WO2022265096A1 - エポキシ樹脂、硬化性樹脂組成物、およびその硬化物 - Google Patents
エポキシ樹脂、硬化性樹脂組成物、およびその硬化物 Download PDFInfo
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- WO2022265096A1 WO2022265096A1 PCT/JP2022/024317 JP2022024317W WO2022265096A1 WO 2022265096 A1 WO2022265096 A1 WO 2022265096A1 JP 2022024317 W JP2022024317 W JP 2022024317W WO 2022265096 A1 WO2022265096 A1 WO 2022265096A1
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- epoxy resin
- resin composition
- curable resin
- epoxy
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- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Images
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
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- 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
Definitions
- the present invention relates to an epoxy resin having a specific structure, a curable resin composition, and a cured product thereof.
- Epoxy resin is excellent in electrical properties (dielectric constant/dielectric loss tangent, insulating properties), mechanical properties, adhesive properties, and thermal properties (heat resistance, etc.). It is widely used in the fields of electrical and electronic materials, structural materials, adhesives, and paints.
- Patent Document 1 In recent years, in the electrical and electronic fields, performance improvements such as flame retardancy, moisture resistance, adhesion, and dielectric properties of resin compositions, high purity, low viscosity for high filling of fillers (inorganic or organic fillers) There is a demand for further improvement in various properties such as improved reactivity in order to shorten the molding cycle (Patent Document 1). In addition, as structural materials, lightweight materials with excellent mechanical properties are required for use in aerospace materials, leisure and sports equipment, and the like.
- an aromatic cross-linking unit is sometimes introduced for the purpose of improving the heat resistance of the resin composition, but in this case, since the main skeleton is aromatic, it is easily carbonized and the tracking resistance deteriorates. Further, when the heat resistance is improved by increasing the molecular weight, the thermal decomposition temperature rises due to the increase in the molecular weight, and the tracking resistance deteriorates. In other words, since there is a trade-off relationship between heat resistance and tracking characteristics, it is extremely difficult to satisfy these tracking characteristics while maintaining heat resistance. Furthermore, when a resin containing a polysensitive aromatic compound is blended to impart properties such as flame retardancy, the tracking resistance tends to deteriorate, making it difficult to achieve both high tracking resistance and flame retardancy.
- a performance level category is set by the value of CTI. Since the PLC belongs to a smaller class, the design size (creepage distance) of the device can be reduced, so the PLC is preferably 3 or less, particularly preferably 1 or less.
- PLC and CTI have the following relationship. PLC1: CTI 600 or more, PLC2: CTI 400 or more and less than 600, PLC3: 250 or more and less than 400, PLC4: 100 or more and less than 175, PLC5: less than 100.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide an epoxy resin and a curable resin composition whose cured product is excellent in heat resistance and tracking resistance.
- the present invention relates to an epoxy resin having a specific structure, a curable resin composition, and a cured product thereof, which is excellent in heat resistance and tracking resistance. Therefore, the present invention can be applied to insulating materials for electric and electronic parts (such as highly reliable semiconductor sealing materials), laminated boards (printed wiring boards, build-up boards, etc.), various composite materials such as CFRP, adhesives, paints, etc. Useful.
- insulating materials for electric and electronic parts such as highly reliable semiconductor sealing materials
- laminated boards printed wiring boards, build-up boards, etc.
- various composite materials such as CFRP, adhesives, paints, etc. Useful.
- FIG. 1 shows a GPC chart of Synthesis Example 1.
- FIG. 2 shows a GPC chart of Synthesis Example 2.
- FIG. 1 shows a GPC chart of Synthesis Example 3.
- FIG. 1 shows a GPC chart of Example 1.
- FIG. 2 shows a GPC chart of Example 2.
- FIG. The GPC chart of Example 3 is shown.
- 1 shows a GPC chart of Comparative Synthesis Example 1.
- FIG. 2 shows a GPC chart of Comparative Synthesis Example 2.
- FIG. A GPC chart of FAE-2500 is shown.
- TMA charts of Examples 4 and 5 and Comparative Examples 1 and 2 are shown.
- 4 shows a GPC chart of Synthesis Example 4.
- FIG. The GPC chart of Example 7 is shown. CTI measurement results of Examples 10 to 13 and Comparative Examples 5 to 8 are shown.
- the epoxy resin of the present invention is represented by the following formula (1), and the value obtained by dividing the epoxy equivalent (g/eq.) by the softening point (°C) is 2.0 or more and less than 2.2.
- n can be calculated from the number average molecular weight obtained by measurement by gel permeation chromatography (GPC, detector: UV 254 nm), or from the area ratio of each separated peak. n is more preferably a real number of 1-5, and particularly preferably a real number of 2-4.
- the melt viscosity of the resin is an index, and the viscosity is preferably 2 Pa ⁇ s or less in the viscosity measurement (ICI melt viscosity) by the cone-plate method at 150°C.
- the viscosity is preferably 0.4 Pa ⁇ s or more. In consideration of the balance between heat resistance and thermal decomposition properties, it is more preferably 0.45 Pa ⁇ s or more, and particularly preferably 0.5 Pa ⁇ s or more.
- the compound of formula (1) where n is less than 1 is preferably contained at a rate of 0.5 to 10 area %, more preferably 0.5 to 5 area %, and particularly preferably 0.5 ⁇ 2.5 area %.
- the epoxy resin of the present invention is usually in the form of a solid resin at room temperature, and its softening point is preferably 90°C or higher, more preferably 95°C or higher. Moreover, the upper limit is 150 degreeC. If the softening point is higher than 150° C., the solvent tends to remain when the resin is taken out, and voids tend to occur during curing. In addition, there are major problems in production, such as the tendency to foam when the solvent is distilled off. On the other hand, when the softening point is 90° C. or lower, there is an adverse effect on heat resistance and thermal decomposition characteristics. Also, its epoxy equivalent is 200 to 300 g/eq. is preferably 205 to 250 g/eq. is. Epoxy equivalent is 200g/eq.
- the epoxy equivalent was measured according to JIS K-7236.
- the softening point was measured using a softening point measuring instrument FP90 manufactured by METLER TOLEDO.
- the epoxy resin of the present invention preferably has a high softening point and a large number of functional groups per unit molecular weight.
- the softening point tends to increase as the molecular weight increases. This means that the softening point measures the fluidity of the resin when heated, and that the larger the molecular weight, the more difficult it is for the molecules to move, that is, the higher the softening point. On the other hand, it is generally said that the higher the softening point, the better the heat resistance. However, it is more effective to increase the number of functional groups per unit weight to increase the heat resistance, and the epoxy equivalent is a value linked to the number of functional groups. becomes.
- the parameter A is the value obtained by dividing the epoxy equivalent (g/eq.) by the softening point (°C), and the parameter A is preferably 2.0 or more and less than 2.2. If the parameter A is less than 2.0, the epoxy equivalent is too small, so some impurities may remain. It means that it is low, and heat resistance and thermal decomposition characteristics cannot be compatible.
- the thermal decomposition characteristic is said to be a parameter that affects the tracking resistance characteristic, and it is thought that the lower the thermal decomposition temperature in the trunking test, the more difficult it is to conduct between the electrodes, so it can withstand high voltages. Normally, increasing the molecular weight tends to increase the thermal decomposition temperature, but in the present invention, even if the molecular weight is increased, there is no large difference in the thermal decomposition temperature, and it is believed that high tracking resistance can be maintained.
- the method for producing the epoxy resin of the present invention is not particularly limited, it can be obtained, for example, by adding or ring-closing a phenol resin represented by the following formula (2) and epihalohydrin in the presence of a solvent and a catalyst.
- n can be calculated from the number average molecular weight obtained by measurement by gel permeation chromatography (GPC, detector: UV 254 nm), or from the area ratio of each separated peak. n is more preferably 1-5, and particularly preferably 1-3.
- the method for producing the phenolic resin represented by the formula (2) is not particularly limited, but specifically alkylphenols (3-methyl-6-t-butylphenol and 4-methyl-2-t-butylphenol) and p-hydroxybenzaldehyde is polycondensed under acidic conditions to form a novolak.
- Alkylphenols (3-methyl-6-t-butylphenol and 4-methyl-2-t-butylphenol) and p-hydroxybenzaldehyde are preferably reacted at a ratio of 3:2 to 2:1.
- the ratio of 3-methyl-6-t-butylphenol and 4-methyl-2-t-butylphenol is preferably 3-methyl-6-t-butylphenol at 90% by weight or more in the alkylphenol, and this ratio is suitable for the production of phenolic resin. Adjust with the amount of alkylphenol blended at times. Specifically, the alkylphenol as a raw material is charged according to the target introduction ratio of the alkylphenol. The resulting phenolic resin has a hydroxyl equivalent weight of 140 to 170 g/eq. is preferably 145 to 165 g/eq. Especially preferably 150 to 160 g/eq. is.
- the acidic catalyst used in synthesizing the phenolic resin represented by the formula (2) includes hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid, Examples include activated clay and ion exchange resins. These may be used alone or in combination of two or more.
- the amount of the catalyst used is 0.1 to 50% by weight, preferably 1 to 30% by weight, based on the phenolic hydroxyl groups used. Become slow.
- the reaction may be carried out using an organic solvent, if necessary, or may be carried out without a solvent.
- a solvent capable of azeotroping with water since the reaction can proceed more efficiently by azeotropically dehydrating the water to be purified during the reaction.
- a hydrocarbon-based organic solvent such as toluene or xylene.
- the softening point of the phenol resin represented by the formula (2) is very high, it is preferably taken out by a technique such as reprecipitation or recrystallization. For example, a technique such as precipitation by replacing the solvent with a poor solvent. is applicable.
- the total amount of residual raw material monomers is preferably 5 area % or less, and each peak is preferably less than 1.5 area %. The amount of this monomer affects the residual amount of low-molecular-weight epoxy resin, and this amount affects heat resistance and the like.
- the amount of epihalohydrin to be used is generally 1.0 to 20.0 mol, preferably 1.5 to 10.0 mol, per 1 mol of phenolic hydroxyl group of the phenolic resin.
- Alkali metal hydroxides that can be used in the epoxidation reaction include sodium hydroxide and potassium hydroxide.
- the alkali metal hydroxide may be solid or its aqueous solution may be used.
- an aqueous solution is used, an aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, and water is removed by liquid separation. Alternatively, epihalohydrin may be continuously returned to the reaction system.
- the amount of the alkali metal hydroxide to be used is generally 0.9 to 2.5 mol, preferably 0.95 to 1.5 mol, per 1 mol of the phenolic hydroxyl group of the phenolic resin.
- a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, or trimethylbenzylammonium chloride may be added as a catalyst to promote the above reaction.
- the amount of the quaternary ammonium salt to be used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the phenolic hydroxyl group of the phenolic resin. If the amount used is too small, a sufficient reaction acceleration effect cannot be obtained, and if the amount used is too large, the amount of quaternary ammonium salt remaining in the epoxy resin increases, which may cause deterioration in electrical reliability.
- an alcohol such as methanol, ethanol and isopropyl alcohol
- an aprotic polar solvent such as dimethylsulfone, dimethylsulfoxide, tetrahydrofuran and dioxane
- the amount used is generally 2-50% by weight, preferably 4-20% by weight, based on the amount of epihalohydrin used.
- an aprotic polar solvent it is usually 5-100% by weight, preferably 10-80% by weight, based on the amount of epihalohydrin used.
- the reaction temperature is usually 30-90°C, preferably 35-80°C.
- the reaction time is usually 0.5 to 100 hours, preferably 1 to 30 hours.
- epihalohydrin, solvent, etc. are removed from the reactant by heating under reduced pressure after washing with water or without washing with water.
- the recovered epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added. can also be used to ensure ring closure.
- the alkali metal hydroxide is used in an amount of usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per 1 mol of the phenolic hydroxyl group of the phenolic resin used for glycidylation.
- the reaction temperature is generally 50-120° C., and the reaction time is generally 0.5-24 hours.
- the salt produced 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 represented by the formula (1) may be used alone, or may be used in combination with other epoxy resins.
- the ratio of the epoxy resin represented by the formula (1) to the total epoxy resin is preferably 10 to 98% by weight, more preferably 30 to 95% by weight, and still more preferably 60 to 95% by weight. % by weight.
- epoxy resins that can be used in combination with the epoxy resin represented by formula (1) include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols (phenol, alkyl Substituted phenol, aromatic substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaric aldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); the above phenols and various diene compounds (dicyclopenta
- Resins alicyclic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, and the like can be mentioned, but the epoxy resins that are commonly used are not limited to these. These may be used independently and may use 2 or more types.
- curing agents examples include amine-based curing agents, acid anhydride-based curing agents, amide-based curing agents, and phenol-based curing agents.
- Specific examples of usable curing agents include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 3,3′-diamino Diphenylsulfone, 2,2'-diaminodiphenylsulfone, diethyltoluenediamine, dimethylthiotoluenediamine, diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4' -diaminodiphenylmethane, 4,4'
- an aromatic amine in order to secure a pot life
- an aliphatic amine in order to impart quick curing.
- amide compounds such as polyamide resin synthesized from dicyandiamide, dimer of linolenic acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydro Acid anhydride compounds such as phthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride; bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.) or phenols ( Phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formal
- the amount of the curing agent used in the curable resin composition of the present invention is preferably 0.5 to 1.5 equivalents, more preferably 0.6 to 1.2 equivalents, relative to 1 equivalent of the epoxy group of the epoxy resin. is particularly preferred. Good cured physical properties can be obtained by setting the equivalent weight to 0.5 to 1.5.
- a curing accelerator may be used in combination when performing a curing reaction using the above curing agent.
- Curing accelerators that can be used include, for example, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl)phenol, triethylenediamine, tertiary amines such as triethanolamine and 1,8-diazabicyclo(5,4,0)undecene-7; organic phosphines such as triphenylphosphine, diphenylphosphine and tributylphosphine; metal compounds such as tin octylate; Tetraphenylphosphonium/tetraphenylborate, tetrasubstituted phosphonium/tetrasubstituted borate such as tetraphenylphosphonium/ethyltriphenylborate, 2-
- Carboxylic acid compounds such as phenyl boron salts, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthoic acid, and salicylic acid.
- a carboxylic acid compound such as salicylic acid is preferred from the viewpoint of promoting the curing reaction between the amine compound and the epoxy resin. 0.01 to 15 parts by weight of the curing accelerator is used as needed with respect to 100 parts by weight of the epoxy resin.
- an inorganic filler can be added to the curable resin composition of the present invention, if necessary.
- Inorganic fillers include powders of crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, etc. Beads formed by spheroidizing are included, but are not limited to these. These may be used independently and may use 2 or more types. The amount of these inorganic fillers used varies depending on the application.
- the curable resin composition it is preferably used in a proportion of 20% by weight or more, more preferably 30% by weight or more, and in particular 70 to 95% by weight in order to improve the coefficient of linear expansion with the lead frame % is more preferable.
- the content of the inorganic filler is important for improving the anti-tracking performance.
- the content of the inorganic filler in the total amount of the curable resin composition of the present invention is preferably 74% by weight or more and 95% by weight or less, and particularly preferably 78% by weight or more and 95% by weight or less.
- the anti-tracking performance is greatly improved when the content is 74% by weight or more. Epoxy resin and advantage becomes smaller.
- a release agent can be added to the curable resin composition of the present invention to improve release from the mold during molding.
- the mold release agent any of those conventionally known can be used. system waxes and the like. These may be used alone or in combination of two or more.
- the blending amount of these release agents is preferably 0.5 to 3% by weight based on the total organic components. If the amount is too small, the release from the mold will be poor, and if the amount is too large, adhesion to the lead frame or the like will be poor.
- a coupling agent can be added to the curable resin composition of the present invention in order to increase the adhesion between the inorganic filler and the resin component.
- the coupling agent any of conventionally known ones can be used. Examples include various alkoxysilane compounds such as silane, alkoxytitanium compounds, and aluminum chelates. These may be used alone or in combination of two or more.
- the coupling agent may be added by first treating the surface of the inorganic filler with the coupling agent and then kneading it with the resin, or by mixing the coupling agent with the resin and then kneading the inorganic filler. .
- additives can be added to the curable resin composition of the present invention as necessary.
- additives that can be used include polybutadiene and its modified products, modified acrylonitrile copolymers, polyphenylene ethers, polystyrene, polyethylene, polyimide, fluororesins, maleimide compounds, cyanate ester compounds, silicone gels, and silicone oils. and coloring agents such as carbon black, phthalocyanine blue and phthalocyanine green.
- the curable resin composition of the present invention is obtained by uniformly mixing the above components.
- the curable resin composition of the present invention can be easily cured by the same method as conventionally known methods. For example, an epoxy resin and a curing agent, and if necessary, a curing accelerator, an inorganic filler, a release agent, a silane coupling agent, and an additive are mixed until uniform using an extruder, a kneader, a roll, etc.
- the curable resin composition of the present invention is obtained by thorough mixing, which is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, or the like.
- a cured product can be obtained by heating for a period of time.
- the curable resin composition of the present invention may contain a solvent as necessary.
- a curable resin composition containing a solvent is a prepreg obtained by impregnating a fibrous substance (base material) such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and heating and drying it.
- a cured product of the curable resin composition of the present invention can be obtained by hot press molding.
- the solvent content of this curable resin composition is usually 10 to 70% by weight, preferably about 15 to 70% by weight.
- the solvent examples include amide solvents such as ⁇ -butyrolactones, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide and N,N-dimethylimidazolidinone; sulfones such as tetramethylenesulfone; Ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, propylene glycol monobutyl ether, preferably lower (1 to 3 carbon atoms) alkylene glycol mono- or di-lower (1 carbon atom) 3) Alkyl ethers; ketone-based solvents such as methyl ethyl ketone and methyl isobutyl ketone, preferably two alkyl groups may be the same or different. Di-lower (C 1-3) alkyl ketones; aromatic solvents such as toluene and x
- a sheet-like adhesive can be obtained by coating the release film with the epoxy resin varnish, removing the solvent under heating, and performing B-stage.
- This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates and the like.
- thermosetting resins such as epoxy resins
- molding materials including sheets, films, FRP, etc.
- insulating materials printed circuit boards, wire coating, etc.
- sealing agents additives to other resins, and the like.
- Adhesives include adhesives for civil engineering, construction, automobiles, general office and medical use, as well as adhesives for electronic materials.
- adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, adhesives for semiconductors such as underfill, underfill for BGA reinforcement, anisotropic conductive films ( ACF), mounting adhesives such as anisotropic conductive paste (ACP), and the like.
- ⁇ Epoxy equivalent was measured by a method according to JIS K-7236.
- ⁇ A hydroxyl equivalent sample is acetylated using acetic anhydride in a pyridine solution, and after the acetylation is completed, the remaining acid anhydride is decomposed with water. This was titrated with a 0.5N KOH ethanol solution using a potentiometric titrator to measure the amount of free acetic acid, and the hydroxyl equivalent was determined from the results.
- a GPC chart (measurement condition 1) is shown in FIG.
- a GPC chart (measurement condition 1) is shown in FIG.
- a GPC chart (measurement condition 1) is shown in FIG.
- Example 1 Thermometer, cooling tube, fractionating tube, while purging a flask equipped with a stirrer, 310 parts of the phenolic resin (P1) obtained in Synthesis Example 1, 973 parts of epichlorohydrin, 274 parts of dimethyl sulfoxide, 15 parts of water was added, and the internal temperature was raised to 45°C. After adding 16 parts of sodium hydroxide in portions over 1.5 hours, the mixture was reacted at 45° C. for 2 hours and at 70° C. for 1 hour. Unreacted epichlorohydrin and the solvent were distilled off under heating and reduced pressure. 1040 parts of MIBK was added and the organic layer was washed once with 440 parts of water.
- the organic layer was returned to the reaction vessel, 20 parts of a 30% by weight sodium hydroxide aqueous solution was added, and the mixture was reacted at 70° C. for 2 hours. After allowing to cool, the organic layer was washed four times with 130 parts of water, and the solvent was distilled off under heating and reduced pressure to obtain 170 parts of epoxy resin (E1) as a solid resin.
- the epoxy equivalent is 214 g/eq.
- the ICI viscosity (150° C.) was 0.57 Pa ⁇ s
- the softening point was 100° C.
- the parameter A was 2.14.
- a GPC chart (measurement condition 2) is shown in FIG.
- Example 2 Thermometer, cooling tube, fractionating tube, while purging a flask equipped with a stirrer, 310 parts of the phenolic resin (P1) obtained in Synthesis Example 1, 584 parts of epichlorohydrin, 274 parts of dimethyl sulfoxide, 15 parts of water was added, and the internal temperature was raised to 45°C. After adding 16 parts of sodium hydroxide in portions over 1.5 hours, the mixture was reacted at 45° C. for 2 hours and at 70° C. for 1 hour. Unreacted epichlorohydrin and the solvent were distilled off under heating and reduced pressure. 1040 parts of MIBK was added and the organic layer was washed once with 440 parts of water.
- the organic layer was returned to the reaction vessel, 20 parts of a 30 wt % sodium hydroxide aqueous solution was added, and the mixture was reacted at 70° C. for 2 hours. After allowing to cool, the organic layer was washed four times with 130 parts of water, and the solvent was distilled off under heating and reduced pressure to obtain 141 parts of epoxy resin (E2) as a solid resin.
- the epoxy equivalent is 225 g/eq.
- the ICI viscosity (150° C.) was 1.92 Pa ⁇ s
- the softening point was 110° C.
- the parameter A was 2.05.
- a GPC chart (measurement condition 2) is shown in FIG.
- Example 3 Thermometer, cooling tube, fractionating tube, while purging a flask equipped with a stirrer, 310 parts of the phenolic resin (P3) obtained in Synthesis Example 3, 778 parts of epichlorohydrin, 274 parts of dimethyl sulfoxide, 15 parts of water was added, and the internal temperature was raised to 45°C. After adding 16 parts of sodium hydroxide in portions over 1.5 hours, the mixture was reacted at 45° C. for 2 hours and at 70° C. for 1 hour. Unreacted epichlorohydrin and the solvent were distilled off under heating and reduced pressure. 1040 parts of MIBK was added and the organic layer was washed once with 440 parts of water.
- P3 phenolic resin obtained in Synthesis Example 3
- the organic layer was returned to the reaction vessel, 20 parts of a 30% by weight sodium hydroxide aqueous solution was added, and the mixture was reacted at 70° C. for 2 hours. After allowing to cool, the organic layer was washed four times with 130 parts of water, and the solvent was distilled off under heating and reduced pressure to obtain 303 parts of epoxy resin (E3) as a solid resin.
- the epoxy equivalent is 216 g/eq.
- total chlorine was 440 ppm (ISO21627-3 compliant)
- inorganic chloride ion concentration was 0.3 ppm
- ICI viscosity (150°C) was 0.64 Pa s
- softening point was 100°C
- parameter A was 2.16. .
- a GPC chart (measurement condition 3) is shown in FIG.
- the organic layer was returned to the reaction vessel, 20 parts of a 30% by weight sodium hydroxide aqueous solution was added, and the mixture was reacted at 70° C. for 2 hours. After standing to cool, the organic layer was washed four times with 130 parts of water, and the solvent was distilled off under heating and reduced pressure to obtain 165 parts of epoxy resin (E4) as a solid resin.
- the epoxy equivalent is 223 g/eq.
- the ICI viscosity (150° C.) was 0.60 Pa ⁇ s
- the softening point was 99.7° C.
- the parameter A was 2.24.
- a GPC chart (measurement condition 2) is shown in FIG.
- the organic layer was returned to the reaction vessel, 20 parts of a 30% by weight sodium hydroxide aqueous solution was added, and the mixture was reacted at 70° C. for 2 hours. After allowing to cool, the organic layer was washed four times with 130 parts of water, and the solvent was distilled off under heating and reduced pressure to obtain 161 parts of epoxy resin (E5) as a solid resin.
- the epoxy equivalent is 224 g/eq.
- the ICI viscosity (150° C.) was 0.66 Pa ⁇ s
- the softening point was 100.9° C.
- the parameter A was 2.22.
- a GPC chart (measurement condition 2) is shown in FIG.
- the epoxy equivalent of FAE-2500 is 213 g/eq.
- the ICI viscosity (150° C.) was 0.30 Pa ⁇ s
- the softening point was 93.5° C.
- the parameter A was 2.28.
- a GPC chart (measurement condition 2) is shown in FIG.
- Table 1 shows the results of measuring the test piece for evaluation under the following conditions. A TMA chart is shown in FIG.
- DMA Dynamic viscoelasticity measurement
- TMA Thermo-mechanical property measurement
- Tg glass transition temperature
- CTE coefficient of linear expansion change
- TG-DTA ⁇ Thermogravimetric differential thermal measurement
- Epoxy resin (E1) epoxy resin (E6, FAE-2500 (manufactured by Nippon Kayaku)), Zylock-type phenolic resin (MEHC-7800SS manufactured by Meiwa Kasei) as a curing agent, triphenylphosphine (TPP, manufactured by Tokyo Kasei Co., Ltd.) as a catalyst ), silica gel (fused silica MSR-2212, manufactured by Tatsumori) as an inorganic filler, carnauba wax (manufactured by Celarica Noda) as a release agent, and a silane coupling agent (trade name: KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.) as an additive.
- KBM-303 silane coupling agent
- Test sample shape Diameter 50 mm Thickness 3 mm 1 point measurement per sheet
- a GPC chart (measurement condition 1) is shown in FIG.
- Example 7 Thermometer, cooling tube, fractionating tube, while purging a flask equipped with a stirrer, 320 parts of the phenolic resin (P4) obtained in Synthesis Example 4, 973 parts of epichlorohydrin, 274 parts of dimethyl sulfoxide, 15 parts of water was added, and the internal temperature was raised to 45°C. After adding 16 parts of sodium hydroxide in portions over 1.5 hours, the mixture was reacted at 45° C. for 2 hours and at 70° C. for 1 hour. Unreacted epichlorohydrin and the solvent were distilled off under heating and reduced pressure. 1040 parts of MIBK was added and the organic layer was washed once with 440 parts of water.
- the organic layer was returned to the reaction vessel, 20 parts of a 30% by weight sodium hydroxide aqueous solution was added, and the mixture was reacted at 70° C. for 2 hours. After allowing to cool, the organic layer was washed four times with 130 parts of water, and the solvent was distilled off under heating and reduced pressure to obtain 107 parts of epoxy resin (E7) as a solid resin.
- the epoxy equivalent is 220 g/eq.
- the ICI viscosity (150° C.) was 0.8 Pa ⁇ s or more
- the softening point was 108.5° C.
- the parameter A was 2.03.
- a GPC chart (measurement condition 3) is shown in FIG. In addition, each peak had a retention time of 35.619 minutes at 1.75%, and other peaks at 1.5 area% or less.
- Epoxy resins E3 and E7 obtained in the above examples trisphenolmethane type phenol resin (Nippon Kayaku KAYAHARD KTG-105 hydroxyl equivalent 102 g / eq.) as a curing agent, biphenyl aralkyl type phenol resin (Nippon Kayaku KAYAHARD GPH-65 curing agent hydroxyl equivalent 200 g / eq.), triphenylphosphine (TPP, manufactured by Tokyo Kasei Co., Ltd.) as a catalyst, silica gel (fused silica MSR-2212, manufactured by Tatsumori) as an inorganic filler, carnauba wax as a release agent (manufactured by Celarica Noda) and a silane coupling agent (trade name: KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.) as an additive, blended in the proportions (parts by weight) shown in Table 3, and mixed uniformly using a mixing
- Epoxy resin E1 obtained in the above example biphenyl aralkyl epoxy resin (manufactured by Nippon Kayaku, NC-3000), Zylock type phenolic resin (manufactured by Meiwa Kasei MEHC-7800SS) as a curing agent, triphenylphosphine as a catalyst ( TPP, manufactured by Tokyo Kasei Co., Ltd.), silica gel (fused silica MSR-2212, manufactured by Tatsumori) as an inorganic filler, carnauba wax (manufactured by Celarica Noda) as a release agent, and a silane coupling agent as an additive (trade name: KBM- 303 manufactured by Shin-Etsu Chemical Co., Ltd.), and the mixture was uniformly mixed and kneaded using a mixing roll to obtain a curable resin composition.
- This curable resin composition was pulverized and then tableted with a tablet machine.
- the tableted curable resin composition was subjected to transfer molding (175° C. for 60 to 15 minutes) and further cured under the conditions of 160° C. ⁇ 2 hours+180° C. ⁇ 6 hours after demolding to obtain test pieces for evaluation. A tracking resistance test was performed using this test piece. The measurement results are shown in Table 4.
- Epoxy resin E1 obtained in the above example biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku, NC-3000), Zylock type phenol resin as a curing agent (Meiwa Kasei MEHC-7800SS), biphenyl aralkyl type phenol resin ( Nippon Kayaku KAYAHARD GPH-65), triphenylphosphine (TPP, Tokyo Kasei Co., Ltd.) as a catalyst, silica gel (fused silica MSR-2212, Tatsumori) as an inorganic filler, carnauba wax (Celarica Noda ), and a silane coupling agent (trade name: KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.) as an additive, were uniformly mixed and kneaded using a mixing roll to obtain a curable resin composition.
- This curable resin composition was pulverized and then tableted with a tablet machine.
- the tableted curable resin composition was subjected to transfer molding (175° C. for 60 to 15 minutes) and further cured under the conditions of 160° C. ⁇ 2 hours+180° C. ⁇ 6 hours after demolding to obtain test pieces for evaluation. A tracking resistance test was performed using this test piece.
- CTI CTI
- IEC-Pub. 60112-2003 4th edition
- the cured product using the epoxy resin of the present invention maintains a relatively high CTI. , confirmed that the rate of increase in CTI is higher.
- the epoxy resin of the present invention is useful for automotive materials, particularly power device peripheral materials, and is particularly effective for applications that require heat resistance and a high comparative tracking index (CTI).
- CTI comparative tracking index
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Abstract
Description
一般にはCTIの値によりperformance level category(PLC)が設定される。PLCがより小さいクラスに属することでそのデバイスの設計のサイズ(沿面距離)などを小さくすることができるため、PLCは3以下であることが好ましく、1以下であることが特に好ましい。
なお、PLCとCTIは以下の関係にある。
PLC1:CTI600以上、PLC2:CTI400以上600未満、PLC3:250以上400未満、PLC4:100以上175未満、PLC5:100未満。
[1]
下記式(1)で表され、エポキシ当量(g/eq.)を軟化点(℃)で除した値が2.0以上2.2未満であるエポキシ樹脂。
[2]
前項[1]に記載のエポキシ樹脂を含有する硬化性樹脂組成物。
[3]
硬化性樹脂組成物総量中、無機充填剤の含有量が74重量%以上95重量%以下である前項[2]に記載の硬化性樹脂組成物。
[4]
前項[2]または[3]に記載の硬化性樹脂組成物を硬化した硬化物。
そのため、本発明は電気電子部品用絶縁材料(高信頼性半導体封止材料など)及び積層板(プリント配線板、ビルドアップ基板など)やCFRPを始めとする各種複合材料、接着剤、塗料等に有用である。
前記式(2)で表されるフェノール樹脂の製法は特に限定されないが、具体的にはアルキルフェノール(3-メチル-6-t-ブチルフェノールおよび4-メチル-2-t-ブチルフェノール)とp-ヒドロキシベンズアルデヒドを酸性条件にて重縮合を行い、ノボラック化を行う。アルキルフェノール(3-メチル6-t-ブチルフェノールおよび4-メチル-2-t-ブチルフェノール)とp-ヒドロキシベンズアルデヒドの比率を3:2~2:1の割合で反応させることが好ましい。3-メチル-6-t-ブチルフェノールと4-メチル-2-t-ブチルフェノールの比率はアルキルフェノール中90重量%以上が3-メチル6-t-ブチルフェノールであることが好ましく、この比率はフェノール樹脂の製造時に配合するアルキルフェノールの量で調整する。具体的には目的とするアルキルフェノールの導入比率通りに原料となるアルキルフェノールを仕込む。
得られるフェノール樹脂の水酸基当量は140~170g/eq.であることが好ましく、さらに好ましくは145~165g/eq.特に好ましくは150~160g/eq.である。
その後、水洗や中和などの工程を行い、溶剤流居後樹脂取り出し、あるいは再沈殿や再結晶などの手法により樹脂を取り出すことができる。前記式(2)で表されるフェノール樹脂の軟化点が非常に高いことから再沈殿や再結晶などの手法により取り出すことが好ましく、例えば、溶剤を貧溶剤に置換することで析出させるなどの手法が適用できる。
上述したように、本発明のエポキシ樹脂の製法は特に限定されないが、たとえば前記式(2)で表されるフェノール樹脂とエピハロヒドリンを溶剤、触媒の存在下に付加もしくは閉環反応させることで得ることができる。
エピハロヒドリンの使用量はフェノール樹脂のフェノール性水酸基1モルに対し通常1.0~20.0モル、好ましくは1.5~10.0モルである。
反応終了後、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トルエン、メチルイソブチルケトンなどの溶剤に溶解し、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できる。この場合アルカリ金属水酸化物の使用量はグリシジル化に使用したフェノール樹脂のフェノール性水酸基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0.5~24時間である。反応終了後、生成した塩を濾過、水洗などにより除去し、更に加熱減圧下溶剤を留去することにより本発明のエポキシ樹脂が得られる。
本発明の硬化性樹脂組成物において用いるエポキシ樹脂は、前記式(1)で表されるエポキシ樹脂を単独で使用してもよいが、他のエポキシ樹脂と併用して使用することもできる。併用する場合、前記式(1)で表されるエポキシ樹脂が全エポキシ樹脂中に占める割合は10~98重量%であることが好ましく、より好ましくは30~95重量%、さらに好ましくは60~95重量%である。前記式(1)で表されるエポキシ樹脂の添加量を10%以上とすることで弾性率向上や低吸水性を発現することができる。
なお、本発明において特に耐トラッキング性能を向上させるうえで無機充填剤の含有量が重要となる。耐トラッキング性能を加味した場合、本発明の硬化性樹脂組成物総量中無機充填剤の好ましい含有量は74重量%以上95重量%以下であり、特に好ましくは78重量%以上95重量%以下である。本発明のエポキシ樹脂構造の場合、74重量%以上であると耐トラッキング性能が大きく向上することが確認できており、74重量%未満の場合、たとえば70重量%未満の場合、トラッキング性能は他のエポキシ樹脂と優位性が小さくなる。
JIS K-7236に準じた方法で測定した。
・軟化点
METLER TOLEDO社軟化点測定器FP90を用い測定した。
・水酸基当量
サンプルをピリジン溶液中、無水酢酸を用いてアセチル化を行い、アセチル化完了後に水で残存する酸無水物を分解。これを0.5NのKOHエタノール溶液を用いて、電位差滴定機で滴定することで遊離の酢酸量を測定を行い、その結果から水酸基当量を求めた。
(測定条件1)
装置 Waters e2695
カラム:SHODEX GPC KF-401HQ、KF-402HQ、KF-403HQ、KF-404HQ 合計4本
流速 0.3 ml/min
カラム温度:40℃
使用溶剤:THF(テトラヒドロフラン)
検出器:UV 254nm
(測定条件2)
装置 東ソー株式会社 HLC-8220GPC
カラム:東ソー株式会社 TSK gel G3000HXL 1本 TSK gel G2000HXL 2本 合計3本
流速 1.065ml/min
カラム温度:40℃
使用溶剤:THF(テトラヒドロフラン)
検出器:UV 254nm
(測定条件3)
装置 東ソー株式会社 HLC-8420GPC
カラム:東ソー株式会社 TSK gel G3000HXL 1本 TSK gel G2000HXL 2本 合計3本
流速 1.065ml/min
カラム温度:40℃
使用溶剤:THF(テトラヒドロフラン)
検出器:UV 254nm
標準ポリスチレン(東ソー株式会社)
PStQuickC, PStQuickD(分子量測定時は内部標準としてスチレンを添加して補正した)
温度計、冷却管、分留管、撹拌機を取り付けたフラスコに窒素パージを施しながら、3-メチル-6-t-ブチルフェノール137.2部、4-メチル-2-t-ブチルフェノール0.16部、p-ヒドロキシベンズアルデヒド60部、トルエン142部、p-トルエンスルホン酸1.4部を加え、110~115℃で8時間反応を行った。反応終了後、25%NaOH 水を加えた後、トルエンを共沸脱水により留去。その後、75%硫酸を加え、pHを5~7に調整し、析出した樹脂粉体をろ過し、60℃で乾燥することで、フェノール樹脂(P1)186部を得た。得られたフェノール樹脂(PI)は粉状であり、軟化点150℃以上、水酸基当量155g/eq.であり、GPCによるn=1は48.8面積%であった。GPCチャート(測定条件1)は図1に示す。
温度計、冷却管、分留管、撹拌機を取り付けたフラスコに窒素パージを施しながら、3-メチル-6-t-ブチルフェノール153.1部、4-メチル-2-t-ブチルフェノール0.17部、p-ヒドロキシベンズアルデヒド60部、トルエン142部、p-トルエンスルホン酸0.6部を加え、100~105℃で6時間反応を行った。反応終了後、25%NaOH 水を加えた後、トルエンを共沸脱水により留去。その後、75%硫酸を加え、pHを5~7に調整し、析出した樹脂粉体をろ過し、60℃で乾燥することで、フェノール樹脂(P2)198部を得た。得られたフェノール樹脂(P2)は粉状であり、軟化点150℃以上、水酸基当量144g/eq.であり、GPCによるn=1は51.7面積%であった。GPCチャート(測定条件1)は図2に示す。
温度計、冷却管、分留管、撹拌機を取り付けたフラスコに窒素パージを施しながら、3-メチル-6-t-ブチルフェノール137.2部、4-メチル-2-t-ブチルフェノール0.16部、pヒドロキシベンズアルデヒド60部、トルエン142部、pトルエンスルホン酸1.4部を加え、110~115℃で8時間反応を行った。反応終了後、25%NaOH 水を加えた後、トルエンを共沸脱水により留去。その後、75%硫酸を加え、pHを5~7に調整し、析出した樹脂粉体をろ過し、60℃で乾燥することで、フェノール樹脂(P3)180部を得た。得られたフェノール樹脂(P3)は粉状であり、軟化点150℃以上、水酸基当量153g/eq.であり、GPCによるn=1は47.6面積%であった。GPCチャート(測定条件1)は図3に示す。
温度計、冷却管、分留管、撹拌機を取り付けたフラスコに窒素パージを施しながら、合成例1で得られたフェノール樹脂(P1)310部、エピクロルヒドリン973部、ジメチルスルホキシド274部、水15部を加え、内温を45℃まで昇温した。水酸化ナトリウム16部を1.5時間かけて分割添加後、45℃で2時間、70℃で1時間反応させた。加熱減圧下で未反応のエピクロルヒドリンおよび溶剤を留去した。MIBK1040部を加え、水440部で有機層を1回洗浄した。有機層を反応容器に戻し、30重量%水酸化ナトリウム水溶液20部を加え、70℃で2時間反応させた。放冷後、水130部で有機層を4回洗浄し、加熱減圧下、溶剤を留去し、固形樹脂としてエポキシ樹脂(E1)を170部得た。エポキシ当量は214g/eq.、ICI粘度(150℃)は0.57Pa・s、軟化点は100℃であり、パラメータAは2.14であった。GPC(検出器 UV254nm)より概算される平均の繰り返し単位nは2.4、n=1は42.3面積%、n=1未満は、1.57面積%であった。GPCチャート(測定条件2)は図4に示す。
温度計、冷却管、分留管、撹拌機を取り付けたフラスコに窒素パージを施しながら、合成例1で得られたフェノール樹脂(P1)310部、エピクロルヒドリン584部、ジメチルスルホキシド274部、水15部を加え、内温を45℃まで昇温した。水酸化ナトリウム16部を1.5時間かけて分割添加後、45℃で2時間、70℃で1時間反応させた。加熱減圧下で未反応のエピクロルヒドリンおよび溶剤を留去した。MIBK1040部を加え、水440部で有機層を1回洗浄した。有機層を反応容器に戻し、30wt%水酸化ナトリウム水溶液20部を加え、70℃で2時間反応させた。放冷後、水130部で有機層を4回洗浄し、加熱減圧下、溶剤を留去し、固形樹脂としてエポキシ樹脂(E2)を141部得た。エポキシ当量は225g/eq.、ICI粘度(150℃)は1.92Pa・s、軟化点は110℃であり、パラメータAは2.05であった。GPC(検出器 UV254nm)より概算される平均の繰り返し単位nは2.9、n=1は31.1面積%、n=1未満は、1.28面積%であった。GPCチャート(測定条件2)は図5に示す。
温度計、冷却管、分留管、撹拌機を取り付けたフラスコに窒素パージを施しながら、合成例3で得られたフェノール樹脂(P3)310部、エピクロルヒドリン778部、ジメチルスルホキシド274部、水15部を加え、内温を45℃まで昇温した。水酸化ナトリウム16部を1.5時間かけて分割添加後、45℃で2時間、70℃で1時間反応させた。加熱減圧下で未反応のエピクロルヒドリンおよび溶剤を留去した。MIBK1040部を加え、水440部で有機層を1回洗浄した。有機層を反応容器に戻し、30重量%水酸化ナトリウム水溶液20部を加え、70℃で2時間反応させた。放冷後、水130部で有機層を4回洗浄し、加熱減圧下、溶剤を留去し、固形樹脂としてエポキシ樹脂(E3)を303部得た。エポキシ当量は216g/eq.、全塩素は440ppm(ISO21627-3準拠)、無機塩素イオン濃度0.3ppm、ICI粘度(150℃)は0.64Pa・s、軟化点は100℃であり、パラメータAは2.16であった。GPC(検出器 UV254nm)より概算されるMnは1059、Mwは2001(ポリスチレン換算)、n=1は39.5面積%、n=1未満は1.95面積%であった。GPCチャート(測定条件3)は図6に示す。
温度計、冷却管、分留管、撹拌機を取り付けたフラスコに窒素パージを施しながら、合成例2で得られたフェノール樹脂(P2)288部、エピクロルヒドリン584部、ジメチルスルホキシド274部、水15部を加え、内温を45℃まで昇温した。水酸化ナトリウム16部を1.5時間かけて分割添加後、45℃で2時間、70℃で1時間反応させた。加熱減圧下で未反応のエピクロルヒドリンおよび溶剤を留去した。MIBK1040部を加え、水440部で有機層を1回洗浄した。有機層を反応容器に戻し、30重量%水酸化ナトリウム水溶液20部を加え、70℃で2時間反応させた。放冷後、水130部で有機層を4回洗浄し、加熱減圧下、溶剤を留去し、固形樹脂としてエポキシ樹脂(E4)を165部得た。エポキシ当量は223g/eq.、ICI粘度(150℃)は0.60Pa・s、軟化点は99.7℃であり、パラメータAは2.24であった。GPCより概算される平均の繰り返し単位nは2.4、n=1は43.9面積%、n=1未満は、1.9面積%であった。GPCチャート(測定条件2)は図7に示す。
温度計、冷却管、分留管、撹拌機を取り付けたフラスコに窒素パージを施しながら、合成例2で得られたフェノール樹脂(P2)288部、エピクロルヒドリン487部、ジメチルスルホキシド274部、水15部を加え、内温を45℃まで昇温した。水酸化ナトリウム16部を1.5時間かけて分割添加後、45℃で2時間、70℃で1時間反応させた。加熱減圧下で未反応のエピクロルヒドリンおよび溶剤を留去した。MIBK1040部を加え、水440部で有機層を1回洗浄した。有機層を反応容器に戻し、30重量%水酸化ナトリウム水溶液20部を加え、70℃で2時間反応させた。放冷後、水130部で有機層を4回洗浄し、加熱減圧下、溶剤を留去し、固形樹脂としてエポキシ樹脂(E5)を161部得た。エポキシ当量は224g/eq.、ICI粘度(150℃)は0.66Pa・s、軟化点は100.9℃であり、パラメータAは2.22であった。GPCより概算される平均の繰り返し単位nは2.3、n=1は43面積%、n=1未満は、2.1面積%であった。GPCチャート(測定条件2)は図8に示す。
実施例、合成例で得られたエポキシ樹脂E1、E2、E4、およびE6としてFAE-2500(日本化薬製、分析結果は後述)、硬化剤としてトリスフェノールメタン型フェノール樹脂(日本化薬製 KAYAHARD KTG-105)を用い、触媒としてトリフェニルホスフィンを使用し、トリスフェノールメタン型フェノール樹脂をエポキシ樹脂に対し等当量、トリフェニルホスフィンをエポキシ樹脂に対して1phr.配合し、ミキシングロールを用いて均一に混合・混練し、更に脱型後、160℃で2時間、180℃で6時間の条件で硬化し、評価用試験片を得た。
動的粘弾性試験機を用いてガラス転移温度(tanδが最大値のときの温度)、およびそのときのtanδの値を測定した。
・動的粘弾性測定器:TA-instruments製DMA-2980
・昇温速度:2℃/分
熱機械特性測定装置を用いてガラス転移温度(Tg)、線膨張変化率(CTE)を評価した。
TG-DTAを用いて熱分解温度および500℃における残炭素量を測定した。
測定サンプル:粉状(100μmメッシュ通過、75μmメッシュオン)5~10mg使用
測定条件:昇温速度10℃/min Air flow 200ml
エポキシ樹脂(E1)、エポキシ樹脂(E6、FAE-2500(日本化薬製))、硬化剤としてザイロック型フェノール樹脂(明和化成製 MEHC-7800SS)、触媒としてトリフェニルホスフィン(TPP、東京化成社製)、無機充填剤としてシリカゲル(溶融シリカ MSR-2212、龍森製)、離型剤としてカルナバワックス(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-303 信越化学工業製)を使用し、ミキシングロールを用いて均一に混合・混練し、硬化性樹脂組成物を得た。
この硬化性樹脂組成物を粉砕後、タブレットマシーンにてタブレット化した。タブレット化した硬化性樹脂組成物をトランスファー成型(175℃ 60~150分)し、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。本試験片を用いて以下の評価を行った。測定結果は表2に記す。
適合規格 IEC-Pub.60112-2003(第4版)及びJIS-C2134-2007
対象試験電圧 400V~600V
試験液 塩化アンモニウム 0.1%水溶液
滴下数 50滴 50滴未満で試験片が破壊した場合はNGと判定した。
試験室の温度と湿度 21℃~23℃ 40~45%RH
試験装置 ヤマヨ試験機有限会社製 YST-112型 耐トラッキング試験機
試験サンプル形状 直径50mm 厚み 3mm
1枚につき1点測定
温度計、冷却管、分留管、撹拌機を取り付けたフラスコに窒素パージを施しながら、3-メチル-6-t-ブチルフェノール130.3部、4-メチル-2-t-ブチルフェノール0.2部、pヒドロキシベンズアルデヒド60部、トルエン142部、pトルエンスルホン酸1.4部を加え、110~115℃で8時間反応を行った。反応終了後、25%NaOH 水を加えた後、トルエンを共沸脱水により留去。その後、75%硫酸を加え、pHを5~7に調整し、析出した樹脂粉体をろ過し、60℃で乾燥することで、フェノール樹脂(P4)186部を得た。得られたフェノール樹脂(P4)は粉状であり、軟化点200℃以上、水酸基当量160g/eq.であり、GPCによるn=1は37.0面積%であった。GPCチャート(測定条件1)は図11に示す。
温度計、冷却管、分留管、撹拌機を取り付けたフラスコに窒素パージを施しながら、合成例4で得られたフェノール樹脂(P4)320部、エピクロルヒドリン973部、ジメチルスルホキシド274部、水15部を加え、内温を45℃まで昇温した。水酸化ナトリウム16部を1.5時間かけて分割添加後、45℃で2時間、70℃で1時間反応させた。加熱減圧下で未反応のエピクロルヒドリンおよび溶剤を留去した。MIBK1040部を加え、水440部で有機層を1回洗浄した。有機層を反応容器に戻し、30重量%水酸化ナトリウム水溶液20部を加え、70℃で2時間反応させた。放冷後、水130部で有機層を4回洗浄し、加熱減圧下、溶剤を留去し、固形樹脂としてエポキシ樹脂(E7)を107部得た。エポキシ当量は220g/eq.、ICI粘度(150℃)は0.8Pa・s以上、軟化点は108.5℃であり、パラメータAは2.03であった。GPC(検出器 UV254nm)より概算される平均の繰り返し単位nは3.4、n=1は24.9面積%、n=1未満は、2.91面積%であった。GPCチャート(測定条件3)は図12に示す。また各々のピークはリテンションタイムが35.619分の物が1.75%、それ以外のピークは1.5面積%以下であった。
上記実施例で得られたエポキシ樹脂E3、E7、硬化剤としてトリスフェノールメタン型フェノール樹脂(日本化薬製 KAYAHARD KTG-105 水酸基当量102g/eq.)、ビフェニルアラルキル型フェノール樹脂(日本化薬製 KAYAHARD GPH-65 硬化剤 水酸基当量200g/eq.)、触媒としてトリフェニルホスフィン(TPP、東京化成社製)、無機充填剤としてシリカゲル(溶融シリカ MSR-2212、龍森製)、離型剤としてカルナバワックス(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-303 信越化学工業製)を使用し、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、更に脱型後、160℃で2時間、180℃で6時間の条件で硬化し、評価用試験片を得た。本試験片を用いて耐トラッキング性試験を行った。測定結果は表3に記す。
上記実施例で得られたエポキシ樹脂E1、ビフェニルアラルキル型エポキシ樹脂、(日本化薬製、NC-3000)、硬化剤としてザイロック型フェノール樹脂(明和化成製 MEHC-7800SS)、触媒としてトリフェニルホスフィン(TPP、東京化成社製)、無機充填剤としてシリカゲル(溶融シリカ MSR-2212、龍森製)、離型剤としてカルナバワックス(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-303 信越化学工業製)を使用し、ミキシングロールを用いて均一に混合・混練し、硬化性樹脂組成物を得た。
この硬化性樹脂組成物を粉砕後、タブレットマシーンにてタブレット化した。タブレット化した硬化性樹脂組成物をトランスファー成型(175℃ 60~15分)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。本試験片を用いて耐トラッキング性試験を行った。測定結果は表4に記す。
上記実施例で得られたエポキシ樹脂E1、ビフェニルアラルキル型エポキシ樹脂、(日本化薬製、NC-3000)、硬化剤としてザイロック型フェノール樹脂(明和化成製 MEHC-7800SS)、ビフェニルアラルキル型フェノール樹脂(日本化薬製 KAYAHARD GPH-65)、触媒としてトリフェニルホスフィン(TPP、東京化成社製)、無機充填剤としてシリカゲル(溶融シリカ MSR-2212、龍森製)、離型剤としてカルナバワックス(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-303 信越化学工業製)を使用し、ミキシングロールを用いて均一に混合・混練し、硬化性樹脂組成物を得た。
この硬化性樹脂組成物を粉砕後、タブレットマシーンにてタブレット化した。タブレット化した硬化性樹脂組成物をトランスファー成型(175℃ 60~15分)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。本試験片を用いて耐トラッキング性試験を行った。特にCTIに関してはIEC-Pub.60112-2003(第4版)に準拠した測定法を用い測定を行った。測定結果は表5、図13に記す。
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