Composition with a low content of volatile organic compounds for the manufacture of laminated plastics (options), and a method of manufacturing laminated plastics for electrical purposes

 

(57) Abstract:

Describes a new composition comprising: (1) an epoxy resin of low viscosity, (2) phenolic chain extension containing an average of more than 1 and less than 3 phenolic, hydroxyl groups on the molecule and the concentration of which is equal to from 0.1 to 0.6 phenolic hydroxyl groups per equivalent of the epoxy resin of low viscosity, (3) a catalyst which contains not more than 1 active hydrogen in the molecule and which promotiom reaction samootverzhenij between epoxy groups, (4) inhibitor, which is the Lewis acid and which is present in an amount of from 0.3 to 3 moles per mole of catalyst: a halide, oxide, hydroxide or alkoxide of zinc, tin, titanium, cobalt, manganese, iron, silicon, boron or aluminum, in addition to boron halide, (5) the volatile organic solvent is present in amount of less than 25 wt.% the total weight of the composition, and (6) may polyfunctional crosslinking agent. The composition may be used for the manufacture of laminated plastics for electrical purposes. It increases the molecular weight of the b-stage, so to prevent dripping, but it can easily produce a laminate of PR the f-crystals, table 2.

The present invention relates to cured compositions containing epoxy resin, and, in particular, to compositions useful for the manufacture of laminated plastics for electrical purposes.

Known manufacturing laminated plastics for electrical purposes and other composite materials of the fibrous substrate and curing the binder containing epoxy resin. Examples of suitable methods typically include the following stages:

1) On a substrate by rolling, dipping, spraying, other known methods and/or their combinations applied composition containing epoxy resin. The substrate is typically a woven or non-woven fibrous Mat containing, for example, glass fiber.

2) Impregnated substrate "In-Stavrou" by heating at a temperature sufficient for removal of the solvent in the epoxy composition, and selection for partial curing epoxy compositions so that you can easily contact with the impregnated substrate. The operation of the "b-staging" is usually carried out at a temperature between 90 and 210oC and during the period of time between 1 minute and 15 minutes Impregnated substrate, resulting In the print materials and 130 -180oC for laminated plastics for electrical purposes.

3) One or more sheets of the prepreg stack of alternating layers with one or more sheets of conductive material, such as copper foil, if desired laminated material for electrical purposes.

4) Stacked sheets are pressed at high temperature and pressure for a time sufficient to cure the resin and formation of the laminate, the temperature of the manufacture of the laminate is usually between 100 and 230oC, and usually between 165 and 190oC. Stage of manufacturing of the laminate can also be carried out in two or more stages, for example the first stage between 100 and 150oC and the second stage between 165 and 190oC. the Pressure is typically in the range between 50 and 500 H/cm2. Stage of manufacturing of the laminate is usually carried out for 10-100 min, and most often within 45-90 minutes At the selection stage of manufacturing of the laminate can be performed at a higher temperature for shorter periods of time (for example, when continuous processes for the manufacture of laminates).

5) Optional the resulting laminate, square the like at high temperature and ambient pressure. The temperature of the subsequent processing is normally in the range between 120 and 250oC. the duration of the subsequent processing is normally in the range between 30 minutes and 12 hours.

Laminated plastics for electrical purposes and the ways in which they are made, are described in more detail in numerous sources, such as, for example, U.S. patent 5. 314.720 (24 may 1994) and Delmonte, Hoqqatt & May; "Fiber-reinforced Epoxy Composites," Epoxy Resins, Chemistry and Technoloqy (2d Ed.) at 889-921 (Marcel Dekker, Inc. 1988).

Compositions used in such methods typically include: 1) an advanced epoxy resin having an epoxy equivalent weight 400-530; 2) a curing agent such as dicyandiamide; 3) a catalyst for promoting the reaction of resin and hardener, such as 2-Mei; and 4) 30-40 EU.% volatile organic solvent such as ketone, glycol ether, dimethylformamide and xylene. It is known that the composition may contain certain other additives. For example:

1) Compositions which contain boric acid, as proposed in U.S. patent 5.308.895 (3 may 1994) and U.S. patent 5.314.720 (24 may 1994).

2) Compositions that contain the extension circuits, such as bisphenol a or tetrabromobisphenol A, described in Tay 1992) and U.S. patent 3.738.862 (June 12, 1973).

It would be desirable to reduce the amount of volatile organic solvent used in the composition. Volatile organic solvents off - road and they need to be removed from waste gases B-stage before the gas is returned to the atmosphere. However, the composition with low VOC (volatile organic compounds) should be selected to ensure the required viscosity because the viscosity is important in the processes of manufacturing laminated plastics. See, for example, Delmonte, Hoqqatt & May at 903. In conventional compositions, it is impossible to reduce the VOC, because the viscosity of the composition would be too high. Resin with high viscosity changes the position of the fibers in the substrate and difficult to be absorbed into it.

The viscosity of the compositions with low VOC can be reduced if an advanced epoxy resin to replace the resin with a lower molecular weight and extension chain. It was reported about the use of such compositions with low viscosity for other purposes. For example, in EPO publication 0 260 768 A2 (March 23, 1988) is proposed composition for encapsulation, which contains liquid epoxy resin, 0.6 to 1 equivalent of bisphenol a, and the catalyst of the amino-boron TRIFLUORIDE. According to the Lu, extension chains and catalysts or catalyst complexes and partially cured resin is used in curing resins.

Compositions which contain a liquid epoxy resin and extender chains are usually not used in the processes of manufacturing laminated plastics, because of their viscosity in an impregnating machine, and the prepreg was often too low. In an impregnating machine composition to flow and drip until completion of the B-stage. In addition, after placing the prepreg in a press for molding laminated plastic flows too many songs. The resin is extruded from laminates in the press, and the resulting laminate is too thin.

To facilitate rapid reaction of epoxy resin and extender chains in an impregnating machine in the composition can be added catalysts in order to arise dripping formed developed resins with higher molecular weight. However, these catalysts accelerate the curing of the resin and hardener. It is difficult to prevent the generation of viscosity too high for an effective process for manufacturing laminated plastics. In addition, compositions which contain too much cat and have a short shelf life when stored.

What is needed is a composition with a low content of VOC, which: 1) has a low viscosity in the stage of impregnation; 2) quickly increases the molecular weight at the expense of the regulated growth of chains on the B-stage for minimizing dripping; 3) regulates adverse reactions curing to prevent excessive increase of molecular weight in an impregnating machine or during storage; and 4) provides B-sterowany the prepreg with a viscosity sufficient for the manufacture of laminates without significant loss of resin. Another aim of the invention is to propose a composition based on epoxy resin, which is compatible with existing manufacturing equipment for manufacturing laminated plastics for electrical purposes, obtained from compositions based on the advanced epoxy resin.

The claimed invention provides these and other significant features, which will become apparent from the full description and examples in it.

One aspect of the present invention is a composition containing:

1) epoxy resin with low viscosity;

2) phenolic extension of the chains, the concentration of which is less than 0.6 equivalents of phenolic hydroxyl is samootverzhenij between epoxy groups;

4) inhibitor, which is a Lewis acid;

5) less than 25 wt.% volatile organic solvent; and

6) perhaps a multifunctional crosslinking agent. The second aspect of the invention is the composition of the precursor containing:

1) epoxy resin with low viscosity;

2) phenolic extension of the chains, the concentration of which is less than 0.6 equivalents of phenolic hydroxyl groups per equivalent of epoxy resin with low viscosity;

3) a Lewis acid; and

4) not more than 20 wt.% volatile organic solvent.

The third aspect of the present invention is the use of the above composition in the manufacturing processes of composite materials and laminates for electrical purposes described earlier.

The composition according to the second aspect of the invention is used to obtain the compositions according to the first aspect of the invention. These compositions are suitable for producing the above-described laminated plastics for electrical purposes. These compositions can also be used to kapsulirovanie, coating and manufacture of structural composite materials. The invention is further described in more detail.paxinou resin with low viscosity is used one of two things:

1) liquid at 20oC; or

2) having the average formula epoxy equivalent of not more than 350 for all smoke zero halogen atoms in the molecule. (For example, diglycidyl ether of bisphenol A contains no halogen and has an average weight according to the formula equal to 340. Therefore, the mass according to the formula epoxy equivalent dipyridamole ether of bisphenol A is 170. Diglycidyl ether tetrabromobisphenol has A molecular mass equal to 656. However, the average weight by the formula smoke zero halogen atoms is 336 and thus the average weight according to the formula on the epoxy equivalent is 168 to smoke zero halogen atoms in diglycidylether the air tetrabromobisphenol A. diglycidyl ether of bisphenol A, and diglycidyl ether tetrabromobisphenol are A epoxy resin with low viscosity" in the sense of this definition).

Average weight according to the formula on the epoxy equivalent is preferably not more than 250 and more preferably not more than 190 for smoke zero halogen atoms in the epoxy resin with low viscosity. It is preferably at least 70, more preferably at least 100 and most preferably at least 160 for megalogenis more than 1 epoxy group, and preferably, on average, contains at least a 1.8 epoxy groups per molecule. On the average it contains preferably less than 5 epoxy groups per molecule, more preferably less than 3 epoxy groups per molecule, and most preferably not more than 2,1 epoxy groups in the molecule. (For certain special applications, for example, for use at high temperatures can be optimal resin with a large number of epoxy groups, such as triglycerol ether three(oxyphenyl)of methane, which is commercially available as resin TACT1Xx742 (trademark of Dow chemical of Camel"). Epoxy resin with low viscosity preferably is a compound pilgramage ester, complex ester or amide.

More preferably, the epoxy resin with low viscosity was diglycidyl ether diol. Diol preferably contains 2 phenolic hydroxyl groups per molecule (avoidany phenol). Diol and diglycidyl ether is preferably represented by formula I

< / BR>
in which each "A" independently represents an aliphatic group, an aromatic group or multiple aromatic groups (including halogenated and/or substituted aromatic the group, carbonyl group, sulfonyloxy group or oxygen atom. Aliphatic groups preferably comprise less than 50% of "A", more preferably less than 30% and most preferably 0%. Aliphatic groups are preferably alkyl groups or polyalkylbenzene groups. Each "A" is most preferable is a benzene ring or two benzene rings connected by a lower alkyl group or halogenated species.

Each Q is a hydroxyl group in diola and part pilgramage ether represented by formula II

< / BR>
in epoxy.

Each "R" represents a hydrogen atom, halogen or lower alkyl group. Each "R" is preferably a hydrogen atom.

"n" represents the number of repeating units. "n" can on average be equal to 0-2, but preferably 0.1 to 0.2 in epoxy with low viscosity.

Examples of preferred diols are resorcinol, catechin, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4 oksifenil)-1-Penilaian), bisphenol F, bisphenol K, or their halogenated species. Epoxy resin with low viscosity most preferably is digli the diversified resins with low viscosity are derived pilgramage ether of 1,1,1-tri- (oxyphenyl)-alkanes and their halogenated species. Examples of suitable epoxy resins and methods for their preparation are also described in H. Lee &K. Neville, Handbook of Epoxy Resins at 2-1 to 3-20 (MeGraw-Hill Book Co. 1967).

The compositions also contain phenolic extension circuits. Phenolic extension circuits may be any compound which on average contains more than 1 and less than 3 phenolic hydroxyl groups per molecule. He's in the middle contains preferably 1,8-2,1 phenolic hydroxyl groups and more preferably about 2 phenolic hydroxyl groups per molecule. Phenolic extension circuits has a similar broad description and preferred options of the incarnation as avoidany phenol, described previously as the basis for the epoxy resin with low viscosity (except that the "n" in formula I is preferably less than 0.2, more preferably less than 0.1 and most preferably 0).

Phenolic extension chain preferably is a liquid or solid substance which is soluble in the liquid epoxy resin to reduce to a minimum the need for volatile organic solvents. It preferably has a melting point above 100oC, and most preferably at least about 125oC and not higher than about 300oC. When f is least 100 and more preferably at least 185. Molecular weight is preferably equal to not more than 800, more preferably not more than 500 and most preferably not more than 250. For halogenated phenolic extension chain weight according to the formula smoke zero halogen atoms in the extension circuits preferably satisfies the above preferred limitations, and the total molecular weight is preferably within the preferred options plus formula weight of halogen. Phenolic extension circuits can be blocked by phenol oligomer (such as oligomer, which satisfies the formula I in which Q is a hydroxyl group, and "n" in the middle is in the range between 0.2 and 2), but the extension circuits preferably is simply a monomer (in which "n" satisfies the above limits). Phenolic onlinelet chain most preferred is bisphenol A or commercially available brominated bisphenol A.

The number of extension circuits must be less than stoichiometric with epoxy resin. Extender chain preferably contains not greater than 0.55 hydroxyl equivalents to epoxy equivalents and more preferably not more than 0.5 hydroxyl equivalent of the ilen equivalents to epoxy equivalents, more preferably, at least 0.2 to phenolic hydroxyl equivalents to epoxy equivalents and most preferably at least 0.3 to phenolic hydroxyl equivalents to epoxy equivalents. When epoxy resin with low viscosity is diglycidyl ether of bisphenol A, and the extension circuits - tetrabromobisphenol A, the concentration of the extender chain is preferably sufficient to obtain a resin containing 17 to 30 wt.% bromine, and more preferably sufficient to obtain a resin containing 19-22 wt.% bromine.

The compositions of the present invention contain a catalyst that can catalyze the epoxy-epoxy reactions of the curing reaction of epoxy groups with one another for education utverzhdenii resin. Such the curing reaction is described in Vol. 6 Encyclopedia of Poly.Sci. & Enq. (2d Ed.) "Epoxy Resins" at 341-343 (J. Wiley & Sons 1986). Examples of suitable catalysts are compounds containing part of the amine, phosphine, heterocyclic nitrogen, ammonium, phosphonium, Arcania and sulfone. The preferred catalysts are the heterocyclic nitrogen and amino compounds compounds, and even more preferred catalysts - heterocyclic AZ on average no more than about 1 active hydrogen part of the molecule. The number of active hydrogen of the parts are hydrogen atoms associated with the amino group, phenolic hydroxyl group or carboxylic acid group. For example, in catalysts aminovymi and phosphine parts are preferably tertiary amine or phosphine parts, and ammonium and phosphonium parts, preferably Quaternary ammonium and postname part.

Examples of suitable heterocyclic nitrogen catalysts are those described in U.S. patent 4925901 (15 may 1990) on the name of Bertram. Among the preferred heterocyclic secondary and tertiary amino or nitrogen-containing catalysts that may be used in this case include, for example, imidazoles, benzimidazole, imidazoline, imidazoline, oksazolov, pyrrole, thiazole, pyridine, pyrazine, morpholines, pyridazine, pyrimidines, pyrrolidine, pyrazoles, cinoxacin, heatline, phthalazine, quinoline, purine, indazols, indoles, indolizine, phenazine, phenarsazine, phenothiazines, pyrroline, piperidine, piperazines and their combinations. Especially preferred are the alkyl substituted imidazoles; 2,5 - chloro-4-ethylimidazole and phenylsilane the imidazoles and mixtures thereof. Even more preferred are the venerated 2-Mei.

Among the preferred tertiary amines that can be used as catalysts, are mono - or polyamine, having a structure with an open-chain or cyclic structure, in which the whole of amine hydrogen substituted by suitable substituents, such as hydrocarbon radicals, preferably aliphatic, cycloaliphatic or aromatic radicals. Examples of these amines, among others, are methyldiethanolamine, triethylamine, tributylamine, dimethylbenzylamine, triphenylamine, tricyclohexyltin, pyridine and quinoline. Preferred amines are trialkylamines, tricyclohexyltin and Truelove amines, such as triethylamine, triphenylamine, three-(2,3-dimethylcyclohexyl) amine, and alkyldiethanolamine amines, as for example, methyldiethanolamine, and trialkanolamines, as for example, triethanolamine.

Especially preferred weak tertiary amines, such as amines, which in aqueous solution give a pH of less than 10 at 1M concentration of aqueous solutions. Particularly preferred tertiary amine catalysts are benzyldimethylamine and tridimensionality.

The concentration of the catalyst is preferably at least 0.05 in the 3 o'clock 100 including the resin, and more preferably not more than 1 part in 100 including the resin. (For the purposes of this application, the expression "parts per 100 parts resin" refers to weight. part of the material per 100 weight. including the United epoxy resin with low viscosity and extender chain).

The present invention also relates to an inhibitor that inhibits the activity of the catalyst during the B-stage. Inhibitor is a Lewis acid. Examples of preferred inhibitors are the halides, oxides, hydroxides and alkoxides of zinc, tin, titanium, cobalt, manganese, iron, silicon, boron, aluminum and similar compounds (except boron halides), such as boric acid, braccini (such as trimethoxybenzyl), boron oxide, alkylborane, zinc halides such as zinc chloride and other Lewis acid, which exhibit a tendency to have relatively weak conjugate base. When the composition is intended for use in laminated plastics for electrical purposes, then the inhibitor preferably does not contain any significant amounts of halogen. The preferred inhibitor is boric acid. In this case, boric acid is used as cispa least of 0.3 mole of inhibitor per mole of catalyst, and more preferably, at least, of 0.6 mole of inhibitor per mole of catalyst. The composition preferably contains not more than 3 moles of inhibitor per mole of catalyst, and more preferably not more than 2 moles of inhibitor per mole of catalyst.

In the composition of the present invention the inhibitor and catalyst can be added separately or in the form of a complex. This complex is formed in contact and thorough mixing of the solution of the inhibitor to the solution of the catalyst. The choice may be acid having a weak nucleophilic anion. Such contacting is usually carried out at ambient temperature, although they can be used and other temperatures, for example temperatures from 0 to 100oC, more preferably from 20 to 60oC. the Duration of such contact should be sufficient to complete formation of the complex and depends on temperature, comprising preferably from 1 to 120 minutes and more preferably 10-60 minutes

According to theory without intending to be bound to her reaction when interacting epoxy resin with phenolic extension circuits and the curing reaction of epoxy cm the treatment speed one reaction it will also increase the speed of the other reactions. On the other hand, the inhibitors used in the present invention, slow down the curing reaction of epoxy resin with the epoxy resin at temperatures of B-stage, but have no impact or do not accelerate the reaction in the interaction of epoxy resin with phenolic extension chains in the B-stage. The effect of the inhibitor is reduced at elevated temperatures, so that at the stage of manufacturing of the laminate can occur epoxy-epoxy reactions. This facilitates the control of the viscosity increase in the B-stage by selecting the epoxy resin and phenolic chain extension and establishing relationships between them.

In addition, the preferred composition with a low content of organic solvent. More preferred is a content of a mixture of solvents suitable for dissolving the individual components in the composition. Well-known preferred volatile organic solvents for dissolving the epoxy resin, and know how to apply them to obtain the desired viscosity. Examples of suitable solvents are given in H. Lee &K. Neville, Handbook of Epoxy Resins at 24-31 (MeGraw-Hill Book Co. 1967). Examples of preferred solution is; glycols; glycol ethers; C1-C8alcohols and aromatic hydrocarbons (such as xylene). The catalyst and the inhibitor is preferably dissolved in polar solvents, such as dimethylsulfoxide (DMSO), glycerol, or dimethylformamide, and, more preferably, with alcohols having from 1 to 6 carbon atoms, glycols having from 2 to 6 carbon atoms. As described in European patent application 0 567 248, the solvent may also contain up to 30 % of water.

The composition preferably contains not more than 20 wt.% volatile organic solvent and more preferably not more than 15 wt.%. The content of volatile organic solvent in the composition may be so small as 0 wt.%, but it is the content of volatile organic solvent, equal to at least 5 wt.%.

In addition, the composition preferably contains a multifunctional crosslinking agent. Such multifunctional crosslinking agents are described in numerous sources, such as, Vol. 6, Encyclopedia of Poly.Sci. & Enq. "Epoxy resins" at 348-56 (J. Willey Sons 1986). Examples of suitable crosslinking agents are known hardeners for epoxy resins, as for example, polyamine, polyamides, polinger the additional examples of the multifunctional cross-linking agents include dicyandiamide and polyphenols, such as Novolac. Examples of other multi-functional cross-linking agents that may be used are polyanhydride proposed in PCT publication WO 94/11415 (published may 26, 1994).

Multifunctional crosslinking agents (in contrast to the catalysts and extension chain) preferably contain on average more than two active hydrogen parts per molecule. For example, a crosslinking agent preferably contains many secondary amino groups, one or more primary amino groups, more than two phenolic hydroxyl groups, many primary aminogroup or more than two carboxylic acid groups.

The amount of multifunctional crosslinking agent is preferably chosen so that the composition contain a stoichiometric excess of epoxy resin with low viscosity over a combination of phenolic extension chain and a multifunctional crosslinking agent. (For the purposes of this application, the dicyandiamide is accepted as having 5-7 centers curing molecule). The composition preferably contains not more than 0.75 equivalents of extension chains and cross-linking agent to the epoxy equivalent, more preferably not more than 0.6 equivalential cross-linking agent, but preferably, at least 0.01 equivalents to epoxy equivalents, more preferably at least about 0.05 equivalents and most preferably at least 0.1 equivalents. When the multifunctional crosslinking agent is dicyandiamide, the composition preferably contains at least 0,05 including dicyandiamide 100 including the resin, and more preferably at least 0.1 to including dicyandiamide 100 including the resin. It preferably contains not more than 2.25 hours at 100 including the resin, and more preferably not more than 1.5 hours at 100 hours resins.

In addition, the composition preferably contains a stabilizer to prevent premature reaction of epoxy resin with low viscosity and extender chain during storage and transport. As installed, as inhibitors of the reaction is particularly effective are strong inorganic and organic acids and anhydrides and esters of these acids (including palefire and partial esters). The term "strong acid" refers to an organic acid having a pH value below 4, preferably below 2.5. Examples of preferred inhibitors of the reaction are inorganic acids, such as, for example, chloride is the ID of phosphoric acid (P2O5), esters of inorganic acids, as for example, alkalemia, arrowie and Arakelova and substituted alkalemia; aryl - and Arakishvili, such as p-toluensulfonate and vinylsulfonate, and more strong organic carboxylic acids, such as trichloroacetic acid, and alkalemia esters of these acids, such as alkyl esters of p-toluenesulfonic acid, such as methyl-p-toluensulfonate, ethyl-p-toluensulfonate and methyl ether methanesulfonate acid. The preferred inhibitors of the reaction are alkalemia esters of sulfuric acid, arylsulfonic or aralkylamines. The most preferred stabilizer is low (C1-C6) alkilany ester p-toluenesulfonic acid. The amount of the stabilizer is preferably 0-1 hours 100 hours resins.

The viscosity of the composition at 20oC is preferably not more than 800 mPas and more preferably not more than 500 mPas. (Viscosity measured on a viscometer CANNON-FENSKE according to the usual instructions for work). The viscosity of the composition is preferably at least 50 mPas, and more preferably at least 100 mPas.

The above compositions can be presenting the background to the creation of the invention. The compositions have a relatively low viscosity, but quickly and in a controlled way polymerize during the B-stage, preventing dripping, and otverzhdajutsja with getting a good laminated plastics with the operation of their production. In addition, the presence of the inhibitor in the composition increases the total amount of heat released during the curing of the composition. This means that the cured compositions have an increased cross-linking density.

For packaging and transportation can be a convenient supply of pre-composition, as described in the second aspect of the invention. Preliminary composition contains epoxy resin with low viscosity, phenolic extension circuits, the inhibitor and the solvent, as described previously. Ratios such as previously described, except that the composition contains a solvent is preferably not more than 15 wt.% and more preferably not more than 10 wt.%. The composition contains a solvent preferably at least 1% and more preferably at least 5%. The composition comprises an inhibitor preferably at least 0,05 h 100 h of the resin and more preferably at least 0,2 h 100 h of the resin. It contains inhibitor varicella composition preferably contains less catalyst. For example, the concentration of the catalyst is preferably less than 0.1 hours to 100 hours in the resin, more preferably less than 0.05 hours to 100 hours in the resin, and most preferably less than 0.01 hours to 100 hours in the resin. Preliminary composition preferably contains less cross-linking agent than would be required for curing the composition. The concentration of crosslinking agent in the preliminary composition is preferably less than 0.1 equivalents to epoxy equivalents, more preferably less than 0.05 equivalents and most preferably less than 0.01 equivalents. The concentration of catalyst and hardener most preferably be about 0.

Such compositions can be stored for long periods of time without loss of stability. The invention more detail is illustrated by the following specific examples.

Example 1

Compositions containing an inhibitor of boric acid and a crosslinking agent of dicyandiamide

Six compositions were prepared. Each composition contained 65,6 including a liquid epoxy resin D. E. R. 330 (trademark company Dau of camel"), to 34.5 hours of tetrabromobisphenol A and 5,26 including methyl ethyl ketone. To this mixture was added 10% solution of boric acid in ethanolivia songs during the night then typed the following additional components: was 9.33 PM the solution containing the 7.5 hours of dicyandiamide dissolved in 30,5 hours of dimethylformamide and 62 hours nanometrology ether of propylene glycol; 1,25 including a 20% aqueous solution of 2-methylimidazole in ethanol and methyl ethyl ketone in an amount sufficient to dilute the composition to 80% solids content. Compositions were loaded into aluminum coulometrically capsule. For removal of the solvent each composition within one hour was kept under vacuum at room temperature. The development of circuits and curing of each composition was investigated by the method of differential scanning calorimetry (DSC) using a calorimeter METTLER DSC 30 and when the temperature rises by 10oC per minute.

When the composition And the wide peak of the development of chains stretched from about 105oC to peak at 160oC, and the sharp peak curing had a maximum at 165oC, essentially at the top of the peak of the development chain. When composition 1 peak development chains remained at a maximum of about 160oC, but the maximum peak curing was slightly shifted to about 170oC. When the composition 2 two peaks were almost completely separated, since the development of chains showed a broad peak at 160oC, and curing - wide peak at about 195oC. was Prostyles from about 110 to about 170oC for a maximum of about 155oC. Peak curing stretched from about 175 to about 225oC with a maximum at about 205oC. experiments show that by increasing the concentration of boric acid in the composition of the reaction, the development of circuits and the curing reaction is divided into two main different peaks, which occur at two different temperatures. This separation enables fast, controlled the development of chains in the B-stage without excessive curing.

Example 2

A composition comprising boric acid and phenolic crosslinking agent

To prepare the composition, which contained: 65,5 including a liquid epoxy resin D. E. R. 330 (trademark of Dow chemical of camel"), to 34.5 hours of tetrabromobisphenol A, 5,26 hours of melilitites and 5 o'clock of a solution containing 20 wt.% boric acid in methanol. The solution was left overnight. Then added the following components: 4 h solution containing 50 wt.% phenolic Novolac resin PERSTAR 85-36-28 (marketed by the company PERSTORP speakers, Perstorp, Sweden and contains 4-5,5 phenolic hydroxyl groups per molecule) in acetone, 3.5 parts of a solution containing 20 wt.% 2-methylimidazole dissolved in methanol; and methyl ethyl ketone in an amount sufficient to rasba the method DSK, described in example 1. The scan shows a broad peak development chain from 100 to 160oC with two maxima at about 135 and 145oC and a broad peak curing from about 160 to 220oC with a maximum height at about 210oC. experiments show that this separation of the development of circuits and curing occurs when the cross-linking agent is a phenol resin, instead of dicyandiamide.

Example 3

The manufacture of prepregs

The composition prepared as described in example 2, except that the crosslinking agent contained a mixture of phenolic novolak PERSTORP and tetraphenyltin 50/50. The viscosity of the composition was measured at 25oC with the use of the device 1CI with a cone and plate when using cone "With". The viscosity was equal to 80 MPa.with. Composition by dipping method was applied on a substrate of glass (type 7628, which you can buy from "Parser textiles, Bodinieri, FR-38300, Burgon-Galle, France or "Interglas textiles GmbH, Ulm/ Donau, Germany). The impregnated substrate was passed through the experimental impregnating machine "KARACH" (manufactured "Karach AG, Bremgarten, Switzerland) with a 3-meter horizontal furnace at a temperature of 152oC when skorostemerov resins. B-ladirovannye resin was utverjdali in a differential scanning calorimeter according to the method described in example 1. The first three experiments gave essentially the same results: only a broad peak from about 150 to 280oC with a maximum height at about 210oC. the Last experiment (1.8 m/min) showed a similar broad peak, but he also showed a small broad hump from about 100 to 150oC with a maximum at about 135oC. We attribute this hump incomplete development of circuits. Experiments show that within reasonable limits the composition provides a relatively controlled and consistent B-staging regardless of the speed impregnating machine and time.

Example 4

Manufacture of laminated plastics

Compositions were prepared as described in examples 1 and 2 and shown in table II. Each composition contained 80 wt.% solids and 20 weight. % volatile organic solvents. The composition was applied to a glass cloth as described in example 3. Fiberglass was passed through the experimental impregnating machine "KARACH", with a 3-meter horizontal furnace, while air temperature and speed of the winding shown in table II. Included is latkany size 10 cm x 10 cm and method 1PC-L-109B, 1PC - 650: 2,3,16 (developed by the Institute for inter-connection and packaging electronic circuits, Lincolnwood, PCs Illinois, USA). The results are presented in table II. Eight sheets of each prepreg were stacked alternating layers with sheets of copper foil. Stacked prepregs were utverjdali under pressure 250 H/cm2according to the following temperature profile: the temperature for 40 min was increased from room temperature to 170oC, then for 60 min was maintained at 170 -185oC and then for 20 min reduced from 185oC to room temperature. The resulting layered plastics are not subjected to any subsequent treatment.

Every utverzhdennym laminate conducted the following tests:

a) Absorption of N-methylpyrrolidone (NRM) was measured by weighing the sheet laminate size 5 cm x 5 cm, by immersion for 30 min in the NRM at the 23oC and then re-weighing. The results, expressed in percentage growth, are presented in table II.

b) the Strength otder copper was measured by the method JPB-L-115B, 1PC-TM-650: 2,4,8. The results, expressed in H/cm, are presented in table II.

C) a glass transition Temperature of the laminate was measured using a DSC from the party who ve the glass transition temperature. The results are presented in table II inoC.

g) water resistance was measured by placing the laminate in an autoclave at 120 min according to the method IPC-A-6OO, 1PC-M1-660 and 1PC-TM-650:2,6,16. All layered plastics passed this test at 100 %.

1. A composition comprising (1) an epoxy resin of low viscosity, (2) phenolic chain extension containing an average of more than 1 and less than 3 phenolic, hydroxyl groups on the molecule and the concentration of which is equal to from 0.1 to 0.6 phenolic hydroxyl groups per equivalent of the epoxy resin of low viscosity, (3) a catalyst which contains not more than 1 active hydrogen in the molecule and which promotiom reaction samootverzhenij between epoxy groups, (4) inhibitor, which is the Lewis acid and which is present in an amount of from 0.3 to 3 moles per mole of catalyst, the halide, oxide, hydroxide or alkoxide of zinc, tin, titanium, cobalt, manganese, iron, silicon, boron or aluminum, in addition to boron halide, (5) the volatile organic solvent is present in amount of less than 25 wt.% the total weight of the composition, and (6) may polyfunctional crosslinking agent.

2. The composition of the precursor containing (1) an epoxy resin of low viscosity, (2) foncentral which is equal to from 0.1 to 0.6 phenolic hydroxyl groups per equivalent of the epoxy resin of low viscosity, (3) inhibitor, which is the Lewis acid and which is present in an amount of from 0.05 to 2 parts per 100 parts resin, a halide, oxide, hydroxide or alkoxide of zinc, tin, titanium, cobalt, manganese, iron, silicon, boron or aluminum, in addition to boron halide, (4) not more than 20 wt.% volatile organic solvent.

3. Composition under item 1 or 2, characterized in that the epoxy resin with a low viscosity liquid is diglycidyl ether diatomic phenol.

4. Composition under item 1 or 2, characterized in that the extension of the chains is diatomic phenol or halogenated species, having a melting point above 100oC.

5. Composition under item 1 or 2, characterized in that the inhibitor is boric acid, metaboric acid, noroxin, boron oxide or alkylborane.

6. Composition according to any one of p. 1 or 3 to 5, characterized in that the multifunctional crosslinking agent is polyamine, polyamide, polyanhydride, polyphenolic or polyacidic compound which contains on average more than two active centers in the molecule, and the concentration of the multifunctional cross-linking agent is at least 0.05 equivalents of epoxide is of equivalentof extension circuits based on phenolic hydroxyl groups, epoxy equivalent of at least 0.01 equivalents of crosslinking agent to the epoxy equivalent of not more than 0.75 United equivalents extension chain and a crosslinking agent for epoxy equivalent.

8. Composition according to any one of paragraphs.1 or 3 to 7, characterized in that the catalyst contains part of the amine, phosphine, heterocyclic nitrogen, ammonium, phosphonium, arsonia or sulfone and has a concentration of from 0.05 to less than 3 weight. hours at 100 weight.h. the resin.

9. Composition according to any one of p. 1 or 3 to 8, characterized in that it contains less than 20% volatile organic solvent.

10. Composition according to any one of paragraphs.2 to 7, characterized in that it contains less than 0.05 parts catalyst to 100 parts of the resin and less than 0.05 equivalents of a multifunctional cross-linking agent to the epoxy equivalent.

11. A method of manufacturing laminated plastics for electrical purposes with the use of a composition according to any one of paragraphs.1 or 3 to 9, containing stages: 1) applying the composition to the substrate by rolling, dipping, spraying or other known method and/or their combination, 2) heating the impregnated substrate at a temperature sufficient sources of ionizing radiation to form the prepreg, 3) placing one or more sheets of the prepreg alternating layers with one or more sheets of conductive material, and (4) pressing the stacked sheets at high temperature and pressure during the time required for curing of the resin and formation of the laminate.

 

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