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WO1997011105A1 - Epoxy resin composition for electrolaminates having aryl substituted guanidine and/or biguanide as cross-linking agent - Google Patents

Epoxy resin composition for electrolaminates having aryl substituted guanidine and/or biguanide as cross-linking agent Download PDF

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Publication number
WO1997011105A1
WO1997011105A1 PCT/EP1996/003995 EP9603995W WO9711105A1 WO 1997011105 A1 WO1997011105 A1 WO 1997011105A1 EP 9603995 W EP9603995 W EP 9603995W WO 9711105 A1 WO9711105 A1 WO 9711105A1
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WO
WIPO (PCT)
Prior art keywords
epoxy resin
resin composition
bromine
resin
biguanide
Prior art date
Application number
PCT/EP1996/003995
Other languages
French (fr)
Inventor
Antonius Johannes Wilhelmus Buser
Jan Andre Jozef Schutyser
Original Assignee
Akzo Nobel N.V.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Akzo Nobel N.V. filed Critical Akzo Nobel N.V.
Publication of WO1997011105A1 publication Critical patent/WO1997011105A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/30—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/145—Organic substrates, e.g. plastic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O

Definitions

  • the present invention pertains to a bromine-containing epoxy resin composition for printed wiring board substrates, i.e., for electrolaminates.
  • bromine-containing epoxy resins cured with about 3 wt.% of dicyandiamide (also known as cyanoguanidine or dicy) as cross-linking agent.
  • dicyandiamide also known as cyanoguanidine or dicy
  • the most common electrolaminate in the electronics industry is referred to as the FR-4 laminate.
  • Difunctional brominated epoxy resins such as DER535®, ex Dow Chemical, and Epikote 1143®, ex Shell, cured with 3% of dicy are employed in the FR-4 laminate.
  • the glass transition temperature (Tg) of this laminate is 125°C.
  • a woven glass fabric is passed through the resin solution; next, the impregnated woven glass fabric is freed of solvent in a treater (hot- air column) and the resin present is partially cured to the B-stage. After this, a stack of prepregs with copper foil on the outside is compressed to form an electrolaminate.
  • a treater hot- air column
  • Dicy is poorly soluble both in pure bromine-containing epoxy resin and in bromine- containing epoxy resin dissolved in acetone and/or methylethyl ketone.
  • solvents such as dimethyl formamide (DMF) and mixtures of DMF and methylethyl ketone (MEK) or acetone is required.
  • DMF dimethyl formamide
  • MEK methylethyl ketone
  • DMF has a higher boiling point (153°C) than MEK (80°C) and acetone (56°C) and, on the other, there is the requirement in this sector of industry to have prepregs containing less than 1 % of solvent, a higher treater temperature is needed to evaporate the DMF.
  • solvent-free compositions or compositions dissolved exclusively in MEK and acetone are less expensive in terms of energy consumption than DMF-containing compositions.
  • the search is on for liquid bromine-containing epoxy resin compositions suitable for impregnating woven glass fabric without the use of any additional solvent. This will put an end to the emission of solvents from the treater, and so to further harm to the environment.
  • EP-A1-0 584 863 it is attempted to avoid the use of DMF and other solvents hazardous to man and the environment such as ethylene glycolmonomethyl ether by preparing a pre-adduct of dicy and a less than stoichiometric amount of brominated epoxy resin. Dissolved in an acceptable solvent, this pre-adduct can be used as a curing agent for brominated epoxy resin.
  • this pre-adduct can be used as a curing agent for brominated epoxy resin.
  • this is an expensive way of solving the problem, given that an extra reaction step is required and the solvents proposed are significantly higher-boiling than MEK.
  • EP-A2-0472 830 the problem of crystal formation in prepregs is solved by first partially curing the resin with dicy at elevated temperature, roughly in the same way as in EP-A1-0 584 863, and then curing again at a lower temperature. Again, the same drawbacks apply, and preference is given to the hazardous ethylene glycol monomethyl ether besides.
  • EP-A2-0 196 077 dicy is replaced wholly or in part by cyanamide, which readily dissolves in organic solvents such as MEK. Cyanamide is more compatible with epoxy resin and there is little or no crystal formation. What this publication does not mention is whether the product's processing into prepreg and electrolaminate and the electrolaminate's end properties meet minimum FR-4 standards.
  • EP-A2-0 306 451 and EP-A2-0 310 545 the use of disubstituted cyanoguanidines and oligomers of cyanoguanidines in pure resins is described.
  • epoxy resins not containing bromine are employed.
  • Tg Tg
  • dicy tetrafunctional
  • the curing agents as disclosed in EP-A2-0 306 451 and EP-A2-0 310 545 will be formed mostly into linear polymers having few branches. This results in a lower Tg and a higher coefficient of expansion than in the case of branched polymers such as those obtained using dicy as hardener.
  • a further disadvantage of the curing agents according to these publications is that they are not available commercially.
  • WO 88/02012 is concemed with halogenated epoxy resins having a halogen in the meta position with respect to the glycidyl ether group attached to an aromatic ring.
  • Various curing agents are mentioned among which dicy and o- tolyl biguanide.
  • This publication does not mention the problems arising with the use of dicy.
  • the only example directed to an electrolaminate uses dicy as a curing agent and used DMF as additional solvent.
  • the other examples are directed to resin compositions for encapsulation and are cured with methylene diamine without any solvent.
  • the present invention provides a bromine-containing epoxy resin composition in which the use of dicy as hardener is avoided and environmentally acceptable solvents such as acetone and methylethyl ketone can be employed or may even be omitted.
  • the epoxy resin composition according to the invention comprises:
  • aryl substituted guanidine or biguanide as hardener permits the use of environmentally acceptable solvents such as methylethyl ketone and acetone. If the combinations of bromine-containing and bromine-free epoxy resins are sufficiently fluid at room temperature and/or elevated temperature, additional solvents need not be added and the resin can be used as a solvent-free resin.
  • (bi)guanidine (derivatives) as a hardener for epoxy resins: EP-A2-0 176 484, EP-A2-0 468 292, and EP-A1-0 087 790.
  • EP-A2-0 176484 describes the use of diphenyl biguanide in epoxy resins, particularly for powder coatings.
  • the polyglycidyl ether of tetrabromobisphenol A is mentioned as a suitable epoxy resin.
  • the publication mentions MEK and acetone as suitable solvents for these resin compositions.
  • the publication does not mention the combination of liquid bromine-containing epoxy resins and aryl substitited guanidine or biguanide and MEK or acetone and the advantages of such.
  • the resin composition has to meet very specific requirements such as a Tg above 125 ' C, low electric conduction, fire retardancy V-0 in accordance with the UL-94 standard, sufficient copper peel strength and water resistance to prevent delamination on soldering.
  • the woven glass fabric commonly present in the electrolaminate has to be readily impregnatable with resin and after passing through the treater yield tack-free prepregs which when compressed into a laminate display the desired flow behaviour and the proper resin content. Furthermore, when stored at room temperature the prepreg has to remain stable for at least three months.
  • the resin compositions described in the aforementioned patent publications fail to meet these criteria.
  • epoxy resin are meant curable compositions of oxirane ring-containing compounds, such as described in CA.
  • epoxy resins are phenol types, such as those based on the diglycidyl ether of bisphenol A, on polyglycidyl ethers of phenol- formaldehyde Novolac or cresol-formaldehyde Novolac, on the triglyci dyl ether of tris(p- hydroxyphenol)methane, or on the tetraglycidyl ether of tetraphenyl ethane; cyclo-aliphatic types, such as those based on 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexane carboxylate.
  • epoxy resin also covers the reaction products of compounds containing an excess of epoxy (e.g., of the types mentioned above) and aromatic dihydroxy compounds.
  • bromine-containing epoxy resins can be broadly divided into three groups: The first group is made up of tetrabromobisphenol A diglycidyl ether. The resin compositions according to this group contain about 50% of bromine and are more expensive than the resin compositions according to the second group. They are used less frequently in actual practice. The second group is made up of the reaction products of bisphenol A glycidyl ether and tetrabromobisphenol A or the reaction products of tetrabromobisphenol A glycidyl ether and bisphenol A.
  • Resin compositions according to this group which have a bromine content of about 20% are the ones suitable for FR-4 laminates and are by far the most fre quently used. They are supplied dissolved in MEK or acetone.
  • the third group is made up of polyglycidyl derivatives of brominated cresol or phenol novolac resin. This group is not very widely used in actual practice.
  • Solvent-free epoxy resin compositions are obtained by mixing tetrabro mobisphenol A diglycidyl ether and diglycidyl ether bisphenol A or low-melting resins. In the process liquid resin mixtures are formed which provide good impregnation of the woven glass fabric at elevated temperature.
  • the epoxy resin composition according to the invention has to contain 15 to 25 wt.% of bromine to meet the fire retardancy requirements.Therefore, these compositions are preferred.
  • Suitable guanidine and biguanide are covered by general formula:
  • R 1 represents -phenyl, Ci-Ce alkyl substituted phenyl, -H
  • R 2 represents C1-C6 alkyl, -H, -Cl, -Br
  • m is an integer 0-5.
  • 1,3-diphenyl guanidine, 1,3-di-ortho-tolyl guanidine, and o-tolyl biguanide preference is given to 1,3-diphenyl guanidine for its low price and dominant market volume.
  • 1,3-diphenyl guanidine for its low price and dominant market volume.
  • Aryl substituted guanidine and biguanide are used in quantities ranging from 2 to 15 wt.%, with 2 to 7 wt.% preferably being used in the overall solid formulation.
  • the reactivity of FR-4 epoxy resin con taining the cross-linking agent according to the invention and of FR-4 epoxy resins containing about 3% of dicy can be set a comparable levels by employing the proper catalysts.
  • the reactivity can be adjusted such that prepregs having the required characteristics (e.g., being tack-free) can be made at tern peratures below 170 ' C. It should be noted for both solvent- containing and for solvent-free systems that the prepregs can be made at lower temperatures than conventional FR-4/dicy systems. This makes for reduced prepreg production costs and benefits the environment.
  • the laminates are compressed in the same manner in conformity with electronics industry requirements.
  • Suitable catalysts are the well-known catalysts for epoxy polymers such as imidazoles, imine- and amine-type catalysts.
  • suitable imidazoles include 2-ethyl imidazole, 2-methyl imidazole, 2,4-methylethyl imidazole, 2- phenyl imidazole, 1 -cyanoethyl-2-phenyl- imidazole, 1 -(2-cyanoethyl)-2- ethyl-4-methyl imidazole, 4-phenyl imi dazole, 1 -benzyl-2-methyl imidazole, 1 -butyl imidazole.
  • Suitable amines include diethylene triamine, 2,4,6-tris-N,N'dimethyl aminoethyl phenol, benzyl dimethyl amine, ⁇ - methyl benzyl dimethyl amine, dimethyl aminophenol.
  • the amount of catalyst used is dependent on the type of epoxy resin, the type of cross-linking agent, the type of solvent (if present), the type of catalyst, and the reactivity desired, but generally will be in the range of 0.01 to 5.0, preferably 0.01-1.5%, calculated on the overall weight of epoxy resin and cross-linking agent. While the use of a catalyst is not strictly necessary, in general it is advisable to shorten the reaction time or lower the temperature.
  • one or more co-hardeners notably (brominated) poly hydric phenols such as tetrabromobisphenol A and/or cyclic anhydrides such as nadic methyl anhydride, may be employed.
  • co-hardener notably (brominated) poly hydric phenols such as tetrabromobisphenol A and/or cyclic anhydrides such as nadic methyl anhydride.
  • tetrabromobisphenol A as co-hardener offers the opportunity of introducing bromine into the system and the formation upon puin situpu curing of a bromine-containing epoxy from bromine-free epoxy such as Epikote 828 and this substance.
  • the structure will not be the same as that of a commercially available bromine-containing resin.
  • ring-containing allyl network-forming compounds such as triallyl cyanurate and peroxide may also be added to the formulation found. This makes it possible to prepare interpenetrating polymeric networks (IPNs) in a manner analogous to the one disclosed in EP-0 413 386.
  • the resin composition according to the invention can be used to make electrolaminates in a well-known manner.
  • a prepreg is prepared by passing woven fabric or cloth of glass, quartz, carbon, and aramid filaments or fibres, more particularly woven glass fabric, through the resin solution.
  • a treater hot-air column
  • the impregnated woven glass fabric is freed of solvent, and the resin pre sent is partially cured to the B- stage.
  • a stack of prepregs is then compressed to form an electrolaminate.
  • the invention is also aimed at electrolaminates comprising the (cured) resin composition according to the invention.
  • the invention will be further elucidated with reference to a number of examples. These are intended to illustrate the invention and are not to be construed as limiting in any manner the scope thereof.
  • Epikote 1143 B80® and DER 535 EK80® are well-known FR-4 epoxy resins prepared by "advancing" or reacting tetrabromobisphenol A and an excess of diglycidyl ether bisphenol A *Epikote 828®, ex Shell, is the diglycidyl ether of bisphenol A.
  • MEK methylethyl ketone
  • Perkacit DPG® ex Akzo Chemicals
  • TGA Thermogravimetric Analysis, under a nitrogen atmosphere, heating rate 10°C/min.
  • a mixture of 61 g of liquid Epikote 828®, 38 g of solid Epikote 5050®, and 3 g of DPG was heated rapidly to 110°C in a microwave oven and then cooled, with stirring, to 80°C.
  • To the homogeneous mixture at 80°C 1 of 2-ethyl-4-methyl imidazole (2E4MI) was added, with stirring.
  • the solvent-free clear and thinly viscous mixture at 80°C was poured into aluminium moulds to a resin thickness of about 0.5 mm. Next, the moulds were placed in a forced-circulation air oven at
  • Example 14 In the same manner as in Example 6 solvent-free resins were formulated, with the multifunctional epoxy cresol novolac resin (Araldite ECN 1280®) being employed to increase the Tg. The composition and its properties are shown in TABLE 4. Example 14
  • the same mixture was prepared as described in Example 6. However, prior to the addition of the 2E4MI the viscosity was measured with a Brookfield viscometer. The viscosity was 450 mPa.s at 80°C and 110 mPa.s at 100°C. The viscosity remained unchanged over a storage period of 8 hours at 80°C. After the addition of 1.4% of catalyst the completely homogeneous resin mixture was used to impregnate type 7628 woven glass fabric (finish Z6032). The impregnation procedure involved passing A4-size glass mats slowly through an impregnating vessel, in which the resin was kept at 80°C.
  • a heater was used to create a heated zone (of about 10 cm) directly above the impregnating vessel (temperature about 100 * C).
  • the resulting prepregs were tacky and comparatively highly resinous.
  • One by one these prepregs were placed in an oven set to a temperature of 160)C. After a contact period of 2 minutes the prepregs were no longer tacky once they had cooled down to room temperature.
  • the resin content ranged from 46 to 50 wt.%.
  • Tg measured on the laminate was 137 ⁇ 3°C (TMA-method).

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Abstract

The present invention pertains to a bromine-containing epoxy resin composition for printed wiring board substrates, i.e., for electrolaminates. The present invention provides a bromine-containing epoxy resin composition where the use of dicy as cross-linking agent is avoided and environmentally acceptable solvents such as acetone and methylethyl ketone can be employed. When liquid bromine-containing epoxy resins are employed, additional solvents can in fact be avoided altogether (this gives so-called solvent-free resin compositions). The epoxy resin composition according to the invention comprises: bromine-containing epoxy resin; aryl substituted guanidine or biguanide as cross-linking agent; optionally, epoxy resin not containing bromine; optionally, a catalyst and; optionally methylethyl ketone or acetone as a solvent, no additional solvents being present. Particular preference is given to the use of diphenyl guanidine and o-tolyl biguanide as cross-linking agents. The invention is also aimed at electrolaminates comprising the resin composition according to the invention.

Description

EPOXY RESIN COMPOSITION FOR ELECTROLAMINATES HAVING ARYL SUBSTITUTED GUANIDINE AND/OR BIGUANIDE AS CROSS-LINKING AGENT
The present invention pertains to a bromine-containing epoxy resin composition for printed wiring board substrates, i.e., for electrolaminates. These days, in the production of electrolaminates principally use is made of bromine-containing epoxy resins cured with about 3 wt.% of dicyandiamide (also known as cyanoguanidine or dicy) as cross-linking agent. The most common electrolaminate in the electronics industry is referred to as the FR-4 laminate. Difunctional brominated epoxy resins such as DER535®, ex Dow Chemical, and Epikote 1143®, ex Shell, cured with 3% of dicy are employed in the FR-4 laminate. The glass transition temperature (Tg) of this laminate is 125°C.
To make prepregs, a woven glass fabric is passed through the resin solution; next, the impregnated woven glass fabric is freed of solvent in a treater (hot- air column) and the resin present is partially cured to the B-stage. After this, a stack of prepregs with copper foil on the outside is compressed to form an electrolaminate.
However, there are several drawbacks to the use of dicy. Dicy is poorly soluble both in pure bromine-containing epoxy resin and in bromine- containing epoxy resin dissolved in acetone and/or methylethyl ketone. In consequence, the use of solvents such as dimethyl formamide (DMF) and mixtures of DMF and methylethyl ketone (MEK) or acetone is required. Even when these solvents are employed, the formation of crystals of dicy in the prepreg tends to be a problem. Furthermore, dimethyl formamide is both toxic and expensive. Because, on the one hand, DMF has a higher boiling point (153°C) than MEK (80°C) and acetone (56°C) and, on the other, there is the requirement in this sector of industry to have prepregs containing less than 1 % of solvent, a higher treater temperature is needed to evaporate the DMF. Hence solvent-free compositions or compositions dissolved exclusively in MEK and acetone are less expensive in terms of energy consumption than DMF-containing compositions. For that reason, the search is on for liquid bromine-containing epoxy resin compositions suitable for impregnating woven glass fabric without the use of any additional solvent. This will put an end to the emission of solvents from the treater, and so to further harm to the environment.
In EP-A1-0 584 863 it is attempted to avoid the use of DMF and other solvents hazardous to man and the environment such as ethylene glycolmonomethyl ether by preparing a pre-adduct of dicy and a less than stoichiometric amount of brominated epoxy resin. Dissolved in an acceptable solvent, this pre-adduct can be used as a curing agent for brominated epoxy resin. However, this is an expensive way of solving the problem, given that an extra reaction step is required and the solvents proposed are significantly higher-boiling than MEK. In EP-A2-0472 830 the problem of crystal formation in prepregs is solved by first partially curing the resin with dicy at elevated temperature, roughly in the same way as in EP-A1-0 584 863, and then curing again at a lower temperature. Again, the same drawbacks apply, and preference is given to the hazardous ethylene glycol monomethyl ether besides. In other publications such as EP-A2-0 196 077 dicy is replaced wholly or in part by cyanamide, which readily dissolves in organic solvents such as MEK. Cyanamide is more compatible with epoxy resin and there is little or no crystal formation. What this publication does not mention is whether the product's processing into prepreg and electrolaminate and the electrolaminate's end properties meet minimum FR-4 standards. Notably, it is to be expected that substituting the difunctional cyanamide for the tetrafunctional dicy will result in a lower degree of hardening and a lower Tg. In WO 93/10168 it is proposed to use bis-dicyandiamides to replace dicy. Using the proposed bis-dicyandiamides with brominated epoxy resins generally gives a Tg of less than 125 after curing. Moreover, these compounds are poorly soluble in ketones. For that reason in the resin formulations mostly use is still made of high-boiling glycol ethers such as 1- methoxy-2-propanol (in combination with ketones) to dissolve these hardeners.
In EP-A2-0 306 451 and EP-A2-0 310 545 the use of disubstituted cyanoguanidines and oligomers of cyanoguanidines in pure resins is described. In the examples only epoxy resins not containing bromine are employed. Although fairly high Tgs are achieved with these epoxy resins which do not contain bromine, it is open to question whether (bromine- containing) resin formulations will produce the desired properties for FR-4 laminates. After all, the Tg is lowered by the use of bromine-containing resins. The curing agents proposed in these publications are difunctional, whereas dicy is tetrafunctional. Accordingly, the curing agents as disclosed in EP-A2-0 306 451 and EP-A2-0 310 545 will be formed mostly into linear polymers having few branches. This results in a lower Tg and a higher coefficient of expansion than in the case of branched polymers such as those obtained using dicy as hardener. A further disadvantage of the curing agents according to these publications is that they are not available commercially.
In WO 92/01726 and WO 94/14866 mono-substituted cyanoguanidine is used for brominated epoxide curing starting from resin formulations in solvents which are harmless to the environment and resin formulations without or with hardly any solvents, respectively. In the examples use is made of mixtures of diglycidyl ether of bisphenol A (DGEBA) and diglycidyl ether of tetrabromobisphenol A (brominated DGEBA, about 50% Br). However, resin formulations for FR-4 laminates are not employed, and it is open to question whether the hardeners proposed in this publication will give the properties desired for FR-4 laminates. The resin compositions applied in these publications will give a Tg of 125X, but since resin compositions for FR-4 laminates have a lower degree of curing than they do, FR-4 resin compositions are expected to have a lower Tg. Furthermore, the cross-linking agents proposed in these publications are not available commercially.
WO 88/02012 is concemed with halogenated epoxy resins having a halogen in the meta position with respect to the glycidyl ether group attached to an aromatic ring. Various curing agents are mentioned among which dicy and o- tolyl biguanide. This publication does not mention the problems arising with the use of dicy. In fact, the only example directed to an electrolaminate uses dicy as a curing agent and used DMF as additional solvent. The other examples are directed to resin compositions for encapsulation and are cured with methylene diamine without any solvent. The present invention provides a bromine-containing epoxy resin composition in which the use of dicy as hardener is avoided and environmentally acceptable solvents such as acetone and methylethyl ketone can be employed or may even be omitted.
The epoxy resin composition according to the invention comprises:
- bromine-containing epoxy resin,
- aryl substituted guanidine or biguanide as a cross-linking agent,
- optionally, epoxy resin not containing bromine, - optionally, a catalyst,
-and optionally methyl ethyl ketone and/or acetone as a solvent, no additional solvents being present.
Employing aryl substituted guanidine or biguanide as hardener permits the use of environmentally acceptable solvents such as methylethyl ketone and acetone. If the combinations of bromine-containing and bromine-free epoxy resins are sufficiently fluid at room temperature and/or elevated temperature, additional solvents need not be added and the resin can be used as a solvent-free resin. For completeness' sake reference may be had to the following publications disclosing the use of (bi)guanidine (derivatives) as a hardener for epoxy resins: EP-A2-0 176 484, EP-A2-0 468 292, and EP-A1-0 087 790. EP-A2-0 176484 describes the use of diphenyl biguanide in epoxy resins, particularly for powder coatings. The polyglycidyl ether of tetrabromobisphenol A is mentioned as a suitable epoxy resin. The publication mentions MEK and acetone as suitable solvents for these resin compositions. The publication does not mention the combination of liquid bromine-containing epoxy resins and aryl substitited guanidine or biguanide and MEK or acetone and the advantages of such. To be suitable for use in electrolaminates the resin composition has to meet very specific requirements such as a Tg above 125'C, low electric conduction, fire retardancy V-0 in accordance with the UL-94 standard, sufficient copper peel strength and water resistance to prevent delamination on soldering. In addition, the woven glass fabric commonly present in the electrolaminate has to be readily impregnatable with resin and after passing through the treater yield tack-free prepregs which when compressed into a laminate display the desired flow behaviour and the proper resin content. Furthermore, when stored at room temperature the prepreg has to remain stable for at least three months. The resin compositions described in the aforementioned patent publications fail to meet these criteria. In the resin composition according to the invention use may be made of all bromine-containing epoxy resins known to be suitable for use in electrolaminates. By "epoxy resin" are meant curable compositions of oxirane ring-containing compounds, such as described in CA. May, Epoxy Resins, 2nd ed., (New York & Basel: Marcel Dekker Inc., 1988). Examples of epoxy resins are phenol types, such as those based on the diglycidyl ether of bisphenol A, on polyglycidyl ethers of phenol- formaldehyde Novolac or cresol-formaldehyde Novolac, on the triglyci dyl ether of tris(p- hydroxyphenol)methane, or on the tetraglycidyl ether of tetraphenyl ethane; cyclo-aliphatic types, such as those based on 3,4-epoxycyclohexylmethyl-3,4- epoxycyclohexane carboxylate. The term epoxy resin also covers the reaction products of compounds containing an excess of epoxy (e.g., of the types mentioned above) and aromatic dihydroxy compounds. Commercially available bromine-containing epoxy resins can be broadly divided into three groups: The first group is made up of tetrabromobisphenol A diglycidyl ether. The resin compositions according to this group contain about 50% of bromine and are more expensive than the resin compositions according to the second group. They are used less frequently in actual practice. The second group is made up of the reaction products of bisphenol A glycidyl ether and tetrabromobisphenol A or the reaction products of tetrabromobisphenol A glycidyl ether and bisphenol A. These reaction products are known as "advanced products." Resin compositions according to this group which have a bromine content of about 20% are the ones suitable for FR-4 laminates and are by far the most fre quently used. They are supplied dissolved in MEK or acetone. The third group is made up of polyglycidyl derivatives of brominated cresol or phenol novolac resin. This group is not very widely used in actual practice. Solvent-free epoxy resin compositions are obtained by mixing tetrabro mobisphenol A diglycidyl ether and diglycidyl ether bisphenol A or low-melting resins. In the process liquid resin mixtures are formed which provide good impregnation of the woven glass fabric at elevated temperature. To obtain electrolaminates of high Tg (at least 150°C) multi functional epoxides in higher concentrations are employed as the prin cipal or sole epoxy component. The epoxy resin composition according to the invention has to contain 15 to 25 wt.% of bromine to meet the fire retardancy requirements.Therefore, these compositions are preferred. Suitable guanidine and biguanide are covered by general formula:
Figure imgf000009_0001
wherein R1 represents -phenyl, Ci-Ce alkyl substituted phenyl, -H, R2 represents C1-C6 alkyl, -H, -Cl, -Br, m is an integer 0-5.
Particular preference is given to 1,3-diphenyl guanidine, 1,3-di-ortho-tolyl guanidine, and o-tolyl biguanide, since these compounds are readily available on the market. More especially, preference is given to 1,3-diphenyl guanidine for its low price and dominant market volume. It should be noted that in a manner analogous to that of the cyano group in dicy, the presence of aryl groups reduced the NH-groups' basicity and reactivity to the desired level, thus ensuring prepreg stability. Aryl substituted guanidine and biguanide are used in quantities ranging from 2 to 15 wt.%, with 2 to 7 wt.% preferably being used in the overall solid formulation. As is clear from the examples, the reactivity of FR-4 epoxy resin con taining the cross-linking agent according to the invention and of FR-4 epoxy resins containing about 3% of dicy can be set a comparable levels by employing the proper catalysts.
This comparable reactivity is shown, int. al., by comparable resin gelling times, pot lives, and pressing cycles. Using the cross-linking agent according to the inven tion, solvent-containing as well as solvent-free systems yield Tgs which are as high or higher than those of laminates obtained using conventional (solvent-containing) FR-4/dicy-containing systems.As was stated earlier, environmentally acceptable solvents such as acetone and methylethyl ketone can be utilised in the resin compositions according to the invention. It was found that when the resin com position is used as a solvent- free system, the viscosity is low enough to impregnate woven glass fabric at temperatures below 150X. In this case the reactivity can be adjusted such that prepregs having the required characteristics (e.g., being tack-free) can be made at tern peratures below 170'C. It should be noted for both solvent- containing and for solvent-free systems that the prepregs can be made at lower temperatures than conventional FR-4/dicy systems. This makes for reduced prepreg production costs and benefits the environment. The laminates are compressed in the same manner in conformity with electronics industry requirements.
Suitable catalysts are the well-known catalysts for epoxy polymers such as imidazoles, imine- and amine-type catalysts. Examples of suitable imidazoles include 2-ethyl imidazole, 2-methyl imidazole, 2,4-methylethyl imidazole, 2- phenyl imidazole, 1 -cyanoethyl-2-phenyl- imidazole, 1 -(2-cyanoethyl)-2- ethyl-4-methyl imidazole, 4-phenyl imi dazole, 1 -benzyl-2-methyl imidazole, 1 -butyl imidazole. Examples of suitable amines include diethylene triamine, 2,4,6-tris-N,N'dimethyl aminoethyl phenol, benzyl dimethyl amine, α- methyl benzyl dimethyl amine, dimethyl aminophenol. The amount of catalyst used is dependent on the type of epoxy resin, the type of cross-linking agent, the type of solvent (if present), the type of catalyst, and the reactivity desired, but generally will be in the range of 0.01 to 5.0, preferably 0.01-1.5%, calculated on the overall weight of epoxy resin and cross-linking agent. While the use of a catalyst is not strictly necessary, in general it is advisable to shorten the reaction time or lower the temperature.
If so desired, one or more co-hardeners, notably (brominated) poly hydric phenols such as tetrabromobisphenol A and/or cyclic anhydrides such as nadic methyl anhydride, may be employed. As the skilled person knows, the addition of tetrabromobisphenol A as co-hardener offers the opportunity of introducing bromine into the system and the formation upon puin situpu curing of a bromine-containing epoxy from bromine-free epoxy such as Epikote 828 and this substance. However, because of the competitive reaction with the proposed cross-linking agents, the structure will not be the same as that of a commercially available bromine-containing resin.
If so desired, ring-containing allyl network-forming compounds such as triallyl cyanurate and peroxide may also be added to the formulation found. This makes it possible to prepare interpenetrating polymeric networks (IPNs) in a manner analogous to the one disclosed in EP-0 413 386.
The resin composition according to the invention can be used to make electrolaminates in a well-known manner. In general, a prepreg is prepared by passing woven fabric or cloth of glass, quartz, carbon, and aramid filaments or fibres, more particularly woven glass fabric, through the resin solution. Next, in a treater (hot-air column) the impregnated woven glass fabric is freed of solvent, and the resin pre sent is partially cured to the B- stage. A stack of prepregs is then compressed to form an electrolaminate. The invention is also aimed at electrolaminates comprising the (cured) resin composition according to the invention. The invention will be further elucidated with reference to a number of examples. These are intended to illustrate the invention and are not to be construed as limiting in any manner the scope thereof.
EXAMPLES
The following epoxy resins were used in the examples:
Εpikote 1143 B80®, ex Shell, having an epoxy equivalent weight (EEW) of about 504 (grams of resin per mole of epoxy functions), solids content of 80 wt.% in MEK and a bromine wt.% (relative to the solids) of about 21 %.
*DER 535 EK 80®, ex Dow Chemical, having an EEW of about 415, Br % = about 19, 80% of solids in MEK.
Both Epikote 1143 B80® and DER 535 EK80® are well-known FR-4 epoxy resins prepared by "advancing" or reacting tetrabromobisphenol A and an excess of diglycidyl ether bisphenol A *Epikote 828®, ex Shell, is the diglycidyl ether of bisphenol A.
EEW = about 187, liquid resin.
*Epikote 5050®, ex Shell, is the diglycidyl ether of tetrabromq1/ - bisphenol A. EEW = about 385, bromine % = about 49, solid product having a melting point of 64°C. *Quatrex 6410®, ex Dow Chemical, EEW = 450, otherwise comparable with Epikote 5050® D
*Araldite ECN 1280®, ex Ciba Geigy, EEW = 230, is the polyglycidyl ether of a cresol formaldehyde Novolac, solid resin. Methods
Except where indicated otherwise, all methods employed are in accordance with the IPC (Institute for Connecting and Packaging Electronic Circuits) test methods TM 650.
Example 1
To 121 g of Epikote 1143 B80® (= 97 g of solid Epikote 1143) were successively added, with stirring, 42.7 g of methylethyl ketone (MEK) and 3 g of solid diphenyl guanidine (Perkacit DPG®, ex Akzo Chemicals). To the homogeneous solution with a solids content of 60 wt.% were then added 2.4 g of a 10% solution of 2-methyl imidazole (2-MI) in 1-methoxy-2- propanol. (This is 0.4% of solid 2-MI relative to solid epoxy resin plus hardener.) Next, the resin solution was poured into aluminium moulds, such as to give a layer thickness of the resin solution of about 0.5 to 1 mm. The samples were then placed in a forced- circulation air oven at 80°C, after which the oven was heated to 120°C, a temperature which was maintained for 90 minutes, followed finally by one hour at 175°C. After slow cooling to room temperature and releasing the orangy-brown, homogeneously transparent plates from the moulds, the plates were postcured for another hour at 175°C and slowly cooled to room temperature. The properties measured subsequently are listed in TABLE 1. Comparative Example 1
Fed to 121 g of Epikote 1143 B80< were successively, with stirring, 30 g of a 10% solution of dicyandiamide (dicy) in dimethyl formamide (DMF) and 15.7 g of MEK. To the homogeneous solution having a solids content of 60 wt.% was then added 0.6 g of a 10% solution of 2-methyl imidazole (2-MI) in 1 -methoxy-2-propaπol. This is 0.1 % of solid 2-MI relative to solid epoxy resin plus hardener. In the same manner as described in Example 1 the resin solution was processed and cured to make plates. The properties measured are listed in TABLE 1.
Examples 2 to 4
In the same manner as described in Example 1 resin plates were made, except that they had different concentrations of diphenyl guanidine (DPG) and contained o-tolyl biguanide (o-TBG).
TABLE 1
Ex 1 Ex 2 Ex 3 Ex 4 comp. Ex 1 composition
% E 1143 97 94 90 97 97
% DPG 3 6 10
% o-TBG 3
% dicy 3
% 2MI 0.4 0.3 0.4 0.2 0.1 resin gel. time at 183 238 160 243 215
171 °C(s)1
Tg (DSC) °C 130 125 122 127 121
TGA2 % loss at 2.0 3.0 3.0
300 °C (TGA)
1Over a period of 2 days following preparation of the resin solution
2TGA = Thermogravimetric Analysis, under a nitrogen atmosphere, heating rate 10°C/min.
Example 5
To 600 g of DER535 EK80® were added, with stirring, 148.5 g of a 10 wt.% DPG solution in MEK. Next, 153.5 g of MEK were added, followed by 2.88 g of 2-MI, both with stirring. A 905 g clear resin solution with a solids content of 55% and a viscosity of 30 mPa.s was prepared in this manner.
E-glass woven fabric, type 7628 (finishing agent Z 6032), which is commonly used in the electrolaminate industry, was impregnated with the resin solution by hand. Subsequently, the impregnated woven fabrics were kept in a forced-circulation air oven at 160°C for 2 minutes. In this way tack-free prepregs were obtained which had a gelling time at 171°C of 120 seconds and a resin content of 44 ± 3 wt.% measured in accordance with IPC.
Eight prepregs stacked one on top of the other were compressed in an autoclave under a specific pressure of 15 ato. at a temperature of 171°C for 60 minutes. The heating and cooling rates were 5°C/min. Laminate coated on both sides with copper (1 ounce, electrodeposited type) as well as uncoated laminate having a thickness of from 1.50 to 1.60 mm were made in this manner. The properties of the laminate are listed in TABLE 2 together with those of the reference laminate of Example 2.
Comparative Example 2
600 g of DER535 B80® were mixed, with stirring, with 148 g of MEK. To this mixture were added, with stirring, 148.5 g of a 10% dicy solution in DMF and, finally, 3.6 g of a 10% 2-MI solution in 1-methoxy-2- propanol. The resin solution having a solids content of 55 wt.% and a viscosity of 30 mPa.s had a gelling time at 171°C of 255 seconds. Prepregs and laminates were made from this solution in the same manner as described in Example 5, except that this time the prepreg material was prepared in the oven at 180°C for 2 minutes. The prepreg properties compared closely with those disclosed in Example 5. The laminate properties are listed in TABLE 2.
TABLE 2: Laminate properties for Ex. 5 and Reference ex. 2
Ex. 5 comp. ex. 2 resin composition:
% DER 535 97 97
%DPG 3
%Dicy 3
%bromine 18 18 laminate properties:
Tg (°C)
* in accordance with 125 115
TMA
*in accordance with 130 125
DSC
T.E.C.z (ppm/°C, 175 180
% loss at 300 °C (TGA) 1.0 1.0 water absoφtion % 0.14 0.15 cupper peel strength
Fire retardancy UL94, V0 V0 class Example 6
A mixture of 61 g of liquid Epikote 828®, 38 g of solid Epikote 5050®, and 3 g of DPG was heated rapidly to 110°C in a microwave oven and then cooled, with stirring, to 80°C. To the homogeneous mixture at 80°C 1 of 2-ethyl-4-methyl imidazole (2E4MI) was added, with stirring. The solvent-free clear and thinly viscous mixture at 80°C was poured into aluminium moulds to a resin thickness of about 0.5 mm. Next, the moulds were placed in a forced-circulation air oven at
120°C. After 30 minutes at 120°C the oven was heated to 150°C and kept at this temperature for 30 minutes, after which the resin was kept at 175°C for another 90 minutes before being cooled down to room temperature. The properties are listed in TABLE 3.
Examples 7 through 10
In the same manner as in Example 6 resin mixtures of other DPG concentrations were formulated and cured. The results are listed in TABLE 3.
Examples 11 through 13
In the same manner as in Example 6 solvent-free resins were formulated, with the multifunctional epoxy cresol novolac resin (Araldite ECN 1280®) being employed to increase the Tg. The composition and its properties are shown in TABLE 4. Example 14
The same mixture was prepared as described in Example 6. However, prior to the addition of the 2E4MI the viscosity was measured with a Brookfield viscometer. The viscosity was 450 mPa.s at 80°C and 110 mPa.s at 100°C. The viscosity remained unchanged over a storage period of 8 hours at 80°C. After the addition of 1.4% of catalyst the completely homogeneous resin mixture was used to impregnate type 7628 woven glass fabric (finish Z6032). The impregnation procedure involved passing A4-size glass mats slowly through an impregnating vessel, in which the resin was kept at 80°C. A heater was used to create a heated zone (of about 10 cm) directly above the impregnating vessel (temperature about 100*C). The resulting prepregs were tacky and comparatively highly resinous. One by one these prepregs were placed in an oven set to a temperature of 160)C. After a contact period of 2 minutes the prepregs were no longer tacky once they had cooled down to room temperature. The resin content ranged from 46 to 50 wt.%.
Four of these prepregs were stacked one on top of the other and compressed in an autoclave to form a laminate. The moulding conditions were as follows: a specific (all-side) pressure of 15 bar, heating and cooling rates of 5 °C/min., a residence time of 60 minutes at 175°C.
The Tg measured on the laminate was 137 ±3°C (TMA-method). TABLE 3
Ex 6 Ex.7 Ex. 8 Ex.9 Ex. 10
Composition
% epikote 828 61 59 58 56 51
% epikote 5050 36 36 35
% Quatrex 6410 34 36
% DPG 3 5 7 10 13
%2E4MI 1.0 1.0 0.7 0.7 0.7
Br% 18 18 18 17 18 resin gel. time at 175 133 199 133 159
171 °C (s)
Tg (TMA) (βC) 140 129 135 124 111
T.E.C.z (ppm/°C 135 140 133 140 145 average over 20-
250°C
% loss at 300 °C 1.5 2.5 in accordance with TGA
TABLE 4
Ex. 11 Ex. 12 Ex. 13
Composition
% Epikote 828 41 49 43
% Epikote 5050 34 36 36
% aral;dite ECN 1280 18 12 18
% DPG 7 4 4
%2E4MI 0.8 0.75 0.75
Br% 17 18 16
Resin gel. time ate 100 152 130
171 °C (seconds)
Tg (TMA) °C 151 152 169
T.E.C.z (ppm/°C, 130 110 120 average over 20-250
°C)

Claims

1. An epoxy resin composition for electrolaminates comprising: -bromine-containing epoxy resin,
-aryl substituted guanidine or biguanide as cross-linking agent,
-optionally, epoxy resin not containing bromine,
-optionally, a catalyst and, -optionally methyl ethyl ketone or acetone as a solvent, no additional solvents being present.
2. An epoxy resin composition according to claim 1 , characterised in that the epoxy resin composition is fluid and comprises glycidyl ether of tetrabromobisphenol A and glycidyl ether of bisphenol A and no additional solvents are present in the composition.
3. An epoxy resin composition according to claim 1 , characterised in that the epoxy resin composition comprises an epoxy resin composition for FR-4 laminate.
4. An epoxy resin composition according to any one of the preceding claims, characterised in that the guanidine is diphenyl guanidine.
5. An epoxy resin composition according to any one of preceding claims 1-3, characterised in that the biguanide is o-tolyl biguanide.
6. A process for preparing the epoxy resin composition according to any one of the preceding claims, characterised in that the epoxy resin composition contains 15 to 25 wt.% of bromine (relative to the solids overall).
7. An electrolaminate comprising an epoxy resin composition according to any one of preceding claims 1-6.
PCT/EP1996/003995 1995-09-13 1996-09-11 Epoxy resin composition for electrolaminates having aryl substituted guanidine and/or biguanide as cross-linking agent WO1997011105A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6143615A (en) * 1984-08-07 1986-03-03 Mitsui Petrochem Ind Ltd Epoxy resin composition
EP0176484A2 (en) * 1984-09-27 1986-04-02 Ciba-Geigy Ag Durable mixtures containing diethylphenyl-biguanide, and their use
WO1988002012A1 (en) * 1986-09-15 1988-03-24 The Dow Chemical Company Halogenated epoxy resins and advanced resins prepared therefrom
JPS63305126A (en) * 1987-06-05 1988-12-13 Mitsubishi Rayon Co Ltd epoxy resin composition
JPS63305124A (en) * 1987-06-05 1988-12-13 Mitsubishi Rayon Co Ltd epoxy resin composition
US4960634A (en) * 1990-03-14 1990-10-02 International Business Machines Corporation Epoxy composition of increased thermal conductivity and use thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6143615A (en) * 1984-08-07 1986-03-03 Mitsui Petrochem Ind Ltd Epoxy resin composition
EP0176484A2 (en) * 1984-09-27 1986-04-02 Ciba-Geigy Ag Durable mixtures containing diethylphenyl-biguanide, and their use
WO1988002012A1 (en) * 1986-09-15 1988-03-24 The Dow Chemical Company Halogenated epoxy resins and advanced resins prepared therefrom
JPS63305126A (en) * 1987-06-05 1988-12-13 Mitsubishi Rayon Co Ltd epoxy resin composition
JPS63305124A (en) * 1987-06-05 1988-12-13 Mitsubishi Rayon Co Ltd epoxy resin composition
US4960634A (en) * 1990-03-14 1990-10-02 International Business Machines Corporation Epoxy composition of increased thermal conductivity and use thereof

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Title
DATABASE WPI Derwent World Patents Index; AN 86-098069(15), XP002002807 *
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