WO2008117839A1 - Nouveau composé hydroxy polyvalent, procédé de production de celui-ci, résine époxyde utilisant ce composé et composition de résine époxyde et produit durci de celle-ci - Google Patents

Nouveau composé hydroxy polyvalent, procédé de production de celui-ci, résine époxyde utilisant ce composé et composition de résine époxyde et produit durci de celle-ci Download PDF

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Publication number
WO2008117839A1
WO2008117839A1 PCT/JP2008/055798 JP2008055798W WO2008117839A1 WO 2008117839 A1 WO2008117839 A1 WO 2008117839A1 JP 2008055798 W JP2008055798 W JP 2008055798W WO 2008117839 A1 WO2008117839 A1 WO 2008117839A1
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Prior art keywords
epoxy resin
hydroxy compound
resin composition
sar
carbon atoms
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PCT/JP2008/055798
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English (en)
Japanese (ja)
Inventor
Hisashi Yamada
Hideyasu Asakage
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Tohto Kasei Co., Ltd.
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Priority claimed from JP2007076307A external-priority patent/JP2008231071A/ja
Priority claimed from JP2007084061A external-priority patent/JP2008239853A/ja
Application filed by Tohto Kasei Co., Ltd. filed Critical Tohto Kasei Co., Ltd.
Publication of WO2008117839A1 publication Critical patent/WO2008117839A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
    • 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
    • C08G59/302—Di-epoxy compounds containing atoms other than carbon, hydrogen, oxygen and nitrogen containing sulfur
    • 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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

Definitions

  • Novel polyhydric hydroxy compound process for producing the compound, epoxy resin, epoxy resin composition and cured product thereof using the compound
  • the present invention relates to a sulfide structure-containing polyhydric hydroxy compound, a sulfide structure-containing epoxy resin useful as an epoxy resin curing agent, modifier, and the like, an epoxy resin composition using the same, and a cured product thereof. It is suitably used as an insulating material in the electrical and electronic fields such as printed wiring boards and semiconductor encapsulation. Background art
  • Epoxy resins have been used in a wide range of industrial applications, but their required performance has become increasingly sophisticated in recent years.
  • semiconductor encapsulating materials are a typical field of resin compositions based on epoxy resins, but as the degree of integration of semiconductor elements increases, the package size is becoming larger and thinner, and the mounting method However, the transition to surface mounting is progressing, and the development of materials with excellent solder heat resistance is desired. Therefore, as a sealing material, in addition to low 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 shows that a naphthal aralkyl resin is applied to a semiconductor sealing material.
  • naphthol aralkyl resin is excellent in low hygroscopicity, low thermal expansion, etc.
  • 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 poor curability.
  • both naphthalene-based resins and biphenyl-based resins have a main skeleton composed of only hydrocarbons, so that they were not sufficient for the development of flame retardancy and adhesion.
  • Patent Document 3 discloses an epoxy resin composition containing a bifunctional hydroxy compound having a sulfide structure.
  • the bifunctional hydroxy compound has a high melting point
  • an epoxy resin curing agent is disclosed.
  • it is a bifunctional compound, it has a disadvantage that it is inferior in heat resistance as compared with a polyfunctional compound.
  • epoxy resins that satisfy these requirements are not yet known.
  • the well-known bisphenol type epoxy resin is widely used because it is liquid at room temperature, has excellent workability, and is easy to mix with hardeners, additives, etc.
  • moisture resistance There is a problem in terms of moisture resistance.
  • nopolac-type epoxy resins are known as improved heat resistance, but there are problems in adhesion, moisture resistance, and the like.
  • conventional epoxy resins whose main skeleton is composed only of hydrocarbons have no flame retardancy.
  • a method of adding a phosphate ester flame retardant is disclosed.
  • the method using phosphate ester flame retardants does not have sufficient moisture resistance.
  • the phosphoric acid ester is hydrolyzed under high temperature and high humidity, which reduces the reliability as an insulating material.
  • Patent Documents 2 and 4 disclose examples in which a aralkyl epoxy resin having a biphenyl structure is applied to a semiconductor encapsulant as one that improves flame retardancy without containing phosphorus atoms or halogen atoms.
  • Patent Document 5 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, adhesion and heat resistance.
  • Patent Documents 6, 7 and 8 disclose naphthol-based aralkyl-type epoxy resins and semiconductor encapsulants containing the same, but nothing focuses on flame retardancy.
  • Patent Document 9 includes Although a polyhydric hydroxy compound having an phenyl ether structure and an epoxidized product thereof are disclosed, it does not focus on adhesion and flame retardancy. Further, Patent Document 10 discloses a semiconductor sealing material using a bifunctional epoxy resin having a sulfide structure. However, these epoxy resins have insufficient heat resistance and are difficult. It is not focused on flammability.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 5- 1 09 9 3 4
  • Patent Document 2 Japanese Patent Laid-Open No. 11 1 1 4 0 1 6 6
  • Patent Document 3 Japanese Patent Application Laid-Open No. 6-1 4 5 3 0 6
  • Patent Document 4 Japanese Patent Laid-Open No. 2 00 0-1 2 90 92
  • Patent Document 5 Japanese Patent Application Laid-Open No. 2004-5 9 7 92
  • Patent Document 6 Japanese Patent Laid-Open No. 3-90 075
  • Patent Document 7 Japanese Patent Laid-Open No. 3-2 8 1 6 2 3
  • Patent Document 8 Japanese Patent Laid-Open No. 4 1 1 7 3 8 3 1
  • Patent Document 9 Japanese Patent Laid-Open No. 10-2 6 5 5 5 4
  • Patent Document 10 Japanese Patent Laid-Open No. 6 1 4 5 3 0 0 Disclosure of Invention
  • the purpose of the present invention is to have excellent performance in adhesion to a metal substrate and flame retardancy in applications such as lamination, molding, casting, and adhesion, as well as excellent heat resistance.
  • Providing sulfido structure-containing polyhydric hydroxy compounds useful as hardeners, modifiers, etc. providing excellent adhesion to metal substrates and flame retardancy, as well as excellent heat resistance.
  • the object is to provide an epoxy resin composition useful for sealing electrical and electronic parts that give a cured product, circuit board materials, etc., and to provide the cured product.
  • the sulfido structure-containing polyhydric hydroxy compound of the present invention is represented by the following general formula (1).
  • A represents either a benzene ring or a naphthalene ring which may be substituted with a hydrocarbon group having 1 to 8 carbon atoms
  • R 2 represents a hydrogen atom which may be the same or different, or a carbon number of 1 to 6 represents an alkyl group
  • G represents a hydrogen atom or a glycidyl group
  • n represents a number from 1 to 10
  • m represents an integer from 1 to 2.
  • This sulfide structure-containing epoxy resin has the following general formula (2)
  • A represents either a benzene ring or a naphthalene ring which may be substituted with a hydrocarbon group having 1 to 8 carbon atoms
  • R 2 represents a hydrogen atom which may be the same or different, or carbon number 1 Any one of ⁇ 6 alkyl groups
  • n is a number from 1 to 10
  • m is an integer from 1 to 2.
  • the polyhydric hydroxy compound containing a sulfido structure is a cross-linking agent represented by the following formula (5) with respect to 1 mol of the hydroxy compound represented by the following formula (3) or (4): 0.1 to 0.9 It can be obtained by reacting with mol.
  • R 3 represents an alkyl group having 1 to 8 carbon atoms
  • p represents an integer of 0 to 3
  • m represents an integer of 1 to 2.
  • R 2 represents a hydrogen atom which may be the same or different, or an alkyl group having 1 to 6 carbon atoms
  • R 4 represents OH, alkoxy or halogen.
  • the novel polyhydric hydroxy compound represented by the general formula (1) of the present invention can be obtained by reacting a specific hydroxy compound with a specific cross-linking agent.
  • A represents a benzene ring or a naphthalene ring, and these rings may be substituted with a hydrocarbon group having 1 to 8 carbon atoms.
  • A is a benzene ring or naphthalene ring which is unsubstituted or substituted with a methyl tomb.
  • R 1 and R 2 each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a methyl group, and these may be the same or different.
  • m is 1 or 2, but is preferably 1.
  • n represents the average number of repetitions, and is 1 to 10, preferably 1 to 5.
  • a polyhydric hydroxy compound can be obtained by reacting the hydroxy compound represented by the general formula (2) or (3) with the cross-linking agent represented by the general formula (4).
  • R 3 is a hydrocarbon group having 1 to 8 carbon atoms, preferably an alkyl group, more preferably a methyl group.
  • p is an integer of 0 to 3, preferably 0.
  • SAR sulfide structure-containing polyhydric hydroxy compound of the present invention is represented by the general formula (1). Since SAR can be epoxidized into an epoxy resin (hereinafter also referred to as SAE), SAR is also an epoxy resin intermediate.
  • the softening point of S A R is preferably 40 to 200 ° C., preferably 50 to 200 ° C., more preferably 60 to 120 ° C.
  • the softening point refers to a softening point measured based on the ring and ball method of JISK— 6 9 1 1. If it is lower than this, the heat resistance of the cured product is lowered when it is added to an epoxy resin, and if it is higher than this, the fluidity during molding is lowered.
  • the SAR of the present invention is useful as an epoxy resin curing agent and modifier, and when applied to an epoxy resin composition, it has excellent adhesion to dissimilar materials, as well as excellent flame retardancy and heat resistance. It is possible to give a hardened material and to use it suitably for applications such as sealing electrical and electronic parts and circuit board materials. If the epoxy resin composition containing the SAR of the present invention is heat-cured, it can be made into an epoxy resin cured product, and this cured product is excellent in terms of adhesion, flame retardancy, high heat resistance, etc. It can be used suitably for applications such as sealing ih for electrical and electronic parts, circuit board materials, etc.
  • the SAE of the present invention when applied to an epoxy resin composition, is excellent in high adhesion to dissimilar materials and gives a cured product with excellent flame retardancy and heat resistance, sealing of electrical and electronic parts, circuit It can be suitably used for applications such as substrate materials. If the epoxy resin composition containing the SAE or SAR of the present invention is cured by heating, it can be made into an epoxy resin cured product. This cured product is in terms of adhesion, flame retardancy, and high heat resistance. It can be used for applications such as sealing electrical and electronic parts and circuit board materials.
  • FIG. 1 is a 1 H-NMR spectrum of SAR-A obtained in Example 1.
  • FIG. 2 is an infrared absorption spectrum of SAR_A obtained in Example 1.
  • FIG. 3 is a GP C chart of SAR-A obtained in Example 1.
  • FIG. 4 shows the SAR-A FD-MS chart obtained in Example 1.
  • FIG. 5 is the 1 H-NMR spectrum of S AE-A obtained in Example 8.
  • FIG. 6 is an infrared absorption spectrum of SAE-A obtained in Example 8.
  • FIG. 7 is a GP C chart of SAE-A obtained in Example 8. BEST MODE FOR CARRYING OUT THE INVENTION
  • the SAR of the present invention can itself be a component of a phenol resin composition or an epoxy resin composition.
  • a sulfido structure-containing polyhydric hydroxy compound is added to a halogenated alkyl compound, a halogenated alkylke.
  • thiol compounds, epihalohydrin compounds, etc. some or all of the hydrogen atoms of OH groups in the sulfido structure-containing polyhydric hydroxy compounds are substituted with alkyl groups, alkenyl groups, glycidyl groups, etc. be able to.
  • the SAR of the present invention can be synthesized by reacting a hydroxy compound represented by the formula (3) or (4) with a cross-linking agent represented by the formula (5).
  • 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 hydroxy compound. If it is smaller than this, the amount of unreacted hydroxy compounds increases during synthesis, the softening point of the synthesized SAR is lowered, and the heat resistance of the cured product when used as an epoxy resin curing agent decreases. If it is larger than this, the softening point of SAR will increase, and in some cases, SAR may gel during synthesis.
  • 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, dimethylsulfuric acid, and jetylsulfuric acid
  • this reaction is usually performed at 10 to 25 ° C. for 1 to 20 hours.
  • alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol monole, methyl cetosolve, ethylcele solve, etc.
  • ketones such as acetone, methinoreethylketone, methylisobutylketone
  • ethers such as dimethyl ether, jetyl ether, diisopropyl ether, tetrahydrofuran, and dioxane
  • aromatic compounds such as benzene, toluene, black benzene, and dichlorobenzene can be used as the solvent.
  • phenols represented by the general formula (3) or naphthols represented by the general formula (4) include, for example, phenol monole, o-crezonore, m_crezo monole, p-crezonore, Ethylphenols, Isopropylphenols, Tertiarybutylphenols, Arylphenols, Phenylphenols, 2,6-Xylenol, 2,6-Gethinorephenol, Noridoquinone, Resorcinol, Catechol, 1 Naphth Toilet, 21 Naphthol, 1,5—Naphthalenediol, 1,6—Naphthalenediol, 1,7-Naphthalenediole, 2,6—Naphthalenediole, 2,7—Naphthalenediole And so on. These phenols or naphthols may be used alone or in combination of two or more.
  • R 2 represents either the same or different hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 4 represents any of OH, alkoxy, or halogen. Indicates.
  • the crosslinking agent represented by the general formula (5) diphenylsulfide dimethyl compounds, dimethylol compounds or dialkyl ethers thereof can be used. Examples of such cross-linking agents include 4,4′-dichloromethyldiphenylsulfide, 2,4′-dichloromethinoresiphenylsulfide, and 2,2′-dichloromethinoresidenylsulfide.
  • Ref. 4, 4'—Dihydroxymethyldiph; nilsulfide, 2,4'—Dihydroxymethyldiphenylsulfonyl, 2,2 'Dihydroxymethyldiphenylsulfide, 4,4' Dimethoxy Simethino Resifenil / Refuid, 2, 4'-dimethymethinoresin phenylsulfide, 2,2'-dimethoxymethyldiphenylsulfide, 4,4'-diisopropoxymethyldiphenylsulfide, 2,4'-diisopropoxymethyldiph ⁇ Nylsulfide, 2,2'-Diisopropoxymethyldiphenylenosenolide, 4,4'-Dibutoxymethinoresinenoresulphide, 2,4'-Dibutoxymethyldiphenylsulfide 2, 2, 1-dibutoxymethyldiphenylsulfide.
  • the substitution position of the chloromethyl group and methylol group or its alkyl ether group with respect to the diphenyls / ref ide may be any of 4, 4 '1 position, 2, 4' 1 position, and 2, 2 '1 position.
  • Desirable compound as agent is 4, 4 'integral, and 4, 4' integral is 50% in total condensing agent. Those containing 0 or more are particularly preferred. If it is less than this, there are disadvantages such as a decrease in the curing rate when the synthesized resin is cured and the resulting cured product becomes brittle.
  • the phenol resin composition of the present invention comprises the above S A R in a polyvalent phenolic compound.
  • the content of SAR is in the range of 2 to 200 parts by weight, preferably 5 to 100 parts by weight, more preferably 10 to 80 parts by weight with respect to 100 parts by weight of the polyvalent phenolic compounds. It is. If it is less than this, the effects of modification such as low hygroscopicity, heat resistance, adhesion, and flame retardancy will be small, and if it is more than this, the viscosity will increase and the moldability will deteriorate.
  • the polyhydric phenolic compounds mentioned here refer to all compounds having two or more phenolic hydroxyl groups in one molecule.
  • trivalent or higher phenols represented by ethane, phenenorenovolak, o-cresol / lenovolac, naphthol novolak, polybutanol and the like.
  • polyhydric phenolic compounds may be described as being representative of phenolic
  • the softening point of the phenol resin is usually 40 to 20 ° C., preferably 60 to 15 ° C. C (D range. If it is lower than this range, the heat resistance of the cured product obtained by using it as a curing agent for epoxy resin will decrease. If it is higher than this range, the miscibility with S A R will decrease.
  • the phenol resin composition of the present invention comprises a melt mixing method in which mixing is performed by stirring, kneading, etc. at a temperature equal to or higher than the softening point of either the phenol resin or SAR, and a solvent that dissolves each of them. It can be obtained by a method such as a solution mixing method in which it is dissolved and uniformly mixed by stirring, kneading or the like. Solvents used in the solution mixing method include, for example, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycolate, methinocele sonorebu, ethylcelesolve, acetone, methylethylketone, methylisobutylketone, etc.
  • Ketones dimethyl ether, jetyl ether, diisopropyl ether, ethers such as tetrahydrofuran, dioxane, and aromatic solvents such as benzene, toluene, xylene, black benzene, and dichlorobenzene. it can.
  • an epoxy resin, an inorganic filler, another phenol resin, and other additives (materials) can be blended.
  • the phenol resin composition of the present invention can be made into a phenol resin cured product by using it in combination with a curing agent generally used in phenol resin compositions such as hexamethyltetramine.
  • the epoxy resin composition of the present invention contains at least an epoxy resin and a curing agent, and is a composition in which the SAR is blended as a part or all of the curing agent.
  • the amount of SAR 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 adhesion and flame retardancy and heat resistance will be small, and if it is more than this, there will be a problem that the strength of the moldable paste will be reduced.
  • the sulfide structure-containing epoxy resin (hereinafter also referred to as SAE) of the present invention is represented by the general formula (1).
  • the sulfido structure-containing polyhydric hydroxy compound (S AR) is represented by the general formula (2).
  • SAE can be obtained by epoxidizing SAR.
  • the SAE of the present invention is advantageously produced by reacting the SAR represented by the general formula (2) with epichlorohydrin, but is not limited to this reaction.
  • SAR and a halogenated halide can be reacted to form a allylic ether compound and then reacted with a peroxide.
  • the reaction of reacting the above SAR with epichlorohydrin can be carried out in the same manner as a normal epoxidation reaction.
  • an alkali metal hydroxide such as sodium hydroxide or hydroxy hydroxide
  • 20 to 150 ° C preferably The method of making it react for 1 to 10 hours in the range of 30 to 80 degreeC is mentioned.
  • the amount of the metal hydroxide used is 0.8 to 1.5 mol, preferably 0.9 to 1.2 mol, based on 1 mol of the SAR hydroxyl group. is there.
  • epichlorohydrin is used in excess relative to 1 mol of hydroxyl group in SAR, but usually 1.5 to 30 mol, preferably 2 to 15 mol, relative to 1 mol of hydroxyl group in SAR. Range.
  • the epoxy resin composition of the present invention contains at least an epoxy resin and a curing agent, and there are the following two types.
  • blended said SAE as a part or all of an epoxy resin 2) A composition in which SAE and SAR are blended as part or all of epoxy resin and curing agent.
  • epoxy resin component other types of epoxy resins may be blended in addition to SAE represented by the general formula (1).
  • epoxy resin in this case all ordinary epoxy resins having two or more epoxy groups in the molecule can be used. Examples include bisphenol A, bisphenol S, fluorene bisphenol, 4,
  • Bivalent phenols such as biphenol, 2, 2, monobiphenol, hydroquinone and resorcin, or tris (4-hydroxyphenenole) methane, 1, 1, 2, 2— Halogenation of tetrakis (4-hydroxyphenyl) ethane, phenol nopolac, o — trihydric or higher phenols such as cresol novolac, phenol aralkyl resins, naphthol aralkyl resins, or tetrabromobisphenol A
  • Examples include darcidyl etherified compounds derived from bisphenols. These epoxy resins can be used alone or in combination of two or more. And of the present invention
  • the amount of SAE represented by the general formula (8) is 5 to 100%, preferably 60 to 100% of the entire epoxy resin. It should be a range.
  • the amount of SAR is usually 2 to 200 parts by weight, preferably 5 to 80 parts by weight with respect to 100 parts by weight of the epoxy resin. is there. If it is less than this, the effect of improving the adhesion and flame retardancy is small, and 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 SAR is usually determined in consideration of the equivalent balance of OH groups in SAR and epoxy groups in epoxy resin.
  • the equivalent ratio of the epoxy resin and the curing agent is usually in the range of 0.2 to 5.0, and preferably in the range of 0.5 to 2.0. 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 SAR of the present invention can be used in combination as a curing agent.
  • Other curing The blending amount of the agent is determined within the range in which the blending amount of the SAR is normally maintained 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. Is done. If the amount of SAR is less than this, the effect of improving low moisture absorption, adhesion and flame retardancy is small, and if it is too much, there is a problem that the moldability and the strength of the cured product are lowered.
  • epoxy resin curing agents other than SAR
  • epoxy resin curing agents 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. Specific examples of curing agents are shown below.
  • acid anhydride curing agents examples include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrohydrate-free hydrophthalic acid, and methyl anhydride hymic. Acid, dodecynyl succinic anhydride, nadic anhydride, trimellitic anhydride.
  • polyhydric phenols examples include bisphenol A, bisphenol F, bisphenol nore S, flossed lenbisphenol nore, 4, 4'-biphenolate, 2, 2'-bivenol, hydroquinone, resorcin, naphthalenediol.
  • Divalent phenols such as tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetraxane (4-hydroxyoxyphenyl) ethane, phenolenonopolak, 0-crezo
  • trivalent phenols such as mono-renoborak, naphthol novolak, and polybuhlphenol.
  • amines examples include 4,4'-diaminodiphenylmethane and 4,4'-diaminodiph.
  • Aromatic amines such as ennenopropane, 4,4'-diaminodiphenenolesnolephone, m-phenylenediamine, p-xylylenediamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, and aliphatic amines such as triethylenetetramine There is.
  • Aromatic amines such as ennenopropane, 4,4'-diaminodiphenenolesnolephone, m-phenylenediamine, p-xylylenediamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, and aliphatic amines such as triethylenetetramine There is.
  • One or more of these curing agents can be mixed and used in the composition.
  • an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, indene-coumarone resin, phenoxy resin, or the like is modified. You may mix
  • the addition amount is usually in the range of 2 to 30 parts by weight with respect to 100 parts by weight of the epoxy resin.
  • the epoxy resin composition of the present invention may contain additives such as inorganic fillers, pigments, flame retardants, thixotropic agents, coupling agents, fluidity improvers and the like.
  • inorganic fillers 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% by weight or more, more preferably 80% by weight or more.
  • Examples of the pigment include organic or inorganic extender pigments, scaly pigments, and the like.
  • wrinkle-modifying agents include silicon, castor oil, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite.
  • 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, benzyldimethylamine.
  • Tertiary amine such as triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methyl imidazole, 2-phenyl-1-phenyl 4 -Imidazoles such as methyl imidazole and 2-heptadecyl imidazole, tryptyl phosphine, methyl diphenyl phosphine, triphenyl Organic phosphines such as norephosphine, diphenenorephosphine, and phenenolephosphine, tetrafenenorephosphonium tetrafeninoreporate, tetrafenenorephosphonium ethyltriphenyl borate, tetrabutylphosphonium tetraptylborate And tetraphenylboron salts such as tetra-substituted
  • the resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a coupling agent such as ⁇ -glycidoxyprovir trimethyoxysilane, a colorant such as carbon black, and the like. Flame retardants such as antimony oxide, low stress agents such as silicon oil, lubricants such as calcium stearate, etc. can be used.
  • the epoxy resin composition of the present invention is made into a varnish in which an organic solvent is dissolved, and then impregnated into a fibrous material such as glass cloth, a polyamide nonwoven fabric, a polyester nonwoven fabric such as a liquid crystal polymer, and the like, and then the solvent is removed. It can be a pre-preda. In some cases, a laminate can be formed by coating on a sheet-like material such as copper foil, stainless steel foil, polyimide film, polyester film or the like.
  • an epoxy resin cured product can be obtained.
  • This cured product is excellent in terms of low hygroscopicity, high heat resistance, adhesion, flame retardancy, and the like. Become.
  • This cured product can be obtained by molding the epoxy resin composition by a method such as casting, compression molding, transfer molding or the like. The temperature at this time is usually in the range of 120-20 ° C.
  • the viscosity was measured using a B-type viscometer, and the softening point was measured by the ring-and-ball method according to JISK 169 1.11.
  • the GPC measurement conditions are as follows: Equipment: HL C-8 2A (manufactured by Tosohichi Co., Ltd.), column: TSK-GE L 2 00 0 X 3 and TSK-GE L 40 0 0 X 1 (Both Tosoh (Manufactured by Co., Ltd.), solvent: tetrahydrofuran, flow rate: 1 m 1 Zmin, temperature: 38 ° C, detector: RI, and polystyrene standard solution was used for the calibration curve.
  • 0-cresol novolac type epoxy resin (OCNE; epoxy equivalent 200, softening point 65 ° C) as epoxy resin component, SAR-A, SAR-B, examples obtained in Examples 1 and 2 as curing agents
  • the phenol resin composition obtained in 3 (resin composition A), phenol novolac (Hardener A: Gunei Chemical Co., PSM— 4 2 6 1; OH equivalent 10 3, softening point 8 2 ° C), phenol aralkyl resin (Hardener B; Meiwa Kasei, MEH— 7 8 0 0 SS, OH equivalent 1 75, softening point 6 7 ° C), silica as filler (average particle size 18 / ⁇ ⁇ ), trif as curing accelerator;
  • the composition shown in Table 3 was kneaded to obtain an epoxy resin composition.
  • This epoxy resin composition was molded at 1755 ° C. and post-cured at 1755 ° C. for 12 hours to obtain a cured test piece, which was then subjected to various
  • the glass transition point (T g) and linear expansion coefficient (C T E) were measured at a rate of temperature increase of 10 ° CZ using a thermomechanical measurement device. Also, the water absorption is 50 mm in diameter and 3 mni in thickness, and the water absorption is 10 hours at 85 ° C and 85% RH. Using the composition, a disk having a diameter of 50 mm and a thickness of 3 mm was formed, and the weight change rate after post-curing was absorbed at 1 33 ° C., 3 atm, 96 hours. The adhesive strength was 25 mmX 1 2.5 mmX 0.5 miii between two copper plates, formed at 1 75 ° C with a compression molding machine, and 12 hours at 180 ° C.
  • SAE-A o_cresol novolak type epoxy resin synthesized in Example 8 (OCNE; ⁇ poxy equivalent 20 0, softening point 65 ° C), bifunctional diphenylsulfide type epoxy Resin (manufactured by Tohto Kasei Co., Ltd., YSLV—50 TE; epoxy equivalent 170, melting point 45 ° C.) was used as a curing agent component
  • SAR—A phenol novolak
  • curing agent A Made by Gunei Chemical Co., Ltd., P SM— 42 6 1; OH equivalent 10 3, softening point 8 2 ° C
  • 1 naphthol aralkyl type resin curing agent B: Toto Kasei, SN 4 7 5; OH equivalent 2 1 0, softening point 7 7 ° C).
  • Epoxy resin compositions were obtained with the formulations shown in Tables 5 and 7 (average particle size 18 ⁇ m), using triphenylphosphine as a curing accelerator.
  • surface shows the weight part in a mixing
  • molding was carried out at 1755 ° C., and post-curing was carried out at 1755 ° C. for 12 hours to obtain a cured specimen, which was then subjected to various physical property measurements. The results are shown in Table 4.
  • the SAR of the present invention is useful as a curing agent and modifier for epoxy resins, When applied to a resin composition, it provides excellent adhesion to dissimilar materials, and provides a cured product with excellent flame resistance and heat resistance. For applications such as sealing electrical and electronic parts, circuit board materials, etc. It can be used suitably.
  • SAE blended with the SAR of the present invention when applied to an epoxy resin composition, is excellent in high adhesion to dissimilar materials and gives a cured product with excellent flame retardancy and heat resistance. It can be suitably used for applications such as sealing and circuit board materials. If the epoxy resin composition containing SAE or SAR of the present invention is cured by heating, an epoxy resin cured product can be obtained. This cured product is excellent in terms of adhesion, flame retardancy, and high heat resistance. It can be used suitably for applications such as sealing electrical and electronic parts and circuit board materials.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

L'invention concerne un nouveau composé hydroxy polyvalent et une résine époxyde pouvant être représentés chacun par la formule générale (1). Cette résine présente d'excellentes propriétés d'adhérence intime à une matière d'une espèce différente, et permet d'obtenir un produit durci qui possède d'excellentes propriétés ignifuges et de résistance à la chaleur. Dans la formule, A représente un noyau benzène ou un noyau naphthalène pouvant être substitué par un groupe hydrocarbure comportant 1-8 atomes de carbone; R1 et R2 peuvent être identiques ou différents et représentent un atome d'hydrogène ou un groupe alkyle possédant 1-6 atomes de carbone; G représente un atome d'hydrogène ou un groupe glycidyle; n représente un nombre compris entre 1 et 10; et m représente un nombre entier compris entre 1 et 2.
PCT/JP2008/055798 2007-03-23 2008-03-19 Nouveau composé hydroxy polyvalent, procédé de production de celui-ci, résine époxyde utilisant ce composé et composition de résine époxyde et produit durci de celle-ci WO2008117839A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2007-076307 2007-03-23
JP2007076307A JP2008231071A (ja) 2007-03-23 2007-03-23 新規多価ヒドロキシ化合物並びにエポキシ樹脂組成物及びその硬化物
JP2007084061A JP2008239853A (ja) 2007-03-28 2007-03-28 エポキシ樹脂並びにエポキシ樹脂組成物及びその硬化物
JP2007-084061 2007-03-28

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WO2008117839A1 true WO2008117839A1 (fr) 2008-10-02

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02185515A (ja) * 1989-01-12 1990-07-19 Dainippon Ink & Chem Inc エポキシ樹脂およびエポキシ樹脂組成物
JPH0959248A (ja) * 1995-08-22 1997-03-04 Sumitomo Seika Chem Co Ltd 新規含硫黄化合物及びその製造方法
JP2002338541A (ja) * 2001-05-21 2002-11-27 Sumitomo Seika Chem Co Ltd 誘電体形成物質及び誘電体フィルム

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02185515A (ja) * 1989-01-12 1990-07-19 Dainippon Ink & Chem Inc エポキシ樹脂およびエポキシ樹脂組成物
JPH0959248A (ja) * 1995-08-22 1997-03-04 Sumitomo Seika Chem Co Ltd 新規含硫黄化合物及びその製造方法
JP2002338541A (ja) * 2001-05-21 2002-11-27 Sumitomo Seika Chem Co Ltd 誘電体形成物質及び誘電体フィルム

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