WO2019189023A1 - フェノール樹脂及びその製造方法、並びにエポキシ樹脂組成物及びその硬化物 - Google Patents
フェノール樹脂及びその製造方法、並びにエポキシ樹脂組成物及びその硬化物 Download PDFInfo
- Publication number
- WO2019189023A1 WO2019189023A1 PCT/JP2019/012584 JP2019012584W WO2019189023A1 WO 2019189023 A1 WO2019189023 A1 WO 2019189023A1 JP 2019012584 W JP2019012584 W JP 2019012584W WO 2019189023 A1 WO2019189023 A1 WO 2019189023A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- resin composition
- phenol resin
- less
- phenol
- Prior art date
Links
- 0 *c(cccc1)c1O Chemical compound *c(cccc1)c1O 0.000 description 1
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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
-
- 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 a phenol resin and a method for producing the same.
- the present invention also relates to an epoxy resin composition containing the phenol resin and a cured product of the epoxy resin composition. Furthermore, this invention relates to the semiconductor device containing this hardened
- Epoxy resin compositions are widely used in the fields of electrical / electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance, etc.
- the resin composition ensures and balances handling properties, solder resistance, flame resistance, and moldability while improving fluidity more than before. And realizing them at low cost has become an important issue.
- the problem of the present invention is that a cured product obtained when used as a curing agent for an epoxy resin has low water absorption, a low elastic modulus when heated, and further balances good curability, moldability and flame retardancy. It is to provide a phenol resin having a good cost at a low cost. Moreover, it is providing the epoxy resin composition excellent in the heat resistance (reflow resistance) and handling property containing this phenol resin, and its hardened
- a phenol resin which is an o-position-substituted phenol resin represented by the following general formula (1) and has a melt viscosity at 150 ° C. of 0.20 Pa ⁇ s or less.
- R is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 or more.
- the phenol resin as described in 1 or 2 above. 4).
- the phenol resin according to any one of 1 to 3, which is not more than%. 5.
- the melt viscosity at 150 ° C. is 0.01 Pa ⁇ s or more and less than 0.04 Pa, and the softening point is 60 ° C. or more and 65 ° C. or less.
- An epoxy resin composition comprising the phenol resin according to any one of 1 to 5 and an epoxy resin. 7.
- the epoxy resin composition according to 6 above which comprises the phenol resin as described in 5 above and a biphenyl type epoxy resin. 9.
- the epoxy resin composition according to 6 above which contains the phenol resin as described in 5 above and gives a cured product having a storage elastic modulus at 270 ° C. of 0.2 GPa or more and 0.7 GPa or less.
- a cured product obtained by curing the epoxy resin composition according to any one of 6 to 10. 12 A semiconductor device comprising the cured product as described in 11 above.
- the cured product obtained when used as a curing agent for epoxy resin has low water absorption, low elastic modulus at the time of heating, and also has good balance of curability, moldability and flame retardancy.
- a phenol resin can be obtained at low cost.
- cured material can be obtained.
- a semiconductor device having the cured product can be obtained.
- the phenol resin of the present invention is an o-position substituted phenol resin represented by the following general formula (1), and has a melt viscosity at 150 ° C. of 0.20 Pa ⁇ s or less.
- R is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 or more.
- the phenol resin of the present invention has a substituent R at the ortho position (o-position) with respect to the phenolic hydroxyl group. Therefore, the phenol resin of the present invention has a lower melt viscosity with respect to the softening point than a phenol resin having no substituent at the ortho position (o-position).
- the softening point When the phenol resin does not have the substituent R (unsubstituted), the softening point also decreases when the molecular weight is decreased and the melt viscosity is decreased.
- the softening point is low, there is a problem in handling in handling due to blocking or the like when the phenol resin itself or the epoxy resin composition is used.
- the phenol resin having the substituent R at the meta position (m-position) or para position (p-position) other than the o-position has a lower molecular weight than the phenol resin having the substituent R at the o-position.
- the phenol resin of the present invention has a high fluidity and moldability when an epoxy resin composition is formed by having a substituent R at the ortho position (o-position) with respect to the phenolic hydroxyl group. Moreover, the hardened
- the upper limit of the melt viscosity at 150 ° C. of the phenol resin of the present invention is 0.20 Pa ⁇ s or less.
- the epoxy resin composition has high fluidity (low viscosity).
- the upper limit of the melt viscosity at 150 ° C. is more preferably 0.10 Pa ⁇ s or less, and most preferably 0.05 Pa ⁇ s or less.
- the lower limit of the melt viscosity at 150 ° C. is preferably as low as possible from the viewpoint of fluidity when an epoxy resin composition is used, but it is preferably 0.01 Pa ⁇ s or more, such as the phenol resin itself or the epoxy resin composition. It is preferable from the viewpoint of handling properties in handling due to blocking or the like. Therefore, the range of the melt viscosity at 150 ° C. of the phenol resin of the present invention is preferably 0.01 Pa ⁇ s to 0.20 Pa ⁇ s, more preferably 0.01 Pa ⁇ s to 0.10 Pa ⁇ s. s or less, and most preferably 0.01 Pa ⁇ s or more and 0.05 Pa ⁇ s or less.
- the melt viscosity at 150 ° C. can be determined by the method described in the following examples.
- the substituent R is a linear or branched alkyl group having 1 to 4 carbon atoms.
- the substituent R is not limited, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an iso-butyl group, and a tert-butyl group.
- the substituent R is preferably a methyl group, an ethyl group, a propyl group, or n.
- n represents the number of repetitions and is an integer of 0 or more. Since the phenol resin represented by the general formula (1) is an aggregate of compounds having various repeating numbers n, the value of n can be expressed as an average value n ′ in the aggregate.
- the average value n ′ is a value such that the melt viscosity of the phenol resin at 150 ° C. is 0.20 Pa ⁇ s or less.
- the range of the average value n ′ is preferably 0.01 Pa ⁇ s to 0.20 Pa ⁇ s, more preferably 0.01 Pa ⁇ s to 0.15 Pa ⁇ s, and still more preferably 0.01 Pa ⁇ s to 0.
- the value is preferably 10 Pa ⁇ s or less, and most preferably 0.01 Pa ⁇ s or more and 0.05 Pa ⁇ s or less.
- the average value n ′ can be calculated based on the weight average molecular weight (Mw) described later.
- the weight average molecular weight (Mw) in terms of standard polystyrene as measured by gel permeation chromatography (GPC) is preferably 400 or more and 1000 or less, more preferably 500 or more and 800 or less, and most preferably 500. It is 700 or less.
- GPC gel permeation chromatography
- a weight average molecular weight (Mw) is measured by GPC (gel permeation chromatography), and can be calculated
- the area ratio of permeation chromatography (GPC) analysis is preferably 12% or more and 30% or less, more preferably 15% or more and 30% or less, still more preferably 22% or more and 30% or less, and particularly preferably Is from 26% to 29%, most preferably from 26% to 28%.
- GPC gel permeation chromatography
- the content rate of a binuclear body is measured by GPC (gel permeation chromatography), and can be calculated
- the softening point is preferably 50 ° C. or higher and 90 ° C. or lower, more preferably 60 ° C. or higher and 80 ° C. or lower, and most preferably 60 ° C. or higher and 70 ° C. or lower.
- handling in handling such as blocking when phenol resin itself or epoxy resin composition is used, and handling of kneading work with inorganic filler when epoxy resin composition is used From the viewpoint of sex.
- a softening point can be adjusted by making a weight average molecular weight (Mw) into the said range.
- one of preferred embodiments is that the substituent R is a methyl group, the melt viscosity at 150 ° C. is 0.20 Pa ⁇ s or less, and the gel
- Mw weight average molecular weight
- GPC area ratio of gel permeation chromatography
- handling in handling due to blocking or the like in the case of a phenol resin itself or an epoxy resin composition and handling in a kneading operation with an inorganic filler or the like in the case of an epoxy resin composition, and an epoxy resin High fluidity (low viscosity) when used as a composition can be achieved at the same time.
- moldability when used as an epoxy resin composition and mechanical properties such as bending strength of the resulting cured product are increased. The water absorption of the cured product is lowered, and the flame retardancy is increased.
- Mw weight average molecular weight
- GPC gel permeation chromatography
- the phenol resin of the present invention represented by the general formula (1) is obtained by subjecting a phenol compound (a1) represented by the following general formula (2) and formaldehyde (a2) to a condensation polymerization reaction under an acidic catalyst. be able to. That is, the phenol resin of the present invention is a phenol novolac type resin.
- the phenol compound (a1) represented by the general formula (2) is not particularly limited, and examples thereof include 2-methylphenol (orthocresol), 2-ethylphenol, 2-propylphenol, 2-isopropylphenol, 2 -N-butylphenol, 2-sec-butylphenol, and 2-tert-butylphenol.
- the phenol compound represented by the general formula (2) is preferably 2-methyl Phenol, 2-ethylphenol, 2-propylphenol, or 2-n-butylphenol, more preferably 2-methylphenol or 2-ethylphenol, and most preferably 2-methylphenol.
- These phenol compounds can be used individually by 1 type or in combination of 2 or more type within the scope of the effect of the present invention.
- the formaldehyde (a2) is not particularly limited, but an aqueous formaldehyde solution may be used, and a polymer that decomposes in the presence of an acid such as paraformaldehyde or trioxane to formaldehyde may be used.
- a formaldehyde aqueous solution that is easy to handle.
- a commercially available 42% aqueous formaldehyde solution can be suitably used as it is.
- the condensation polymerization reaction can be carried out under an acidic catalyst.
- the acid catalyst used in the polycondensation reaction is not particularly limited, and known acids such as hydrochloric acid, oxalic acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid can be used alone or in combination of two or more. Particularly preferred is oxalic acid or paratoluenesulfonic acid.
- a solvent may be used for the purpose of facilitating the reaction.
- the solvent at this time include water and lower alcohols (aliphatic alcohols having 1 to 6 carbon atoms). Specific examples include methanol, ethanol, propanol, butanol, pentanol, hexanol, and cyclohexanol.
- the amount of the solvent is preferably 0.1% by weight or more with respect to the phenol compound from the viewpoint of sufficiently exerting the effect of using the solvent.
- the reaction temperature of the condensation polymerization reaction is not particularly limited, and is usually 50 to 200 ° C, preferably 70 to 180 ° C, more preferably 80 to 170 ° C. If it is 50 degreeC or more, it can make it easy to advance reaction, and if it is 200 degreeC or less, it will be easy to control reaction and the target phenol resin of this invention can be obtained stably.
- reaction time The reaction time of the condensation polymerization reaction is usually about 0.1 to 20 hours, although it depends on the reaction temperature.
- the reaction pressure for the condensation polymerization reaction is usually carried out under normal pressure, but it may be carried out under pressure or under reduced pressure.
- the base for neutralizing the acid catalyst is not particularly limited, and any base that neutralizes the acid catalyst and forms a salt that is soluble in water can be used.
- examples thereof include inorganic bases such as metal hydroxides and metal carbonates, organic bases such as organic amines, and ammonia.
- Specific examples of the inorganic base include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium bicarbonate, calcium carbonate and the like.
- Specific examples of the organic amine include trimethylamine, triethylamine, diethylamine, tributylamine and the like. Of these, organic amines are preferably used. Although the amount used depends on the amount of the acid catalyst, it is preferably used in such an amount that the pH in the reaction system after neutralizing the acid catalyst falls within the range of 4-8.
- the amount of water used in the water washing and the number of times of water washing are not particularly limited. In order to remove the acid catalyst to an amount that does not affect the actual use, including the economic viewpoint, the number of water washings is about 1 to 5 times. preferable.
- the temperature of the water used in the water washing is not particularly limited, but it is preferably 40 to 95 ° C. from the viewpoint of the efficiency of removing the catalyst species and workability. If the separation between the phenol resin and the washing water is insufficient during washing, the temperature of the water used for washing is increased or a solvent other than water is added to reduce the viscosity of the mixture. Is effective. Solvent species other than water are not particularly limited, and any solvent can be used as long as it dissolves the phenol resin and lowers the viscosity.
- the temperature of the reaction system is usually increased to 130 to 230 ° C., for example, under reduced pressure of 20 to 50 torr, volatilization of unreacted raw materials remaining in the reaction mixture, organic solvents, etc.
- the target phenol resin can be suitably separated and recovered.
- Epoxy resin composition and cured product thereof contains the phenol resin of this invention mentioned above as a hardening
- the epoxy resin examples include glycidyl ether type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, triphenolmethane type epoxy resin, biphenyl type epoxy resin, and glycidyl.
- examples thereof include an epoxy resin having two or more epoxy groups in the molecule, such as an ester type epoxy resin, a glycidylamine type epoxy resin, and a halogenated epoxy resin.
- epoxy resins can be used alone or in admixture of two or more.
- preferable epoxy resins include glycidyl ether type epoxy resins
- particularly preferable epoxy resins include biphenyl type epoxy resins.
- the phenol resin is used as a curing agent for the epoxy resin in the epoxy resin composition of the present invention.
- the epoxy resin composition of the present invention may contain a curing agent other than the phenol resin of the present invention.
- a curing agent other than the phenol resin of the present invention there is no limitation in particular in the kind of other hardening
- curing agents can be used.
- other phenol resins than the general formula (1), amine-based curing agents, amide-based curing agents, acid anhydride-based curing agents, and the like can be used.
- the ratio of the phenol resin composition of the present invention to all the curing agents is sufficiently high in the thermal elastic modulus and molding shrinkage of the cured product obtained from the epoxy resin composition. From the viewpoint of achieving this, a higher ratio is preferable.
- the proportion of the phenol resin composition of the present invention in all curing agents is preferably 30% by mass or more, more preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably. It is 90% by mass or more, particularly preferably 100% by mass.
- the ratio of the hydroxyl group equivalent number of the phenol resin to the epoxy group equivalent number of the epoxy resin is 0.5 or more and 2.0 or less. Is preferably 0.8 or more and 1.2 or less, and is most preferably 1.
- the number of functional group equivalents such as the number of hydroxyl group equivalents and the number of epoxy group equivalents is B / A (purity of the compound) when the functional group equivalent is A (g / eq) and the charged amount is B (g). Can be obtained by [B ⁇ C / 100] / A).
- functional group equivalents such as hydroxyl group equivalent and epoxy group equivalent represent the molecular weight of the compound per functional group
- number of functional group equivalents refers to the number of functional groups (number of equivalents) per compound mass (preparation amount).
- a known curing accelerator for curing an epoxy resin with a phenol resin can be used.
- organic phosphine compounds and boron salts thereof, tertiary amines, quaternary ammonium salts, tetraphenyl boron salts of imidazoles and the like can be mentioned, among which triphenylphosphine is preferable from the viewpoint of curability and moisture resistance.
- a heat-latent curing accelerator that exhibits activity by heat treatment is preferable, and tetraphenylphosphonium derivatives such as tetraphenylphosphonium and tetraphenylborate are preferable.
- the ratio of the addition of the curing accelerator to the epoxy resin composition can be the same as the ratio in the known epoxy resin composition, for example, 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the epoxy resin. It can be.
- the epoxy resin composition of the present invention can suitably contain an organic or inorganic filler.
- the filler is not particularly limited and is selected depending on the application.
- a filler can be mentioned suitably.
- amorphous silica, crystalline silica, or the like is suitably used as the inorganic filler.
- the blending ratio in the epoxy resin composition when blending the inorganic filler is not limited, but is 30 to 98 mass. %, Preferably about 40 to 95% by mass.
- the blending ratio of the inorganic filler is 60 to 95% by mass, preferably 70 to 95% by mass, more preferably 75 to 90% by mass, and still more preferably 80 to 90%. It is also mass%, and the blending ratio of the inorganic filler can be made high.
- the proportion of the inorganic filler is not less than the lower limit of the above range, the water absorption of the cured product of the epoxy resin composition can be reduced. Moreover, the fluidity
- the epoxy resin composition of the present invention can further contain additives such as mold release agents, colorants, coupling agents, flame retardants and the like used in ordinary epoxy resin compositions, and solvents.
- the epoxy resin composition of the present invention can be suitably obtained by melting and mixing at least an epoxy resin and a phenol resin, for example, using a mixing device such as a biaxial kneader or a two-roller, as necessary. it can.
- the obtained epoxy resin composition is suitably pulverized by a pulverizer.
- the epoxy resin composition of the present invention can be cured by, for example, heat treatment at 100 to 350 ° C. for 0.01 to 20 hours to obtain a cured product.
- the temperature of the curing reaction can be easily cured by setting it to 100 ° C. or higher, and the performance degradation due to thermal decomposition can be prevented by setting it to 350 ° C. or lower.
- the curing reaction time is set to 0.01 hours or longer, whereby the reaction is easily completed, and the setting time is set to 20 hours or shorter to improve productivity.
- a cured product of an epoxy resin using the phenol resin of the present invention as a curing agent has a low elastic modulus (storage elastic modulus at 270 ° C.) when heated.
- the elastic modulus at storage is preferably 0.2 GPa or more and 0.7 GPa or less, and more preferably 0.3 GPa or more and 0.6 GPa or less.
- the storage elastic modulus at 270 ° C. of the cured product is in the above range, it has excellent solder heat resistance (reflow resistance) and can achieve high flame resistance.
- the phenol resin of the present invention includes, for example, 83 wt% inorganic filling with respect to the total weight of the phenol resin, an epoxy resin represented by the following formula with an equivalent number of the phenol resin, and the epoxy resin composition: Materials (manufactured by Tatsumori Co., Ltd., high-purity spherical silica MSR-2212 (Top size 75 ⁇ m, average particle size 25.5 ⁇ m, specific surface area 3.0 m 2 / g, Fluy ON 75 ⁇ ON 0.0%)), A cured product of an epoxy resin composition obtained by kneading 0.33% by mass of a curing accelerator (triphenylphosphine manufactured by Hokuko Chemical Co., Ltd.) with respect to the total mass of the epoxy resin composition, is obtained at 250 ° C. It is preferable to provide a range of storage modulus.
- Materials manufactured by Tatsumori Co., Ltd., high-purity spherical silica MSR-2212 (Top size 75
- the epoxy resin composition of the present invention can be blended with a high proportion of inorganic filler, has excellent fluidity and moldability, and its cured product has excellent low water absorption and flame retardancy. For this reason, the epoxy resin composition of this invention can be used especially suitably for a semiconductor device as a semiconductor sealing material.
- the 150 degreeC melt viscosity (Pa * s) was measured using the following apparatuses. Equipment used: BROOKFIELD B-type viscometer DV2T Eihiro Seiki Co., Ltd. Measurement temperature: 150 ° C Measuring method: The furnace temperature of the B-type viscometer is set to 150 ° C., and a predetermined amount of sample is weighed in a cup. A cup in which a sample is weighed is put into a furnace to melt the resin, and a spindle is inserted from the top. Rotate the spindle and read the melted viscosity when the displayed viscosity value becomes stable.
- the softening point was measured using the following equipment. Equipment used: FP83HT dropping point / softening point measurement system, manufactured by METTLER TOLEDO Co., Ltd. Measurement conditions: heating rate 2 ° C./min Measuring method: Pour molten sample into sample cup, cool and harden. Insert the cartridge in the top and bottom of the sample-filled cup and insert it into the furnace. The resin softens and flows down the orifice, and the temperature when the lower end passes through the optical path is detected by the photocell as the softening point (° C.).
- the melting point was measured using the following equipment. Equipment used: Q-2000 manufactured by TA Instruments Measurement temperature range: -20 ° C to 150 ° C, heating rate 10 ° C / min Measurement environment: N 2 (50 mL / min) atmosphere Measurement method: The temperature at which melting starts was defined as the melting point (° C.).
- Example 2 [Synthesis of Resin B] Except that the blending amount of 92 mass% paraform used in Example 1 was changed to 42.78 parts by mass (1.3 mol), 204 parts by mass of Resin B was obtained in the same manner as in Example 1. The evaluation results of this resin are shown in Table 1.
- Example 3 Synthesis of Resin C Except that the blending amount of 92% by mass paraform used in Example 1 was changed to 48.91 parts by mass (1.5 mol), 222 parts by mass of Resin C was obtained in the same manner as in Example 1. The evaluation results of this resin are shown in Table 1.
- the bending strength (MPa) was measured according to JIS K 7171 for the test piece of the cured product of the epoxy resin composition. Test piece size: 80 mm x 10 mm x 4 mm
- Tg glass transition point
- storage elastic modulus The glass transition point (Tg) and the storage elastic modulus were measured for the test piece of the cured product of the epoxy resin composition using the following equipment.
- the peak temperature of Tan ⁇ was defined as Tg (° C.).
- test piece was created with the transfer molding machine using the 40 (PHI) tablet created using the obtained epoxy resin composition.
- the moldability at this time was evaluated based on the above evaluation criteria.
- curing material was obtained by performing a postcure 180 degreeC x 8 hours about a test piece. The physical properties of the cured epoxy resin were evaluated. These evaluation results are shown in Table 3.
- Comparative Example 6 having a molecular weight exceeding the preferred range of the phenolic resin of the present invention, results of poor fluidity and poor in flammability and heat resistance were obtained. Further, in Comparative Examples 7 and 8 using a phenol resin having a substituent at the m-position or p-position, the moldability was remarkably lowered, and an epoxy resin cured product could not be obtained. Since it is necessary to increase the molecular weight in order to obtain a cured epoxy resin, a highly fluid epoxy resin composition cannot be obtained due to an increase in viscosity and softening point.
- a highly fluid epoxy resin composition having a good balance between good curability and moldability is obtained, and by curing the composition, low water absorption is achieved. It can be seen that a cured product having a low elastic modulus at the time of heating can be obtained.
- the phenol resin of the present invention it is possible to obtain an epoxy resin composition having good moldability and cured material properties and having high fluidity and a cured product thereof. Therefore, according to the present invention, it is possible to provide a phenol resin that can be suitably used for an epoxy resin composition for a semiconductor device including a semiconductor encapsulating material that is lighter, thinner, and shorter.
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)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020207023030A KR20200138171A (ko) | 2018-03-27 | 2019-03-25 | 페놀 수지 및 그 제조 방법, 그리고 에폭시 수지 조성물 및 그 경화물 |
CN201980016886.XA CN111936540B (zh) | 2018-03-27 | 2019-03-25 | 酚醛树脂及其制造方法、以及环氧树脂组合物及其固化物 |
JP2019566373A JP6724264B2 (ja) | 2018-03-27 | 2019-03-25 | フェノール樹脂及びその製造方法、並びにエポキシ樹脂組成物及びその硬化物 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018060488 | 2018-03-27 | ||
JP2018-060488 | 2018-03-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019189023A1 true WO2019189023A1 (ja) | 2019-10-03 |
Family
ID=68060005
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/012584 WO2019189023A1 (ja) | 2018-03-27 | 2019-03-25 | フェノール樹脂及びその製造方法、並びにエポキシ樹脂組成物及びその硬化物 |
Country Status (5)
Country | Link |
---|---|
JP (3) | JP6724264B2 (zh) |
KR (1) | KR20200138171A (zh) |
CN (1) | CN111936540B (zh) |
TW (1) | TWI801541B (zh) |
WO (1) | WO2019189023A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023090317A1 (ja) | 2021-11-19 | 2023-05-25 | ナミックス株式会社 | 硬化性樹脂組成物 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102623238B1 (ko) * | 2020-09-11 | 2024-01-10 | 삼성에스디아이 주식회사 | 반도체 소자 밀봉용 에폭시 수지 조성물 및 이를 사용하여 밀봉된 반도체 소자 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04220422A (ja) * | 1990-12-20 | 1992-08-11 | Nippon Kayaku Co Ltd | エポキシ樹脂の製造方法 |
JP2000239349A (ja) * | 1998-12-24 | 2000-09-05 | Sumitomo Chem Co Ltd | エポキシ樹脂、組成物、および樹脂封止型半導体装置 |
JP2000290352A (ja) * | 1999-04-07 | 2000-10-17 | Sumitomo Durez Co Ltd | エポキシ樹脂硬化剤およびその製造方法 |
JP2002220563A (ja) * | 2000-10-20 | 2002-08-09 | Kansai Paint Co Ltd | 缶内面用水性被覆組成物 |
WO2004020492A1 (ja) * | 2002-08-30 | 2004-03-11 | Asahi Organic Chemicals Industry Co., Ltd. | ノボラック型フェノール樹脂の製造方法 |
JP2005329420A (ja) * | 2004-05-19 | 2005-12-02 | Asahi Organic Chem Ind Co Ltd | 鋳型用有機粘結剤及びこれを用いて得られる鋳物砂組成物並びに鋳型 |
JP2016150975A (ja) * | 2015-02-17 | 2016-08-22 | アイカSdkフェノール株式会社 | フェノール樹脂、フェノール樹脂の製造方法、樹脂組成物およびポリウレタンフォーム |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08258077A (ja) | 1996-04-22 | 1996-10-08 | Nitto Denko Corp | 半導体装置 |
JP4435791B2 (ja) | 2001-11-16 | 2010-03-24 | 旭有機材工業株式会社 | ノボラック型フェノール樹脂の製造方法及びレジンコーテッドサンド |
WO2010103745A1 (ja) * | 2009-03-11 | 2010-09-16 | 住友ベークライト株式会社 | 半導体封止用樹脂組成物及び半導体装置 |
US8394911B2 (en) * | 2010-02-03 | 2013-03-12 | Dic Corporation | Phenol resin composition, production method therefor, curable resin composition, cured product thereof, and printed circuit board |
-
2019
- 2019-03-25 KR KR1020207023030A patent/KR20200138171A/ko not_active Application Discontinuation
- 2019-03-25 CN CN201980016886.XA patent/CN111936540B/zh active Active
- 2019-03-25 WO PCT/JP2019/012584 patent/WO2019189023A1/ja active Application Filing
- 2019-03-25 JP JP2019566373A patent/JP6724264B2/ja active Active
- 2019-03-26 TW TW108110500A patent/TWI801541B/zh active
-
2020
- 2020-05-14 JP JP2020085127A patent/JP7347322B2/ja active Active
-
2023
- 2023-08-23 JP JP2023135098A patent/JP2023166442A/ja active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04220422A (ja) * | 1990-12-20 | 1992-08-11 | Nippon Kayaku Co Ltd | エポキシ樹脂の製造方法 |
JP2000239349A (ja) * | 1998-12-24 | 2000-09-05 | Sumitomo Chem Co Ltd | エポキシ樹脂、組成物、および樹脂封止型半導体装置 |
JP2000290352A (ja) * | 1999-04-07 | 2000-10-17 | Sumitomo Durez Co Ltd | エポキシ樹脂硬化剤およびその製造方法 |
JP2002220563A (ja) * | 2000-10-20 | 2002-08-09 | Kansai Paint Co Ltd | 缶内面用水性被覆組成物 |
WO2004020492A1 (ja) * | 2002-08-30 | 2004-03-11 | Asahi Organic Chemicals Industry Co., Ltd. | ノボラック型フェノール樹脂の製造方法 |
JP2005329420A (ja) * | 2004-05-19 | 2005-12-02 | Asahi Organic Chem Ind Co Ltd | 鋳型用有機粘結剤及びこれを用いて得られる鋳物砂組成物並びに鋳型 |
JP2016150975A (ja) * | 2015-02-17 | 2016-08-22 | アイカSdkフェノール株式会社 | フェノール樹脂、フェノール樹脂の製造方法、樹脂組成物およびポリウレタンフォーム |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023090317A1 (ja) | 2021-11-19 | 2023-05-25 | ナミックス株式会社 | 硬化性樹脂組成物 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2019189023A1 (ja) | 2020-04-30 |
JP7347322B2 (ja) | 2023-09-20 |
KR20200138171A (ko) | 2020-12-09 |
CN111936540B (zh) | 2023-10-03 |
TWI801541B (zh) | 2023-05-11 |
TW201942170A (zh) | 2019-11-01 |
CN111936540A (zh) | 2020-11-13 |
JP6724264B2 (ja) | 2020-07-15 |
JP2020117734A (ja) | 2020-08-06 |
JP2023166442A (ja) | 2023-11-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5170493B2 (ja) | フェノール系重合体、その製法及びその用途 | |
JP5104308B2 (ja) | ビフェニレン架橋フェノールノボラック樹脂ならびにその用途 | |
JP2023166442A (ja) | フェノール樹脂及びその製造方法、並びにエポキシ樹脂組成物及びその硬化物 | |
JP5413488B2 (ja) | フェノールノボラック樹脂、その製造方法、それを用いたエポキシ樹脂組成物および硬化物 | |
JP6469654B2 (ja) | フェノール樹脂、該フェノール樹脂を含むエポキシ樹脂組成物、該エポキシ樹脂組成物の硬化物、及び該硬化物を有する半導体装置 | |
WO2013125620A1 (ja) | 多価ヒドロキシ樹脂、エポキシ樹脂、それらの製造方法、エポキシ樹脂組成物及びその硬化物 | |
TWI640569B (zh) | Epoxy resin composition, encapsulating material, hardened material thereof and phenol resin | |
JP2010229304A (ja) | フェノール樹脂、該樹脂の製造方法及び該樹脂を含むエポキシ樹脂組成物、ならびにその硬化物 | |
JP7314489B2 (ja) | フェノール樹脂及びその製造方法、並びにエポキシ樹脂組成物及びその硬化物 | |
JP5268404B2 (ja) | フェノール系重合体、その製法およびその用途 | |
JP6497639B2 (ja) | 熱硬化性樹脂組成物、硬化物及び変性フェノール樹脂の製造方法 | |
JP5721519B2 (ja) | フェノール系重合体、その製法およびその用途 | |
JP2002241471A (ja) | エポキシ樹脂組成物及び半導体装置 | |
JP5515583B2 (ja) | フェノール樹脂及びエポキシ樹脂並びにエポキシ樹脂硬化物 | |
JPH07268081A (ja) | エポキシ樹脂硬化剤、フェノール樹脂の製造方法及び電子部品封止用エポキシ樹脂成形材料 | |
JP2012172122A (ja) | フェノール系重合体、その製法およびその用途 | |
JP4979251B2 (ja) | フェノール系重合体、その製法及びその用途 | |
JP2001261790A (ja) | エポキシ樹脂組成物及び半導体装置 | |
JP2018059095A (ja) | フェノール樹脂組成物、硬化剤、エポキシ樹脂組成物、硬化物、及び半導体装置 | |
JP2006273907A (ja) | フェノール樹脂とその製造方法、エポキシ樹脂硬化剤、およびエポキシ樹脂組成物 | |
JP2003261651A (ja) | エポキシ樹脂硬化剤 | |
JP2014062153A (ja) | 電子材料用エポキシ樹脂組成物及び電子部品 | |
JP2006273906A (ja) | フェノール樹脂、エポキシ樹脂硬化剤、及びエポキシ樹脂組成物 |
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: 19777900 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2019566373 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: 19777900 Country of ref document: EP Kind code of ref document: A1 |