JP2015178627A - Metal stabilizers for epoxy resins and dispersion process - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of incorporating a metal stabilizer for increasing thermal stability into an epoxy resin without settling.SOLUTION: A method comprises (a) mixing a stabilizer comprising a metal-containing compound, the metal-containing compound comprising a metal selected from among Group 11-13 metals and combinations thereof, with a dispersant to provide a dispersion; and (b) adding the dispersion to a varnish. The dispersant contains a brominated epoxy resin.

Description

The embodiments disclosed herein relate to dispersions. More specifically, the embodiments disclosed herein relate to dispersions used in varnishes containing epoxy resins.

Recent legislation requiring lead-free solder raises the temperature at which printed circuit boards (PCBs) are exposed to about 260 ° C. These temperatures exceed the inherent thermal stability of current brominated epoxy resin-dicyandiamide (DICY) curing technology, with the exception of simple substrates where some failure can be tolerated. This increased temperature, in other words, exposes the electrical laminate to fluid soldering and reworking with very different temperature profiles, which in turn requires increased heat resistance for the electrical laminate. . As a result of this problem, the industry is converting from DICY to phenolic curing agents. Although the use of phenolic curing agents provides acceptable heat resistance, new problems have arisen, including brittleness, poor adhesion to copper and glass, and laminates that are of thickness tolerance limits. It includes certain difficulties in manufacturing within range. Brittleness causes a rough drill hole surface,
As a result, brittleness is a special problem because it causes problems with copper plating and ultimately causes substrate failure.

It would therefore be desirable to increase the thermal stability of the epoxy resin without having a significant adverse effect on other laminate properties. One method is to add a metal stabilizer to the epoxy resin. However, metal stabilizers can settle over time, thereby hindering storage stability. The desired shelf life for epoxy resins is 12 months, however, metal stabilizers can settle after a few days.
This non-uniformity is undesirable from a commercial point of view. Therefore, a method for incorporating a metal stabilizer into an epoxy resin that reduces the amount of sedimentation may be desirable.

In one embodiment of the present invention, to provide a dispersion comprising (a) a metal-containing compound comprising a metal selected from the group consisting of Group 11 to Group 13 metals and combinations thereof. And (b) adding the dispersion to the varnish, or consisting of (a) and (b) above, or (a) and (b) above ) Is essentially disclosed.

In one embodiment of the present invention, to provide a dispersion comprising (a) a metal-containing compound comprising a metal selected from the group consisting of Group 11 to Group 13 metals and combinations thereof. And (b) adding the dispersion to the varnish, or consisting of (a) and (b) above, or (a) and (b) above ) Is essentially disclosed.

Any suitable metal-containing compound can be used as a stabilizer in the embodiments disclosed herein. In general, the metal in the metal-containing compound is the 11th element in the periodic table.
It is selected from the group consisting of metals from Groups 13 to 13 and combinations thereof. These metals include
Copper, silver, gold, zinc, cadmium, mercury, boron, aluminum, gallium, indium and thallium are included. In addition to Group 11 to Group 13 metals, lead and tin can also be used. In one embodiment, the metal is zinc.

In the embodiments disclosed herein, the metal-containing compound is generally a metal salt, metal hydroxide, metal oxide, metal acetylacetonate, organometallic compound, and combinations of any two or more thereof. obtain. In one embodiment where the metal is zinc, the metal-containing compound is selected from the group consisting of zinc salts, zinc hydroxide, zinc oxide, zinc acetylacetonate, organozinc compounds, and combinations of any two or more thereof. The In one embodiment, the metal-containing compound can be zinc oxide. In one embodiment, the metal-containing compound is zinc dimethyldithiocarbamate (also known as “ziram”).

Stabilizers can generally be present in amounts ranging from about 0.1 weight percent to about 40 weight percent, based on the total weight of the resin formulation.

Any suitable dispersant can be used. Examples include, but are not limited to polyphenols, polyepoxides, anhydrides and polyamines.

Examples of polyphenols include novolaks (eg, phenol novolac, cresol novolac, bisphenol A novolak, etc.), bisphenols (eg, bisphenol F (bis (4-hydroxyphenyl) methane), bisphenol A, tetrabromobisphenol A, etc.), and And phenol oligomers prepared by condensing excess polyphenols with diepoxides.

Examples of polyepoxides include the glycidyl ethers of the polyphenols listed above, ie, solid epoxy resins that are condensation products of polyphenols and polyepoxides, specific examples being E. H. (Trademark) series of oligomers (e.g.
E. H. (Trademarks) 661 and 663) and flow control agents (for example, D.E.R.
(Trademark) 692 and D.I. E. R. (Trademark) 6508). Other examples include bromine-containing epoxides (eg, tetrabromobisphenol A diglycidyl ether),
And brominated oligomers (e.g., DER ™ 592, DER ™)
593, D.M. E. R. (Trademark) 539, D.I. E. R. (Trademark) 530, D.I. E. R. (Trademark) 538, D.I. E. R. (Trademark) 514 and D.I. E. R. (Trademark) 560).

Examples of the anhydride include nadonic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and a copolymer of maleic anhydride and an olefin (for example, styrene).

Examples of polyamines include dicyandiamide, aromatic amines such as methylenedianiline and toluenediamine, alicyclic amines such as ethanolamine, aminated polyol, ethylenediamine, diethylenetriamine and related oligomers, and the like.
Alicyclic amines such as N-aminoethylpiperazine, isophoronediamine, 1,4-bis (aminomethyl) cyclohexane and isomers can be mentioned.

In one embodiment, high shear mixing can be utilized to mix the stabilizer with the dispersant. These generally include a driven vertical axis and a high shear disk-like blade. The blades create a radial flow pattern inside the stationary mixture container. The blade creates a vortex that draws the contents of the container toward the sharp edge of the blade. The blade tip then tears the solids apart, thereby reducing their size and simultaneously dispersing the solid particles in the dispersant. These mixers have very high speeds and generally have at least 500 rpm.

Another method that is useful for mixing the stabilizer with the dispersant is by coextrusion.
Stabilizers and dispersants are added to the powder mixer to break the solids into smaller particle sizes. These components are then introduced into an extruder and coextruded at a temperature above the glass transition temperature of the epoxy resin, generally between 0 ° C and 200 ° C. The screw speed at which the components are coextruded is generally between 0 rpm and 500 rpm.

Another method that is useful for mixing the stabilizer with the dispersant is a ball mill. The stabilizer / dispersant mixture is charged into a vertical column chamber along with an amount of glass beads.
Under the stirring of two circular discs, the glass beads collide with each other and crush,
The solid agglomerates break up more efficiently, thereby creating a strong shear force that is intended to provide a smaller average particle size of the stabilizer in the final mixture. On an industrial scale, a zirconium pump coated glass bead with a diaphragm pump connected to a horizontal mill chamber to more efficiently charge the stabilizer / dispersant mixture and having much greater hardness, Used to replace glass beads.

The dispersion can then be added to the varnish. The varnish can then be ready for use without first needing to stir the settled solid particles. In addition to the epoxy resin, the varnish can also contain a curing agent, a curing agent and a catalyst.

The epoxy resin component comprises a composition, including any material that contains one or more reactive oxirane groups (herein referred to as “epoxy groups” or “epoxy functionality”). Any type of epoxy resin that is useful in molding is possible. Epoxy resins useful in the embodiments disclosed herein can include monofunctional epoxy resins, multifunctional or polyfunctional epoxy resins, and combinations thereof. Monomeric and polymeric epoxy resins can be aliphatic, cycloaliphatic, aromatic or heterocyclic epoxy resins. Polymeric epoxies include linear polymers having terminal epoxy groups (eg, diglycidyl ethers of polyoxyalkylene glycols), oxirane units in the polymer backbone (eg, polybutadiene polyepoxides), and polymers having pendant epoxy groups (eg, , A polymer or copolymer of glycidyl methacrylate). These epoxies may be pure compounds, but are generally a mixture of compounds containing one or more epoxy groups per molecule. In some embodiments, the epoxy resin can also react with an anhydride, organic acid, amino resin, phenolic resin, or epoxy group (when catalyzed) at elevated temperatures to cause further crosslinking. -OH groups can be included. In one embodiment, the epoxy resin is made by contacting glycidyl ether with a bisphenol compound (such as bisphenol A or tetrabromobisphenol A) to form an oxazolidinone component.

In general, the epoxy resin can be a glycidylated resin, an alicyclic resin, an epoxidized oil, or the like. Glycidyl resins often glycidyl ether (e.g., epichlorohydrin, etc.) and bisphenol compound (e.g., bisphenol A) the reaction product _of; C 4 _{-C 28} alkyl glycidyl _ethers; C 2 _{-C 28} alkyl - and alkenyl - glycidyl _esters; C 1 _{-C 28} alkyl - monophenols glycidyl ethers and _C 1 _{-C 28} alkyl - polyphenol glycidyl ether; polyhydric phenols (e.g.,
Pyrocatechol, resorcinol, hydroquinone, 4,4′-dihydroxydiphenylmethane (ie, bisphenol F), 4,4′-dihydroxy-3,3′-dimethyldiphenylmethane, 4,4′-dihydroxydiphenyldimethylmethane (ie, bisphenol A) ), 4,4′-dihydroxydiphenylmethylmethane, 4,4′-dihydroxydiphenylcyclohexane, 4,4′-dihydroxy-3,3′-dimethyldiphenylpropane, 4,4′-dihydroxydiphenylsulfone and tris (4- Polyglycidyl ethers of hydroxyphenyl) methane etc .; chlorinated and brominated products of the above diphenols; polyglycidyl ethers of novolacs; polyglycidyl ethers of novolacs; salts of aromatic hydrocarboxylic acids with dihaloalkanes or Polyglycidyl ethers of diphenols obtained by esterification of ethers of diphenols obtained by esterification with halogen dialkyl ethers; condensation of phenolic compounds with long-chain halogen paraffins containing at least two halogen atoms It is polyglycidyl ether of polyphenol obtained by doing. Other examples of epoxy resins useful in the embodiments disclosed herein include bis-4,4 ′-(1-methylethylidene) phenol diglycidyl ether and (chloromethyl) oxirane bisphenol A diglycidyl ether. Is mentioned.

In some embodiments, epoxy resins may include glycidyl ether types, glycidyl ester types, decyclic types, heterocyclic types, halogenated epoxy resins, and the like. Non-limiting examples of suitable epoxy resins can include cresol novolac epoxy resins, phenol novolac epoxy resins, biphenyl epoxy resins, hydroquinone epoxy resins, stilbene epoxy resins, and mixtures and combinations thereof.

Suitable polyepoxy compounds include resorcinol diglycidyl ether (1,3-bis (2,3-epoxypropoxy) benzene), diglycidyl ether of bisphenol A (2,2-bis (p- (2,3-epoxy) Propoxy) phenyl) propane), triglycidyl p-aminophenol (4- (2,3-epoxypropoxy) -N, N-bis (2
, 3-epoxypropyl) aniline), diglycidyl ether of bromobisphenol A (2,2-bis (4- (2,3-epoxypropoxy) 3-bromo-phenyl) propane), diglycidyl ether of bisphenol F (2 , 2-bis (p- (2,3-epoxypropoxy) phenyl) methane), meta- and / or para-aminophenol triglycidyl ether (3- (2,3-epoxypropoxy) N, N-bis ( 2,3-
Epoxypropyl) aniline) and tetraglycidylmethylenedianiline (N, N)
, N ′, N′-tetra (2,3-epoxypropyl) 4,4′-diaminodiphenylmethane), as well as mixtures of two or more polyepoxy compounds. A more comprehensive listing of useful epoxy resins found can be found in Lee, H. et al. And Neville, K .; , Handbook
of Epoxy Resins, McGraw-Hill Book Company (reissued in 1982).

Other suitable epoxy resins include polyepoxy compounds based on aromatic amines and epichlorohydrin, such as N, N′-diglycidyl-aniline; N, N′-dimethyl-N, N′-diglycidyl. -4,4'-diaminodiphenylmethane; N, N, N ', N'
-Tetraglycidyl-4,4'-diaminodiphenylmethane; N-diglycidyl-4-aminophenylglycidyl ether; and N, N, N ', N'-tetraglycidyl-1,3
-Propylene bis-4-aminobenzoate etc. are mentioned. Epoxy resin also
One or more glycidyl derivatives of aromatic diamines, aromatic monoprimary amines, aminophenols, polyhydric phenols, polyhydric alcohols, polycarboxylic acids may be included.

Useful epoxy resins include, for example, polyhydric polyols (eg, ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,5-pentanediol, 1
, 2,6-hexanetriol, glycerol, and 2,2-bis (4-hydroxycyclohexyl) propane); aliphatic and aromatic polycarboxylic acids (eg, oxalic acid, succinic acid, glutar) Polyglycidyl ethers of acids, terephthalic acid, 2,6-naphthalenedicarboxylic acid and dimerized linoleic acid; polyphenols (eg bisphenol A, bis-phenol F, 1,1-bis (4-hydroxyphenyl) ethane, 1 , 1-bis (4-hydroxyphenyl) isobutane and 1,5-
And polyglycidyl ethers of dihydroxynaphthalene); modified epoxy resins having acrylate or urethane components; glycidyl amine epoxy resins; and novolak resins.

The epoxy compound can be an alicyclic epoxide or a decyclic epoxide. Examples of alicyclic epoxides include diepoxides of alicyclic esters of dicarboxylic acids, such as bis (3,
4-epoxycyclohexylmethyl) oxalate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl)
Examples include adipate and bis (3,4-epoxycyclohexylmethyl) pimelate; vinylcyclohexene diepoxide; limonene diepoxide; and dicyclopentadiene diepoxide. Other suitable diepoxides of alicyclic esters of dicarboxylic acids are described, for example, in US Pat. No. 2,750,395.

Other alicyclic epoxides include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate compounds, such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; 3,4-epoxy-1-methylcyclohexyl-methyl-3,4-epoxy-1-methylcyclohexanecarboxylate; 6-methyl-3,4-epoxycyclohexylmethylmethyl-6-methyl-3,4-epoxycyclohexanecarboxy 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylate; 3,4-epoxy-3-methylcyclohexyl-methyl-3,4-epoxy-3-methylcyclohexane Carboxa DOO; 3,4-epoxy-5-methylcyclohexyl -, methyl-3,4-epoxy-5-methylcyclohexane carboxylate and the like. Other suitable 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate compounds are described, for example, in US Pat. No. 2,890,194.

Additional epoxy-containing materials that are useful include those based on glycidyl ether monomers. An example is a diglycidyl ether or polyglycidyl ether of a polyhydric phenol obtained by reacting a polyhydric phenol (such as a bisphenol compound) with an excess of chlorohydrin (such as epichlorohydrin). Such polyhydric phenols include resorcinol, bis (4-hydroxyphenyl) methane (which is known as bisphenol F), 2,2-bis (4-hydroxyphenyl) propane (
This is known as bisphenol A), 2,2-bis (4'-hydroxy-3 ',
5'-dibromophenyl) propane, 1,1,2,2-tetrakis (4'-hydroxy-
Phenyl) ethane or a condensate of phenolic compound and formaldehyde obtained under acid conditions (for example, phenol novolak and cresol novolak). An example of this type of epoxy resin is described in US Pat. No. 3,018,262.
Other examples include diglycidyl or polyglycidyl ethers of polyhydric alcohols (such as 1,4-butanediol) or polyalkylene glycols (such as polypropylene glycol), and alicyclic polyols (such as 2 , 2-bis (4-hydroxycyclohexyl) propane, etc.) diglycidyl ether or polyglycidyl ether. Another example is a monofunctional resin, such as cresyl glycidyl ether or butyl glycidyl ether.

Another class of epoxy compounds are polyglycidyl esters and poly (β-methylglycidyl) esters of polyvalent carboxylic acids such as phthalic acid, terephthalic acid, tetrahydrophthalic acid or hexahydrophthalic acid. Further types of epoxy compounds are amines,
N-glycidyl derivatives of amides and heterocyclic nitrogen bases, for example, N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidylbis (4-amino) Phenyl) methane, triglycidyl isocyanurate, N, N′-diglycidylethylurea, N, N′-diglycidyl-5,5-dimethylhydantoin and N, N′-diglycidyl-5-isopropylhydantoin.

Yet another epoxy-containing material is a copolymer of an acrylate ester of glycidol (eg, glycidyl acrylate and glycidyl methacrylate) and one or more copolymerizable vinyl compounds. Examples of such copolymers are 1: 1 styrene-glycidyl methacrylate, 1: 1 methyl-methacrylate glycidyl acrylate, and 62.5: 24: 13.5 methyl methacrylate-ethyl acrylate. Glycidyl methacrylate.

Easily available epoxy compounds include octadecylene oxide; glycidyl methacrylate; diglycidyl ether of bisphenol A; E. R. (Trademark) 3
31 (liquid epoxy resin of bisphenol A) and D.I. E. R. (Trademark) 332 (diglycidyl ether of bisphenol A) (these are The Dow Chemical
Company (available from Midland, Michigan); vinylcyclohexene dioxide; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; 3,4-epoxy-6-methylcyclohexyl-methyl-3, 4-epoxy-6-methylcyclohexanecarboxylate; bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate; bis (2,3-epoxycyclopentyl) ether; aliphatic epoxy modified with polypropylene glycol; dipentene di Oxides; Epoxidized polybutadienes; Silicone resins containing epoxy functionality; Flame retardant epoxy resins (eg, The Dow Chemical Company (Mi
dland, Michigan). E. R. (Trademark) 530, 539
Brominated bisphenol type epoxy resins available under the trade names of 542, 560, 592 and 593); polyglycidyl ethers of phenol formaldehyde novolac (for example, The Dow Chemical Company (Midland,
Available from Michigan). E. N. (Trademark) 431 and D.I. E. N. (Trademark) available under the trade name 438); and resorcinol diglycidyl ether. Although not specifically shown, The Dow Chemical Compa
D. available from ny. E. R. (Trademark) and D.I. E. N. Other epoxy resins under the trade name (trademark) can also be used.

Other suitable epoxy resins are described, for example, in U.S. Patent Nos. 7,163,973 and 6,631.
No. 2,893, No. 6,242,083, No. 7,037,958, No. 6,572
, 971, 6,153,719 and 5,405,688, and US Patent Publication Nos. 20060293172 and 20050171237, each of which is hereby incorporated by reference. Incorporated herein by reference).

Other suitable epoxy resins include phenolic resins, benzoxazine resins, aryl cyanate resins, aryl triazine resins and maleimide resins. Mixtures of any of the epoxy resins listed above can of course also be used.

A curing agent (or curing agent) can be provided to promote crosslinking of the curable composition to form the thermosetting composition. Curing agents can be used individually or 2
Can be used as a mixture of two or more. In some embodiments, the curing agent can include dicyandiamide (dicy) or a phenolic curing agent (eg, novolak, resole, bisphenol, etc.). Other curing agents, some of which are disclosed above, may include improved (oligomeric) epoxy resins. Examples of improved epoxy resin curing agents may include, for example, epoxy resins prepared from bisphenol A diglycidyl ether (or diglycidyl ether of tetrabromobisphenol A) and excess bisphenol or (tetrabromobisphenol). . Anhydrides such as poly (styrene-co-maleic anhydride) can also be used.

Curing agents can also include primary and secondary polyamines and their adducts, anhydrides, and polyamides. For example, multifunctional amines include aliphatic amine compounds such as diethylenetriamine (DEH.TM. 20, which is The Do
w Chemical Company (available from Midland, Michigan)), triethylenetetramine (DEH ™ 24), which is
Dow Chemical Company (available from Midland, Michigan)), tetraethylenepentamine (DEH ™ 26,
he Dow Chemical Company (Midland, Michigan)
As well as adducts of the above amines with epoxy resins, diluents or other amine-reactive compounds. Aromatic amines (such as metaphenylene diamine and diamine diphenyl sulfone), aliphatic polyamines (such as aminoethylpiperazine and polyethylene polyamine) and aromatic polyamines (such as metaphenylene diamine, diaminodiphenyl sulfone and diethyl toluene diamine)
Can also be used.

Anhydride curing agents include, for example, nadic methyl anhydride, among others.
), Hexahydrophthalic anhydride, trimellitic anhydride, dodecenyl succinic anhydride, phthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride and methyltetrahydrophthalic anhydride.

For the curing agent, phenol-derived novolak or substituted phenol-derived novolak, or
Anhydrides may be included. Non-limiting examples of suitable curing agents include phenol novolac curing agents, cresol novolac curing agents, dicyclopentadiene bisphenol curing agents, limonene type curing agents, anhydrides and mixtures thereof.

In some embodiments, the phenol novolac hardener can contain a biphenyl component or a naphthyl component. A phenolic hydroxy group can be attached to the biphenyl or naphthyl component of the compound. This type of curing agent can be prepared, for example, according to the method described in EP915118A1. For example, a curing agent containing a biphenyl component can be prepared by reacting phenol with bismethoxy-methylene biphenyl.

In other embodiments, the curing agent can include dicyandiamide, boron trifluoride monoethylamine, and diaminocyclohexane. Curing agents can also include imidazole compounds, their salts and adducts. These epoxy hardeners are typically solid at room temperature. Examples of suitable imidazole hardeners are disclosed in EP 906927A1. Other curing agents include phenolic, benzoxazine, aromatic amine, amidoamine, aliphatic amine, anhydride and phenolic compounds.

In some embodiments, the curing agent can be a polyamide or amino compound having a molecular weight of up to 500 per amino group, such as an aromatic amine or guanidine derivative.
Examples of amino curing agents include 4-chlorophenyl-N, N-dimethyl-urea and 3,4-dichlorophenyl-N, N-dimethyl-urea.

Other examples of curing agents useful in the embodiments disclosed herein include 3,3′-
Diaminodiphenyl sulfone and 4,4′-diaminodiphenyl sulfone; methylene dianiline; bis (4-amino-3,5-dimethylphenyl) -1,4-diisopropylbenzene (available as EPON 1062 from Hexion Chemical Co.) And bis (4-aminophenyl) -1,4-diisopropylbenzene (
This is the same as Hexion Chemical Co. Available from EPON 1061).

Thiol based curing agents for epoxy compounds can also be used and are described, for example, in US Pat. No. 5,374,668. As used herein, “
“Thiol” also includes polythiol-based or polymercaptan-based curing agents. Exemplary thiols include aliphatic thiols such as methanedithiol, propanedithiol, cyclohexanedithiol, 2-mercaptoethyl-2,3-dimercaptosuccinate, 2,3-dimercapto-1-propanol (2-mercapto Acetate),
Diethylene glycol bis (2-mercaptoacetate), 1,2-dimercaptopropyl methyl ether, bis (2-mercaptoethyl) ether, trimethylolpropane tris (thioglycolate), pentaerythritol tetra (mercaptopropionate)
, Pentaerythritol tetra (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris (β-thiopropionate), a tris-mercaptan derivative of a tri-glycidyl ether of a propoxylated alkane, and dipentaerythritol poly (Β-thiopropionate) etc .; halogen-substituted derivatives of aliphatic thiols; aromatic thiols such as dimercaptobenzene, trismercaptobenzene or tetramercaptobenzene, bis (mercaptoalkyl) benzene, tris (mercaptoalkyl) Benzene or tetrakis (mercaptoalkyl) benzene, dimercaptobiphenyl, toluene dithiol and naphthalenedithiol; halogen-substituted derivatives of aromatic thiols; Thiol-containing, such as amino-4,6-dithiol-sy
m-triazine, alkoxy-4,6-dithiol-sym-triazine, aryloxy-4,6-dithiol-sym-triazine, 1,3,5-tris (3-mercaptopropyl) isocyanurate, etc .; Halogen-substituted derivatives of thiols; thiol compounds having at least two mercapto groups and containing sulfur atoms in addition to mercapto groups, such as bis (mercaptoalkylthio) benzene, tris (mercaptoalkylthio) benzene or tetrakis ( Mercaptoalkylthio) benzene, bis (
Mercaptoalkylthio) alkane, tris (mercaptoalkylthio) alkane or tetrakis (mercaptoalkylthio) alkane, bis (mercaptoalkyl) disulfide, hydroxyalkylsulfide bis (mercaptopropionate), hydroxyalkylsulfide bis (mercaptoacetate), mercaptoethyl ether Bis (mercaptopropionate), 1,4-dithian-2,5-diol bis (mercaptoacetate), thiodiglycolic acid bis (mercaptoalkyl ester), thiodipropionic acid bis (2-mercaptoalkyl ester), 4 , 4-thiobutyric acid bis (2-mercaptoalkyl ester), 3,4-thiophenedithiol, bismuththiol and 2
, 5-dimercapto-1,3,4-thiadiazole and the like.

The curing agent can also be a nucleophilic material such as an amine, a tertiary phosphine, a quaternary ammonium salt with a nucleophilic anion, a quaternary phosphonium salt with a nucleophilic anion, an imidazole compound. A tertiary arsenium salt with a nucleophilic anion, and
Tertiary sulfonium salts with nucleophilic anions are possible.

Aliphatic polyamines modified by adduct formation with epoxy resins, acrylonitrile or methacrylates are also optionally utilized as curing agents. In addition, various Mannich bases can be used. An aromatic amine in which the amine group is directly bonded to the aromatic ring is also optionally used.

Quaternary ammonium salts with nucleophilic anions that are useful as curing agents in the embodiments disclosed herein include tetraethylammonium chloride, tetrapropylammonium acetate, hexyltrimethylammonium bromide, benzyltrimethylammonium Cyanide, cetyltriethylammonium azide, N, N-dimethylpyrrolidinium isocyanate, N-methylpyridinium phenolate, N-methyl-o-chloropyridinium chloride, methyl viologen dichloride, and the like may be included.

The suitability of the curing agent for use herein can be determined by reference to the manufacturer's specifications or by routine experimentation. The manufacturer's specifications can be used to determine if the curing agent is an amorphous solid or a crystalline solid at the desired temperature for mixing with the liquid or solid epoxy. Alternatively, a solid curing agent is sought for the amorphous or crystalline nature of the solid curing agent and the suitability of the curing agent for mixing with the resin composition in either liquid or solid form. Therefore, it can be tested using differential scanning calorimetry (DSC).

Mixtures of one or more of the epoxy curing agents (or curing agents) described above can also be used.

If necessary, the catalyst can be added to the varnish described above. For the catalyst,
Compounds having one imidazole ring per molecule (for example, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-
Heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2-phenyl-4-benzylimidazole, 1-cyanoethyl-
2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1
-Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-isopropylimidazole, 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6- [
2′-Methylimidazolyl- (1) ′]-ethyl-s-triazine, 2,4-diamino-
6- [2′-ethyl-4-methylimidazolyl- (1) ′]-ethyl-s-triazine,
2,4-diamino-6- [2′-undecylimidazolyl- (1) ′]-ethyl-s-triazine, 2-methylimidazolium-isocyanuric acid adduct, 2-phenylimidazolium-isocyanuric acid adduct, 1-aminoethyl-2-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, etc. ) And the hydroxymethyl-containing imidazole compounds named above (eg, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4)
-Methyl-5-hydroxymethylimidazole and 2-phenyl-4-benzyl-5-hydroxymethylimidazole) and the like, and two or more imidazoles per molecule obtained by condensing them with formaldehyde Various imidazole compounds may be included, including but not limited to compounds having a ring (eg, 4,4′-methylene-bis- (2-ethyl-5-methylimidazole, etc.)).

In other embodiments, suitable catalysts include amine-based catalysts such as N-alkylmorpholines, N-alkylalkanolamines, N, N-dialkylcyclohexylamines and alkylamines where the alkyl group is methyl, ethyl, Propyl, butyl and their isomeric forms), heterocyclic amines and the like.

Non-amine based catalysts can also be used. Organometallic compounds of bismuth, lead, tin, titanium, iron, antimony, uranium, cadmium, cobalt, thorium, aluminum, mercury, zinc, nickel, cerium, molybdenum, vanadium, copper, manganese and zirconium can be used. Illustrative examples include bismuth nitrate, lead 2-ethylhexanoate, lead benzoate, ferric chloride, antimony trichloride, stannous acetate, stannous octoate and stannous 2-ethylhexanoate. Can be mentioned. Other catalysts that can be used are disclosed, for example, in PCT Publication No. WO 00/15690, which is incorporated by reference in its entirety.

In some embodiments, suitable catalysts include nucleophilic amines and phosphines, especially nitrogen heterocyclic compounds such as alkylated imidazoles (eg, 2-phenylimidazole, 2-methylimidazole, 1-methylimidazole). , 2-methyl-4-ethylimidazole) and other heterocyclic compounds such as diazabicycloundecene (DBU),
Diazabicyclooctene, hexamethylenetetramine, morpholine, piperidine, etc.); trialkylamine (eg, triethylamine, trimethylamine, benzyldimethylamine); phosphine (eg, triphenylphosphine, tritolylphosphine, triethylphosphine, etc.); Quaternary salts such as triethylammonium chloride, tetraethylammonium chloride, tetraethylammonium acetate, triphenylphosphonium acetate and triphenylphosphonium iodide can be included. Mixtures of one or more of the catalysts described above can also be used.

In one embodiment, a solvent can also be added to the varnish. Suitable solvents include, but are not limited to, water and organic solvents having a boiling point less than 200 ° C. Examples of these solvents include acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropanol, n-butanol and isobutanol, various methoxypropanols (ie Dowanol ™ PM), various methoxypropyl acetates. Tart (Dowanol ™ PMA) and N, N′-dimethylformamide.

It may be advantageous to use a metal stabilizer that has been surface treated to aid the dispersion process. Such a surface treatment allows the particles to be separated relatively easily and reduces the tendency to reagglomerate. Examples of surface treatments include carboxylic acids, sulfonic acids and sulfuric acids, phosphoric acids and phosphonic acids, and related surfactants. A specific example is
Aliphatic carboxylic acids (for example, acetic acid, oleic acid, stearic acid, etc.), phenylsulfonic acid, toluenesulfonic acid, sulfate esters of long chain alcohols. Other treatments include silane and silicone.

Such treatment is typically designed to change the surface properties of a solid by forming an inert surface layer. Alternatively, a treatment designed to coat the surface and interact with the components of the present invention is possible. Specific examples are various aminopropyltrimethoxysilanes, various epoxysilanes, and methacryloxypropyltrimethoxysilane.

Dispersing aids added to the formulation are well known in the art. A large number of trademarked additives are available, for example those obtained from BYK.

In some embodiments, fillers can be used. Suitable fillers include, for example, silica, alumina, glass, talc, metal powder, titanium dioxide, wetting agents, pigments, colorants, mold release agents, coupling agents, ion scavengers, UV stabilizers, softeners and A tackifier may be included. Additives and fillers also include fumed silica, aggregates (eg, glass beads), polytetrafluoroethylene, polyol resins, polyester resins, phenolic resins, graphite, molybdenum disulfide, abrasive pigments, viscosity reducing agents, among others. Boron nitride, mica, nucleating agents and stabilizers may be included. Fillers may include functional or non-functional particulate fillers that may have particle sizes ranging from 0.5 nm to 100 microns, and may include, for example, alumina trihydrate, aluminum oxide, Examples include aluminum hydroxide oxide, metal oxides and nanotubes. Fillers and modifiers can be preheated to drive off moisture prior to addition to the epoxy resin composition. In addition, these additives, used as needed, can have an effect on the properties of the composition before and / or after curing and are considered when formulating varnish and desired reaction products. Must be put in. Silane treated fillers can be used.

In other embodiments, the varnishes disclosed herein can also include nanofillers. The nanofiller can be inorganic or organic or metallic and can be in the form of a powder, whisker, fiber, plate or film. Nanofillers are generally any filler that has at least one size (length, width or thickness) of from about 0.1 nanometers to about 100 nanometers, or any combination of such fillers. Is possible.
For example, for powders, at least one size can be characterized as a particle size; for whiskers and fibers, at least one size is a diameter; for plates and films, at least one size is a thickness. is there. For example, clay can be dispersed in a matrix based on an epoxy resin, and clay can be broken into very thin component layers when dispersed in an epoxy resin under shear. Nanofillers include clays, organic clays, carbon nanotubes, nanowhiskers (eg, SiC, etc.), SiO ₂ , elements selected from the s group, p group, d group, and f group of the periodic table, and so on. One or more elemental anions or salts, metals, metal oxides and ceramics may be included.

In some embodiments, the composite can be formed by curing the varnish disclosed herein. In other embodiments, the composite can be formed by applying a curable epoxy resin composition to a substrate or reinforcement, for example, impregnating the substrate or reinforcement, or It can be formed by coating to form a prepreg and curing the prepreg under pressure to form an electrical laminate composition.

After the varnish has been produced as described above, the varnish can be placed on, within or between the surfaces of the substrate before, during or after curing of the electrical laminate composition.
For example, the composite can be formed by coating the substrate with a varnish. Coating can be done by a variety of procedures including spray coating, curtain flow coating, roll coater or gravure coater coating, brushing, and dipping or dip coating.

In various embodiments, the substrate can be a single layer or multiple layers. For example, the substrate can be, for example, a composite of two alloys, a multilayer polymer article, and a metallized polymer, among others. In various other embodiments, one or more layers of the curable composition can be disposed on the substrate. Other multi-layer composites formed by various combinations of substrate layers and electrical laminate composition layers are also contemplated herein.

In some embodiments, heating of the varnish can be localized, for example, to avoid overheating the temperature sensitive substrate. In other embodiments, the heating can include heating the substrate and the composition.

Curing of the varnish disclosed herein is at least about 30 ° C. to about about 30 minutes, ranging from minutes to hours, depending on the epoxy resin, curing agent, and catalyst (if used). Temperatures up to 250 ° C may be required. In other embodiments, curing can be performed at a temperature of at least 100 ° C. for periods ranging from minutes to hours. Post-treatment can be used as well, and such post-treatment is typically at temperatures between about 100 ° C and 250 ° C.

In some embodiments, curing can be performed in stages to prevent heat generation. In the staging, for example, curing at a certain temperature for a predetermined period, and then curing at a higher temperature for a predetermined period can be mentioned. Staged curing can include two or more curing stages, which can be initiated at a temperature below about 180 ° C. in some embodiments and at a temperature below about 150 ° C. in other embodiments. You can start with.

In some embodiments, the curing temperature is 30 ° C, 40 ° C, 50 ° C, 60 ° C, 70 ° C.
80 ° C, 90 ° C, 100 ° C, 110 ° C, 120 ° C, 130 ° C, 140 ° C, 150 ° C,
From the lower limit of 60 ° C, 170 ° C or 180 ° C, 250 ° C, 240 ° C, 230 ° C, 220 ° C,
It can range up to 210 ° C, 200 ° C, 190 ° C, 180 ° C, 170 ° C, 160 ° C (however, the range can be from any lower limit to any upper limit).

The varnishes disclosed herein may be useful in composites containing high strength filaments or fibers such as carbon (graphite), glass and boron. The composite may contain from about 30% to about 70% of these fibers in some embodiments, and in other embodiments from 40% to 70% of these fibers, based on the total volume of the composite. Fibers can be included.

For example, fiber reinforced composites can be formed by hot melt prepreg. The prepreg method is as described herein in a molten form in a continuous fiber band or fabric to obtain a prepreg that is stacked and cured to provide a composite of fiber and epoxy resin. Characterized by impregnation with a thermosetting composition.

Other processing techniques can be used to form electrical laminate composites containing the compositions disclosed herein. For example, filament winding, solvent prepreg and drawing are typical processing techniques in which varnish can be used. In addition, the fibers in the form of bundles can be coated with varnish, stacked, for example, by filament winding, and cured to form a composite.

Varnishes and composites described herein are for adhesives, structural and electrical laminates, coatings, marine coatings, composites, powder coatings, adhesives, injection moldings, aerospace industries It can be useful as a circuit board for the electronics industry.

In some embodiments, the varnish can be used in composites, coatings, adhesives or sealants that can be placed on, within, or between various substrates. In other embodiments, varnish can be applied to a substrate to obtain an epoxy based prepreg. As used herein, substrates include, for example, glass cloth, glass fiber, glass paper, paper, and similar substrates of polyethylene and polypropylene. The obtained prepreg can be cut into a desired size. An electrically conductive layer can be formed on the surface of the laminate / prepreg with an electrically conductive material. As used herein, suitable electrically conductive materials include electrically conductive metals such as copper, gold, silver, platinum and aluminum. Such electrical laminates can be used, for example, as multilayer printed circuit boards for electrical or electronics equipment. Laminates made from a blend mixture of maleimide-triazine-epoxy polymers are particularly useful for making HDI (High Density Interconnect) substrates. Examples of HDI substrates include substrates used in mobile phones or substrates used for interconnect (IC) substrates.

The following examples are intended to illustrate the present invention and to teach one of ordinary skill how to make and use the invention. The following examples are not intended to limit the invention in any way.

In the examples below, the ingredients are as follows:
D. E. R. 530-A80: Brominated epoxy prepared by condensing excess bisphenol A diglycidyl ether with tetrabromobisphenol A (80% solids in acetone)
D. E. R. ™ 592-A80: Brominated epoxy prepared by condensing excess bisphenol A diglycidyl ether with methylene diisocyanate and tetrabromobisphenol A (80% solids in acetone)
D. E. R. (Trademark) 383: diglycidyl ether of bisphenol A E. N. TM 438EK85 is a novolak prepared by condensation polymerization of acetone and phenol (85% solids in MEK).
Nano-ZnO is zinc oxide obtained from Aldrich and has an average particle size of less than 1 μm.
NanoTek ™ ZnO is zinc oxide obtained from Nanophase Technologies, with an average particle size of less than 100 mnm.
NanoGard ™ ZnO is a Nanophase Technologies.
Zinc oxide obtained from the above, having an average particle size of less than 100 nm.
Zn (acac) ₂ is zinc acetylacetonate obtained from Aldrich.
MEK is methyl ethyl ketone obtained from Aldrich.
In the examples below, four masterbatches were dispersed using a high shear mixer.

Example 1
50 grams of D.I. E. R. TM 530-A80 and 17.15 grams of Nan
o-ZnO was dispersed with a high shear mixer. High shear mixer, 3000r with heat generation
Operated at pm-5000 rpm. A 30 mL amount of MEK was added to adjust the viscosity. The mixture became fluid. When 20 mL of MEK was used, the mixture was a non-flowing paste. The weight percent of stabilizer was 30.01 wt% (based on total solids). The weight percentage of total solids was 62.70%.

Example 2
50 grams of D.I. E. R. TM 530-A80 and 17.15 grams of Zn (
acac) ₂ was dispersed with a high shear mixer. High shear mixer with heat generation 3000
Operated at rpm to 5000 rpm. No further solvent was added, resulting in a mixture that was a slowly flowing paste. Stabilizer weight percent (based on total solids)
It was 30.01 wt%. The weight percentage of total solids was 85.11%.

Example 3
50 grams of D.I. E. R. ™ 592-A80 and 17.15 grams of Nan
o-ZnO was dispersed with a high shear mixer. High shear mixer, 3000r with heat generation
Operated at pm-5000 rpm. A 20 mL amount of MEK was added to adjust the viscosity. The mixture was a free flowing paste. 30.0% by weight of stabilizer (based on total solids)
It was 1 wt%. The weight percent of total solids was 68.73%.

Example 4
A 25 gram amount of D.P. E. R. TM 530-A80 and 8.57 grams of Zn (a
cac) ₂ was dispersed with a high shear mixer. 30 high shear mixer with intense heat generation
Operating at 00-5000 rpm, this resulted in a very viscous paste. 1
A 0 mL amount of MEK was added. However, the mixture had to be shaken to achieve a homogeneous paste. Stabilizer weight percent (based on total solids) 30.00w
t%. The weight percentage of total solids was 85.11%.

Examples 5 to 12
Examples 5-12 are detailed in Table I below.

Example 13
A solid masterbatch was prepared by coextrusion as detailed in Table II below. Neat D.E. E. R. TM 592 and ZnO are weighed into a 2 gallon plastic bucket. The mixture is then washed 230 ° C. at a constant temperature of 26 ° C.
The blend was mixed with a Prism mixer at 0 rpm for 15 seconds. This blend mixing process was repeated two more times. A twin screw extruder (Prism TSE-24-PC powder coated extruder) where the powdery mixture is then operated at a screw speed of 400 rpm.
To be introduced. The extruder was equipped with three heating zones set at 25 ° C, 75 ° C and 90 ° C. The resulting off-white solid was flaked with a small drum flaker.

Example 14
In this example, the dispersion was prepared by dropwise addition of pre-dispersed zinc oxide to the epoxy resin and then stirred for 1 hour with gentle shaking. This is described in detail in Table III below.

Example 16
The dispersion was prepared by ball mill mixing. The raw material and glass beads were stirred with a 2 L ball mill for 30 minutes at 2800 rpm while circulating cooling water through the jacket. The glass beads were then removed by a filter attached near the bottom of the canister. The amount of components in the dispersion is detailed in Table IV below.

Although the invention has been described in detail for purposes of illustration, the invention should not be construed as limited thereby, but encompasses all variations and modifications that are within its spirit and scope. Is intended.

Claims (18)

(A) mixing a stabilizer comprising a metal-containing compound comprising a metal selected from the group consisting of Group 11 to Group 13 metals and combinations thereof with the dispersant to provide a dispersion;
(B) A method comprising adding the dispersion to a varnish.   The method of claim 1, wherein the mixing is high shear mixing.   The method of claim 2, wherein the high shear mixing rate is at least 500 rpm.   The method of claim 1, wherein the mixing is ball mill mixing. The method of claim 1, wherein the mixing is performed in a powder mixer followed by coextrusion.   The method of claim 1, wherein the period for mixing is at least 30 seconds. The method of claim 1, wherein the dispersant is selected from the group consisting of polyphenols, polyepoxides, anhydrides, polyamines, and combinations thereof.   The method of claim 1, wherein the metal is zinc. The metal-containing compound is a zinc salt, zinc hydroxide, zinc oxide, zinc acetylacetonate,
9. The method of claim 8, wherein the method is selected from the group consisting of organozinc compounds and combinations of any two or more thereof. The method of claim 1, wherein the varnish further comprises a component selected from the group consisting of an inert filler, a solvent, and mixtures thereof. The method of claim 1, wherein the stabilizer is present in the dispersion in a range of about 5 weight percent to about 75 weight percent, based on the total weight of the dispersion.   A varnish produced by the method according to claim 1.   A prepreg prepared from the varnish of claim 12.   An electrical laminate prepared from the varnish of claim 12.   A coating prepared from the varnish of claim 12.   A composite prepared from the varnish of claim 12.   An injection-molded article prepared from the varnish according to claim 12.   An adhesive prepared from the varnish of claim 12.