in the art can bases Technical solution of the present invention and technical concept make other various corresponding changes and modifications, and all these change and modification are all It should belong to the range of the claims in the present invention.

Claims

1. a kind of compositions of thermosetting resin, which is characterized in that include epoxy resin, curing agent and ester terminated phosphorous poly- Close object；

The curing agent includes at least SMA resin；

Shown in the ester terminated phosphorous polymer structural formula such as formula (I)；

Wherein, n₁For 1~20 integer；

Wherein, R₁For any one in phenyl, naphthalene, xenyl, the linear or branched alkyl group containing carbon number 1~4；

Wherein, Ar₁For In any one；

Wherein, Ar₂ForIn any one；

Wherein, n₂For 0~5 integer；n₃For 0~7 integer；

Wherein, R₂For any one in the linear or branched alkyl group containing carbon number 1~4；

The epoxy resin accounts for epoxy resin in the compositions of thermosetting resin, curing agent and ester terminated phosphorous polymerization The 30%~55% of object total weight；

The SMA resin accounts for epoxy resin in the compositions of thermosetting resin, curing agent and ester terminated phosphorous polymerization The 35%~60% of object total weight；

The ester terminated phosphorous polymer accounts for epoxy resin in the compositions of thermosetting resin, curing agent and ester group envelope The 10%~35% of the phosphorous polymer total weight at end.

2. compositions of thermosetting resin as described in claim 1, which is characterized in that the SMA resin is styrene and Malaysia Acid anhydrides is copolymerized to obtain in the ratio of 1:1~8:1.

3. compositions of thermosetting resin as claimed in claim 1 or 2, which is characterized in that the curing agent also includes cyanate Resin and/or bismaleimide-triazine resin.

4. compositions of thermosetting resin as claimed in claim 3, which is characterized in that the cyanate ester resin and/or span come Acid imide-cyanate resin accounts for 2%~20% of epoxy resin and curing agent total weight in the compositions of thermosetting resin.

5. compositions of thermosetting resin as claimed in claim 1 or 2, which is characterized in that the curing agent also includes phenolic aldehyde tree Rouge.

6. compositions of thermosetting resin as claimed in claim 5, which is characterized in that the phenolic resin accounts for the thermosetting property tree The 2%~20% of epoxy resin and curing agent total weight in oil/fat composition.

7. compositions of thermosetting resin as claimed in claim 1 or 2, which is characterized in that the compositions of thermosetting resin is also Include filler and/or promotor.

8. the compositions of thermosetting resin as described in one of claim 1~7 is in resin sheet, resin laminated metal foil, preimpregnation Application in material, laminate, metal-clad laminate or printed wiring board.