WO2013125620A1 - Résine hydroxy polyvalente, résine époxy, procédé de production de celle-ci, composition de résine époxy et produit durci de celle-ci - Google Patents

Résine hydroxy polyvalente, résine époxy, procédé de production de celle-ci, composition de résine époxy et produit durci de celle-ci Download PDF

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WO2013125620A1
WO2013125620A1 PCT/JP2013/054278 JP2013054278W WO2013125620A1 WO 2013125620 A1 WO2013125620 A1 WO 2013125620A1 JP 2013054278 W JP2013054278 W JP 2013054278W WO 2013125620 A1 WO2013125620 A1 WO 2013125620A1
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polyvalent hydroxy
epoxy resin
aralkyl
resin
hydroxy compound
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PCT/JP2013/054278
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English (en)
Japanese (ja)
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山田　尚史
栄次郎 青柳
圭介 渡邊
岡崎　豊
秀安 朝蔭
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新日鉄住金化学株式会社
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Application filed by 新日鉄住金化学株式会社 filed Critical 新日鉄住金化学株式会社
Priority to KR1020147026281A priority Critical patent/KR101987946B1/ko
Priority to SG11201405075SA priority patent/SG11201405075SA/en
Priority to CN201380010483.7A priority patent/CN104334597B/zh
Priority to JP2014500754A priority patent/JP6124865B2/ja
Publication of WO2013125620A1 publication Critical patent/WO2013125620A1/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
    • 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

Definitions

  • the present invention is an epoxy resin that gives a cured product having excellent curability and mechanical strength, flame retardancy, moisture resistance, and low elasticity, a polyvalent hydroxy resin suitable as an intermediate thereof, a production method thereof, and the like
  • the present invention relates to the epoxy resin composition used and its cured product, and is suitably used for insulating materials in the electric and electronic fields such as semiconductor sealing materials and printed wiring boards.
  • Epoxy resins have been used in a wide range of industrial applications, but their required performance has become increasingly sophisticated in recent years.
  • a semiconductor sealing material in a typical field of a resin composition mainly composed of an epoxy resin, but as the integration degree of semiconductor elements is improved, the package size is becoming larger and thinner, and the mounting method is also increased. 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 reducing moisture absorption, improvement in adhesion and adhesion at the interface between different materials such as lead frames and chips is strongly demanded.
  • Patent Document 1 discloses an application of a naphthol aralkyl resin to a semiconductor sealing material. It is flame retardant, low moisture absorption, and low thermal expansion. It is described that it is excellent.
  • Patent Document 2 proposes a curing agent having a biphenyl structure and describes that it is effective for improving flame retardancy.
  • naphthol aralkyl resins and biphenyl aralkyl resins have drawbacks that are inferior in curability, and there are cases where the effect of improving flame retardancy is not sufficient.
  • an epoxy resin that satisfies these requirements is not yet known.
  • the well-known bisphenol type epoxy resin is in a liquid state at room temperature and is widely used because it is excellent in workability and easy to mix with a curing agent, an additive, etc.
  • moisture resistance There is a problem in terms of moisture resistance.
  • an o-cresol novolac type epoxy resin is known as an improved heat resistance, but the flame retardancy is insufficient.
  • a method of adding a phosphate ester flame retardant is disclosed.
  • the method using a phosphate ester flame retardant does not have sufficient moisture resistance.
  • the phosphoric acid ester is hydrolyzed under a high temperature and humidity environment, and there is a problem that the reliability as an insulating material is lowered.
  • Patent Documents 2 and 3 disclose examples in which an aralkyl epoxy resin having a biphenyl structure is applied to a semiconductor encapsulant.
  • Patent Document 4 discloses an example in which an aralkyl type epoxy resin having a naphthalene structure is used.
  • these epoxy resins have insufficient performance in any of flame retardancy, moisture resistance or heat resistance.
  • Patent Document 5 discloses benzylated polyphenol and its epoxy resin as examples focusing on improving heat resistance, moisture resistance and crack resistance, but these do not focus on flame retardancy. Further, Patent Document 6 discloses a method for producing a styrene-modified novolak, but it is not noted as an epoxy resin composition.
  • Patent Documents 7 and 8 disclose a styrene-modified phenol novolac resin and an epoxy resin composition using the epoxy resin. Also, there are no examples in which the molecular weight distribution of styrenated phenol novolac and epoxy resin has been studied in detail.
  • the molecular weight distribution (dispersion) is represented by Mw / Mn.
  • Patent Document 9 discloses an styrene-modified phenol novolac resin and an epoxy resin composition using the epoxy resin as an example focusing on improving flame retardancy.
  • a resin whose hydroxyl equivalent or epoxy equivalent is adjusted high by increasing the modification amount is used.
  • high flame retardancy can be expressed by relatively reducing the content of an aliphatic component derived from an epoxy group.
  • the object of the present invention is to provide an epoxy resin having excellent properties such as flame retardancy, moisture resistance and low elasticity, as well as excellent curability and mechanical properties in applications such as lamination, molding, casting and adhesion.
  • Epoxy useful for sealing electrical and electronic components, circuit board materials, etc. that have excellent curability and mechanical properties, and also provides cured products with excellent flame retardancy, moisture resistance, low elasticity, etc.
  • the object is to provide a resin composition and to provide a cured product thereof.
  • the present invention reacts a polyvalent hydroxy compound represented by the following general formula (1) with an aralkylating agent to convert a substituent derived from the aralkylating agent represented by the formula (a) to a polyvalent hydroxy.
  • the present invention relates to an aralkyl-modified polyvalent hydroxy resin.
  • R 1 and R 2 represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms
  • R 3 and R 4 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • n represents 1 to 5
  • a polyvalent hydroxy compound represented by the above general formula (1) is reacted with styrenes, and a substituent derived from styrene represented by the formula (a2) is converted into a polyvalent hydroxy compound.
  • a polyhydroxy compound represented by the above general formula (1) is reacted with an aralkylating agent represented by the following formula (b1) or (b2) to form the above formula (a)
  • an aralkylating agent represented by the following formula (b1) or (b2) to form the above formula
  • R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms
  • R 3 and R 4 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • X represents halogen, OH or OR 5.
  • R 5 represents an alkyl group having 1 to 6 carbon atoms
  • aralkyl-modified polyvalent hydroxy resin 0.1 to 1.5 mol of an aralkylating agent is reacted with 1 mol of a hydroxy group of a polyvalent hydroxy compound, or the aralkylating agent is styrene. preferable.
  • Another aspect of the present invention is an epoxy resin composition
  • an epoxy resin composition comprising an epoxy resin and a curing agent, wherein the aralkyl-modified polyvalent hydroxy resin is an essential component as part or all of the curing agent. It is a composition and its hardened
  • Another aspect of the present invention is an epoxy resin obtained by reacting the above aralkyl-modified polyvalent hydroxy resin with epichlorohydrin.
  • Another embodiment is a method for producing an epoxy resin, characterized in that the aralkyl-modified polyvalent hydroxy resin and epichlorohydrin are reacted to make the hydroxy group of the aralkyl-modified polyvalent hydroxy resin a glycidyl ether group.
  • Another aspect of the present invention is an epoxy resin composition
  • an epoxy resin composition comprising the above epoxy resin as an essential component in an epoxy resin composition comprising an epoxy resin and a curing agent, and a cured epoxy resin product thereof.
  • GPC chart of polyvalent hydroxy compound A GPC chart of polyvalent hydroxy compound B GPC chart of polyvalent hydroxy compound C GPC chart of modified polyhydroxy resin A GPC chart of modified polyhydroxy resin B GPC chart of modified polyvalent hydroxy resin C GPC chart of modified polyvalent hydroxy resin D GPC chart of epoxy resin A GPC chart of epoxy resin B GPC chart of epoxy resin C GPC chart of epoxy resin D
  • the hydroxypropyl group produced by the reaction between the epoxy group and the hydroxyl group is said to burn easily.
  • an aralkyl group to the polyvalent hydroxy compound to increase the hydroxyl equivalent, The aliphatic carbon ratio of the flammable component derived from the group is low, and a high level of flame retardancy can be expressed.
  • the addition of an aralkyl group rich in aromaticity further improves the aromaticity of the polyvalent hydroxy resin, and is effective in improving moisture resistance in addition to flame retardancy.
  • the polyvalent hydroxy compound used in the present invention is a narrowly dispersed polyvalent hydroxy compound represented by the general formula (1), it is also referred to as a polyvalent hydroxy compound (1) or a narrowly dispersed polyvalent hydroxy compound. Moreover, since it is also 1 type of novolak resin, it is also called a phenol novolac.
  • hardenability, mechanical strength, a flame retardance, etc. using these, especially the epoxy resin composition for semiconductor sealing are obtained. That is, in addition to excellent curability in these compositions, physical properties excellent in mechanical strength, high flame retardancy, moisture resistance and low elasticity are expressed. Using this material, highly reliable electrical and electronic parts Sealing, circuit board materials, etc. are obtained.
  • the aralkyl-modified polyvalent hydroxy resin of the present invention is called StPN, and the polyvalent hydroxy compound represented by the general formula (1) used for obtaining this is called a polyvalent hydroxy compound or a narrowly dispersed polyvalent hydroxy compound.
  • Aralkyl in the aralkyl-modified polyvalent hydroxy resin means a group represented by the formula (a).
  • the aralkylating agent used to obtain StPN refers to a compound represented by the formula (c1) or (c2).
  • the aralkylating agent may be represented by styrene, and the aralkyl-modified polyvalent hydroxy resin may be referred to as a styrene-modified polyvalent hydroxy resin.
  • the narrowly dispersed polyhydroxy compound used in the present invention can be obtained by removing low molecular weight components from a crude polyhydroxy compound obtained by adjusting the molar ratio of phenols and aldehydes.
  • the molar ratio of phenols to aldehydes is indicated by the molar ratio of aldehydes to 1 mole of phenols, and is produced in the range of 0.1 to 0.9.
  • PNStPN of the present invention can be obtained by addition reaction of a narrowly dispersed polyvalent hydroxy compound represented by the general formula (1) and an aralkylating agent.
  • the ratio of the polyvalent hydroxy compound to the aralkylating agent is, when the balance between the flame retardancy and curability of the resulting cured product is taken into consideration, the ratio of the aralkylating agent used relative to 1 mol of the polyvalent hydroxy compound is 0.
  • the range is preferably 1 to 1.5 mol, more preferably 0.1 to 1.0 mol, and still more preferably 0.3 to 0.8 mol.
  • the amount is less than this range, the properties of the starting polyvalent hydroxy compound are not improved.
  • the amount is more than this range, the functional group density tends to be too low and the curability tends to decrease.
  • R 3 and R 4 represent a hydrogen atom or a C1-6 alkyl group.
  • the alkyl group is preferably a methyl group. More preferably, one or both of R 3 and R 4 are a hydrogen atom or a methyl group, and more preferably one or both are a hydrogen atom. When both are hydrogen atoms, it is a benzyl group, and when one is a hydrogen atom, it is an ⁇ -alkyl-substituted benzyl group.
  • the benzene ring of this benzyl group or ⁇ -alkyl-substituted benzyl group may be substituted with a substituent R 2 .
  • the aralkyl group is added at the vacant ortho and / or para position of the polyvalent hydroxy compound, but mainly at the para position.
  • the melt viscosity of the StPN of the present invention at 150 ° C. is preferably in the range of 0.01 to 10.0 Pa ⁇ s. From the viewpoint of workability, the melt viscosity is preferably as low as possible within the above range.
  • the softening point is preferably 40 to 150 ° C., and preferably in the range of 50 to 100 ° C.
  • the softening point refers to a softening point measured based on the ring and ball method of JIS-K-2207. When lower than this, when this is mix
  • the amount of aralkyl group added can be adjusted by the amount of aralkylating agent used, and usually 0.1 to 2.5 aralkyl groups are added to the benzene ring of the polyvalent hydroxy compound. This means the average number (number average) of aralkyl groups substituted on one phenol ring.
  • the addition amount is preferably 0.1 to 1.5 mol, 0.1 to 1.0 mol, and 0.3 to 0.8 mol in order of 1 mol of the benzene ring of the polyvalent hydroxy compound.
  • a maximum of 4 aralkyl groups can be substituted for the phenol ring at both ends, and a maximum of 3 aralkyl groups can be substituted for the intermediate phenol ring, so when n is 1, a maximum of 8 aralkyl groups can be substituted. it can.
  • R 2 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, and more preferably hydrogen. This R 2 is determined by the aralkylating agent used as a reaction raw material.
  • n represents a number of 1 to 5, preferably in the range of 1.9 to 3.4 as an average (number average). More preferably, it is in the range of 2.0 to 3.0, but it is necessary to satisfy the above dispersion. From another viewpoint, it is preferable that the component having n of 1 to 5 is a main component.
  • the main component means 80 wt% or more, preferably 90 wt% or more, more preferably substantially all.
  • R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Phenol novolacs are suitable as the polyvalent hydroxy compound represented by the general formula (1) used in the method for producing StPN of the present invention. Phenol novolacs can be obtained from phenols and aldehydes.
  • Phenols used to obtain this polyvalent hydroxy compound are mainly phenol. These phenols may contain small amounts of other phenol components. Examples include o-cresol, m-cresol, p-cresol, ethylphenols, isopropylphenols, tertiary butylphenols, allylphenols, and phenylphenols. These phenols may be used alone or in combination of two or more.
  • aralkylating agent used for the reaction with the polyvalent hydroxy compound a compound represented by the above formula (c1) or (c2) is used.
  • the compound represented by the formula (c1) is called styrenes.
  • Styrenes are styrene or styrene substituted with a hydrocarbon group having 1 to 6 carbon atoms.
  • R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms, preferably hydrogen.
  • These styrenes may contain a small amount of other reaction components, and examples of other reaction components include unsaturated bond-containing components such as divinylbenzene, indene, coumarone, benzothiophene, indole, and vinylnaphthalene. In the case of blending these, it is preferable to keep it at 30 wt% or less, preferably 20 wt% or less.
  • R 2, R 3 and R 4 are the same meaning as R 2, R 3 and R 4 of formula (a).
  • X is a halogen atom, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group.
  • R 2, R 3 are same meaning as R 2, R 3 of formula (a).
  • aralkylating agent represented by the above formula (c2) when X is a halogen atom, benzyl chloride, benzyl bromide, benzyl iodide, o-methylbenzyl chloride, m-methylbenzyl chloride, p-methylbenzyl chloride, p-ethylbenzyl chloride, p-isopropylbenzyl chloride, p-tert-butylbenzyl chloride, p-cyclohexylbenzyl chloride, p-phenylbenzyl chloride, ⁇ -methylbenzyl chloride, ⁇ , ⁇ -dimethylbenzyl chloride, etc.
  • X is an alkoxy group
  • it is preferably an alkoxy group having 1 to 4 carbon atoms, such as benzyl methyl ether, o-methylbenzyl methyl ether, m- methylbenzyl methyl ether, p-methylbenzyl methyl.
  • Ether p-ethylbenzyl methyl ether, benzyl ethyl ether, benzyl isopropyl ether, benzyl n-propyl ether, benzyl isobutyl ether, benzyl n-butyl ether, p-methylbenzyl methyl ether, and the like.
  • Alcohol o-methylbenzyl alcohol, m -methylbenzyl alcohol, p-methylbenzyl alcohol, p-ethylbenzyl alcohol, p-isopropylbenzyl alcohol, p-tert-butylbenzyl alcohol, p-cyclohexylbenzyl alcohol, p-phenylbenzyl
  • Examples include alcohol, ⁇ -methylbenzyl alcohol, ⁇ , ⁇ -dimethylbenzyl alcohol and the like.
  • Examples of the aralkylating agent represented by the formula (c1) include styrene, alkylstyrene having a C1-6 alkyl group substituted on the benzene ring of styrene, ⁇ -alkylstyrenes, etc., preferably alkylstyrene or styrene. More preferably, it is styrene.
  • the aralkylation reaction with an aralkylating agent can be carried out in the presence of an acid catalyst, and the amount of the catalyst is used in the range of 10 to 1000 ppm (wt), preferably in the range of 100 to 500 ppm. If it is more than this, the methylene cross-linking bond of the polyvalent hydroxy compound will be easily cleaved, and the curability and heat resistance will be lowered by the unit price phenol component by-produced by the row opening reaction. On the other hand, if the amount is less than this, the reactivity is lowered and a large amount of unreacted aralkylating agent remains.
  • the catalyst amount here means the amount of the catalyst with respect to the total weight of the polyvalent hydroxy compound and the aralkylating agent used in the reaction.
  • the oxalic acid catalyst can be appropriately selected from known inorganic acids and organic acids.
  • mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid
  • organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, dimethyl sulfuric acid, diethyl sulfuric acid, zinc chloride, aluminum chloride, iron chloride, trifluoride.
  • Lewis acids such as boron fluoride or ion exchange resins, activated clay, silica-alumina, solid acids such as zeolite, and the like.
  • the reaction temperature in this reaction is in the range of 40 to 120 ° C. If it is lower than this, the reactivity is lowered and the reaction time is prolonged. On the other hand, if it is higher than this, a part of the methylene cross-linked bond of the polyvalent hydroxy compound is easily cleaved, and the curability and heat resistance are lowered by the unit price phenol component by-produced by the row opening reaction.
  • This reaction is usually performed for 1 to 20 hours. Further, during the reaction, alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl ether, diethyl ether, diisopropyl ether, Ethers such as tetrahydrofuran and dioxane, aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene can be used as the solvent.
  • alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl ether, diethyl ether, di
  • all raw materials are charged in a lump and reacted at a predetermined temperature as it is, or a polyvalent hydroxy compound and a catalyst are charged and maintained at a predetermined temperature while aralkylating.
  • a method of reacting while dropping the agent is common. At this time, the dropping time is preferably 5 hours or less, and usually 1 to 10 hours.
  • the catalyst component can be removed if necessary, and then the solvent can be distilled off to obtain the resin of the present invention. If the solvent is not used, it can be discharged directly when heated. The object can be obtained.
  • the epoxy resin (StPNE) of the present invention can be obtained by epoxidizing StPN.
  • SStPNE of the present invention is advantageously produced by reacting the above StPN with epichlorohydrin.
  • the reaction of reacting StPN with epichlorohydrin can be performed in the same manner as a normal epoxidation reaction.
  • an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide
  • it is 1 to 10 in the range of 20 to 150 ° C., preferably 30 to 80 ° C.
  • the method of making it react for time is mentioned.
  • the amount of alkali metal hydroxide used at this time is in the range of 0.8 to 1.5 mol, preferably 0.9 to 1.2 mol, per mol of StPN hydroxyl group.
  • Epichlorohydrin is used in excess with respect to 1 mol of hydroxyl group in StPN, but is usually in the range of 1.5 to 30 mol, preferably 2 to 15 mol, relative to 1 mol of hydroxyl group in StPN.
  • the epoxy resin composition of the present invention contains at least an epoxy resin and a curing agent, and there are the following three types. 1) The composition which mix
  • StPN is included as an essential component.
  • the blending amount of StPN is usually in the range of 2 to 200 parts by weight, preferably 5 to 80 parts by weight, per 100 parts by weight of the epoxy resin. If it is less than this, the effect of improving flame retardancy and moisture resistance 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 StPN is usually determined in consideration of the equivalent balance of the OH group of StPN and the epoxy group 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, 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 and the like of the cured product are lowered.
  • a curing agent other than StPN can be used in combination as a soot curing agent.
  • the blending amount of the other curing agent is determined so that the blending amount of StPN is normally 2 to 200 parts by weight, preferably 5 to 80 parts by weight with respect to 100 parts by weight of the epoxy resin. .
  • the blending amount of StPN is less than this, the effect of improving low hygroscopicity, adhesion and flame retardancy is small, and when it is more than this, there is a problem that the moldability and the strength of the cured product are lowered.
  • the equivalent ratio of the epoxy resin and the curing agent (total) is in the above range.
  • curing agent other than PNStPN all those generally known as curing agents for epoxy resins can be used, and examples thereof include dicyandiamide, acid anhydrides, polyhydric phenols, aromatic and aliphatic amines.
  • polyhydric phenols are preferably used as a curing agent in a field where high electrical insulation properties such as a semiconductor sealing material are required.
  • the blending amount of StPN is 50 to 100%, preferably 60 to 100% in the entire curing agent.
  • curing agents other than StPN is shown.
  • Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl hymic anhydride, dodecynyl succinic anhydride, nadic anhydride, There are trimellitic anhydride and the like.
  • polyhydric phenols examples include divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, and naphthalenediol, or , Tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolak, naphthol novolak, polyvinylphenol and the like having a valence of 3 or more. There are phenols.
  • divalent phenols such as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcin, naphthalenediol
  • polyhydric phenolic compounds synthesized by a condensing agent such as formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene dichloride, bischloromethylbiphenyl, bischloromethylnaphthalene, and the like.
  • amines examples include aromatic amines such as 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylpropane, 4,4′-diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine, ethylenediamine, There are aliphatic amines such as hexamethylenediamine, diethylenetriamine, and triethylenetetramine. One or more of these curing agents can be mixed and used in the composition.
  • the epoxy resin used in the composition is selected from those having two or more epoxy groups in one molecule.
  • These epoxy resins can be used alone or in combination of two or more.
  • StPNE is included as an essential component.
  • the epoxy resin in this case all ordinary epoxy resins having two or more epoxy groups in the molecule can be used. Examples include divalent phenols such as bisphenol A, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-biphenol, hydroquinone, resorcin, or tris- (4-hydroxyphenyl) methane.
  • an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene resin, indene-coumarone resin, phenoxy resin, etc. is used as another modifier. 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 can contain additives such as inorganic fillers, pigments, 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, mica, talc, calcium carbonate, alumina, hydrated alumina, and the like.
  • a preferable blending amount when used for a stopper is 70% by weight or more, and more preferably 80% by weight or more.
  • soot pigment examples include organic or inorganic extender pigments and scaly pigments.
  • examples of the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, polyethylene oxide wax, and organic bentonite.
  • a curing accelerator can be used in the epoxy resin composition of the present invention as necessary.
  • examples include amines, imidazoles, organic phosphines, Lewis acids, etc., specifically 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, Tertiary amines such as ethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2- Imidazoles such as heptadecylimidazole, organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine, tetraphenylphosphonium tetraphenylbor
  • the resin composition of the present invention includes a release agent such as carnauba wax and OP wax, a coupling agent such as ⁇ -glycidoxypropyltrimethoxysilane, a colorant such as carbon black, and trioxide. Flame retardants such as antimony, low stress agents such as silicone 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, aramid nonwoven fabric, polyester nonwoven fabric such as liquid crystal polymer, and the like, and then the solvent is removed. It can be. Moreover, it can be set as a laminated body by apply
  • an epoxy resin cured product can be obtained.
  • This cured product is excellent in terms of curability, flame retardancy, low hygroscopicity, low elasticity, and the like.
  • 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 to 220 ° C.
  • Synthesis example 1 A 1 L 4-neck flask was charged with 250 g of phenol and 0.75 g of oxalic acid dihydrate as an acid catalyst, stirred while introducing nitrogen gas, heated and heated. Addition of 47.4 g of 37.4% formalin was started at 80 ° C., and the addition was completed in 30 minutes. Further, the reaction was carried out for 3 hours while maintaining the reaction temperature at 92 ° C. The temperature was raised to 110 ° C. while removing the reaction product water out of the system. The residual phenol was collected at 160 ° C. under reduced pressure. The temperature was further raised to recover a part of the binuclear body.
  • the obtained polyvalent hydroxy compound had a hydroxyl group equivalent of 104, a softening point of 68 ° C., and a melt viscosity at 150 ° C. of 0.07 Pa ⁇ s.
  • This resin is referred to as polyvalent hydroxy compound A.
  • a GPC chart of the polyvalent hydroxy compound A is shown in FIG.
  • Synthesis example 2 A 1 L 4-neck flask is charged with 250 g of phenol, 47.4 g of 7.4% formalin, and 150 g of 89% phosphoric acid as an acid catalyst, and heated under a cloudy state (two-phase mixture) formed by stirring and mixing. Went and warmed up. The reaction was further continued for 6 hours while maintaining the reflux temperature. Next, methyl isobutyl ketone was added to dissolve the resin component, and then allowed to stand to separate into a resin solution phase and a phosphoric acid aqueous solution phase. After removing the phosphoric acid solution phase, washing with water was further performed. Subsequently, the residual phenol was collected at 160 ° C. under reduced pressure.
  • the temperature was further raised to recover a part of the binuclear body.
  • the obtained polyvalent hydroxy compound had a hydroxyl group equivalent of 103, a softening point of 65 ° C., and a melt viscosity at 150 ° C. of 0.06 Pa ⁇ s.
  • This resin is referred to as polyvalent hydroxy compound B.
  • a GPC chart of the polyvalent hydroxy compound B is shown in FIG.
  • Example 1 A 1 L 4-necked flask was charged with 104 g of the polyhydroxy compound A obtained in Synthesis Example 1 as a polyvalent hydroxy compound component and 0.053 g (300 ppm) of p-toluenesulfonic acid as an acid catalyst. did. Next, while stirring at 120 ° C., 72.8 g (0.7 mol) of styrene was dropped over 3 hours to be reacted. Furthermore, after reacting at 120 ° C. for 1 hour, 168 g of a styrene-modified polyvalent hydroxy resin was obtained. The hydroxyl equivalent was 177, the softening point was 78 ° C., and the melt viscosity at 150 ° C. was 0.13 Pa ⁇ s. This resin is referred to as modified polyvalent hydroxy resin A (StPN-A). A GPC chart of StPN-A is shown in FIG.
  • Example 2 A 1 L 4-neck flask was charged with 103 g of the polyhydroxy compound B obtained in Synthesis Example 2 as a polyvalent hydroxy compound component and 0.053 g (300 ppm) of p-toluenesulfonic acid as an acid catalyst, and the temperature was raised to 120 ° C. did. Next, while stirring at 120 ° C., 72.8 g (0.7 mol) of styrene was dropped over 3 hours to be reacted. Furthermore, after reacting at 120 ° C. for 1 hour, 167 g of an aralkylstyrene-modified polyvalent hydroxy resin was obtained.
  • the hydroxyl equivalent was 176, the softening point was 78 ° C., and the melt viscosity at 150 ° C. was 0.13 Pa ⁇ s.
  • This resin is referred to as a modified polyvalent hydroxy resin B (StPN-B).
  • StPN-B modified polyvalent hydroxy resin B
  • Example 3 In a 1 L four-necked flask, 104 g of polyvalent hydroxy compound A obtained in Synthesis Example 1 and 1.0 g of water were charged as a polyvalent hydroxy compound component, and the temperature was raised to 120 ° C. Next, while stirring at 120 ° C., 88.6 g (0.7 mol) of benzyl chloride was dropped over 3 hours to be reacted. Furthermore, after reacting at 120 ° C. for 1 hour, 160 g of benzyl-modified polyvalent hydroxy resin was obtained. The hydroxyl equivalent was 168, the softening point was 70 ° C., and the melt viscosity at 150 ° C. was 0.09 Pa ⁇ s. This resin is referred to as modified polyvalent hydroxy resin C (StPN-C). A GPC chart of StPN-C is shown in FIG.
  • Example 4 In a four-necked separable flask, 150 g of StPN-A obtained in Example 1, 470 g of epichlorohydrin, and 71 g of diethylene glycol dimethyl ether were stirred and dissolved. After uniformly dissolving, maintaining at 65 ° C. under a reduced pressure of 130 mmHg, 70.6 g of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours, and the water and epichlorohydrin refluxed during the addition were separated in a separation tank, and epichlorohydrin was The mixture was returned to the reaction vessel, and water was removed from the system to react.
  • Example 5 In a four-necked separable flask, 150 g of StPN-B obtained in Example 2, 473 g of epichlorohydrin and 71 g of diethylene glycol dimethyl ether were added and dissolved by stirring. After uniformly dissolving, maintaining at 65 ° C. under a reduced pressure of 130 mmHg, 71.0 g of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours, and water and epichlorohydrin distilled under reflux were separated in the dropping tank, and epichlorohydrin was The mixture was returned to the reaction vessel, and water was removed from the system to react.
  • Example 6 In a four-necked separable flask, 150 g of StPN-C obtained in Example 3, 495 g of epichlorohydrin, and 74 g of diethylene glycol dimethyl ether were added and dissolved by stirring. After uniformly dissolving, maintaining at 65 ° C. under a reduced pressure of 130 mmHg, 74.4 g of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours, and water and epichlorohydrin distilled off during the addition were separated in a separation tank, and epichlorohydrin was The mixture was returned to the reaction vessel, and water was removed from the system to react.
  • Comparative Example 2 In a four-neck separable flask, 150 g of StPN-D obtained in Comparative Example 1, 468 g of epichlorohydrin, and 70 g of diethylene glycol dimethyl ether were added and dissolved by stirring. After uniformly dissolving, maintaining at 65 ° C. under a reduced pressure of 130 mmHg, 70.3 g of 48% aqueous sodium hydroxide solution was added dropwise over 4 hours, and the water and epichlorohydrin distilled off during the addition were separated in a separation tank, and epichlorohydrin was The mixture was returned to the reaction vessel, and water was removed from the system to react.
  • Examples 7-9 and Examples 10-11 (comparison) An o-cresol novolac type epoxy resin (OCNE; epoxy equivalent 200, softening point 65 ° C.) was used as an epoxy resin component, and StPN-A obtained in Example 1 and StPN-B obtained in Example 2 were used as curing agents. In addition to StPN-C obtained in Example 3 and StPN-D obtained in Comparative Example 1, phenol novolak (PN; PSM-4261 (manufactured by Gunei Chemical Industry); OH equivalent 103, softening point 82 ° C.) was used. .
  • PN o-cresol novolac type epoxy resin
  • Tg Glass transition point
  • CTE linear expansion coefficient
  • Examples 12-14 and Examples 15-16 (comparison) As epoxy resin components, StPNE-A obtained in Example 4, StPNE-B obtained in Example 5, StPNE-C obtained in Example 6, StPNE-D obtained in Comparative Example 2, and o-cresol Uses novolak epoxy resin (OCNE; epoxy equivalent 200, softening point 65 ° C.), and uses phenol aralkyl resin (PA; MEH-7800SS (Maywa Kasei), OH equivalent 175, softening point 67 ° C.) as a curing agent component. It was.
  • OCNE novolak epoxy resin
  • PA phenol aralkyl resin
  • PA MEH-7800SS
  • spherical silica (average particle size 18 ⁇ m) was used as a filler, triphenylphosphine was used as a curing accelerator, and an epoxy resin composition was obtained with the formulation shown in Table 3.
  • surface shows the weight part in a mixing
  • the epoxy resin and polyvalent hydroxy resin of the present invention When applied to an epoxy resin composition, the epoxy resin and polyvalent hydroxy resin of the present invention give a cured product that is excellent in curability and mechanical properties, and also excellent in flame retardancy, moisture resistance, and low elasticity. -It can be suitably used for applications such as sealing electronic parts and circuit board materials. In particular, the curability and flame retardancy are excellent, and the use of a flame retardant having an environmental load is made unnecessary or reduced while ensuring excellent moldability.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une résine époxy, une résine hydroxy polyvalente et une composition de celle-ci qui ont une excellente aptitude au durcissement, qui fournissent des produits durcis ayant d'excellentes résistance mécanique, résistance à la flamme, résistance à l'humidité, une faible élasticité, etc. et qui sont appropriés à des applications telles que l'encapsulation de composants électroniques, les matériaux de carte de circuit imprimé, etc. Cette résine hydroxy polyvalente est une résine hydroxy polyvalente dénaturée aralkyle qui est obtenue par réaction d'un composé hydroxy polyvalent à dispersion étroite avec un agent d'aralkylation de styrènes, etc., le composé hydroxy polyvalent à dispersion étroite comprenant 15% ou moins de n = 1 composant et 50% ou plus d'un total de n = 2 et n = 3 composants, et ayant une Mw/Mn de 1,2 ou moins. En outre, la présente invention est une résine epoxy obtenue par réaction d'une résine hydroxy polyvalente dénaturée aralkyle avec de l'épichlorohydrine. En outre, la présente invention est une composition de résine époxy qui contient, en tant que composant essentiel, la résine hydroxy polyvalente dénaturée aralkyle ou la résine époxy.
PCT/JP2013/054278 2012-02-23 2013-02-21 Résine hydroxy polyvalente, résine époxy, procédé de production de celle-ci, composition de résine époxy et produit durci de celle-ci WO2013125620A1 (fr)

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KR1020147026281A KR101987946B1 (ko) 2012-02-23 2013-02-21 다가 하이드록시 수지, 에폭시 수지, 그들의 제조방법, 에폭시 수지 조성물 및 그 경화물
SG11201405075SA SG11201405075SA (en) 2012-02-23 2013-02-21 Polyvalent hydroxy resin, epoxy resin, method for producing same, epoxy resin composition and cured product thereof
CN201380010483.7A CN104334597B (zh) 2012-02-23 2013-02-21 多元羟基树脂、环氧树脂、它们的制造方法、环氧树脂组合物及其固化物
JP2014500754A JP6124865B2 (ja) 2012-02-23 2013-02-21 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

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JP5614520B1 (ja) * 2012-11-12 2014-10-29 Dic株式会社 フェノール性水酸基含有樹脂、エポキシ樹脂、硬化性樹脂組成物、その硬化物、及び半導体封止材料
WO2017188455A1 (fr) * 2016-04-28 2017-11-02 日立化成株式会社 Composition de résine époxy et dispositif à composant électronique
JP2019104887A (ja) * 2017-12-14 2019-06-27 パナソニックＩｐマネジメント株式会社 封止用エポキシ樹脂組成物、硬化物、及び半導体装置
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JP5614520B1 (ja) * 2012-11-12 2014-10-29 Dic株式会社 フェノール性水酸基含有樹脂、エポキシ樹脂、硬化性樹脂組成物、その硬化物、及び半導体封止材料
WO2017188455A1 (fr) * 2016-04-28 2017-11-02 日立化成株式会社 Composition de résine époxy et dispositif à composant électronique
KR20180136494A (ko) * 2016-04-28 2018-12-24 히타치가세이가부시끼가이샤 에폭시 수지 조성물 및 전자 부품 장치
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KR102127589B1 (ko) * 2016-04-28 2020-06-26 히타치가세이가부시끼가이샤 에폭시 수지 조성물 및 전자 부품 장치
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JP2019104887A (ja) * 2017-12-14 2019-06-27 パナソニックＩｐマネジメント株式会社 封止用エポキシ樹脂組成物、硬化物、及び半導体装置
JP7142233B2 (ja) 2017-12-14 2022-09-27 パナソニックＩｐマネジメント株式会社 封止用エポキシ樹脂組成物、硬化物、及び半導体装置
US20220306794A1 (en) * 2021-03-29 2022-09-29 Chang Chun Plastics Co. Ltd. Polyhydric phenol resin, glycidyl ether of polyhydric phenol resin, and uses thereof
US11629216B2 (en) * 2021-03-29 2023-04-18 Chang Chun Plastics Co., Ltd. Polyhydric phenol resin, glycidyl ether of polyhydric phenol resin, and uses thereof

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SG11201405075SA (en) 2014-10-30
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