WO2008041749A1 - Résine époxy, résine de phénol, leurs procédés de production, composition de résine époxy et produit durci - Google Patents

Résine époxy, résine de phénol, leurs procédés de production, composition de résine époxy et produit durci Download PDF

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Publication number
WO2008041749A1
WO2008041749A1 PCT/JP2007/069482 JP2007069482W WO2008041749A1 WO 2008041749 A1 WO2008041749 A1 WO 2008041749A1 JP 2007069482 W JP2007069482 W JP 2007069482W WO 2008041749 A1 WO2008041749 A1 WO 2008041749A1
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Prior art keywords
epoxy resin
general formula
resin
represented
phenol
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PCT/JP2007/069482
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English (en)
Japanese (ja)
Inventor
Kazuhiko Nakahara
Masasi Kaji
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Nippon Steel Chemical Co., Ltd.
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Application filed by Nippon Steel Chemical Co., Ltd. filed Critical Nippon Steel Chemical Co., Ltd.
Priority to CN200780036932XA priority Critical patent/CN101522739B/zh
Priority to JP2008537550A priority patent/JP5515058B2/ja
Priority to KR1020097008024A priority patent/KR101423170B1/ko
Publication of WO2008041749A1 publication Critical patent/WO2008041749A1/fr

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    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
    • 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
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • 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
    • 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
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • 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
    • 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 is an epoxy resin that gives a cured product that is excellent in low viscosity and also excellent in moisture resistance, heat resistance, flame retardancy, etc., a phenol resin suitable as an intermediate thereof, a method for producing them,
  • the present invention relates to an epoxy resin composition using an epoxy resin and a cured product thereof, and is suitably used for insulating materials in the electrical and electronic fields such as semiconductor encapsulation and printed wiring boards.
  • epoxy resin having low moisture absorption, high heat resistance and low viscosity is desired.
  • low-viscosity epoxy resins bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc. are generally widely used.
  • those epoxy resins having low viscosity are liquid at normal temperature and are used for transfer molding. It is difficult to obtain a resin composition.
  • these epoxy resins are not sufficient in terms of heat resistance, mechanical strength and moisture resistance.
  • biphenyl epoxy resins are excellent in low hygroscopicity and high heat resistance.
  • JP-A-58-39677 and bisphenol-based epoxy resins JP-A-6-345850 have been proposed, but are not sufficient in terms of adhesion to metal substrates. Also close contact From the viewpoint of improving the properties, an epoxy resin having a sulfur structure containing a sulfur atom (Japanese Patent Laid-Open No. 6-145300) has been proposed. The heat resistance is not sufficient. Also, conventionally known epoxy resins having a sulfone structure are high! /, although they have heat resistance, they have high water absorption and sufficient adhesion! /.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 58-39677
  • Patent Document 2 JP-A-6-345850
  • Patent Document 3 JP-A-6-145300
  • the object of the present invention is suitably used for encapsulating electronic components of semiconductor elements that give a cured product excellent in fluidity, high filler filling property, moisture resistance, heat resistance, flame retardancy, and the like. It is to provide an epoxy resin and a composition thereof.
  • the present invention relates to an epoxy resin represented by the following general formula (3).
  • R R independently represents a hydrogen atom or a substituent represented by the following formula (a) or (b):
  • X is a single bond, —CH 2 —CH 2 (CH 2)
  • the present invention also relates to a phenol resin represented by the following general formula (1).
  • the present invention relates to a method for producing a phenol resin having a substituent represented by the above formula (a) or (b).
  • the present invention is characterized in that the phenol resin represented by the above general formula (1) or the phenol resin obtained by the above method for producing a phenol resin is reacted with epichlorohydrin. This is a method for producing an epoxy resin.
  • the present invention also relates to an epoxy resin obtained by the method for producing the epoxy resin.
  • the present invention is an epoxy resin composition
  • an epoxy resin composition comprising an epoxy resin and a curing agent, wherein the epoxy resin composition is blended with the epoxy resin as an epoxy resin component, and the epoxy resin composition is cured. It relates to the cured product obtained.
  • the epoxy resin of the present invention is represented by the general formula (3). Where R to R are hydrogen atoms
  • R to R are represented by the general formula (a).
  • R to R may be a hydrogen atom which may be a hydrogen atom and a substituent represented by the formula (a).
  • the substituent represented by the formula (a) or the substituent represented by the formula (b) may be composed of the substituent represented by the formula ⁇ and the formula (b). You can just make it! /
  • X is a single bond, — CH— — CH (CH) — — C (CH) — — CO— — O—
  • a linking group selected from S and SO- is shown. Single bond from the viewpoint of low viscosity
  • n represents a number of 0 50, and a preferable value of n varies depending on an application to be applied. For example, for semiconductor encapsulant applications that require a high filling factor of the filler, a low viscosity is desired.
  • the value of n is 0.5, preferably 0.12, and more preferably n. Those with 0 are those that contain more than 50wt%.
  • n means an average value (number average). In this case, more preferably n-force SO.
  • high molecular weight epoxy resins are preferably used.
  • the value of n is 250, preferably 240.
  • the above range is good as the average value n. In this case, if the average value is 50 or less, a molecule in which n is an integer of 50 or more may be included.
  • the epoxy resin of the present invention reacts, for example, with an aromatic olefin selected from indene or acenaphthylene (hereinafter sometimes simply referred to as aromatic olefin) to the bisphenol compound represented by the general formula (2).
  • aromatic olefin selected from indene or acenaphthylene
  • the resulting phenol resin is obtained as an intermediate and can be produced by a method such as reacting this phenol resin with epichlorohydrin.
  • Indene and wasennaphthylene are one of the aromatic olefins and can be replaced by the benzene ring of the bisphenol compound represented by the general formula (2) by the Friedel-Crafts reaction.
  • the benzene ring is substituted as a substituent represented by the formula (a) or (b) (hereinafter sometimes simply referred to as a substituent). Note that up to two of these substituents can be substituted on one benzene ring due to steric hindrance.
  • the substituent represented by formula (a) is a structure in which one hydrogen atom is removed from indene
  • the substituent represented by formula (b) is a structure in which one hydrogen atom is removed from acenaphthylene, It can be said to be a group derived from indene or acenaphthylene, respectively.
  • R and X correspond to RR and X in general formula (3). Therefore, preferred RR And X are the same as RR and X in general formula (3).
  • X is a single bond, —CH 2 —CH 2 (CH 2) —C (CH 2) —CO
  • linking group X 4, 4 'first, 3, 4'-position, 3, 3' first, 2, 4'- 2, 3 'first 2, 2' first There is.
  • These may be compounds consisting of a single isomer or a mixture of these isomers! /, But the steric hindrance of the above formula (a) or (b) is great! Therefore, from the viewpoint of reactivity when an epoxy resin is used, those containing a 2,4 ′ body or a 2,2 ′ body are preferred. In this case, the total amount of the 2,4 ′ body and 2,2 ′ body should be 30 mol% or more, preferably 50 mol% or more of the whole. The same applies to X in the general formulas (1) and (3).
  • the phenol resin of the present invention comprises an aromatic olefin selected from indene or acenaphthylene as the bisphenol compound represented by the general formula (2), and 14 mol of aromatic olefin relative to 1 mol of the bisphenol compound. It can be obtained by reacting.
  • aromatic olefin selected from indene or acenaphthylene is added to the bisphenol compound represented by the general formula (2), and aromatic olefin is added to 1 mol of the bisphenol compound.
  • This is a method in which the above substituent is substituted with a benzene ring by reacting with 24 moles.
  • the reaction amount of the aromatic olefin with respect to 1 mol of the bisphenol compound is in the range of 0.24.0 mol, preferably 0.54.0. It is in the range of mono, more preferably 1.0-3.0 mono. If it is less than this, the effect of improving the moisture resistance and flame retardancy when using epoxy resin will not be sufficiently exhibited. On the other hand, if it exceeds the above range, the viscosity becomes high and the high filling property and moldability of the filler are lowered.
  • the amount used as a reaction raw material when reacting a bisphenol compound with an aromatic olefin is almost the same as the target number of substituted moles (number of moles of substituents per mole of bisphenol compound). Based on this, the usage amount may be determined. It is also possible to adopt reaction conditions in which any of the raw materials remain unreacted, but in this case as well, the amount of aromatic olefin used per mole of bisphenol compound should be in the range of 0.2 6.0 mol. That power S is good. If any raw material remains unreacted, it is desirable to separate it
  • the aromatic olefin used for the reaction with the bisphenol compound is indene, isenaphthylene, or a mixture thereof. From the viewpoint of low viscosity, those containing indene as the main component are preferable. From the viewpoint of flame retardancy, those containing asanaphthylene as the main component are preferable.
  • the aromatic olefin used in the reaction contains, as other reactive components, an unsaturated bond-containing component such as styrene, ⁇ -methylolstyrene, divininolebenzene, coumarone, benzothiophene, indanol and vinylinonaphthalene.
  • an unsaturated bond-containing component such as styrene, ⁇ -methylolstyrene, divininolebenzene, coumarone, benzothiophene, indanol and vinylinonaphthalene.
  • the indene and acenaphthylene content in all the reaction components is 50 wt% or more, preferably 70 wt% or more. If it is less than this, the effect of improving heat resistance and flame retardancy is small.
  • aromatic olefins may contain non-reactive compounds such as toluene, dimethylbenzene, trimethylbenzene, indane, naphthalene, methylnaphthalene, dimethylnaphthalene, and acenaphthene. From the viewpoint of improving characteristics such as heat resistance and flame retardancy, these non-reactive compounds should be excluded from the system. Preferably, the total amount is 5 wt% or less, more preferably 2 wt% or less.
  • a removal method generally, a method such as vacuum distillation is applied.
  • the aromatic olefin used in the reaction contains, as another reactive component, an unsaturated bond-containing component such as styrene, ⁇ -methylenstyrene, divininolebenzene, coumarone, benzothiophene, indanol or vinino naphthalene,
  • the resulting phenolic resin will include compounds in which the groups resulting from these are substituted on the benzene ring.
  • the phenol resin obtained by the method for producing a phenol resin of the present invention may include a phenol resin having such a substituent.
  • the epoxy resin obtained by the method for producing an epoxy resin of the present invention may contain an epoxy resin having such a substituent.
  • a reaction method using a known freedelcraft catalyst such as an acid catalyst can be employed.
  • a phenol resin in which the above substituent is substituted on the benzene ring of the bisphenol compound is obtained.
  • This phenol resin is usually a mixture having different numbers of substituents and different substitution positions, but it should have an average of 0.4 to 4, preferably 1 to 4 substituents.
  • phenol resin can also be purified or isolated as a target product.
  • the method for producing the epoxy resin of the present invention is the phenol resin represented by the general formula (1) or the phenol resin obtained by the method for producing the phenol resin (hereinafter, when it is not necessary to distinguish between the two). (Also simply referred to as phenolic resin) and epichlorohydrin.
  • the reaction between phenolic resin and epichlorohydrin is 0.80-1.20 times the hydroxyl group in the phenolic resin! : Preferably (O. 85-1.05 times equivalent !: Hydroxyl hydroxide HJ cumum, alkali metal hydroxide such as potassium hydroxide, etc. If less than this, the remaining hydrolyzable chlorine
  • the metal hydroxide is used in the form of an aqueous solution, an alcohol solution or a solid.
  • an excessive amount of epichlorohydrin is used with respect to the phenol resin.
  • the amount is higher than this, the production efficiency is lowered, and when the amount is lower than this, the amount of the high molecular weight polymer of the epoxy resin increases and the viscosity is increased.
  • the reaction is usually performed at a temperature of 120 ° C or lower. If the temperature is high during the reaction, the amount of so-called non-hydrolyzable chlorine increases and high purity becomes difficult. Preferably below 100 ° C More preferably, the temperature is 85 ° C or lower.
  • a quaternary ammonium salt or a polar solvent such as dimethyl sulfoxide, diglyme may be used.
  • the quaternary ammonium salt include tetramethyl ammonium chloride, tetilaptyl ammonium chloride, benzyltriethyl ammonium chloride, etc., and the amount added is 0.1 with respect to the phenol resin. The range of ⁇ 2. Owt% is preferred. If the amount is less than this, the effect of adding quaternary ammonium salt is small. If the amount is more than this, the amount of hardly hydrolyzable chlorine produced increases, making it difficult to achieve high purity.
  • the addition amount of the polar solvent is preferably in the range of 10 to 200 wt% with respect to the phenol resin. If the amount is less than this, the effect of addition is small. If the amount is more than this, the volumetric efficiency is lowered, which is not preferable in the economy.
  • the obtained epoxy resin is further added to the remaining hydrolyzable chlorine;! ⁇ 30 times the amount of alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, A ring closure reaction takes place.
  • the reaction temperature at this time is usually 100 ° C. or lower, preferably 90 ° C. or lower.
  • the epoxy resin obtained by the method for producing an epoxy resin of the present invention is preferably an epoxy resin represented by the above general formula (3) or an epoxy resin containing this as a main component (50 wt% or more). .
  • the substituent may have an average of 0.;! To 2.0, preferably 0.5 to 2.0 per benzene ring.
  • the phenol resin obtained by the method for producing a phenol resin of the present invention is preferably a phenol resin represented by the above general formula (1) or a phenol resin mainly composed thereof.
  • the substituent may have an average of 0.;! To 2.0, preferably 0.5 to 2.0, per benzene ring.
  • the epoxy resin composition of the present invention includes an epoxy resin represented by the above general formula (1), an epoxy resin mainly composed of the epoxy resin, or an epoxy resin obtained by the method for producing the epoxy resin ( Hereinafter, these are also collectively referred to as the present epoxy resin) and a curing agent. It is an essential ingredient.
  • the curing agent to be blended in the epoxy resin composition of the present invention all those generally known as epoxy resin curing agents can be used. Examples include dicyandiamide, polyvalent phenols, acid anhydrides, aromatic and aliphatic amines.
  • examples of polyhydric phenols include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4, 4'-biphenol, 2, 2, monobiphenol, hydroquinone. , Resorcinol, naphthalenediol and other divalent phenols, or tris (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenenole) ethane, phenol novolak, o— There are trihydric or higher phenols such as cresol novolac, naphthol nopolac, polybuhlphenol. Furthermore, monovalent phenols such as phenols and naphthols, bisphenol A and bisphenols?
  • Bisphenols such as bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2, 2, monobiphenol, hydroquinone, resorcin, naphthalene diol, formaldehyde, acetoaldehyde, benzaldehyde, p —Polyhydric phenolic compounds synthesized by condensing agents such as hydroxy benzaldehyde and p-xylylene alcohol. Further, those obtained by reacting these phenolic curing agents with indene or acenaphthylene may be used as the curing agent.
  • Acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, nadic anhydride, trimellitic anhydride Etc.
  • amines examples include 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylsulfone, m-phenylenediamine, p-xylylenediamine, and the like.
  • aliphatic amines such as aromatic amines, ethylenediamine, hexamethylenediamine, jetylenetriamine, and triethylenetetramine.
  • epoxy resin composition of the present invention one or two or more of these curing agents are used in combination.
  • the epoxy resin composition of the present invention may contain other types of epoxy resins in addition to the present epoxy resin as an epoxy resin component.
  • a normal epoxy resin having two or more epoxy groups in the molecule can be used as another type of epoxy resin.
  • bisphenol A bisphenol S, fluorene bisphenol, 4, 4, — bivalent phenols such as biphenol, 2, 2, 1 biphenol, hydroquinone, resorcin, or tris (4— Trivalent or higher phenols such as hydroxyphenyl) methane, 1,1,2,2,2-tetrakis (4-hydroxyphenenole) ethane, phenol novolak, o-cresol novolak or tetrabromobisphenol A And the like, and darcidyl etherified compounds derived from them.
  • These epoxy resins can be used alone or in combination of two or more.
  • the compounding quantity of this epoxy resin is 5-100 wt% in the whole epoxy resin, Preferably it is the range of 60-100 wt%.
  • the epoxy resin composition of the present invention may contain an inorganic filler.
  • the inorganic filler examples include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, and glass powder.
  • the amount of inorganic filler used is usually 75 wt% or more. From the viewpoint of low moisture absorption and high solder heat resistance, 80 wt% or more is preferable! / ,.
  • the epoxy resin composition of the present invention appropriately contains an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyester, polyurethane, petroleum resin, indene coumarone resin, or phenoxy resin.
  • additives such as pigments, refractory agents, thixotropic agents, coupling agents, and fluidity improvers may be blended.
  • the pigment include organic or inorganic extender pigments and scale-like pigments.
  • thixotropic agents include silicon, castor oil, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite.
  • the epoxy resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a coupling agent such as ⁇ -glycidoxypropyltrimethoxysilane, and a colorant such as carbon black.
  • a release agent such as carnauba wax and OP wax
  • a coupling agent such as ⁇ -glycidoxypropyltrimethoxysilane
  • a colorant such as carbon black.
  • flame retardants such as antimony trioxide, low stress agents such as silicone oil, lubricants such as calcium stearate, and the like can be used.
  • the epoxy resin composition of the present invention can be used with a known curing accelerator.
  • a known curing accelerator examples include amines, imidazoles, organic phosphines, and noNA acids.
  • the amount added is usually in the range of 0.2 to 5 parts by weight per 100 parts by weight of the epoxy resin.
  • the amount of curing agent added is usually 100 wt. The range is 10 to 100 parts by weight with respect to parts.
  • the cured product of the present invention obtained by curing the resin composition of the present invention can be molded and processed 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 to 220 ° C.
  • Epoxy resin A had an epoxy equivalent of 278 g / eq., Hydrolyzable chlorine of 420 ppm, and a softening point of 58 ° C. and 150 ° C., and a melt viscosity of 0 ⁇ 045 Pa ′s.
  • hydrolyzable chlorine is a sample obtained by dissolving 0.5 g of a sample in 30 ml of dioxane, adding 10 ml of 1 ⁇ _ ⁇ , boiling and refluxing for 30 minutes, cooling to room temperature, and then adding 100 ml of 80% acetone water. Measured by potentiometric titration with 0.002N-AgNO aqueous solution.
  • the softening point is a value obtained by a ball & ring method at a heating rate of 5 ° C / min, and the viscosity was measured using a Brookfield cone plate viscometer.
  • GPC measurement conditions were as follows: apparatus; MODEL151 (manufactured by Waters Co., Ltd.), column; TSK-GEL 2000 X 3 and TSK-GEL4000 X 1 (Le, also from Tosoh Co., Ltd.), solvent; tetrahydride Mouth furan, flow rate: 1 ml / min, temperature: 38 ° C, detector; The infrared absorption spectrum was determined by the KBr tablet molding method, and the NMR spectrum was measured in acetone-d6 using an apparatus; JNM_LA400 manufactured by JEOL Ltd.
  • Fig. 1 shows the infrared absorption spectrum of epoxy resin A.
  • Fig. 2 shows the NMR spectrum.
  • Example 2 Into a 3 L 4-separable flask, add 300 g of the phenolic resin B synthesized in Example 2 After dissolving in 810 g of oral hydrin and 122 g of diglyme, the reaction was conducted in the same manner as in Example 4 using 96 g of 48% aqueous sodium hydroxide solution at 60 ° C. under reduced pressure to obtain 335 g of a pale yellow epoxy resin.
  • Epoxy resin B The epoxy equivalent was 336 g / eq., Hydrolyzable chlorine was 340 ppm, the soft rice crack point was 76 ° C, and the molten rice occupancy at 150 ° C was 0.136 Pa's.
  • epoxy resins A to C synthesized in Examples 4 to 6, bisphenol F type epoxy resin (epoxy resin D; manufactured by Tohto Kasei, YDF-170, epoxy equivalent 1 69), biphenyl type epoxy resin ( Epoxy resin E: Made by Japan Epoxy Resin, YX-4000H, Epoxy equivalent 195, Melting point 105 ° C), Phenolic nopolac as curing agent (Curing agent A; OH equivalent 107, Softening point 82 ° C), phenol aralkyl resin (Curing agent B: Mitsui Chemicals, XL_225-LL, OH equivalent 175, softening point 74 ° C), silica (average particle size, 22 m) as filler, and triphenylphosphine as curing accelerator in Table 1.
  • An epoxy resin composition was obtained by kneading with the formulation shown.
  • the epoxy resin composition was 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 amounts shown in Table 1 are parts by weight.
  • the glass transition point (Tg) was determined by a thermomechanical measurement device under a temperature increase rate of 10 ° C / min.
  • the water absorption is the value obtained when the epoxy resin composition is used to form a disk with a diameter of 50 mm and a thickness of 3 mm, and after post-curing, it is absorbed for 100 hours at 85 ° C and 85% relative humidity. is there.
  • the epoxy resin of the present invention and the epoxy resin obtained by the production method of the present invention have excellent moldability, high filler filling property, moisture resistance, and heat resistance.
  • it provides a cured product having excellent flame retardancy, and can be suitably used for applications such as sealing of electric and electronic parts, circuit board materials, and the like. In particular, it makes unnecessary or reduces the use of flame retardants with excellent flame retardancy and environmental impact.

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

Abstract

La présente invention concerne une résine époxy ayant une excellente fluidité et une propriété de remplissage élevé de garnissage, qui fournit un produit durci excellent en termes de résistance à l'humidité, de résistance thermique et de caractère ignifuge. Cette résine époxy est appropriée pour sceller des composants électroniques et utilisée en tant que matériaux de carte de circuit imprimé. La présente invention concerne également une composition d'une telle résine époxy. La présente invention concerne spécifiquement une résine époxy représentée par la formule générale (3), qui est obtenue par la réaction de l'épichlorhydrine avec une résine de phénol obtenue par la réaction de 0,2 à 6,0 moles d'indène ou d'acénaphtylène avec de 1 mole d'un composé bisphénol représenté par la formule générale (2). (Dans les formules, X représente une liaison simple, -CH2-, -CH(CH3)-, -C(CH3)2-, -CO-, -O-, -S- ou -SO2-; et les groupes R1 à R4 représentent indépendamment un atome d'hydrogène ou un substituant dérivé de l'indène ou de l'acénaphtylène.)
PCT/JP2007/069482 2006-10-04 2007-10-04 Résine époxy, résine de phénol, leurs procédés de production, composition de résine époxy et produit durci WO2008041749A1 (fr)

Priority Applications (3)

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CN200780036932XA CN101522739B (zh) 2006-10-04 2007-10-04 环氧树脂、酚醛树脂、这些的制造方法、环氧树脂组合物及固化物
JP2008537550A JP5515058B2 (ja) 2006-10-04 2007-10-04 エポキシ樹脂、フェノール樹脂、それらの製造方法、エポキシ樹脂組成物及び硬化物
KR1020097008024A KR101423170B1 (ko) 2006-10-04 2007-10-04 에폭시 수지, 페놀 수지, 그들의 제조방법, 에폭시 수지 조성물 및 경화물

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JP2006272566 2006-10-04
JP2006-272566 2006-10-04

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WO2008041749A1 true WO2008041749A1 (fr) 2008-04-10

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CN (1) CN101522739B (fr)
TW (1) TWI427093B (fr)
WO (1) WO2008041749A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011178836A (ja) * 2010-02-26 2011-09-15 Nippon Steel Chem Co Ltd 結晶性エポキシ樹脂、その製造方法、それを用いたエポキシ樹脂組成物および硬化物
WO2012014715A1 (fr) * 2010-07-30 2012-02-02 Dic株式会社 Composition de résine durcissable, produit durci obtenu à partir de cette composition, résine phénolique, résine époxy et matériau d'étanchéité pour semi-conducteurs
WO2012043563A1 (fr) * 2010-09-29 2012-04-05 Dic株式会社 Composition de résine durcissable, substance résultant du durcissement de celles-ci, résine phénolique, résine époxy et matériau de scellement pour semi-conducteur
WO2013187185A1 (fr) * 2012-06-12 2013-12-19 新日鉄住金化学株式会社 Résine de polyhydroxypolyéther, procédé de fabrication de résine de polyhydroxypolyéther, composition de résine contenant de la résine de polyhydroxypolyéther et produit durci obtenu à partir de celle-ci

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JP5324712B2 (ja) * 2010-09-27 2013-10-23 新日鉄住金化学株式会社 多価ヒドロキシ樹脂、エポキシ樹脂、それらの製造方法、エポキシ樹脂組成物及びその硬化物
WO2020017399A1 (fr) * 2018-07-19 2020-01-23 パナソニックＩｐマネジメント株式会社 Composition de résine, préimprégné, film avec résine, feuille métallique avec résine, stratifié metallisé et circuit imprimé
CN114149659B (zh) * 2021-12-31 2023-07-14 苏州生益科技有限公司 树脂组合物及其应用

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JP2000204141A (ja) * 1999-01-12 2000-07-25 Nippon Steel Chem Co Ltd 多価ヒドロキシ樹脂、エポキシ樹脂及びそれらを用いたエポキシ樹脂組成物並びにその硬化物
WO2003104295A1 (fr) * 2002-06-11 2003-12-18 新日鐵化学株式会社 Resine phenolique modifiee par acenaphthylene et composition de resine epoxyde

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JP2000204141A (ja) * 1999-01-12 2000-07-25 Nippon Steel Chem Co Ltd 多価ヒドロキシ樹脂、エポキシ樹脂及びそれらを用いたエポキシ樹脂組成物並びにその硬化物
WO2003104295A1 (fr) * 2002-06-11 2003-12-18 新日鐵化学株式会社 Resine phenolique modifiee par acenaphthylene et composition de resine epoxyde

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011178836A (ja) * 2010-02-26 2011-09-15 Nippon Steel Chem Co Ltd 結晶性エポキシ樹脂、その製造方法、それを用いたエポキシ樹脂組成物および硬化物
WO2012014715A1 (fr) * 2010-07-30 2012-02-02 Dic株式会社 Composition de résine durcissable, produit durci obtenu à partir de cette composition, résine phénolique, résine époxy et matériau d'étanchéité pour semi-conducteurs
WO2012043563A1 (fr) * 2010-09-29 2012-04-05 Dic株式会社 Composition de résine durcissable, substance résultant du durcissement de celles-ci, résine phénolique, résine époxy et matériau de scellement pour semi-conducteur
JP5136729B2 (ja) * 2010-09-29 2013-02-06 Ｄｉｃ株式会社 硬化性樹脂組成物、その硬化物、フェノール樹脂、エポキシ樹脂、及び半導体封止材料
US8703845B2 (en) 2010-09-29 2014-04-22 Dic Corporation Curable resin composition, cured product thereof, phenolic resin, epoxy resin, and semiconductor sealing material
WO2013187185A1 (fr) * 2012-06-12 2013-12-19 新日鉄住金化学株式会社 Résine de polyhydroxypolyéther, procédé de fabrication de résine de polyhydroxypolyéther, composition de résine contenant de la résine de polyhydroxypolyéther et produit durci obtenu à partir de celle-ci
JPWO2013187185A1 (ja) * 2012-06-12 2016-02-04 新日鉄住金化学株式会社 ポリヒドロキシポリエーテル樹脂、ポリヒドロキシポリエーテル樹脂の製造方法、そのポリヒドロキシポリエーテル樹脂を含有する樹脂組成物、及びそれから得られる硬化物

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CN101522739B (zh) 2012-09-05
JP5515058B2 (ja) 2014-06-11
CN101522739A (zh) 2009-09-02
JPWO2008041749A1 (ja) 2010-02-04
TW200833728A (en) 2008-08-16
TWI427093B (zh) 2014-02-21
KR101423170B1 (ko) 2014-07-25
KR20090075826A (ko) 2009-07-09

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