WO2008114766A1 - Nouveau composé hydroxy polyvalent, procédé de fabrication du composé, résine époxy et composition de résine époxy utilisant chacune le composé, et produit durci de la composition - Google Patents

Nouveau composé hydroxy polyvalent, procédé de fabrication du composé, résine époxy et composition de résine époxy utilisant chacune le composé, et produit durci de la composition Download PDF

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Publication number
WO2008114766A1
WO2008114766A1 PCT/JP2008/054846 JP2008054846W WO2008114766A1 WO 2008114766 A1 WO2008114766 A1 WO 2008114766A1 JP 2008054846 W JP2008054846 W JP 2008054846W WO 2008114766 A1 WO2008114766 A1 WO 2008114766A1
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group
epoxy resin
carbon atoms
hydrogen atom
compound
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PCT/JP2008/054846
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English (en)
Japanese (ja)
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Hisashi Yamada
Hideyasu Asakage
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Tohto Kasei Co., Ltd.
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Priority claimed from JP2007062102A external-priority patent/JP2008222837A/ja
Priority claimed from JP2007062106A external-priority patent/JP2008222838A/ja
Application filed by Tohto Kasei Co., Ltd. filed Critical Tohto Kasei Co., Ltd.
Publication of WO2008114766A1 publication Critical patent/WO2008114766A1/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
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08G59/40—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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0326—Organic insulating material consisting of one material containing O

Definitions

  • the present invention relates to a novel polyhydric hydroxy compound, a method for producing the compound, an epoxy resin using the compound, an epoxy resin composition, and a cured product thereof.
  • the present invention relates to a novel sulfide structure-containing polyhydric hydroxy compound, a sulfide structure-containing epoxy resin obtained by epoxidizing the compound, the epoxy resin-containing epoxy resin composition, and a cured product thereof, a printed wiring board, It is suitably used for insulating materials in the electrical and electronic fields such as semiconductor encapsulation.
  • 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 naphthol aralkyl resin is applied to a semiconductor sealing material.
  • naphthol aralkyl resins are excellent in low hygroscopicity, low thermal expansion, etc., but are curable.
  • Patent Document 2 proposes a curing agent having a bifunil structure and describes that it is effective for improving flame retardancy, but has a disadvantage 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.
  • Patent Documents 2 and 4 disclose an example 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 semiconducting materials containing them, but nothing focuses on flame retardancy.
  • Patent Document 9 includes Although aralkyl type resins using phenols are disclosed, they do not focus on adhesion and flame retardancy. Furthermore, 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 to perform. It does not focus on flammability.
  • Patent document 1 Japanese Patent Laid-Open No. 5-10093 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 9 0 9 2
  • Patent Document 5 Japanese Patent Laid-Open No. 2 0 4 5 9 7 9 2
  • 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 Application Laid-Open No. 6-222071
  • Patent Document 10 Japanese Patent Application Laid-Open No. 6-1 4 5 300 Disclosure of Invention
  • the object of the present invention is to have excellent performance in heat resistance and the like in addition to excellent adhesion to a metal substrate and flame retardancy in applications such as lamination, molding, casting and adhesion, and a thermosetting resin composition Provided with a sulfide structure-containing polyhydric hydroxy compound that is useful as a material hardener, modifier, etc., as well as excellent adhesion to metal substrates and flame retardancy, as well as excellent heat resistance Providing a sulfide structure-containing epoxy resin that has performance and is useful for applications such as lamination, molding, casting, and adhesion, as well as excellent moldability, adhesion, flame resistance, and heat resistance An object of the present invention is to provide an epoxy resin composition useful for sealing electric and electronic parts that give excellent cured products, circuit board materials, and the like, and to provide cured products thereof.
  • the sulfide structure-containing polyhydric hydroxy compound and the sulfide structure-containing epoxy resin of the present invention are represented by the following general formula (1). H- L!-(X- (1)
  • R 2 , R 3 , R 4 and R 5 independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms
  • B represents a benzene ring, biphenyl ring or naphthalene.
  • G represents either a hydrogen atom or a glycidyl group, and n represents a number from 0 to 20.
  • the epoxy resin containing a sulfide structure is represented by the general formula (3) H- L 2- (X-L 2 ) n -H (3)
  • L 2 is the following formula (4)
  • N represents a number from 0 to 20;
  • This sulfido structure-containing polyhydric hydroxy compound is represented by the following formula (6), (7), (8) or (9) with respect to 1 mol of the hydroxy compound represented by the following formula (5). It can be obtained by reacting 0.1 to 0.9 mol of a crosslinking agent.
  • R 2 , R 3 , R 4 and R 5 independently represent a hydrogen atom or A hydrocarbon group having 1 to 6 carbon atoms
  • B represents a group consisting of a benzene ring, a biphenyl ring or a naphthalene ring
  • Y and Z independently represent OH, alkoxy or halogen.
  • SAR sulfido structure-containing polyhydric compound represented by the general formula (1) according to the present invention is epoxidized to sulfide structure-containing epoxy resin (hereinafter also referred to as SAE). SAR is also an intermediate of epoxy resin (S AE).
  • FIG. 1 is a 1 H-NMR spectrum of SAR-A obtained in Example 1.
  • Figure 2 shows the infrared absorption spectrum of SAR-A obtained in Example 1.
  • FIG. 3 is a G P C chart of SAR-A obtained in Example 1.
  • Figure 4 is a 1 H- NMR spectrum of SAE- A obtained in Example 1 1
  • Figure 5 is an infrared absorption space of S AE one A obtained in Example 1 1 It is.
  • FIG. 6 is a GP C chart of SAE A obtained in Example 11. BEST MODE FOR CARRYING OUT THE INVENTION
  • G represents either a hydrogen atom or a glycidyl group, and represents a hydrogen atom, a hydroxyl group, a glycidyloxy group, an alkoxy group having 1 to 8 carbon atoms, a halogen atom, or a carbon atom having 1 to 8 carbon atoms.
  • One of hydrogen groups is shown.
  • X is a bridging group represented by the formula (a) or (b), but R 2 , R 3 , R 4 and R 5 independently represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
  • B represents a group consisting of a benzene ring, a biphenyl ring or a naphthalene ring. In addition, these rings constituting B may be substituted with a hydrocarbon group having 1 to 6 carbon atoms.
  • X crosslinks 1 ⁇ , but the substitution position of X with respect to the group represented by the formula (2) constituting Li is not particularly limited.
  • the softening point of SAR is preferably 40 to 20 and is preferably in the range of 50 to: I 60 ° C., more preferably 60 to 120.
  • the softening point refers to a softening point measured based on the ring and ball method of JIS—K—2 2 0 7. 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 SAR according to the present invention can itself be a component of a thermosetting resin composition.
  • a sulfido structure-containing polyhydric hydroxy compound is added to a halogenated alkyl compound or a halogenated alkenyl compound.
  • an epihalohydrin compound or the like part or all of the hydrogen atoms of the OH group in the sulfido structure-containing polyhydric hydroxy compound can be substituted with an alkyl group, an alkenyl group, a glycidyl group, or the like.
  • the SAR according to the present invention is synthesized by reacting a hydroxy compound represented by the formula (5) with a crosslinking agent represented by the formula (6), the formula (7), (8) or (9). can do.
  • 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 the 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. On the other hand, if it is larger than this, the softening point of SAR becomes high, 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, zinc chloride, aluminum chloride, iron chloride, trifluoride
  • Lewis acids such as fluorine fluoride or ion exchange resins, activated clays, silica-alumina, and solid acids such as zeolite.
  • this reaction is usually performed at 10 to 25 ° C. for 1 to 20 hours.
  • alcohols such as methanol, ethanol, prono "? Norole, butanol, ethylene glycolate, methyl cetylsolve, ethylcetol sorb, ketones such as acetone, methylethyl ketone, methylisobutylketone,
  • solvents are ethers such as dimethyl ether, jetyl ether, diisopropyl ether, tetrahydrofuran, dioxane and the like, and aromatic compounds such as benzene, toluene, black benzene and dichlorobenzene.
  • Examples of the hydroxy compound used as a raw material include dihydroxy diphenyl sulfide substituted with a hydroxyl group, an alkoxy group, a halogen atom, or a hydrocarbon group as a substituent, in addition to dihydroxy diphenyl sulfide.
  • a halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, etc.
  • an alkoxy group includes a methoxy group, a ethoxy group, a butyl ether group, an isopropoxy group, a allyloxy group, a propargyl ether group, a ptoxy group, a phenoxy group. Is mentioned.
  • Hydrocarbon groups include methyl, ethyl, bur, ethyne, isopropyl, aryl, propargyl, buty
  • Various substituted dihydroxydiphenyl sulfides having an alkyl group, an amyl group, a phenyl group, a benzyl group and the like can be used, and dihydroxydiphenyl sulfide is preferred.
  • crosslinking agent examples include aldehydes such as formaldehyde, acetoaldehyde, propyl aldehyde, butyl aldehyde, amyl aldehyde and benzaldehyde represented by the formula (6), with formaldehyde being preferred.
  • Preferred formaldehyde raw material forms for use in the reaction include formalin aqueous solution, paraformaldehyde, trioxane and the like.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetophenone represented by the formula (7) can be used as a crosslinking agent.
  • the crosslinking agent represented by the formula (8) includes P-xylylene glycol, p-xylylene glycol dimethyl ether, p-xylylene dichloride, 4, 4'-dimethylmethylbiphenyl, 4 , 4'-dichloromethylbiphenyl, dimethoxymethylnaphthalene, dichloromethylnaphthalene.
  • divinylbenzenes, divinylbiphenyls, dibulaphthalenes and the like represented by the formula (9) can also be used as a crosslinking agent.
  • the sulfide structure-containing epoxy resin (S A E) of the present invention is represented by the general formula (1).
  • the sulfido structure-containing polyhydric hydroxy compound (S A R) is represented by the general formula (3).
  • S A E can be obtained by epoxidizing S A R.
  • G represents a hydrogen atom or a glycidyl group, and represents a hydrogen atom, a hydroxyl group, a glycidyloxy group, an alkoxy group having 1 to 8 carbon atoms, a halogen atom, or a carbon atom having 1 to 8 carbon atoms.
  • 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 ptoxy group, a phenoxy group, and a benzyloxy group, and a halogen atom.
  • Hydrocarbon groups include methyl, ethyl, bur, ethyne, n-propyl, isopropyl, and aryl.
  • X is a bridging group represented by the formula (a) or (b), but R 2 , R 3 , R 4 and Shaku 5 are independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
  • B represents a group consisting of a benzene ring, a biphenyl ring or a naphthalene ring. Note that these rings constituting B may be substituted with a hydrocarbon group having 1 to 6 carbon atoms.
  • X bridges L i, but the substitution position of X with respect to the group represented by the formula (2) constituting L i is not particularly limited.
  • the SAE of the present invention is advantageously produced by reacting the SAR represented by the general formula (3) 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 20 to 150 ° C
  • a method of reacting in the range of 30 to 80 for 1 to 10 hours the amount of the alkali metal hydroxide used is in the range of 0.8 to 1.5 mol, preferably 0.9 to 1.2 mol, per 1 mol of the SAR hydroxyl group.
  • epichlorohydrin is used in excess relative to 1 mol of hydroxyl group in SAR, but usually 1.5 to 30 mol, preferably 2 to 1 mol, relative to 1 mol of hydroxyl group in SAR. The range is 5 moles.
  • 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. 1) The composition which mix
  • 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 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 SAR OH groups and epoxy groups in the 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 and mechanical strength of the cured product are lowered.
  • Curing agents other than SAR can be used in combination.
  • the amount of the other curing agent is such that the amount of the 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. Determined within. 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 more than this, 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.
  • 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.
  • Examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrohydrous phthalic acid, methylhydric anhydride, Examples include dodecyl succinic anhydride, nadic anhydride, and trimellitic anhydride.
  • Examples of the polyhydric phenols include bisphenol A, bisphenol F, bisphenolore S, funoleolene bisphenolate, 4, 4 '— biphenolate, 2, 2' — biphenolate, hydrodroquinone, resornoresin, naphthalene.
  • Divalent phenol / Les such as dioreno, or tris- (4-hydroxyphenyl) methane, 1, 1, 2, 2-tetraxyl (4-hydroxyphenyl) ethane, phenol monovolak, There are trihydric or higher phenols such as 0-cresol novolac, naphthol novolak, and polybuhlphenol.
  • phenols, naphthols, bisphenol A, bisphenol enole F, bisphenol nore S, funole ren bisphenolenore, 4, 4'-biphenolate, 2, 2'-biphenol, hydroquinone Multivalent phenolic compounds synthesized by divalent phenols such as resorcinol and naphthalene diol, and condensing agents such as formaldehyde, acetoaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene render alcohol, etc.
  • the above-mentioned phenol resin composition can also be blended.
  • -Amines include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine, p-xylylenediamine Aromatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.
  • the epoxy resin used in the composition is selected from those having two or more epoxy groups in one molecule.
  • the epoxy resin used in the composition is selected from those having two or more epoxy groups in one molecule.
  • darcidyl etherified products of trihydric or higher phenolic compounds such as resins.
  • any of the curing agents generally known as epoxy resin curing agents can be used.
  • epoxy resin curing agents there are dicyandiamide, polyhydric phenols, acid anhydrides, aromatic and aliphatic amines, and the like.
  • S A R represented by the general formula (3) is also preferably exemplified.
  • One or more of these hardeners can be mixed and used in this resin composition.
  • epoxy resin in this epoxy resin composition, you may mix
  • the epoxy resin in this case all ordinary epoxy resins having two or more epoxy groups in the molecule can be used.
  • Trivalent or higher phenols, phenolic aralkyl resins, naphth Examples include toll-based aralkyl resins, and darcidyl ethers derived from halogenated bisphenols such as tetrabromobisphenol A.
  • These epoxy resins can be used alone or in combination of two or more.
  • the amount of SAE represented by the general formula (1) is 5 to 100%, preferably 60 to 1% in the whole epoxy resin. It should be in the range of 0 0%.
  • the epoxy resin composition of the present invention other oligomers or polymer compounds such as polyester, polyamide, polyimide, polyester, polyurethane, petroleum resin, indene resin, indene coumarone resin, and phenoxy resin are used. You may mix
  • the epoxy resin composition of the present invention may contain additives such as inorganic fillers, pigments, flame retardants, thixotropic agents, coupling agents, and fluidity improvers.
  • the inorganic filler examples include spherical or fractured fused silica, silica powder such as 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 sealing material is 70% by weight or more, and more preferably 80% by weight or more.
  • pigment examples include organic or inorganic extender pigments, scaly pigments, and the like.
  • thixotropic agent examples 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 amines such as triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl 1-methylimidazole, 2-imidazole such as 2-heptadecylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylenophosphine, diphenylenophosphine, and phenylenophosphine, Norrephosphonium Te Te Tetra-substit
  • the resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a coupling agent such as ⁇ -glycidoxyprovir trimethoxysilane, Colorants such as Nblack, flame retardants such as antimony trioxide, low stress reducing agents such as silicon oil, lubricants such as calcium stearate, and the like can be used.
  • a release agent such as carnauba wax and OP wax
  • a coupling agent such as ⁇ -glycidoxyprovir trimethoxysilane
  • Colorants such as Nblack
  • flame retardants such as antimony trioxide
  • low stress reducing agents such as silicon oil
  • lubricants such as calcium stearate, and the like
  • 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.
  • a laminate can be formed by coating on a sheet-like material such as a copper foil, a stainless steel foil, a polyimide film, or a polyester film.
  • 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.
  • the viscosity was measured using a B-type viscometer, and the softening point was measured by the ring-and-ball method according to JIS-K-2207.
  • the GPC measurement conditions were as follows: equipment: HLC-8 2 A (manufactured by Tosohichi Co., Ltd.), column: TSK-GE L 2 000 X 3 and TSK-GE L 400 0 X 1 (both Tosoh Co., Ltd.), solvent: tetrahydrofuran, flow rate: 1 m 1 Zmin, temperature: 38, detector: RI, polystyrene standard solution was used for the calibration curve.
  • Fig. 1 shows the 1 H-NMR spectrum of SAR-A
  • Fig. 2 shows the infrared absorption spectrum
  • Fig. 3 shows the GPC chart.
  • Example 4 The reaction was conducted in the same manner as in Example 2 using 200,0 g of 4,4′-dihydroxydiphenylsulfide, 61.9 g of bischloromethylnaphthalene, and 17.5 g of monochlorobenzene. Droxy compound 240. lg was obtained. This compound is called SAR-C. The softening point of the obtained resin was 93, and the melt viscosity at 150 3 was 0.75 Pa ′s.
  • Example 4 The softening point of the obtained resin was 93, and the melt viscosity at 150 3 was 0.75 Pa ′s.
  • thermosetting resin composition (resin composition A) obtained in Example 5, phenol novolak (curing agent A: manufactured by Gunei Chemical Co., Ltd., P SM— 4 2 6 1; 0 H equivalent 10 3, softening point 8 2), phenol aralkyl resin (curing agent B; made by Meiwa Kasei, ME H—780 0 SS, OH equivalent 1 75, softening point 6 7 ° ) Was used, and kiri force (average particle size 18 ⁇ m) as a filler and triphenylphosphine as a curing accelerator were mixed and kneaded to obtain a thermosetting resin composition.
  • Table 1 shows the composition of the thermosetting resin. Using this thermosetting resin composition, it was molded at 17
  • the glass transition point (T g) and the coefficient of linear expansion (CTE) using this thermosetting resin composition were measured at a heating rate of 10 / min using a thermomechanical measuring device.
  • the water absorption rate is 85 mm and 85 mm RH using a circular test piece with a diameter of 50 mm and a thickness of 3 mm.
  • a disk having a diameter of 50 mm and a thickness of 3 mm was formed using the object, and the weight change rate after post-curing and absorbing moisture for 1 3 3 ⁇ , 3 atm, 96 hours.
  • the adhesive strength was 25 mm 'x 1 2.5 mm x 0.5 mm between two copper plates, molded in 1 75 5 3 ⁇ 4 with a compression molding machine, and post-pressed for 1 2 hours at 1800.
  • the glass transition point (T g) and the coefficient of linear expansion (CTE) using this epoxy resin composition were measured at a heating rate of 10 / min using a thermomechanical measuring device.
  • the water absorption rate is Using a circular test piece with a diameter of 5 Omm and a thickness of 3 mm, the water absorption rate obtained by absorbing moisture for 10 hours under the conditions of 85% and 85% RH was 50 mm in diameter and thick with this epoxy resin composition. A 3 mm-thick disk was formed, and the rate of weight change after post-curing was 1 3 3 and absorbed moisture at 3 atm for 96 hours.
  • Adhesive strength is 25 mm X 1 2.5 mm X 0.5 mm between two copper plates, molded at 1 75 with a compression molding machine, and postcured at 180 for 12 hours Evaluation was made by determining the tensile shear strength. Flame retardancy was measured by UL 94 V-0 standard after molding a test specimen with a thickness of 1 Z 16 inches and expressed as the total burning time of five specimens.
  • Fig. 4 shows the 1 H-NMR spectrum of SAE-A
  • Fig. 5 shows the infrared absorption spectrum
  • Fig. 6 shows the GPC chart.
  • SAE-A 0-cresol novolac type epoxy resin synthesized in Example 12 (OCNE; epoxy equivalent of 200, with softening point 65), diphenyl sulfide type epoxy resin (Toto) Kasei, YS LV—50 TE; epoxy equivalent 1700, melting point 45 V), and as a curing agent component, SAR—A synthesized in Example 1, phenol novolak (curing agent A: manufactured by Gunei Chemical Co., Ltd.) , P SM— 4 26 1; OH equivalent of 10 3 with softening point of 8 2), 1—naphthol aralkyl type resin (curing agent B: manufactured by Tohto Kasei, SN—4 7 5; 0 20
  • the SAR of the present invention is useful as a curing agent and modifier for epoxy resins, and is excellent in adhesiveness to dissimilar materials when applied to thermosetting resin compositions, particularly epoxy resin compositions. At the same time, it gives a cured product with excellent flame resistance and heat resistance, and can be suitably used for applications such as sealing of electric / electronic parts and circuit board materials.
  • the sulfide structure-containing epoxy resin (SAE) of the present invention when applied to an epoxy resin composition, is excellent in high adhesion with different materials and gives a cured product excellent in flame retardancy and heat resistance. It can be used suitably for applications such as sealing of electric / electronic parts, circuit board materials, and the like.
  • the epoxy resin composition containing the SAE or sulfide structure-containing polyhydric hydroxy compound (hereinafter also referred to as SAR) of the present invention is cured by heating, it can be made into an epoxy resin cured product, and this cured product is adhered closely Excellent in terms of heat resistance, flame retardancy, high heat resistance, etc., and can be suitably used for applications such as sealing of electric and electronic parts and circuit board materials.

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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)
  • 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)

Abstract

L'invention porte sur un nouveau composé hydroxy polyvalent et sur une résine époxy, chacun représenté par la formule générale (1) ci-après. La résine est excellente en adhésion étroite sur une matière différente, et permet d'obtenir un produit durci ayant un excellent retard de flamme et une excellente résistance à la chaleur. H-L1-(X-L1)n-H (1) Dans la formule générale (1), L1 représente un groupe représenté par la formule générale suivante (2) : (où R1 représente un atome d'hydrogène, un groupe hydroxy, un groupe glycidyloxy, un groupe alcoxy ayant 1-8 atomes de carbone, un atome d'halogène ou un groupe hydrocarboné ayant 1-8 atomes de carbone; et G représente un atome d'hydrogène ou un groupe glycidyle); et X représente un groupe réticulant représenté par la formule suivante (a) ou la formule suivante (b). Dans les formules (a) et (b), R2, R3, R4 et R5 représentent indépendamment un atome d'hydrogène ou un groupe hydrocarboné ayant 1-6 atomes de carbone; B représente un groupe composé d'un noyau benzénique, d'un noyau biphénylique ou d'un noyau naphtalénique; et n représente un nombre de 0-20.
PCT/JP2008/054846 2007-03-12 2008-03-11 Nouveau composé hydroxy polyvalent, procédé de fabrication du composé, résine époxy et composition de résine époxy utilisant chacune le composé, et produit durci de la composition WO2008114766A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2007-062102 2007-03-12
JP2007062102A JP2008222837A (ja) 2007-03-12 2007-03-12 新規多価ヒドロキシ化合物、該ヒドロキシ化合物の製造法、及び該ヒドロキシ化合物含有熱硬化性樹脂組成物並びにその硬化物
JP2007-062106 2007-03-12
JP2007062106A JP2008222838A (ja) 2007-03-12 2007-03-12 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

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WO2008114766A1 true WO2008114766A1 (fr) 2008-09-25

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS505084B1 (fr) * 1970-09-16 1975-02-28
JPS514293A (en) * 1974-05-17 1976-01-14 Ruhrchemie Ag 4 4** chioobisu * jiarukirufuenooru ** horumuarudehido shukugobutsunoseihooyobi gaishukugobutsunyorupurasuchitsukuno anteikaho
JPS62288626A (ja) * 1986-06-06 1987-12-15 Mitsui Toatsu Chem Inc ビス−（４−ヒドロキシ−３−メチルフエニル）スルフイド型ノボラツクの製造法
JPS6399215A (ja) * 1986-06-06 1988-04-30 Mitsui Toatsu Chem Inc ４、４’−チオジフエノ−ル型ノボラツクの製造法
JPH03275707A (ja) * 1990-03-26 1991-12-06 Teijin Ltd ヒドロキシカルボン酸誘導体の製造法
JPH04202219A (ja) * 1990-11-29 1992-07-23 Mitsui Toatsu Chem Inc フェノール重合体の製造方法
JPH0625393A (ja) * 1992-07-10 1994-02-01 Mitsui Toatsu Chem Inc フェノール重合体、その製造方法およびその用途
JPH072979A (ja) * 1993-06-21 1995-01-06 Mitsui Toatsu Chem Inc アミノ基含有フェノール樹脂およびその製造方法
JP2002020463A (ja) * 2000-07-10 2002-01-23 Nippon Kayaku Co Ltd フェノールアラルキル樹脂の製造法
JP2002212270A (ja) * 2001-01-19 2002-07-31 Japan Epoxy Resin Kk エポキシ樹脂用硬化剤、及びエポキシ樹脂組成物
JP2003192771A (ja) * 2001-12-28 2003-07-09 Japan Epoxy Resin Kk フェノール樹脂、その製法、エポキシ樹脂用硬化剤、エポキシ樹脂組成物及び半導体装置

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS505084B1 (fr) * 1970-09-16 1975-02-28
JPS514293A (en) * 1974-05-17 1976-01-14 Ruhrchemie Ag 4 4** chioobisu * jiarukirufuenooru ** horumuarudehido shukugobutsunoseihooyobi gaishukugobutsunyorupurasuchitsukuno anteikaho
JPS62288626A (ja) * 1986-06-06 1987-12-15 Mitsui Toatsu Chem Inc ビス−（４−ヒドロキシ−３−メチルフエニル）スルフイド型ノボラツクの製造法
JPS6399215A (ja) * 1986-06-06 1988-04-30 Mitsui Toatsu Chem Inc ４、４’−チオジフエノ−ル型ノボラツクの製造法
JPH03275707A (ja) * 1990-03-26 1991-12-06 Teijin Ltd ヒドロキシカルボン酸誘導体の製造法
JPH04202219A (ja) * 1990-11-29 1992-07-23 Mitsui Toatsu Chem Inc フェノール重合体の製造方法
JPH0625393A (ja) * 1992-07-10 1994-02-01 Mitsui Toatsu Chem Inc フェノール重合体、その製造方法およびその用途
JPH072979A (ja) * 1993-06-21 1995-01-06 Mitsui Toatsu Chem Inc アミノ基含有フェノール樹脂およびその製造方法
JP2002020463A (ja) * 2000-07-10 2002-01-23 Nippon Kayaku Co Ltd フェノールアラルキル樹脂の製造法
JP2002212270A (ja) * 2001-01-19 2002-07-31 Japan Epoxy Resin Kk エポキシ樹脂用硬化剤、及びエポキシ樹脂組成物
JP2003192771A (ja) * 2001-12-28 2003-07-09 Japan Epoxy Resin Kk フェノール樹脂、その製法、エポキシ樹脂用硬化剤、エポキシ樹脂組成物及び半導体装置

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