WO2010079672A1 - Novolac resin and thermosetting resin composition - Google Patents

Novolac resin and thermosetting resin composition Download PDF

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Publication number
WO2010079672A1
WO2010079672A1 PCT/JP2009/070879 JP2009070879W WO2010079672A1 WO 2010079672 A1 WO2010079672 A1 WO 2010079672A1 JP 2009070879 W JP2009070879 W JP 2009070879W WO 2010079672 A1 WO2010079672 A1 WO 2010079672A1
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formula
resin
ortho
represented
epoxy resin
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PCT/JP2009/070879
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French (fr)
Japanese (ja)
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進一 瀧本
能理善 小野
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昭和高分子株式会社
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Priority to KR1020117015549A priority Critical patent/KR101348993B1/en
Priority to CN200980154133.1A priority patent/CN102282187B/en
Publication of WO2010079672A1 publication Critical patent/WO2010079672A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • 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
    • C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • the present invention relates to a novolak resin having good moisture resistance and heat resistance and a thermosetting resin composition containing the novolak resin.
  • Phenolic resins have heat resistance and are used in various fields. For example, when used as a curing agent for epoxy resin, it is excellent in heat resistance, adhesion and electrical insulation, etc., and is used for resin compositions for printed circuit boards and printed circuit boards and resin-attached copper foils, It is used for resin compositions for electronic parts sealing materials, resist inks, conductive pastes (containing conductive fillers), paints, adhesives, composite materials, and the like. Furthermore, with recent technological innovations, phenol resins used as curing agents in epoxy resin compositions are also required to have improved moisture resistance, heat resistance, flame retardancy, and the like.
  • Phenol is generally a resin having heat resistance, but since the hydroxyl group and methylene group in the resin are susceptible to oxidation, further improvement in heat resistance can be expected by improving this point. For this reason, the use of aromatic aldehydes and the improvement of heat resistance of resins by co-condensation of alkoxybenzenes and phenols have been studied (see Patent Documents 1 and 2).
  • Patent Document 1 describes an invention in which a phenol and an aromatic aldehyde are reacted in the presence of an acid catalyst.
  • the cured product of the novolak resin and the epoxy resin thus obtained has a glass transition temperature higher than that in the case of using a normal novolac resin, but on the other hand, there is a drawback that the bending strength is lowered due to the residual stress at the time of curing. there were.
  • the hydroxyl group concentration in the resin is increased, there is a problem that the moisture resistance of the molded product is lowered.
  • Patent Document 2 describes an invention in which a methylene group is partially introduced as a crosslinking group in order to lower the melt viscosity of a novolak resin obtained by condensation of phenols and aromatic aldehydes described in Patent Document 1. .
  • the resin obtained in this way has improved fluidity, the hydroxyl group concentration is still high, so that there remains a problem in the moisture resistance of the molded product.
  • the present invention has been made based on the above circumstances, and provides a novolak resin having excellent moisture resistance and heat resistance and a thermosetting resin composition containing the novolak resin as a curing agent. Objective.
  • the present invention is based on the finding that the above-mentioned problem is achieved by a novolak resin in which the proportion of the ortho position of the phenol and the ortho position of the orthohydroxybenzaldehyde is 70 mol% or more of the total bonds. Is. That is, the present invention has the following configuration.
  • the phenol represented by the formula (II ′) and the phenol represented by the formula (II ′′) are selected from phenol and cresol, the number average molecular weight is 300 to 600, and the degree of dispersion (weight average molecular weight / The novolak resin according to 1 above, wherein the number average molecular weight is 1.5 or less, 3.
  • An epoxy resin composition comprising the novolak resin according to 1 or 2 as a curing agent, 4).
  • a novolak resin having excellent moisture resistance and heat resistance and a thermosetting resin composition containing the novolac resin as a curing agent.
  • FIG. 1 is a 1 NMR chart of novolak resin A obtained in Example 1.
  • FIG. 2 is a 1 NMR chart of novolak resin D obtained in Comparative Example 1.
  • FIG. 1 is a 1 NMR chart of novolak resin A obtained in Example 1.
  • FIG. 2 is a 1 NMR chart of novolak resin D obtained in Comparative Example 1.
  • the novolak resin of the present invention includes an orthohydroxybenzaldehyde represented by the formula (I), a phenol represented by the formula (II ′), and a phenol represented by the phenol represented by the formula (II ′′). It is obtained by the reaction.
  • the phenols represented by the formula (II ′) and the phenols represented by the formula (II ′′) may be the same or different.
  • the phenols represented by the above formula (II ′) and the phenols represented by the above formula (II ′′), R 1 , R 2 and R 3 Each represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxyl 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, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group.
  • n-pentyl group isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, etc. Can be mentioned.
  • the alkoxyl group having 1 to 10 carbon atoms may be linear or branched, and is a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, Examples thereof include a tert-butoxy group, an n-pentyloxy group, an isopentyloxy group, a neopentyloxy group, various hexyloxy groups, various heptyloxy groups, various octyloxy groups, various nonyloxy groups, and various decyloxy groups.
  • k represents an integer of 0 to 3.
  • K representing the number of substituents R 1 on the benzene ring is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably an integer of 0 or 1.
  • R 1 may be the same or different.
  • R 1 , R 2 , R 3 and k are the same as described above.
  • the alkyl group having 1 to 10 carbon atoms and the alkoxyl group having 1 to 10 carbon atoms are orthohydroxybenzaldehydes represented by the formula (I), phenols represented by the formula (II ′) and the formula (II ′′). It is as having mentioned in phenols represented by these.
  • orthohydroxybenzaldehydes represented by the formula (I) include salicylaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2-hydroxy-3-methylbenzaldehyde.
  • orthohydroxybenzaldehydes such as 2-hydroxy-5-methylbenzaldehyde and the like can be used alone or in admixture of two or more.
  • any phenol can be used as long as it is used for the production of general phenol resins.
  • phenol and various cresols are practically preferable.
  • the aldehydes to be reacted with the phenols represented by the formula (II ′) and the phenols represented by the following formula (II ′′) include the ortho represented by the formula (I).
  • Hydroxybenzaldehydes but other aldehydes that can be used in the production of phenolic resins, such as formaldehyde, acetaldehyde, benzaldehyde, parahydroxybenzaldehyde, metahydroxybenzaldehyde, paraformaldehyde, propylaldehyde, butyraldehyde, isovaler Aldehyde, hexylaldehyde, glyoxal, crotonaldehyde, glutaraldehyde and the like can be used alone or in admixture of two or more.
  • aldehydes are collectively referred to as aldehydes.
  • the aldehyde is used in an amount of 0.3 to 1.0 mol, preferably 0.4 to 0.9 mol, based on 1 mol of the total amount of phenols. If the amount of aldehyde used is less than 0.3 mol, the remaining phenolic monomer increases, which is not efficient. On the other hand, when the amount of aldehydes used exceeds 1.0 mol, the molecular weight of the resulting resin is increased, which is not preferable.
  • boric acid and an acid having a pKa of 5.0 or less are used.
  • hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, para-toluenesulfonic acid, oxalic acid, etc. are used.
  • an aldehyde other than formaldehyde and paraformaldehyde is used as the aldehyde, sufficient reactivity cannot be obtained unless it is a strong acid such as hydrochloric acid, nitric acid, sulfuric acid, and paratoluenesulfonic acid.
  • a novolak resin having an ortho-ortho-ortho bond ratio of 70 mol% or more of all bonds cannot be obtained.
  • the resin of the present invention can be obtained only when boric acid and an acid having a pKa of 5.0 or less are used in combination.
  • the acid having a pKa of 5.0 or less may be any acid as long as it is used for the production of a general novolak resin.
  • Examples thereof include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid, and oxalic acid. It can be used alone or in combination of two or more.
  • An acid having a pKa of more than 5.0 is not practical because of poor catalyst effect.
  • an acid having a pKa of 0.0 to 4.0 is preferable, and examples thereof include oxalic acid, phosphoric acid, salicylic acid, and tartaric acid.
  • the amount of the acid having a pKa of 5.0 or less is 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of phenols. It is preferable to use in the ratio.
  • Aldehydes such as orthohydroxybenzaldehydes represented by the formula (I)
  • a method in which a catalyst is charged all at once, or a phenols and a catalyst are charged and the ortho represented by the formula (I) at a predetermined reaction temperature examples thereof include a method of adding aldehydes such as hydroxybenzaldehydes.
  • the reaction temperature is preferably in the range of 30 to 120 ° C.
  • 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, butylene glycol monomethyl ether Glycol ethers such as butylene glycol monoethyl ether and 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 acetate, etc.
  • alcohols such as propyl alcohol and butanol
  • glycols such as ethylene glycol and propylene glycol
  • ethylene glycol monomethyl ether ethylene glycol monoethyl ether
  • Esters and ethers such as 1,4-dioxane alone , Or it can be used in combination of two or more.
  • the organic solvent can be used in an amount of about 0 to 1,000 parts by mass, preferably about 10 to 100 parts by mass with respect to 100 parts by mass of phenols.
  • the condensed water may be removed by distillation, or, if necessary, the remaining acid 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 represented by the above formula (III) of the present invention has a number average molecular weight of 300 to 600, preferably 350 to 550, more preferably 350 to 500. If the number average molecular weight exceeds 600, the ratio of ortho-ortho-ortho bonds decreases, which is not preferable. Further, the dispersity (weight average molecular weight / number average molecular weight) is 1.5 or less, preferably 1.4 or less. A dispersity of 1.5 or less means that there are few high molecular weight polynuclear bodies in the novolak resin. As the number of polynuclear bodies increases, the proportion of ortho-ortho-ortho bonds decreases, which is not preferable.
  • the novolak resin of the present invention is preferably one using a compound selected from phenol and various cresols as the phenol represented by the formula (II ′) and the phenol represented by the following formula (II ′′).
  • thermosetting resin composition of the present invention Since the novolak resin of the present invention is useful as a curing agent for an epoxy resin, the present invention can provide a thermosetting resin composition in which the epoxy resin and the novolak resin are blended. Here, it does not specifically limit as an epoxy resin used, 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, resorcin 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, naphtho Lunovolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin,
  • a triphenylmethane type epoxy resin is preferable, and an epoxy resin obtained by epoxidizing the novolak resin of the present invention is more preferable.
  • these epoxy resins may be used independently and may use 2 or more types together.
  • the mixing ratio of the modified novolak resin and the epoxy resin is 0.8 to 1.2 equivalents, preferably 0.9 to 1.2 equivalents of the epoxy resin with respect to 1.0 equivalent of the modified novolak resin.
  • 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, phosphorus compounds, secondary and tertiary amines, tin octylate, Lewis acids, amine complex salts, and the like. More than one species can be used in combination.
  • 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 a thermosetting resin and a thermosetting resin used as a filler, a modifier, a pigment, a silane coupling agent, a release agent, and the like as necessary.
  • Various compounding agents can be added according to the purpose.
  • fillers 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
  • inorganic fillers such as magnesium hydroxide.
  • the fused silica can be used in either a crushed shape or a spherical shape.
  • the preferred range varies depending on the application and desired properties, but for example, when used in semiconductor encapsulant applications, the higher the ratio is preferable in view of the linear expansion coefficient and flame retardancy, and the total amount of the composition It is preferably 65% by weight or more, particularly preferably about 85 to 90% by weight.
  • electrically conductive fillers such as silver powder and copper powder, can be used.
  • thermosetting resins and thermoplastic resins used as the modifier can be used.
  • An ether resin, a polyphenylene sulfide resin polyester resin, a polystyrene resin, a polyethylene terephthalate resin, and the like can be used as long as they do not impair the effects of the present invention.
  • 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.
  • Example 1 A flask equipped with a condenser and a stirrer was charged with 100 g of orthocresol, 56 g of salicylaldehyde, 1 g of boric acid and 1 g of oxalic acid, and reacted at 100 ° C. for 8 hours. Next, the catalyst was removed by washing twice with 100 g of pure water. Subsequently, the distillate was removed under reduced pressure at 180 ° C. and 50 mmHg to obtain 102 g of novolak resin A.
  • a 1 NMR chart of the novolak resin A is shown in FIG.
  • Example 2 A reaction was carried out in the same manner as in Example 1 except that 100 g of metacresol was used as a phenol, to obtain 110 g of novolak resin B.
  • Example 3 A reaction was carried out in the same manner as in Example 1 except that 45 g of salicylaldehyde and 3 g of paraformaldehyde were used as aldehydes to obtain 105 g of novolak resin C.
  • Comparative Example 1 A flask equipped with a condenser and a stirrer was charged with 100 g of orthocresol, 56 g of salicylaldehyde, and 1 g of paratoluenesulfonic acid, and reacted at 100 ° C. for 8 hours. Subsequently, the catalyst was removed by washing several times with 100 g of pure water. Subsequently, the distillate was removed under reduced pressure at 180 ° C. and 50 mmHg to obtain 90 g of novolak resin D. A 1 NMR measurement chart of the novolak resin D is shown in FIG.
  • Comparative Example 3 A flask equipped with a condenser and a stirrer was charged with 100 g of orthocresol, 63 g of 37% formalin and 1 g of oxalic acid. After reacting at 100 ° C. for 5 hours, unreacted phenol was removed under reduced pressure of 180 ° C. and 50 mmHg, and novolak resin F70g was obtained.
  • Table 1 shows analytical values of the novolak resins obtained in Examples 1 to 3 and the novolak resins obtained in Comparative Examples 1 to 3.
  • the analysis method of resin is as follows.
  • Ortho-ortho-ortho bond ratio Ortho-ortho-ortho (5.8-6.1 ppm), ortho-para-ortho (5.4-5.6 ppm), ortho by 1 H-NMR (300 MHz) spectrum Calculated from the integral ratio of methine binding of -para-para (5.0-5.2 ppm).
  • the column configuration was KF-804 + KF-804 manufactured by Showa Denko KK, tetrahydrofuran was used as a solvent, and measurement was performed at a flow rate of 1 ml / min.
  • the molecular weight was calculated in terms of polystyrene, and the content was calculated as a percentage of the total peak area.
  • the degree of dispersion was calculated by weight average molecular weight / number average molecular weight.
  • Table 1 shows that the modified novolak resin of the present invention has an extremely high ortho-ortho-ortho bond ratio as compared with the novolak resin of the comparative example.
  • Example 4 (Production of epoxy resin) A flask equipped with a condenser and a stirrer was charged with 100 g of the novolak resin of Example 1, 400 g of epichlorohydrin, and 0.1 g of tetramethylammonium chloride, and the internal temperature was maintained at 60 ° C. for 1 hour. A 100% aqueous potassium hydroxide solution was added dropwise over 3 hours. At that time, the inside of the system was depressurized, and water was removed out of the mixture of epichlorohydrin and water distilled out, and the reaction was carried out while returning epichlorohydrin to the system.
  • Epoxy resin Resin H Triphenylmethane type epoxy resin Product name 1032H60 Made by Japan Epoxy Resin Co., Ltd.
  • Resin I Biphenyl aralkyl type epoxy resin Product name NC-3000H Nippon Kayaku Co., Ltd.
  • Triphenylphosphine Wako Pure Chemical Industries, Ltd.
  • Melting Silica Trade name MSR-2212: Made by Tatsumorisha
  • thermosetting resin composition of the present invention the water absorption rate is much lower than that of the conventional novolac resin, and the glass transition temperature, the bending strength, etc. show the same or better performance than the conventional novolak resin. I understand that.
  • the novolak resin of the present invention has excellent moisture resistance and heat resistance, and when used as a curing agent for epoxy resin, the cured product has good moisture resistance, heat resistance, flexibility, mechanical properties, electrical insulation. And adhesion to metal. Therefore, specifically, 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 a resin, a conductive paste (conductive filler) Containment), paints, adhesives and composite materials.

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  • 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)

Abstract

Disclosed are a modified novolac resin having excellent moisture resistance and heat resistance, and a thermosetting resin composition wherein the modified novolac resin is blended as a curing agent.  Specifically disclosed is a novolac resin represented by formula (III), wherein the ratio of ortho-ortho-ortho bonds produced by condensing a hydrogen atom in the ortho position of a phenol represented by formula (II') and a phenol represented by formula (II'') with an aldehyde group of an orthohydroxybenzaldehyde is not less than 70% by mole of the total bonds.  Also specifically disclosed is an epoxy resin composition containing the novolac resin.

Description

ノボラック樹脂および熱硬化性樹脂組成物Novolac resin and thermosetting resin composition
　本発明は、耐湿性および耐熱性が良好なノボラック樹脂ならびに前記ノボラック樹脂を配合した熱硬化性樹脂組成物に関するものである。 The present invention relates to a novolak resin having good moisture resistance and heat resistance and a thermosetting resin composition containing the novolak resin.
　フェノール樹脂は耐熱性があり様々な分野に使用されている。
　例えば、エポキシ樹脂の硬化剤として用いた場合、耐熱性、密着性および電気絶縁性などに優れ、プリント基板用樹脂組成物やプリント基板および樹脂付き銅箔に使用する層間絶縁材料用樹脂組成物、電子部品の封止材用樹脂組成物、レジストインキ、導電ペースト（導電性充填剤含有）、塗料、接着剤、複合材料などに用いられている。
　更に、近年の技術革新に伴い、エポキシ樹脂組成物において、硬化剤として用いられるフェノール樹脂にも耐湿性、耐熱性および難燃性などの向上が求められている。
　フェノールは一般的に耐熱性を有する樹脂であるが、樹脂中の水酸基およびメチレン基は酸化の影響を受けやすいため、この点を改良することで更なる耐熱性の向上が期待できる。
　そのため、芳香族アルデヒド類の使用や、アルコキシベンゼン類とフェノール類の共縮合などによる樹脂の耐熱性向上が検討されてきた（特許文献１および２を参照）。 Phenolic resins have heat resistance and are used in various fields.
For example, when used as a curing agent for epoxy resin, it is excellent in heat resistance, adhesion and electrical insulation, etc., and is used for resin compositions for printed circuit boards and printed circuit boards and resin-attached copper foils, It is used for resin compositions for electronic parts sealing materials, resist inks, conductive pastes (containing conductive fillers), paints, adhesives, composite materials, and the like.
Furthermore, with recent technological innovations, phenol resins used as curing agents in epoxy resin compositions are also required to have improved moisture resistance, heat resistance, flame retardancy, and the like.
Phenol is generally a resin having heat resistance, but since the hydroxyl group and methylene group in the resin are susceptible to oxidation, further improvement in heat resistance can be expected by improving this point.
For this reason, the use of aromatic aldehydes and the improvement of heat resistance of resins by co-condensation of alkoxybenzenes and phenols have been studied (see Patent Documents 1 and 2).
　特許文献１では、フェノール類と芳香族アルデヒドを酸触媒の存在下で反応させる発明が記載されている。
　こうして得られるノボラック樹脂とエポキシ樹脂との硬化物は、通常のノボラック樹脂を用いた場合と比較してガラス転移温度が高くなるが、一方で硬化時の残存応力により曲げ強度が低下するという欠点があった。
　また、樹脂中の水酸基濃度が高くなるため、成型物の耐湿性が低下するといった問題があった。
　一方、特許文献２には、特許文献１記載のフェノール類と芳香族アルデヒドの縮合により得られたノボラック樹脂の溶融粘度を下げるため、架橋基としてメチレン基を一部導入する発明が記載されている。
　こうして得られた樹脂は、流動性は改善されるものの水酸基濃度は依然として高いため、成型品の耐湿性に課題が残った。 Patent Document 1 describes an invention in which a phenol and an aromatic aldehyde are reacted in the presence of an acid catalyst.
The cured product of the novolak resin and the epoxy resin thus obtained has a glass transition temperature higher than that in the case of using a normal novolac resin, but on the other hand, there is a drawback that the bending strength is lowered due to the residual stress at the time of curing. there were.
Moreover, since the hydroxyl group concentration in the resin is increased, there is a problem that the moisture resistance of the molded product is lowered.
On the other hand, Patent Document 2 describes an invention in which a methylene group is partially introduced as a crosslinking group in order to lower the melt viscosity of a novolak resin obtained by condensation of phenols and aromatic aldehydes described in Patent Document 1. .
Although the resin obtained in this way has improved fluidity, the hydroxyl group concentration is still high, so that there remains a problem in the moisture resistance of the molded product.
特開平２－１７３０２３号公報Japanese Patent Laid-Open No. 2-173023 特開２００２－２７５２２８号公報JP 2002-275228 A
　本発明は、以上のような事情に基づいてなされたものであり、優れた耐湿性および耐熱性を有するノボラック樹脂および前記ノボラック樹脂を硬化剤として配合した熱硬化性樹脂組成物を提供することを目的とする。 The present invention has been made based on the above circumstances, and provides a novolak resin having excellent moisture resistance and heat resistance and a thermosetting resin composition containing the novolak resin as a curing agent. Objective.
　本発明は、上記課題がフェノール類のオルソ位とオルソヒドロキシベンズアルデヒド類のオルソ位が結合した割合が、全結合の７０モル％以上であるノボラック樹脂によって達成されることが見出されたことに基づくものである。
　即ち、本発明は以下の構成からなる。 The present invention is based on the finding that the above-mentioned problem is achieved by a novolak resin in which the proportion of the ortho position of the phenol and the ortho position of the orthohydroxybenzaldehyde is 70 mol% or more of the total bonds. Is.
That is, the present invention has the following configuration.
１．下式（I）で表されるオルソヒドロキシベンズアルデヒド類と下式（II’）で表され
るフェノール類および下式（II’’）で表されるフェノール類を反応させてなるノボラック樹脂であって、前記下式（II’）で表されるフェノール類および下式（II’’）で表されるフェノール類のオルソ位の水素原子と前記オルソヒドロキシベンズアルデヒド類のアルデヒド基が縮合して生成したオルソ－オルソ－オルソ結合の割合が、全結合の７０モル％以上であることを特徴とする下式（III）で表されるノボラック樹脂、
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｒ1は水素原子、水酸基、炭素数１～１０のアルキル基または炭素数１～１０のアルコキシル基を示し、ｋは０～３の整数を示す。）
Figure JPOXMLDOC01-appb-C000005
 〔式（II’）および式（II’’）中、Ｒ2およびＲ3は水素原子、水酸基、炭素数１～１０のアルキル基を示す。〕
Figure JPOXMLDOC01-appb-C000006
 （式中、Ｒ1、Ｒ2、Ｒ3及びｋは、上記と同様である。）
２．式（II’）で表されるフェノール類および式（II’’）で表されるフェノール類が、フェノールおよびクレゾールから選ばれ、数平均分子量が３００～６００であり、分散度（重量平均分子量／数平均分子量）が１．５以下である上記１に記載のノボラック樹脂、
３．上記１または２に記載のノボラック樹脂を硬化剤として含むエポキシ樹脂組成物、
４．エポキシ樹脂が、トリフェニルメタン構造を有する上記３に記載のエポキシ樹脂組成物、
５．エポキシ樹脂が、上記１または２に記載のノボラック樹脂をエポキシ化したものである請求項３に記載のエポキシ樹脂組成物 1. A novolac resin obtained by reacting an orthohydroxybenzaldehyde represented by the following formula (I) with a phenol represented by the following formula (II ′) and a phenol represented by the following formula (II ″): Ortho formed by the condensation of the hydrogen atom at the ortho position of the phenol represented by the formula (II ′) and the phenol represented by the formula (II ″) with the aldehyde group of the orthohydroxybenzaldehyde. A novolac resin represented by the following formula (III), wherein the ratio of ortho-ortho bonds is 70 mol% or more of all bonds:
Figure JPOXMLDOC01-appb-C000004
 (Wherein R 1 represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxyl group having 1 to 10 carbon atoms, and k represents an integer of 0 to 3)
Figure JPOXMLDOC01-appb-C000005
 [In Formula (II ′) and Formula (II ″), R 2 and R 3 represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms. ]
Figure JPOXMLDOC01-appb-C000006
 (Wherein R 1 , R 2 , R 3 and k are the same as above).
2. The phenol represented by the formula (II ′) and the phenol represented by the formula (II ″) are selected from phenol and cresol, the number average molecular weight is 300 to 600, and the degree of dispersion (weight average molecular weight / The novolak resin according to 1 above, wherein the number average molecular weight is 1.5 or less,
3. An epoxy resin composition comprising the novolak resin according to 1 or 2 as a curing agent,
4). The epoxy resin composition according to 3 above, wherein the epoxy resin has a triphenylmethane structure,
5). The epoxy resin composition according to claim 3, wherein the epoxy resin is obtained by epoxidizing the novolak resin according to 1 or 2 above.
　本発明によれば、優れた耐湿性および耐熱性を有するノボラック樹脂および前記ノボラック樹脂を硬化剤として配合した熱硬化性樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a novolak resin having excellent moisture resistance and heat resistance and a thermosetting resin composition containing the novolac resin as a curing agent.
実施例１で得られたノボラック樹脂Ａの1ＮＭＲチャートである。1 is a 1 NMR chart of novolak resin A obtained in Example 1. FIG. 比較例１で得られたノボラック樹脂Ｄの1ＮＭＲチャートである。2 is a 1 NMR chart of novolak resin D obtained in Comparative Example 1. FIG.
　以下、本発明を詳しく説明する。
　本発明のノボラック樹脂は、式（Ｉ）で表されるオルソヒドロキシベンズアルデヒド類と式（II’）で表されるフェノール類および式（II’’）で表されるフェノール類で表されるフェノール類との反応で得られる。
　なお、式（II’）で表されるフェノール類と式（II’’）で表されるフェノール類は同一でも異なっていてもよい。
　上記式（Ｉ）で表されるオルソヒドロキシベンズアルデヒド類、上記式（II’）で表されるフェノール類および上記式（II’’）で表されるフェノール類において、Ｒ1、Ｒ2およびＲ3は、それぞれ、水素原子、水酸基、炭素数１～１０のアルキル基または炭素数１～１０のアルコキシル基を示す。
　炭素数１～１０のアルキル基としては、直鎖状でも分岐状でもよく、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、イソペンチル基、ｓｅｃ－ペンチル基、ｔｅｒｔ－ペンチル基、ネオペンチル基、ｎ－ヘキシル基、イソへキシル基、各種ヘプチル基、各種オクチル基、各種ノニル基および各種デシル基等が挙げられる。
　また、炭素数１～１０のアルコキシル基としては、直鎖状でも分岐状でもよく、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、イソブトキシ基、ｓｅｃ－ブトキシ基、ｔｅｒｔ－ブトキシ基、ｎ－ペンチルオキシ基、イソペンチルオキシ基、ネオペンチルオキシ基、各種ヘキシルオキシ基、各種ヘプチルオキシ基、各種オクチルオキシ基、各種ノニルオキシ基および各種デシルオキシ基等を挙げることができる。
　また、上記式（Ｉ）で表されるオルソヒドロキシベンズアルデヒド類において、ｋは０～３の整数を示す。
　ベンゼン環上の置換基Ｒ1の数を示すｋは、０～３の整数であり、好ましくは０～２の整数、より好ましくは０または１の整数である。
　ｋが２または３の場合には、Ｒ1は同一であっても異なっていてもよい。
　また、上記式（III）で表されるノボラック樹脂において、Ｒ1、Ｒ2、Ｒ3およびｋは上記と同様である。
　炭素数１～１０のアルキル基および炭素数１～１０のアルコキシル基は、式（Ｉ）で表されるオルソヒドロキシベンズアルデヒド類、式（II’）で表されるフェノール類および式（II’’）で表されるフェノール類において述べたとおりである。 The present invention will be described in detail below.
The novolak resin of the present invention includes an orthohydroxybenzaldehyde represented by the formula (I), a phenol represented by the formula (II ′), and a phenol represented by the phenol represented by the formula (II ″). It is obtained by the reaction.
The phenols represented by the formula (II ′) and the phenols represented by the formula (II ″) may be the same or different.
In the orthohydroxybenzaldehydes represented by the above formula (I), the phenols represented by the above formula (II ′) and the phenols represented by the above formula (II ″), R 1 , R 2 and R 3 Each represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxyl 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, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group. Group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, etc. Can be mentioned.
The alkoxyl group having 1 to 10 carbon atoms may be linear or branched, and is a methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, Examples thereof include a tert-butoxy group, an n-pentyloxy group, an isopentyloxy group, a neopentyloxy group, various hexyloxy groups, various heptyloxy groups, various octyloxy groups, various nonyloxy groups, and various decyloxy groups.
In the orthohydroxybenzaldehydes represented by the above formula (I), k represents an integer of 0 to 3.
K representing the number of substituents R 1 on the benzene ring is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably an integer of 0 or 1.
When k is 2 or 3, R 1 may be the same or different.
In the novolak resin represented by the above formula (III), R 1 , R 2 , R 3 and k are the same as described above.
The alkyl group having 1 to 10 carbon atoms and the alkoxyl group having 1 to 10 carbon atoms are orthohydroxybenzaldehydes represented by the formula (I), phenols represented by the formula (II ′) and the formula (II ″). It is as having mentioned in phenols represented by these.
　式（Ｉ）で表されるオルソヒドロキシベンズアルデヒド類の具体例としては、サリチルアルデヒド、２，３－ジヒドロキシベンズアルデヒド、２，４－ジヒドロキシベンズアルデヒド、２，５－ジヒドロキシベンズアルデヒド、２－ヒドロキシ－３－メチルベンズアルデヒドおよび２－ヒドロキシ－５－メチルベンズアルデヒドなどのオルソヒドロキシベンズアルデヒド類が挙げられ、単独若しくは２種以上を混合して使用することができる。 Specific examples of the orthohydroxybenzaldehydes represented by the formula (I) include salicylaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2-hydroxy-3-methylbenzaldehyde. And orthohydroxybenzaldehydes such as 2-hydroxy-5-methylbenzaldehyde and the like can be used alone or in admixture of two or more.
　式（II’）で表されるフェノール類および下式（II’’）で表されるフェノール類で表されるフェノール類としては、一般的なフェノール樹脂の製造に使用されるものであれば良く、例えば、フェノール、各種クレゾール、各種エチルフェノール、各種キシレノール、各種ブチルフェノール、各種オクチルフェノール、各種ノニルフェノール、各種フェニルフェノール、各種シクロヘキシルフェノール、各種トリメチルフェノール、ビスフェノールＡ、カテコール、レゾシノール、ハイドロキノン、ナフトールおよびピロガロールなどを、単独又は２種以上を混合して使用することができる
　これらのうち、フェノールや各種クレゾールが実用上好ましい。 As the phenols represented by the formula (II ′) and the phenols represented by the following formula (II ″), any phenol can be used as long as it is used for the production of general phenol resins. For example, phenol, various cresols, various ethylphenols, various xylenols, various butylphenols, various octylphenols, various nonylphenols, various phenylphenols, various cyclohexylphenols, various trimethylphenols, bisphenol A, catechol, resorcinol, hydroquinone, naphthol and pyrogallol. These can be used alone or in admixture of two or more. Of these, phenol and various cresols are practically preferable.
　一方、式（II’）で表されるフェノール類および下式（II’’）で表されるフェノール類で表されるフェノール類と反応させるアルデヒド類としては、式（Ｉ）で表されるオルソヒドロキシベンズアルデヒド類であるが、その他にフェノール樹脂の製造に使用可能とされているアルデヒド類、例えば、ホルムアルデヒド、アセトアルデヒド、ベンズアルデヒド、パラヒドロキシベンズアルデヒド、メタヒドロキシベンズアルデヒド、パラホルムアルデヒド、プロピルアルデヒド、ブチルアルデヒド、イソバレルアルデヒド、ヘキシルアルデヒド、グリオキザール、クロトンアルデヒドおよびグルタルアルデヒドなどを単独もしくは２種以上を混合して使用することができる。
　以下、これらのアルデヒド類を合わせて、単にアルデヒド類という。
　上記アルデヒド類の使用量は、フェノール類の合計量１モルに対して、０．３～１．０モル、好ましくは０．４～０．９モルの割合で用いるのが好ましい。
　アルデヒド類の使用量が０．３モル未満であると、残存するフェノール類モノマーが多くなるため効率的でない。
　一方、アルデヒド類の使用量が１．０モルを超えると、得られる樹脂の分子量が高くなるため好ましくない。 On the other hand, the aldehydes to be reacted with the phenols represented by the formula (II ′) and the phenols represented by the following formula (II ″) include the ortho represented by the formula (I). Hydroxybenzaldehydes, but other aldehydes that can be used in the production of phenolic resins, such as formaldehyde, acetaldehyde, benzaldehyde, parahydroxybenzaldehyde, metahydroxybenzaldehyde, paraformaldehyde, propylaldehyde, butyraldehyde, isovaler Aldehyde, hexylaldehyde, glyoxal, crotonaldehyde, glutaraldehyde and the like can be used alone or in admixture of two or more.
Hereinafter, these aldehydes are collectively referred to as aldehydes.
The aldehyde is used in an amount of 0.3 to 1.0 mol, preferably 0.4 to 0.9 mol, based on 1 mol of the total amount of phenols.
If the amount of aldehyde used is less than 0.3 mol, the remaining phenolic monomer increases, which is not efficient.
On the other hand, when the amount of aldehydes used exceeds 1.0 mol, the molecular weight of the resulting resin is increased, which is not preferable.
　上記反応を行う際に存在させる触媒としては、ホウ酸およびｐＫａが５．０以下の酸を使用する。
　通常、ノボラック樹脂を製造する場合、塩酸、硝酸、硫酸、リン酸、パラトルエンスルホン酸、シュウ酸などを使用する。
　特に、アルデヒド類としてホルムアルデヒド、パラホルムアルデヒド以外のアルデヒド類を使用する場合は、塩酸、硝酸、硫酸、パラトルエンスルホン酸などの強酸でないと十分な反応性は得られない。
　しかし、これらの酸触媒単独では、式（II’）で表されるフェノール類および式（II’’）で表されるフェノール類のパラ位とアルデヒド類との反応の割合が高くなるため、本発明のオルソ－オルソ－オルソ結合の割合が、全結合の７０モル％以上のノボラック樹脂は得られない。
　ホウ酸およびｐＫａが５．０以下の酸を併用したときのみ本発明の樹脂が得られる。
　ｐＫａが５．０以下の酸としては、一般的なノボラック樹脂の製造に使用されるものであれば良く、例えば塩酸、硝酸、硫酸、リン酸、パラトルエンスルホン酸、シュウ酸などが挙げられ、単独若しくは２種類以上混合して使用することができる。
　ｐＫａが５．０を超える酸では触媒としての効果が乏しく実用的でない。
　反応設備への腐食およびノボラック樹脂の収率などを考慮すると、ｐＫａが０．０～４．０である酸が好ましく、例えばシュウ酸、リン酸、サリチル酸、酒石酸などが挙げられる。
　前記ｐＫａが５．０以下の酸の使用量は、フェノール類１００質量部に対して０．１～２０質量部、好ましくは０．１～１０重量部、更に好ましくは０．２～５重量部の割合で用いるのが好ましい。 As a catalyst to be present when performing the above reaction, boric acid and an acid having a pKa of 5.0 or less are used.
Usually, when manufacturing a novolak resin, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, para-toluenesulfonic acid, oxalic acid, etc. are used.
In particular, when an aldehyde other than formaldehyde and paraformaldehyde is used as the aldehyde, sufficient reactivity cannot be obtained unless it is a strong acid such as hydrochloric acid, nitric acid, sulfuric acid, and paratoluenesulfonic acid.
However, these acid catalysts alone increase the rate of reaction between the para-position of the phenols represented by formula (II ′) and the phenols represented by formula (II ″) and aldehydes. A novolak resin having an ortho-ortho-ortho bond ratio of 70 mol% or more of all bonds cannot be obtained.
The resin of the present invention can be obtained only when boric acid and an acid having a pKa of 5.0 or less are used in combination.
The acid having a pKa of 5.0 or less may be any acid as long as it is used for the production of a general novolak resin. Examples thereof include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid, and oxalic acid. It can be used alone or in combination of two or more.
An acid having a pKa of more than 5.0 is not practical because of poor catalyst effect.
Considering corrosion to the reaction equipment and the yield of novolak resin, an acid having a pKa of 0.0 to 4.0 is preferable, and examples thereof include oxalic acid, phosphoric acid, salicylic acid, and tartaric acid.
The amount of the acid having a pKa of 5.0 or less is 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of phenols. It is preferable to use in the ratio.
　式（II’）で表されるフェノール類および下式（II’’）で表されるフェノール類で表されるフェノール類とアルデヒド類とを反応させる方法には、特に制限はなく、例えば、フェノール類、式（Ｉ）で表されるオルソヒドロキシベンズアルデヒド類などのアルデヒド類、触媒を一括で仕込み反応させる方法、またはフェノール類、触媒を仕込み、所定の反応温度において式（Ｉ）で表されるオルソヒドロキシベンズアルデヒド類などのアルデヒド類を添加する方法等が挙げられる。
　このとき、反応温度は３０～１２０℃の範囲で行うのがよい。
　３０℃未満であると反応の進行が遅く、かつ未反応のフェノール類が残存するため好ましくなく、また１２０℃を超える温度では高分子量成分の生成が促進されるため好ましくない。
　反応時間には、特に制限はなく、式（Ｉ）で表されるオルソヒドロキシベンズアルデヒド類などのアルデヒド類、触媒の酸の量および反応温度により調整すればよい。
　反応の際、有機溶剤を使用することももちろん可能である。
　有機溶媒としては、プロピルアルコール、ブタノール等のアルコール類、エチレングリコール、プロピレングリコール等のグリコール類、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ブチレングリコールモノメチルエーテル、ブチレングリコールモノエチルエーテル、ブチレングリコールモノプロピルエーテル等のグリコールエーテル類、メチルエチルケトン、メチルイソブチルケトン等のケトン類、酢酸プロピル、酢酸ブチル、乳酸エチル、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のエステル類、１，４－ジオキサン等のエーテル類等が単独で、若しくは二種以上を併用して使用できる。
　前記有機溶媒は、フェノール類１００質量部に対して、０～１，０００質量部、好ましくは１０～１００質量部程度となるように使用することができる。
　反応後は蒸留により縮合水を除去したり、また、必要に応じて、水洗して残存している酸を除去してもよい。
　更に、減圧蒸留或いは水蒸気蒸留を行って未反応のフェノール類や未反応アルデヒド類を除去してもよい。 There is no particular limitation on the method of reacting the phenols represented by the formula (II ′) and the phenols represented by the following formula (II ″) with aldehydes. , Aldehydes such as orthohydroxybenzaldehydes represented by the formula (I), a method in which a catalyst is charged all at once, or a phenols and a catalyst are charged and the ortho represented by the formula (I) at a predetermined reaction temperature. Examples thereof include a method of adding aldehydes such as hydroxybenzaldehydes.
At this time, the reaction temperature is preferably in the range of 30 to 120 ° C.
When the temperature is lower than 30 ° C., the reaction proceeds slowly and unreacted phenols remain, which is not preferable, and when the temperature exceeds 120 ° C., formation of a high molecular weight component is promoted, which is not preferable.
There is no restriction | limiting in particular in reaction time, What is necessary is just to adjust with aldehydes, such as orthohydroxybenzaldehyde represented by Formula (I), the quantity of the acid of a catalyst, and reaction temperature.
It is of course possible to use an organic solvent during the reaction.
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, butylene glycol monomethyl ether Glycol ethers such as butylene glycol monoethyl ether and 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 acetate, etc. Esters and ethers such as 1,4-dioxane alone , Or it can be used in combination of two or more.
The organic solvent can be used in an amount of about 0 to 1,000 parts by mass, preferably about 10 to 100 parts by mass with respect to 100 parts by mass of phenols.
After the reaction, the condensed water may be removed by distillation, or, if necessary, the remaining acid may be removed by washing with water.
Furthermore, unreacted phenols and unreacted aldehydes may be removed by distillation under reduced pressure or steam distillation.
　本発明の上記式（III）で表されるノボラック樹脂は、数平均分子量が３００～６００であり、好ましくは３５０～５５０、より好ましくは３５０～５００である。
　数平均分子量が６００を超えると、オルソ－オルソ－オルソ結合の割合が低下するため好ましくない。
　また、分散度（重量平均分子量／数平均分子量）は１．５以下であり、好ましくは１．４以下である。
　分散度が１．５以下であることは、ノボラック樹脂中の高分子量の多核体が少ないことを意味する。
　多核体数が多くなるほど、オルソ－オルソ－オルソ結合の割合が低下するため好ましくない。
　本発明のノボラック樹脂は、式（II’）で表されるフェノール類および下式（II’’）で表されるフェノール類としてフェノールおよび各種クレゾールから選ばれる化合物を用いたものが好ましい。 The novolak resin represented by the above formula (III) of the present invention has a number average molecular weight of 300 to 600, preferably 350 to 550, more preferably 350 to 500.
If the number average molecular weight exceeds 600, the ratio of ortho-ortho-ortho bonds decreases, which is not preferable.
Further, the dispersity (weight average molecular weight / number average molecular weight) is 1.5 or less, preferably 1.4 or less.
A dispersity of 1.5 or less means that there are few high molecular weight polynuclear bodies in the novolak resin.
As the number of polynuclear bodies increases, the proportion of ortho-ortho-ortho bonds decreases, which is not preferable.
The novolak resin of the present invention is preferably one using a compound selected from phenol and various cresols as the phenol represented by the formula (II ′) and the phenol represented by the following formula (II ″).
　次に、本発明の熱硬化性樹脂組成物について説明する。
　本発明のノボラック樹脂は、エポキシ樹脂の硬化剤として有用であるので、本発明では、エポキシ樹脂と前記ノボラック樹脂を配合した熱硬化性樹脂組成物を提供することができる。
　ここで、用いられるエポキシ樹脂としては、特に限定するものではなく、公知のエポキシ樹脂を使用できる。
　エポキシ樹脂の具体例としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、レゾルシン型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、カテコール型エポキシ樹脂、ジヒドロキシナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、テトラメチルビフェニル型エポキシ樹脂などの二価のフェノール類から誘導されるエポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂、ジシクロペンタジエン－フェノール変性型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ビフェニルアラルキル型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ナフトール－フェノール共縮ノボラック型エポキシ樹脂、ナフトール－クレゾール共縮ノボラック型エポキシ樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂型エポキシ樹脂、ビフェニル変性ノボラック型エポキシ樹脂などの三価以上のフェノール類から誘導されるエポキシ樹脂、有機リン化合物で変性されたエポキシ樹脂などが挙げられる。
　これら中で、トリフェニルメタン型エポキシ樹脂が好ましく、更には本発明のノボラック樹脂をエポキシ化したエポキシ樹脂が好ましい。
　また、これらのエポキシ樹脂は単独で用いてもよく、二種以上を併用してもよい。
　この場合の変性ノボラック樹脂とエポキシ樹脂の混合割合は、変性ノボラック樹脂１．０当量に対し、エポキシ樹脂を０．８～１．２当量、好ましくは０．９～１．２当量である。 Next, the thermosetting resin composition of the present invention will be described.
Since the novolak resin of the present invention is useful as a curing agent for an epoxy resin, the present invention can provide a thermosetting resin composition in which the epoxy resin and the novolak resin are blended.
Here, it does not specifically limit as an epoxy resin used, A well-known epoxy resin can be used.
Specific examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, resorcin 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, naphtho Lunovolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenolic resin type epoxy resin, biphenyl-modified novolac type epoxy resin And epoxy resins derived from trivalent or higher valent phenols, epoxy resins modified with organic phosphorus compounds, and the like.
Among these, a triphenylmethane type epoxy resin is preferable, and an epoxy resin obtained by epoxidizing the novolak resin of the present invention is more preferable.
Moreover, these epoxy resins may be used independently and may use 2 or more types together.
In this case, the mixing ratio of the modified novolak resin and the epoxy resin is 0.8 to 1.2 equivalents, preferably 0.9 to 1.2 equivalents of the epoxy resin with respect to 1.0 equivalent of the modified novolak resin.
　この熱硬化性樹脂組成物には、硬化反応を促進する目的で、硬化促進剤を適宜使用することもできる。
　そのような硬化促進剤としては、例えば、イミダゾール、リン系化合物、第２、３級アミン、オクチル酸スズなどの有機酸金属塩、ルイス酸、アミン錯塩などが挙げられ、これらは単独で若しくは二種以上を併用して使用することができる。
　上記のうち、イミダゾール系化合物としては、イミダゾール、２－メチルイミダゾール、２－エチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、２－ウンデシルイミダゾール、１－ベンジル－２－メチルイミダゾール、２－ヘプタデシルイミダゾール、４、５－ジフェニルイミダゾール、２－メチルイミダゾリン、２－フェニルイミダゾリン、２－ウンデシルイミダゾリン、２－ヘプタデシルイミダゾリン、２－イソプロピルイミダゾール、２、４－ジメチルイミダゾール、２－フェニル－４－メチルイミダゾール、２－エチルイミダゾリン、２－イソプロピルイミダゾリン、２、４－ジメチルイミダゾリン、２－フェニル－４－メチルイミダゾリンなどが挙げられる。
　これらイミダゾール系化合物は、マスク剤によりマスクされていてもよい。
　マスク化剤としては、アクリロニトリル、フェニレンジイソシアネート、トルイジンイソシアネート、ナフタレンジイソシアネート、メチレンビスフェニルイソシアネート、メラミンアクリレートなどが挙げられる。
　有機リン系化合物としては、エチルホスフィン、プロピルホスフィン、ブチルホスフィン、フェニルホスフィン、トリメチルホスフィン、トリエチルホスフィン、トリブチルホスフィン、トリオクチルホスフィン、トリフェニルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフィン／トリフェニルボラン錯体、テトラフェニルホスホニウムテトラフェニルボレートなどが挙げられる。
　第２級アミン系化合物としては、モルホリン、ピペリジン、ピロリジン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジイソプロピルアミン、ジブチルアミン、ジベンジルアミン、ジシクロヘキシルアミン、Ｎ－アルキルアリールアミン、ピペラジン、ジアリルアミン、チアゾリン、チオモルホリンなどが挙げられる。
　第３級アミン系化合物としては、ベンジルジメチルアミン、２－（ジメチルアミノメチル）フェノール、２，４，６－トリス（ジアミノメチル）フェノールなどが挙げられる。 In this thermosetting resin composition, a curing accelerator can be appropriately used for the purpose of accelerating the curing reaction.
Examples of such curing accelerators include organic acid metal salts such as imidazole, phosphorus compounds, secondary and tertiary amines, tin octylate, Lewis acids, amine complex salts, and the like. More than one species can be used in combination.
Among the above, 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.
Examples of the masking agent include acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, and melamine acrylate.
Examples of 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.
　また、本発明の熱硬化性樹脂組成物には、必要に応じて、充填剤、改質剤として使用される熱硬化性樹脂および熱硬化性樹脂、顔料、シランカップリング剤、離型剤などの種々の配合剤を目的に応じて添加することができる。
　このうち、充填材としては、例えば、溶融シリカ、結晶シリカ、アルミナ、ジルコン、珪酸カルシウム、炭酸カルシウム、炭化珪素、窒化珪素、窒化ホウ素、ジルコニア、フォステライト、ステアタイト、スピネル、チタニア、水酸化アルミニウム、水酸化マグネシウムなどの無機充填材が挙げられる。
　溶融シリカは破砕状、球状のいずれでも使用可能であるが、溶融シリカの配合量を高め、且つ成形材料の溶融粘度の上昇を抑制するためには、球状のものを主に用いる方が好ましい。
　更に、球状シリカの配合量を高めるためには、球状シリカの粒度分布を適当に調整することが好ましい。
　その配合率は適用用途や所望特性によって、好ましい範囲が異なるが、例えば半導体封止材用途に使用する場合は、線膨張係数や難燃性を鑑みれば高い方が好ましく、組成物全体量に対して６５重量％以上が好ましく、特に好ましくは８５～９０重量％程度である。
　また、導電ペーストや導電フィルムなどの用途に使用する場合は、銀粉や銅粉などの導電性充填剤を用いることができる。 In addition, the thermosetting resin composition of the present invention includes a thermosetting resin and a thermosetting resin used as a filler, a modifier, a pigment, a silane coupling agent, a release agent, and the like as necessary. Various compounding agents can be added according to the purpose.
Among these, as fillers, 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 shape or a spherical shape. However, in order to increase the blending amount of the fused silica and to suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape.
Furthermore, in order to increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica.
The preferred range varies depending on the application and desired properties, but for example, when used in semiconductor encapsulant applications, the higher the ratio is preferable in view of the linear expansion coefficient and flame retardancy, and the total amount of the composition It is preferably 65% by weight or more, particularly preferably about 85 to 90% by weight.
Moreover, when using for uses, such as an electrically conductive paste and an electrically conductive film, electrically conductive fillers, such as silver powder and copper powder, can be used.
　改質剤として使用される熱硬化性樹脂および熱可塑性樹脂としては公知の種々のものが全て使用できるが、例えばフェノキシ樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリエーテルイミド樹脂、ポリエーテルサルホン樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンスルフィド樹脂ポリエステル樹脂、ポリスチレン樹脂、ポリエチレンテレフタレート樹脂などを、必要に応じて本発明の効果を損なわない範囲で使用することができる。
　シランカップリング剤としては、アミノシラン系化合物、ビニルシラン系化合物、スチレン系シラン化合物、メタクリルシラン系化合物などのシランカップリング剤を挙げることができる。
　また、離型剤としては、ステアリン酸、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン酸アルミニウム、ステアリン酸マグネシウムおよびカルナバワックスなどを挙げることができる。 Various known thermosetting resins and thermoplastic resins used as the modifier can be used. For example, phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene An ether resin, a polyphenylene sulfide resin polyester resin, a polystyrene resin, a polyethylene terephthalate resin, and the like can be used as long as they do not impair the effects of the present invention.
Examples of the silane coupling agent include silane coupling agents such as amino silane compounds, vinyl silane compounds, styrene silane compounds, and methacryl silane compounds.
Examples of the mold release agent include stearic acid, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, and carnauba wax.
　以下に、実施例を掲げて更に本発明を詳細に説明するが、本発明はこれらに限定されることはない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
実施例１
　冷却管、攪拌機を備えたフラスコに、オルソクレゾール１００ｇ、サリチルアルデヒド５６ｇ、ホウ酸１ｇ、シュウ酸１ｇを仕込み、１００℃で８時間反応させた。
　次いで、純水１００ｇで２回洗浄を行い、触媒を除去した。
　次いで、１８０℃、５０ｍｍＨｇの減圧下で溜出分を除去し、ノボラック樹脂Ａ１０２ｇを得た。
　ノボラック樹脂Ａの1ＮＭＲチャートを図１に示す。 Example 1
A flask equipped with a condenser and a stirrer was charged with 100 g of orthocresol, 56 g of salicylaldehyde, 1 g of boric acid and 1 g of oxalic acid, and reacted at 100 ° C. for 8 hours.
Next, the catalyst was removed by washing twice with 100 g of pure water.
Subsequently, the distillate was removed under reduced pressure at 180 ° C. and 50 mmHg to obtain 102 g of novolak resin A.
A 1 NMR chart of the novolak resin A is shown in FIG.
実施例２
　フェノール類としてメタクレゾール１００ｇを使用した以外は実施例１と同様に反応を行い、ノボラック樹脂Ｂ１１０ｇを得た。 Example 2
A reaction was carried out in the same manner as in Example 1 except that 100 g of metacresol was used as a phenol, to obtain 110 g of novolak resin B.
実施例３
　アルデヒド類としてサリチルアルデヒド４５ｇ、パラホルムアルデヒド３ｇを使用した以外は実施例１と同様に反応を行い、ノボラック樹脂Ｃ１０５ｇを得た。 Example 3
A reaction was carried out in the same manner as in Example 1 except that 45 g of salicylaldehyde and 3 g of paraformaldehyde were used as aldehydes to obtain 105 g of novolak resin C.
比較例１
　冷却管、攪拌機を備えたフラスコに、オルソクレゾール１００ｇ、サリチルアルデヒド５６ｇ、パラトルエンスルホン酸１ｇを仕込み、１００℃で８時間反応させた。
　次いで、純水１００ｇで数回洗浄を行い触媒を除去した。
　次いで、１８０℃、５０ｍｍＨｇの減圧下で溜出分を除去し、ノボラック樹脂Ｄ９０ｇを得た。
　ノボラック樹脂Ｄの1ＮＭＲ測定チャートを図２に示す。 Comparative Example 1
A flask equipped with a condenser and a stirrer was charged with 100 g of orthocresol, 56 g of salicylaldehyde, and 1 g of paratoluenesulfonic acid, and reacted at 100 ° C. for 8 hours.
Subsequently, the catalyst was removed by washing several times with 100 g of pure water.
Subsequently, the distillate was removed under reduced pressure at 180 ° C. and 50 mmHg to obtain 90 g of novolak resin D.
A 1 NMR measurement chart of the novolak resin D is shown in FIG.
比較例２
　サリチルアルデヒドの代わりにメタヒドロキシベンズアルデヒド５６ｇを使用した以外は実施例１と同様に反応を行い、ノボラック樹脂Ｅ９２ｇを得た。 Comparative Example 2
A reaction was carried out in the same manner as in Example 1 except that 56 g of metahydroxybenzaldehyde was used instead of salicylaldehyde to obtain 92 g of novolak resin E92.
比較例３
　冷却管、攪拌機を備えたフラスコに、オルソクレゾール１００ｇ、３７％ホルマリン６３ｇ、シュウ酸１ｇを仕込み、１００℃で５時間反応後、１８０℃、５０ｍｍＨｇの減圧下で未反応フェノールを除去し、ノボラック樹脂Ｆ７０ｇを得た。
　実施例１～３で得られたノボラック樹脂、比較例１～３で得られたノボラック樹脂の分析値を表１に示す。
　樹脂の分析方法は以下の通りである。 Comparative Example 3
A flask equipped with a condenser and a stirrer was charged with 100 g of orthocresol, 63 g of 37% formalin and 1 g of oxalic acid. After reacting at 100 ° C. for 5 hours, unreacted phenol was removed under reduced pressure of 180 ° C. and 50 mmHg, and novolak resin F70g was obtained.
Table 1 shows analytical values of the novolak resins obtained in Examples 1 to 3 and the novolak resins obtained in Comparative Examples 1 to 3.
The analysis method of resin is as follows.
（１）オルソ－オルソ－オルソ結合比率
　1Ｈ－ＮＭＲ（３００ＭＨｚ）スペクトルによるオルソ－オルソ－オルソ（５．８－６．１ｐｐｍ）、オルソ－パラ－オルソ（５．４－５．６ｐｐｍ）、オルソ－パラ－パラ（５．０－５．２ｐｐｍ）のメチン結合の積分比から算出した。
　オルソ－オルソ－オルソ結合比率（モル％）
　　　　　　　＝（オルソ－オルソ－オルソ結合／全メチン、メチレン結合）×１００
（２）数平均分子量、重量平均分子量、分散度
　カラム構成は昭和電工（株）製のＫＦ－８０４＋ＫＦ－８０４で行い、溶媒としてテトラヒドロフランを使用し、流量１ｍｌ／分で測定した。
　分子量はポリスチレン換算、含有率は全ピーク面積中の百分率で算出した。
　分散度は重量平均分子量／数平均分子量で算出した。 (1) Ortho-ortho-ortho bond ratio Ortho-ortho-ortho (5.8-6.1 ppm), ortho-para-ortho (5.4-5.6 ppm), ortho by 1 H-NMR (300 MHz) spectrum Calculated from the integral ratio of methine binding of -para-para (5.0-5.2 ppm).
Ortho-ortho-ortho bond ratio (mol%)
= (Ortho-ortho-ortho bond / total methine, methylene bond) x 100
(2) Number average molecular weight, weight average molecular weight, dispersity The column configuration was KF-804 + KF-804 manufactured by Showa Denko KK, tetrahydrofuran was used as a solvent, and measurement was performed at a flow rate of 1 ml / min.
The molecular weight was calculated in terms of polystyrene, and the content was calculated as a percentage of the total peak area.
The degree of dispersion was calculated by weight average molecular weight / number average molecular weight.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表１から、本発明の変性ノボラック樹脂では、比較例のノボラック樹脂と比較すると、オルソ－オルソ－オルソ結合比率が極めて高いことがわかる。 Table 1 shows that the modified novolak resin of the present invention has an extremely high ortho-ortho-ortho bond ratio as compared with the novolak resin of the comparative example.
実施例４（エポキシ樹脂の製造）
　冷却管、攪拌機を備えたフラスコに、実施例１のノボラック樹脂１００ｇ、エピクロロヒドリン４００ｇ、塩化テトラメチルアンモニウム０．１ｇを仕込み、内温を６０℃で１時間保持した後、同一温度で４８％水酸化カリウム水溶液１００ｇを３時間かけて滴下した。
　その際系内は減圧とし、溜出するエピクロロヒドリンと水の混合物の内、水は系外に除去し、エピクロロヒドリンは系内に戻しながら反応を行った。
　滴下終了後、同温度で１時間反応した後、減圧蒸留で未反応エピクロロヒドリンを回収除去した。
　こうして得られたエポキシ樹脂に、メチルイソブチルケトン４００ｇを加え、数回水洗を行い塩を除去した。
　次いで、メチルイソブチルケトンを減圧蒸留によって除去し、エポキシ当量１９１のエポキシ樹脂Ｇを得た。 Example 4 (Production of epoxy resin)
A flask equipped with a condenser and a stirrer was charged with 100 g of the novolak resin of Example 1, 400 g of epichlorohydrin, and 0.1 g of tetramethylammonium chloride, and the internal temperature was maintained at 60 ° C. for 1 hour. A 100% aqueous potassium hydroxide solution was added dropwise over 3 hours.
At that time, the inside of the system was depressurized, and water was removed out of the mixture of epichlorohydrin and water distilled out, and the reaction was carried out while returning epichlorohydrin to the system.
After completion of the dropwise addition, the mixture was reacted at the same temperature for 1 hour, and then unreacted epichlorohydrin was recovered and removed by distillation under reduced pressure.
400 g of methyl isobutyl ketone was added to the epoxy resin thus obtained, and washed several times to remove salts.
Next, methyl isobutyl ketone was removed by distillation under reduced pressure to obtain an epoxy resin G having an epoxy equivalent of 191.
　実施例１～３で得られた変性ノボラック樹脂、比較例１～３で得られたノボラック樹脂のそれぞれについて、表２に示す配合量（質量部）で溶融混練して熱硬化性樹脂組成物１～６を得た。
　得られた樹脂組成物のガラス転移温度、吸水率および曲げ強度を次の方法により評価した。
　評価結果を表２に示す。
（３）ガラス転移温度（℃）
　ＳＩＩ社製ＳＳＣ／５２００を使用してＴＭＡ法にてガラス転移温度を測定した。昇温速度は１０℃／分で行った。
（４）吸水率（質量％）
　楠本化成社製プレッシャークッカーを使用して、１２１℃で２０時間保持した後の質量増加率を測定した。
（５）曲げ強度（ＭＰａ）
　ＪＩＳ　Ｋ－６９１１に準拠した方法で測定した。 Each of the modified novolak resins obtained in Examples 1 to 3 and the novolak resins obtained in Comparative Examples 1 to 3 was melt-kneaded in the blending amounts (parts by mass) shown in Table 2, and the thermosetting resin composition 1 ~ 6 were obtained.
The glass transition temperature, water absorption rate and bending strength of the obtained resin composition were evaluated by the following methods.
The evaluation results are shown in Table 2.
(3) Glass transition temperature (° C)
The glass transition temperature was measured by the TMA method using SSC / 5200 manufactured by SII. The heating rate was 10 ° C./min.
(4) Water absorption (mass%)
Using a pressure cooker manufactured by Enomoto Kasei Co., Ltd., the mass increase rate after holding at 121 ° C. for 20 hours was measured.
(5) Bending strength (MPa)
It was measured by a method according to JIS K-6911.
Figure JPOXMLDOC01-appb-T000008
 ここで、
　エポキシ樹脂　樹脂Ｈ：トリフェニルメタン型エポキシ樹脂
　　　　　　　　　　　　商品名１０３２Ｈ６０　ジャパンエポキシレジン社製
　エポキシ樹脂　樹脂Ｉ：ビフェニルアラルキル型エポキシ樹脂
　　　　　　　　　　　　商品名ＮＣ－３０００Ｈ　日本化薬社製
　トリフェニルホスフィン：和光純薬工業社製
　溶融シリカ：商品名ＭＳＲ－２２１２：龍森社製
Figure JPOXMLDOC01-appb-T000008
 here,
Epoxy resin Resin H: Triphenylmethane type epoxy resin Product name 1032H60 Made by Japan Epoxy Resin Co., Ltd. Resin I: Biphenyl aralkyl type epoxy resin Product name NC-3000H Nippon Kayaku Co., Ltd. Triphenylphosphine: Wako Pure Chemical Industries, Ltd. Melting Silica: Trade name MSR-2212: Made by Tatsumorisha
　表２より、本発明の熱硬化性樹脂組成物においては、従来のノボラック樹脂よりもはるかに低い吸水率を示し、かつガラス転移温度や曲げ強度などは従来のノボラック樹脂と同等以上の性能を示すことが分かる。
　以上、本発明により、耐湿性および耐熱性が良好で溶融粘度の低い変性ノボラック樹脂、および熱硬化性樹脂組成物を提供することが可能になった。 From Table 2, in the thermosetting resin composition of the present invention, the water absorption rate is much lower than that of the conventional novolac resin, and the glass transition temperature, the bending strength, etc. show the same or better performance than the conventional novolak resin. I understand that.
As described above, according to the present invention, it is possible to provide a modified novolak resin and a thermosetting resin composition having good moisture resistance and heat resistance and low melt viscosity.
　本発明のノボラック樹脂は、優れた耐湿性および耐熱性を有し、エポキシ樹脂の硬化剤として用いた場合、その硬化物は良好な耐湿性、耐熱性、可とう性、機械的特性、電気絶縁性、金属との接着性などを有する。
　このため、具体的には電子部品の封止材用樹脂組成物、プリント基板用樹脂組成物、プリント基板および樹脂付き銅箔に使用する層間絶縁材料用樹脂組成物、導電ペースト（導電性充填剤含有）、塗料、接着剤および複合材料などに好適に用いることができる。 The novolak resin of the present invention has excellent moisture resistance and heat resistance, and when used as a curing agent for epoxy resin, the cured product has good moisture resistance, heat resistance, flexibility, mechanical properties, electrical insulation. And adhesion to metal.
Therefore, specifically, 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 a resin, a conductive paste (conductive filler) Containment), paints, adhesives and composite materials.

Claims (5)

  1. 　下式（I）で表されるオルソヒドロキシベンズアルデヒド類と下式（II’）で表される
    フェノール類および下式（II’’）で表されるフェノール類を反応させてなるノボラック樹脂であって、前記下式（II’）で表されるフェノール類および下式（II’’）で表されるフェノール類のオルソ位の水素原子と前記オルソヒドロキシベンズアルデヒド類のアルデヒド基が縮合して生成したオルソ－オルソ－オルソ結合の割合が、全結合の７０モル％以上であることを特徴とする下式（IＩI）で表されるノボラック樹脂。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ1は水酸基、炭素数１～１０のアルキル基または炭素数１～１０のアルコキシル基を示し、ｋは０～３の整数を示す。）
    Figure JPOXMLDOC01-appb-C000002
     〔式（II’）および式（II’’）中、Ｒ2およびＲ3は水素原子、水酸基、炭素数１～１０のアルキル基を示す。〕
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ1、Ｒ2、Ｒ3及びｋは、上記と同様である。）     A novolac resin obtained by reacting an orthohydroxybenzaldehyde represented by the following formula (I) with a phenol represented by the following formula (II ′) and a phenol represented by the following formula (II ″): Ortho formed by the condensation of the hydrogen atom at the ortho position of the phenol represented by the formula (II ′) and the phenol represented by the formula (II ″) with the aldehyde group of the orthohydroxybenzaldehyde. -A novolak resin represented by the following formula (III), wherein the ratio of ortho-ortho bonds is 70 mol% or more of all bonds.
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R 1 represents a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxyl group having 1 to 10 carbon atoms, and k represents an integer of 0 to 3)
    Figure JPOXMLDOC01-appb-C000002
     [In Formula (II ′) and Formula (II ″), R 2 and R 3 represent a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms. ]
    Figure JPOXMLDOC01-appb-C000003
     (Wherein R 1 , R 2 , R 3 and k are the same as above).
  2. 　式（II’）で表されるフェノール類および式（II’’）で表されるフェノール類が、フェノールおよびクレゾールから選ばれ、数平均分子量が３００～６００であり、分散度（重量平均分子量／数平均分子量）が１．５以下である上記１に記載のノボラック樹脂。 The phenol represented by the formula (II ′) and the phenol represented by the formula (II ″) are selected from phenol and cresol, the number average molecular weight is 300 to 600, and the degree of dispersion (weight average molecular weight / 2. The novolak resin according to 1 above, wherein the number average molecular weight is 1.5 or less.
  3. 　請求項１または２に記載のノボラック樹脂を硬化剤として含むエポキシ樹脂組成物。 An epoxy resin composition comprising the novolak resin according to claim 1 or 2 as a curing agent.
  4. 　エポキシ樹脂が、トリフェニルメタン構造を有する上記３に記載のエポキシ樹脂組成物。 3. The epoxy resin composition as described in 3 above, wherein the epoxy resin has a triphenylmethane structure.
  5. 　エポキシ樹脂が、請求項１または２に記載のノボラック樹脂をエポキシ化したものである請求項３に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 3, wherein the epoxy resin is obtained by epoxidizing the novolak resin according to claim 1 or 2.
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CN104119500A (en) * 2013-04-23 2014-10-29 宝山钢铁股份有限公司 Epoxy-resin curing agent and preparation method thereof
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004043777A (en) * 2002-04-22 2004-02-12 Tokyo Ohka Kogyo Co Ltd Novolac resin solution, positive type photoresist composition and method of preparing the same
JP2004269613A (en) * 2003-03-06 2004-09-30 Sumitomo Bakelite Co Ltd Phenol resin composition for friction material
JP2004361638A (en) * 2003-06-04 2004-12-24 Tokyo Ohka Kogyo Co Ltd Positive photoresist composition for manufacture of system lcd and resist pattern forming method
JP2006249178A (en) * 2005-03-09 2006-09-21 Dainippon Ink & Chem Inc Epoxy resin composition, its cured product, and phenolic resin composition
WO2007037500A1 (en) * 2005-09-30 2007-04-05 Sumitomo Bakelite Co., Ltd. Epoxy resin composition and semiconductor device
JP2008262206A (en) * 2007-04-13 2008-10-30 Samsung Electronics Co Ltd Photoresist composition and method of manufacturing thin film transistor substrate using the same

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6034567B2 (en) * 1978-04-28 1985-08-09 松下電工株式会社 Manufacturing method of phenolic resin
DE2849115A1 (en) * 1978-11-11 1980-05-22 Bayer Ag METHOD FOR ISOLATING BORN PHENOL FORMALDEHYDE RESINS
JPS61176638A (en) * 1985-02-01 1986-08-08 Mitsui Petrochem Ind Ltd Production of semi-incombustible organic expanded material
JPH0751611B2 (en) * 1988-01-25 1995-06-05 旭有機材工業株式会社 Method for producing phenolic resin and bisphenol
NO891063L (en) * 1988-03-31 1989-10-02 Thiokol Morton Inc NOVOLAK RESINES OF MIXED ALDEHYDES AND POSITIVE PHOTORESIST MATERIALS MADE FROM SUCH RESINES.
JPH09227646A (en) * 1996-02-20 1997-09-02 Mitsubishi Chem Corp Production of aromatic carboxylic ester of novolac phenol resin
US5789522A (en) * 1996-09-06 1998-08-04 Shipley Company, L.L.C. Resin purification process
JPH10218815A (en) * 1997-02-14 1998-08-18 Honshu Chem Ind Co Ltd New trisphenol compound
JPH11268219A (en) * 1998-03-26 1999-10-05 Mitsubishi Electric Corp Laminate
JP2002167416A (en) 2000-11-30 2002-06-11 Hitachi Chem Co Ltd Phenolic resin, resin composition and resin molding material for sealing using the same, and electronic component device
JP3833940B2 (en) * 2001-01-11 2006-10-18 エア・ウォーター株式会社 Phenol polymer, process for producing the same, and epoxy resin curing agent using the same
TW200306324A (en) * 2002-04-22 2003-11-16 Tokyo Ind Co Ltd Novolak resin solution, positive photoresist composition, and method of producing same
CN100489023C (en) * 2002-12-13 2009-05-20 茵迪斯佩克化学公司 Phenolic modified resorcinolic resins for rubber compound formula
JP2004296613A (en) * 2003-03-26 2004-10-21 Renesas Technology Corp Semiconductor device
JP2006257136A (en) 2005-03-15 2006-09-28 Dainippon Ink & Chem Inc Method for producing novolak type phenol resin
CN100445310C (en) * 2006-09-15 2008-12-24 中国科学院山西煤炭化学研究所 Preparation method of boron modified phenolic resin

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004043777A (en) * 2002-04-22 2004-02-12 Tokyo Ohka Kogyo Co Ltd Novolac resin solution, positive type photoresist composition and method of preparing the same
JP2004269613A (en) * 2003-03-06 2004-09-30 Sumitomo Bakelite Co Ltd Phenol resin composition for friction material
JP2004361638A (en) * 2003-06-04 2004-12-24 Tokyo Ohka Kogyo Co Ltd Positive photoresist composition for manufacture of system lcd and resist pattern forming method
JP2006249178A (en) * 2005-03-09 2006-09-21 Dainippon Ink & Chem Inc Epoxy resin composition, its cured product, and phenolic resin composition
WO2007037500A1 (en) * 2005-09-30 2007-04-05 Sumitomo Bakelite Co., Ltd. Epoxy resin composition and semiconductor device
JP2008262206A (en) * 2007-04-13 2008-10-30 Samsung Electronics Co Ltd Photoresist composition and method of manufacturing thin film transistor substrate using the same

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