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WO2024095521A1 - Curable composition - Google Patents

Curable composition Download PDF

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Publication number
WO2024095521A1
WO2024095521A1 PCT/JP2023/021900 JP2023021900W WO2024095521A1 WO 2024095521 A1 WO2024095521 A1 WO 2024095521A1 JP 2023021900 W JP2023021900 W JP 2023021900W WO 2024095521 A1 WO2024095521 A1 WO 2024095521A1
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WO
WIPO (PCT)
Prior art keywords
component
area
composition
curable composition
compound
Prior art date
Application number
PCT/JP2023/021900
Other languages
French (fr)
Japanese (ja)
Inventor
忠明 山岸
貴洋 角田
莉久 川本
忠史 横浦
敬太朗 宮川
Original Assignee
本州化学工業株式会社
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Publication of WO2024095521A1 publication Critical patent/WO2024095521A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols

Definitions

  • the present invention relates to a curable composition, a cured product obtained by curing the composition, a curing agent for resol-type phenolic resins, and an adhesive containing the curable composition.
  • Phenolic resins are polymers obtained from phenol and formaldehyde as raw materials, and are known to be classified into two types: thermoplastic novolac-type phenolic resins obtained using an acid catalyst, and thermosetting resol-type phenolic resins obtained using an alkali catalyst. Both phenolic resins are characterized by excellent heat resistance, mechanical strength, chemical resistance, and electrical insulation, and are therefore widely used in various fields such as automobile parts, insulation materials, resist materials, and adhesives. In particular, phenolic resins with high heat resistance and mechanical strength have been attracting attention in recent years as alternative materials to metals.
  • Resole-type phenolic resins have methylol groups, which are functional groups that react when heated, and crosslinks are formed by condensation of the methylol groups with hydrogen on the aromatic ring and with the methylol groups themselves when heated. This crosslinking reaction progresses everywhere, and the resol-type phenolic resin forms a random three-dimensional network to become a cured product.
  • the curing of resol-type phenolic resins that do not contain any curing accelerator is inferior to the curing of novolac-type phenolic resins in curing at low temperatures (150 to 200°C). This results in insufficient curing at low temperatures, and a cured product with excellent heat resistance cannot be obtained.
  • solutions to this problem have been proposed (for example, Patent Document 1, etc.), a satisfactory solution has not yet been found.
  • the objective of the present invention is to provide a curable composition that can be cured at low temperatures and the cured product has improved heat resistance, a cured product obtained by curing the composition, a curing agent for resol-type phenolic resins, and an adhesive containing the curable composition.
  • the present inventors investigated the possibility of obtaining a cured product with improved heat resistance by adding a curing agent to a resol-type phenolic resin to increase the reactivity of methylol groups that remain unreacted by heating alone.
  • a curing agent that is relatively flexible and has a low melting point
  • the resin would be mixed uniformly with the resol-type phenolic resin, increasing its reactivity.
  • the curing agent having a bis(hydroxyphenyl)methane skeleton was selected, and it was found that the resin could be cured at low temperatures and that the heat resistance of the cured product was improved, thereby completing the present invention.
  • a curable composition comprising the following component (A) and component (B): Component (A): A resol-type phenolic resin.
  • a cured product obtained by curing the curable composition according to 1. 3.
  • a curing agent for resol-type phenolic resins comprising the following component (B): Component (B): A composition comprising component (B1) consisting of the following compounds (1), (2), and (3), wherein the total amount of component (B1) is in the range of 40 area % to 70 area % based on the total amount of all components detected by gel permeation chromatography using a differential refractometer as a detector. 4.
  • An adhesive comprising the curable composition according to 1.
  • the curable composition of the present invention can be cured at a lower temperature than the conventionally known resol-type phenolic resins, and therefore the temperature in the molding process of the curable resin can be lowered, which enables efficiency improvement by shortening heating and cooling times and saving energy.
  • the composition can be used on materials (substrates) that are sensitive to heat, making it extremely useful.
  • the cured product of the compound of the present invention has significantly improved heat resistance compared to the cured product of a conventionally known resol-type phenolic resin cured only with resol, and is therefore a highly useful material with excellent stability and reliability at high temperatures.
  • the curable composition of the present invention and a cured product thereof can be suitably used as a resin raw material for varnishes that can be applied to various substrates, prepregs impregnated with the varnish, printed circuit boards, sealants for electronic components, electric/electronic molded components, automobile components, laminates, paints, resist inks, and the like.
  • FIG. 1 shows differential scanning calorimetry (DSC) curves for Example 5 (solid line) and Comparative Example 10 (dotted line).
  • the component (A) contained in the curable composition of the present invention is a resol type phenolic resin.
  • the resol type phenolic resin used in the present invention can be obtained by reacting a phenolic compound such as phenol, cresol, or bisphenol A with an aldehyde compound such as formaldehyde, paraformaldehyde, or glyoxal in the presence of an alkali catalyst.
  • the alkali catalyst can be an inorganic system such as an oxide or hydroxide of an alkali metal or an alkaline earth metal, or an organic system such as an amine or ammonia.
  • the resol-type phenolic resin of component (A) in the present invention is preferably one obtained by reacting a mononuclear phenolic compound such as phenol or cresol with an aldehyde compound, more preferably one obtained by reacting phenol or cresol with an aldehyde compound, and particularly preferably one obtained by reacting phenol with an aldehyde compound.
  • the weight average molecular weight (Mw) of component (A) is preferably 4,000 or more, more preferably 8,000 or more, even more preferably 12,000 or more, and particularly preferably 15,000 or more, with the upper limit being preferably 50,000 or less, more preferably 40,000 or less, even more preferably 30,000 or less, and particularly preferably 20,000 or less.
  • the weight average molecular weight (Mw)/number average molecular weight (Mn) ratio (Mw/Mn) of component (A) is preferably 3.0 or more, more preferably 6.0 or more, even more preferably 10.0 or more, and particularly preferably 15.0 or more, with the upper limit being preferably 20.0 or less, more preferably 19.0 or less, even more preferably 18.0 or less, and particularly preferably 17.0 or less.
  • Component (B) contained in the curable composition of the present invention, or component (B) contained in the curing agent for resol-type phenolic resin of the present invention is intended to cure the resol-type phenolic resin of component (A) of the present invention, and is a composition which contains component (B1) consisting of the following compounds (1), (2), and (3), and in which the total amount of component (B1) is in the range of 40 area % or more and 70 area % or less based on the total amount of all components detected by measurement by gel permeation chromatography using a differential refractometer as a detector.
  • the component (B) in the present invention preferably contains the component (B1) consisting of the above-mentioned compounds (1), (2) and (3) in a total amount, as measured by the gel permeation chromatography, in the range of 50 area % or more and 67 area % or less, and more preferably in the range of 53 area % or more and 65 area % or less.
  • component (B1) consisting of compound (1), compound (2), and compound (3) preferably contains compound (1)/compound (2) in an area ratio of 35/65 to 55/45, and more preferably 40/60 to 50/50, based on measurement of compound (1) and compound (2) at a wavelength of 280 nm by high performance liquid chromatography using an ultraviolet absorptiometer as a detector.
  • component (B1) in the present invention preferably contains the sum of compound (1) and compound (2) and compound (3) in an area ratio of compound (1) + compound (2) / compound (3) of 95/5 to 80/20, and more preferably an area ratio of 90/10 to 85/15, based on measurement at a wavelength of 280 nm by high performance liquid chromatography using an ultraviolet absorptiometer as a detector.
  • the component (B) in the present invention can be obtained by reacting phenol with formaldehyde in the presence of an acid catalyst, setting the amount of phenol to be used in the range of 3 to 8 moles per mole of formaldehyde, and removing unreacted phenol and the like from the resulting reaction mixture by distillation or the like. After the reaction, neutralization treatment and washing with water to remove neutralization salts may be performed as necessary.
  • the amount of phenol used in the reaction is preferably in the range of 3.7 to 7.2 moles, more preferably in the range of 4.3 to 6.7 moles, per mole of formaldehyde.
  • the acid catalyst is preferably oxalic acid, and when an oxalic acid catalyst is used, it is preferable to produce component (B) by removing low boiling point substances such as phenol by distillation directly from the obtained reaction mixture.
  • the amount of oxalic acid used is preferably in the concentration range of 1 to 0.01% by weight, more preferably 0.5 to 0.05% by weight, based on the total amount of phenol and formaldehyde used in the reaction.
  • the reaction temperature is preferably 60 to 100°C, more preferably 70 to 90°C.
  • the component (B) of the present invention prepared by such a production method contains, in addition to the component (B1), a polycondensate of a phenol other than the component (B1) and formaldehyde.
  • the polycondensate preferably contains the component (B2) described below, more preferably contains the components (B2) and (B3), and further preferably contains the components (B2), (B3) and (B4).
  • Components (B2) to (B4) are described in detail below.
  • Component (B2) contained in component (B) in the present invention is a group of compounds represented by the following general formula (b2) which are produced by substituting a (4-hydroxyphenyl)methyl group or a (2-hydroxyphenyl)methyl group at the para-position or ortho-position of the hydroxyl group in the above-mentioned compounds (1), (2), and (3).
  • the bonding position of the methylene group is the para-position or ortho-position of the hydroxyl group.
  • Examples of the compound represented by the above general formula (b2) include the compounds shown below.
  • component (B2) contained in component (B) in the present invention is preferably 20 to 30 area %, more preferably 22 to 28 area %, and even more preferably 24 to 26 area %, based on the total amount of all components detected by gel permeation chromatography using a differential refractometer as a detector.
  • Component (B3) and Component (B4) > Component (B3) that may be contained in component (B) in the present invention consists of a group of compounds having a structure in which a (4-hydroxyphenyl)methyl group or a (2-hydroxyphenyl)methyl group is substituted at the para-position or ortho-position of the hydroxyl group of the compound represented by general formula (b2) above.
  • component (B4) which may be contained in component (B) in the present invention consists of a group of compounds having a structure in which a (4-hydroxyphenyl)methyl group or a (2-hydroxyphenyl)methyl group is substituted at the para- or ortho-position of the hydroxyl group of the compound contained in component (B3), and a group of compounds having a structure obtained by repeating a reaction one or more times in which the obtained compound is further substituted with a (4-hydroxyphenyl)methyl group or a (2-hydroxyphenyl)methyl group.
  • the component (B) in the present invention may contain, in addition to the components (B1) and (B2), the component (B3) and/or the component (B4).
  • component (B) in the present invention contains components (B3) and (B4)
  • the content of component (B3) is preferably in the range of 18 to 28 area %, more preferably in the range of 20 to 26 area %, even more preferably in the range of 21 to 25 area %, and particularly preferably 22 to 24.5 area %, based on the total content (area %) of components (B2), (B3), and (B4) detected by measurement by gel permeation chromatography using a differential refractometer as a detector.
  • the molecular weight of component (B2) is preferably in the range of 440 to 490, more preferably in the range of 450 to 480, and the molecular weight of component (B3) is preferably in the range of 580 to 630, more preferably in the range of 590 to 620.
  • the curable composition of the present invention contains a resol type phenolic resin as component (A) and component (B), and component (B) is contained as a curing agent in an amount of preferably 1 to 25 parts by weight, more preferably 5 to 20 parts by weight, and even more preferably 8 to 13 parts by weight, per 100 parts by weight of the resol type phenolic resin (A).
  • the curable composition of the present invention is preferably obtained by mixing the resol type phenolic resin of component (A) with component (B) in a temperature environment of about 90° C. within a time period of about 10 minutes.
  • the curable composition of the present invention may contain materials such as inorganic fillers such as silicon oxide, aluminum oxide, magnesium oxide, boron nitride, aluminum nitride, silicon nitride, silicon carbide, and hexagonal boron nitride, and reinforcing fibers such as carbon fiber, glass fiber, organic fiber, boron fiber, steel fiber, and aramid fiber.
  • the amount of the above-mentioned materials that can be used in combination in the curable composition of the present invention is preferably within a range of 0.01 to 100 parts by weight per 1 part by weight of the total of the resol type phenolic resin of component (A) and component (B).
  • the curable composition of the present invention is preferably subjected to a vacuum degassing treatment as a pretreatment to prevent bubbles from being generated during curing if the composition contains water or residual solvent.
  • the temperature of the vacuum degassing treatment is not particularly limited as long as the curable composition of the present invention is in a molten state, but it is preferable to perform the treatment at an upper limit of 90°C because the curing does not proceed and degassing is easy.
  • the pressure of the vacuum degassing treatment is not particularly limited, but it is better to perform it at a low pressure (high degree of vacuum), and it may be performed either in air or in a nitrogen-substituted atmosphere. The vacuum degassing treatment is performed until bubbles cannot be visually confirmed.
  • the cured product of the present invention can be obtained by curing the curable composition of the present invention containing the resol type phenolic resin of component (A) and component (B).
  • methods for producing the cured product of the present invention include a method in which the material is heated to a predetermined temperature to be cured, a method in which the material is heated and melted and poured into a mold or the like and the mold is further heated to be cured and molded, and a method in which the molten material is poured into a preheated mold and cured.
  • the curable composition of the present invention is usually cured at a curing temperature in the range of 140 to 220°C, preferably in the range of 150 to 200°C, more preferably in the range of 160 to 190°C, and even more preferably in the range of 165 to 185°C.
  • the reaction time may be about 5 to 30 minutes.
  • the curable composition of the present invention has a lower curing temperature than conventionally known resol-type phenolic resins, and therefore can be used for materials (substrates) that are sensitive to heat, and is very useful, since it can be made more efficient by shortening the heating and cooling time and saving energy in the molding process of the curable resin.
  • the cured product has a significantly improved heat resistance compared to conventionally known cured products, and is therefore a material that is excellent in stability and reliability at high temperatures, and is very useful.
  • the curable composition of the present invention can cause the curing reaction to proceed and be completed at a lower temperature than conventional ones, and therefore can be suitably used as an adhesive, a sealant, a coating material, a sizing agent, etc. Furthermore, the cured product of the curable composition of the present invention can be suitably used in fields requiring ultra-heat resistance and good dielectric properties (e.g., electronic information devices, home appliances, automobiles, precision machinery, aircraft, space industry equipment, etc.).
  • ⁇ Analysis method> Gel permeation chromatography for analyzing the concentrations of components (B1) to (B4): GPC
  • the components (B1) to (B4) contained in the component (B) of the present invention are identified by the area percentages of all the components detected by this analysis.
  • High performance liquid chromatography measurement Measurement equipment: High-performance liquid chromatography analyzer (UFLC) (manufactured by Shimadzu Corporation) Pump: LC-20AD Column oven: CTO-20A Detector: SPD-20A (UFLC), cell length 5 mm Column: HALO-C18 (column 3.0 x 75 mm, particle size 2.7 ⁇ m, manufactured by Advanced Materials Technology) [Measurement condition] Oven temperature: 50°C Flow rate: 0.8 mL/min.
  • UFLC High-performance liquid chromatography analyzer
  • SPD-20A SPD-20A
  • Oven temperature 50°C Flow rate: 0.8 mL/min.
  • Thermogravimetric analysis (TGA) Equipment SII NanoTechnology's differential thermal and thermogravimetric simultaneous measurement equipment (TG/DTA6200) 5.0 mg to 7.0 mg of the cured product was placed in an aluminum pan for DSC, and the temperature was increased from 100° C. to 600° C. at a rate of 10° C./min in a nitrogen atmosphere. The 5% weight loss temperature (Td5%) of the cured product during the temperature rise process was measured.
  • GPC Measurement device High-performance liquid chromatography analyzer (Chromaster 5110) manufactured by Hitachi High-Tech Science Co., Ltd. Column oven: Chromaster 5310 (Hitachi High-Tech Science Co., Ltd.) UV detector: Chromaster 5410 (Hitachi High-Tech Science Co., Ltd.) Column: Shodex styrene-divinylbenzene copolymer packed column (LF-804 x 2) Other: GL Science degassing unit (DG660B) [Measurement condition] Flow rate: 1.0 mL/min.
  • composition (B'-1) different from the component (B) of the present invention was obtained as the residual liquid.
  • the content of component (B1) was 32.7 area % (less than 40 area %)
  • the content of component (B2) was 23.3 area %
  • the content of component (B3) was 14.9 area %
  • the content of component (B4) was 29.1 area %.
  • the composition of component (B1) as determined by HPLC was 14.2 area % of compound (1), 14.5 area % of compound (2), and 3.2 area % of compound (3).
  • composition (B-1) of component (B) was obtained as the residual liquid.
  • the content of component (B1) was 56.7 area %
  • the content of component (B2) was 25.0 area %
  • the content of component (B3) was 10.5 area %
  • the content of component (B4) was 7.8 area %.
  • component (B1) as determined by HPLC was 20.9 area % of compound (1), 26.6 area % of compound (2), and 6.7 area % of compound (3).
  • the polystyrene-equivalent molecular weights measured by GPC were 313 for component (B1), 457 for component (B2), and 593 for component (B3).
  • composition (B-2) of component (B) was obtained as a residual liquid.
  • the content of component (B1) was 62.0 area %
  • the content of component (B2) was 24.5 area %
  • the content of component (B3) was 8.4 area %
  • the content of component (B4) was 5.1 area %.
  • component (B1) as determined by HPLC was 22.1 area % of compound (1), 30.6 area % of compound (2), and 8.5 area % of compound (3).
  • the polystyrene-equivalent molecular weights measured by GPC were 324 for component (B1), 474 for component (B2), and 611 for component (B3).
  • composition (B'-3) obtained in Production Example 4 was added to 1.00 g of the mixture obtained in Production Example 1, and the mixture was gradually heated to 130 to 180°C to melt, and then cooled to obtain composition (B'-4) which is different from component (B).
  • the content of component (B1) was 75.3 area %
  • the content of component (B2) was 15.5%
  • the content of component (B3) was 5.5%
  • the content of component (B4) was 3.7%.
  • Example 1 0.9 g of a commercially available resol type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd.) was added to a 10 mL sample tube, and 0.1 g of composition (B-1) of component (B) with a content of component (B1) of 56.7 area % obtained in Production Example 3 was added thereto.
  • This sample tube was heated in an oil bath at 90°C for 10 minutes while stirring and mixed.
  • the mixed composition was cooled to room temperature and then heated at 170°C for 10 minutes to obtain a cured product.
  • the Td5% of the resulting cured product was measured.
  • the commercially available resol type phenolic resin used was confirmed by GPC measurement to have a number average molecular weight (Mn) of 960 and a weight average molecular weight (Mw) of 16,000.
  • Example 2 A cured product was obtained by heating in the same manner as in Example 1, except that the curing temperature was 180°C. The Td5% of the resulting cured product was measured.
  • Example 3 A cured product was obtained by heating in the same manner as in Example 2, except that 0.1 g of composition (B-2) of component (B) containing 62.0 area % of component (B1) obtained in Production Example 5 was added instead of adding 0.1 g of composition (B-1) of component (B) containing 56.7 area % of component (B1). The Td5% of the resulting cured product was measured.
  • Example 4 A cured product was obtained by heating in the same manner as in Example 1, except that the curing temperature was 200°C. The Td5% of the resulting cured product was measured.
  • ⁇ Comparative Examples 1 to 3> 1.0 g of the same commercially available resol-type phenolic resin as in Example 1 was used, and cured products were obtained by heating in the same manner as in Example 1, except that the composition of component (B) was not added and curing was carried out at temperatures of 170° C. (Comparative Example 1), 180° C. (Comparative Example 2), and 200° C. (Comparative Example 3). The Td5% of each of the resulting cured products was measured.
  • ⁇ Comparative Example 4> A cured product was obtained by heating in the same manner as in Example 1, except that 0.1 g of composition (B'-1) obtained in Production Example 1, which had a component (B1) content of 32.7%, was added instead of adding 0.1 g of composition (B-1) of component (B) containing 56.7% of component (B1). The Td5% of the resulting cured product was measured.
  • Example 5 A cured product was obtained by heating in the same manner as in Example 1, except that 0.1 g of composition (B'-2) obtained in Production Example 2, which had a component (B1) content of 13.3%, was added instead of adding 0.1 g of composition (B-1) of component (B) containing 56.7% of component (B1). The Td5% of the resulting cured product was measured.
  • Comparative Example 9 A composition was prepared in the same manner as in Comparative Example 8, except that the mixed composition was heated at 170° C. for 10 minutes without cooling to obtain a cured product. The Td5% of the obtained cured product was measured and found to be 366° C.
  • curable composition of the present invention is very useful because it can be used for materials (substrates) that are sensitive to heat.
  • Example 5 0.9 g of a commercially available resol type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd.) and 0.1 g of the composition (B-1) of component (B) obtained in Production Example 3, in which the content of component (B1) was 56.7 area %, were mixed and cooled in the same manner as in Example 1. The obtained mixture was measured using a differential scanning calorimeter under the above-mentioned measurement conditions.
  • a commercially available resol type phenolic resin manufactured by Sumitomo Bakelite Co., Ltd.
  • DSC Differential scanning calorimetry
  • Example 5 had a calorific value ( ⁇ H) of 192 J/g and a peak top temperature of 200°C, while Comparative Example 10 had a calorific value ( ⁇ H) of 216 J/g and a peak top temperature of 202°C. From these results, it was revealed that the curable composition of the present invention can be cured in a short time with less heat generation compared to the conventionally known resol-type phenolic resins, and therefore the curable composition of the present invention can be highly useful because it can reduce the heating and cooling time and save energy.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention addresses the problem of providing: a curable composition which can be cured under low temperature conditions and a cured product of which has improved heat resistance; a cured product obtained by curing same; a curing agent for resole-type phenolic resin; and a curable composition-containing adhesive. To solve the problem, provided is a curable composition containing the following component (A) and the following component (B).　Component (A) is a resole-type phenolic resin. Component (B) is a composition comprising a component (B1) composed of compound (1), compound (2), and compound (3), wherein the total amount of component (B1) falls within the range of 40 area% to 70 area% of the total amount of all components detected by gel permeation chromatography using a differential refractometer.

Description

硬化性組成物Curable Composition
　本発明は、硬化性組成物、それを硬化させた硬化物、レゾール型フェノール樹脂用硬化剤及び、硬化性組成物を含有する接着剤に関する。 The present invention relates to a curable composition, a cured product obtained by curing the composition, a curing agent for resol-type phenolic resins, and an adhesive containing the curable composition.
　フェノール樹脂は、フェノールとホルムアルデヒドを原料として得られる高分子で、酸触媒を用いて得られる熱可塑性のノボラック型フェノール樹脂と、アルカリ触媒を用いて得られる熱硬化性のレゾール型フェノール樹脂の２種類に分類されることが知られている。何れのフェノール樹脂も、耐熱性や機械的強度、耐薬品性や電気絶縁性に優れるという特徴を有するため、自動車部品や断熱材料、レジスト材料、接着剤など、様々な分野で幅広く利用されている。特に、耐熱性や機械的強度の高いフェノール樹脂は、金属の代替材料としても、近年注目されている。
　レゾール型フェノール樹脂は、熱により反応する官能基であるメチロール基を有しており、加熱によりメチロール基と芳香環の水素及びメチロール基同士が縮合することにより架橋が形成される。この架橋反応がいたるところで進行し、レゾール型フェノール樹脂はランダムな３次元ネットワークを構築して硬化物となる。
　硬化促進剤を全く含まないレゾール型フェノール樹脂の硬化は、ノボラック型フェノール樹脂の硬化に比較して、低温（１５０～２００℃）での硬化性に劣るため、低温での硬化が不十分となり、耐熱性に優れる硬化物が得られないという問題があり、その解決法の提案がなされている（例えば、特許文献１等）ものの、未だ充分な解決には至っていない。 Phenolic resins are polymers obtained from phenol and formaldehyde as raw materials, and are known to be classified into two types: thermoplastic novolac-type phenolic resins obtained using an acid catalyst, and thermosetting resol-type phenolic resins obtained using an alkali catalyst. Both phenolic resins are characterized by excellent heat resistance, mechanical strength, chemical resistance, and electrical insulation, and are therefore widely used in various fields such as automobile parts, insulation materials, resist materials, and adhesives. In particular, phenolic resins with high heat resistance and mechanical strength have been attracting attention in recent years as alternative materials to metals.
Resole-type phenolic resins have methylol groups, which are functional groups that react when heated, and crosslinks are formed by condensation of the methylol groups with hydrogen on the aromatic ring and with the methylol groups themselves when heated. This crosslinking reaction progresses everywhere, and the resol-type phenolic resin forms a random three-dimensional network to become a cured product.
The curing of resol-type phenolic resins that do not contain any curing accelerator is inferior to the curing of novolac-type phenolic resins in curing at low temperatures (150 to 200°C). This results in insufficient curing at low temperatures, and a cured product with excellent heat resistance cannot be obtained. Although solutions to this problem have been proposed (for example, Patent Document 1, etc.), a satisfactory solution has not yet been found.
特開２００２－１０５２８２号公報JP 2002-105282 A
　本発明は、低い温度条件で硬化が可能でありかつ、その硬化物は向上した耐熱性を有する、硬化性組成物、それを硬化させた硬化物、レゾール型フェノール樹脂用硬化剤及び、硬化性組成物を含有する接着剤を提供することを課題とする。 The objective of the present invention is to provide a curable composition that can be cured at low temperatures and the cured product has improved heat resistance, a cured product obtained by curing the composition, a curing agent for resol-type phenolic resins, and an adhesive containing the curable composition.
　本発明者は、レゾール型フェノール樹脂に硬化剤を添加することで、加熱のみでは未反応のまま残存するメチロール基の反応性を高めて、向上した耐熱性を有する硬化物を得ることを検討した。
　詳しくは、比較的柔軟で融点の低い硬化剤を採用することにより、レゾール型フェノール樹脂と均一に混合して反応性が高くなると考え、ビス（ヒドロキシフェニル）メタン骨格を有する硬化剤を選択した結果、低い温度条件で硬化が可能であり、かつ、その硬化物の耐熱性が向上することを見出し、本発明を完成した。 The present inventors investigated the possibility of obtaining a cured product with improved heat resistance by adding a curing agent to a resol-type phenolic resin to increase the reactivity of methylol groups that remain unreacted by heating alone.
In detail, by adopting a curing agent that is relatively flexible and has a low melting point, it was thought that the resin would be mixed uniformly with the resol-type phenolic resin, increasing its reactivity. As a result, the curing agent having a bis(hydroxyphenyl)methane skeleton was selected, and it was found that the resin could be cured at low temperatures and that the heat resistance of the cured product was improved, thereby completing the present invention.
　本発明は以下のとおりである。
１．下記成分（Ａ）及び、下記成分（Ｂ）を、含有する硬化性組成物。
　成分（Ａ）：レゾール型フェノール樹脂
　成分（Ｂ）：下記化合物（１）、化合物（２）及び化合物（３）からなる成分（Ｂ１）を含み、成分（Ｂ１）の合計量が示差屈折計を検出器とするゲル浸透クロマトグラフィーによる測定により、検出される全ての成分の全量に対して４０面積％以上７０面積％以下の範囲で含有する組成物
２．１．に記載の硬化性組成物を硬化させてなる硬化物。
３．下記成分（Ｂ）を含有する、レゾール型フェノール樹脂用硬化剤。
　成分（Ｂ）：下記化合物（１）、化合物（２）及び化合物（３）からなる成分（Ｂ１）を含み、成分（Ｂ１）の合計量が示差屈折計を検出器とするゲル浸透クロマトグラフィーによる測定により、検出される全ての成分の全量に対して４０面積％以上７０面積％以下の範囲で含有する組成物
４．１．に記載の硬化性組成物を含有する接着剤。 The present invention is as follows.
1. A curable composition comprising the following component (A) and component (B):
Component (A): A resol-type phenolic resin. Component (B): A composition comprising component (B1) consisting of the following compounds (1), (2), and (3), in which the total amount of component (B1) is in the range of 40 area % to 70 area % based on the total amount of all components detected by gel permeation chromatography using a differential refractometer as a detector.
2. A cured product obtained by curing the curable composition according to 1.
3. A curing agent for resol-type phenolic resins, comprising the following component (B):
Component (B): A composition comprising component (B1) consisting of the following compounds (1), (2), and (3), wherein the total amount of component (B1) is in the range of 40 area % to 70 area % based on the total amount of all components detected by gel permeation chromatography using a differential refractometer as a detector.
4. An adhesive comprising the curable composition according to 1.
　本発明の硬化性組成物は、従来公知のレゾール型フェノール樹脂に比べて、低温で硬化することができるため、硬化性樹脂の成型プロセスにおける温度を下げることができ、加熱及び冷却の時間短縮や省エネルギー化による効率化が可能であるほか、熱に弱い材料（基材）にも使用できるので非常に有用である。
　また、本発明化合物の硬化物は、レゾールのみで硬化させた従来公知のレゾール型フェノール樹脂の硬化物に比べて、大きく向上した耐熱性を有するため、高温下での安定性や信頼性に優れる材料であり、非常に有用である。
　本発明における硬化性組成物や、それを硬化させた硬化物は、各種基材に塗布可能なワニス、ワニスを含浸させたプリプレグ、プリント回路基板、電子部品の封止剤、電気・電子成型部品、自動車部品、積層材、塗料、レジストインク等の樹脂原料として好適に用いることができる。 The curable composition of the present invention can be cured at a lower temperature than the conventionally known resol-type phenolic resins, and therefore the temperature in the molding process of the curable resin can be lowered, which enables efficiency improvement by shortening heating and cooling times and saving energy. In addition, the composition can be used on materials (substrates) that are sensitive to heat, making it extremely useful.
Furthermore, the cured product of the compound of the present invention has significantly improved heat resistance compared to the cured product of a conventionally known resol-type phenolic resin cured only with resol, and is therefore a highly useful material with excellent stability and reliability at high temperatures.
The curable composition of the present invention and a cured product thereof can be suitably used as a resin raw material for varnishes that can be applied to various substrates, prepregs impregnated with the varnish, printed circuit boards, sealants for electronic components, electric/electronic molded components, automobile components, laminates, paints, resist inks, and the like.
実施例５（実線）と比較例１０（点線）の示差走査熱量測定（ＤＳＣ）曲線を、示す図である。FIG. 1 shows differential scanning calorimetry (DSC) curves for Example 5 (solid line) and Comparative Example 10 (dotted line).
＜成分（Ａ）＞
　本発明の硬化性組成物に含まれる成分（Ａ）は、レゾール型フェノール樹脂である。本発明で用いるレゾール型フェノール樹脂としては、フェノール、クレゾール、ビスフェノールＡ等のフェノール化合物と、ホルムアルデヒド、パラホルムアルデヒド、グリオキザール等のアルデヒド化合物とを、アルカリ触媒存在下で反応させて得られるものが挙げられる。そのアルカリ触媒としては、無機系では、アルカリ金属、アルカリ土類金属の酸化物や水酸化物等があり、有機系では、アミン類、アンモニア等がある。
　本発明における成分（Ａ）のレゾール型フェノール樹脂としては、フェノールやクレゾール等の単核のフェノール化合物を、アルデヒド化合物と反応して得られるものが好ましく、フェノール、クレゾールをアルデヒド化合物と反応して得られるものがより好ましく、フェノールをアルデヒド化合物と反応して得られるものが特に好ましい。
　成分（Ａ）の重量平均分子量（Ｍｗ）は、４，０００以上が好ましく、８，０００以上がより好ましく、１２，０００以上がさらに好ましく、１５，０００以上が特に好ましく、上限としては５０，０００以下が好ましく、４０，０００以下がより好ましく、３０，０００以下がさらに好ましく、２０,０００以下が特に好ましい。また、成分（Ａ）の重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）は、３．０以上が好ましく、６.０以上がより好ましく、１０．０以上がさらに好ましく、１５．０以上が特に好ましく、上限としては２０．０以下が好ましく、１９．０以下がより好ましく、１８．０以下がさらに好ましく、１７．０以下が特に好ましい。 <Component (A)>
The component (A) contained in the curable composition of the present invention is a resol type phenolic resin. The resol type phenolic resin used in the present invention can be obtained by reacting a phenolic compound such as phenol, cresol, or bisphenol A with an aldehyde compound such as formaldehyde, paraformaldehyde, or glyoxal in the presence of an alkali catalyst. The alkali catalyst can be an inorganic system such as an oxide or hydroxide of an alkali metal or an alkaline earth metal, or an organic system such as an amine or ammonia.
The resol-type phenolic resin of component (A) in the present invention is preferably one obtained by reacting a mononuclear phenolic compound such as phenol or cresol with an aldehyde compound, more preferably one obtained by reacting phenol or cresol with an aldehyde compound, and particularly preferably one obtained by reacting phenol with an aldehyde compound.
The weight average molecular weight (Mw) of component (A) is preferably 4,000 or more, more preferably 8,000 or more, even more preferably 12,000 or more, and particularly preferably 15,000 or more, with the upper limit being preferably 50,000 or less, more preferably 40,000 or less, even more preferably 30,000 or less, and particularly preferably 20,000 or less. The weight average molecular weight (Mw)/number average molecular weight (Mn) ratio (Mw/Mn) of component (A) is preferably 3.0 or more, more preferably 6.0 or more, even more preferably 10.0 or more, and particularly preferably 15.0 or more, with the upper limit being preferably 20.0 or less, more preferably 19.0 or less, even more preferably 18.0 or less, and particularly preferably 17.0 or less.
＜成分（Ｂ）＞
　本発明の硬化性組成物に含まれる成分（Ｂ）又は、本発明のレゾール型フェノール樹脂用硬化剤に含まれる成分（Ｂ）は、本発明における成分（Ａ）のレゾール型フェノール樹脂を硬化させるためのものであり、下記化合物（１）、化合物（２）及び化合物（３）からなる成分（Ｂ１）を含み、成分（Ｂ１）の合計量が示差屈折計を検出器とするゲル浸透クロマトグラフィーによる測定により、検出される全ての成分の全量に対して４０面積％以上７０面積％以下の範囲で含有する組成物である。
　本発明における成分（Ｂ）は、上記化合物（１）、化合物（２）及び化合物（３）からなる成分（Ｂ１）を、前記ゲル浸透クロマトグラフィーによる測定による合計量として、５０面積％以上６７面積％以下の範囲で含有することが好ましく、５３面積％以上６５面積％以下の範囲で含有することがより好ましい。
　本発明において、化合物（１）、化合物（２）及び化合物（３）からなる成分（Ｂ１）は、化合物（１）と化合物（２）とを、紫外吸光計を検出器とする高速液体クロマトグラフィーによる波長２８０ｎｍでの測定に基づいて、化合物（１）／化合物（２）を３５／６５～５５／４５の面積比で含有することが好ましく、４０／６０～５０／５０の面積比で含有することがより好ましい。
　また、本発明における成分（Ｂ１）は、化合物（１）と化合物（２）の合計と化合物（３）を、紫外吸光計を検出器とする高速液体クロマトグラフィーによる波長２８０ｎｍでの測定に基づいて、化合物（１）＋化合物（２）／化合物（３）を９５/５～８０/２０の面積比で含有することが好ましく、９０/１０～８５/１５の面積比で含有することがより好ましい。 <Component (B)>
Component (B) contained in the curable composition of the present invention, or component (B) contained in the curing agent for resol-type phenolic resin of the present invention, is intended to cure the resol-type phenolic resin of component (A) of the present invention, and is a composition which contains component (B1) consisting of the following compounds (1), (2), and (3), and in which the total amount of component (B1) is in the range of 40 area % or more and 70 area % or less based on the total amount of all components detected by measurement by gel permeation chromatography using a differential refractometer as a detector.
The component (B) in the present invention preferably contains the component (B1) consisting of the above-mentioned compounds (1), (2) and (3) in a total amount, as measured by the gel permeation chromatography, in the range of 50 area % or more and 67 area % or less, and more preferably in the range of 53 area % or more and 65 area % or less.
In the present invention, component (B1) consisting of compound (1), compound (2), and compound (3) preferably contains compound (1)/compound (2) in an area ratio of 35/65 to 55/45, and more preferably 40/60 to 50/50, based on measurement of compound (1) and compound (2) at a wavelength of 280 nm by high performance liquid chromatography using an ultraviolet absorptiometer as a detector.
Furthermore, component (B1) in the present invention preferably contains the sum of compound (1) and compound (2) and compound (3) in an area ratio of compound (1) + compound (2) / compound (3) of 95/5 to 80/20, and more preferably an area ratio of 90/10 to 85/15, based on measurement at a wavelength of 280 nm by high performance liquid chromatography using an ultraviolet absorptiometer as a detector.
　本発明における成分（Ｂ）は、酸触媒の存在下、フェノールとホルムアルデヒドを、反応させる際、フェノールの使用量をホルムアルデヒド１モルに対して３～８モルの範囲とし、得られた反応混合物から未反応のフェノール等を蒸留等により除去することにより得ることができる。反応後、必要に応じて、中和処理や中和塩除去のための水洗操作を行ってもよい。反応に使用するフェノールの量は、ホルムアルデヒド１モルに対して、３．７～７．２モルの範囲が好ましく、４．３～６．７モルの範囲がより好ましい。
　酸触媒はシュウ酸が好ましく、シュウ酸触媒を用いた場合は、得られた反応混合物からそのまま蒸留によりフェノール等の低沸点物を除去して成分（Ｂ）を製造する方法が好ましい。シュウ酸の使用量は反応に使用するフェノールとホルムアルデヒドの合計量に対して１～０．０１重量％の濃度範囲とすることが好ましく、０．５～０．０５重量％の濃度範囲とすることがより好ましい。反応温度としては、６０～１００℃が好ましく、７０～９０℃がより好ましい。
　このような製造方法により調製した本発明の成分（Ｂ）は、成分（Ｂ１）以外に、成分（Ｂ１）以外のフェノールとホルムアルデヒドとの重縮合物を含有するものである。当該重縮合物は、以下に説明する成分（Ｂ２）を含有するものが好ましく、成分（Ｂ２）及び成分（Ｂ３）を含有するものがより好ましく、成分（Ｂ２）、成分（Ｂ３）及び成分（Ｂ４）を含有するものがさらに好ましい。成分（Ｂ２）～（Ｂ４）について、以下に詳しく説明する。 The component (B) in the present invention can be obtained by reacting phenol with formaldehyde in the presence of an acid catalyst, setting the amount of phenol to be used in the range of 3 to 8 moles per mole of formaldehyde, and removing unreacted phenol and the like from the resulting reaction mixture by distillation or the like. After the reaction, neutralization treatment and washing with water to remove neutralization salts may be performed as necessary. The amount of phenol used in the reaction is preferably in the range of 3.7 to 7.2 moles, more preferably in the range of 4.3 to 6.7 moles, per mole of formaldehyde.
The acid catalyst is preferably oxalic acid, and when an oxalic acid catalyst is used, it is preferable to produce component (B) by removing low boiling point substances such as phenol by distillation directly from the obtained reaction mixture. The amount of oxalic acid used is preferably in the concentration range of 1 to 0.01% by weight, more preferably 0.5 to 0.05% by weight, based on the total amount of phenol and formaldehyde used in the reaction. The reaction temperature is preferably 60 to 100°C, more preferably 70 to 90°C.
The component (B) of the present invention prepared by such a production method contains, in addition to the component (B1), a polycondensate of a phenol other than the component (B1) and formaldehyde. The polycondensate preferably contains the component (B2) described below, more preferably contains the components (B2) and (B3), and further preferably contains the components (B2), (B3) and (B4). Components (B2) to (B4) are described in detail below.
＜成分（Ｂ２）＞
　本発明における成分（Ｂ）が含有する成分（Ｂ２）は、上記化合物（１）、化合物（２）及び化合物（３）の水酸基のパラ位又はオルソ位に、（４－ヒドロキシフェニル）メチル基又は（２－ヒドロキシフェニル）メチル基が置換して生成した、下記一般式（ｂ２）で表される化合物群である。

（式中、メチレン基の結合位置は、水酸基のパラ位又はオルソ位である。）
　上記一般式（ｂ２）で表される化合物としては、例えば、下記に示す化合物等が挙げられる。

　本発明における成分（Ｂ）が含有する成分（Ｂ２）の含有量は、示差屈折計を検出器とするゲル浸透クロマトグラフィーによる測定より検出される全ての成分の全量に対して、２０～３０面積％が好ましく、２２～２８面積％がより好ましく、２４～２６面積％がさらに好ましい。 <Component (B2)>
Component (B2) contained in component (B) in the present invention is a group of compounds represented by the following general formula (b2) which are produced by substituting a (4-hydroxyphenyl)methyl group or a (2-hydroxyphenyl)methyl group at the para-position or ortho-position of the hydroxyl group in the above-mentioned compounds (1), (2), and (3).

(In the formula, the bonding position of the methylene group is the para-position or ortho-position of the hydroxyl group.)
Examples of the compound represented by the above general formula (b2) include the compounds shown below.

The content of component (B2) contained in component (B) in the present invention is preferably 20 to 30 area %, more preferably 22 to 28 area %, and even more preferably 24 to 26 area %, based on the total amount of all components detected by gel permeation chromatography using a differential refractometer as a detector.
＜成分（Ｂ３）、成分（Ｂ４）＞
　本発明における成分（Ｂ）が含有し得る成分（Ｂ３）は、上記一般式（ｂ２）で表される化合物の水酸基のパラ位又はオルソ位に、（４－ヒドロキシフェニル）メチル基又は（２－ヒドロキシフェニル）メチル基が置換した構造の化合物群からなるものである。
　さらに、本発明における成分（Ｂ）が含有し得る成分（Ｂ４）は、成分（Ｂ３）に含まれる化合物の水酸基のパラ位又はオルソ位に、（４－ヒドロキシフェニル）メチル基又は（２－ヒドロキシフェニル）メチル基が置換した構造の化合物群及び、得られた化合物にさらに（４－ヒドロキシフェニル）メチル基又は（２－ヒドロキシフェニル）メチル基が置換する反応が１回以上繰り返されて得られる、構造の化合物群からなるものである。
　本発明における成分（Ｂ）は、成分（Ｂ１）及び成分（Ｂ２）以外に、成分（Ｂ３）及び／又は成分（Ｂ４）を含有し得るものである。
　本発明における成分（Ｂ）が成分（Ｂ３）及び成分（Ｂ４）を含有する場合は、成分（Ｂ３）の含有量が、示差屈折計を検出器とするゲル浸透クロマトグラフィーによる測定より検出される成分（Ｂ２）、成分（Ｂ３）及び成分（Ｂ４）の含有量（面積％）の合計に対して、１８～２８面積％の範囲であることが好ましく、２０～２６面積％の範囲がより好ましく、２１～２５面積％の範囲がさらに好ましく、２２～２４．５面積％が特に好ましい。 <Component (B3) and Component (B4)>
Component (B3) that may be contained in component (B) in the present invention consists of a group of compounds having a structure in which a (4-hydroxyphenyl)methyl group or a (2-hydroxyphenyl)methyl group is substituted at the para-position or ortho-position of the hydroxyl group of the compound represented by general formula (b2) above.
Furthermore, component (B4) which may be contained in component (B) in the present invention consists of a group of compounds having a structure in which a (4-hydroxyphenyl)methyl group or a (2-hydroxyphenyl)methyl group is substituted at the para- or ortho-position of the hydroxyl group of the compound contained in component (B3), and a group of compounds having a structure obtained by repeating a reaction one or more times in which the obtained compound is further substituted with a (4-hydroxyphenyl)methyl group or a (2-hydroxyphenyl)methyl group.
The component (B) in the present invention may contain, in addition to the components (B1) and (B2), the component (B3) and/or the component (B4).
When component (B) in the present invention contains components (B3) and (B4), the content of component (B3) is preferably in the range of 18 to 28 area %, more preferably in the range of 20 to 26 area %, even more preferably in the range of 21 to 25 area %, and particularly preferably 22 to 24.5 area %, based on the total content (area %) of components (B2), (B3), and (B4) detected by measurement by gel permeation chromatography using a differential refractometer as a detector.
＜成分（Ｂ２）、（Ｂ３）のポリスチレン換算分子量＞
　成分（Ｂ２）、（Ｂ３）のゲル浸透クロマトグラフィー（ＧＰＣ）測定によるポリスチレン換算分子量について、成分（Ｂ２）は４４０～４９０の範囲が好ましく、４５０～４８０の範囲がより好ましく、成分（Ｂ３）は５８０～６３０の範囲が好ましく、５９０～６２０の範囲がより好ましい。 <Polystyrene-equivalent molecular weight of components (B2) and (B3)>
With respect to the polystyrene-equivalent molecular weights of components (B2) and (B3) as measured by gel permeation chromatography (GPC), the molecular weight of component (B2) is preferably in the range of 440 to 490, more preferably in the range of 450 to 480, and the molecular weight of component (B3) is preferably in the range of 580 to 630, more preferably in the range of 590 to 620.
＜本発明の硬化性組成物＞
　本発明の硬化性組成物は、成分（Ａ）のレゾール型フェノール樹脂及び、成分（Ｂ）を含有するものであり、成分（Ｂ）は硬化剤として、レゾール型フェノール樹脂（Ａ）１００重量部に対して１～２５重量部の範囲で含有することが好ましく、５～２０重量部の範囲で含有することがより好ましく、８～１３重量部の範囲で含有することがさらに好ましい。
　本発明の硬化性組成物は、９０℃程度の温度環境下において１０分程度の時間内で、成分（Ａ）のレゾール型フェノール樹脂と成分（Ｂ）を混合して得ることが好ましい。
　本発明の硬化性組成物は、成分（Ａ）のレゾール型フェノール樹脂と成分（Ｂ）以外に、酸化珪素、酸化アルミニウム、酸化マグネシウム、窒化ホウ素、窒化アルミニウム、窒化珪素、炭化珪素、六方晶窒化ホウ素等の無機フィラーや、炭素繊維、ガラス繊維、有機繊維、ボロン繊維、スチール繊維、アラミド繊維等の強化繊維などの材料を配合しても良い。
　本発明の硬化性組成物における、併用し得る上記材料の配合量は、成分（Ａ）のレゾール型フェノール樹脂と成分（Ｂ）の合計１重量部に対して、０．０１重量部～１００重量部の範囲が好ましい。
　本発明の硬化性組成物は、組成物中に水や残存溶媒を含んでいると硬化時に気泡が発生してしまうので、これを防ぐために前処理として真空脱気処理を行ったものが好ましい。この真空脱気処理の温度は、本発明の硬化性組成物が溶融状態となる温度であれば特に制限されないが、硬化が進行せず、かつ、脱気がしやすいとの理由により９０℃を上限として行うのが好ましい。真空脱気処理の圧力は、特に制限はないが、低い（減圧度の高い）方がよく、空気中でも窒素置換雰囲気下中の何れで行ってもよい。この真空脱気処理は、気泡が目視で確認できなくなるまで行う。 <Curable composition of the present invention>
The curable composition of the present invention contains a resol type phenolic resin as component (A) and component (B), and component (B) is contained as a curing agent in an amount of preferably 1 to 25 parts by weight, more preferably 5 to 20 parts by weight, and even more preferably 8 to 13 parts by weight, per 100 parts by weight of the resol type phenolic resin (A).
The curable composition of the present invention is preferably obtained by mixing the resol type phenolic resin of component (A) with component (B) in a temperature environment of about 90° C. within a time period of about 10 minutes.
In addition to the resol type phenolic resin of component (A) and component (B), the curable composition of the present invention may contain materials such as inorganic fillers such as silicon oxide, aluminum oxide, magnesium oxide, boron nitride, aluminum nitride, silicon nitride, silicon carbide, and hexagonal boron nitride, and reinforcing fibers such as carbon fiber, glass fiber, organic fiber, boron fiber, steel fiber, and aramid fiber.
The amount of the above-mentioned materials that can be used in combination in the curable composition of the present invention is preferably within a range of 0.01 to 100 parts by weight per 1 part by weight of the total of the resol type phenolic resin of component (A) and component (B).
The curable composition of the present invention is preferably subjected to a vacuum degassing treatment as a pretreatment to prevent bubbles from being generated during curing if the composition contains water or residual solvent. The temperature of the vacuum degassing treatment is not particularly limited as long as the curable composition of the present invention is in a molten state, but it is preferable to perform the treatment at an upper limit of 90°C because the curing does not proceed and degassing is easy. The pressure of the vacuum degassing treatment is not particularly limited, but it is better to perform it at a low pressure (high degree of vacuum), and it may be performed either in air or in a nitrogen-substituted atmosphere. The vacuum degassing treatment is performed until bubbles cannot be visually confirmed.
＜本発明の硬化性組成物を硬化させた硬化物＞
　本発明の硬化物は、成分（Ａ）のレゾール型フェノール樹脂及び成分（Ｂ）を含有する本発明の硬化性組成物を硬化させて得ることができる。
　本発明の硬化物の製造方法としては、例えば、所定の温度まで加熱して硬化させる方法、加熱融解させて金型等に注ぎ金型を更に加熱して硬化成型させる方法、溶融物を予め加熱された金型に注入して硬化させる方法等を挙げることができる。
　本発明の硬化性組成物の硬化温度としては、通常１４０～２２０℃の範囲で硬化させるものであるが、１５０～２００℃の範囲で硬化させることが好ましく、１６０～１９０℃の範囲で硬化させることがより好ましく、１６５～１８５℃の範囲で硬化させることがさらに好ましい。
　このような温度の範囲において硬化を行う場合には、反応時間は５～３０分程度であればよい。
　本発明の硬化性組成物は、従来公知のレゾール型フェノール樹脂と比べて硬化温度が低いことから、硬化性樹脂の成型プロセスにおける、加熱及び冷却の時間短縮や省エネルギー化による効率化が可能であるほか、熱に弱い材料（基材）にも使用できるため、非常に有用である。更に、その硬化物は、従来公知の硬化物と比べて、大きく向上した耐熱性を有することから、高温下での安定性や信頼性に優れる材料であり、非常に有用である。 <Cured product obtained by curing the curable composition of the present invention>
The cured product of the present invention can be obtained by curing the curable composition of the present invention containing the resol type phenolic resin of component (A) and component (B).
Examples of methods for producing the cured product of the present invention include a method in which the material is heated to a predetermined temperature to be cured, a method in which the material is heated and melted and poured into a mold or the like and the mold is further heated to be cured and molded, and a method in which the molten material is poured into a preheated mold and cured.
The curable composition of the present invention is usually cured at a curing temperature in the range of 140 to 220°C, preferably in the range of 150 to 200°C, more preferably in the range of 160 to 190°C, and even more preferably in the range of 165 to 185°C.
When curing is carried out within this temperature range, the reaction time may be about 5 to 30 minutes.
The curable composition of the present invention has a lower curing temperature than conventionally known resol-type phenolic resins, and therefore can be used for materials (substrates) that are sensitive to heat, and is very useful, since it can be made more efficient by shortening the heating and cooling time and saving energy in the molding process of the curable resin. Furthermore, the cured product has a significantly improved heat resistance compared to conventionally known cured products, and is therefore a material that is excellent in stability and reliability at high temperatures, and is very useful.
＜接着剤＞
　本発明の硬化性組成物は、上述のとおり従来に比べて低温で硬化反応を進行させ、完了することができるため、接着剤、封止剤、塗料、サイジング剤等として好適に使用することができる。
　また、本発明の硬化性組成物の硬化物は、超耐熱性及び良好な誘電特性が求められる分野（例えば、電子情報機器、家電、自動車、精密機械、航空機、宇宙産業用機器等）において好適に使用することができる。 <Adhesive>
As described above, the curable composition of the present invention can cause the curing reaction to proceed and be completed at a lower temperature than conventional ones, and therefore can be suitably used as an adhesive, a sealant, a coating material, a sizing agent, etc.
Furthermore, the cured product of the curable composition of the present invention can be suitably used in fields requiring ultra-heat resistance and good dielectric properties (e.g., electronic information devices, home appliances, automobiles, precision machinery, aircraft, space industry equipment, etc.).
　以下、実施例により、本発明をさらに具体的に説明する。
＜分析方法＞
１．（Ｂ１）～（Ｂ４）成分濃度分析用ゲル浸透クロマトグラフィー：ＧＰＣ
　本発明の成分（Ｂ）に含まれる成分（Ｂ１）～（Ｂ４）は、本分析による検出される全ての成分の面積百分率の数値により特定される。
　測定装置：東ソー株式会社製　ＨＬＣ－８３２０ＧＰＣ
　検出器：ＲＩ検出器
　カラム：ＴＳＫｇｅｌ　ｇｕａｒｄｃｏｌｕｍｎ　ＳｕｐｅｒＭＰ(ＨＺ)－Ｎ、ＴＳＫｇｅｌ　ＳｕｐｅｒＭｕｌｔｉｐｏｒｅＨＺ－Ｎ×３本(４．６ｍｍＩ．Ｄ．×１５ｃｍ、微粒子充填剤:３～６μｍ)
［測定条件］
　流速：０．３５ｍＬ／ｍｉｎ．
　移動相：テトラヒドロフラン
　カラム温度：４０℃
　試料濃度：０．５ｗｔ％（テトラヒドロフラン溶液）
　注入量：１０μＬ
［分子量測定］
　分子量はポリスチレン標準物をもとに算出した。 The present invention will now be described more specifically with reference to examples.
<Analysis method>
1. Gel permeation chromatography for analyzing the concentrations of components (B1) to (B4): GPC
The components (B1) to (B4) contained in the component (B) of the present invention are identified by the area percentages of all the components detected by this analysis.
Measuring device: Tosoh Corporation HLC-8320GPC
Detector: RI detector Column: TSKgel guard column Super MP (HZ)-N, TSKgel Super Multipore HZ-N x 3 (4.6 mm ID x 15 cm, fine particle filler: 3 to 6 μm)
[Measurement condition]
Flow rate: 0.35 mL/min.
Mobile phase: tetrahydrofuran Column temperature: 40°C
Sample concentration: 0.5 wt% (tetrahydrofuran solution)
Injection volume: 10 μL
[Molecular Weight Measurement]
Molecular weights were calculated based on polystyrene standards.
２．高速液体クロマトグラフィー測定（ＨＰＬＣ測定）
　測定装置：高速液体クロマトグラフィー分析装置（ＵＦＬＣ）（株式会社島津製作所製）
　ポンプ：ＬＣ－２０ＡＤ
　カラムオーブン：ＣＴＯ－２０Ａ
　検出器：ＳＰＤ－２０Ａ（ＵＦＬＣ）、セル長５ｍｍ
　カラム：ＨＡＬＯ－Ｃ１８（カラム３．０×７５ｍｍ、粒子径２．７μｍ、ａｄｖａｎｃｅｄ　ｍａｔｅｒｉａｌｓ　ｔｅｃｈｎｏｌｏｇｙ社製）
［測定条件］
　オーブン温度：５０℃
　流量：０．８ｍＬ／ｍｉｎ．
　移動相：（Ａ）０．２ｖｏｌ％酢酸水溶液、（Ｂ）メタノール
　グラジエント条件：（Ｂ）体積％（分析開始からの時間）１０％（０分）→１０％（２．６分）→１００％（１３．６分）→１００％(２５．０分)
　検出波長：２８０ｎｍ
　試料濃度：２．０ｍｇ／ｍＬ（メタノール溶液）
　試料注入量：５μＬ 2. High performance liquid chromatography measurement (HPLC measurement)
Measurement equipment: High-performance liquid chromatography analyzer (UFLC) (manufactured by Shimadzu Corporation)
Pump: LC-20AD
Column oven: CTO-20A
Detector: SPD-20A (UFLC), cell length 5 mm
Column: HALO-C18 (column 3.0 x 75 mm, particle size 2.7 μm, manufactured by Advanced Materials Technology)
[Measurement condition]
Oven temperature: 50°C
Flow rate: 0.8 mL/min.
Mobile phase: (A) 0.2 vol% acetic acid aqueous solution, (B) methanol Gradient conditions: (B) Volume % (time from start of analysis) 10% (0 min) → 10% (2.6 min) → 100% (13.6 min) → 100% (25.0 min)
Detection wavelength: 280 nm
Sample concentration: 2.0 mg/mL (methanol solution)
Sample injection volume: 5 μL
３．熱重量分析測定（ＴＧＡ）
　装置：エスアイアイ・ナノテクノロジー製示差熱熱重量同時測定装置（ＴＧ／ＤＴＡ６２００）
　硬化物５．０ｍｇ～７．０ｍｇをＤＳＣ用アルミニウム製パンに入れ、窒素雰囲気下で昇温速度１０℃／分で１００℃から６００℃まで昇温した。
　昇温過程での硬化物の５％重量減少温度（Ｔｄ５％）を測定した。 3. Thermogravimetric analysis (TGA)
Equipment: SII NanoTechnology's differential thermal and thermogravimetric simultaneous measurement equipment (TG/DTA6200)
5.0 mg to 7.0 mg of the cured product was placed in an aluminum pan for DSC, and the temperature was increased from 100° C. to 600° C. at a rate of 10° C./min in a nitrogen atmosphere.
The 5% weight loss temperature (Td5%) of the cured product during the temperature rise process was measured.
４．レゾール樹脂分析用ゲル浸透クロマトグラフィー：ＧＰＣ
　測定装置：（株）日立ハイテクサイエンス製高速液体クロマトグラフィー分析装置（Ｃｈｒｏｍａｓｔｅｒ　５１１０）
　カラムオーブン：Ｃｈｒｏｍａｓｔｅｒ　５３１０（（株）日立ハイテクサイエンス製）
　ＵＶ検出器：Ｃｈｒｏｍａｓｔｅｒ　５４１０（（株）日立ハイテクサイエンス製）
　カラム：Ｓｈｏｄｅｘ製スチレンジビニルベンゼン共重合体充填カラム（ＬＦ－８０４×２本)
　その他：ジーエルサイエンス製デガッシングユニット（ＤＧ６６０Ｂ）
　［測定条件］
　流速：１．０ｍＬ／ｍｉｎ．
　移動相：テトラヒドロフラン
　カラム温度：２５℃
　測定波長：２７０ｎｍ
　試料濃度：５ｍｇ／ＴＨＦ４～５ｍＬ
　注入量：２０μＬ
　換算分子量はポリスチレン標準物をもとに算出した。 4. Gel Permeation Chromatography for Analyzing Resol Resins: GPC
Measurement device: High-performance liquid chromatography analyzer (Chromaster 5110) manufactured by Hitachi High-Tech Science Co., Ltd.
Column oven: Chromaster 5310 (Hitachi High-Tech Science Co., Ltd.)
UV detector: Chromaster 5410 (Hitachi High-Tech Science Co., Ltd.)
Column: Shodex styrene-divinylbenzene copolymer packed column (LF-804 x 2)
Other: GL Science degassing unit (DG660B)
[Measurement condition]
Flow rate: 1.0 mL/min.
Mobile phase: tetrahydrofuran Column temperature: 25°C
Measurement wavelength: 270 nm
Sample concentration: 5 mg/THF 4-5 mL
Injection volume: 20 μL
The molecular weight was calculated based on polystyrene standards.
５．示差走査熱量分析（ＤＳＣ）
　硬化性組成物をアルミパンに精密に秤量し、示差走査熱量測定装置（（株）日立ハイテクサイエンス製：ＤＳＣ－７０２０）を用いて、空のアルミパンを対照として下記条件により測定した。
（測定条件）
　昇温速度：１０℃／ｍｉｎ．
　測定温度範囲：３０～２００℃
　測定雰囲気：開放、窒素５０ｍＬ／ｍｉｎ．
　サンプル量：３ｍｇ±１ｍｇ 5. Differential Scanning Calorimetry (DSC)
The curable composition was precisely weighed into an aluminum pan, and the composition was measured under the following conditions using a differential scanning calorimeter (DSC-7020, Hitachi High-Tech Science Corp.) with an empty aluminum pan as a control.
(Measurement condition)
Heating rate: 10° C./min.
Measurement temperature range: 30 to 200°C
Measurement atmosphere: open, nitrogen 50 mL/min.
Sample amount: 3 mg ± 1 mg
＜製造例１＞
　コンデンサー、撹拌機、温度計を備えた４つ口フラスコに、フェノール３３０．４ｇ（３．５１モル）及び１０％シュウ酸水溶液２．２６ｇを仕込み、７０℃に昇温した後に、３５％ホルムアルデヒド水溶液１２２．０ｇ（１．４２モル）を、５分以内で添加した。添加終了後、９０℃に昇温し、６．５時間撹拌を続けた。反応終了後、８０℃、４７ｋＰａの条件で蒸留を開始し、３．５時間かけて内温１４５℃（３ｋＰａ）まで昇温し、３時間保持したところ、フェノールの留出が停止した。その後、１４５℃、１４ｋＰａで水を滴下し、残存フェノールの除去を行った。その後、１５５℃、１ｋＰａで１時間保持し、水を除去した後、残液として、本発明の成分（Ｂ）とは異なる組成物（Ｂ’－１）を得た。
　得られた組成物（Ｂ’－１）のＧＰＣ測定の結果、成分（Ｂ１）の含有量は３２．７面積％（４０面積％未満）、成分（Ｂ２）の含有量は、２３．３面積％、成分（Ｂ３）の含有量が１４．９面積％、成分（Ｂ４）の含有量は２９．１面積％であった。
　ＨＰＬＣ測定による成分（Ｂ１）の構成は、化合物（１）が１４．２面積％、化合物（２）が１４．５面積％、化合物（３）が３．２面積％であった。 <Production Example 1>
A four-neck flask equipped with a condenser, a stirrer, and a thermometer was charged with 330.4 g (3.51 mol) of phenol and 2.26 g of a 10% aqueous oxalic acid solution, and the temperature was raised to 70 ° C., and then 122.0 g (1.42 mol) of a 35% aqueous formaldehyde solution was added within 5 minutes. After the addition was completed, the temperature was raised to 90 ° C., and stirring was continued for 6.5 hours. After the reaction was completed, distillation was started under conditions of 80 ° C. and 47 kPa, and the internal temperature was raised to 145 ° C. (3 kPa) over 3.5 hours, and when it was held for 3 hours, the distillation of phenol stopped. Thereafter, water was dropped at 145 ° C. and 14 kPa to remove the remaining phenol. Thereafter, it was held at 155 ° C. and 1 kPa for 1 hour, and after removing the water, a composition (B'-1) different from the component (B) of the present invention was obtained as the residual liquid.
As a result of GPC measurement of the obtained composition (B'-1), the content of component (B1) was 32.7 area % (less than 40 area %), the content of component (B2) was 23.3 area %, the content of component (B3) was 14.9 area %, and the content of component (B4) was 29.1 area %.
The composition of component (B1) as determined by HPLC was 14.2 area % of compound (1), 14.5 area % of compound (2), and 3.2 area % of compound (3).
＜製造例２＞
　フェノール３０３．２ｇ（３．２２モル）、１０％シュウ酸水溶液２．４３ｇ及び３５％ホルムアルデヒド水溶液１８３．８g（２．１４モル）を使用した以外は、製造例１と同様に反応し、蒸留処理を行い成分（Ｂ）とは異なる組成物（Ｂ’－２）を得た。
　得られた組成物（Ｂ’－２）のＧＰＣ測定の結果、成分（Ｂ１）の含有量は１３．３面積％（４０面積％未満）、成分（Ｂ２）の含有量は１２．２面積％、成分（Ｂ３）の含有量が９．９面積％、成分（Ｂ４）の含有量６４．６面積％であった。
　ＨＰＬＣ測定による成分（Ｂ１）の構成は、化合物（１）が７．４面積％、化合物（２）が５．７面積％、化合物（３）が１．１面積％であった。 <Production Example 2>
The reaction was carried out in the same manner as in Production Example 1, except that 303.2 g (3.22 mol) of phenol, 2.43 g of a 10% aqueous oxalic acid solution, and 183.8 g (2.14 mol) of a 35% aqueous formaldehyde solution were used, and distillation treatment was carried out to obtain a composition (B'-2) different from component (B).
As a result of GPC measurement of the obtained composition (B'-2), the content of component (B1) was 13.3 area % (less than 40 area %), the content of component (B2) was 12.2 area %, the content of component (B3) was 9.9 area %, and the content of component (B4) was 64.6 area %.
The composition of component (B1) as determined by HPLC was 7.4 area % of compound (1), 5.7 area % of compound (2), and 1.1 area % of compound (3).
＜製造例３＞
　コンデンサー、撹拌機、温度計を備えた４つ口フラスコに、フェノール３２２８．０ｇ、水３８８．８ｇ及び１０％シュウ酸水溶液２１．４ｇを仕込み、７０℃に昇温した後に３５％ホルムアルデヒド水溶液６５３．４ｇを、５分以内で添加した。添加終了後、９０℃に昇温し、６．０時間撹拌を続けた。反応終了後、８０℃、４７ｋＰａの条件で蒸留を開始し、１１．５時間かけて内温１４５℃（３ｋＰａ）まで昇温し、３時間保持したところ、フェノールの留出が停止した。その後、１４５℃、１４ｋＰａで水を滴下し、残存フェノールの除去を行った。その後に１５５℃、１ｋＰａで１時間保持して、水を除去した後、残液として成分（Ｂ）の組成物（Ｂ－１）を得た。
　得られた組成物（Ｂ－１）のＧＰＣ測定の結果、成分（Ｂ１）の含有量は５６．７面積％、成分（Ｂ２）の含有量は２５．０面積％、成分（Ｂ３）の含有量が１０．５面積％、成分（Ｂ４）の含有量７．８面積％であった。
　ＨＰＬＣ測定による成分（Ｂ１）の構成は、化合物（１）が２０．９面積％、化合物（２）が２６．６面積％、化合物（３）が６．７面積％であった。
　また、ＧＰＣ測定によるポリスチレン換算分子量は、成分（Ｂ１）が３１３、成分（Ｂ２）が４５７、成分（Ｂ３）が５９３であった。 <Production Example 3>
A four-neck flask equipped with a condenser, a stirrer, and a thermometer was charged with 3228.0 g of phenol, 388.8 g of water, and 21.4 g of a 10% aqueous oxalic acid solution, and the temperature was raised to 70 ° C., and 653.4 g of a 35% aqueous formaldehyde solution was added within 5 minutes. After the addition was completed, the temperature was raised to 90 ° C., and stirring was continued for 6.0 hours. After the reaction was completed, distillation was started under conditions of 80 ° C. and 47 kPa, and the internal temperature was raised to 145 ° C. (3 kPa) over 11.5 hours, and when it was held for 3 hours, the distillation of phenol stopped. Thereafter, water was dropped at 145 ° C. and 14 kPa to remove the remaining phenol. After that, it was held at 155 ° C. and 1 kPa for 1 hour, and after removing the water, a composition (B-1) of component (B) was obtained as the residual liquid.
As a result of GPC measurement of the obtained composition (B-1), the content of component (B1) was 56.7 area %, the content of component (B2) was 25.0 area %, the content of component (B3) was 10.5 area %, and the content of component (B4) was 7.8 area %.
The composition of component (B1) as determined by HPLC was 20.9 area % of compound (1), 26.6 area % of compound (2), and 6.7 area % of compound (3).
The polystyrene-equivalent molecular weights measured by GPC were 313 for component (B1), 457 for component (B2), and 593 for component (B3).
＜製造例４＞
　フェノール４０５１重量部、水１４２.７重量部、１０％シュウ酸水溶液１７．４重量部及び３５％ホルムアルデヒド水溶液１２５ｇを用いた以外は、製造例３と同様に反応を行い、蒸留処理を行い成分（Ｂ）とは異なる組成物（Ｂ’－３）を得た。
　得られた組成物（Ｂ’－３）のＧＰＣ測定の結果、成分（Ｂ１）の２核体含有量は９０．６面積％（７０面積％超）、成分（Ｂ２）の含有量は、９．４面積％であり、成分（Ｂ３）及び成分（Ｂ４）は検出されなかった。
　ＨＰＬＣ測定による成分（Ｂ１）の構成、化合物（１）が３１．２面積％、化合物（２）が４３．９面積％、化合物（３）が１５．２面積％であった。 <Production Example 4>
A reaction was carried out in the same manner as in Production Example 3, except that 4,051 parts by weight of phenol, 142.7 parts by weight of water, 17.4 parts by weight of a 10% aqueous oxalic acid solution, and 125 g of a 35% aqueous formaldehyde solution were used, and a distillation treatment was carried out to obtain a composition (B'-3) different from component (B).
As a result of GPC measurement of the obtained composition (B'-3), the binuclear content of component (B1) was 90.6 area % (more than 70 area %), the content of component (B2) was 9.4 area %, and components (B3) and (B4) were not detected.
The composition of component (B1) as determined by HPLC was 31.2 area % of compound (1), 43.9 area % of compound (2), and 15.2 area % of compound (3).
＜製造例５＞
　コンデンサー、撹拌機、温度計を備えた４つ口フラスコに、フェノール４９３．７ｇ（５．２４モル）及び１０％シュウ酸水溶液２．８９ｇを仕込み、７０℃に昇温した後に、３５％ホルムアルデヒド水溶液８４．４ｇ（０．９９モル）を、５分以内で添加した。添加終了後、９０℃に昇温し、６時間撹拌を続けた。反応終了後、８０℃、４７ｋＰａの条件で蒸留を開始し、３．５時間かけて内温１４５℃（３ｋＰａ）まで昇温し、３時間保持したところ、フェノールの留出が停止した。その後、１４５℃、１４ｋＰａで水を滴下し、残存フェノールの除去を行った。その後、１５５℃、１ｋＰａで１時間保持し、水を除去して、残液としての成分（Ｂ）の組成物（Ｂ－２）を得た。
　得られた組成物（Ｂ－２）のＧＰＣ測定の結果、成分（Ｂ１）の含有量は６２．０面積％、成分（Ｂ２）の含有量は２４．５面積％、成分（Ｂ３）の含有量が８．４面積％、成分（Ｂ４）の含有量５．１面積％であった。
　ＨＰＬＣ測定による成分（Ｂ１）の構成は、化合物（１）が２２．１面積％、化合物（２）が３０．６面積％、化合物（３）が８．５面積％であった。
　また、ＧＰＣ測定によるポリスチレン換算分子量は、成分（Ｂ１）が３２４、成分（Ｂ２）が４７４、成分（Ｂ３）が６１１であった。 <Production Example 5>
A four-neck flask equipped with a condenser, a stirrer, and a thermometer was charged with 493.7 g (5.24 mol) of phenol and 2.89 g of a 10% aqueous oxalic acid solution, and the temperature was raised to 70 ° C., and then 84.4 g (0.99 mol) of a 35% aqueous formaldehyde solution was added within 5 minutes. After the addition was completed, the temperature was raised to 90 ° C., and stirring was continued for 6 hours. After the reaction was completed, distillation was started under conditions of 80 ° C. and 47 kPa, and the internal temperature was raised to 145 ° C. (3 kPa) over 3.5 hours, and when it was held for 3 hours, the distillation of phenol stopped. Thereafter, water was dropped at 145 ° C. and 14 kPa to remove the remaining phenol. Thereafter, it was held at 155 ° C. and 1 kPa for 1 hour, and the water was removed, and a composition (B-2) of component (B) was obtained as a residual liquid.
As a result of GPC measurement of the obtained composition (B-2), the content of component (B1) was 62.0 area %, the content of component (B2) was 24.5 area %, the content of component (B3) was 8.4 area %, and the content of component (B4) was 5.1 area %.
The composition of component (B1) as determined by HPLC was 22.1 area % of compound (1), 30.6 area % of compound (2), and 8.5 area % of compound (3).
The polystyrene-equivalent molecular weights measured by GPC were 324 for component (B1), 474 for component (B2), and 611 for component (B3).
＜製造例６＞
　製造例１で得られた混合物１．００ｇに製造例４で得られた組成物（Ｂ’－３）１．２５ｇを加えて段階的に１３０～１８０℃に加熱して溶融させた後、冷却し、成分（Ｂ）とは異なる組成物（Ｂ’－４）を得た。
　得られた組成物（Ｂ’－４）のＧＰＣ測定の結果、成分（Ｂ１）の含有量が７５．３面積％、成分（Ｂ２）の含有量が１５．５％、成分（Ｂ３）の含有量が５．５％、成分（Ｂ４）の含有量が、３．７％であった。 <Production Example 6>
1.25 g of composition (B'-3) obtained in Production Example 4 was added to 1.00 g of the mixture obtained in Production Example 1, and the mixture was gradually heated to 130 to 180°C to melt, and then cooled to obtain composition (B'-4) which is different from component (B).
As a result of GPC measurement of the obtained composition (B'-4), the content of component (B1) was 75.3 area %, the content of component (B2) was 15.5%, the content of component (B3) was 5.5%, and the content of component (B4) was 3.7%.
＜実施例１＞
　１０ｍＬサンプル管に市販レゾール型フェノール樹脂（住友ベークライト株式会社製）を０．９ｇ加え、そこに製造例３で得られた成分（Ｂ１）の含有量が５６．７面積％の成分（Ｂ）の組成物（Ｂ－１）を０．１ｇ加えた。このサンプル管をオイルバス内において９０℃で１０分間撹拌しながら加熱して混合した。混合した組成物を室温まで冷却した後、１７０℃で１０分間加熱することで、硬化物を得た。
　得られた硬化物のＴｄ５％を測定した。
　なお、使用した市販レゾール型フェノール樹脂は、ＧＰＣ測定より、数平均分子量（Ｍｎ）９６０であり、重量平均分子量（Ｍｗ）１６，０００であることが確認された。 Example 1
0.9 g of a commercially available resol type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd.) was added to a 10 mL sample tube, and 0.1 g of composition (B-1) of component (B) with a content of component (B1) of 56.7 area % obtained in Production Example 3 was added thereto. This sample tube was heated in an oil bath at 90°C for 10 minutes while stirring and mixed. The mixed composition was cooled to room temperature and then heated at 170°C for 10 minutes to obtain a cured product.
The Td5% of the resulting cured product was measured.
The commercially available resol type phenolic resin used was confirmed by GPC measurement to have a number average molecular weight (Mn) of 960 and a weight average molecular weight (Mw) of 16,000.
＜実施例２＞
　１８０℃で硬化させた以外は実施例１と同様に加熱して、硬化物を得た。
　得られた硬化物のＴｄ５％を測定した。 Example 2
A cured product was obtained by heating in the same manner as in Example 1, except that the curing temperature was 180°C.
The Td5% of the resulting cured product was measured.
＜実施例３＞
　成分（Ｂ１）の含有量が５６．７面積％の成分（Ｂ）の組成物（Ｂ－１）を０．１ｇ加える代わりに、製造例５で得られた成分（Ｂ１）の含有量が６２．０面積％の成分（Ｂ）の組成物（Ｂ－２）を０．１ｇ加えた以外は実施例２と同様に加熱して、硬化物を得た。
　得られた硬化物のＴｄ５％を測定した。 Example 3
A cured product was obtained by heating in the same manner as in Example 2, except that 0.1 g of composition (B-2) of component (B) containing 62.0 area % of component (B1) obtained in Production Example 5 was added instead of adding 0.1 g of composition (B-1) of component (B) containing 56.7 area % of component (B1).
The Td5% of the resulting cured product was measured.
＜実施例４＞
　２００℃で硬化させた以外は実施例１と同様に加熱して、硬化物を得た。
　得られた硬化物のＴｄ５％を測定した。 Example 4
A cured product was obtained by heating in the same manner as in Example 1, except that the curing temperature was 200°C.
The Td5% of the resulting cured product was measured.
＜比較例１～３＞
　実施例１と同じ市販レゾール型フェノール樹脂を１．０ｇ使用し、成分（Ｂ）の組成物を添加せず、１７０℃（比較例１）、１８０℃（比較例２）、２００℃（比較例３）の各温度で硬化させた以外は、実施例１と同様に加熱して、硬化物を得た。
　得られた各硬化物のＴｄ５％を測定した。 <Comparative Examples 1 to 3>
1.0 g of the same commercially available resol-type phenolic resin as in Example 1 was used, and cured products were obtained by heating in the same manner as in Example 1, except that the composition of component (B) was not added and curing was carried out at temperatures of 170° C. (Comparative Example 1), 180° C. (Comparative Example 2), and 200° C. (Comparative Example 3).
The Td5% of each of the resulting cured products was measured.
＜比較例４＞
　成分（Ｂ１）の含有量が５６．７％の成分（Ｂ）の組成物（Ｂ－１）を０．１ｇ加える代わりに、製造例１で得られた成分（Ｂ１）の含有量が３２．７％である組成物（Ｂ’－１）を０．１ｇ加えた以外は実施例１と同様に加熱して、硬化物を得た。
　得られた硬化物のＴｄ５％を測定した。 <Comparative Example 4>
A cured product was obtained by heating in the same manner as in Example 1, except that 0.1 g of composition (B'-1) obtained in Production Example 1, which had a component (B1) content of 32.7%, was added instead of adding 0.1 g of composition (B-1) of component (B) containing 56.7% of component (B1).
The Td5% of the resulting cured product was measured.
＜比較例５＞
　成分（Ｂ１）の含有量が５６．７％の成分（Ｂ）の組成物（Ｂ－１）を０．１ｇ加える代わりに、製造例２で得られた成分（Ｂ１）の含有量が１３．３％である組成物（Ｂ’－２）を０．１ｇ加えた以外は実施例１と同様に加熱して、硬化物を得た。
　得られた硬化物のＴｄ５％を測定した。 <Comparative Example 5>
A cured product was obtained by heating in the same manner as in Example 1, except that 0.1 g of composition (B'-2) obtained in Production Example 2, which had a component (B1) content of 13.3%, was added instead of adding 0.1 g of composition (B-1) of component (B) containing 56.7% of component (B1).
The Td5% of the resulting cured product was measured.
＜比較例６＞
　成分（Ｂ１）の含有量が５６．７％の成分（Ｂ）の組成物（Ｂ－１）を０．１ｇ加える代わりに、製造例６で得られた成分（Ｂ１）の含有量が７５．３％である組成物（Ｂ’－４）を０．１ｇ加えた以外は実施例１と同様に加熱して、硬化物を得た。
　得られた硬化物のＴｄ５％を測定した。 <Comparative Example 6>
A cured product was obtained by heating in the same manner as in Example 1, except that 0.1 g of composition (B'-4) obtained in Production Example 6, which had a component (B1) content of 75.3%, was added instead of adding 0.1 g of composition (B-1) of component (B) containing 56.7% of component (B1).
The Td5% of the resulting cured product was measured.
＜比較例７＞
　成分（Ｂ１）の含有量が５６．７％の成分（Ｂ）の組成物（Ｂ－１）を０．１ｇ加える代わりに、製造例６で得られた成分（Ｂ１）の含有量が７５．３％である組成物（Ｂ’－４）を０．１ｇ加え、硬化温度を１８０℃とする以外は実施例１と同様に加熱して、硬化物を得た。
　得られた硬化物のＴｄ５％を測定した。 <Comparative Example 7>
Instead of adding 0.1 g of composition (B-1) of component (B) containing 56.7% of component (B1), 0.1 g of composition (B'-4) obtained in Production Example 6 containing 75.3% of component (B1) was added, and the mixture was heated in the same manner as in Example 1, except that the curing temperature was 180°C, to obtain a cured product.
The Td5% of the resulting cured product was measured.
＜比較例８＞
　実施例と同様に１０ｍＬサンプル管に市販レゾール型フェノール樹脂（住友ベークライト株式会社製）を０．９ｇ加え、そこに製造例４で得られた、成分（Ｂ１）の含有量が９０．６面積％の組成物（Ｂ’－３）を０．１ｇ加えた。このサンプル管をオイルバス内において９０℃で１０分間撹拌しながら加熱して混合した。混合した組成物を室温まで冷却したところ結晶が析出した。
　本発明の成分（Ｂ）において、成分（Ｂ１）が多すぎると、レゾール型フェノール樹脂との相溶性が低下し、保存安定性が低下した。
　一方、成分（Ｂ１）の含有量が４０面積％以上７０面積％以下である本発明の成分（Ｂ）を用いる実施例１～３は、成分（Ａ）のレゾール型フェノール樹脂と成分（Ｂ）との相溶性が良好であり、冷却後も均一に混合したままで保存安定性が良好であった。 <Comparative Example 8>
As in the examples, 0.9 g of a commercially available resol type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd.) was added to a 10 mL sample tube, and 0.1 g of composition (B'-3) obtained in Production Example 4, in which the content of component (B1) was 90.6 area %, was added thereto. This sample tube was heated in an oil bath at 90°C for 10 minutes while stirring and mixed. When the mixed composition was cooled to room temperature, crystals were precipitated.
In the component (B) of the present invention, if the amount of the component (B1) is too large, the compatibility with the resol type phenolic resin decreases, and the storage stability decreases.
On the other hand, in Examples 1 to 3 using the component (B) of the present invention in which the content of component (B1) is 40 area % or more and 70 area % or less, the compatibility between the resol type phenolic resin of component (A) and component (B) was good, and the mixture remained uniformly mixed even after cooling, and the storage stability was good.
＜比較例９＞
　混合した組成物を冷却せず、１７０℃で１０分間加熱することで、硬化物を得た以外は、比較例８と同様に組成物を作成した。得られた硬化物のＴｄ５％を測定した結果、３６６℃であった。 <Comparative Example 9>
A composition was prepared in the same manner as in Comparative Example 8, except that the mixed composition was heated at 170° C. for 10 minutes without cooling to obtain a cured product. The Td5% of the obtained cured product was measured and found to be 366° C.
　上記実施例１～４及び比較例１～７の硬化物について、成分（Ｂ１）の含有量（面積％）、硬化温度、Ｔｄ５％を下記表１にまとめて示す。
 The content (area %) of component (B1), curing temperature, and Td5% for the cured products of Examples 1 to 4 and Comparative Examples 1 to 7 are summarized in Table 1 below.
　表１中の実施例１と比較例１、４～６、９、実施例２、３と比較例２、７、実施例４と比較例３の結果より、成分（Ｂ１）を特定量含有する本発明の硬化性組成物（実施例１～４）は、同じ温度条件で硬化した場合において、得られた硬化物の５％重量減少温度（Ｔｄ）が高く、耐熱性が大きく向上することが確認された。
　表１に示すとおり、本発明の硬化性組成物は、従来公知のレゾール型フェノール樹脂に比べて、低温で硬化し得ることが明らかとなった。これにより、本発明の硬化性組成物は、硬化性樹脂の成型プロセスにおける温度を下げることができ、加熱及び冷却の時間短縮や省エネルギー化による効率化が可能であるほか、熱に弱い材料（基材）にも使用できるので非常に有用であることも明らかとなった。 From the results of Example 1 and Comparative Examples 1, 4 to 6, and 9, Examples 2 and 3 and Comparative Examples 2 and 7, and Example 4 and Comparative Example 3 in Table 1, it was confirmed that the curable compositions of the present invention (Examples 1 to 4) containing a specific amount of component (B1) have high 5% weight loss temperatures (Td) of the obtained cured products and significantly improved heat resistance when cured under the same temperature conditions.
As shown in Table 1, it was revealed that the curable composition of the present invention can be cured at a lower temperature than the conventionally known resol-type phenolic resins. This makes it possible to lower the temperature in the molding process of the curable resin, thereby enabling efficiency improvement through shortening the heating and cooling time and saving energy, and it is also clarified that the curable composition of the present invention is very useful because it can be used for materials (substrates) that are sensitive to heat.
＜実施例５＞
　市販レゾール型フェノール樹脂（住友ベークライト株式会社製）０．９ｇと、製造例３で得られた成分（Ｂ１）の含有量が５６．７面積％の成分（Ｂ）の組成物（Ｂ－１）０．１ｇとを、実施例１と同様に混合して、冷却した。得られた混合物は、示差走査熱量測定装置を用いて、上記測定条件により測定した。 Example 5
0.9 g of a commercially available resol type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd.) and 0.1 g of the composition (B-1) of component (B) obtained in Production Example 3, in which the content of component (B1) was 56.7 area %, were mixed and cooled in the same manner as in Example 1. The obtained mixture was measured using a differential scanning calorimeter under the above-mentioned measurement conditions.
＜比較例１０＞
　市販レゾール型フェノール樹脂（住友ベークライト株式会社製）を、示差走査熱量測定装置を用いて、上記測定条件により測定した。 <Comparative Example 10>
A commercially available resol type phenolic resin (manufactured by Sumitomo Bakelite Co., Ltd.) was measured using a differential scanning calorimeter under the above measurement conditions.
　実施例５と比較例１０の示差走査熱量測定（ＤＳＣ）曲線を、実施例５を実線で、比較例１０は点線で図１に示す。図１中の実線横矢印及び点線横矢印において、左端が硬化開始温度、右端が硬化終了温度を示す。
　図１中の実線横矢印及び点線横矢印が示すとおり、成分（Ｂ１）を特定量含有する本発明の硬化性組成物（実施例５）は、従来公知のレゾール型フェノール樹脂（比較例１０）に比べて、同じ測定条件で昇温した結果、硬化開始温度は同じでも硬化終了温度が低く、短時間で硬化が完了することが明らかとなった。
　示差走査熱量測定（ＤＳＣ）により、実施例５の発熱量（ΔＨ）は１９２Ｊ／ｇ、ピークトップ温度は２００℃であり、比較例１０の発熱量（ΔＨ）は２１６Ｊ／ｇ、ピークトップ温度は２０２℃であった。
　この結果より、本発明の硬化性組成物は、従来公知のレゾール型フェノール樹脂に比べて、短時間で、少ない発熱量で硬化完了することが明らかとなった。これにより、本発明の硬化性組成物は、加熱及び冷却の時間短縮や省エネルギー化による効率化が可能であり、非常に有用であることも明らかとなった。
 
  Differential scanning calorimetry (DSC) curves of Example 5 and Comparative Example 10 are shown in Figure 1, with a solid line for Example 5 and a dotted line for Comparative Example 10. In Figure 1, the left end of the solid horizontal arrow and the dotted horizontal arrow indicate the curing start temperature and the right end of the curing end temperature.
As shown by the solid horizontal arrow and the dotted horizontal arrow in FIG. 1, when the curable composition of the present invention (Example 5) containing a specific amount of component (B1) was heated under the same measurement conditions as a conventionally known resol-type phenolic resin (Comparative Example 10), it was found that although the curing initiation temperature was the same, the curing end temperature was lower and curing was completed in a shorter time.
By differential scanning calorimetry (DSC), Example 5 had a calorific value (ΔH) of 192 J/g and a peak top temperature of 200°C, while Comparative Example 10 had a calorific value (ΔH) of 216 J/g and a peak top temperature of 202°C.
From these results, it was revealed that the curable composition of the present invention can be cured in a short time with less heat generation compared to the conventionally known resol-type phenolic resins, and therefore the curable composition of the present invention can be highly useful because it can reduce the heating and cooling time and save energy.

Claims (4)

  1. 　下記成分（Ａ）及び、下記成分（Ｂ）を、含有する硬化性組成物：
    　成分（Ａ）　レゾール型フェノール樹脂、
    　成分（Ｂ）　下記化合物（１）、化合物（２）及び化合物（３）からなる成分（Ｂ１）を含み、成分（Ｂ１）の合計量が示差屈折計を検出器とするゲル浸透クロマトグラフィーによる測定により、検出される全ての成分の全量に対して４０面積％以上７０面積％以下の範囲で含有する組成物。
     A curable composition comprising the following component (A) and the following component (B):
    Component (A) resol type phenolic resin,
    Component (B): A composition comprising component (B1) consisting of the following compounds (1), (2), and (3), wherein the total amount of component (B1) is in the range of 40 area % or more and 70 area % or less based on the total amount of all components detected by gel permeation chromatography using a differential refractometer as a detector:
  2. 　請求項１に記載の硬化性組成物を硬化させてなる硬化物。 A cured product obtained by curing the curable composition according to claim 1.
  3. 　下記成分（Ｂ）を含有する、レゾール型フェノール樹脂用硬化剤：
    　成分（Ｂ）　下記化合物（１）、化合物（２）及び化合物（３）からなる成分（Ｂ１）を含み、成分（Ｂ１）の合計量が示差屈折計を検出器とするゲル浸透クロマトグラフィーによる測定により、検出される全ての成分の全量に対して４０面積％以上７０面積％以下の範囲で含有する組成物。
     A curing agent for resol-type phenolic resins, comprising the following component (B):
    Component (B): A composition comprising component (B1) consisting of the following compounds (1), (2), and (3), wherein the total amount of component (B1) is in the range of 40 area % or more and 70 area % or less based on the total amount of all components detected by gel permeation chromatography using a differential refractometer as a detector:
  4. 　請求項１に記載の硬化性組成物を含有する接着剤。
          An adhesive comprising the curable composition according to claim 1.
PCT/JP2023/021900 2022-11-01 2023-06-13 Curable composition WO2024095521A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3870670A (en) * 1972-06-19 1975-03-11 Reichhold Albert Chemie Ag Process for the manufacture of dispersions of thermosetting reaction products
JP2003286387A (en) * 2002-03-28 2003-10-10 Sumitomo Bakelite Co Ltd Resin composition, prepreg and paper base phenolic resin laminate
JP2005154613A (en) * 2003-11-27 2005-06-16 Sumitomo Bakelite Co Ltd Liquid phenol resin composition

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3870670A (en) * 1972-06-19 1975-03-11 Reichhold Albert Chemie Ag Process for the manufacture of dispersions of thermosetting reaction products
JP2003286387A (en) * 2002-03-28 2003-10-10 Sumitomo Bakelite Co Ltd Resin composition, prepreg and paper base phenolic resin laminate
JP2005154613A (en) * 2003-11-27 2005-06-16 Sumitomo Bakelite Co Ltd Liquid phenol resin composition

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