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WO1997011105A1 - Composition de resine epoxy pour des electrostratifies comprenant une guanidine a substitution aryle et/ou un biguanide a substitution aryle comme agent de reticulation - Google Patents

Composition de resine epoxy pour des electrostratifies comprenant une guanidine a substitution aryle et/ou un biguanide a substitution aryle comme agent de reticulation 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
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy resin
resin composition
bromine
resin
biguanide
Prior art date
Application number
PCT/EP1996/003995
Other languages
English (en)
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/fr

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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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Reinforced Plastic Materials (AREA)

Abstract

L'invention concerne une composition de résine époxy contenant du brome, pour des substrats destinés à des plaquettes de circuits imprimés, c'est-à-dire des électrostratifiés. L'invention concerne une composition de résine époxy contenant du brome, pour laquelle on évite l'utilisation de dicyandiamide comme agent de réticulation et on peut utiliser des solvants organiques acceptables pour l'environnement, tels que l'acétone et la méthyléthylcétone. Quand on utilise des résines époxy contenant du brome qui sont liquides, on peut à ce moment se passer complètement de solvant additionnel (ce sont les compositions de résines dites sans solvant). La composition de résine époxy selon l'invention comprend: une résine époxy contenant du brome, une guanidine à substitution aryle ou un biguanide à substitution aryle comme agent de réticulation, éventuellement une résine époxyde ne contenant pas de brome, éventuellement un catalyseur et éventuellement de la méthyléthylcétone ou de l'acétone comme solvant, sans autre solvant additionnel. On donne la préférence à la diphényl-guanidine ou à l'o-tolyl-biguanide comme agents de réticulation. L'invention concerne également des électrostratifiés comprenant la composition de résine selon l'invention.
PCT/EP1996/003995 1995-09-13 1996-09-11 Composition de resine epoxy pour des electrostratifies comprenant une guanidine a substitution aryle et/ou un biguanide a substitution aryle comme agent de reticulation WO1997011105A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1001189 1995-09-13
NL1001189 1995-09-13

Publications (1)

Publication Number Publication Date
WO1997011105A1 true WO1997011105A1 (fr) 1997-03-27

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6143615A (ja) * 1984-08-07 1986-03-03 Mitsui Petrochem Ind Ltd エポキシ樹脂組成物
EP0176484A2 (fr) * 1984-09-27 1986-04-02 Ciba-Geigy Ag Mélanges durcissables contenant du diéthylphényl-biguanide, et leur utilisation
WO1988002012A1 (fr) * 1986-09-15 1988-03-24 The Dow Chemical Company Resines epoxy halogenees et resines perfectionnees preparees a partir de ces substances
JPS63305126A (ja) * 1987-06-05 1988-12-13 Mitsubishi Rayon Co Ltd エポキシ樹脂組成物
JPS63305124A (ja) * 1987-06-05 1988-12-13 Mitsubishi Rayon Co Ltd エポキシ樹脂組成物
US4960634A (en) * 1990-03-14 1990-10-02 International Business Machines Corporation Epoxy composition of increased thermal conductivity and use thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6143615A (ja) * 1984-08-07 1986-03-03 Mitsui Petrochem Ind Ltd エポキシ樹脂組成物
EP0176484A2 (fr) * 1984-09-27 1986-04-02 Ciba-Geigy Ag Mélanges durcissables contenant du diéthylphényl-biguanide, et leur utilisation
WO1988002012A1 (fr) * 1986-09-15 1988-03-24 The Dow Chemical Company Resines epoxy halogenees et resines perfectionnees preparees a partir de ces substances
JPS63305126A (ja) * 1987-06-05 1988-12-13 Mitsubishi Rayon Co Ltd エポキシ樹脂組成物
JPS63305124A (ja) * 1987-06-05 1988-12-13 Mitsubishi Rayon Co Ltd エポキシ樹脂組成物
US4960634A (en) * 1990-03-14 1990-10-02 International Business Machines Corporation Epoxy composition of increased thermal conductivity and use thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 86-098069(15), XP002002807 *
DATABASE WPI Derwent World Patents Index; AN 89-029606(04), XP002002806 *
DATABASE WPI Derwent World Patents Index; AN 89-029608(04), XP002002805 *

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