CN1267314A

CN1267314A - Flame retardant epoxy resin composition

Info

Publication number: CN1267314A
Application number: CN98808244A
Authority: CN
Inventors: J·甘; A·古德森; R·A·凯尼格; J·P·埃弗雷特
Original assignee: Dow Chemical Co
Current assignee: Dow Chemical Co
Priority date: 1997-06-26
Filing date: 1998-06-25
Publication date: 2000-09-20
Also published as: EP0991711A1; WO1999000451A1; GB9713526D0; KR20010020528A; JP2002506480A

Abstract

A novel epoxy resin having reduced flammability is presented. Phosphonic acid esters in an amount of from 0.2 to 5 percent phosphorous in epoxy resin are employed. Electrical laminate circuit boards having reduced flammability may be made from these compositions.

Description

Fire retarded epoxy resin composition

The present invention relates to contain the curable formulations system of Resins, epoxy, be particularly useful for making the formula system of printed-wiring board (PWB) with veneer sheet.

Known and to have made electronic shell pressing plate and other matrix materials with fabric reinforcement and the resin matrix that contains epoxy group(ing).The example of usability methods has following steps usually:

(1) by the combination of roller coat, dip-coating, spraying, other known technology and/or these technology, the formula system that will contain epoxy group(ing) is applied to base material.Typically, base material is to weave or non-woven fibre mat, for example contains the pad of glass fibre.

(2) at a certain temperature, heat the base material of impregnated mistake, this temperature should be enough to remove the solvent in the epoxy systems, and not necessarily makes epoxy systems partly solidified, and impregnated base material is just by " B stageization ", and impregnated like this base material is just handled easily." B stageization " step is carried out under 90 ℃ to 210 ℃ usually, and be 1 minute to 15 minutes heat-up time.After stage, the base material of impregnated mistake is referred to as prepreg through B.In the ordinary course of things, be 100 ℃ for the matrix material Heating temperature, be 130 ℃～200 ℃ for electronic shell pressing plate Heating temperature.

(3), with one or more layers prepreg and one or more layers electro-conductive material, stack up, be alternately shop layer as Copper Foil if wish to make the electronic shell pressing plate.

(4) the synergetic prepreg of compacting under high temperature and high pressure, the time of compacting should be enough to make resin solidification and form layers pressing plate.Usually between 100 ℃ to 230 ℃, the most frequently used temperature range is between 165 ℃ to 190 ℃ to temperature laminated into type.Process laminated into type also can be divided into two stages or more the multistage carry out, for example the fs is between 100 ℃ to 150 ℃, subordinate phase is between 165 ℃ to 190 ℃.Pressure normally at 50 newton/square centimeters between 500 newton/square centimeters.Process laminated into type was carried out between 1 minute to 200 minutes usually, and the most frequent is to finish between 90 minutes at 45 minutes.Process laminated into type can be chosen in the time of under the higher temperature, lacking and finish (as the continuous laminating method of forming), perhaps finishes (as the pressing process of less energy-consumption) in the time of under lower temperature, growing.

(5) not necessarily, the copper clad laminate that obtains can be heated for some time under high temperature and environmental stress, carry out aftertreatment.Post-processing temperature normally carries out between 120 ℃ to 250 ℃.Normally 30 minutes to 12 hours aftertreatment time.

Usually when preparation contains the veneer sheet of epoxy group(ing), in composition epoxy resin, add various additives, to improve the flame retardant properties of obtained veneer sheet.Existing many kinds of flame-retardant additives are halogen-containing flame-retardant additives at the most widely used commercial additive still, and as the tetrabromo dihydroxyphenyl propane, perhaps the diglycidyl ether of dihydroxyphenyl propane and tetrabromo dihydroxyphenyl propane react prepared Resins, epoxy.General in order to reach required flame retardant rating (the V-0 level of the testing method UL94 of standard " Underwriters Laboratory (Underwriters Laboratory) "), the required content of this compounds should be able to provide the bromine content that accounts for the 10wt%～25wt% of total polymer weight in the goods.

Although halogen-containing flame-retardant additive is effective, from the viewpoint to environment, the someone thinks that they are undesirable, and in recent years, not halogen-containing epoxy-resin systems can satisfy fire-retardant requirement, and causes people's interest day by day.

Proposed to replace halogenated fire-retardants (for example EP-A-0384939, EP-A-0384940, EP-A-0408990, DE-A-4308184, DE-A-4308185, DE-A-4308187, WO-A-96/07685, and WO-A-96/07686) with phosphine flame retardant.In these systems, phosphonium flame retardant generates two senses or polyfunctional epoxy resin through pre-reaction, and this makes the Resins, epoxy price relatively costly.

Phosphonic acid ester is (as Amgard at the industrial fire retardant material that obtains easily ^TMV19 and Amgard ^TMP45 is provided by Britain Albright and Wilson company limited).These phosphonic acid esters can be solid or liquid.Phosphonic acid ester and epoxy resin compatibility that alkyl and aryl replace.Especially phosphonic is rudimentary (is C ₁-C ₄) alkyl ester, owing to contain the phosphoric of higher proportion, can give the resin that added flame retardant properties preferably, therefore have certain application value.But the inventor finds, in the manufacturing of electronic circuit veneer sheet, they also are not suitable as the substitute of halogenated flame in the Resins, epoxy, because after adding is enough to produce the consumption of necessary flame retardant properties, can make the easier absorption moisture of Resins, epoxy after the curing.The suction temperature of solidified veneer sheet is extremely important, because the higher veneer sheet of moisture content when immersing in the liquid flux down for about 260 ℃, is easy to generate bubble and scraps, is a typical process making printed-wiring board (PWB) and immerse liquid flux.

EP-A-0754728 has narrated the production process of fire retarding epoxide resin system, is about to Resins, epoxy and phosphonic acid ester and mixes, and make in the resin after phosphonic acid ester mixes curing.This piece bibliography is pointed out, satisfies the requirement of UL 94 V-0 in order to make resin system, and needs are the phosphor-included additive of (above 18wt%) in a large number.

We find now, by adopting the relatively low phosphonate fire retardant (making the phosphorus that contains 0.2wt%～5wt% in the solid resin) of content, specific combination in conjunction with promotor and catalyzer, and in preferred embodiments, also will be in conjunction with the Resins, epoxy of particular type, can produce the Resins, epoxy that meets flame-retardant standard, and not need halogen-containing fire retardant, perhaps use the halogen-containing flame retardant that many littler at least than conventional amount used.With regard to promotor and catalyzer self, they are known, but the phosphonate fire retardant of they and lower aq combines use, to make existing flame retardant resistance preferably the composition of enough low water absorbables is arranged again, yet there are no report up to now.

According to the present invention, a kind of fire retarded epoxy resin composition that is no more than the 10wt% halogen that contains is provided, it contains:

A) Resins, epoxy,

B) phosphonic acid ester, its consumption is provided at the phosphorus of 0.2wt%～5wt% in the composition,

C) nitrogenous linking agent, its amine functionality is at least 2, and its consumption is to make 10%～80% of the required stoichiometric amount of epoxy resin cure,

D) catalyzer, its consumption is 0.1wt%～3wt%, it can accelerate the speed of response of phosphonic acid ester and Resins, epoxy, can also accelerate the curing speed of Resins, epoxy and linking agent and not necessarily,

E) Lewis acid, its consumption are at most every mol catalyst 2 moles of Lewis acids.

The phosphonic acid ester of the Shi Yonging ester class that preferably molecular formula is following in the present invention:

R wherein ¹Be C ₁～C ₃Alkyl, R ⁴Be C ₁～C ₃Alkylidene group, R ²And R ³Each is C naturally ₁～C ₃Alkyl or C ₆～C ₁₀Aryl, perhaps R ²And R ³Represent glycol or residue of polyol altogether.

Preferred phosphonic acid ester for example is methane phosphonic acid and polyol, as the ester of two pure and mild polyvalent alcohols etc.This polyol phosphonic acid ester can have paradigmatic structure and/or ring texture.

Specific preferred embodiment is the polymkeric substance with following repeating unit And/or have a following ring texture: N is 2～10, R ⁵Be C ₁～C ₃Alkylidene group or glycol or residue of polyol,

R ⁶It is for example residue of glycerol or TriMethylolPropane(TMP) of trivalent alcohol.

Preferred phosphonic acid ester is that the methyl adjacent with phosphorus atom or the ester of methylene radical are arranged.Preferred phosphonic acid ester has following molecular formula:

In order to obtain satisfied water absorption resistance energy, importantly, based on the gross weight of composition epoxy resin, the consumption of phosphonic acid ester is 1wt%～18wt%, and preferably 4wt%～15wt% is more preferably 7wt%～15wt%.The consumption of phosphonic acid ester preferably is provided at the phosphorus content of 0.2wt%～5wt% in the composition, and preferred phosphorus content is 1wt%～5wt%.

Composition of the present invention contains catalyzer, and it can accelerate the speed of response of phosphonic acid ester and Resins, epoxy, can also improve the curing speed of Resins, epoxy.

Catalyzer can contain the single catalyst composition, can either accelerate the speed of response of phosphonic acid ester and Resins, epoxy, can improve the curing speed of Resins, epoxy again.Perhaps, catalyzer is the combination of multiple composition, and in resin solidification, each composition of catalyzer plays the katalysis bigger than another composition to an aspect of resin solidification wherein.

The example of the catalyzer that is suitable for comprises the compound that contains amine, phosphine or An, Phosphonium, clock or sulfonium structure division.Particularly preferred catalyzer is a nitrogen-containing heterocycle compound.Particularly when catalyzer is amine, also preferably use Lewis acid, especially the nitrogen heterocyclic ring amine.Preferably, per molecule catalyzer (being different from linking agent) on average contains and is no more than an about active hydrogen structure division.The active hydrogen structure division comprises the hydrogen atom on amido, phenolic hydroxyl group or the carboxylic acid group.For example, preferred amine and phosphine structure division are tertiary amine or phosphine structure division in the catalyzer, and preferred An is with the Phosphonium structure division is that quaternary ammonium is with the Phosphonium structure division.

In the tertiary amine that can be used as catalyzer, preferably have the monoamine or the polyamine of open chain or ring texture, all hydrogen atoms are replaced by suitable substituents in the amine, as hydrocarbyl group, preferably aliphatics, alicyclic or aromatic group.

The example of these amine has methyldiethanolamine, triethylamine, Tributylamine, dimethyl benzylamine, triphenylamine, thricyclohexyl amine, pyridine and quinoline.Preferred amine compound has trialkylamine, tricyclic alkyl amine and triarylamine, and for example triethylamine, triphenylamine, three-(2, the 3-Dimethylcyclohexyl) amine, and alkyl two alkanolamines as methyldiethanolamine, also have trialkanolamine, as trolamine.Particularly preferably be the more weak tertiary amine of alkalescence, for example concentration be in the aqueous solution of 1M its pH value less than 10 amine.Especially preferred tertiary amine catalyst is benzyl dimethyl amine and three-(dimethylaminomethyl) phenol.

Be suitable for use as the nitrogen heterocyclic of catalyzer, the example is included in described in the US-A-4925901.For example comprise imidazoles, benzoglyoxaline, imidazolidine, tetrahydroglyoxaline, oxazole, pyrroles, thiazole, pyridine, pyrazine, morpholine, pyridazine, pyrimidine, tetramethyleneimine, pyrazoles, quinoxaline, quinazoline, phthalazines, quinoline, purine, indazole, indoles, indoles amine, azophenlyene, phenarsazine, thiodiphenylamine, pyrroline, indoline, piperidines, piperazine and their combination at this preferred heterocyclic secondary that can be used and tertiary amine or nitrogenous catalyzer.Particularly preferably be alkyl substituted imidazole; 2,5-chloro-4-ethyl imidazol(e); With the phenyl substituted imidazole; And their mixture.N-Methylimidazole more preferably; Glyoxal ethyline; 2-ethyl-4-methylimidazole; 1,2 dimethylimidazole; And glyoxal ethyline.Especially preferred is the 2-phenylimidazole.

Preferably the nitrogen heterocyclic that is used in combination with the Lewis acid examples for compounds of powering is at EP-A-526488, described in EP-A-0458502 and the GB-A-9421405.3.In these reference, think that Lewis acid is an inhibitor, speed of response reduces because it makes original chemical.The lewis acidic example that is suitable for comprises halogenide, oxide compound, oxyhydroxide and the alkoxide of zinc, tin, titanium, cobalt, manganese, iron, silicon, aluminium and boron, as the Lewis acid of boron and the lewis acidic acid anhydrides of boron, such as boron oxide compound, boric acid alkyl ester, halogenation boron, the zinc halide (as zinc chloride) of the boroxin (as the trimethoxy boroxin) of boric acid, metaboric acid, nonessential replacement, nonessential replacement, and relative other the more weak Lewis acids of conjugate base.Preferably, Lewis acid is the Lewis acid of boron and Louis's acid anhydrides of boron, the boroxin of boric acid, metaboric acid, nonessential replacement (such as trimethoxy boroxin, trimethylboroxin, triethyl boroxin) for example, the oxide compound of the boron of nonessential replacement, or boric acid alkyl ester.Most preferred Lewis acid is a boric acid.

When making epoxy resin cure, these Lewis acids are very effective when above-mentioned nitrogen-containing heterocycle compound is used in combination.Especially in solidification process, they are combined as a whole phosphonic acid ester and Resins, epoxy.

In order to prepare the curing catalysts composition, Lewis acid and amine can mix before the adding system, also can mix on the spot with catalyzer.

Preferred Lewis acid consumption is that every mole of nitrogen heterogeneous ring compound has 0.1 mole of Lewis acid at least, and preferred, every mole of nitrogen heterogeneous ring compound has 0.3 mole of Lewis acid at least.

Every mol catalyst has and is no more than 3 moles Lewis acid in the preferred system, and more preferably every mol catalyst has and is no more than 2 moles Lewis acid.Total consumption of catalyzer accounts for the 0.1wt%～3wt% of composition gross weight, and preferred consumption is 0.1wt%～2wt%.

All catalystic materials mentioned above, both to the reaction of phosphonic acid ester and Resins, epoxy, the curing reaction to Resins, epoxy played katalysis to a certain extent again.But in the curing reaction of the reaction of phosphonic acid ester and Resins, epoxy and Resins, epoxy, (1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene (DBU) tends to bigger katalysis is played in the reaction of phosphonic acid ester and Resins, epoxy.

The amine functionality of nitrogenous linking agent is at least 2.In a lot of reference, the multifunctional linking agent that is suitable for is described to some extent, as " polymer science and engineering encyclopedia ", the 6th volume, " Resins, epoxy ", the 348th～356 page of (J.Wiley ﹠amp; Sons 1986).The example of the nitrogenous linking agent that is suitable for comprises polyamines, polymeric amide, sulfanilic amide, diaminodiphenylsulfone(DDS) and diaminodiphenylmethane.Preferred cross-linking agents is a Dyhard RU 100.

The consumption of nitrogenous linking agent be that epoxy content solidifies required stoichiometric amount in the Resins, epoxy that makes in the system 10%～80%.

The total content of nitrogen in the preferred compositions (comprise the nitrogen element that comes from any nitrogenous compound, any nitrogenous compound can component part catalyzer, the perhaps precursor monomer of Resins, epoxy) is 1wt%～8wt%.

Preferably, the stoichiometric calculation proportioning with Resins, epoxy and nitrogenous linking agent contains the Resins, epoxy of Duoing than stoichiometry in the system.(for this reason, the per molecule Dyhard RU 100 has been considered to 6 cure site.) like this, every epoxy equivalent (weight) contains and is no more than 0.8 normal nitrogenous linking agent in the system, preferably is no more than 0.75 equivalent, more preferably is no more than 0.6 equivalent, most preferably is no more than 0.5 normal nitrogenous linking agent.When multifunctional linking agent is Dyhard RU 100, preferably, contain the Dyhard RU 100 of 0.65wt% at least in the system, preferred consumption is 1.9wt% at least.Preferred Dyhard RU 100 consumption is to be no more than 5.2wt%, and preferred consumption is to be no more than 2.6wt%.

In the present invention, employed Resins, epoxy per molecule on average contains more than 1 epoxide group, and preferably at least 1.8, at least 2 epoxide groups more preferably.From the wideest scope of the present invention, Resins, epoxy can be to contain more than 11, any saturated or undersaturated aliphatics of 2-epoxide group, alicyclic, aromatic series or heterogeneous ring compound.The example of heterocyclic ring oxygen compound is diepoxy glycerine glycolylurea or three epoxy glycerite isocyanuric acid esters (TGIC).

Preferably, Resins, epoxy does not have low alkyl group aliphatics substituting group, for example the glycidyl ether of phenol linear phenolic resin, the perhaps glycidyl ether of bisphenol-f.

Most preferred Resins, epoxy is epoxidized phenolic novolae (be meant the epoxidation linear phenolic resin sometimes, this term comprises epoxy phenol resol and epoxy cresol novolac resin).The general molecular formula of this compound is as follows: general formula I I:

Wherein " R " is the alkyl of hydrogen atom or C1-C3, and as methyl, " n " is 0 or 1～10 integer.

Epoxidized phenolic novolae (comprising the epoxy cresol linear phenolic resin) obtains industrial being easy to, and for example trade name is D.E.N. ^TM, Quatrex ^TM, Tactix ^TM, (trade mark of DOW chemical company).Industrial materials generally include the mixture of the various materials with top molecular formula.A facilitated method that characterizes said mixture is to quote the mean value n ' of the n value of various materials.N ' the value that is used for preferred epoxidized phenolic novolae of the present invention is from about 2.05 to about 10, preferred n ' value from about 2.5 to about 5.

Preferred Resins, epoxy is the epoxy compounds (for example above-described epoxy compounds) that contains at least 2 epoxide groups and the reaction product of chainextender.The chain extension monomer can be the phenols chainextender, and per molecule phenols chainextender on average contains more than one, is no more than three phenolic hydroxyl groups.Preferred this class phenols chainextender on average contains 1.8～2.1 phenolic hydroxyl groups.More preferably, per molecule phenols chainextender on average contains 2 phenolic hydroxyl groups of having an appointment.Preferred phenols chainextender is a dihydric phenol.Preferably, before the composition system that contains fire retardant, solidifying agent and catalyzer formed, chainextender and epoxy compounds reaction formed Resins, epoxy.But, also chainextender and epoxy resin compound can be added composition, form Resins, epoxy on the spot.

Preferred Resins, epoxy is solid under 20 ℃, and is for example defined according to the Mettler softening temperature testing method of ASTM D3104 and DIN51920, is that softening temperature is 50 ℃ or higher Resins, epoxy.With regard to itself, the phenols chainextender can be the reaction product of dibasic alcohol and epoxy compounds.

For example, it can be dibasic alcohol or the compound that contains two phenolic group, with the glycidyl ether of phenol linear phenolic resin or with the reaction product of the glycidyl ether of Bisphenol F.Preferably, the carbon atom less than 50% in the chainextender is to be positioned on the aliphatic group, more preferably less than 30%, and most preferably 0%.

The example of the phenols chainextender of particularly suitable has Resorcinol, pyrocatechol, Resorcinol, bis-phenol, dihydroxyphenyl propane, bisphenol-ap (1, two (4-the hydroxy phenyl)-1-diphenylphosphino ethanes of 1-), Bisphenol F and bis-phenol K.

But preferred chainextender is a nitrogen containing monomer, for example isocyanic ester, amine or acid amides.

Preferred nitrogenous chainextender comprises polyisocyanate compound, and it forms epoxy-capped De Ju oxazolidone, and this reports in US-A-5112932 to some extent.Preferably, in the present invention the polyisocyanate compound of Shi Yonging is diphenylmethanediisocyanate (MDI).Preferably, MDI can use the form that obtains easily industrial, and pure 4-4 is arranged, MDI, the mixture of isomers and sense homologue (generally being meant " polymeric MDI ").Also can use isocyanate compound in the present invention, for example tolylene diisocyanate (TDI) and isomers thereof.

Nitrogenous chainextender for example also can be, contains the compound of amido, perhaps contains the compound of amino amides, and they form epoxy-capped amine compound, have two can with the N-H key of epoxide group reaction.Be applicable to that amino-contained compound of the present invention comprises, for example, the general molecular formula is R-NH ₂Unary primary amine, wherein R is alkyl, cycloalkyl or aromatic structure part; The general molecular formula is R-NH-R '-NH-R " binary secondary amine, wherein R, R ', R " be alkyl, cycloalkyl or aromatic structure part; And heterocycle binary secondary amine, two N atoms or one of them are the parts of nitrogen-containing heterocycle compound, for example:

Reason for reactive behavior, and for better gate ring oxygen groups and two functional amines' antedating response, preferably, amine groups such as binary secondary amine, binary primary amine with space steric effect is preferably used, for example 2,6-dimethylcyclohexylamine or 2,6-xylidine (1-amino-2,6-dimethyl benzene).

In the present invention, can be used as the derivative that the amino amides compound for example comprises carboxylic acid amide that contains of chainextender, and the derivative that has the sulfonic acid amides of a primary amine groups or two secondary amine in addition.The preferred embodiment of these compounds has amino-aryl carboxylic acid acid amides and amino-aryl sulfonic acid acid amides.For example, preferably this compounds has sulfanilic amide (4-amido phenylamino sulphonyl) and anthranilamide (2-amido benzamide).

Preferably, the chainextender consumption is the 5wt%～30wt% of Resins, epoxy.

Composition of the present invention also contains one or more auxiliary flame retardants, red phosphorus for example, perhaps liquid or solid P contained compound, such as ammonium polyphosphate, phosphite, or 9, the 10-dihydro-9-oxy is mixed-phospho hetero phenanthrene-10-oxide compound (HCA), phosphine piperazine (phosphazene), contain nitrogen combustion inhibitor and/or compatibility agent, trimeric cyanamide for example, urea, cyanamide, guanidine, cyanuric acid, the derivative of isocyanuric acid and these nitrogenous compounds, halogenated fire-retardants, halogenated epoxy resin (especially brominated epoxy resin), the synergistic system of phosphorous-halogen, it contains organic hydrochlorate, the inorganic metal hydrate, the compound of boron or antimony.The example of the auxiliary flame retardant that is suitable for is introduced in one piece of paper in " fire retardant-101 substantially dynamically-create with the effort in past the opportunity of tomorrow " to some extent, fire retardant chemistry association, Baltimore Marriot Inner Harbour Hotel, BaltimoreMaryland, 24-27 day in March, 1996.When having phosphorous auxiliary flame retardant in addition in the system, its consumption makes usually that the total content of phosphoric is 0.2wt%～5wt% in the composition epoxy resin.

Can all the components be mixed according to any order, prepare composition of the present invention.Preferably, composition of the present invention can prepare in accordance with the following methods: at first preparation contains first composition of Resins, epoxy, and preparation contains second composition of curing catalysts then.Also contain phosphonic acid ester and nitrogenous linking agent in first composition or second composition.Other all the components can exist in same composition, or some compositions are in first composition, and other compositions are in second composition.First composition mixes with second composition then, solidifies the back and generates the Resins, epoxy with flame retardant properties.

In following specific embodiment, many preferred embodiments of the present invention are illustrated.Preparation method A has the general production process of the Resins, epoxy (a) of higher nitrogen content

Under nitrogen protection; in the reactor that is equipped with electric mixer, air and nitrogen inlet, thief hole, condenser and thermopair, be that 3.6 industrial producible epoxidized phenolic novolae (D.E.N.438) is heated to 100 ℃ with the functionality of 92.5 weight parts.(the total consumption with epoxidized phenolic novolae in the product and isocyanic ester is a benchmark) adds 1 of 1500ppm, 8-diazabicyclo (5,4,0) 11 carbon-7-alkene (catalysts, AMICURE BU-E ^TM, originate in Anchor), mixture is heated to 130 ℃～140 ℃.MDI (ISONATE with 7.5 parts ^TM, DOW chemical company) add in the Resins, epoxy by other funnel gradation.Under exothermic heat of reaction, temperature of charge rises at least 150 ℃.Behind reinforced the end, the temperature of reaction mixture rises to 165 ℃, remains on this temperature, reaches re-set target up to the epoxy equivalent (weight) of MDI and epoxidized phenolic novolae multipolymer.Solid resin further uses methylethylketone and propylene glycol monomethyl ether (50/50) to be diluted to the solution that solid content is 80wt%, is cooled to room temperature then.The general production process of preparation method B curing agent solution

Under nitrogen protection, in the reactor that is equipped with motor machine agitator, air and nitrogen inlet, thief hole, condenser and thermopair, (Amgard P45 or AmgardV19) is heated to 120 ℃ with phosphonate fire retardant.Dyhard RU 100 and sulfanilic amide are added in the mixture, stir, after forming uniform mixture.In mixture, add propylene glycol monomethyl ether, make in the solution that solid content is 80wt%.In addition, also can before joining insoluble flame-retardant additive in the resin solution, it be added curing agent solution.The production process of polyepoxy compound/polyisocyanates/HCA multipolymer (" Resin A ")

Under about 160 ℃, with 9 of 3.77wt%, 10-two-hydrogen-9-oxa--phospho hetero phenanthrene-10-oxide compound (HCA) joins in the prepared solid epoxy of preparation method A of 96.23wt%, and insulation reaches 232 re-set target up to epoxy equivalent (weight).Solid cooled to about 130 ℃, is added methylethylketone and propylene glycol monomethyl ether (50/50), and forming solid content is the solution of 75 wt%.

The boric acid that the preparation of embodiment 1-" resin B " will be dissolved in methyl alcohol adds in the multipolymer of D.E.N.438/MDI.After mixture mixes fully, phosphonic acid ester (Amgard V19) fire retardant is added in the resin.The glyoxal ethyline catalyzer is added in the resin solution.At last, add Dyhard RU 100 (being dissolved in the 7.5wt% solution in the mixture of 50/50 dimethyl formamide and propylene glycol monomethyl ether).In following table, listed prescription moiety, system performance and by its preimpregnation material that makes and the performance of veneer sheet.

Resin A and C are to the preparation of N

Epoxy resin solution, curing agent solution, catalyst solution (the normally methanol solution of 50wt%), and nonessential boric acid solution at room temperature mixed 15 minutes with mechanical stirrer, formed uniform mixture.Add the solvent (methylethylketone) that replenishes, adjust viscosity to 30～50 second (No. 4 Ford cup) of varnish.With the varnish age overnight.

Varnish is used for impregnated glass fiber pad (model is Nr.7628/36, uses the amino containing silane surface treatment, is produced by the Porcher SA of France), adopts Caratsch pilot scale dip coater (3 meters long).The temperature of warm air is 160 ℃～170 ℃ in the baking oven.At table 1, in 2,3,4, summarized the performance of clear coat composition, dip coater condition, preimpregnation material and veneer sheet.

As follows, the IPC testing method of employing is electronic shell pressing plate industrial standards (Evanston, Illinois 60203 for the interconnected and encapsulation association of electronic circuit, 3451 Church Street).

Method	IPC-testing method numbering:
Method	IPC-testing method numbering:	Reactive behavior (varnish)	IPC-TM-650-5.1.410
170 ℃ of static gel times, second	IPC-TM-650-2.3.18	Reactive behavior (varnish)	IPC-TM-650-5.1.410
170 ℃ of static gel times, second	IPC-TM-650-2.3.18	Mil flows, wt.%	IPC-TM-650-2.3.17
Second-order transition temperature, ℃	IPC-TM-650-2.4.25	Mil flows, wt.%	IPC-TM-650-2.3.17
Second-order transition temperature, ℃	IPC-TM-650-2.4.25	The Copper Foil stripping strength	IPC-TM-650-2.4.8
The NMP-absorptivity	DOW testing method C-TS-AA-1012.00	The Copper Foil stripping strength	IPC-TM-650-2.4.8
The NMP-absorptivity	DOW testing method C-TS-AA-1012.00	Steaming and decocting under high pressure experiment, water regain wt.% and the percentage ratio by 260 ℃ of solder bath	? ? IPC-TM-650-2.6.16
UL94 combustibility	IPC-TM-650-2.3.10		? ? IPC-TM-650-2.6.16

Table 1 composite formula, character, preimpregnation material and veneer sheet performance

Form the solid weight umber	????B	????C	????D	????E
Form the solid weight umber	????B	????C	????D	????E	The resin that preparation method A produces	????86	????84	????84
Epoxidized phenolic novolae, functionality are 3.6				? ????85	The resin that preparation method A produces	????86	????84	????84
Epoxidized phenolic novolae, functionality are 3.6				? ????85

					Amgard?V19	????14		????14
Amgard?P45		????14		????14	Amgard?V19	????14		????14
Amgard?P45		????14		????14	Dyhard RU 100 (being dissolved in Amgard V19 or Amgard P45)		2 (being dissolved in Amgard P45)	2 (being dissolved in Amgard V19)	2 (being dissolved in Amgard P45)
B					Dyhard RU 100 (being dissolved in Amgard V19 or Amgard P45)		2 (being dissolved in Amgard P45)	2 (being dissolved in Amgard V19)	2 (being dissolved in Amgard P45)
B					Boric acid	????1	????0.3		????-
The 2-phenylimidazole		????1.7	????2	????1	Boric acid	????1	????0.3		????-
The 2-phenylimidazole		????1.7	????2	????1	Glyoxal ethyline	????1
The solvent that replenishes		????MEK	????MEK	????MEK	Glyoxal ethyline	????1
The solvent that replenishes		????MEK	????MEK	????MEK	Dyhard RU 100 solution (7.5wt%)	? ????1
The varnish characteristic					Dyhard RU 100 solution (7.5wt%)	? ????1
The varnish characteristic					Viscosity (Ford cup 4#), second	????76	????38	????126	????36
Reactive behavior, 170 ℃ 150 ℃ of second gel times	? ????85	? ????102 ????242	? ????151	? ????109 ????322	Viscosity (Ford cup 4#), second	????76	????38	????126	????36
Reactive behavior, 170 ℃ 150 ℃ of second gel times	? ????85	? ????102 ????242	? ????151	? ????109 ????322	Dip coater condition oven temperature, ℃ pulling speed, rice/minute	? ????185 ????2.3	? ????168 ????1.4	? ????152 ????1.1
Preimpregnation material characteristic						? ????185 ????2.3	? ????168 ????1.4	? ????152 ????1.1
Preimpregnation material characteristic					Resin content, wt%	????41	????43.4	????45	????42.6
170 ℃ of static gel times, second	Fusion	????10	????14	????15	Resin content, wt%	????41	????43.4	????45	????42.6
170 ℃ of static gel times, second	Fusion	????10	????14	????15	The Mil .wt% that flows	????10	????10.5	????15	????15.3
The veneer sheet performance					The Mil .wt% that flows	????10	????10.5	????15	????15.3
The veneer sheet performance					The veneer sheet curing cycle	1 hour, 170 ℃ 1 hour, 230 ℃	1 hour, 170 ℃ 1 hour, 230 ℃	100 minutes 200 ℃ 90 minutes 230 ℃	1 hour, 170 ℃ 1 hour, 230 ℃
Veneer sheet thickness, mm	????1.4-1.5	????1.52-1.57	????1.7-1.8	????1.47-1.70	The veneer sheet curing cycle	1 hour, 170 ℃ 1 hour, 230 ℃	1 hour, 170 ℃ 1 hour, 230 ℃	100 minutes 200 ℃ 90 minutes 230 ℃	1 hour, 170 ℃ 1 hour, 230 ℃
Veneer sheet thickness, mm	????1.4-1.5	????1.52-1.57	????1.7-1.8	????1.47-1.70	Second-order transition temperature-Tg1/2, ℃	????158/159	????158/162	????149/146	Do not measure
Steaming and decocting under high pressure experiment, the percentage ratio of water regain wt.%/by 260 ℃ of solder bath	Wt%/% passes through	Wt%/% passes through	Wt%/% passes through	Wt%/% passes through	Second-order transition temperature-Tg1/2, ℃	????158/159	????158/162	????149/146	Do not measure
	Wt%/% passes through	Wt%/% passes through	Wt%/% passes through	Wt%/% passes through	30 minutes	????0.38/100	No data/100	????0.53/100
40 minutes					30 minutes	????0.38/100	No data/100	????0.53/100
40 minutes					50 minutes	????0.53/100
60 minutes		????0.64/100		????0.60/100	50 minutes	????0.53/100
60 minutes		????0.64/100		????0.60/100	Burning total time, second	????69&35	????36	????30	????46
UL94	????V-1&V-0	????V-0	????V-0	????V-0	Burning total time, second	????69&35	????36	????30	????46

Table 2 composite formula, performance, preimpregnation material and veneer sheet performance

Form the solid weight umber	????F	????G	Resin A
Form the solid weight umber	????F	????G	Resin A	The resin that preparation method A produces	????79.5	????83.5
The resin SANKO/HCA that preparation method A produces			????81.5	The resin that preparation method A produces	????79.5	????83.5
The resin SANKO/HCA that preparation method A produces			????81.5	Amgard?P45	????14	????14	????12
Dyhard RU 100 (being dissolved in Amgard P45)		????2		Amgard?P45	????14	????14	????12
Dyhard RU 100 (being dissolved in Amgard P45)		????2		Sulfanilic amide (being dissolved in Amgard P45)	????6		????6
Boric acid	????0.5	????0.5	????0.5	Sulfanilic amide (being dissolved in Amgard P45)	????6		????6
Boric acid	????0.5	????0.5	????0.5	The 2-phenylimidazole	????2.0	????2.0	????2.0
The solvent that replenishes	????MEK	????MEK	????MEK	The 2-phenylimidazole	????2.0	????2.0	????2.0
The solvent that replenishes	????MEK	????MEK	????MEK	The varnish characteristic
Viscosity (Ford cup 4#), second	????45	????39	????45	The varnish characteristic
Viscosity (Ford cup 4#), second	????45	????39	????45	Reactive behavior. 170 ℃ 150 ℃ of second gel times	? ????90 ????240	? ????87 ????220	? ????132 ????---
Dip coater condition oven temperature, ℃ pulling speed, rice/minute	? ????163 ????1.2	? ????163 ????1.1	? ????161 ????0.7	Reactive behavior. 170 ℃ 150 ℃ of second gel times	? ????90 ????240	? ????87 ????220	? ????132 ????---
	? ????163 ????1.2	? ????163 ????1.1	? ????161 ????0.7	Preimpregnation material characteristic
Resin content, wt%	????45	????44	????45	Preimpregnation material characteristic
Resin content, wt%	????45	????44	????45	170 ℃ of static gel times, second	????8	????10	????24
The Mil .wt% that flows	????13	????15	????21	170 ℃ of static gel times, second	????8	????10	????24
The Mil .wt% that flows	????13	????15	????21	The veneer sheet performance
The veneer sheet curing cycle	90 minutes 190 ℃			The veneer sheet performance
The veneer sheet curing cycle	90 minutes 190 ℃			Veneer sheet thickness, mm	????1.6-1.7	????1.6-1.8	????1.57-1.70
Second-order transition temperature-Tg1/2, ℃	????160/166	????161/167	????157/160	Veneer sheet thickness, mm	????1.6-1.7	????1.6-1.8	????1.57-1.70
Second-order transition temperature-Tg1/2, ℃	????160/166	????161/167	????157/160	Copper Foil stripping strength N/cm	????15.7	????17.0	????16.3
The NMP-absorptivity, %				Copper Foil stripping strength N/cm	????15.7	????17.0	????16.3
The NMP-absorptivity, %				The steaming and decocting under high pressure experiment, water regain wt.%﹠ is by the percentage ratio of 260 ℃ of solder bath	Wt%/% passes through	Wt%/% passes through	Wt%/% passes through
40 minutes	????0.52/100	????0.6/75	????0.53/100		Wt%/% passes through	Wt%/% passes through	Wt%/% passes through
40 minutes	????0.52/100	????0.6/75	????0.53/100	60 minutes	????0.64/75	????0.75/75	????0.69/50
				60 minutes	????0.64/75	????0.75/75	????0.69/50
				Burning total time, second	????53	????47	????34
UL94	????V-1	????V-0	????V-0	Burning total time, second	????53	????47	????34

Table 3: clear coat composition, characteristic, prepared by the glyoxal ethyline catalyst system

Preimpregnation material and veneer sheet performance

Form the solid weight umber	????I	????J
Form the solid weight umber	????I	????J	The resin that preparation method A produces	????85	????86
Amgard?V19	????14	????14	The resin that preparation method A produces	????85	????86
Amgard?V19	????14	????14
Dyhard RU 100 (being dissolved in Amgard V19)	????1	????1
Dyhard RU 100 (being dissolved in Amgard V19)	????1	????1	Boric acid	????1	????-
Glyoxal ethyline	????1	????1	Boric acid	????1	????-
Glyoxal ethyline	????1	????1	The solvent that replenishes	????MEK	????MEK
The varnish characteristic			The solvent that replenishes	????MEK	????MEK
The varnish characteristic			Viscosity (Ford cup 4#), second	????132	????137
Reactive behavior, 170 ℃ 150 ℃ of second gel times	? ????109 ????178	? ????70 ????150	Viscosity (Ford cup 4#), second	????132	????137
Reactive behavior, 170 ℃ 150 ℃ of second gel times	? ????109 ????178	? ????70 ????150	Dip coater condition oven temperature, ℃ pulling speed, rice/minute	? ????160 ????0.8	? ????160 ????1.3
Preimpregnation material characteristic				? ????160 ????0.8	? ????160 ????1.3
Preimpregnation material characteristic			Resin content, wt%	????45.1	????41.2
170 ℃ of static gel times, second	????0	????9	Resin content, wt%	????45.1	????41.2
170 ℃ of static gel times, second	????0	????9	Mil flows, wt%	????17.0	????18.0
The veneer sheet performance			Mil flows, wt%	????17.0	????18.0
The veneer sheet performance			The veneer sheet curing cycle	90 minutes 230 ℃
Veneer sheet thickness, mm	????1.6-1.7	????1.40-1.48	The veneer sheet curing cycle	90 minutes 230 ℃
Veneer sheet thickness, mm	????1.6-1.7	????1.40-1.48	Second-order transition temperature-Tg1/2, ℃	????166/169	????143/148
The steaming and decocting under high pressure experiment, water regain wt.%﹠ is by the percentage ratio of 260 ℃ of solder bath	Wt%/% passes through	Wt%/% passes through	Second-order transition temperature-Tg1/2, ℃	????166/169	????143/148
	Wt%/% passes through	Wt%/% passes through	40 minutes	????0.57/100	????0.55/100
60 minutes	????0.77/0	????0.75/0	40 minutes	????0.57/100	????0.55/100
60 minutes	????0.77/0	????0.75/0
Burning total time, second	????54	????49
Burning total time, second	????54	????49	UL94	????V-1	????V-0

Table 4: composite formula, characteristic contains the preimpregnation material and the veneer sheet characteristic of filler systems

Form the solid weight umber	????K	????L	????M
Form the solid weight umber	????K	????L	????M	The resin that preparation method A produces	????84.00	????84.00	????74.50
Amgard?P45	????10.00	????10.00	????10.00	The resin that preparation method A produces	????84.00	????84.00	????74.50
Amgard?P45	????10.00	????10.00	????10.00	Dyhard RU 100 (being dissolved in P45)	? ????2.00	? ????2.00
Sulfanilic amide (being dissolved in P45)			? ????6.00	Dyhard RU 100 (being dissolved in P45)	? ????2.00	? ????2.00
Sulfanilic amide (being dissolved in P45)			? ????6.00	Hostaflam ^TMAP 423 polyphosphonic acid ammoniums	? ????5.00		? ????7.00
Hostaflam TP RP 605 red phosphorus		1.50 it is maximum		Hostaflam ^TMAP 423 polyphosphonic acid ammoniums	? ????5.00		? ????7.00
Hostaflam TP RP 605 red phosphorus		1.50 it is maximum		Boric acid	????0.5	????0.5	????0.5
The 2-phenylimidazole	????2.0	????2.0	????2.0	Boric acid	????0.5	????0.5	????0.5
The 2-phenylimidazole	????2.0	????2.0	????2.0	The solvent that replenishes	????MEK/Dowanol?PM	????MEK/Dowanol?PM	????MEK/Dowanol?PM
The varnish characteristic				The solvent that replenishes	????MEK/Dowanol?PM	????MEK/Dowanol?PM	????MEK/Dowanol?PM
The varnish characteristic				Viscosity (Ford cup 4#), second	????120	????63	????60
Reactive behavior. 170 ℃ 150 ℃ of second gel times	? ????77	? ????70	? ????77	Viscosity (Ford cup 4#), second	????120	????63	????60
Reactive behavior. 170 ℃ 150 ℃ of second gel times	? ????77	? ????70	? ????77	Dip coater condition oven temperature, ℃ pulling speed, rice/minute	? ????157 ????1.3	? ????157 ????1.4	? ????157 ????1.5
Preimpregnation material characteristic					? ????157 ????1.3	? ????157 ????1.4	? ????157 ????1.5
Preimpregnation material characteristic				Resin content, wt%	????39.5	????41	????40.8
170 ℃ of static gel times, second	????23	????20	????23	Resin content, wt%	????39.5	????41	????40.8
170 ℃ of static gel times, second	????23	????20	????23	Mil flows, wt%	????11.9	????16.5	????15.7
The veneer sheet performance				Mil flows, wt%	????11.9	????16.5	????15.7
The veneer sheet performance				The veneer sheet curing cycle	190 ℃ following 90 minutes	190 ℃ following 90 minutes	190 ℃ following 90 minutes
Veneer sheet thickness, mm	????1.45	????1.55	????1.45	The veneer sheet curing cycle	190 ℃ following 90 minutes	190 ℃ following 90 minutes	190 ℃ following 90 minutes
Veneer sheet thickness, mm	????1.45	????1.55	????1.45	Second-order transition temperature-Tg1/2, ℃	????166.6/170.7	????170.2/171.4	????172.7/171.3
Copper Foil stripping strength N/cm	? ????0.083	? ????0.034	? ????0.017	Second-order transition temperature-Tg1/2, ℃	????166.6/170.7	????170.2/171.4	????172.7/171.3
Copper Foil stripping strength N/cm	? ????0.083	? ????0.034	? ????0.017	The NMP-absorptivity, %
Steaming and decocting under high pressure experiment, water regain wt.% and the percentage ratio by 260 ℃ of solder bath	Wt%/% passes through	Wt%/% passes through	Wt%/% passes through	The NMP-absorptivity, %
	Wt%/% passes through	Wt%/% passes through	Wt%/% passes through	60 minutes	????100	????100	????50
75 minutes	????50	????100	????50	60 minutes	????100	????100	????50
75 minutes	????50	????100	????50	90 minutes	????0	????50
Burning total time, second	????32	????29	????26	90 minutes	????0	????50
Burning total time, second	????32	????29	????26	UL94	????V-0	????V-0	????V-0

Claims

1. fire retarded epoxy resin composition, it contains the halogen that is no more than 10wt%, comprises:

A) Resins, epoxy;

B) phosphonic acid ester, its consumption can be provided at the phosphorus of 0.2～5wt% in the composition;

C) nitrogenous linking agent, the amine functionality is at least 2, and its consumption is to make 10～80% of the required stoichiometric amount of epoxy resin cure;

D) catalyzer, its consumption is 0.1～3wt%, both can accelerate the chemical reaction velocity of phosphonic acid ester and Resins, epoxy, can improve the curing speed of Resins, epoxy and linking agent again, and dispensable

E) Lewis acid, its consumption are no more than every mol catalyst 2 moles of Lewis acids.

2. the composition of claim 1, wherein, the softening temperature of Resins, epoxy is 50 ℃ (ASTM D3104) at least.

3. claim 1 or 2 composition, wherein, the Resins, epoxy per molecule contains and is no more than two alkyl groups.

4. the composition of claim 3, wherein, the Resins, epoxy per molecule contains and is no more than 1 alkyl group.

5. each composition during aforesaid right requires, wherein Resins, epoxy is monomer and the monomeric reaction product of two sense chain extensions (perhaps mixture) that contains at least two epoxide groups, perhaps also contains two other sense chain extension monomers in the composition.

6. the composition of claim 5, wherein two sense chain extension monomers are diphenylmethanediisocyanate (MDI), tolylene diisocyanate (TDI), 2,6-dimethylhexylamine, sulfanilic amide or anthranilamide.

7. claim 5 or 6 composition, wherein, the monomer that contains at least two epoxide groups is the glycidyl ether of phenol linear phenolic resin, or the glycidyl ether of Bisphenol F.

8. each composition during aforesaid right requires, wherein the consumption based on solid content Resins, epoxy is 50～95wt% of composition.

9. each composition during aforesaid right requires, wherein the consumption based on solid content Resins, epoxy is 80～90wt% of composition.

10. each composition during aforesaid right requires, wherein phosphonic acid ester is the ester with following molecular formula: R wherein ¹Be C ₁～C ₃Alkyl, R ⁴Be C ₁～C ₃Alkylidene group, R ²And R ³Be respectively C ₁～C ₃Alkyl or C ₆～C ₁₀Aryl, perhaps R ²And R ³Represent glycol or residue of polyol altogether.

11. the composition of claim 10, wherein R ¹Be methyl, R ⁴Be methylene radical, R ²And R ³Independently be methyl, ethyl, phenyl or hydroxyphenyl separately.

Each composition during 12. aforesaid right requires, wherein phosphonic acid ester is the compound with following molecular formula:

13. the composition of claim 11 or 12, wherein, the consumption of phosphonic acid ester is the 4wt%-15wt% of composition.

14. the composition of claim 13, wherein, the consumption of phosphonic acid ester is 7～15wt% of composition.

Each composition during 15. aforesaid right requires, wherein, the consumption of phosphonic acid ester can be provided at the phosphorus of 0.5wt%～5wt% in the composition.

16. the composition of claim 15, wherein, the consumption of phosphonic acid ester can be provided at the phosphorus of 1wt%～3.8wt% in the composition.

17. the composition of claim 16, wherein, the consumption of phosphonic acid ester can be provided at the phosphorus of 1.4wt%～3.1wt% in the composition.

Each composition during 18. aforesaid right requires, wherein to be at least 2 nitrogenous linking agent be Dyhard RU 100, sulfanilic amide, diaminodiphenylsulfone(DDS) and/or diaminodiphenylmethane to the amine functionality.

Each composition during 19. aforesaid right requires, wherein, total consumption of nitrogenous linking agent is no more than with Resins, epoxy and reacts 80% of required stoichiometric amount in the composition.

Each composition during 20. aforesaid right requires, wherein, total consumption of nitrogenous compound is 1～8% the total nitrogen content that composition can be provided in the composition.

Each composition during 21. aforesaid right requires, wherein, catalyzer comprises the single catalyst composition, can accelerate the speed of response of phosphonic acid ester and Resins, epoxy, can improve the curing speed of Resins, epoxy again.

22. each composition in the claim 1 to 20, wherein, the catalyst component that catalyzer contains in the curing speed of the speed of response of phosphonic acid ester and Resins, epoxy and Resins, epoxy, plays bigger katalysis to the former.

23. the composition of claim 22, wherein, catalyst composition is 1,8-diazabicyclo (5,4,0) 11 carbon-7-alkene.

Each composition during 24. aforesaid right requires, wherein, total consumption of catalyzer is 0.1%～2wt% of composition.

Each composition during 25. aforesaid right requires, it also comprises the assisting flame-resistant additive.

26. the composition of claim 25, wherein the assisting flame-resistant additive is polyphosphonic acid ammonium, red phosphorus, phosphite, 9, the 10-dihydro-9-oxy is assorted-phospho hetero phenanthrene-10-oxide compound (HCA), phosphine piperazine, contain nitrogen combustion inhibitor, halogenated fire-retardants, halogenated epoxy resin, phosphorous-halogen fire retardant, organic acid salt, inorganic metal hydrate, the compound of boracic or antimony.

27. prepare the method for composition epoxy resin, composition epoxy resin comprises:

Resins, epoxy,

Phosphonic acid ester,

Nitrogenous linking agent, the amine functionality is at least 2,

Catalyzer both can have been accelerated the chemical reaction velocity of phosphonic acid ester and Resins, epoxy, can improve the curing speed of Resins, epoxy and linking agent again, and dispensable Lewis acid, and its consumption is no more than every mol catalyst 2 moles of Lewis acids,

This method comprises: preparation contains first composition of Resins, epoxy and contains second composition of curing catalysts, and wherein, first or second composition also contains phosphonic acid ester and amine functionality and is at least 2 nitrogenous linking agent;

First composition and second composition are mixed, composition is solidified, make solidified fire retarding epoxide resin.

28. the method for claim 27, wherein, phosphonic acid ester, nitrogenous linking agent and catalyzer all are present in second composition.

29. the method for claim 27, wherein, phosphonic acid ester, nitrogenous linking agent are present in first composition, and catalyzer is present in second composition.