WO2016076403A1 - ノボラック型フェノール樹脂の製造方法、ノボラック型フェノール樹脂、熱硬化性樹脂組成物及び硬化物 - Google Patents

ノボラック型フェノール樹脂の製造方法、ノボラック型フェノール樹脂、熱硬化性樹脂組成物及び硬化物 Download PDF

Info

Publication number
WO2016076403A1
WO2016076403A1 PCT/JP2015/081899 JP2015081899W WO2016076403A1 WO 2016076403 A1 WO2016076403 A1 WO 2016076403A1 JP 2015081899 W JP2015081899 W JP 2015081899W WO 2016076403 A1 WO2016076403 A1 WO 2016076403A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin
aldehyde
producing
novolac
novolak
Prior art date
Application number
PCT/JP2015/081899
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
千巳 山腰
進一 瀧本
Original Assignee
アイカＳｄｋフェノール株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by アイカＳｄｋフェノール株式会社 filed Critical アイカＳｄｋフェノール株式会社
Priority to JP2016559109A priority Critical patent/JP6729863B2/ja
Publication of WO2016076403A1 publication Critical patent/WO2016076403A1/ja

Links

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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes

Definitions

  • the present invention relates to a method for producing a novolac type phenol resin, a novolac type phenol resin, a thermosetting resin composition, and a cured product obtained by curing them.
  • Phenolic resins are used in various fields because of their heat resistance.
  • One example is use as a curing agent for epoxy resins. In that case, it is excellent in heat resistance, adhesion, and electrical insulation, and is a resin composition for printed circuit boards, a resin composition for interlayer insulation materials used for printed circuit boards and copper foils with resin, and a resin composition for sealing materials for electronic components. , Resist inks, conductive pastes, paints, adhesives, composite materials and the like. With recent technological innovations, further improvements in heat resistance, moisture resistance, flame retardancy and the like of epoxy resin compositions are required. In particular, when used as an electronic component or a material around it, it is expected that the material is required to have flexibility because the use site is becoming smaller and thinner.
  • one means for solving the problems of heat resistance, moisture resistance and flame retardancy is an increase in the amount of filler used.
  • By increasing the amount of the filler it is possible to reduce the linear expansion coefficient of the molded product, reduce the moisture absorption rate, and improve the flame retardancy.
  • an increase in the filling amount causes a problem that the fluidity of the blend decreases and the moldability deteriorates.
  • the elastic modulus of the molded product tends to increase by increasing the amount of filler.
  • the resin component in the composition is required to have a resin skeleton capable of improving fluidity and imparting more flexibility.
  • the heat resistance, moisture resistance and flame retardancy of the cured product and the flexibility of the cured product and the fluidity of the compound for obtaining the cured product are contradictory properties, and it has been difficult to achieve both. It was.
  • a novolak-type phenol resin (hereinafter also referred to as “novolak resin”) is produced by addition condensation of phenols and aldehydes in the presence of an acidic catalyst.
  • the molar ratio of aldehydes to 1 mol of phenols is used in the range of 1.0 mol or less, and the molecular weight of the resin obtained is controlled by adjusting the molar ratio.
  • the molar ratio of aldehydes to 1 mol of phenols must be reduced. In this case, a large amount of unreacted phenolic monomers remains. Although the unreacted phenolic monomer in the novolak resin can be reduced by distillation under reduced pressure, a larger amount of phenolic monomer is removed by distillation as the novolak resin has a lower molar ratio of aldehydes to 1 mole of phenol. Therefore, a decrease in yield is inevitable. On the other hand, if a phenolic monomer remains in the novolak resin, it causes a decrease in the dimensional stability of the molded product and generation of voids. Therefore, it is preferable that the phenol monomer in the novolak resin is as small as possible.
  • Patent Document 1 discloses a method for obtaining fluidity of a novolak resin by increasing the content of a dimer component by causing a heterogeneous reaction between phenols and formaldehyde in the presence of a phosphoric acid catalyst. ing.
  • the catalyst is limited to phosphoric acid, aldehydes that are less reactive than paraformaldehyde, for example, aliphatic aldehydes such as acetaldehyde and butyraldehyde, benzaldehyde and salicyl
  • aldehydes that are less reactive than paraformaldehyde, for example, aliphatic aldehydes such as acetaldehyde and butyraldehyde, benzaldehyde and salicyl
  • Patent Document 2 a phenol derivative is reacted with a biomass containing an alkyl chain unsaturated bond under strong acidity to obtain a biomass derivative, and then this biomass derivative is reacted with an aldehyde source to produce a novolac-type phenol.
  • a technique for obtaining a resin and thereby imparting flexibility and heat resistance to a cured product is disclosed. According to this method, although the flexibility of the cured product is improved by introducing an alkyl chain skeleton, a strong acid is used during the resin production process. Limitation will occur. In addition, since ionic impurities are likely to remain, the use is also limited, which is not practical.
  • the present invention has been made based on the above circumstances, and the flowability of the novolak resin is improved, and the flexibility of the cured product of the resin composition using the novolak resin is improved, and moisture resistance is also imparted.
  • An object of the present invention is to provide a method for producing a novolac resin.
  • a phenol and a saturated aliphatic aldehyde having 6 to 20 carbon atoms are represented by the following general formula (1) B- (OR) 3 (1) (In the formula, three R's each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) and an acid having a pKa at 25 ° C. of 5.0 or less.
  • a process for producing a novolac-type phenolic resin characterized by reacting in the presence of [2] The method for producing a novolac type phenol resin according to [1], wherein an aromatic aldehyde is reacted in addition to the phenols and the saturated aliphatic aldehyde. [3] The method for producing a novolac type phenol resin according to [2], wherein the aromatic aldehyde is represented by the general formula (2).
  • A represents a residue obtained by removing a + 1 hydrogen atom from a monocyclic or polycyclic aromatic hydrocarbon, and each R 1 independently represents an alkyl group having 1 to 6 carbon atoms, a hydroxy group, or a carbon atom.
  • a method for producing a novolac resin in which the fluidity of the novolak resin is improved, the flexibility of the cured product of the resin composition using the novolac resin is improved, and moisture resistance is also provided. Can do.
  • FIG. 2 is a GPC chart of novolac resin A in Example 1.
  • FIG. 10 is a GPC chart of novolac resin I in Example 9.
  • 4 is a GPC chart of novolac resin J in Comparative Example 1.
  • the novolac type phenol resin is also referred to as “novolac resin” hereinafter.
  • the method for producing a novolac type phenolic resin of the present invention comprises a phenol and a saturated aliphatic aldehyde having 6 to 20 carbon atoms represented by the following general formula (1): B- (OR) 3 (1) (In the formula, three R's each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) and an acid having a pKa at 25 ° C. of 5.0 or less. In the presence of
  • an aromatic aldehyde may be reacted in addition to the phenols and the saturated aliphatic aldehyde.
  • A represents a residue obtained by removing a + 1 hydrogen atom from a monocyclic or polycyclic aromatic hydrocarbon, and each R 1 independently represents an alkyl group having 1 to 6 carbon atoms, a hydroxy group, or a carbon atom. Represents any one of an alkoxy group of formulas 1 to 6 and a halogen atom, and a is an integer of 0 to 3.
  • Phenols refer to compounds having a phenol skeleton, and include, in addition to phenol, compounds in which one or more hydrogen atoms of the aromatic ring of phenol are substituted with an alkyl group, a cycloalkyl group, or an aryl group.
  • phenol, cresol, ethylphenol, xylenol, butylphenol, octylphenol, nonylphenol, phenylphenol, cyclohexylphenol, trimethylphenol, bisphenol A, catechol, resorcinol, hydroquinone, naphthol, pyrogallol, etc., alone or in combination Can be used.
  • phenol or cresol because of its high versatility and easy availability of raw materials.
  • the saturated aliphatic aldehyde used for the production of the novolak resin is a saturated aliphatic aldehyde having 6 to 20 carbon atoms, preferably a saturated aliphatic aldehyde having 6 to 12 carbon atoms, more preferably the number of carbon atoms. 6 to 10 saturated aliphatic aldehydes.
  • a saturated aliphatic aldehyde having 6 to 10 carbon atoms is referred to as a lower aldehyde
  • a saturated aliphatic aldehyde having 11 to 20 carbon atoms is referred to as a higher aldehyde, both of which have a straight chain branch.
  • saturated aliphatic aldehyde used in the production of the novolak resin include valeraldehyde, hexyl aldehyde, heptyl aldehyde, octyl aldehyde, nonyl aldehyde, decyl aldehyde, undecyl aldehyde, dodecyl aldehyde, tridecyl aldehyde, tetra Decylaldehyde, pentadecylaldehyde, glyoxal, glyoxylic acid, glutaraldehyde, 2-ethylhexanal, 2-methylvaleraldehyde, isobutyraldehyde, 2-methylbutyraldehyde, 3-methylbutyraldehyde, 3- (methylthio) -propionaldehyde, etc.
  • hexylaldehyde, 2-methylvaleraldehyde, and octylaldehyde are preferably used from the viewpoint of availability of raw materials, easy reaction, and imparting curability characteristics.
  • the aromatic aldehyde that may be used for the production of the novolak resin is a compound containing an aromatic group and an aldehyde group.
  • an aromatic aldehyde represented by the general formula (2) is preferable.
  • A represents a residue obtained by removing a + 1 hydrogen atom from a monocyclic or polycyclic aromatic hydrocarbon, and each a 1 R 1 is independently an alkyl group having 1 to 6 carbon atoms or a hydroxy group. Represents an alkoxy group having 1 to 6 carbon atoms or a halogen atom, and a is an integer of 0 to 3.
  • the alkyl group having 1 to 6 carbon atoms of R 1 is preferably 1 carbon atom.
  • Specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
  • the alkoxy group having 1 to 6 carbon atoms is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably an alkoxy group having 1 to 3 carbon atoms.
  • Specific examples include a methoxy group, an ethoxy group, and a propoxy group.
  • the halogen atom include fluorine, chlorine, bromine, iodine atom, and the like, preferably a fluorine atom.
  • Specific examples of A include residues obtained by removing a + 1 hydrogen atoms from aromatic hydrocarbons such as a benzene ring, a naphthalene ring, and an anthracene ring.
  • aromatic aldehyde examples include benzaldehyde, salicylaldehyde, dihydroxybenzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, trimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, dibutylbenzaldehyde, methoxybenzaldehyde, dimethoxybenzaldehyde, cuminaldehyde, penta Methylbenzaldehyde, hydroxymethylbenzaldehyde, phenoxybenzaldehyde, phenylbenzaldehyde, phthalaldehyde, chlorbenzaldehyde, dichlorobenzaldehyde, trichlorobenzaldehyde, tetrachlorobenzaldehyde, bromobenzaldehyde, dibromobenzaldehyde, tribro
  • total aldehydes are used when two or more saturated aliphatic aldehydes are used, or when one or more saturated aliphatic aldehydes and one or more aromatic aldehydes are used in combination. Refers to all aldehydes produced.
  • the total molar amount of the total aldehydes is preferably 0.3 to 1.0 mol, more preferably 0.4 to 0.8 mol, and still more preferably 0.5 to 1 mol of the total amount of the phenols. It is preferably used at a ratio of ⁇ 0.7 mol. Since the total molar amount of total aldehydes is within the above range with respect to 1 mol of the total amount of phenols, the remaining phenols can be kept at an appropriate amount, and the yield of novolak resin is reduced. In addition, a decrease in dimensional stability of a molded article using a novolac resin, generation of voids, and the like are suppressed.
  • the molar ratio of the two is preferably 8: 2 to 3: 7, more preferably 7: 3 to 4: 6, The ratio is preferably 6: 4 to 4: 6.
  • the boron compound used in the production of the novolak resin has the following formula (1): B- (OR) 3 (1) (In the formula, three R's each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).
  • R is an alkyl group having 1 to 10 carbon atoms
  • the alkyl group having 1 to 10 carbon atoms may be linear or branched, and is a methyl group, ethyl group, propyl group, isopropyl group, butyl group , Isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, octyl, decyl, etc. Is mentioned.
  • boron compound represented by the formula (1) examples include boric acid, trimethyl borate, triethyl borate, triisopropyl borate, tributyl borate and the like, and are used alone or in combination of two or more. Boric acid is more preferred.
  • the acid used for the production of the novolak resin is an acid having the pKa of 5.0 or less at 25 ° C.
  • an acid may be any one that is used for the production of a general novolak resin,
  • hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, oxalic acid and the like can be mentioned, and these can be used alone or in combination of two or more.
  • an acid having a pKa of 5.0 or less at 25 ° C. as a catalyst, a novolak resin having the characteristics described later can be obtained.
  • an acid having a pKa of 0.0 to 4.0 is preferable.
  • an acid is a polybasic acid, if pK a1 is 5.0 or less, it is applicable. In the method for producing a novolak resin of the present invention, the reason is not clear, but it is presumed that a sufficient catalytic action for advancing the reaction can be obtained by using the boron compound and an acid together.
  • the boron compound is used in an amount of 0.05 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of phenols. It is preferable to use in the ratio.
  • the acid is used in an amount of 0.05 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of phenols. Preferably used in proportion.
  • the total amount of the boron compound and the acid used is 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.2 parts by weight based on 100 parts by weight of phenols. It is preferably used at a ratio of ⁇ 5 parts by mass.
  • the total amount of the boron compound and the acid is 0.1 parts by mass or more and 20 parts by mass or less, a sufficient effect as a catalyst can be obtained, and a phenomenon in which the molecular weight increases during synthesis (decomposition and decomposition).
  • the novolak resin described later can be obtained by suppressing the (arrangement).
  • the method of reacting phenols with aldehydes is not particularly limited. For example, phenols, total aldehydes, and acid catalyst are charged together and reacted, or phenols and acid catalyst are charged at a predetermined reaction temperature. And a method of adding aldehydes. In the latter case, the method of addition may be added one by one in order or after a plurality of aldehydes are mixed in advance.
  • the reaction temperature is preferably 30 to 130 ° C., preferably 50 to 100 ° C., more preferably 60 to 80 ° C.
  • the reaction temperature is 30 ° C. or higher and 130 ° C. or lower, it reacts at an appropriate reaction rate, and it becomes difficult for unreacted phenols to remain, and generation of a novolak resin having a high molecular weight component is suppressed.
  • limiting in particular in reaction time What is necessary is just to adjust with the quantity of aldehydes and an acid catalyst, and reaction temperature. For example, by reacting for 6 to 10 hours, it becomes difficult for unreacted phenols to remain, and generation of a novolak resin having a high molecular weight component is suppressed.
  • Organic solvent It is also possible to use an organic solvent in the reaction during production.
  • organic solvents include alcohols such as propyl alcohol and butanol, glycols such as ethylene glycol and propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and butylene.
  • Glycol ethers such as glycol monomethyl ether, butylene glycol monoethyl ether, butylene glycol monopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, propyl acetate, butyl acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Esters such as acetate, ethers such as 1,4-dioxane Etc. are alone, or in combination of two or more can be used.
  • the organic solvent can be used in an amount of 0 to 1,000 parts by weight, preferably 10 to 100 parts by weight, and more preferably about 20 to 50 parts by weight with respect to 100 parts by weight of phenols.
  • the condensed water may be removed by distillation or, if necessary, the remaining catalyst may be removed by washing with water.
  • unreacted phenols and unreacted aldehydes may be removed by distillation under reduced pressure or steam distillation.
  • the novolak resin of the present invention is obtained by the production method described above.
  • the novolac resin is represented, for example, by the following general formula (3).
  • R 2 and R 3 each independently represents an alkyl group having 1 to 12 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 12 carbon atoms, and R 4 represents one having 5 to 19 carbon atoms.
  • R 4 represents one having 5 to 19 carbon atoms.
  • b to c are each independently an integer of 0 to 3
  • n is an integer of 1 to 10.
  • the novolak resin of the present invention in which a part of the aliphatic aldehyde having 6 to 20 carbon atoms is replaced with an aromatic aldehyde is represented, for example, by the following general formula (4).
  • A represents a residue obtained by removing a + 1 hydrogen atom from a monocyclic or polycyclic aromatic hydrocarbon, and each R 1 independently represents an alkyl group having 1 to 6 carbon atoms, a hydroxy group, or a carbon atom.
  • R 2 , R 3 and R 5 each independently represents an alkyl group having 1 to 12 carbon atoms, a hydroxy group, or an alkoxy group having 1 to 12 carbon atoms, and R 4 represents 5 to 5 carbon atoms.
  • 19 represents an alkyl group (including those having a side chain)
  • a to d are each independently an integer of 0 to 3
  • n and m are each independently an integer of 1 to 10. However, the units of n and m may be connected alternately or randomly. )
  • the thermosetting resin composition of the present invention contains a novolac resin and an epoxy resin.
  • the novolak resin is preferably a novolak resin obtained by the above-described method for producing a novolak resin or a novolak resin having the above-described structure.
  • Epoxy resin It does not specifically limit as an epoxy resin used by this invention, A well-known epoxy resin can be used.
  • the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, resorcinol type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type Epoxy resins derived from dihydric phenols such as epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane Type epoxy resin, dicyclopentadiene-phenol modified epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, na Tall novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-
  • the mixing ratio of the epoxy resin and the novolak resin is such that the hydroxyl equivalent of the novolak resin is preferably in the range of 0.6 to 1.2, more preferably 0.7 to 1.1, with respect to the epoxy equivalent of 1.0 of the epoxy resin. A range, even more preferably 1.0.
  • a curing accelerator can be appropriately used for the purpose of accelerating the curing reaction.
  • curing accelerators include organic acid metal salts such as imidazole, organic phosphorus compounds, secondary and tertiary amines, tin octylate, Lewis acids, amine complex salts, and the like.
  • the imidazole compounds include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole.
  • 2-heptadecylimidazole 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2- Examples include phenyl-4-methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline. These imidazole compounds may be masked with a masking agent.
  • the masking agent examples include acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, and melamine acrylate.
  • organophosphorus compounds include ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane complex, tetra And phenylphosphonium tetraphenylborate.
  • Secondary amine compounds include morpholine, piperidine, pyrrolidine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, dibenzylamine, dicyclohexylamine, N-alkylarylamine, piperazine, diallylamine, thiazoline, thiol.
  • Examples include morpholine.
  • Examples of the tertiary amine compound include benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, and the like.
  • thermosetting resin composition of the present invention includes various kinds of fillers, thermosetting resins and thermoplastic resins used as modifiers, pigments, silane coupling agents, mold release agents, and the like as necessary. These compounding agents can be added depending on the purpose. Among these, for example, fused silica, crystalline silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, aluminum hydroxide And inorganic fillers such as magnesium hydroxide.
  • the fused silica can be used in either a crushed or spherical shape, but in order to increase the content of the fused silica in the thermoplastic resin composition and to suppress an increase in the melt viscosity of the molding material, a spherical one is mainly used. It is preferable to use for the above. Furthermore, in order to increase the content of the spherical silica relative to the thermoplastic resin composition, it is preferable to appropriately adjust the particle size distribution of the spherical silica.
  • the desired content of the filler content varies depending on the application and desired characteristics. However, for example, when used for a semiconductor encapsulant, a higher content is preferable in view of the coefficient of linear expansion and flame retardancy.
  • the amount is preferably 65% by mass or more, particularly preferably about 80 to 90% by mass with respect to the total amount of the curable resin composition.
  • electrically conductive fillers such as silver powder and copper powder, can be used.
  • thermosetting and thermoplastic resins used as the modifier can be used.
  • phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene ether Resins, polyphenylene sulfide resins, polyester resins, polystyrene resins, polyethylene terephthalate resins, and the like can be used as long as they do not impair the effects of the present invention.
  • the silane coupling agent include silane coupling agents such as amino silane compounds, vinyl silane compounds, styrene silane compounds, and methacryl silane compounds.
  • the mold release agent include stearic acid, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, and carnauba wax.
  • FIG. 1 shows a gel permeation chromatography (GPC) chart of Resin A. The horizontal axis indicates the elution time (minutes).
  • Example 2 shows a GPC chart of resin I
  • FIG. 2 shows a GPC chart of resin I
  • the novolak resin obtained by the present invention has a feature that it is difficult to produce a high molecular weight component, and as shown in Tables 1 and 2, it can be confirmed that the resin has a low melt viscosity and a higher fluidity.
  • the higher the aldehyde / phenol reaction molar ratio or the reaction temperature the easier it is to produce a high molecular weight component, and the fluidity of the resin tends to decrease.
  • the resin obtained by the present invention has a low melt viscosity even in a resin having a high reaction molar ratio, and it can be confirmed that the fluidity is good.
  • thermosetting resin composition was pressure-molded in a mold at 150 ° C. for 30 minutes and at a pressure of 30 kg / cm 2 . Thereafter, it was post-cured at 180 ° C. for 5 hours to produce a test piece having a length of 95 mm, a width of 10 mm, and a thickness of 4 mm.
  • the glass transition temperature, the water absorption, and the bending elastic modulus in 25 degreeC conditions and 260 degreeC conditions were evaluated with the following method.
  • Glass transition temperature The glass transition temperature was measured by TMA method using the product name "SSC / 5200" made by Seiko Instruments Inc. (SII).
  • the heating rate was 10 ° C./min, the sample size was 4 mm wide ⁇ 10 mm long ⁇ 8 mm thick.
  • Flexural modulus Tensilon universal testing machine (trade name “Tensilon UTM-5T” manufactured by Toyo Baldwin Co., Ltd.) was used to measure in accordance with JIS K-6911.
  • the elastic modulus shown in Table 2 is The elastic modulus is 25 ° C. at room temperature and 260 ° C. when heated.
  • Epoxy resin manufactured by Mitsubishi Chemical Corporation (Triphenylmethane type epoxy resin), trade name “1032H60” Triphenylphosphine: Wako Pure Chemical Industries, Ltd. Fused silica: Tatsumori Co., Ltd., trade name “MSR-2212”
  • the cured product of the thermosetting resin composition obtained by using the resin of the present invention resulted in a reduction in water absorption relative to the comparative example and a low elastic modulus at 260 ° C. . That is, it can be said that the water absorption / flexibility is lower than that in the case of using a phenol / formaldehyde novolak resin (Comparative Examples 9 and 10) which is a conventional material.
  • a novolak resin excellent in fluidity it becomes possible to obtain a cured product excellent in moisture resistance and flexibility by using it.
  • Example 19 to 21, Comparative Example 14, Reference Example 1 A reaction was carried out in the same manner as in Example 1 except that the compounds and reaction conditions described in Table 5 were used to obtain novolak resins O and Q to T. Table 5 shows the results.
  • the pKa of valeric acid used in Comparative Example 14 is 5.17.
  • thermosetting resin was prepared with the composition shown in Table 6 using the obtained novolak resins O, Q, and S, a test piece was prepared, and evaluation was performed.
  • Table 6 shows the glass transition temperature, water absorption, and values of the flexural modulus at 25 ° C. and 260 ° C. of the obtained test piece.
  • the method for producing a novolak resin of the present invention improves the fluidity of the produced novolak resin, improves the flexibility of the cured product of the resin composition using the novolak resin, and can also provide moisture resistance.
  • a novolak resin is provided.
  • the novolac resin obtained by the method for producing the novolak resin is a resin composition for an electronic component sealing material, a resin composition for a printed circuit board, a resin composition for an interlayer insulating material used for a printed circuit board and a copper foil with resin. , Conductive paste (containing conductive filler), paint, adhesive, composite material, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2015/081899 2014-11-13 2015-11-12 ノボラック型フェノール樹脂の製造方法、ノボラック型フェノール樹脂、熱硬化性樹脂組成物及び硬化物 WO2016076403A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016559109A JP6729863B2 (ja) 2014-11-13 2015-11-12 ノボラック型フェノール樹脂の製造方法、ノボラック型フェノール樹脂、熱硬化性樹脂組成物及び硬化物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014230714 2014-11-13
JP2014-230714 2014-11-13

Publications (1)

Publication Number Publication Date
WO2016076403A1 true WO2016076403A1 (ja) 2016-05-19

Family

ID=55954480

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/081899 WO2016076403A1 (ja) 2014-11-13 2015-11-12 ノボラック型フェノール樹脂の製造方法、ノボラック型フェノール樹脂、熱硬化性樹脂組成物及び硬化物

Country Status (3)

Country Link
JP (1) JP6729863B2 (zh)
TW (1) TWI682947B (zh)
WO (1) WO2016076403A1 (zh)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4904753A (en) * 1988-03-23 1990-02-27 Ashland Oil, Inc. Acid/oxidizer catalyst system for storage stable, quick-cure phenolic resins of the resole or benzylic ether resole type
JP2010180399A (ja) * 2009-01-09 2010-08-19 Showa Highpolymer Co Ltd ノボラック樹脂の製造方法およびノボラック樹脂

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4904753A (en) * 1988-03-23 1990-02-27 Ashland Oil, Inc. Acid/oxidizer catalyst system for storage stable, quick-cure phenolic resins of the resole or benzylic ether resole type
JP2010180399A (ja) * 2009-01-09 2010-08-19 Showa Highpolymer Co Ltd ノボラック樹脂の製造方法およびノボラック樹脂

Also Published As

Publication number Publication date
TW201630956A (zh) 2016-09-01
TWI682947B (zh) 2020-01-21
JP6729863B2 (ja) 2020-07-29
JPWO2016076403A1 (ja) 2017-10-05

Similar Documents

Publication Publication Date Title
JP5466362B2 (ja) カシューノボラック樹脂、その製造方法、およびエポキシ樹脂用硬化剤
TWI465488B (zh) 酚醛清漆樹脂及其製造方法
JP5845528B2 (ja) フェノール樹脂組成物および熱硬化性樹脂組成物
JP5876976B2 (ja) ノボラック樹脂および熱硬化性樹脂組成物
JP6232271B2 (ja) フェノール樹脂組成物、熱硬化性樹脂組成物、及び硬化物
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
JP6729863B2 (ja) ノボラック型フェノール樹脂の製造方法、ノボラック型フェノール樹脂、熱硬化性樹脂組成物及び硬化物
JP2016196592A (ja) エポキシ樹脂およびそれを含む熱硬化性樹脂組成物
JP5635258B2 (ja) 変性ノボラック樹脂および前記変性ノボラック樹脂を配合した熱硬化性樹脂組成物
JP2015074673A (ja) 熱硬化性樹脂組成物及びこれを硬化して得られる硬化物
JP2010013601A (ja) 変性ノボラック樹脂および前記変性ノボラック樹脂を配合した熱硬化性樹脂組成物
JP2010037501A (ja) トリアゾール系共縮合物およびその製造方法
JP6519917B2 (ja) エポキシ樹脂および熱硬化性樹脂組成物
JP6368473B2 (ja) 熱硬化性樹脂組成物及び硬化物

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: 15858825

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016559109

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: 15858825

Country of ref document: EP

Kind code of ref document: A1