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WO1995006675A1 - Composition durcissable a base de resine epoxyde - Google Patents

Composition durcissable a base de resine epoxyde Download PDF

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Publication number
WO1995006675A1
WO1995006675A1 PCT/EP1994/002887 EP9402887W WO9506675A1 WO 1995006675 A1 WO1995006675 A1 WO 1995006675A1 EP 9402887 W EP9402887 W EP 9402887W WO 9506675 A1 WO9506675 A1 WO 9506675A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy resin
resin composition
group
curable
formula
Prior art date
Application number
PCT/EP1994/002887
Other languages
English (en)
Inventor
Takao Fukuzawa
Tetsuro Imura
Masayuki Ohta
Original Assignee
Shell Internationale Research Maatschappij B.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 Shell Internationale Research Maatschappij B.V. filed Critical Shell Internationale Research Maatschappij B.V.
Publication of WO1995006675A1 publication Critical patent/WO1995006675A1/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
    • C08G59/20—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

Definitions

  • the present invention relates to curable epoxy resin compositions, to articles comprising such curable co ⁇ ositions in the cured state and to the use of such a curable compositions.
  • the curable epoxy resin compositions according to the invention in particular have excellent heat resistance and cracking resistance in the cured state.
  • epoxy resins in general have good electro-insulating properties, good heat resistance, good chemical resistance, good mechanical properties and good processability they are frequently used in the electrical and electronic fields, for example as semi ⁇ conductor sealants, in laminates for printed circuits, and as insulating varnishes.
  • Epoxy resin casting compositions used for insulating electrical and electronic instruments are currently often based on a bisphenol-A type epoxy resin and an acid anhydride curing agent.
  • cured epoxy resin compositions comprising a blend of a bisphenol-A type epoxy resin and a polyfunctional epoxy resin such as a novolak type epoxy resin have improved heat resistance as compared to cured epoxy resins comprising only a bisphenol-A type epoxy resin, they are often very brittle which is reflected in a very low cracking resistance.
  • an epoxy resin of which the epoxy groups have been modified or wherein flexible components have been incorporated may have a positive effect on the cracking resistance of to the cured composition, if negatively affects the heat resistance thereof.
  • the present invention aims at providing an epoxy resin composition that can be used as a casting composition for insulation of electrical and electronic instruments and that provides cured products that combine a good heat resistance with a good cracking resistance.
  • the present invention thus relates to a curable epoxy resin composition
  • a curable epoxy resin composition comprising an epoxy resin and an acid anhydride curing agent, wherein the epoxy resin has a bromine content of from 15% by weight to 70% by weight, has, on average, more than one glycidyl group per molecule and comprises at least one structure of the general formula (1), (2) or (3) as presented below:
  • the groups X 1 to X* ⁇ ° each individually may represent a hydrogen atom, a hydrocarbon residual group having from 1 to 20 carbon atoms, an alkoxy group, an aroxy group or a halogen atom; and wherein
  • R represents a single bond, a hydrocarbon residual group having from 1 to 20 carbon atoms, or -0-, -S-, -SO2-, -CO-, -COO-, -OCOO-, -NHCO- or -NHCOO-.
  • Preferred groups R in the structure according to the formula (1) are methylene, ethylidene, ⁇ -methylbenzylidene, cyclohexylidene, isopropylidene, p-xylene- ⁇ , ⁇ '-diyl or fluoren-9- ylidene, or a divalent hydrocarbon residual group derived from addition of a phenolic compound to a cyclic terpene compound such as dicyclopentadiene, limonene, terpinolene, pinene, terpinene or menthadiene.
  • Suitable epoxy resins used in the curable composition according to the invention comprising a structure of formula (1) are for example, epoxy resins based on tetrabromobiphenol, tetrabromobisphenol F, 4,4'-dihydroxy-3,3'-dibromo-5,5'- dimethyldiphenylme hane, tetrabromobisphenol A, 4,4'-dihydroxy- 3,3' ,5,5'-tetrabromobenzophenone, tetrabromonobisphenol S and 4,4'-dihydroxy-3,3',5,5'-tetrabromodiphenyl ether.
  • Suitable epoxy resins comprising a structure of formula (2) are for example, epoxy resins based on hydroquinone, resorcinol and catechol derivatives.
  • Suitable epoxy resins comprising a structure of formula (3) are for example, dihydroxynaphthalene derivatives. If the epoxy resin has a bromine content of less than 15% by weight, the heat resistance and cracking resistance of the epoxy resin composition according to the invention in the cured state is insufficient. On the other hand, if the epoxy resin has a bromine content of more than 70% by weight, the epoxy resin composition will be extremely difficult to prepare and to process.
  • the epoxy resin used in the epoxy resin composition of the present invention preferably has a bromine content in the range of from 20% by weight to 65% by weight.
  • Suitable epoxy resins are obtained by reacting one or more dihydroxy compounds comprising a structure of the formula (1), (2) or (3), with epichlorohydrin, optionally in the presence of one or more compounds selected from the group consisting of dihydroxy compounds, excluding the dihydroxy compounds comprising a structure of formula (1), (2) or (3), followed by cyclization of the resulting intermediate in the presence of an alkali metal hydroxide.
  • epoxy resins (II) are obtained by reacting the above-mentioned epoxy resin (I) optionally in the presence of epoxy compound(s) other than the above-mentioned epoxy resins (I) with one or more compound(s) selected from the group consisting of phenols, polyphenols and carboxylic acids in the presence of a catalyst such as for example, a compound selected from the group consisting of alkali hydroxides, tertiary amines, imidazoles, quaternary ammonium salts, phosphines and phosphonium salts.
  • a catalyst such as for example, a compound selected from the group consisting of alkali hydroxides, tertiary amines, imidazoles, quaternary ammonium salts, phosphines and phosphonium salts.
  • epoxy resins (III) are obtained by reacting a polyfunctional epoxy resin with one or more dihydroxy compounds comprising a structure of the formula (1), (2) or (3), optionally in the presence of one or more dihydroxy compounds other than the dihydroxy compounds having the structure of formula (1), (2) or (3), phenols, polyphenols and carboxylic acids in the presence of a catalyst, such as for example one of the above-mentioned catalytic compounds.
  • suitable epoxy resins are blends of two or more of the epoxy resins (I), (II) and (III) referred to above or blends of one or more of the above referred to epoxy resins I, II and III with one or more other epoxy resin(s).
  • Epoxy resins that can also be used in the curable epoxy resin according to the present invention are reaction products of any one of the afore-mentioned epoxy resins with compounds having a group capable of reacting with an epoxy group such as, for example, phenols, carboxylic acids, amines and alcohols provided only part of the epoxy groups of the epoxy resin have reacted.
  • the epoxy resins and/or the starting compounds used to prepare the epoxy resins may be subjected to recrystallization, reprecipitation, distillation, fractionation, extraction or partition chromatography in order to isolate epoxy resins or starting compounds or isomers thereof having particular chemical structures or having particular molecular weight distributions, before use.
  • Suitable acid anhydride curing agents for use in the epoxy resin composition according to the present invention are for example methylhexahydrophthalic anhydride, methyltetrahydro- phthalic anhydride, tetrahydrophthalic anhydride, hexa- hydrophthalic anhydride and methylnadic anhydride.
  • the amount of the acid anhydride curing agent used in the epxoy resin composition of the present invention is generally in the range of 0.7 to 1.2 acid equivalents, preferably of from 0.8 to 1.0 acid equivalents, per equivalent epoxy group of the epoxy resin present in the composition.
  • the epoxy resin composition of the present invention generally contains a curing accelerator.
  • Suitable accelerators comprise imidazoles, tertiary amines, trisdimethylaminomethyl- phenol, 1,8-diazabicyclo(5,4,0)undecene-7, phosphines, various metal salts, Lewis acid salts.
  • the epoxy resin composition of the present invention may further comprise contain a filler.
  • Suitable fillers are for example, inorganic fillers such as silica, alumina, mica powder, calcium carbonate, aluminium hydroxide, magnesium carbonate, talc, clay, kaolin, dolomite, silicon carbide, glass powder, titanium dioxide, boron nitride and silicon nitride; and also sheet or tape materials such as mica, glass, polyesters, aramides and polyimides.
  • Mixtures of two or more of these fillers may also be used and these fillers may be surface treated if necessary.
  • the epoxy resin composition according to the present invention may further comprise other additives such as for example pigments, colorants, flame retardants, diluents, coupling agents, flexibility imparting agents, releasing agents, antioxidants and defoaming agents.
  • additives such as for example pigments, colorants, flame retardants, diluents, coupling agents, flexibility imparting agents, releasing agents, antioxidants and defoaming agents.
  • the epoxy resin composition according of the present invention may be prepared by uniformly mixing the epoxy resin, the acid anhydride curing agent and, if desired, the filler and various other additives by methods known in the art.
  • the composition may be shaped by, for example, casting followed by curing at elevated temperature to give a cured article.
  • the epoxy resin composition according to the present invention may be impregnated into a substrate, such as for example cloth or tape woven from fibers, to form a prepreg, which may subsequently be cured to form a cured article.
  • Articles comprising an epoxy resin composition according to the present invention in the cured state have a similar or higher glass transition point, a better heat resistance and a much higher cracking resistance than articles comprising conventional epoxy resins in the cured state.
  • Example A The present invention is illustrated by means of the following examples.
  • Example A is illustrated by means of the following examples.
  • Example B 237 pbw of an epoxy resin was obtained in the same manner as in Example A, except that 136 pbw of tetrabromobisphenol A and 57 pbw of bisphenol A were used instead of 272 pbw of tetrabromobisphenol A.
  • the epoxy resin thus obtained had an EEW of 285 g/eq. and a bromine content of 32% by weight (hereafter referred to as Epoxy Resin B) .
  • Example C
  • Example D 230 pbw of an epoxy resin was obtained in the same manner as in Example A, except that 136 pbw of tetrabromobisphenol A and 50 pbw of bisphenol F were used instead of 272 pbw of tetrabromobisphenol A.
  • the epoxy resin thus obtained had an EEW of 288 g/eq. and a bromine content of 33% by weight (hereafter referred to as Epoxy Resin C) .
  • Epoxy Resin C a bromine content of 33% by weight
  • 229 pbw of an epoxy resin was obtained in the same manner as in Example A, except that 136 pbw of tetrabromobisphenol A and 49 pbw of a novolak resin obtained by the condensation of phenol and salicylaldehyde in the presence of an acid catalyst and having a softening point of 105 °C, were used in place of 272 pbw of tetrabromobisphenol A.
  • the epoxy resin thus obtained had an EEW of 272 g/eq. and a bromine content of 33% by weight (hereafter referred to as Epoxy Resin E) .
  • Example F 100 pbw of Epoxy Resin A, 4 pbw of bisphenol A and 0.03 pbw of a catalyst (2-ethyl-4-methylimidazole) were put into a reactor equipped with a thermometer and a stirrer and reacted therein at 150 °C for 180 minutes to obtain an epoxy resin having a EEW of 480 g/eq. and a bromine content of 47% by weight (hereafter referred to as Epoxy Resin F) .
  • Epoxy Resin F 100 pbw of Epoxy Resin A, 4 pbw of bisphenol A and 0.03 pbw of a catalyst (2-ethyl-4-methylimidazole) were put into a reactor equipped with a thermometer and a stirrer and reacted therein at 150 °C for 180 minutes to obtain an epoxy resin having a EEW of 480 g/eq. and a bromine content of 47% by weight (hereafter referred to as Epoxy Res
  • Epoxy Resin H 100 pbw of Epoxy Resin A, 10 pbw of a phenol-novolak-type epoxy resin having an EEW of 178 g/eq., (EPIKOTE 154 available from Yuka Shell Epoxy K.K., EPIKOTE is a trade mark), 15 pbw of tetrabromobisphenol A and 0.03 pbw of 2-ethyl-4-methyli_idazole were put into a reactor equipped with a thermometer and a stirrer and reacted at 150 °C for 180 minutes to obtain an epoxy resin having an EEW of 495 g/eq. and a bromine content of 46% by weight (hereafter referred to as Epoxy Resin H) .
  • Epoxy Resin H 100 pbw of Epoxy Resin A, 10 pbw of a phenol-novolak-type epoxy resin having an EEW of 178 g/eq.
  • Epoxy Resin I 100 pbw of Epoxy Resin A, 5 pbw of p-t-butylphenol and 0.03 pbw of 2-ethyl-4-methylimidazole were put into a reactor equipped with a thermometer and a stirrer and reacted at 150 °C for 180 minutes to obtain an epoxy resin having an EEW of 480 g/eq. and a bromine content of 47% by weight (hereafter referred to as Epoxy Resin I) .
  • Epoxy Resin I 100 pbw of Epoxy Resin A, 5 pbw of p-t-butylphenol and 0.03 pbw of 2-ethyl-4-methylimidazole were put into a reactor equipped with a thermometer and a stirrer and reacted at 150 °C for 180 minutes to obtain an epoxy resin having an EEW of 480 g/eq. and a bromine content of 47% by weight (hereafter referred to as Epoxy Resin
  • Epoxy Resin J 100 pbw of Epoxy Resin A, 10 pbw of 2,4,6-tribromophenol and 0.03 pbw of 2-ethyl-4-methylimidazole were put into a reactor equipped with a thermometer and a stirrer and reacted therein at 150 °C for 180 minutes to obtain an epoxy resin having an EEW of 490 g/eq. and a bromine content of 51% by weight (hereafter referred to as Epoxy Resin J) .
  • Epoxy Resin J 100 pbw of Epoxy Resin A, 10 pbw of 2,4,6-tribromophenol and 0.03 pbw of 2-ethyl-4-methylimidazole were put into a reactor equipped with a thermometer and a stirrer and reacted therein at 150 °C for 180 minutes to obtain an epoxy resin having an EEW of 490 g/eq. and a bromine content of 51% by weight (hereafter referred to as
  • Epoxy Resin K 100 pbw of Epoxy Resin A, 3 pbw of acrylic acid and 0.03 pbw of 2-ethyl-4-methylimidazole were put into a reactor equipped with a thermometer and a stirrer and reacted at 150 °C for 180 minutes to obtain an epoxy resin having an epoxy equivalent of 490 g/eq. and a bromine content of 48% by weight (hereafter referred to as Epoxy Resin K) .
  • Epoxy Resin K 100 pbw of Epoxy Resin A, 3 pbw of acrylic acid and 0.03 pbw of 2-ethyl-4-methylimidazole were put into a reactor equipped with a thermometer and a stirrer and reacted at 150 °C for 180 minutes to obtain an epoxy resin having an epoxy equivalent of 490 g/eq. and a bromine content of 48% by weight (hereafter referred to as Epoxy Resin K) .
  • Epoxy Resin K 100 pbw
  • Example M 143 pbw of an epoxy resin was obtained in the same manner as in Example A, except that 94.5 pbw of 4-bromoresorcinol were used in place of 272 pbw of tetrabromobisphenol A.
  • the epoxy resin thus obtained had an EEW of 181 g/eq. and a bromine content of 26% by weight (hereafter referred to as Epoxy Resin L) .
  • Example M 204 pbw of an epoxy resin was obtained in the same manner as in Example B, except that 159 pbw of 2,5-dibromo-l,6-dihydroxy- naphthalene were used in place of 272 pbw of tetrabromobispheol A.
  • the epoxy resin thus obtained had an EEW of 245 g/eq. and a bromine content of 37% by weight (hereafter referred to as Epoxy Resin M) .
  • Epoxy Resins A to M were combined with a bisphenol A-type epoxy resin having an EEW of 187 g/eq. (EPIKOTE 828 available from Yuka Shell Epoxy K.K.), a bisphenol F-type epoxy resin having an EEW of 168 g/eq. (EPIKOTE 807, available from Yuka Shell Epoxy K.K.), a phenol novolak-type epoxy resin having an epoxy equivalent of 178 g/eq. (EPIKOTE 154, available from Yuka Shell Epoxy K.K.), a low-brominated bisphenol A-type epoxy resin having an epoxy equivalent of 469 g/eq.
  • EPIKOTE 828 available from Yuka Shell Epoxy K.K.
  • EPIKOTE 807 available from Yuka Shell Epoxy K.K.
  • EPIKOTE 154 available from Yuka Shell Epoxy K.K.
  • a low-brominated bisphenol A-type epoxy resin having an epoxy equivalent of 469 g/eq.
  • compositions were cast and cured in an oven at 100 °C for 2 hours followed by 5 hours at 150 °C.
  • the articles thus obtained were tested according to the methods as described below
  • TMA thermal metering apparatus

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)

Abstract

Composition durcissable à base de résine époxyde dont l'agent durcisseur est un anhydride acide, la résine époxyde comportant de 15 à 70 % en poids de bromure ainsi qu'en moyenne plus d'un groupe glycidyle par molécule, et qui présente l'une au moins des trois structures aromatiques spécifiquement définies.
PCT/EP1994/002887 1993-08-30 1994-08-29 Composition durcissable a base de resine epoxyde WO1995006675A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP24842493A JPH0762063A (ja) 1993-08-30 1993-08-30 エポキシ樹脂組成物
JP5/248424 1993-08-30

Publications (1)

Publication Number Publication Date
WO1995006675A1 true WO1995006675A1 (fr) 1995-03-09

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PCT/EP1994/002887 WO1995006675A1 (fr) 1993-08-30 1994-08-29 Composition durcissable a base de resine epoxyde

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JP (1) JPH0762063A (fr)
WO (1) WO1995006675A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119390939A (zh) * 2025-01-02 2025-02-07 深圳市雄毅华绝缘材料有限公司 一种绝缘板用含溴环氧树脂及其制备方法及绝缘板的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012153829A (ja) * 2011-01-27 2012-08-16 Iteq Corp ハロゲンフリーエポキシ樹脂組成物と、それを用いたプリプレグ及び印刷回路基板

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1325223A (fr) * 1961-05-10 1963-04-26 Dow Chemical Co Composés époxydés et résines incombustibles obtenues avec ces composés
US3280216A (en) * 1962-04-20 1966-10-18 Dow Chemical Co Self-extinguishing epoxy resin containing a halogenated polynuclear phenol and a hardening agent
US3378434A (en) * 1964-06-18 1968-04-16 Westinghouse Electric Corp Fire-resistant paper-base epoxy resin laminates
DE1494182A1 (de) * 1960-01-20 1969-01-16 Minnesota Mining & Mfg Verfahren zum Herstellen flammfester Formteile durch Hitzehaerten von Formmassen
EP0119617A1 (fr) * 1983-03-17 1984-09-26 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Composition de résine epoxyde ignifugée utilisée dans la fabrication de laminés électriques
DE3442375A1 (de) * 1983-11-30 1985-06-05 Telefonaktiebolaget L M Ericsson, Stockholm Selbstloeschende epoxykunststoffe, epoxyharzzusammensetzung und die verwendung derselben fuer elektrische zwecke

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1494182A1 (de) * 1960-01-20 1969-01-16 Minnesota Mining & Mfg Verfahren zum Herstellen flammfester Formteile durch Hitzehaerten von Formmassen
FR1325223A (fr) * 1961-05-10 1963-04-26 Dow Chemical Co Composés époxydés et résines incombustibles obtenues avec ces composés
US3280216A (en) * 1962-04-20 1966-10-18 Dow Chemical Co Self-extinguishing epoxy resin containing a halogenated polynuclear phenol and a hardening agent
US3378434A (en) * 1964-06-18 1968-04-16 Westinghouse Electric Corp Fire-resistant paper-base epoxy resin laminates
EP0119617A1 (fr) * 1983-03-17 1984-09-26 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Composition de résine epoxyde ignifugée utilisée dans la fabrication de laminés électriques
DE3442375A1 (de) * 1983-11-30 1985-06-05 Telefonaktiebolaget L M Ericsson, Stockholm Selbstloeschende epoxykunststoffe, epoxyharzzusammensetzung und die verwendung derselben fuer elektrische zwecke

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119390939A (zh) * 2025-01-02 2025-02-07 深圳市雄毅华绝缘材料有限公司 一种绝缘板用含溴环氧树脂及其制备方法及绝缘板的制备方法

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Publication number Publication date
JPH0762063A (ja) 1995-03-07

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