WO2013183735A1 - エポキシ樹脂、エポキシ樹脂組成物および硬化物 - Google Patents
エポキシ樹脂、エポキシ樹脂組成物および硬化物 Download PDFInfo
- Publication number
- WO2013183735A1 WO2013183735A1 PCT/JP2013/065755 JP2013065755W WO2013183735A1 WO 2013183735 A1 WO2013183735 A1 WO 2013183735A1 JP 2013065755 W JP2013065755 W JP 2013065755W WO 2013183735 A1 WO2013183735 A1 WO 2013183735A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- ppm
- resin composition
- epoxy
- reaction
- Prior art date
Links
Classifications
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Definitions
- the present invention relates to an epoxy resin, an epoxy resin composition, and a cured product thereof suitable for use in electrical and electronic materials requiring heat resistance.
- Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.
- heat resistance has been regarded as important, but in general, when heat resistance is increased, problems such as poor water absorption properties and poor flame retardancy occur at the same time, making it difficult to achieve both. Therefore, it has been desired to develop an epoxy resin that can satisfy both heat resistance and contradictory characteristics.
- the present invention (1) An epoxy resin containing 70 to 95% (gel permeation chromatography area%) of a compound represented by the following formula (1) as a main component.
- the cured product of the epoxy resin of the present invention has excellent heat resistance, water absorption characteristics, and flame retardancy, it is used for insulating materials for electrical and electronic parts, laminated boards (printed wiring boards, build-up boards, etc.) and CFRP. It is useful for various composite materials, adhesives, paints and the like.
- the epoxy resin of the present invention relates to an epoxy resin having a phenolphthalein skeleton derivative structure.
- the basic skeleton of the epoxy resin of the present invention is disclosed in British Patent No. 1158606 (Patent Document 1).
- epoxy equivalents per kg is 3.4 (294 g / eq.
- hue is Gardner 8 (40% in methyl glycol)
- softening point is 66 ° C. (kolfer heater)
- An epoxy resin having a phenolphthalein skeleton derivative structure having a chlorine content of 2.2% is disclosed.
- cured physical properties with DDS diaminodiphenyl sulfone
- the epoxy resin of the present invention has the following formula (1)
- the electrical reliability is lowered and a large coloring is caused, so that the epoxy resin having a phenolphthalein structure is not preferable, preferably 2 % Or less, particularly preferably 1% or less.
- the epoxy resin having this phenolphthalein structure is greatly influenced by impurities derived from raw materials. If it exceeds 2%, coloring is particularly strong, which is not preferable.
- R is a hydrogen atom.
- alkyl group having 1 to 6 carbon atoms represented by R include alkyl groups having a linear, branched or cyclic structure such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. Can be mentioned.
- R is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
- alkoxy group having 1 to 6 carbon atoms represented by R include an alkoxy group having a linear, branched or cyclic structure such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.
- R is preferably a methoxy group, an ethoxy group, or a propoxy group, and particularly preferably a methoxy group.
- the epoxy equivalent is 1.02 to 1.13 times the theoretical epoxy equivalent. More preferably, it is 1.03 to 1.10 times. If the ratio is less than 1.02, the epoxy synthesis and purification may be very expensive. If the ratio is more than 1.11, the problem may be caused by the amount of chlorine as described above. Further, the total chlorine remaining in the epoxy resin obtained by the reaction is preferably 5000 ppm or less, more preferably 3000 ppm or less, and particularly preferably 2000 ppm or less. The adverse effect of the chlorine amount is the same as described above. In addition, about chlorine ion and sodium ion, 5 ppm or less is preferable respectively, More preferably, it is 3 ppm or less.
- Chlorine ions are described above. Needless to say, cations such as sodium ions are also very important factors particularly in power device applications, and contribute to a defective mode when a high voltage is applied.
- the theoretical epoxy equivalent refers to an epoxy equivalent calculated when the phenolic hydroxyl group of the phenol compound represented by the following formula (P) is glycidylated without excess or deficiency.
- the epoxy resin of the present invention has a resinous form having a softening point.
- the softening point is preferably from 70 to 130 ° C, more preferably from 80 to 120 ° C.
- the temperature is particularly 70 to 120 ° C, more preferably 80 to 110 ° C. If the softening point is too low, blocking during storage becomes a problem, and there are many problems such as handling at low temperatures. On the other hand, if the softening point is too high, problems such as poor handling may occur during kneading with other resins.
- the melt viscosity is preferably 1 Pa ⁇ s or less (ICI melt viscosity, 150 ° C., cone plate method). When mixing and using an inorganic material (filler etc.), the fluidity
- the epoxy resin of the present invention is excellent in transparency (hue). It is preferably 2 or less, more preferably 1.5 or less by Gardner colorimetric method (visually 40% MEK (methyl ethyl ketone) solution). In particular, development on optical materials as well as ordinary PCB substrates and the like affect the color of the substrate, so that a material with less coloring is required.
- the epoxy resin of the present invention has a high refractive index. It is preferably 1.61 or more, more preferably 1.62 or more, and particularly preferably 1.62 to 1.65. Particularly in the field where refractive index adjustment is required, if the refractive index is high, the amount of aromatic rings in the composition used can be reduced, which can contribute to improvement in light resistance. In addition, in applications such as lenses, a lens having a smaller distortion can be produced as the refractive index is higher.
- the epoxy resin of the present invention containing the compound represented by the formula (1) is represented by the formula (P) synthesized from a phenolphthalein derivative and an aminobenzene derivative (for example, Japanese Patent Application Laid-Open No. 2005-2005). 290378), which is obtained by the reaction of a phenolic compound (DPPI) and epihalohydrin.
- P phenolphthalein derivative
- DPPI phenolic compound
- phenolphthalein derivatives can be synthesized with phthalic acid and various corresponding phenols. If the phenols used are phenol, phenolphthalein is obtained, and if cresols, cresolphthalein is obtained. .
- examples of the various phenols include phenol, cresol, ethylphenol, propylphenol, xylenol, and methylbutylphenol.
- the structure represented by following formula (2) is mentioned, for example.
- aminobenzene derivatives include those represented by the following formula (3).
- the amount of residual phenolphthalein derivative in the phenol compound (DPPI) is preferably 2% or less, more preferably 1% or less, still more preferably 0.5% or less, and particularly preferably 0.1% or less (high performance liquid chromatography). Measured graphically). When this phenolphthalein derivative remains, coloring tends to increase during the reaction. The same applies to aminobenzene derivatives. Further, the remaining iron content (ICP emission analysis) is one of the factors caused by coloring. The residual iron content is preferably 100 ppm or less, more preferably 50 ppm or less, and particularly preferably 10 ppm or less.
- the phenol compound (DPPI) as the main body is desired to have a purity of 98% or more. The amount of residual phenolphthalein derivative can be adjusted by purification of DPPI (washing, recrystallization, reprecipitation, etc.).
- the epihalohydrin is preferably epichlorohydrin which is easily available industrially.
- the amount of epihalohydrin used is usually 3.0 to 15 mol, preferably 3.0 to 10 mol, more preferably 3.5 to 8.5 mol, particularly preferably 1 mol per mol of the hydroxyl group of the phenol compound (DPPI). 5.5 to 8.5 moles. If the amount is less than 3.0 mol, the epoxy equivalent may increase, and the workability of the resulting epoxy resin may deteriorate. If it exceeds 15 moles, the amount of solvent becomes large.
- alkali metal hydroxide examples include sodium hydroxide, potassium hydroxide and the like, and a solid substance may be used, or an aqueous solution thereof may be used. From the viewpoint of solubility and handling, it is preferable to use a solid material molded into a flake shape.
- the amount of the alkali metal hydroxide used is usually 0.90 to 1.5 mol, preferably 0.95 to 1.25 mol, more preferably 0.99 to 1 mol per mol of hydroxyl group in the raw material phenol mixture. .15 moles.
- quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride may be added as a catalyst.
- the amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of hydroxyl group in the raw material phenol mixture.
- a nonpolar proton solvent dimethyl sulfoxide, dioxane, dimethylimidazolidinone, etc.
- an alcohol having 1 to 5 carbon atoms include alcohols such as methanol, ethanol and isopropyl alcohol.
- the amount of the nonpolar protic solvent or alcohol having 1 to 5 carbon atoms is usually 2 to 50% by weight, preferably 4 to 25% by weight, based on the amount of epihalohydrin used.
- epoxidation may be performed while controlling the moisture in the system by a technique such as azeotropic dehydration.
- the electrical reliability of the obtained epoxy resin may be deteriorated, and the water content is preferably controlled to 5% or less.
- an epoxy resin is obtained using a nonpolar proton solvent, an epoxy resin excellent in electrical reliability can be obtained, and therefore a nonpolar proton solvent can be suitably used.
- the reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. In particular, in the present invention, 60 ° C. or higher is preferable for higher purity epoxidation, and a reaction under conditions close to reflux conditions is particularly preferable.
- the reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 3 hours. If the reaction time is short, the reaction does not proceed, and if the reaction time is long, a by-product is formed, which is not preferable. After the reaction product of these epoxidation reactions is washed with water or without washing with water, the epihalohydrin, the solvent, and the like are removed under reduced pressure by heating.
- the recovered epoxy resin is a solvent of a ketone compound having 4 to 7 carbon atoms (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.). It can also be dissolved, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be added to carry out the reaction to ensure ring closure.
- a ketone compound having 4 to 7 carbon atoms for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.
- the amount of the alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, relative to 1 mol of the hydroxyl group of the starting phenol mixture used for epoxidation.
- the reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
- the reaction with epihalohydrin it is preferably substituted with an inert gas such as nitrogen from the beginning of the reaction, and the oxygen concentration in the cavity is preferably 10% or less. Oxygen residue affects coloration.
- an inert gas such as nitrogen is blown in the atmosphere (in the air or in the liquid) before the phenol compound (DPPI) is charged, or a vacuum is once applied under reduced pressure and then the inert gas is replaced. If there is no substitution with an inert gas, the resulting resin may be colored.
- the inert gas is blown, the amount varies depending on the volume of the reaction vessel, but the amount of inert gas blown can replace 1 to 3 times the volume of the reaction vessel in 0.5 to 10 hours. Is preferred.
- the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention.
- the epoxy resin composition of the present invention contains the epoxy resin of the present invention and a curing catalyst as essential components. Moreover, it is preferable to contain another epoxy resin and a hardening
- the epoxy resin composition of the present invention may contain an epoxy resin in addition to the epoxy resin of the present invention.
- the proportion of the epoxy resin of the present invention in all epoxy resins is preferably 20% by weight or more, more preferably 30% by weight or more, and particularly preferably 40% by weight or more.
- bisphenol A bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetofu Non, o-hydroxy
- the epoxy resin of the present invention is preferably used in combination with an alicyclic epoxy resin or an epoxy resin having a silsesquioxane structure.
- an alicyclic epoxy resin a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
- esterification reaction of cyclohexene carboxylic acid and alcohol or esterification reaction of cyclohexene methanol and carboxylic acid (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980) Or the Tyshenko reaction of cyclohexene aldehyde (method described in Japanese Patent Application Laid-Open No. 2003-170059, Japanese Patent Application Laid-Open No. 2004-262871, etc.), and further transesterification of cyclohexene carboxylic acid ester
- Examples thereof include compounds that can be produced by the method described in Japanese Patent Application Laid-Open No. 2006-052187.
- the alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane.
- Diols diols such as 1,6-hexanediol and cyclohexanedimethanol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, etc.
- carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.
- an acetal compound obtained by an acetal reaction between a cyclohexene aldehyde derivative and an alcohol is exemplified.
- a reaction method it can be produced by applying a general acetalization reaction.
- a method of carrying out a reaction while azeotropically dehydrating using a solvent such as toluene or xylene as a reaction medium US Pat. No. 2,945,008
- concentrated hydrochloric acid A method in which polyhydric alcohol is dissolved in the mixture and then the reaction is carried out while gradually adding aldehydes (Japanese Patent Laid-Open No.
- epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Epolide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel) (Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited thereto (Reference: Review Epoxy Resin Basic Edition I p76-85). These may be used alone or in combination of two or more.
- curing catalyst examples include amine compounds such as triethylamine, tripropylamine, and tributylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, and imidazole.
- Triazole tetrazole 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2- Methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methylimidazole (1 ′)) ethyl -S- Lyazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ′)) ethyl -S
- Diaza compounds and salts thereof such as tetraphenylborate and phenol novolak, salts with the above polyvalent carboxylic acids or phosphinic acids, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide , Trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide, trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydride Ammonium salts such as rhoxide, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate, triphenylphosphine, tri (tolyl) phos
- phosphonium salts, ammonium salts, and metal compounds are particularly preferable in terms of coloring at the time of curing and changes thereof.
- the salt with halogen may leave halogen in the cured product.
- the curing accelerator is used in an amount of 0.01 to 5.0 parts by weight based on the epoxy resin 100 as necessary.
- the epoxy resin composition of the present invention preferably contains a curing agent.
- a curing agent examples thereof include amine compounds, acid anhydride compounds, amide compounds, phenol resins, carboxylic acid compounds, and the like.
- Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and nitrogen-containing compounds such as polyamide resins synthesized from ethylenediamine and amine compounds (amines, Amide compounds); phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydro Phthalic anhydride, but
- the amount of the curing agent used in the curable resin composition of the present invention is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.
- a cyanate ester compound as the other component.
- the cyanate ester compound can be made into a heat-resistant cured product having a higher crosslinking density by a reaction with an epoxy resin in addition to a curing reaction alone.
- the cyanate ester resin include 2,2-bis (4-cyanatephenyl) propane, bis (3,5-dimethyl-4-cyanatephenyl) methane, 2,2-bis (4-cyanatephenyl) ethane, These derivatives, aromatic cyanate ester compounds, etc. are mentioned. Further, for example, as described in the above-mentioned curing material, synthesis can be performed by reaction of various phenol resins with hydrocyanic acid or salts thereof.
- those having a structure not having a methylene structure at the benzyl position in the molecule such as 2,2-bis (4-cyanatephenyl) propane and derivatives thereof (partially polymerized products) are particularly preferable. You may use independently and may use 2 or more types together.
- the epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant imparting component.
- the phosphorus-containing compound may be a reactive type or an additive type.
- Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-
- Phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred.
- the epoxy resin composition of the present invention can be blended with a binder resin as necessary.
- the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these.
- the blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 100 parts by weight in total of the epoxy resin and the curing agent. 0.05 to 20 parts by weight is used as necessary.
- An inorganic filler can be added to the epoxy resin composition of the present invention as necessary.
- inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like.
- the present invention is not limited to these.
- These fillers may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the epoxy resin composition of the present invention.
- the epoxy resin composition of the present invention includes an antioxidant, a light stabilizer, a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate and calcium stearate, various compounding agents such as pigments, Various thermosetting resins can be added.
- the coupling material is preferably added with an epoxy group-containing coupling material or a thiol-containing coupling material.
- the epoxy resin composition of the present invention can be obtained by uniformly mixing each component.
- the epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method.
- an epoxy resin component, a curing agent component, and a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, a compounding agent, and the like if necessary, uniformly using an extruder, kneader, roll, planetary mixer, etc. Mix thoroughly until the epoxy resin composition is obtained. If the resulting epoxy resin composition is liquid, the substrate is impregnated with a potting or casting, or poured into a mold and cast. Or cured by heating.
- the obtained epoxy resin composition is solid, it is molded using a cast after casting or a transfer molding machine, and further cured by heating.
- the curing temperature and time are 80 to 200 ° C. and 2 to 10 hours.
- a curing method it is possible to cure at a high temperature at a stretch, but it is preferable to increase the temperature stepwise to advance the curing reaction.
- initial curing is performed at 80 to 150 ° C.
- post-curing is performed at 100 to 200 ° C.
- the temperature is preferably increased in 2 to 8 stages, more preferably 2 to 4 stages.
- the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. to obtain a curable resin composition varnish, which contains glass fiber, -A prepreg obtained by impregnating a base material such as bon fiber, polyester fiber, polyamide fiber, alumina fiber or paper and drying by heating is subjected to hot press molding to obtain a cured product of the epoxy resin composition of the present invention.
- the solvent is used in an amount of 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.
- the epoxy resin composition of the present invention can be used as a film-type sealing composition.
- the curable resin composition of the present invention is coated on the release film with the varnish, the solvent is removed under heating, and a B-stage adhesive is formed. Get.
- This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like, and a batch film sealing of an optical semiconductor.
- compositions include adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, sealing materials, Sealants, cyanate resin compositions for substrates) and resist curing agents include additives to other resins such as acrylic ester resins.
- insulating material for an electronic material a sealing material including a printed board, a wire coating, etc., as well as a sealing material and a cyanate resin composition for a substrate
- resist curing agents include additives to other resins such as acrylic ester resins.
- adhesives examples include civil engineering, architectural, automotive, general office, and medical adhesives, as well as electronic material adhesives.
- adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).
- sealing agent and substrate potting sealing for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, ICs, LSIs for COB, COF, TAB, etc.
- substrate use with which functionality, such as a network board
- Example 1 A 1 L four-necked flask equipped with a stirrer, a reflux condenser and a stirrer was once evacuated and purged with nitrogen (oxygen concentration: 4.9%), and then subjected to a nitrogen purge (2 L / hr) and a phenol compound (DPPI1 ) (A compound in which the substituent R is all hydrogen atoms in the formula (P) SABIC PPPBP Purity 99% or more Residual phenolphthalein 200 ppm, iron content ⁇ 5 ppm) 256 parts, epichlorohydrin 842 parts, methanol 180 parts, water bath The temperature was raised to 75 ° C.
- epoxy resin (EP1) was obtained by distilling off methyl isobutyl ketone and the like under reduced pressure.
- the epoxy equivalent of the obtained epoxy resin is 266 g / eq. , Softening point 89 ° C, ICI melt viscosity 0.42 Pa ⁇ s (150 ° C), total chlorine amount 1600 ppm, hydrolyzable chlorine 1540 ppm, chlorine ion 2 ppm, sodium ion 0.5 ppm, hue 0.2 or less (Gardner 40% MEK (methyl ethyl ketone) solution).
- the structure of the formula (1) was 93 area% (GPC).
- Example 2 A 1 L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer was once evacuated, purged with nitrogen (oxygen concentration 5.3%), and then subjected to a nitrogen purge (2 L / hr) with a phenol compound (DPPI2 And Example 1 except that the compound in which the substituent R is all hydrogen atoms in the formula (P) SABIC PPPBP purity 99% or more, residual phenolphthalein 200 ppm, iron ⁇ 5 ppm and phenolphthalein 500 ppm added) The reaction was performed in the same manner.
- the epoxy equivalent of the obtained epoxy resin (EP2) was 266 g / eq.
- Example 3 A 1 L four-necked flask equipped with a stirrer, reflux condenser, and stirrer was purged with nitrogen at 4 L / h for 30 minutes (oxygen concentration 6.5%), and then subjected to a nitrogen purge (2 L / hr) and a phenol compound.
- DPPI1 compound in which the substituent R is all hydrogen atoms in the formula (P) SABIC PPPBP purity 99% or more residual phenolphthalein 200 ppm, iron content ⁇ 5 ppm) 256 parts, epichlorohydrin 661 parts, methanol 165 parts are added The water bath was heated to 75 ° C.
- the epoxy equivalent of the obtained epoxy resin was 277 g / eq. , Softening point 96 ° C., ICI melt viscosity 0.62 Pa ⁇ s (150 ° C.), total chlorine amount 2230 ppm, hydrolyzable chlorine 2100 ppm, chlorine ion 0.5 ppm, sodium ion 0.5 ppm, hue 0.2 or less (Gardner 40% MEK solution).
- the structure of the formula (1) was 82 area% (GPC).
- Example 4 A 1 L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer was once evacuated, purged with nitrogen (oxygen concentration 5.2%), and then subjected to a nitrogen purge (2 L / hr) with a phenol compound (DPPI1 ) (A compound in which the substituent R is all hydrogen atoms in the above formula (P) SABIC PPPBP purity 99% or more residual phenolphthalein 200 ppm, iron ⁇ 5 ppm) 256 parts, epichlorohydrin 661 parts, dimethyl sulfoxide 200 parts, The water bath was raised to 45 ° C.
- DPPI1 phenol compound in which the substituent R is all hydrogen atoms in the above formula (P)
- Example 5 A flask equipped with a stirrer, a reflux condenser, and a stirrer is once evacuated and purged with nitrogen. Then, while purging with nitrogen (2 L / hr), the phenol compound (DPPI3) (all the substituents R in the formula (P) are Compound of hydrogen atom SABIC PPPBP Purity 99% or more The reaction was performed in the same manner as in Example 1 except that 210 ppm of residual phenolphthalein and 1% of phenolphthalein were added to iron content ⁇ 5 ppm). The epoxy equivalent of the obtained epoxy resin (EP5) was 262 g / eq.
- an epoxy resin (EP6).
- the epoxy equivalent of the obtained epoxy resin was 297 g / eq. , Softening point 95 ° C., ICI melt viscosity 0.70 Pa ⁇ s (150 ° C.), total chlorine amount 10450 ppm, hydrolyzable chlorine 9700 ppm, chlorine ion 0.5 ppm, sodium ion 0.5 ppm, hue 4 (Gardner 40% MEK Solution).
- the structure of the formula (1) was 65 area% (GPC).
- Example 6 and Comparative Example 2 Epoxy resin (EP1) obtained above and comparative epoxy resin (EP7; trisphenolmethane type epoxy resin, EPPN-502H manufactured by Nippon Kayaku Co., Ltd.), phenol aralkyl resin (Mitsui Chemicals Co., Ltd., Millex XLC) as a curing agent -3L, hereinafter referred to as PN1), and blended in the proportions (parts by weight) shown in Table 1, and uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition for sealing.
- This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C.
- Examples 7 and 8 and Comparative Example 3 Using the epoxy resins (EP1, EP3) obtained above and a comparative epoxy resin (EP5), phenol novolac (H-1 manufactured by Meiwa Kasei Kogyo Co., Ltd., hereinafter referred to as PN2) as a curing agent, It mix
- This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine. The tableted epoxy resin composition was transfer-molded (175 ° C. ⁇ 60 seconds), and after demolding, cured under the conditions of 160 ° C. ⁇ 2 hours + 180 ° C.
- the epoxy resin of the present invention can give a cured product having higher heat resistance than the epoxy resin of the comparative example.
- Example 13 A 1 L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is added to a phenol compound (DPPI1) (a compound in which the substituents R are all hydrogen atoms in the formula (P) SABIC BPPPP purity 99% or more residual phenolphthalein 200 ppm, iron content ⁇ 5 ppm) 295 parts, epichlorohydrin 694 parts, dimethyl sulfoxide 173 parts were added, and the temperature of the water bath was raised to 50 ° C. When the internal temperature exceeded 45 ° C., 66 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 45 ° C.
- DPPI1 a compound in which the substituents R are all hydrogen atoms in the formula (P) SABIC BPPPP purity 99% or more residual phenolphthalein 200 ppm, iron content ⁇ 5 ppm
- the epoxy equivalent of the obtained epoxy resin is 268 g / eq. , Softening point 99 ° C., ICI melt viscosity 1.03 Pa ⁇ s (150 ° C.), total chlorine amount 305 ppm, hydrolyzable chlorine 270 ppm, chlorine ion 0.1 ppm, sodium ion 0.1 ppm, hue 0.6 (Gardner 40 % THF solution).
- the structure of the formula (1) was 85.2 area% (GPC).
- Example 14 A 1 L four-necked flask equipped with a stirrer, a reflux condenser, and a stirrer is added to a phenol compound (DPPI1) (a compound in which the substituents R are all hydrogen atoms in the formula (P) SABIC BPPPP purity 99% or more residual phenolphthalein 295 parts of 200 ppm, iron ⁇ 5 ppm), 971 parts of epichlorohydrin and 165 parts of dimethyl sulfoxide were added, and the temperature of the water bath was raised to 45 ° C. When the internal temperature exceeded 40 ° C., 66 parts of flaky sodium hydroxide was added in portions over 90 minutes, followed by further reaction at 45 ° C. for 2 hours and at 70 ° C.
- DPPI1 a compound in which the substituents R are all hydrogen atoms in the formula (P) SABIC BPPPP purity 99% or more residual phenolphthalein 295 parts of 200 ppm, iron ⁇ 5 ppm), 971
- the epoxy equivalent of the obtained epoxy resin is 267 g / eq. , Softening point 99 ° C., ICI melt viscosity 0.91 Pa ⁇ s (150 ° C.), total chlorine amount 540 ppm, hydrolyzable chlorine 430 ppm, chlorine ion 0.1 ppm, sodium ion 0.1 ppm, hue 0.8 (Gardner 40 % THF solution).
- the structure of the formula (1) was 87.1 area% (GPC).
- Example 15 Epoxy resin (EP10) obtained above, alicyclic epoxy resin (trade name: SEJ-01R made by Nippon Kayaku) as the epoxy resin used in combination, and cationic catalyst (trade name: SI-150 Sanshin) as the curing accelerator Chemical Industries) was blended at a ratio (parts by weight) of 50: 50: 2 to obtain an epoxy resin composition.
- This epoxy resin composition was cast into a mold, and a cured and evaluated test piece was obtained at 150 ° C. for 3 hours.
- Tg was 184 ° C. (Measurement conditions are as described above)
- Example 16 Evaluation was performed in the same manner as in Example 15 except that the epoxy resin (EP10) was changed to the epoxy resin (EP11).
- DMA was measured, Tg was 189 ° C. (Measurement conditions are as described above)
- the epoxy resin of the present invention can achieve both high heat resistance and flame retardancy.
- the epoxy resin of the present invention is an adhesive, paint, coating agent, molding material (including sheets, films, FRP, etc.), insulating material (printed circuit board, electric wire coating, etc.) by forming an epoxy resin composition together with a curing agent and the like.
- a sealing material a sealing material, a cyanate resin composition for a substrate), and a resist curing agent can be used as an additive for other resins such as an acrylate resin.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Medicinal Preparation (AREA)
Abstract
Description
そこで、耐熱性と相反する特性を両立できるエポキシ樹脂の開発が望まれていた。
すなわち本発明は、
(1)
主成分として、下記式(1)で表される化合物を70~95%(ゲルパーミエーションクロマトグラフィー 面積%)含有するエポキシ樹脂。
(2)
エポキシ当量が理論エポキシ当量に対し1.02倍~1.11倍である前項(1)に記載のエポキシ樹脂。
(3)
全塩素含有量が5000ppm以下である前項(1)に記載のエポキシ樹脂。
(4)
前項(1)~(3)のいずれか一項に記載のエポキシ樹脂と硬化剤を必須成分とするエポキシ樹脂組成物。
(5)
前項(1)~(3)のいずれか一項に記載のエポキシ樹脂と硬化触媒を必須成分とするエポキシ樹脂組成物。
(6)
前項(4)~(5)のいずれか一項のエポキシ樹脂組成物を硬化した硬化物。
に関する。
本データから本樹脂は塩素量が非常に多く、電子材料用途には不向きであり、また非常に着色があることから色味の必要とされる用途においては使用が困難であることが示唆される。また、エポキシ当量が294g/eq.と理論値(252.7g/eq.)と比較し大きいこと、また塩素量からエポキシが閉環せずに残留したエピハロヒドリン構造が多く含有されることが示唆され、二官能であるにも関わらず、このようなエポキシ環が完成されていない構造であれば、架橋がうまく進まず、フェノール樹脂による硬化や、イミダゾール等の塩基性触媒によるアニオン重合、オニウム塩等によるカチオン重合を行った際、その機械特性や吸水性といった特性において課題が生じる場合が多い。特に電子材料用途においてはこれらの硬化だけでなく、アミン系の硬化においても硬化時の塩素の遊離が起因となる配線の腐食等が予想され、電気信頼性を落とす要因となる。
近年特に半導体のチップと基板との接合に銅のワイヤを使用することが多くなってきており、こういった電気腐食の課題はいっそう重要となっており、解決すべき課題点となる。
Rが示す、炭素数1~6のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等の直鎖、分岐鎖または環状構造を有するアルコキシ基が挙げられる。ここで、Rはメトキシ基、エトキシ基、プロポキシ基が好ましく、メトキシ基が特に好ましい。
また、反応により得られたエポキシ樹脂に残存している全塩素としては5000ppm以下、より好ましくは3000ppm以下、特に2000ppm以下であることが好ましい。塩素量による悪影響については前述と同様である。なお、塩素イオン、ナトリウムイオンについては各々5ppm以下が好ましく、より好ましくは3ppm以下である。塩素イオンは先に記載し、いうまでも無いが、ナトリウムイオン等のカチオンも、特にパワーデバイス用途においては非常に重要なファクターとなり、高電圧がかかった際の不良モードの一因となる。
ここで、理論エポキシ当量とは、下記式(P)で表されるフェノール化合物のフェノール性水酸基が過不足なくグリシジル化した時に算出されるエポキシ当量を示す。
また本発明のエポキシ樹脂は高い屈折率を有する。好ましくは1.61以上であり、より好ましくは1.62以上、特に好ましくは1.62~1.65である。特に屈折率調整が必要な分野においては、屈折率が高ければ用いる組成物の芳香環量を低減することができ、耐光特性の向上に貢献できる。また、レンズ等の用途においては高屈折率ほどより歪みの小さなレンズを作成する事ができ、好ましい。
前記式(1)で表される化合物を含有する本発明のエポキシ樹脂は、フェノールフタレイン誘導体とアミノベンゼン誘導体から合成される前記式(P)で表される(例えば、日本国特開2005-290378号公報が挙げられる)フェノール化合物(DPPI)とエピハロヒドリンとの反応で得られる。本発明のエポキシ樹脂の具体的な製造方法例を以下に示す。
ここで、前記各種フェノール類としては、例えば、フェノール、クレゾール、エチルフェノール、プロピルフェノール、キシレノール、メチルブチルフェノールなどが挙げられる。
また、前記合成により得られるフェノールフタレイン誘導体としては、例えば下記式(2)で表される構造が挙げられる。
残存フェノールフタレイン誘導体の量はDPPIの精製(洗浄、再結晶、再沈殿等)によって調整可能である。
3.0モルを下回るとエポキシ当量が大きくなることがあり、また、できたエポキシ樹脂の作業性が悪くなる可能性がある。15モルを超えると溶剤量が多量となる。
アルカリ金属水酸化物の使用量は原料フェノール混合物の水酸基1モルに対して通常0.90~1.5モルであり、好ましくは0.95~1.25モル、より好ましくは0.99~1.15モルである。
系中の水分が多い場合には、得られたエポキシ樹脂において電気信頼性が悪くなることがあり、水分は5%以下にコントロールして合成することが好ましい。また、非極性プロトン溶媒を使用してエポキシ樹脂を得た際には、電気信頼性に優れるエポキシ樹脂が得られるため、非極性プロトン溶媒は好適に使用できる。
これらのエポキシ化反応の反応物を水洗後、または水洗無しに加熱減圧下でエピハロヒドリンや溶媒等を除去する。また更に加水分解性ハロゲンの少ないエポキシ樹脂とするために、回収したエポキシ樹脂を炭素数4~7のケトン化合物(たとえば、メチルイソブチルケトン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン等が挙げられる。)を溶剤として溶解し、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物の水溶液を加えて反応を行い、閉環を確実なものにすることも出来る。この場合アルカリ金属水酸化物の使用量はエポキシ化に使用した原料フェノール混合物の水酸基1モルに対して通常0.01~0.3モル、好ましくは0.05~0.2モルである。反応温度は通常50~120℃、反応時間は通常0.5~2時間である。
またエピハロヒドリンとの反応においては反応初期から窒素等の不活性ガスで置換されていることが好ましく、空腔内の酸素濃度は10%以下であることが好ましい。酸素の残留は着色に影響をする。手法としてはフェノール化合物(DPPI)を仕込む前に窒素等不活性ガスを吹き込み(気中、もしくは液中)、もしくは、いったん減圧で真空にした後、不活性ガスで置換する方法が挙げられる。不活性ガスでの置換が無い場合、得られる樹脂に着色が生じる場合がある。不活性ガスの吹き込みを行う場合、その量はその反応容器の容積によっても異なるが、0.5~10時間でその反応容器の容積の1~3倍量が置換できる量の不活性ガスの吹き込みが好ましい。
シクロヘキセン構造を有する化合物としては、シクロヘキセンカルボン酸とアルコール類とのエステル化反応あるいはシクロヘキセンメタノールとカルボン酸類とのエステル化反応(Tetrahedron vol.36 p.2409 (1980)、Tetrahedron Letter p.4475 (1980)等に記載の手法)、あるいはシクロヘキセンアルデヒドのティシェンコ反応(日本国特開2003-170059号公報、日本国特開2004-262871号公報等に記載の手法)、さらにはシクロヘキセンカルボン酸エステルのエステル交換反応(日本国特開2006-052187号公報等に記載の手法)によって製造できる化合物が挙げられる。
アルコール類としては、アルコール性水酸基を有する化合物であれば特に限定されないがエチレングリコール、プロピレングリコール、1,3-プロパンジオール、1,2-ブタンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール、シクロヘキサンジメタノールなどのジオール類、グリセリン、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、2-ヒドロキシメチル-1,4-ブタンジオールなどのトリオール類、ペンタエリスリトールなどのテトラオール類などが挙げられる。またカルボン酸類としてはシュウ酸、マレイン酸、フマル酸、フタル酸、イソフタル酸、アジピン酸、シクロヘキサンジカルボン酸などが挙げられるがこれに限らない。
これらエポキシ樹脂の具体例としては、ERL-4221、UVR-6105、ERL-4299(全て商品名、いずれもダウ・ケミカル製)、セロキサイド2021P、エポリードGT401、EHPE3150、EHPE3150CE(全て商品名、いずれもダイセル化学工業製)及びジシクロペンタジエンジエポキシドなどが挙げられるがこれらに限定されるものではない(参考文献:総説エポキシ樹脂 基礎編I p76-85)。
これらは単独で用いてもよく、2種以上併用してもよい。
硬化促進剤は、エポキシ樹脂100に対して0.01~5.0重量部が必要に応じ用いられる。
本発明においては特に電子材料用途に使用するため、前述のフェノール樹脂が好ましい。
以下に実施例で用いた各種分析方法について記載する。
エポキシ当量: JIS K 7236 (ISO 3001) に準拠
ICI溶融粘度: JIS K 7117-2 (ISO 3219) に準拠
軟化点: JIS K 7234 に準拠
全塩素: JIS K 7243-3 (ISO 21672-3) に準拠
塩素イオン: JIS K 7243-1 (ISO 21672-1) に準拠
ナトリウムイオン: イオンクロマトグラフィーにて測定
鉄分: ICP発光分光分析
屈折率: ISO 5661 に準拠
ガードナー色数:ISO 4630-1 に準拠
GPC:
カラム(Shodex KF-603、KF-602x2、KF-601x2)
連結溶離液はテトラヒドロフラン
流速は0.5ml/min.
カラム温度は40℃
検出:RI(示差屈折検出器)
撹拌機、還流冷却管、撹拌装置を備えた1Lの4つ口フラスコをいったん真空にし、窒素置換した後(酸素濃度4.9%)、窒素パージ(2L/hr)を施しながらフェノール化合物(DPPI1)(前記式(P)において置換基Rがすべて水素原子の化合物 SABIC PPPBP 純度99%以上 残留フェノールフタレイン200ppm、鉄分<5ppm)256部、エピクロロヒドリン842部、メタノール180部を加え、水浴を75℃にまで昇温した。内温が65℃を越えたところでフレーク状の水酸化ナトリウム21部を90分けて分割添加した後、更に70℃で1時間後反応を行った。反応終了後水洗を行い、油層からロータリーエバポレータを用いて140℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去した。残留物にメチルイソブチルケトン600部を加え溶解し、70℃にまで昇温した。撹拌下で30重量%の水酸化ナトリウム水溶液26部を加え、1時間反応を行った後、洗浄水が中性になるまで水洗を行い、得られた溶液を、ロータリーエバポレータを用いて180℃で減圧下にメチルイソブチルケトン等を留去することでエポキシ樹脂(EP1)を305部得た。得られたエポキシ樹脂のエポキシ当量は266g/eq.、軟化点が89℃、ICI溶融粘度0.42Pa・s(150℃)、全塩素量 1600ppm、加水分解性塩素 1540ppm、塩素イオン2ppm、ナトリウムイオン0.5ppm、色相0.2以下(ガードナー 40%MEK(メチルエチルケトン)溶液)であった。また前記式(1)の構造は93面積%(GPC)であった。
撹拌機、還流冷却管、撹拌装置を備えた1Lの4つ口フラスコをいったん真空にし、窒素置換した後(酸素濃度5.3%)、窒素パージ(2L/hr)を施しながらフェノール化合物(DPPI2)(前記式(P)において置換基Rがすべて水素原子の化合物 SABIC PPPBP 純度99%以上 残留フェノールフタレイン200ppm、鉄分<5ppm に フェノールフタレイン500ppm添加したもの)を用いた以外は実施例1と同様に反応を行った。得られたエポキシ樹脂(EP2)のエポキシ当量は266g/eq.、軟化点が90℃、ICI溶融粘度0.44Pa・s(150℃)、全塩素量 2000ppm、加水分解性塩素 1950ppm、塩素イオン1ppm、ナトリウムイオン0.3ppm、色相0.2(ガードナー 40%MEK溶液)であった。また前記式(1)の構造は93面積%(GPC)であった。
撹拌機、還流冷却管、撹拌装置を備えた1Lの4つ口フラスコに4L/hで30分窒素置換した後(酸素濃度6.5%)、窒素パージ(2L/hr)を施しながらフェノール化合物(DPPI1)(前記式(P)において置換基Rがすべて水素原子の化合物 SABIC PPPBP 純度99%以上 残留フェノールフタレイン200ppm、鉄分<5ppm)256部、エピクロロヒドリン661部、メタノール165部を加え、水浴を75℃にまで昇温した。内温が65℃を越えたところでフレーク状の水酸化ナトリウム57部を90分かけて分割添加した後、更に70℃で1時間後反応を行った。反応終了後水洗を行い、油層からロータリーエバポレータを用いて140℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去した。残留物にメチルイソブチルケトン600部を加え溶解し、70℃にまで昇温した。撹拌下で30重量%の水酸化ナトリウム水溶液5部を加え、1時間反応を行った後、洗浄水が中性になるまで水洗を行い、得られた溶液を、ロータリーエバポレータを用いて180℃で減圧下にメチルイソブチルケトン等を留去することでエポキシ樹脂(EP3)を297部得た。得られたエポキシ樹脂のエポキシ当量は277g/eq.、軟化点が96℃、ICI溶融粘度0.62Pa・s(150℃)、全塩素量 2230ppm、加水分解性塩素 2100ppm、塩素イオン0.5ppm、ナトリウムイオン0.5ppm、色相0.2以下(ガードナー 40%MEK溶液)であった。また前記式(1)の構造は82面積%(GPC)であった。
撹拌機、還流冷却管、撹拌装置を備えた1Lの4つ口フラスコをいったん真空にし、窒素置換した後(酸素濃度5.2%)、窒素パージ(2L/hr)を施しながらフェノール化合物(DPPI1)(前記式(P)において置換基Rがすべて水素原子の化合物 SABIC PPPBP 純度99%以上 残留フェノールフタレイン200ppm、鉄分<5ppm)256部、エピクロロヒドリン661部、ジメチルスルホキシド 200部を加え、水浴を45℃にまで昇温した。内温が40℃を越えたところでフレーク状の水酸化ナトリウム57部を90分かけて分割添加した後、更に70℃で1時間後反応を行った。反応終了後水洗を行い、油層からロータリーエバポレータを用いて140℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去した。残留物にメチルイソブチルケトン600部を加え溶解し、70℃にまで昇温した。撹拌下で30重量%の水酸化ナトリウム水溶液16部を加え、1時間反応を行った後、洗浄水が中性になるまで水洗を行い、得られた溶液を、ロータリーエバポレータを用いて180℃で減圧下にメチルイソブチルケトン等を留去することでエポキシ樹脂(EP4)を300部得た。得られたエポキシ樹脂のエポキシ当量は270g/eq.、軟化点が92℃、ICI溶融粘度0.48Pa・s(150℃)、全塩素量 1050ppm、加水分解性塩素 960ppm、塩素イオン0.3ppm、ナトリウムイオン0.1ppm、色相0.6(ガードナー 40%MEK溶液)であった。また前記式(1)の構造は90面積%(GPC)であった。
撹拌機、還流冷却管、撹拌装置を備えたフラスコをいったん真空にし、窒素置換した後、窒素パージ(2L/hr)を施しながらフェノール化合物(DPPI3)(前記式(P)において置換基Rがすべて水素原子の化合物 SABIC PPPBP 純度99%以上 残留フェノールフタレイン210ppm、鉄分<5ppm に フェノールフタレイン1%添加)を用いた以外は実施例1と同様に反応を行った。得られたエポキシ樹脂(EP5)のエポキシ当量は262g/eq.、軟化点が89℃、ICI溶融粘度0.42Pa・s(150℃)、全塩素量 3200ppm、加水分解性塩素 2700ppm、塩素イオン5ppm、ナトリウムイオン0.5ppm、色相3(ガードナー 40%MEK溶液)であった。また前記式(1)の構造は90面積%(GPC)であった。
撹拌機、還流冷却管、撹拌装置を備えたフラスコにフェノール化合物(DPPI1)(前記式(P)において置換基Rがすべて水素原子の化合物 SABIC PPPBP 純度99%以上 残留フェノールフタレイン200ppm、鉄分<5ppm)256部、エピクロロヒドリン842部、ベンジルトリメチルアンモニウムクロライド3部を加え、水浴を70℃にまで昇温した。ここに49%水酸化ナトリウム水溶液100部を90分かけて滴下した後、更に70℃で4時間後反応を行った。反応終了後水洗を行い、油層からロータリーエバポレータを用いて140℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去することでエポキシ樹脂(EP6)を290部得た。得られたエポキシ樹脂のエポキシ当量は297g/eq.、軟化点が95℃、ICI溶融粘度0.70Pa・s(150℃)、全塩素量 10450ppm、加水分解性塩素 9700ppm、塩素イオン0.5ppm、ナトリウムイオン0.5ppm、色相4(ガードナー 40%MEK溶液)であった。また前記式(1)の構造は65面積%(GPC)であった。
前記で得られたエポキシ樹脂(EP1)と比較用のエポキシ樹脂(EP7;トリスフェノールメタン型エポキシ樹脂 日本化薬株式会社製 EPPN-502H)、硬化剤としてフェノールアラルキル樹脂(三井化学株式会社製 ミレックスXLC-3L 以下、PN1と称す。)を使用し、表1の割合(重量部)で配合し、ミキシングロールを用いて均一に混合・混練し、封止用エポキシ樹脂組成物を得た。このエポキシ樹脂組成物をミキサーにて粉砕し、更にタブレットマシーンにてタブレット化した。このタブレット化されたエポキシ樹脂組成物をトランスファー成型(175℃×60秒)し、更に脱型後160℃×2時間+180℃×6時間の条件で硬化、評価用試験片を得た。
なお、硬化物の物性は以下の要領で測定した。
TMA(熱機械測定装置 真空理工(株)製 TM-7000 昇温速度:2℃/分)
前記で得られたエポキシ樹脂(EP1、EP3)と比較用のエポキシ樹脂(EP5)、硬化剤としてフェノールノボラック(明和化成工業株式会社製 H-1 以下PN2と称す。)を使用し、表2の割合(重量部)で配合し、ミキシングロールを用いて均一に混合・混練し、封止用エポキシ樹脂組成物を得た。このエポキシ樹脂組成物をミキサーにて粉砕し、更にタブレットマシーンにてタブレット化した。このタブレット化されたエポキシ樹脂組成物をトランスファー成型(175℃×60秒)し、更に脱型後160℃×2時間+180℃×6時間の条件で硬化、評価用試験片を得た。
なお、硬化物の物性は以下の要領で測定した。
TMA(熱機械測定装置 真空理工(株)製 TM-7000 昇温速度:2℃/分)
前記で得られたエポキシ樹脂(EP1~EP4)と比較用のエポキシ樹脂(EP6)、(EP8;日本化薬製 オルソクレゾールノボラック型エポキシ樹脂 EOCN-1020-65)、硬化剤としてフェノールアラルキル樹脂(三井化学株式会社製 ミレックスXLC-3L 以下、PN1と称す。)、無機充填剤として溶融シリカ(商品名:MSR-2212、龍森製)、硬化促進剤としてトリフェニルホスフィン(商品名:TPP 北興化学工業製)、離型剤としてカルナバワックス1号(セラリカ野田製)、添加剤としてシランカップリング剤(商品名:KBM-403 信越化学製)を表3の割合(重量部)で配合し、ミキシングロールを用いて均一に混合・混練し、封止用エポキシ樹脂組成物を得た。このエポキシ樹脂組成物をミキサーにて粉砕し、更にタブレットマシーンにてタブレット化した。このタブレット化されたエポキシ樹脂組成物をトランスファー成型(175℃×60秒)し、更に脱型後160℃×2時間+180℃×6時間の条件で硬化、評価用試験片を得た。
動的粘弾性測定器:TA-instruments製、DMA-2980
測定温度範囲:-30℃~280℃
温速度:2℃/分
試験片サイズ:5mm×50mmに切り出した物を使用した(厚みは約800μm)。
解析条件
Tg:DMA測定に於けるTanδのピーク点(tanδMAX)をTgとした。
難燃性
・難燃性の判定:UL94に準拠して行った。ただし、サンプルサイズは幅12.5mm×長さ150mmとし、厚さは0.8mmで試験を行った。
・残炎時間:5個1組のサンプルに10回接炎したあとの残炎時間の合計
撹拌機、還流冷却管、撹拌装置を備えた1Lの4つ口フラスコをフェノール化合物(DPPI1)(前記式(P)において置換基Rがすべて水素原子の化合物 SABIC BPPPP 純度99%以上 残留フェノールフタレイン200ppm、鉄分<5ppm)295部、エピクロロヒドリン694部、ジメチルスルホキシド 173部を加え、水浴を50℃にまで昇温した。内温が45℃を越えたところでフレーク状の水酸化ナトリウム66部を90分かけて分割添加した後、更に45℃で2時間、70℃で1時間後反応を行った。反応終了後水洗を行い、油層からロータリーエバポレータを用いて140℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去した。残留物にメチルイソブチルケトン760部を加え溶解し、水洗により生成した塩化ナトリウム等を除去後、有機層を70℃にまで昇温し、撹拌下で30重量%の水酸化ナトリウム水溶液30部を加え、1時間反応を行った後、洗浄水が中性になるまで水洗を行い、得られた溶液を、ロータリーエバポレータを用いて180℃で減圧下にメチルイソブチルケトン等を留去することでエポキシ樹脂(EP10)を355部得た。得られたエポキシ樹脂のエポキシ当量は268g/eq.、軟化点が99℃、ICI溶融粘度1.03Pa・s(150℃)、全塩素量 305ppm、加水分解性塩素 270ppm、塩素イオン0.1ppm、ナトリウムイオン0.1ppm、色相0.6(ガードナー 40%THF溶液)であった。また前記式(1)の構造は85.2面積%(GPC)であった。
撹拌機、還流冷却管、撹拌装置を備えた1Lの4つ口フラスコをフェノール化合物(DPPI1)(前記式(P)において置換基Rがすべて水素原子の化合物 SABIC BPPPP 純度99%以上 残留フェノールフタレイン200ppm、鉄分<5ppm)295部、エピクロロヒドリン971部、ジメチルスルホキシド165部を加え、水浴を45℃にまで昇温した。内温が40℃を越えたところでフレーク状の水酸化ナトリウム66部を90分かけて分割添加した後、更に45℃2時間、70℃で1時間後反応を行った。反応終了後水洗を行い、油層からロータリーエバポレータを用いて140℃で減圧下、過剰のエピクロルヒドリン等の溶剤を留去した。残留物にメチルイソブチルケトン760部を加え溶解し、水洗により生成した塩化ナトリウム等を除去後、有機層を70℃にまで昇温し、撹拌下で30重量%の水酸化ナトリウム水溶液30部を加え、1時間反応を行った後、洗浄水が中性になるまで水洗を行い、得られた溶液を、ロータリーエバポレータを用いて180℃で減圧下にメチルイソブチルケトン等を留去することでエポキシ樹脂(EP11)を353部得た。得られたエポキシ樹脂のエポキシ当量は267g/eq.、軟化点が99℃、ICI溶融粘度0.91Pa・s(150℃)、全塩素量 540ppm、加水分解性塩素 430ppm、塩素イオン0.1ppm、ナトリウムイオン0.1ppm、色相0.8(ガードナー 40%THF溶液)であった。また前記式(1)の構造は87.1面積%(GPC)であった。
前記で得られたエポキシ樹脂(EP10)、併用するエポキシ樹脂として脂環式エポキシ樹脂(商品名:SEJ-01R 日本化薬製)、硬化促進剤としてカチオン系触媒(商品名:SI-150 三新化学工業製)、を50:50:2の割合(重量部)で配合し、エポキシ樹脂組成物を得た。このエポキシ樹脂組成物を金型に注型し、150℃3時間の条件で硬化、評価用試験片を得た。得られた試験片を用い、DMAを測定したところTgは184℃であった。(測定条件は前述のとおり)
エポキシ樹脂(EP10)をエポキシ樹脂(EP11)に変更した以外は、実施例15と同様に評価を行った。DMAを測定したところ、Tgは189℃であった。(測定条件は前述のとおり)
なお、本出願は、2012年6月7日付で出願された日本特許出願(特願2012-129407)に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。
Claims (6)
- エポキシ当量が理論エポキシ当量に対し1.02倍~1.11倍である請求項1に記載のエポキシ樹脂。
- 全塩素含有量が5000ppm以下である請求項1に記載のエポキシ樹脂。
- 請求項1~請求項3のいずれか一項に記載のエポキシ樹脂と硬化剤を必須成分とするエポキシ樹脂組成物。
- 請求項1~請求項3のいずれか一項に記載のエポキシ樹脂と硬化触媒を必須成分とするエポキシ樹脂組成物。
- 請求項4または請求項5に記載のエポキシ樹脂組成物を硬化した硬化物。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201380030250.3A CN104470965B9 (zh) | 2012-06-07 | 2013-06-06 | 环氧树脂、环氧树脂组合物及固化物 |
JP2014520059A JP6366504B2 (ja) | 2012-06-07 | 2013-06-06 | エポキシ樹脂、エポキシ樹脂組成物および硬化物 |
SG11201408157QA SG11201408157QA (en) | 2012-06-07 | 2013-06-06 | Epoxy resin, epoxy resin composition and cured product |
KR1020147032893A KR101952321B1 (ko) | 2012-06-07 | 2013-06-06 | 에폭시 수지, 에폭시 수지 조성물 및 경화물 |
MYPI2014703662A MY175000A (en) | 2012-06-07 | 2013-06-06 | Epoxy resin, epoxy resin composition and cured product |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012129407 | 2012-06-07 | ||
JP2012-129407 | 2012-06-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013183735A1 true WO2013183735A1 (ja) | 2013-12-12 |
Family
ID=49712122
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/065755 WO2013183735A1 (ja) | 2012-06-07 | 2013-06-06 | エポキシ樹脂、エポキシ樹脂組成物および硬化物 |
Country Status (7)
Country | Link |
---|---|
JP (2) | JP6366504B2 (ja) |
KR (1) | KR101952321B1 (ja) |
CN (1) | CN104470965B9 (ja) |
MY (1) | MY175000A (ja) |
SG (1) | SG11201408157QA (ja) |
TW (1) | TWI579313B (ja) |
WO (1) | WO2013183735A1 (ja) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016031643A1 (ja) * | 2014-08-26 | 2016-03-03 | 日本化薬株式会社 | 反応性ポリエステル化合物、それを用いた活性エネルギー線硬化型樹脂組成物 |
KR20160023555A (ko) | 2014-08-22 | 2016-03-03 | 닛뽄 가야쿠 가부시키가이샤 | 에폭시(메타)아크릴레이트 화합물 및 그것을 함유하는 수지 조성물 그리고 그의 경화물, 컬러 필터 및 표시 소자 |
KR20160047415A (ko) * | 2014-10-22 | 2016-05-02 | 아지노모토 가부시키가이샤 | 수지 조성물 |
JP2016079366A (ja) * | 2014-10-22 | 2016-05-16 | 味の素株式会社 | 樹脂組成物 |
WO2016147735A1 (ja) * | 2015-03-18 | 2016-09-22 | 三菱瓦斯化学株式会社 | 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート、及びプリント配線板 |
JP2017071706A (ja) * | 2015-10-08 | 2017-04-13 | 日本化薬株式会社 | エポキシ樹脂組成物、硬化性樹脂組成物およびその硬化物 |
WO2017170521A1 (ja) * | 2016-03-28 | 2017-10-05 | 積水化学工業株式会社 | 樹脂組成物及び多層基板 |
JP2018009177A (ja) * | 2012-06-07 | 2018-01-18 | 日本化薬株式会社 | エポキシ樹脂、エポキシ樹脂組成物および硬化物 |
WO2018117150A1 (ja) * | 2016-12-22 | 2018-06-28 | 日本化薬株式会社 | エポキシ樹脂混合物、エポキシ樹脂組成物およびその硬化物 |
JP2019529661A (ja) * | 2016-09-26 | 2019-10-17 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | 高熱高靱性エポキシ組成物、物品、及びその使用 |
JP2023025100A (ja) * | 2017-12-25 | 2023-02-21 | 太陽インキ製造株式会社 | 熱硬化性樹脂充填材、その硬化物および多層プリント配線板 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109401707B (zh) * | 2018-11-01 | 2020-12-08 | 烟台信友新材料有限公司 | 一种单组份高耐温抗冲击阻燃型结构胶黏剂及其制备方法 |
CN111154376A (zh) * | 2020-01-16 | 2020-05-15 | 宁波宁静新材料科技有限公司 | 一种Ag/BNNSs纳米材料改性环氧树脂复合涂层 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1158606A (en) * | 1966-03-10 | 1969-07-16 | Ciba Ltd | New Polyglycidylethers, their preparation and their use |
JPH01108218A (ja) * | 1987-10-21 | 1989-04-25 | Mitsui Petrochem Ind Ltd | エポキシ樹脂の精製方法 |
JPH01108217A (ja) * | 1987-10-21 | 1989-04-25 | Mitsui Petrochem Ind Ltd | エポキシ樹脂の精製方法 |
JPH0892231A (ja) * | 1994-09-22 | 1996-04-09 | Mitsui Toatsu Chem Inc | スピロビインダンジグリシジルエーテルおよびその製造方法 |
JP2004099744A (ja) * | 2002-09-10 | 2004-04-02 | Mitsui Chemicals Inc | エポキシ樹脂の精製方法 |
WO2004069893A1 (ja) * | 2003-02-03 | 2004-08-19 | Nippon Steel Chemical Co., Ltd. | 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及び硬化物 |
JP2005154719A (ja) * | 2003-04-25 | 2005-06-16 | Mitsui Chemicals Inc | エポキシ樹脂組成物およびその用途 |
WO2008140008A1 (ja) * | 2007-05-08 | 2008-11-20 | Mitsubishi Gas Chemical Company, Inc. | テトラグリシジルアミノ化合物の製造方法 |
JP2010241872A (ja) * | 2009-04-01 | 2010-10-28 | Nippon Steel Chem Co Ltd | エポキシ樹脂、その製造方法、エポキシ樹脂組成物および硬化物 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4512131B1 (ja) * | 1967-03-10 | 1970-05-02 | ||
JP2556366B2 (ja) * | 1988-11-25 | 1996-11-20 | 日本化薬株式会社 | 高純度エポキシ樹脂及びその製造方法 |
JP2000007757A (ja) * | 1998-04-22 | 2000-01-11 | Asahi Chiba Kk | 新規エポキシ樹脂 |
JP2002114835A (ja) * | 2000-10-06 | 2002-04-16 | Asahi Denka Kogyo Kk | エポキシ樹脂用硬化剤組成物及び塗料組成物 |
TWI300083B (en) * | 2003-04-25 | 2008-08-21 | Mitsui Chemicals Inc | Epoxy resin and its usage |
JP2007063565A (ja) * | 2006-10-17 | 2007-03-15 | Sumitomo Bakelite Co Ltd | 半導体用樹脂ペースト及び半導体装置 |
CN103608305B (zh) * | 2011-05-31 | 2016-04-06 | 康宁股份有限公司 | 精密玻璃辊成形方法和设备 |
SG11201408157QA (en) * | 2012-06-07 | 2015-01-29 | Nippon Kayaku Kk | Epoxy resin, epoxy resin composition and cured product |
-
2013
- 2013-06-06 SG SG11201408157QA patent/SG11201408157QA/en unknown
- 2013-06-06 CN CN201380030250.3A patent/CN104470965B9/zh active Active
- 2013-06-06 JP JP2014520059A patent/JP6366504B2/ja active Active
- 2013-06-06 MY MYPI2014703662A patent/MY175000A/en unknown
- 2013-06-06 WO PCT/JP2013/065755 patent/WO2013183735A1/ja active Application Filing
- 2013-06-06 KR KR1020147032893A patent/KR101952321B1/ko active IP Right Grant
- 2013-06-07 TW TW102120275A patent/TWI579313B/zh active
-
2017
- 2017-08-08 JP JP2017153505A patent/JP2018009177A/ja not_active Withdrawn
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1158606A (en) * | 1966-03-10 | 1969-07-16 | Ciba Ltd | New Polyglycidylethers, their preparation and their use |
JPH01108218A (ja) * | 1987-10-21 | 1989-04-25 | Mitsui Petrochem Ind Ltd | エポキシ樹脂の精製方法 |
JPH01108217A (ja) * | 1987-10-21 | 1989-04-25 | Mitsui Petrochem Ind Ltd | エポキシ樹脂の精製方法 |
JPH0892231A (ja) * | 1994-09-22 | 1996-04-09 | Mitsui Toatsu Chem Inc | スピロビインダンジグリシジルエーテルおよびその製造方法 |
JP2004099744A (ja) * | 2002-09-10 | 2004-04-02 | Mitsui Chemicals Inc | エポキシ樹脂の精製方法 |
WO2004069893A1 (ja) * | 2003-02-03 | 2004-08-19 | Nippon Steel Chemical Co., Ltd. | 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及び硬化物 |
JP2005154719A (ja) * | 2003-04-25 | 2005-06-16 | Mitsui Chemicals Inc | エポキシ樹脂組成物およびその用途 |
WO2008140008A1 (ja) * | 2007-05-08 | 2008-11-20 | Mitsubishi Gas Chemical Company, Inc. | テトラグリシジルアミノ化合物の製造方法 |
JP2010241872A (ja) * | 2009-04-01 | 2010-10-28 | Nippon Steel Chem Co Ltd | エポキシ樹脂、その製造方法、エポキシ樹脂組成物および硬化物 |
Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018009177A (ja) * | 2012-06-07 | 2018-01-18 | 日本化薬株式会社 | エポキシ樹脂、エポキシ樹脂組成物および硬化物 |
KR20160023555A (ko) | 2014-08-22 | 2016-03-03 | 닛뽄 가야쿠 가부시키가이샤 | 에폭시(메타)아크릴레이트 화합물 및 그것을 함유하는 수지 조성물 그리고 그의 경화물, 컬러 필터 및 표시 소자 |
JPWO2016031643A1 (ja) * | 2014-08-26 | 2017-06-08 | 日本化薬株式会社 | 反応性ポリエステル化合物、それを用いた活性エネルギー線硬化型樹脂組成物 |
KR102228850B1 (ko) | 2014-08-26 | 2021-03-17 | 닛뽄 가야쿠 가부시키가이샤 | 반응성 폴리에스테르 화합물, 그것을 이용한 활성 에너지선 경화형 수지 조성물 |
CN106604947B (zh) * | 2014-08-26 | 2019-08-06 | 日本化药株式会社 | 反应性聚酯化合物、使用该化合物的活性能量射线固化型树脂组合物 |
WO2016031643A1 (ja) * | 2014-08-26 | 2016-03-03 | 日本化薬株式会社 | 反応性ポリエステル化合物、それを用いた活性エネルギー線硬化型樹脂組成物 |
CN106604947A (zh) * | 2014-08-26 | 2017-04-26 | 日本化药株式会社 | 反应性聚酯化合物、使用该化合物的活性能量射线固化型树脂组合物 |
KR20170046126A (ko) | 2014-08-26 | 2017-04-28 | 닛뽄 가야쿠 가부시키가이샤 | 반응성 폴리에스테르 화합물, 그것을 이용한 활성 에너지선 경화형 수지 조성물 |
KR20160047415A (ko) * | 2014-10-22 | 2016-05-02 | 아지노모토 가부시키가이샤 | 수지 조성물 |
JP2016079366A (ja) * | 2014-10-22 | 2016-05-16 | 味の素株式会社 | 樹脂組成物 |
KR102411958B1 (ko) * | 2014-10-22 | 2022-06-22 | 아지노모토 가부시키가이샤 | 수지 조성물 |
KR102490151B1 (ko) * | 2015-03-18 | 2023-01-18 | 미츠비시 가스 가가쿠 가부시키가이샤 | 수지 조성물, 프리프레그, 금속박 피복 적층판, 수지 시트, 및 프린트 배선판 |
KR20170129119A (ko) * | 2015-03-18 | 2017-11-24 | 미츠비시 가스 가가쿠 가부시키가이샤 | 수지 조성물, 프리프레그, 금속박 피복 적층판, 수지 시트, 및 프린트 배선판 |
US20180009935A1 (en) * | 2015-03-18 | 2018-01-11 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board |
JPWO2016147735A1 (ja) * | 2015-03-18 | 2018-01-25 | 三菱瓦斯化学株式会社 | 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート、及びプリント配線板 |
JP7046602B2 (ja) | 2015-03-18 | 2022-04-04 | 三菱瓦斯化学株式会社 | 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート、及びプリント配線板 |
WO2016147735A1 (ja) * | 2015-03-18 | 2016-09-22 | 三菱瓦斯化学株式会社 | 樹脂組成物、プリプレグ、金属箔張積層板、樹脂シート、及びプリント配線板 |
JP2017071706A (ja) * | 2015-10-08 | 2017-04-13 | 日本化薬株式会社 | エポキシ樹脂組成物、硬化性樹脂組成物およびその硬化物 |
KR102340503B1 (ko) * | 2016-03-28 | 2021-12-20 | 세키스이가가쿠 고교가부시키가이샤 | 수지 조성물 및 다층 기판 |
TWI706003B (zh) * | 2016-03-28 | 2020-10-01 | 日商積水化學工業股份有限公司 | 樹脂組合物以及多層基板 |
JPWO2017170521A1 (ja) * | 2016-03-28 | 2019-02-07 | 積水化学工業株式会社 | 樹脂組成物及び多層基板 |
KR20180127301A (ko) * | 2016-03-28 | 2018-11-28 | 세키스이가가쿠 고교가부시키가이샤 | 수지 조성물 및 다층 기판 |
WO2017170521A1 (ja) * | 2016-03-28 | 2017-10-05 | 積水化学工業株式会社 | 樹脂組成物及び多層基板 |
JP7385344B2 (ja) | 2016-03-28 | 2023-11-22 | 積水化学工業株式会社 | 熱硬化性樹脂組成物及び多層基板 |
JP2019529661A (ja) * | 2016-09-26 | 2019-10-17 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | 高熱高靱性エポキシ組成物、物品、及びその使用 |
WO2018117150A1 (ja) * | 2016-12-22 | 2018-06-28 | 日本化薬株式会社 | エポキシ樹脂混合物、エポキシ樹脂組成物およびその硬化物 |
JP2023025100A (ja) * | 2017-12-25 | 2023-02-21 | 太陽インキ製造株式会社 | 熱硬化性樹脂充填材、その硬化物および多層プリント配線板 |
JP7441928B2 (ja) | 2017-12-25 | 2024-03-01 | 太陽ホールディングス株式会社 | 熱硬化性樹脂充填材、その硬化物および多層プリント配線板 |
Also Published As
Publication number | Publication date |
---|---|
CN104470965A (zh) | 2015-03-25 |
JP6366504B2 (ja) | 2018-08-01 |
CN104470965B9 (zh) | 2019-01-01 |
TW201412805A (zh) | 2014-04-01 |
KR20150031232A (ko) | 2015-03-23 |
SG11201408157QA (en) | 2015-01-29 |
TWI579313B (zh) | 2017-04-21 |
JPWO2013183735A1 (ja) | 2016-02-01 |
MY175000A (en) | 2020-06-01 |
JP2018009177A (ja) | 2018-01-18 |
CN104470965B (zh) | 2017-04-12 |
KR101952321B1 (ko) | 2019-02-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6366504B2 (ja) | エポキシ樹脂、エポキシ樹脂組成物および硬化物 | |
JP6366590B2 (ja) | エポキシ樹脂混合物、エポキシ樹脂組成物、硬化物および半導体装置 | |
JP6240069B2 (ja) | エポキシ樹脂組成物、およびその硬化物、並びに、硬化性樹脂組成物 | |
JP5273762B2 (ja) | エポキシ樹脂、エポキシ樹脂組成物およびその硬化物 | |
JP5386352B2 (ja) | 液状エポキシ樹脂、エポキシ樹脂組成物、および硬化物 | |
JP6735097B2 (ja) | エポキシ樹脂混合物、エポキシ樹脂組成物、硬化物および半導体装置 | |
JP2017071706A (ja) | エポキシ樹脂組成物、硬化性樹脂組成物およびその硬化物 | |
WO2008020594A1 (fr) | Résine époxy liquide modifiée, composition de résine époxy contenant celle-ci et produit cuit dérivé | |
JP5127160B2 (ja) | エポキシ樹脂、硬化性樹脂組成物、およびその硬化物 | |
JP6302280B2 (ja) | エポキシ樹脂、硬化性樹脂組成物および硬化物 | |
JP6358712B2 (ja) | フェノール樹脂、該フェノール樹脂を含有するエポキシ樹脂組成物、およびその硬化物 | |
JPWO2017057140A1 (ja) | 置換アリルエーテル樹脂、メタリルエーテル樹脂、エポキシ樹脂、エポキシ樹脂組成物及びその硬化物 | |
JP5220488B2 (ja) | エポキシ樹脂、エポキシ樹脂組成物、およびその硬化物 | |
JP6239599B2 (ja) | フェノール樹脂、該フェノール樹脂を含有するエポキシ樹脂組成物、およびその硬化物 | |
JP6544815B2 (ja) | エポキシ樹脂、硬化性樹脂組成物および硬化物 | |
WO2018117150A1 (ja) | エポキシ樹脂混合物、エポキシ樹脂組成物およびその硬化物 | |
JP4776446B2 (ja) | エポキシ樹脂、エポキシ樹脂組成物、およびその硬化物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13800754 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20147032893 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2014520059 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13800754 Country of ref document: EP Kind code of ref document: A1 |