WO2012043414A1 - Epoxy resin composition and cured substance - Google Patents
Epoxy resin composition and cured substance Download PDFInfo
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- WO2012043414A1 WO2012043414A1 PCT/JP2011/071720 JP2011071720W WO2012043414A1 WO 2012043414 A1 WO2012043414 A1 WO 2012043414A1 JP 2011071720 W JP2011071720 W JP 2011071720W WO 2012043414 A1 WO2012043414 A1 WO 2012043414A1
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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
- C08G59/18—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
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
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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
- C08G59/18—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another
Definitions
- the present invention relates to an epoxy resin composition that provides a cured product that is excellent in flame retardancy and also excellent in fluidity and curability during molding, and the cured product.
- JP-A-11-140166 JP 2004-59792 A Japanese Patent Laid-Open No. 4-173831 JP 2000-129092 A Japanese Patent Laid-Open No. 3-90075 JP-A-3-281623 JP-A-8-120039 Japanese Patent Laid-Open No. 5-140265
- Patent Documents 1, 3, and 4 disclose an example in which an aralkyl epoxy resin having a biphenyl structure is applied to a semiconductor sealing material as an element that improves flame retardancy without containing phosphorus atoms or halogen atoms.
- Patent Document 2 discloses an example in which an aralkyl type epoxy resin having a naphthalene structure is used.
- Patent Documents 5 and 6 disclose a naphthol-based aralkyl epoxy resin and a semiconductor sealing material containing the naphthol-based aralkyl epoxy resin, but nothing focuses on flame retardancy.
- Patent Document 7 discloses benzylated polyphenol and its epoxy resin as an example focusing on improving heat resistance, moisture resistance and crack resistance, but these do not focus on flame retardancy.
- benzylated polyphenol type epoxy resins have a problem in flowability during molding as the molecular weight increases due to benzylation.
- Patent Document 8 discloses an epoxy resin composition containing a styrenated phenol novolac type epoxy resin, which is excellent in low water absorption and low stress, but does not focus on flame retardancy, Performance is not sufficient in fluidity during molding.
- the object of the present invention is to ensure non-halogen flame retardancy, and also has excellent performance in fluidity and curability during molding, for use in lamination, molding, casting, adhesion, etc.
- An object of the present invention is to provide a useful epoxy resin composition and a cured product thereof.
- the present invention provides an epoxy resin composition containing an epoxy resin, a phenolic curing agent, and an inorganic filler, wherein the epoxy resin component is an amorphous epoxy resin represented by the following general formula (1) and 150 ° C. Containing a bifunctional crystalline epoxy resin having a melt viscosity of 0.001 to 0.05 Pa ⁇ s, and the content of the amorphous epoxy resin represented by the following general formula (1) with respect to the entire epoxy resin
- the epoxy resin composition is characterized in that the content of the bifunctional crystalline epoxy resin is 30% by weight or more.
- G represents a glycidyl group
- R 1 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms
- R 2 represents a substituent represented by the following formula (a)
- n represents a number from 1 to 20.
- p represents a number from 0.1 to 2.5.
- R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
- the bifunctional crystalline epoxy resin component may be an epoxy resin represented by the following general formula (2).
- R 4 to R 11 are selected from a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms, and all may be the same or different.
- X is a single bond, —CH 2 —, —C ( CH 3 ) 2 —, —CO—, —O—, —S— or —SO 2 —, G represents a glycidyl group, and m represents a number from 0 to 3.
- the curing agent component preferably contains at least one of an aralkyl type phenolic curing agent and a novolac type phenolic curing agent.
- the present invention relates to the above-mentioned epoxy resin composition having an inorganic filler content of 70 to 95% by weight, and an epoxy resin cured product obtained by curing these epoxy resin compositions.
- the epoxy resin composition of the present invention comprises two kinds of epoxy resin components, a phenolic curing agent component and an inorganic filler as essential components.
- these essential components are contained in an amount of 50% by weight or more, preferably 80% by weight or more, more preferably 95% by weight or more.
- the epoxy resin represented by the general formula (1) which is the first type of epoxy resin component in the epoxy resin composition of the present invention will be described.
- the epoxy resin represented by the general formula (1) is an amorphous epoxy resin.
- the epoxy resin represented by the general formula (1) can be obtained by epoxidizing the styrene-added polyvalent hydroxy resin represented by the general formula (3).
- the styrene-added polyvalent hydroxy resin (also referred to as StPN) represented by the general formula (3) comprises a polyvalent hydroxy compound (also referred to as the polyvalent hydroxy compound (4)) represented by the general formula (4) and styrenes. It can be obtained by addition reaction.
- R 1 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms
- R 2 represents a substituent represented by the above formula (a)
- n represents a number of 0 to 20
- p represents 0 . Indicates a number from 1 to 2.5.
- R 1 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms
- n represents a number of 1 to 20
- the hydroxyl equivalent can be arbitrarily adjusted by adding styrene to the basic structure of the polyvalent hydroxy compound (4).
- the addition of styrenes means that the hydrogen of the benzene ring of the polyvalent hydroxy compound (4) is substituted with the substituent represented by the formula (a) (also referred to as a styrenyl group).
- the hydroxypropyl group generated by the reaction between the epoxy group and the hydroxyl group is said to burn easily, but by increasing the hydroxyl equivalent, aliphatic carbon of the flammable component derived from the epoxy group The rate is low and a high degree of flame retardancy can be expressed. Moreover, by adding styrene rich in aromaticity, the aromaticity is further improved, and it is effective in improving moisture resistance in addition to flame retardancy.
- a highly flame-retardant epoxy resin composition particularly an epoxy resin composition for semiconductor encapsulation, can be obtained using these.
- high flame retardancy, moisture resistance and low elasticity are exhibited in addition to excellent curability in these compositions, and highly reliable sealing of electrical and electronic parts and circuits using this material
- a substrate material or the like is obtained.
- StPN can be obtained by addition reaction of the polyvalent hydroxy compound (4) represented by the general formula (4) and styrenes.
- the ratio of the polyvalent hydroxy compound (4) and the styrenes is 0 when the ratio of the styrenes to 1 mol of the polyvalent hydroxy compound is 0 in consideration of the balance between flame retardancy and curability of the resulting cured product.
- the range is preferably from 1 to 2.5 mol, more preferably from 0.1 to 1.0 mol, still more preferably from 0.3 to 0.8 mol. When the amount is less than this range, the properties of the starting polyvalent hydroxy compound are not improved. When the amount is more than this range, the functional group density tends to be too low and the curability tends to decrease.
- R 1 represents a styryl group represented by the above formula (a).
- p represents a number of 0.1 to 2.5, and this means the average number (number average) of styryl groups substituted on one phenol ring.
- p is preferably in the order of 0.1 to 2 mol, 0.1 to 1.0 mol, 0.3 to 1 mol, and 0.3 to 0.8 mol.
- a maximum of 4 styryl groups can be substituted on the phenol ring at both ends, and a maximum of 3 styryl groups can be substituted on the intermediate phenol ring. Therefore, when n is 1, a maximum of 8 styryl groups can be substituted. it can.
- the StPN used in the present invention preferably has a substitution number (number average) of styryl groups per molecule of 1 or more, more preferably 2 or more, and still more preferably 2.6 to 4.
- R 3 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 3 is determined by the styrenes used as reaction raw materials.
- n represents a number of 1 to 20, preferably 1.5 to 5.0 on average.
- StCN is produced by reacting 0.1 to 2.5 moles of styrene in the presence of an acid catalyst with respect to 1 mole of the hydroxy group of the polyvalent hydroxy compound represented by the general formula (4).
- Typical examples of the polyvalent hydroxy compound represented by the general formula (4) include phenol novolac and cresol novolak.
- the amount of styrene used is from 0.1 to 2.5, preferably from 0.1 to 1.0, more preferably from 0.3 to 0.8, per mole of hydroxy group.
- the phenols used for obtaining the polyvalent hydroxy compound (4) are phenols or phenols substituted with a hydrocarbon group having 1 to 6 carbon atoms, preferably phenol or alkyl having 1 to 4 carbon atoms. Phenols substituted with a group, more preferably phenol. When phenol is used as the phenol, it may contain a small amount of other phenol components.
- These phenols or naphthols may contain 2 or more types.
- the styrene used for the reaction with the polyvalent hydroxy compound is styrene or styrene substituted with a hydrocarbon group having 1 to 6 carbon atoms, preferably styrene. These styrenes may contain a small amount of other reaction components. When styrene is used as the styrenes, other reaction components include ⁇ -methylstyrene, divinylbenzene, indene, coumarone, benzothiophene, indole, vinylnaphthalene, etc. In this case, the resulting polyvalent hydroxy compound includes a compound in which a group resulting therefrom is substituted on the aromatic ring.
- the reaction of the polyvalent hydroxy compound with the styrene can be carried out in the presence of an acid catalyst, and the amount of the catalyst used is in the range of 10 to 1000 ppm, preferably in the range of 100 to 500 ppm. If it is more than this, the methylene crosslinks of phenol novolac will be easily cleaved, and the unit price phenol component by-produced by the cleavage reaction will lower the curability and heat resistance. On the other hand, if it is less than this, the reactivity is lowered, and a large amount of unreacted styrene monomer remains.
- This 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 crosslink of phenol novolac is likely to be cleaved, and the unit price phenol component by-produced by the open-chain reaction reduces curability and heat resistance.
- 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 maintaining styrenes.
- a method of reacting while dropping is generally used. 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 a resin for use in the present invention. By doing so, the object can be obtained.
- the epoxy resin used in the present invention is a bifunctional crystalline epoxy resin having an epoxy resin represented by the general formula (1) and a melt viscosity at 150 ° C. of 0.001 to 0.05 Pa ⁇ s.
- the epoxy resin represented by the general formula (1) is abbreviated as StPNE
- a bifunctional crystalline epoxy resin having a melt viscosity at 150 ° C. of 0.001 to 0.05 Pa ⁇ s is referred to as a crystalline epoxy resin.
- StPNE can be obtained by epoxidizing the above StPN.
- G represents a glycidyl group, which is generated by the reaction of the hydroxyl group of the general formula (3).
- R 1 is a styrenyl group.
- PNStPNE used in the present invention is advantageously produced by reacting StPN represented by the above general formula (3) with epichlorohydrin, but is not limited to this reaction.
- StPN and allyl halide can be reacted to form an allyl ether compound and then reacted with peroxide.
- 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 30% by weight or more, preferably 30 to 70% by weight, more preferably 40 to 60% by weight of the epoxy resin represented by the general formula (1) in the total epoxy resin component. To do.
- the epoxy resin composition of the present invention 30 wt. Of bifunctional crystalline epoxy resin having a melt viscosity of 0.001 to 0.05 Pa ⁇ s at 150 ° C. is used as the second epoxy component in all epoxy resin components. % Or more, preferably 30 to 70% by weight, more preferably 40 to 60% by weight. If it is more than this, the flame retardancy will be reduced, and if it is less than this, the fluidity during molding, which is the object of the present invention, will not be sufficiently exhibited.
- the melt viscosity at 150 ° C. of the bifunctional crystalline epoxy resin is 0.001 to 0.05 Pa ⁇ s, preferably 0.005 to 0.03 Pa ⁇ s.
- the melt viscosity is higher than 0.05 Pa ⁇ s, it is difficult to increase the filling rate of the inorganic filler, and improvement in performance such as flame retardancy cannot be expected.
- an epoxy resin represented by the general formula (2) is preferably used.
- R 4 to R 11 are selected from a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. These may all be the same or different.
- X represents a single bond, —CH 2 —, —C (CH 3 ) 2 —, —CO—, —O—, —S— or —SO 2 —.
- G represents a glycidyl group.
- m represents a number from 0 to 3. When m is a resin composed of a plurality of components having different m, m represents the number average value.
- epoxy resins as shown in the following general formulas (5) to (14) are used.
- R 4 to R 11 are selected from a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms, and all may be the same or different.
- G represents a glycidyl group, and m represents a number from 0 to 3.
- the bifunctional crystalline epoxy resin may be used alone or in combination of two or more.
- these epoxy resins it is particularly preferable to use a biphenyl type epoxy resin, a bisphenol F type epoxy resin, and a sulfide type epoxy resin from the viewpoint of achieving both fluidity and flame retardancy.
- the bifunctional crystalline epoxy resin as described above can be synthesized by reacting a compound having a phenolic hydroxyl group typified by a bisphenol compound with epichlorohydrin. This reaction can be performed in the same manner as a normal epoxidation reaction.
- the bisphenol compound is used, for example, the bisphenol compound is dissolved in excess epichlorohydrin, and then in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, preferably at 50 to 150 ° C., preferably 60 to 120 ° C. Examples include a method of reacting for 1 to 10 hours.
- the amount of the alkali metal hydroxide used is 0.8 to 2 mol, preferably 0.9 to 1.2 mol, relative to 1 mol of the hydroxyl group of the bisphenol compound.
- excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove inorganic salts, and then the solvent is distilled off to obtain the desired It can be an epoxy resin.
- the amount of hydrolyzable chlorine in the epoxy resin used in the present invention is preferably small from the viewpoint of improving the reliability of the electronic component to be sealed. Although it does not specifically limit, 1000 ppm or less is preferable, More preferably, it is 500 ppm or less.
- the hydrolyzable chlorine as used in the field of this invention means the value measured by the following method.
- the epoxy resin composition of the present invention uses the epoxy resin represented by the general formula (1) as an epoxy resin component and a bifunctional crystalline epoxy resin as essential epoxy resins, but does not impair the purpose of the present invention.
- Other epoxy resins can be used in combination.
- epoxy resins examples include epoxidized products of divalent phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 2,2 ′ ⁇ -biphenol, resorcin, naphthalenediols (showing crystallinity).
- Epoxides of trivalent or higher phenols such as tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, etc.
- Epoxidized products of co-condensation resins of dicyclopentadiene and phenols Epoxidized products of co-condensation resins of dicyclopentadiene and phenols, epoxidized products of phenol aralkyl resins synthesized from phenols and paraxylylene dichloride, biphenyl arals synthesized from phenols and bischloromethylbiphenyl, etc.
- Le type phenol resin epoxy compound, epoxidized naphthol aralkyl resin and the like which are synthesized from naphthols and para-xylylene dichloride and the like.
- These epoxy resins may be used alone or in combination of two or more. These blending amounts may be in a range that does not impair the object of the present invention, but are less than 50% by weight with respect to the total of StPNE and the bifunctional crystalline epoxy resin.
- phenolic curing agent used in the epoxy resin composition of the present invention include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, and resorcinol.
- Divalent phenols such as catechol and naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol Trivalent or higher phenols represented by novolak, polyvinylphenol, etc., as well as phenols, naphthols, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4'-biphenol, 2,2'-bi Divalent phenols such as phenol, hydroquinone, resorcin, catechol, naphthalenediol and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, p-xylylene glycol, p-xylylene glycol dimethyl ether, divinylbenzene, diisopropenylbenzene And polyphenolic compounds
- the softening point range of the phenolic curing agent is preferably 40 to 150 ° C, more preferably 50 to 120 ° C. If it is lower than this, there is a problem of blocking during storage, and if it is higher than this, there is a problem in kneadability and moldability during preparation of the epoxy resin composition. Further, the melt viscosity at 150 ° C. is preferably 1 Pa ⁇ s or less, more preferably 0.5 Pa ⁇ s or less. When higher than this, there exists a problem in kneadability at the time of preparation of an epoxy resin composition, and a moldability.
- the blending ratio of the epoxy resin and the curing agent is preferably in the range of 0.8 to 1.5 in terms of an equivalent ratio of the epoxy group and the functional group in the curing agent. Outside this range, unreacted epoxy groups or functional groups in the curing agent remain even after curing, and physical properties such as reliability and water absorption when the cured product is reduced.
- Examples of the inorganic filler used in the present invention include silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, mullite, and titania.
- fused silica as a main component, and examples of the form include crushed or spherical ones.
- silica is used in combination with those having several kinds of particle size distributions.
- the average particle diameter of the silica to be combined is preferably 0.5 to 100 ⁇ m.
- the content of the inorganic filler is preferably in the range of 70 to 95% by weight, preferably 80 to 95% by weight, and more preferably 85 to 95% by weight. If it is smaller than this, the content of the organic component becomes high, and the flame retardancy is not sufficiently exhibited. On the other hand, if it is larger than this, the thermal conductivity of the molded product will increase, so that the decomposition rate of the organic component will increase, and the amount of heat-insulating carbonized layer will decrease, making it difficult to exhibit flame retardancy.
- an oligomer or a polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene coumarone resin, or phenoxy resin is appropriately blended as necessary.
- 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 scaly pigments.
- the thixotropic agent include silicon-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax, and organic bentonite-based.
- 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.
- a flame retardant such as antimony, a low stress agent such as silicone oil, a lubricant such as calcium stearate, and the like can be blended.
- the cured product of the present invention can be obtained by curing the epoxy resin composition by a molding method such as casting, compression molding, transfer molding or the like.
- the temperature at which the cured product is produced is usually 120 to 220 ° C.
- Synthesis example 2 Synthesis of epoxy resin
- 150 g of StPN-A obtained in Synthesis 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 refluxed during this 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.
- epoxy resin B epoxidized product of 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylmethane (YSLV-80XY; epoxy equivalent 193, melting point) Melt viscosity at 78 ° C. and 150 ° C. 0.008 Pa ⁇ s, manufactured by Nippon Steel Chemical Co., Ltd.) was used. Further, as a comparative epoxy resin, an epoxy resin C: o-cresol novolac type epoxy resin (epoxy equivalent 200, softening point 65 ° C., manufactured by Nippon Steel Chemical Co., Ltd.) was used.
- phenol aralkyl resin (PA; MEH-7800SS (Maywa Kasei), OH equivalent 175, softening point 67 ° C.) or phenol novolak (PN; PSM-4261 (Gunei Chemical)), OH equivalent 103, softening Point 82 ° C) was used.
- Adhesive strength A molded product of 25 mm x 12.5 mm x 0.5 mm was formed between two copper plates at 175 ° C with a compression molding machine, post-cured at 180 ° C for 12 hours, and then subjected to tensile shear strength. Evaluated by seeking.
- the epoxy resin composition of the present invention is excellent in fluidity and curability, and gives a cured product excellent in flame retardancy, moisture resistance and low elasticity, such as sealing of electric / electronic parts, circuit board materials, etc. It is possible to use it suitably for a use.
- the fluidity 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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Abstract
Description
(一般式(1)において、Gはグリシジル基を示し、R1は水素又は炭素数1~6の炭化水素基を示し、R2は下記式(a)で表される置換基を示し、nは1~20の数を示す。また、pは0.1~2.5の数を示す。式(a)において、R3は水素原子又は炭素数1~6の炭化水素基を示す。)
(In general formula (1), G represents a glycidyl group, R 1 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R 2 represents a substituent represented by the following formula (a), n Represents a number from 1 to 20. p represents a number from 0.1 to 2.5. In the formula (a), R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)
(ここで、R4~R11は水素原子及び炭素数1~6の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。Xは、単結合、-CH2-、-C(CH3)2-、-CO-、-O-、-S-または-SO2-を示す。Gはグリシジル基を示し、mは0~3の数を示す。) The bifunctional crystalline epoxy resin component may be an epoxy resin represented by the following general formula (2).
(Here, R 4 to R 11 are selected from a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms, and all may be the same or different. X is a single bond, —CH 2 —, —C ( CH 3 ) 2 —, —CO—, —O—, —S— or —SO 2 —, G represents a glycidyl group, and m represents a number from 0 to 3.)
(R1は水素又は炭素数1~6の炭化水素基を示し、R2は上記式(a)で表される置換基を示し、nは0~20の数を示す。また、pは0.1~2.5の数を示す。)
(ここで、R1は水素又は炭素数1~6の炭化水素基を示し、nは1~20の数を示す。)
(R 1 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R 2 represents a substituent represented by the above formula (a), n represents a number of 0 to 20, and p represents 0 . Indicates a number from 1 to 2.5.)
(Wherein R 1 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and n represents a number of 1 to 20)
別の観点からは、本発明に使用するStPNは、1分子あたりのスチレニル基の置換数(数平均)は、1以上であることが好ましく、より好ましくは2以上、更に好ましくは2.6~4である。 In general formula (3) and general formula (1), a common symbol has the same meaning. R 1 represents a styryl group represented by the above formula (a). p represents a number of 0.1 to 2.5, and this means the average number (number average) of styryl groups substituted on one phenol ring. p is preferably in the order of 0.1 to 2 mol, 0.1 to 1.0 mol, 0.3 to 1 mol, and 0.3 to 0.8 mol. In addition, a maximum of 4 styryl groups can be substituted on the phenol ring at both ends, and a maximum of 3 styryl groups can be substituted on the intermediate phenol ring. Therefore, when n is 1, a maximum of 8 styryl groups can be substituted. it can.
From another point of view, the StPN used in the present invention preferably has a substitution number (number average) of styryl groups per molecule of 1 or more, more preferably 2 or more, and still more preferably 2.6 to 4.
以下、一般式(1)で示されるエポキシ樹脂をStPNEと略記し、150℃での溶融粘度が0.001~0.05Pa・sである二官能結晶性エポキシ樹脂を結晶性エポキシ樹脂ということがある。StPNEは、上記StPNをエポキシ化することにより得ることができる。 The epoxy resin used in the present invention is a bifunctional crystalline epoxy resin having an epoxy resin represented by the general formula (1) and a melt viscosity at 150 ° C. of 0.001 to 0.05 Pa · s.
Hereinafter, the epoxy resin represented by the general formula (1) is abbreviated as StPNE, and a bifunctional crystalline epoxy resin having a melt viscosity at 150 ° C. of 0.001 to 0.05 Pa · s is referred to as a crystalline epoxy resin. is there. StPNE can be obtained by epoxidizing the above StPN.
(多価ヒドロキシ樹脂の合成)
合成例1
1Lの4口フラスコに、多価ヒドロキシ化合物成分としてフェノールノボラック(昭和高分子製;BRG-555、水酸基当量105g/eq.、軟化点67℃、150℃での溶融粘度0.08Pa・s)を105g、トルエン5.3g、酸触媒としてp-トルエンスルホン酸0.055g(300ppm)を仕込み100℃に昇温した。次に、100℃にて攪拌しながら、スチレン73g(0.7モル)を3時間かけて滴下し反応させた。さらに、100℃にて2時間反応後、30%Na2CO30.049gを添加し中和を行った。次に、MIBK330gに溶解させ、80℃にて5回水洗を行った。続いて、MIBKを減圧留去した後、多価ヒドロキシ樹脂170gを得た。その水酸基当量は178g/eq.、軟化点は78℃、150℃での溶融粘度は0.13Pa・sであった。この樹脂をStPN-Aという。 Hereinafter, based on a synthesis example, an Example, and a comparative example, this invention is demonstrated concretely.
(Synthesis of polyvalent hydroxy resin)
Synthesis example 1
Into a 1 L four-necked flask, phenol novolak (manufactured by Showa Polymer; BRG-555, hydroxyl group equivalent of 105 g / eq., Softening point 67 ° C., melt viscosity 0.080 Pa · s at 150 ° C.) as a polyvalent hydroxy compound component. 105 g, 5.3 g of toluene, and 0.055 g (300 ppm) of p-toluenesulfonic acid as an acid catalyst were charged, and the temperature was raised to 100 ° C. Next, with stirring at 100 ° C., 73 g (0.7 mol) of styrene was dropped over 3 hours to be reacted. Furthermore, after reacting at 100 ° C. for 2 hours, 0.049 g of 30% Na 2 CO 3 was added for neutralization. Next, it was dissolved in 330 g of MIBK and washed 5 times with water at 80 ° C. Subsequently, after MIBK was distilled off under reduced pressure, 170 g of a polyvalent hydroxy resin was obtained. Its hydroxyl equivalent is 178 g / eq. The softening point was 78 ° C., and the melt viscosity at 150 ° C. was 0.13 Pa · s. This resin is referred to as StPN-A.
(エポキシ樹脂の合成)
四つ口セパラブルフラスコに合成例1で得たStPN-A150g、エピクロルヒドリン468g、ジエチレングリコールジメチルエーテル70gを入れ撹拌溶解させた。均一に溶解後、130mmHgの減圧下65℃に保ち、48%水酸化ナトリウム水溶液70.3gを4時間かけて滴下し、この滴下中に還流留出した水とエピクロルヒドリンを分離槽で分離しエピクロルヒドリンは反応容器に戻し、水は系外に除いて反応した。反応終了後、濾過により生成した塩を除き、更に水洗したのちエピクロルヒドリンを留去し、エポキシ樹脂185gを得た(StPNE-A)。得られた樹脂のエポキシ当量は246g/eq.、軟化点は56℃、150℃における溶融粘度は0.10Pa・sであった。 Synthesis example 2
(Synthesis of epoxy resin)
In a four-necked separable flask, 150 g of StPN-A obtained in Synthesis 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 refluxed during this 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. After completion of the reaction, the salt produced by filtration was removed, and after further washing with water, epichlorohydrin was distilled off to obtain 185 g of an epoxy resin (StPNE-A). The epoxy equivalent of the obtained resin was 246 g / eq. The softening point was 56 ° C. and the melt viscosity at 150 ° C. was 0.10 Pa · s.
上記の合成例2で得られたエポキシ樹脂(StPNE-A)、下記に示すエポキシ樹脂、硬化剤、及び無機充填材と硬化促進剤としてのトリフェニルホスフィンと、その他の添加剤を表1~2に示す配合割合で混練してエポキシ樹脂組成物を調製した。表中の数値は配合における重量部を示す。
二官能結晶性エポキシ樹脂として、エポキシ樹脂A:3,3',5,5’-テトラメチル-4,4’-ジヒドロキシビフェニルのエポキシ化物 (YX4000H;エポキシ当量195、融点105℃、150℃での溶融粘度0.011Pa・s、三菱化学製)、エポキシ樹脂B:3,3’,5,5’-テトラメチル-4,4’-ジヒドロキシジフェニルメタンのエポキシ化物 (YSLV-80XY;エポキシ当量193、融点78℃、150℃での溶融粘度0.008Pa・s、新日鐵化学製)を用いた。また、比較のエポキシ樹脂として、エポキシ樹脂C:o-クレゾールノボラック型エポキシ樹脂(エポキシ当量200、軟化点65℃、新日鐵化学製)を用いた。
硬化剤成分として、フェノールアラルキル樹脂(PA;MEH-7800SS(明和化成製)、OH当量175、軟化点67℃)又はフェノールノボラック(PN;PSM-4261(群栄化学製)、OH当量103、軟化点 82℃)を用いた。 Examples 1 to 4 and Comparative Examples 1 to 3
The epoxy resin (StPNE-A) obtained in Synthesis Example 2 above, the epoxy resin shown below, a curing agent, an inorganic filler, triphenylphosphine as a curing accelerator, and other additives are shown in Tables 1-2. An epoxy resin composition was prepared by kneading at a blending ratio shown in FIG. The numerical value in a table | surface shows the weight part in mixing | blending.
As a bifunctional crystalline epoxy resin, epoxy resin A: epoxidized product of 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl (YX4000H; epoxy equivalent 195, melting point 105 ° C., 150 ° C. Melt viscosity 0.011 Pa · s, manufactured by Mitsubishi Chemical), epoxy resin B: epoxidized product of 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylmethane (YSLV-80XY; epoxy equivalent 193, melting point) Melt viscosity at 78 ° C. and 150 ° C. 0.008 Pa · s, manufactured by Nippon Steel Chemical Co., Ltd.) was used. Further, as a comparative epoxy resin, an epoxy resin C: o-cresol novolac type epoxy resin (epoxy equivalent 200, softening point 65 ° C., manufactured by Nippon Steel Chemical Co., Ltd.) was used.
As a hardener component, phenol aralkyl resin (PA; MEH-7800SS (Maywa Kasei), OH equivalent 175, softening point 67 ° C.) or phenol novolak (PN; PSM-4261 (Gunei Chemical)), OH equivalent 103, softening Point 82 ° C) was used.
電位差滴定装置を用い、溶媒としてメチルエチルケトンを使用し、臭素化テトラエチルアンモニウム酢酸溶液を加え、電位差滴定装置にて0.1mol/L過塩素酸-酢酸溶液を用いて測定した。 1) Measurement of epoxy equivalent Using a potentiometric titrator, methyl ethyl ketone was used as a solvent, a brominated tetraethylammonium acetic acid solution was added, and a 0.1 mol / L perchloric acid-acetic acid solution was measured with a potentiometric titrator.
自動軟化点装置(明峰社製作所(株)製、ASP-M4SP)を用い、JIS-K-2207に従い環球法にて測定した。 2) Softening point Measured by the ring and ball method according to JIS-K-2207, using an automatic softening point apparatus (ASP-M4SP, manufactured by Meihosha Mfg. Co., Ltd.).
BROOKFIELD製、CAP2000H型回転粘度計を用いて、150℃にて測定した。 3) Melt viscosity The viscosity was measured at 150 ° C. using a CAP2000H rotational viscometer manufactured by BROOKFIELD.
175℃に加熱しておいたゲル化試験機(日新科学(株)製)のプレート上にエポキシ樹脂組成物を添加し、フッ素樹脂棒を用いて一秒間に2回転の速度で攪拌し、エポキシ樹脂組成物が硬化するまでに要したゲル化時間を調べた。 4) Gel time An epoxy resin composition is added onto a plate of a gelation tester (manufactured by Nisshin Kagaku Co., Ltd.) that has been heated to 175 ° C., and is rotated at a rate of 2 revolutions per second using a fluororesin rod. The gelation time required for stirring and curing of the epoxy resin composition was examined.
スパイラルフローについては、規格(EMMI-1-66)に準拠したスパイラルフロー測定用金型でエポキシ樹脂組成物をスパイラルフローの注入圧力(150Kgf/cm2)、硬化時間3分の条件で成形して流動長を調べた。 5) Spiral flow For spiral flow, the epoxy resin composition was injected into the spiral flow measurement mold in accordance with the standard (EMMI-1-66), the injection pressure of spiral flow (150 kgf / cm 2 ), and the curing time of 3 minutes. And the flow length was examined.
セイコーインスツル製TMA120C型熱機械測定装置により、昇温速度10℃/分の条件で、Tgを求め、α1(Tg以下のCTE)は30~50℃の範囲の平均値を、またα2(Tg以上のCTE)はTgプラス20℃~40℃の範囲の平均値から求めた。 6) Linear expansion coefficient (CTE), glass transition point (Tg)
Using a TMA120C thermomechanical measuring device manufactured by Seiko Instruments Inc., Tg was determined under the condition of a temperature increase rate of 10 ° C./min. Α1 (CTE of Tg or less) was an average value in the range of 30 to 50 ° C., and α2 (Tg The above CTE) was determined from the average value of Tg plus 20 ° C to 40 ° C.
JISK 6911に従い、3点曲げ試験法で常温にて測定した。 7) Bending strength and bending elasticity According to JISK6911, it measured at normal temperature by the three-point bending test method.
銅板2枚の間に25mm×12.5mm×0.5mmの成形物を圧縮成形機により175℃で成形し、180℃にて12時間ポストキュアを行った後、引張剪断強度を求めることにより評価した。 8) Adhesive strength A molded product of 25 mm x 12.5 mm x 0.5 mm was formed between two copper plates at 175 ° C with a compression molding machine, post-cured at 180 ° C for 12 hours, and then subjected to tensile shear strength. Evaluated by seeking.
25℃、相対湿度50%の条件を標準状態とし、85℃、相対湿度85%の条件で100時間吸湿させた後の重量変化率とした。 9) Water absorption rate The conditions of 25 ° C. and 50% relative humidity were set to the standard state, and the weight change rate after absorbing water for 100 hours under the conditions of 85 ° C. and 85% relative humidity.
厚さ1/16インチの試験片を成形し、UL94V-0規格によって評価し、5本の試験片での合計の燃焼時間で表した。 10) Flame retardance A test piece having a thickness of 1/16 inch was molded, evaluated according to the UL94V-0 standard, and represented by the total burning time of five test pieces.
Claims (5)
- エポキシ樹脂、フェノール系硬化剤、及び無機充填材を含有するエポキシ樹脂組成物において、エポキシ樹脂成分が、下記一般式(1)で示される非結晶性のエポキシ樹脂と150℃での溶融粘度が0.001~0.05Pa・sである二官能結晶性エポキシ樹脂を含有し、エポキシ樹脂全体に対し、下記一般式(1)で示される非結晶性のエポキシ樹脂の含有量が30重量%以上であり、二官能結晶性エポキシ樹脂の含有量が30重量%以上であることを特徴とするエポキシ樹脂組成物。
ここで、Gはグリシジル基を示し、R1は水素又は炭素数1~6の炭化水素基を示し、R2は下記式(a)で表される置換基を示し、nは1~20の数を示す。また、pは0.1~2.5の数を示す。
ここで、R3は水素又は炭素数1~6の炭化水素基を示す。 In an epoxy resin composition containing an epoxy resin, a phenolic curing agent, and an inorganic filler, the epoxy resin component has an amorphous epoxy resin represented by the following general formula (1) and a melt viscosity of 0 at 150 ° C. A bifunctional crystalline epoxy resin of 0.001 to 0.05 Pa · s, and the content of the amorphous epoxy resin represented by the following general formula (1) is 30% by weight or more based on the whole epoxy resin And an epoxy resin composition, wherein the content of the bifunctional crystalline epoxy resin is 30% by weight or more.
Here, G represents a glycidyl group, R 1 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R 2 represents a substituent represented by the following formula (a), and n represents 1 to 20 Indicates a number. P represents a number of 0.1 to 2.5.
Here, R 3 represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. - 2官能結晶性エポキシ樹脂成分が、下記一般式(2)で示されるエポキシ樹脂である請求項1に記載のエポキシ樹脂組成物。
ここで、R4~R11は水素及び炭素数1~6の炭化水素基から選ばれ、全てが同一でも異なっていてもよい。Xは、単結合、-CH2-、-C(CH3)2-、-CO-、-O-、-S-または-SO2-を示す。Gはグリシジル基を示し、mは0~3の数を示す。 The epoxy resin composition according to claim 1, wherein the bifunctional crystalline epoxy resin component is an epoxy resin represented by the following general formula (2).
Here, R 4 to R 11 are selected from hydrogen and a hydrocarbon group having 1 to 6 carbon atoms, and all may be the same or different. X represents a single bond, —CH 2 —, —C (CH 3 ) 2 —, —CO—, —O—, —S— or —SO 2 —. G represents a glycidyl group, and m represents a number from 0 to 3. - フェノール系硬化剤成分が、アラルキル型フェノール系硬化剤及びノボラック型フェノール系硬化剤から選ばれる少なくとも1種を含有するものである請求項1に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 1, wherein the phenolic curing agent component contains at least one selected from an aralkyl type phenolic curing agent and a novolac type phenolic curing agent.
- 無機充填材の含有率が70~95重量%である請求項1に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 1, wherein the content of the inorganic filler is 70 to 95% by weight.
- 請求項1~4のいずれかに記載のエポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物。 A cured epoxy resin obtained by curing the epoxy resin composition according to any one of claims 1 to 4.
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JPH08165328A (en) * | 1994-12-14 | 1996-06-25 | Toto Kasei Co Ltd | Lowly dielectric epoxy resin composition |
JP2007297539A (en) * | 2006-05-01 | 2007-11-15 | Nippon Steel Chem Co Ltd | Epoxy resin composition and cured product |
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JPH08165328A (en) * | 1994-12-14 | 1996-06-25 | Toto Kasei Co Ltd | Lowly dielectric epoxy resin composition |
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