WO2006043524A1 - Résine contenant un squelette indole, résine époxyde contenant un squelette indole, composition de résine époxyde et produit durci produit à partir de celle-ci - Google Patents

Résine contenant un squelette indole, résine époxyde contenant un squelette indole, composition de résine époxyde et produit durci produit à partir de celle-ci Download PDF

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Publication number
WO2006043524A1
WO2006043524A1 PCT/JP2005/019079 JP2005019079W WO2006043524A1 WO 2006043524 A1 WO2006043524 A1 WO 2006043524A1 JP 2005019079 W JP2005019079 W JP 2005019079W WO 2006043524 A1 WO2006043524 A1 WO 2006043524A1
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group
epoxy resin
formula
carbon atoms
represented
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PCT/JP2005/019079
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English (en)
Japanese (ja)
Inventor
Hisashi Yamada
Masashi Kaji
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Nippon Steel Chemical Co., Ltd.
Tohto Kasei Co., Ltd.
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Priority claimed from JP2004306972A external-priority patent/JP2006117790A/ja
Application filed by Nippon Steel Chemical Co., Ltd., Tohto Kasei Co., Ltd. filed Critical Nippon Steel Chemical Co., Ltd.
Publication of WO2006043524A1 publication Critical patent/WO2006043524A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring

Definitions

  • the present invention relates to an indole skeleton-containing resin useful as an intermediate of epoxy resin, a curing agent, etc., an indole skeleton-containing epoxy resin, an epoxy resin composition using these, and a cured product thereof. It is preferably used as an insulating material in the electric and electronic fields such as printed wiring boards and semiconductor encapsulation. Background art
  • Epoxy resin has been used in a wide range of industrial applications, but its required performance has become increasingly sophisticated in recent years.
  • a semiconductor encapsulating material in a typical field of a resin composition mainly composed of epoxy resin, but as the integration degree of semiconductor elements increases, the package size is becoming larger and thinner.
  • the mounting method is also shifting to surface mounting, and the development of materials with excellent solder heat resistance is desired. Therefore, as a sealing material, in addition to reducing moisture absorption, improvement in adhesion and adhesion at the interface between different materials such as lead frames and chips is strongly demanded.
  • Patent Document 1 JP-A-5-1099345
  • Patent Document 2 JP-A-11-140166
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-46522
  • Patent Document 4 Japanese Patent Application Laid-Open No. 2004-59792
  • Patent Document 5 Japanese Patent Laid-Open No. 4-173831
  • Patent Document 6 Japanese Unexamined Patent Publication No. 2000-129092
  • Patent Document 7 Japanese Patent Laid-Open No. 3-90075
  • Patent Document 8 JP-A-3-281623
  • Patent Document 1 shows the application of naphthol aralkyl resin to semiconductor encapsulants.
  • naphthol aralkyl rosin is excellent in low hygroscopicity, low thermal expansion, etc., it has a disadvantage of poor curability.
  • Patent Document 2 proposes a curing agent having a biphenyl structure and describes that it is effective for improving flame retardancy, but has a drawback of being inferior in curability.
  • Patent Document 3 describes indole oligomers copolymerized with aromatic olefins.
  • an epoxy resin that satisfies these requirements has not been known yet.
  • the well-known bisphenol type epoxy resin is widely used because it is liquid at room temperature and has excellent workability and is easy to mix with curing agents and additives.
  • resistance and moisture resistance There is a problem in terms of resistance and moisture resistance.
  • novolac type epoxy resin is known as an improved heat resistance, but there are problems in moisture resistance, adhesion and the like.
  • conventional epoxy resins whose main skeleton is composed only of hydrocarbons have no flame retardancy.
  • Patent Documents 2, 5, and 6 disclose examples in which aralkyl epoxy resin having a biphenyl structure is applied to a semiconductor encapsulant as a material that improves flame retardancy without containing phosphorus atoms or halogen atoms. ing.
  • Patent Document 4 discloses an example in which an aralkyl type epoxy resin having a naphthalene structure is used. However, these epoxy resins have insufficient performance in any of flame retardancy, moisture resistance, and heat resistance.
  • Patents References 7 and 8 disclose naphthol-based aralkyl-type epoxy resins and semiconductor encapsulating materials containing them, but nothing focuses on flame retardancy.
  • An object of the present invention is to contain an indole skeleton useful for an intermediate of epoxy resin, a curing agent, etc.
  • Another object of the present invention is to provide an epoxy resin composition useful for circuit board materials and the like, and to provide a cured product thereof.
  • the indole skeleton-containing coffin of the present invention is represented by the following general formula (1).
  • R is a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, a halogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and A is a group having 1 carbon atom. Even if the alkyl group or hydroxyl group of ⁇ 8 is substituted, it represents a group having a benzene ring or naphthalene ring force, and the abundance ratio (molar ratio) of the groups represented by the formulas (2) and (3) is 1: 9-9: 1, where X is the following (a) or formula (b) R, R, R, R, R, R, R
  • B represents a group having a benzene ring, biphenyl ring or naphthalene ring force
  • n 1 to: the number of LOs.
  • This indole skeleton-containing rosin has a molar ratio of indole represented by the following formula (4) and phenol represented by the following formula (5) in the range of 1: 9 to 9: 1. It is obtained by reacting 10 to 90 mol of a crosslinking agent represented by the following formula (6), (7), (8) or (9) with respect to 100 mol.
  • R represents a hydrogen atom, a hydroxyl group, an alkoxy group having 8 carbon atoms, a halogen atom or a hydrocarbon group having 8 to 8 carbon atoms,
  • A represents an alkyl group having 1 to 8 carbon atoms or a group having a benzene ring or naphthalene ring which may be substituted by a hydroxyl group,
  • R, R, R and R independently represent a hydrogen atom or a hydrocarbon group having a carbon number]
  • B represents a group having a benzene ring, biphenyl ring or naphthalene ring,
  • Z and Z independently represent OH, alkoxy or halogen.
  • the indole skeleton-containing epoxy resin of the present invention is represented by the following general formula (10).
  • L is the following formula (11) or formula (12)
  • the ratio of the groups represented by the formulas (11) and (12) (molar ratio) is in the range of 1: 9 to 9: 1,
  • Y represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms or a glycidyl group
  • G represents a glycidyl group
  • n 1 to: the number of L0.
  • This indole skeleton-containing epoxy resin can be advantageously obtained by reacting the indole skeleton-containing resin represented by the general formula (1) with epichlorohydrin.
  • the phenolic resin composition of the present invention is obtained by blending 2 to 200 parts by weight of an indole skeleton-containing resin with 100 parts by weight of a polyhydric phenolic compound.
  • the epoxy resin composition comprising the epoxy resin and the curing agent of the present invention comprises 2 to 200 parts by weight of an Indian skeleton-containing resin as part or all of the curing agent with respect to 100 parts by weight of the epoxy resin.
  • the indole skeleton-containing epoxy resin is blended as a part of or the entire power of the epoxy resin.
  • the epoxy resin cured product of the present invention can be obtained by hardening this phenol resin composition.
  • the indole skeleton-containing rosin (hereinafter also referred to as ISR) of the present invention is represented by the general formula (1).
  • the indole skeleton-containing epoxy resin (hereinafter also referred to as ISE) of the present invention has the general formula (10) It is represented by Since ISE can be obtained by epoxidizing ISR, ISR is also an intermediate of ISE.
  • L is a group selected from the basic forces represented by the formulas (2) and (3), and the abundance ratio thereof is 1: 9 to 9: 1, preferably 3: 7-7: 3.
  • X is a group represented by formula (a) or formula (b), and n is a number from 1 to 10.
  • n + 1 L and n X in the formula (1) may be the same or different from each other, but L is the above-mentioned abundance ratio in the fat and oil in the formula (2) and the formula There is a group represented by (3).
  • rosin is a mixture, it only needs to exist as an average.
  • n since rosin is a mixture, its average (number average) is preferably in the above range.
  • R is a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a carbon atom having 1 to 8, preferably 1 to 7
  • A may be substituted with an alkyl group or a hydroxyl group having 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms, or from phenols (may be polyhydric or polycyclic aromatic funols). The resulting group is indicated.
  • X is a bridging group represented by formula (a) or formula (b). Forces R, R, R and R are independently water
  • An elementary atom or a hydrocarbon group having 1 to 6 carbon atoms and B represents a group consisting of a benzene ring, biphenyl ring or naphthalene ring.
  • these rings constituting B may be substituted with a hydrocarbon group having 1 to 6 carbon atoms.
  • X bridges L, but the substitution position of X with respect to the groups represented by formulas (2) and (3) constituting L is not particularly limited.
  • the 1-position force of the indole ring is also 7-position.
  • a structure in which a hydrogen atom is substituted with a bridging group and linked can be taken, but it is preferable that the hydrogen atom at the 1-position of the indole ring in formula (2) remains.
  • the indole skeleton-containing resin of the present invention functions as a curing agent. Is not fully expressed.
  • the softening point of the ISR is preferably 40 to 200 ° C, more preferably 50 to 160 ° C, and more preferably 60 to 120 ° C.
  • the softening point refers to the softening point measured based on the ring and ball method of JISK-6911. If it is lower than this, the heat resistance of the cured product is lowered when it is added to the epoxy resin, and if it is higher than this, the fluidity during molding is lowered.
  • the ISR of the present invention can itself be a component of a phenol resin composition or an epoxy resin composition, but in some cases, a halogen-alkyl compound, an alkenyl halide is added to an indole skeleton-containing resin.
  • the ISR of the present invention includes an indole represented by the formula (4) and a phenol represented by the formula (5), a formula (6), a formula (7), (8) or (9). It can be synthesized by reacting the represented crosslinking agent.
  • the amount of the crosslinking agent used is in the range of 0.1 to 0.9 mol, preferably in the range of 0.2 to 0.8 mol, with respect to 1 mol of the total of indoles and phenols. is there. If it is smaller than this, the amount of unreacted indoles and phenols will increase during the synthesis, resulting in lower ISR productivity and lower soft point of the synthesized ISR, which was used as an epoxy resin curing agent.
  • the acid catalyst can be appropriately selected from known inorganic acids and organic acids.
  • mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid, P-toluenesulfonic acid, dimethyl sulfuric acid, jetyl sulfuric acid, zinc chloride, aluminum chloride, iron chloride,
  • Lewis acids such as boron fluoride, or solid acids such as ion-exchange resin, activated clay, silica-alumina, and zeolite.
  • This reaction is usually performed at 10 to 250 ° C for 1 to 20 hours. Furthermore, during the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycolol, methinoreserosolve, ethyl acetate, etc., ketones such as acetone, methylethyl ketone, methylisobutylketone, dimethyl ether, jetyl Ethers such as ether, diisopropyl ether, tetrahydrofuran and dioxane, and aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene can be used as the solvent.
  • alcohols such as methanol, ethanol, propanol, butanol, ethylene glycolol, methinoreserosolve, ethyl acetate, etc.
  • ketones such as acetone, methylethyl ketone, methylisobutylketone,
  • Examples of indoles used as a raw material include indoles substituted with a hydroxyl group, an alkoxy group, a halogen atom or a hydrocarbon group as a substituent, in addition to indoles.
  • the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and the like
  • the alkoxy group includes a methoxy group, an ethoxy group, a vinyl ether group, an isopropoxy group, a allyloxy group, a propargyl ether group, a butoxy group, and a phenoxy group. It is done.
  • hydrocarbon group various substituted indoles having a methyl group, an ethyl group, a vinyl group, an ethyne group, an isopropyl group, an aryl group, a propargyl group, a butyl group, an amyl group, a fullyl group, a benzyl group, etc.
  • the power that can be used is preferably indole.
  • the phenols include, in addition to phenols, alkylphenols such as talesols and xylenols, polyhydric phenols such as hydroquinone, polycyclic phenols such as naphthols and naphthalenediols, bisphenol A and bisphenols. Examples thereof include bisphenols such as F, and polyfunctional phenolic compounds such as phenol novolak and phenol aralkyl resin. These monomers can be used singly or in combination of two or more. However, from the viewpoint of the physical properties of the cured product obtained by containing ISR, the content of the indole skeleton is high. There are no particular restrictions.
  • the cross-linking agent is preferably a formaldehyde represented by formula (6) such as aldehydes such as formaldehyde, acetoaldehyde, propyl aldehyde, butyraldehyde, amyl aldehyde, and benzaldehyde.
  • Preferred formaldehyde raw materials used in the reaction include an aqueous formalin solution, paraformaldehyde, trioxane and the like.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone represented by the formula (7) can also be used as a crosslinking agent.
  • the cross-linking agent represented by the formula (8) includes P-xylylenedaricol, P-xylylene glycol dimethyl ether, ⁇ -xylylene dichloride, 4, 4, -dimethoxymethyl biphenyl. 4,4'-dichloromethylbiphenyl, dimethoxymethylnaphthalene, dichloromethylnaphthalene.
  • dibutenebenzenes, dibibiphenols, divinylnaphthalenes and the like represented by the formula (9) can also be used as a crosslinking agent.
  • the obtained ISR contains unreacted indole and phenol. Ru remains. Unreacted remaining indoles and phenols are usually removed out of the system by methods such as distillation under reduced pressure or solvent separation. It is desirable that the amount of unreacted indole and phenols remaining in the ISR be small, usually 5% or less, preferably 3% or less, more preferably 1% or less. If the amount of the remaining indoles and phenols is large, they volatilize during the production of the molded product, which may reduce the molding workability and cause voids in the molded product. In addition, the flame retardancy of the molded product is also reduced.
  • the phenolic resin composition of the present invention comprises the above ISR in a polyhydric phenolic compound.
  • the content of ISR is 2 to 200 parts by weight, preferably 5 to: LOO parts by weight, and more preferably 10 to 80 parts by weight with respect to 100 parts by weight of the polyvalent phenolic compound. If it is less than this, the effects of modification such as low hygroscopicity, heat resistance, adhesion and flame retardancy will be small in winter, and the viscosity will increase and the moldability will decrease.
  • the polyhydric phenol compound referred to here refers to any compound having two or more phenolic hydroxyl groups in one molecule, for example, bisphenol A, bisphenol F, bisphenol S, fluorene bis.
  • Divalent phenols such as phenol, 4, 4, -biphenol, 2, 2, -biphenol, hydrin quinone, resorcin, naphthalenediol, or tris- (4-hydroxyphenol) methane, 1, 1 , 2,2-tetrakis (4-hydroxyphenol) ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinyl phenol and the like.
  • divalent phenols such as phenols, naphthols, bisphenolanol A, bisphenolanol F, bisphenolanol S, fluorenebisphenol, 4,4, -biphenol, 2,2, biphenol, hydroquinone, resorcinol, naphthalenediol, etc.
  • the softening point of the polyhydric phenolic compound is usually in the range of 40 to 200 ° C, preferably 60 to 150 ° C. Lower than this, the cure obtained using epoxy hardener as a curing agent The heat resistance of the object decreases. In addition, the mixing property between ISR and higher is lowered.
  • the phenolic resin composition of the present invention includes a melt mixing method in which mixing is performed by stirring, kneading, and the like at a temperature equal to or higher than the softening point of either the polyhydric phenolic compound or the ISR, It can be obtained by a method such as a solution mixing method in which both are dissolved in a solvent that dissolves each and mixed uniformly by stirring, kneading or the like.
  • Solvents used in the solution mixing method include, for example, alcohols such as methanolol, ethanol, propanol, butanol, ethylene glycolol, methinoresellosonol, ethyl acetate sorb, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketones, dimethyl ether, jetyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and other ethers, and aromatic solvents such as benzene, toluene, xylene, black benzene, and dichlorobenzene.
  • epoxy resin, inorganic filler, other phenolic compounds, and other additives can be blended.
  • the phenol resin composition of the present invention can be made into a phenol resin composition by using in combination with a curing agent generally used for phenol resin compositions such as hexamethyltetramine.
  • L is a group selected by the basic force represented by the formula (11) or the formula (12), and the abundance ratio thereof is 1: 9 to 9: 1, preferably 3: 7 to 7 : 3
  • X is a group represented by the formula (a) or (b), and n is a number from 1 to 10.
  • L and X may be the same or different, but L is the formula (11) and (12 ) Is present. However, since rosin is a mixture, it should be present as an average.
  • R is a hydrogen atom having 1 to 8 carbon atoms, preferably 1
  • the alkoxy group include a methoxy group, an ethoxy group, a butyl ether group, an isopropoxy group, a allyloxy group, a propargyl ether group, a putoxy group, a phenoxy group, and a benzyloxy group
  • the halogen atom includes a fluorine atom and a chlorine atom. Examples thereof include a child and a bromine atom.
  • Hydrocarbon groups include methyl, ethyl, and biphenyl.
  • A is a group formed by epoxy-forming phenols (which may be polyhydric or polycyclic aromatic funols) and has 1 to 8 carbon atoms, preferably 1 to 6 carbon atoms.
  • X and n have the same meaning as X and n in formula (1). That is, X is a bridging group represented by formula (a) or formula (b). n is a number from 1 to 10. In addition, rosin is a mixture, but its average (number average) n is preferably in the above range.
  • the ISE of the present invention is advantageously produced by reacting ISR represented by the general formula (1) with epichlorohydrin, but is not limited to this reaction.
  • the ISR represented by the above general formula (1) is a resin that is at least partly, preferably all of which is H or OH, that is epoxyd with epichlorohydrin. In the formulas (10) to (12), this corresponds to a compound in which the glycidyl ether group is OH and the glycidyl group is H.
  • the epoxy resin composition of the present invention contains at least an epoxy resin and a curing agent, and there are the following three types.
  • composition containing the ISR as a part or all of the curing agent 1) A composition containing the ISR as a part or all of the curing agent.
  • the amount of ISR is usually in the range of 2 to 200 parts by weight, preferably 5 to 80 parts by weight, with respect to 100 parts by weight of the epoxy resin. If it is less than this, the effect of improving the low hygroscopicity, adhesion and flame retardancy is small. If it is more than this, there is a problem that the moldability and the strength of the cured product are lowered.
  • the amount of ISR is usually determined in consideration of the equivalent balance of -NH- groups and -OH groups of ISR and epoxy groups in the epoxy resin. Mix.
  • the equivalent ratio of epoxy resin and curing agent (epoxy group Z (NH group + OH group) molar ratio) is usually in the range of 0.2 force to 5.0, preferably ⁇ or 0.5 force. The range is 0. If it is larger or smaller than this, the curability of the epoxy resin composition is lowered, and the heat resistance, mechanical strength, etc. of the cured product are lowered.
  • a curing agent other than the ISR of the present invention can be used in combination.
  • the amount of the other curing agent is determined within a range in which the range of the ISR is usually within the range of 2 to 200 parts by weight, preferably 5 to 80 parts by weight with respect to 100 parts by weight of the epoxy resin. . If the amount of ISR is less than this, the effect of improving low moisture absorption, adhesion and flame retardancy is small. If it is more than this, there is a problem that the moldability and the strength of the cured product are lowered.
  • curing agents other than ISR all those generally known as epoxy resin hardeners can be used, such as dicyandiamide, acid anhydrides, polyhydric phenols, aromatic and aliphatic amines. Etc.
  • polyhydric phenols are preferably used as curing agents in fields where high electrical insulation properties such as semiconductor encapsulants are required.
  • the following are specific examples of curing agents.
  • Examples of the acid anhydride hardener include phthalic anhydride, tetrahydrophthalic anhydride, and methyl.
  • Examples include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, dodecyl succinic anhydride, nadic anhydride, and trimellitic anhydride.
  • polyhydric phenols examples include bisphenol A, bisphenol F, bisphenol 3, fluorene bisphenol, 4, 4, -biphenol, 2, 2, -biphenol, hydroquinone, resorcin, naphthalenediol
  • Divalent phenols such as tris- (4-hydroxyphenol) methane, 1,1,2,2-tetrakis (4-hydroxyphenol) ethane, phenol novolak, o-cresol novolak
  • trivalent or higher phenols such as naphthol novolac and polyvinyl phenol are available.
  • divalent compounds such as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4, 4, -biphenol, 2, 2, -biphenol, hydroquinone, resorcin, naphthalene diol, etc.
  • polyhydric phenolic compounds synthesized by a condensing agent such as formaldehyde, acetoaldehyde, benzaldehyde, P-hydroxybenzaldehyde, P-xylylene diol and the like.
  • the above-described phenolic resin composition of the present invention can be blended.
  • amines examples include 4,4, -diaminodiphenylmethane, 4,4, -diaminodiphenylpropan, 4,4, -diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine.
  • aromatic amines such as amine
  • aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.
  • One or more of these curing agents can be mixed and used in the composition.
  • the epoxy resin used in the yarn and composite is selected from those having two or more epoxy groups in one molecule.
  • divalent phenols such as bisphenol A, bisphenol F, bisphenol 3, fluorene bisphenol, 4, 4, -biphenol, 2, 2, -biphenol, tetrabromobisphenol A, hydroquinone, resorcin, etc.
  • tris- (4-hydroxyphenol) methane, 1,1,2,2-tetrakis (4-hydroxyphenol) ethane, novolac sesame such as phenol, cresol, naphthol, phenol, sauce
  • glycidyl ethers of phenolic compounds having a valence of 3 or more such as aralkyl resins such as sol and naphthol.
  • These epoxy resins can be used alone or in combination of two or more. It is possible to be.
  • any one generally known as a curing agent for epoxy resin can be used.
  • examples include dicyandiamide, polyvalent phenols, acid anhydrides, aromatic and aliphatic amines described above.
  • an ISR represented by the general formula (1) is also preferably exemplified.
  • One or more of these hardeners can be mixed and used in the resin composition.
  • epoxy resin in addition to the ISE represented by the general formula (10), another type of epoxy resin may be blended in the epoxy resin composition as an epoxy resin component.
  • the epoxy resin in this case, all normal epoxy resins having two or more epoxy groups in the molecule can be used.
  • divalent phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4, 4, 1 biphenol, 2, 2, 1 biphenol, hydroquinone, resorcin, or tris mono (4- Hydroxyphenol) methane, 1,1,2,2-tetrakis (4-hydroxyphenol) ethane, phenol novolak, o-cresol novolak and other trivalent phenols, phenolic aralkyl fats
  • naphthol-based aralkyl resins or darcidyl ether derivatives that are derived from halogen-bisphenols such as tetrabromobisphenol A.
  • epoxy resins can be used alone or in combination of two or more.
  • the amount of ISE represented by the general formula (1) is 5 to: L00 wt%, preferably 60 to 100 wt% in the entire epoxy resin. It should be in the range!
  • ISR and ISE are used as part or all of the epoxy resin and curing agent, but the preferred amount of ISR and ISE when used as a part is as described above.
  • the same epoxy resin or curing agent when other epoxy resin and curing agent are used the same epoxy resin or curing agent as described in the composition can be used.
  • an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, inden resin, inden'coumarone resin, phenoxy resin, etc. May be appropriately blended as other modifiers.
  • the amount added is usually in the range of 2 to 30 parts by weight per 100 parts by weight of the epoxy resin.
  • the epoxy resin composition of the present invention may contain additives such as inorganic fillers, pigments, retardants, thixotropic agents, coupling agents, fluidity improvers and the like.
  • inorganic fillers examples include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, or my strength, talc, calcium carbonate, alumina, hydrated alumina, and the like.
  • a preferable blending amount when used for a semiconductor encapsulant is 70 wt% or more, and more preferably 80 wt% or more.
  • Examples of the pigment include organic or inorganic extender pigments, scaly pigments, and the like.
  • examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, acid-polyethylene nitrate, and organic bentonite-based.
  • a curing accelerator can be used in the epoxy resin composition of the present invention as needed.
  • examples include amines, imidazoles, organic phosphines, Lewis acids, etc., specifically 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethyl.
  • Tertiary amines such as amine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenolimidazole, 2-ethyl-4-methylimidazole, 2-phenol -Ru 4-methylimidazole, imidazoles such as 2-heptadecylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylenophosphine, and phenylophosphine, tetraphenylphosphonium 'Tetraphenolate, tetraphenylphospho-um ⁇ Ethyl trifluorate, tetrabutyl phosphorum ⁇ Tetra-substituted phosphomumes such as tetrabutyl borate, tetra-substituted borate, 2-ethyl 4-methylimidazole
  • the resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a coupling agent such as y-glycidoxypropyltrimethoxysilane, carbon black and the like. Colorants, flame retardants such as antimony trioxide, anti-stress agents such as silicone oil, and lubricants such as calcium stearate.
  • the epoxy resin composition of the present invention is made into a varnish in which an organic solvent is dissolved, After impregnating fibrous materials such as glass cloth, aramid nonwoven fabric, and polyester nonwoven fabric such as liquid crystal polymer, the solvent can be removed to prepare a pre-preda. Moreover, it can be set as a laminated body by apply
  • the epoxy resin composition of the present invention is cured by heating, an epoxy resin composition can be obtained.
  • This cured product has low moisture absorption, high heat resistance, adhesion, flame retardancy, and the like. Excellent in terms.
  • This cured product can be obtained by molding the epoxy resin composition by casting, compression molding, transfer molding or the like. The temperature at this time is usually in the range of 120 to 220 ° C.
  • the viscosity was measured by a ring-and-ball method using a B-type viscometer according to the softening point ⁇ and IS K-6911.
  • the GPC measurement conditions were as follows: apparatus; HLC-82A (manufactured by Tosohichi Co., Ltd.), column; Tetrahydrofuran, flow rate; lml / miiu temperature; 38 ° C, detector; RI, polystyrene standard solution was used for the calibration curve.
  • Fig. 1 shows the NMR ⁇ vector
  • Fig. 2 shows the infrared absorption spectrum
  • Fig. 3 shows the GPC chart.
  • 0-cresol novolak type epoxy resin (OCNE; epoxy equivalent 200, softening point 70 ° C) as epoxy resin component, ISR-A, ISR-B obtained in Examples 1 and 2 as curing agent, Example 3 Phenol resin composition (resin composition A), phenol novolac (curing agent A; OH equivalent 103, soft soft point 82 ° C), phenol aralkyl resin (curing agent B; Mitsui) Glossary, XL 225-LL, OH equivalent 172, softening point 74 ° C), silica (average particle size 2 2 m) as filler, and 2-ethyl-4-methylimidazole as curing accelerator in Table 1.
  • the resulting mixture was kneaded to obtain an epoxy resin composition.
  • This epoxy resin composition was used and molded at 175 ° C., and post-cured at 175 ° C. for 12 hours to obtain a cured product test piece, which was then subjected to various physical property measurements.
  • the glass transition point (Tg) and the coefficient of linear expansion (CTE) were measured at a rate of temperature increase of 10 ° CZ using a thermomechanical measurement device.
  • the water absorption rate is the rate of change in weight after forming a disk with a diameter of 50 mm and a thickness of 3 mm using an epoxy resin thread and post-curing, and absorbing moisture at 133 ° C, 3 atm for 96 hours. did.
  • Table 4 a round test with a diameter of 50 mm and a thickness of 3 mm was used. Using the specimen, the rate of change in weight after absorbing moisture for 100 hours under the conditions of 85 ° C. and 85% RH was used.
  • the adhesive strength was 175 ° C, formed on a copper foil with a compression molding machine using an epoxy resin composition. After post-curing at C for 12 hours, the tensile shear strength was determined and evaluated. However, in Table 4, the adhesive strength is 25 mm X 12.5 mm X O. 5 mm molded product between two copper plates at 175 ° C with a compression molding machine and post-cured at 180 ° C for 12 hours. Then, the tensile shear strength was evaluated. Flame retardancy was measured by the UL94V-0 standard after molding a 1Z16 inch thick test piece and expressed as the total burn time for five test pieces. The results are summarized in Table 2.
  • Example 10 100 g of ISR-A obtained in Example 1 was dissolved in 178 g of epichlorohydrin and 36 g of diethylene glycol dimethyl ether. Thereafter, 33.7 g of 96% potassium potassium hydroxide was added over 3 hours at 50 ° C. with stirring, and the reaction was continued for another hour after the addition was completed. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, epiclorhydrin was distilled off to obtain 110 g of epoxy resin (ISE-A). The obtained epoxy resin had a soft soft point of 78 ° C, a melt viscosity of 0.28 Pa's, and an epoxy equivalent of 278 g / eq. The results of NMR, IR and GPC measurements on ISE-A are shown in FIGS.
  • epoxy resin component As the epoxy resin component, ISE-A, 0-cresol novolac type epoxy resin synthesized in Example 10 (epoxy resin B: Nippon Kayaku Co., Ltd., EOCN-1020-65; epoxy equivalent 200, hydrolyzable Chlorine 400ppm, softening point 65 ° C), biphenyl type epoxy resin (Epoxy resin C: made by Japan Epoxy Resin, YX4000HK; epoxy equivalent 195, hydrolyzable chlorine 450ppm, melting point 105 ° C)
  • agent component As an agent component, IS R-A synthesized in Example 1, phenol novolak (curing agent A: manufactured by Gunei Chemical Co., Ltd., PSM-4261; OH equivalent 103, softening point 80 ° C), 1-naphthol aralkyl-type soot Fat (curing agent B: manufactured by Nippon Steel Engineering Co., Ltd., SN-4 75; OH equivalent 210, softening point 77 ° C.)
  • an epoxy resin composition was obtained with the formulation shown in Table 3, using spherical silica (average particle size 18 m) as a filler and triphenylphosphine as a curing accelerator.
  • surface shows the weight part in a mixing
  • the ISR of the present invention is useful as an epoxy resin intermediate, an epoxy resin curing agent, and a modifier.
  • the ISR When applied to an epoxy resin composition, the ISR has excellent high heat resistance and moisture resistance. It gives a cured product with excellent flame retardancy and high adhesion to different materials, and can be suitably used for applications such as sealing of electronic components and circuit board materials.
  • an epoxy resin composition containing ISR or ISE of the present invention is cured by heating, an epoxy resin is obtained. It is possible to make a cured oil, and this cured product is excellent in terms of flame retardancy, low moisture absorption, high heat resistance, adhesion, etc., and is suitable for applications such as sealing electrical and electronic parts, circuit board materials, etc. It can be used for

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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne une résine époxyde donnant un produit durci qui est excellent en termes de résistance à la chaleur, résistance à l'humidité et ininflammabilité élevées et en termes d'adhérence à différents types de matériaux et également une résine contenant un squelette indole utilisée comme intermédiaire pour la résine époxyde. On prépare la résine contenant un squelette indole ci-dessus en faisant réagir 100 moles au total d'un indole et d'un phénol avec 10 à 90 moles d'un agent réticulant tel qu'un aldéhyde et un xylylèneglycol. On prépare la résine époxyde contenant un squelette indole ci-dessus par époxydation de la résine contenant un squelette indole avec de l'épichlorhydrine. La résine contenant un squelette indole peut être représentée par la formule générale (1) suivante : H-L-(X-L)n-H (1) dans laquelle L est un groupe divalent formé à partir d'un indole ou d'un phénol, la proportion molaire d'un groupe dérivé d'un indole par rapport à un groupe dérivé d'un phénol est comprise dans l'intervalle allant de 1:9 à 9:1, X est un groupe divalent formé à partir d'un agent réticulant tel qu'un aldéhyde, une cétone, un xylylèneglycol ou un divinylbenzène et n représente un nombre de 1 à 10.
PCT/JP2005/019079 2004-10-21 2005-10-18 Résine contenant un squelette indole, résine époxyde contenant un squelette indole, composition de résine époxyde et produit durci produit à partir de celle-ci WO2006043524A1 (fr)

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JP2005031843 2005-02-08
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006249420A (ja) * 2005-02-08 2006-09-21 Nippon Steel Chem Co Ltd インドール骨格含有エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
JP2007297538A (ja) * 2006-05-01 2007-11-15 Nippon Steel Chem Co Ltd インドール骨格含有樹脂、インドール骨格含有エポキシ樹脂、エポキシ樹脂組成物及びその硬化物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002105166A (ja) * 2000-09-27 2002-04-10 Nippon Kayaku Co Ltd エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
WO2003068837A1 (fr) * 2002-02-12 2003-08-21 Nippon Steel Chemical Co., Ltd. Resines indole, resines epoxy et compositions de resines contenant ces composes
JP2003301031A (ja) * 2002-04-10 2003-10-21 Nippon Kayaku Co Ltd フェノール樹脂、エポキシ樹脂及びその製法、樹脂組成物
JP2004238501A (ja) * 2003-02-06 2004-08-26 Nippon Kayaku Co Ltd 結晶性フェノール樹脂、液状エポキシ樹脂およびエポキシ樹脂組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002105166A (ja) * 2000-09-27 2002-04-10 Nippon Kayaku Co Ltd エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
WO2003068837A1 (fr) * 2002-02-12 2003-08-21 Nippon Steel Chemical Co., Ltd. Resines indole, resines epoxy et compositions de resines contenant ces composes
JP2003301031A (ja) * 2002-04-10 2003-10-21 Nippon Kayaku Co Ltd フェノール樹脂、エポキシ樹脂及びその製法、樹脂組成物
JP2004238501A (ja) * 2003-02-06 2004-08-26 Nippon Kayaku Co Ltd 結晶性フェノール樹脂、液状エポキシ樹脂およびエポキシ樹脂組成物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006249420A (ja) * 2005-02-08 2006-09-21 Nippon Steel Chem Co Ltd インドール骨格含有エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
JP2007297538A (ja) * 2006-05-01 2007-11-15 Nippon Steel Chem Co Ltd インドール骨格含有樹脂、インドール骨格含有エポキシ樹脂、エポキシ樹脂組成物及びその硬化物

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