One-pack type composition, furan resin cured product and kit

Abstract

To provide a one-pack type composition which enables production of a furan resin cured product that is curable in a short time and has excellent heat resistance and electric characteristics, a furan resin cured product, and a kit which enables production of the furan resin cured product.SOLUTION: A one-pack type composition contains a furan resin, an acid scavenger, and an acid catalyst, wherein the acid scavenger contains an epoxy resin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a one-part composition, a cured furan resin, and a kit. [Background technology]

[0002] Furan resins have high heat resistance and are therefore widely used as sand binders to form molds for foundries.

[0003] Furan resin is known as a biomass resin made primarily from non-edible plants such as corn cobs, bagasse, and rice husks, and is attracting attention as a sustainable, non-petroleum-derived resource with a low environmental impact.

[0004] However, furan resin has the property of undergoing runaway chemical reactions and polycondensation, and is prone to trapping air bubbles during the curing process, making it difficult to mold into a resin with excellent electrical properties.

[0005] To obtain a resin molded product with excellent electrical properties using a furan resin, it is necessary to carry out polycondensation while suppressing runaway reactions. Specifically, one method involves gradually curing the resin over a long period of time. However, in the mass production of industrial products, the long curing time required leads to a decrease in productivity, and therefore this method tends to be avoided.

[0006] For this reason, it is difficult to use furan resin in the same applications as other cured resins, and it has only been put to practical use in limited applications such as sand binders for molds where the generation of bubbles is not a problem.

[0007] For example, Patent Document 1 discloses a thermosetting furan resin composition containing a furan resin, a curing catalyst, and a curing accelerator, wherein the curing accelerator contains one metal salt or a mixture of two or more metal salts selected from the group consisting of cobalt, nickel, copper, and zinc. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-108059 Summary of the Invention [Problem to be solved by the invention]

[0009] The present inventors have conducted extensive research to broaden the applications of cured furan resins by taking advantage of the inherently high heat resistance of the cured furan resins. Resins (cured products) used in electronic components such as power semiconductors are required to have higher heat resistance and electrical properties as the performance of the electronic components improves, and at the same time, they are also required to have excellent handleability during operation (manufacturing).

[0010] Although cured furan resins are widely known for their high heat resistance, they require long curing times to improve their electrical properties, making them unsuitable for practical use. When using resins in electronic components, there is a demand for resins that can satisfy electrical properties with short curing times in order to minimize damage to electronic components caused by heat.

[0011] An object of the present disclosure is to provide a one-component composition that can be cured in a short time and that can produce a cured furan resin product having excellent heat resistance and electrical properties, a cured furan resin product, and a kit that can produce the cured furan resin product. [Means for solving the problem]

[0012] The present inventors have conducted extensive research to solve the above-mentioned problems and have found that a specific one-component composition containing a furan resin can be cured in a short time and can give a cured furan resin product having excellent heat resistance and electrical properties, and that a cured furan resin product having excellent heat resistance and electrical properties is obtained from a specific raw material composition containing a furan resin, and a kit capable of giving the cured furan resin product, thereby completing the present disclosure.

[0013] An example aspect of this embodiment is described as follows.

[0014] [1] A one-component composition comprising a furan resin, an acid scavenger, and an acid catalyst, wherein the acid scavenger comprises an epoxy resin. [2] The one-component composition according to [1], wherein the amount of cations derived from the acid catalyst is equal to or less than the amount of acid-capturing moieties contained in the acid-capturing agent. [3] The one-component composition according to [1] or [2], wherein the viscosity increase rate after 24 hours when stored at 25°C after preparation is 100% or less. [4] The one-component composition according to any one of [1] to [3], wherein the viscosity increase rate after 24 hours when stored at 40°C after preparation is 100% or less. [5] A cured furan resin, which is a cured product of a raw material composition containing a furan resin, an acid scavenger, and an acid catalyst, wherein the acid scavenger contains an epoxy resin. [6] The cured furan resin according to [5], wherein in the raw material composition, the amount of cations derived from the acid catalyst is equal to or less than the amount of acid-capturing moieties contained in the acid scavenger. [7] The cured furan resin according to [5] or [6], having a relative dielectric constant of 5.0εr or less and a dielectric dissipation factor of 0.1 or less at 1 MHz. [8] Volume resistivity is 1.0 × 10 13 The cured furan resin according to any one of [5] to [7], having a resistivity of Ω·cm or more. [9] The cured furan resin according to any one of [5] to [8], which has a dielectric breakdown voltage of 7 kV or more and a dielectric breakdown strength of 3 kV / mm or more.

[10] A kit comprising a first agent containing a furan resin and a second agent containing an acid scavenger and an acid catalyst. [Effects of the Invention]

[0015] The present disclosure makes it possible to provide a one-component composition that can be cured in a short time and that can produce a cured furan resin product having excellent heat resistance and electrical properties, a cured furan resin product, and a kit that can produce the cured furan resin product. DETAILED DESCRIPTION OF THE INVENTION

[0016] The one-component composition, the cured furan resin, and the kit according to this embodiment will be described in detail below.

[0017] One aspect of this embodiment is a one-component composition comprising a furan resin, an acid scavenger, and an acid catalyst, wherein the acid scavenger comprises an epoxy resin. By including the acid scavenger and the acid catalyst, the one-component composition of this embodiment suppresses runaway chemical reactions that occur when the furan resin comes into contact with the acid catalyst, enabling polycondensation at an appropriate rate. Furthermore, because the one-component composition is a one-component composition, it is also easy to handle. By polycondensing the one-component composition, a cured furan resin of this embodiment can be obtained.

[0018] One aspect of this embodiment is a cured product of a raw material composition containing a furan resin, an acid scavenger, and an acid catalyst, wherein the acid scavenger contains an epoxy resin. The cured furan resin of this embodiment has excellent heat resistance and electrical properties, and therefore can be used in various applications such as components for constituting electronic components including power semiconductors.

[0019] One aspect of this embodiment is a kit containing a first part containing a furan resin and a second part containing an acid scavenger and an acid catalyst. By mixing the first and second parts of the kit of this embodiment, the one-component composition of this embodiment can be obtained, and by polycondensation, the cured furan resin of this embodiment can be obtained.

[0020] This embodiment will be described in detail below.

[0021] (Furan resin) In the present disclosure, the furan resin may be a resin obtained by polymerizing a monomer containing furfuryl alcohol, for example, by polycondensation such as dehydration condensation. Because the monomers constituting the furan resin are highly reactive, other reactions such as intramolecular Diels-Alder reaction, ene reaction, or Michael addition reaction may occur during, before, or after the polycondensation. As a result of such reactions, the furan resin may have a three-dimensional crosslinked structure. The furan resin may be a polymer consisting solely of furfuryl alcohol-derived structural units as monomer units, or a copolymer having furfuryl alcohol-derived structural units and structural units derived from other monomers. Examples of other monomers include aldehydes, urea, ethylene urea, melamine, and phenols, and these may be used alone or in combination of two or more. The furan resin used is one that cures by dehydration condensation in the presence of an acid catalyst.

[0022] In one preferred embodiment, the furan resin is one or more resins selected from the group consisting of a condensate of furfuryl alcohol (polyfurfuryl alcohol), a condensate of furfuryl alcohol and an aldehyde, a condensate of furfuryl alcohol and urea, a condensate of furfuryl alcohol, urea and an aldehyde, a condensate of furfuryl alcohol and ethylene urea, a condensate of furfuryl alcohol, ethylene urea and an aldehyde, a condensate of furfuryl alcohol and melamine, a condensate of furfuryl alcohol, melamine and an aldehyde, and a condensate of furfuryl alcohol, a phenol and an aldehyde.

[0023] Examples of the aldehydes include formaldehyde, acetaldehyde, glyoxal, furfural, terephthalaldehyde, hydroxymethylfurfural, etc., and one or more of these aldehydes can be used. From the viewpoint of availability, it is preferable to use formaldehyde.

[0024] Examples of the phenols include phenol, cresol, resorcinol, bisphenol A, bisphenol C, bisphenol E, and bisphenol F, and one or more of these phenols can be used.

[0025] The furan resin may have a hydroxyl group in the molecule or at the end of the molecule substituted with an ester, an ether, etc. For example, the furan resin of the present disclosure also includes modified furan resins such as an esterified furan resin obtained by condensing a hydroxyl group of a furan resin with a carboxylic acid, and an epoxidized furan resin in which epichlorohydrin is added to a hydroxyl group of a furan resin.

[0026] The furan resin can be produced by a known method, and a commercially available product may be used. The furan resin is not particularly limited in terms of molecular weight, molecular weight distribution, molecular chain length, steric structure, etc. One type of furan resin may be used alone, or two or more types may be used in combination.

[0027] The furan resin may be liquid or solid, but in the case of a solid, a furan resin is used that can be dispersed in, for example, an epoxy resin to form a one-liquid composition as a whole. A typical example of obtaining a furfuryl alcohol condensate (polyfurfuryl alcohol) from furfuryl alcohol is shown in the following general formula (I).

[0028] [ka]

[0029] In the general formula (I), n is preferably 1 to 1000, more preferably 2 to 100. R is not particularly limited, and may have any carbon atom side chain such as H, ether, or ester bonded thereto, or any side chain such as Si, S, or N bonded thereto.

[0030] (acid scavenger) In the present disclosure, the acid scavenger is a component capable of suppressing an explosive reaction of the furan resin by temporarily capturing at least a portion of the acid catalyst. In the present disclosure, the acid scavenger includes an epoxy resin. The epoxy resin is capable of undergoing polycondensation together with the furan resin in the presence of an acid catalyst and is a component that contributes to improving the physical properties of a cured product of the furan resin.

[0031] The acid scavenger may contain an acid scavenger other than the epoxy resin, such as an amine, oxetane, or episulfide. As described in detail below, the ratio of the epoxy resin to the acid scavenger other than the epoxy resin in the acid scavenger is not limited as long as the amount of cations derived from the acid catalyst is equal to or less than the amount of acid scavenger moieties contained in the acid scavenger, i.e., the sum of the amount of acid scavenger moieties contained in the epoxy resin and the amount of acid scavenger moieties contained in the acid scavenger other than the epoxy resin. The proportion of epoxy resin in 100 parts by mass of the acid scavenger is not particularly limited, but is typically 50 parts by mass or more, preferably 60 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more. For example, the acid scavenger is a mixture containing an epoxy resin and an amine. For example, the acid scavenger is a mixture containing an epoxy resin and an oxetane. For example, the acid scavenger is a mixture containing an epoxy resin and an episulfide. For example, the acid scavenger is a mixture containing an epoxy resin, an oxetane, and an amine. For example, the acid scavenger is a mixture containing an epoxy resin, an oxetane, an amine, and an episulfide. The acid scavenger may be substantially free of acid scavengers other than the epoxy resin. "Substantially free" means that the amount of acid scavengers other than the epoxy resin is 1 part by mass or less per 100 parts by mass of the acid scavenger. The acid scavenger is, for example, an epoxy resin.

[0032] Epoxy resins are not particularly limited as long as they contain one or more epoxy groups in the molecule, for example, one (monofunctional epoxy resin), two (difunctional epoxy resin), three, or four or more (multifunctional epoxy resin). Epoxy resins are classified based on the adjacent group of the epoxy group, including glycidyl ether epoxy resins, glycidyl ester epoxy resins such as diglycidyl phthalate, glycidyl amine epoxy resins, glycidyl amide-imide epoxy resins, alicyclic epoxy resins, and phenol novolac epoxy resins. Epoxy resins are classified based on the skeleton, including bisphenol skeletons (e.g., bisphenol A, B, C, E, F, G, M, S, or Z skeleton epoxy resins), naphthalene skeleton epoxy resins, phenoxy skeleton epoxy resins, biphenyl skeleton epoxy resins, and fatty acid (oil-derived) skeleton epoxy resins. In one preferred embodiment, the epoxy resin may be a glycidyl ether-type epoxy resin such as ethylene glycol diglycidyl ether, a bisphenol A-type epoxy resin, a cresol novolac-type epoxy resin, a glycidyl amine-type epoxy resin, an alicyclic epoxy resin, a saturated or unsaturated fatty acid glycidyl, an epoxidized unsaturated fatty acid, or an epoxidized terpene. In one preferred embodiment, the epoxy resin is an alicyclic epoxy resin, which can easily undergo cationic polymerization in the presence of an acid catalyst, from the viewpoint of polymerization properties. An alicyclic epoxy resin is a general term for epoxy resins having a cycloalkane structure. Examples of epoxidized terpenes include isophorone oxide, carveol oxide, carveol dioxide, and limonene dioxide (Celloxide 3000). Examples of saturated and unsaturated fatty acid glycidyls and epoxidized unsaturated fatty acids include glycidyl fatty acid (dimer acid), glycidyl fatty acid (monocarboxylic acid), epoxidized unsaturated fatty acids, glycidyl linoleate, glycidyl oleate, glycidyl palmitate, glycidyl stearate, glycidyl linolenate, glycidyl laurate, glycidyl caprylate, glycidyl caprate, and epoxidized linseed oil and other oil- and fatty acid-derived epoxides. Epoxy resins may be used alone or in combination of two or more.

[0033] Examples of epoxy resins are shown in Table 1 below.

[0034] [Table 1] TIFF2025143828000003.tif242166TIFF2025143828000004.tif207169TIFF2025143828000005.t if243167TIFF2025143828000006.tif244166TIFF2025143828000007.tif248167TIFF2025143828 000008.tif222168TIFF2025143828000009.tif237170TIFF2025143828000010.tif246167TIFF20 25143828000011.tif228169TIFF2025143828000012.tif225168TIFF2025143828000013.tif86166

[0035] Preferred embodiments of the epoxy resin are shown in Table 2 below. [Table 2] TIFF2025143828000015.tif247159TIFF2025143828000016.tif219157TIFF20251438280 00017.tif235159TIFF2025143828000018.tif218157TIFF2025143828000019.tif154156

[0036] More preferred embodiments of the epoxy resin are shown in Table 3 below. [Table 3]

[0037] The epoxy resin may be liquid or solid. In the case of a solid, for example, an epoxy resin is used that can be dispersed in a furan resin to form a one-component composition as a whole. Preferably, at least one of the furan resin and the epoxy resin is liquid. The terms "liquid" and "solid" refer to the states under conditions of 25°C and 1 atmosphere.

[0038] Examples of epoxy resins include commercially available ones such as the EX series (manufactured by Nagase ChemteX Corporation), the ED series (manufactured by ADEKA Corporation), the Adeka Cizer O series (manufactured by ADEKA Corporation), the EP series (manufactured by ADEKA Corporation), the Epo Gosei series (manufactured by Yokkaichi Synthetic Co., Ltd.), the RD series (manufactured by Aditya Birla Chemicals), the NK Oligo EA series (manufactured by Shin-Nakamura Chemical Co., Ltd.), the KBM series (manufactured by Shin-Etsu Chemical Co., Ltd.), the KBE series (manufactured by Shin-Etsu Chemical Co., Ltd.), the X-40 series (manufactured by Shin-Etsu Chemical Co., Ltd.), the KR series (manufactured by Shin-Etsu Chemical Co., Ltd.), the XY series (manufactured by Anhui Xinyuan Technology Co., Ltd.), the DME series (manufactured by New Japan Chemical Co., Ltd.), the YX series (manufactured by Mitsubishi Chemical Corporation), the jER series (manufactured by Mitsubishi Chemical Corporation), the EPICLON HP series (manufactured by DIC Corporation), and the EPICLON Epoxy resins such as the N series (manufactured by DIC Corporation), Epolead PB series (manufactured by Daicel Corporation), Celloxide series (manufactured by Daicel Corporation), Hypro series (manufactured by Huntsman), Sumiepoxy ELM series (manufactured by Sumitomo Chemical Co., Ltd.), TETRAD series (manufactured by Mitsubishi Gas Chemical Company, Inc.), Epocalic series (manufactured by ENEOS Corporation), S series (manufactured by Synasia), TBIS series (manufactured by Taoka Chemical Co., Ltd.), and Wako Pure Chemical Industries, Ltd. may also be used.

[0039] (acid catalyst) In the present disclosure, the acid catalyst is not particularly limited as long as it can polycondense the furan resin. In one preferred embodiment, an acid with a pKa of 3.0 or less is used as the acid catalyst. One acid may be used alone, or two or more acids may be used.

[0040] The acid catalyst may be a water-soluble acid or a fat-soluble acid. The acid catalyst may be a Bronsted acid or a Lewis acid. The Lewis acid may be an acid containing boron, aluminum, titanium, iron, zinc, tin, or zirconium. When the acid is a solid, such as a powder, it may be dissolved in a solvent such as water, ethanol, ethylene glycol, or acetone before use, or may be properly dispersed in the resin without dissolving it.

[0041] Specific examples of the acid catalyst that can be used include paratoluenesulfonic acid, trifluoroacetic acid, borane-based acids (for example, tetrakispentafluorophenylboric acid), and antimony-based acids (for example, hexafluoroantimonic acid).

[0042] (Other ingredients) The one-component composition and kit of this embodiment may contain components other than the furan resin, acid scavenger, and acid catalyst (also referred to as "other components"). While these other components vary depending on the intended use of the cured furan resin, they may include inorganic minerals such as silica gel, alumina, aluminum nitride, calcium carbonate, and talc, as well as their derivatives; elastomers such as fatty acids, silicones, and polybutadiene, as well as their derivatives; and additives such as silane coupling agents, antioxidants, antifoaming agents, and surfactants. The amount of these other components is not particularly limited, but is typically 1 to 100 parts by mass, and preferably 10 to 50 parts by mass, per 100 parts by mass of the furan resin.

[0043] (One-component composition) The one-component composition of the present embodiment comprises a furan resin, an acid scavenger, and an acid catalyst, and the acid scavenger comprises an epoxy resin. The one-component composition of the present disclosure can be cured by polycondensing the furan resin in the presence of an acid catalyst, but the inclusion of the acid scavenger can prevent the polycondensation from proceeding uncontrollably. Therefore, the one-component composition of the present disclosure has excellent handleability. The one-component composition of the present disclosure can be polycondensed to obtain a cured furan resin product of the present embodiment.

[0044] In one preferred embodiment of the one-component composition of the present disclosure, the amount of cations derived from the acid catalyst is equal to or less than the amount of acid-capturing moieties contained in the acid scavenger. The acid-capturing moiety refers to a partial structure of the acid scavenger that can temporarily capture the acid catalyst, and examples of the acid-capturing moiety include an epoxy group in an epoxy resin, an amino group in an amine, and an oxetane ring in an oxetane.

[0045] The amount of cation is, for example, the amount of one hydrogen cation (H + ), the amount of substance of the acid catalyst is the same as that of the acid catalyst, and the acid catalyst has n (n is a natural number) hydrogen cations (H + When the acid scavenger is an epoxy resin, the acid scavenging moiety is an epoxy group, and the epoxy resin has one epoxy group in its molecule, the amount of substance of the acid scavenging moiety is synonymous with the amount of substance of the epoxy resin, and when the epoxy resin has n (n is a natural number) epoxy groups in its molecule, the amount of substance of the acid scavenging moiety is n times the amount of substance of the epoxy resin.

[0046] In the one-component composition of the present disclosure, when the amount of substance of the cation derived from the acid catalyst is taken as 1, the amount of substance of the acid scavenger contained in the acid scavenger is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. Within the above ranges, the viscosity increase rate after 24 hours (pot life) is low, and the composition is excellent in curability, allowing the composition to exhibit heat resistance and electrical properties after curing, which is preferable.

[0047] In the one-component composition of the present disclosure, the content of the furan resin is not limited. In one embodiment, the one-component composition of the present disclosure contains the furan resin in an amount of typically 20% by mass or more, preferably 25% by mass or more, and typically 98% by mass or less, preferably 95% by mass or less, based on the total mass of the one-component composition.

[0048] In the one-component composition of the present disclosure, the content of the acid scavenger is not limited as long as it satisfies the ratio between the amount of substance of the cation derived from the acid catalyst and the amount of substance of the acid scavenger contained in the acid scavenger, as described above.

[0049] The content of the epoxy resin in the one-component composition of the present disclosure is not limited. In one embodiment, the one-component composition of the present disclosure contains the epoxy resin in an amount of typically 1% by mass or more, preferably 10% by mass or more, and typically 100% by mass or less, preferably 50% by mass or less, relative to 100 parts by mass of the furan resin.

[0050] The content of the acid catalyst in the one-component composition of the present disclosure is not limited. In one embodiment, the one-component composition of the present disclosure contains the acid catalyst in an amount of typically 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, and typically 500% by mass or less, preferably 150% by mass or less, more preferably 100% by mass or less, and even more preferably 20% by mass or less, relative to 100 parts by mass of the furan resin.

[0051] Since the one-component composition of the present disclosure is a one-component thermosetting composition, it is preferable to store it under low-temperature conditions such as freezing, refrigeration, etc. In practice, the one-component composition of the present disclosure may be stored at any temperature of 40°C or lower because rapid polymerization does not occur at temperatures of 40°C or lower.

[0052] In one preferred embodiment, the one-component composition of the present disclosure has a viscosity increase rate of 100% or less after 24 hours when stored at 25° C. after preparation. When the viscosity increase rate of 100% or less after 24 hours when stored at 25° C. after preparation is 100%, it can be determined that runaway polycondensation of the furan resin has been sufficiently suppressed, and the composition has particularly excellent handleability.

[0053] In one preferred embodiment, the one-component composition of the present disclosure exhibits a viscosity increase rate of 100% or less after 24 hours when stored at 40°C after preparation. When the viscosity increase rate of 100% or less after 24 hours when stored at 40°C after preparation is 100%, it can be determined that runaway polycondensation of the furan resin has been sufficiently suppressed, and the one-component composition has particularly excellent handleability. In other words, the one-component composition has excellent handleability even in high-temperature environments such as factories in the summer when transporting, using, storing, and discarding it.

[0054] (Method of manufacturing one-liquid composition) The one-component composition can be obtained by dispersing and mixing the components, specifically, the furan resin, the acid scavenger, and the acid catalyst, as well as other components used as needed. When dispersing and mixing the components, the furan resin and the acid catalyst are usually mixed in the presence of an acid scavenger such as an epoxy resin. Specifically, the acid catalyst may be dispersed in the acid scavenger and then mixed with the furan resin, or the acid scavenger and the furan resin may be mixed and then mixed with the acid catalyst. Mixing the furan resin and the acid catalyst in the presence of the acid scavenger can suppress runaway polycondensation of the furan resin.

[0055] Dispersion and mixing can be carried out using a planetary mixer (for example, Thinky Mixer Awatori Rentaro), a Trimix (for example, Inoue Seisakusho Planetary Mixer PLM-2), a Disper, a three-roll mill, a ball mill, a bead mill, or the like.

[0056] Dispersion and mixing may be carried out under atmospheric pressure or under vacuum. Dispersion and mixing may be carried out at room temperature, for example, 15 to 25°C, or, from the viewpoint of workability, may be carried out at elevated temperatures, for example, 25 to 40°C, depending on the properties of the raw materials. The dispersing and mixing time varies depending on other conditions during dispersing and mixing, but is sufficient as long as each component reaches a dispersed or dissolved state, and is, for example, 1 minute to 12 hours, preferably 5 minutes to 6 hours, and more preferably 10 minutes to 3 hours.

[0057] (kit) The kit of the present embodiment includes a first agent containing a furan resin and a second agent containing an acid scavenger and an acid catalyst. The kit of the present disclosure can prepare a composition by mixing the first agent and the second agent, and a cured furan resin can be obtained by polycondensation of the furan resin contained in the composition.

[0058] The amounts of the furan resin, acid scavenger, acid catalyst, and other components used as needed contained in the kit of this embodiment are the same as those in the one-part composition described above. If the kit of this embodiment includes other components, they may be contained in either the first or second agent.

[0059] There are no particular limitations on the method for producing the first and second agents, and they can be prepared by mixing the components contained in each agent.

[0060] (furan resin cured product) The cured furan resin of this embodiment is a cured product of a raw material composition containing a furan resin, an acid scavenger, and an acid catalyst, and the acid scavenger contains an epoxy resin. Examples of the raw material composition include the one-component composition described above and a composition prepared by mixing the first and second parts of the kit described above. The cured furan resin of this embodiment is typically obtained by curing the raw material composition for 1 to 6 hours. Within this range, runaway polycondensation of the furan resin is suppressed, and productivity is not excessively low, which is preferable.

[0061] In the raw material composition, the amount of cations derived from the acid catalyst is preferably equal to or less than the amount of acid-capturing moieties contained in the acid scavenger. More specifically, when the amount of cations derived from the acid catalyst in the raw material composition is taken as 1, the amount of acid-capturing moieties contained in the acid scavenger is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. Within the above ranges, the viscosity increase rate after 24 hours (pot life) is low, and the curing property is excellent, allowing the cured material to exhibit heat resistance and electrical properties, which is preferable.

[0062] Because cured furan resins have excellent heat resistance and electrical properties, they can be used in electronic components such as power semiconductors.

[0063] The furan resin cured product preferably has a dielectric constant of 20.0 εr or less and a dielectric dissipation factor of 0.30 or less at 1 MHz, more preferably a dielectric constant of 10.0 εr or less and a dielectric dissipation factor of 0.20 or less at 1 MHz, and even more preferably a dielectric constant of 5.0 εr or less and a dielectric dissipation factor of 0.10 or less at 1 MHz. There is no particular lower limit for the dielectric constant, but it is usually 1.0 εr or more. There is no particular lower limit for the dielectric dissipation factor, but it is usually 0.001 or more. The above ranges are preferable as insulating materials for electronic components. The dielectric constant and dielectric dissipation factor of the furan resin cured product can be measured using IEC 62631-2-1 (automatic balancing bridge method).

[0064] The volume resistivity of the cured furan resin is 1.0×10 11 It is preferable that the resistance is Ω·cm or more, and 1.0×10 12 It is more preferable that the resistance is Ω·cm or more, and 1.0×10 13 It is more preferable that the volume resistivity is Ω·cm or more. There is no particular upper limit to the volume resistivity, but it is usually 1.0×10 18 The volume resistivity of the cured furan resin is Ω·cm or less. This range is preferable as an insulating material for electronic components. The volume resistivity of the cured furan resin can be measured in accordance with IEC 62631-3-1 or JIS C 2139-3-1.

[0065] The dielectric breakdown voltage of the cured furan resin is preferably 1 kV or more, more preferably 3 kV or more, and even more preferably 7 kV or more. There is no particular upper limit to the dielectric breakdown voltage, but it is usually 100 kV or less. This range is preferable as an insulating material for electronic components. The dielectric breakdown voltage of the cured furan resin can be measured in accordance with IEC 60243-1 or JIS C 2110-1.

[0066] The dielectric breakdown strength of the cured furan resin is preferably 0.5 kV / mm or more, more preferably 1 kV / mm or more, and even more preferably 3 kV / mm or more. There is no particular upper limit to the dielectric breakdown strength, but it is usually 50 kV / mm or less. This range is preferable as an insulating material for electronic components. The dielectric breakdown strength of the cured furan resin can be measured in accordance with IEC 60243-2 or JIS C 2110-1.

[0067] (Method of producing a cured furan resin) The cured furan resin can be obtained by polycondensing the furan resin contained in the raw material composition. Specifically, the cured furan resin can be obtained by heating the raw material composition. The heating may be performed in one step, but from the viewpoint of more stable production of the cured furan resin, it is preferably performed in multiple steps, for example, two or three steps.

[0068] When heating is performed in two stages, it is preferable that the first heating stage is performed for 1 to 2 hours in the range of 40° C. to 100° C., and the second heating stage is performed for 1 to 2 hours in the range of 100° C. to 130° C. In one embodiment of heating in two stages, the first heating stage is performed to carry out a chain polymerization reaction of the furfuryl alcohol units and epoxy units of the furan resin and to remove volatile components (e.g., water) if any are contained in the raw material composition, and the second heating stage is performed to carry out a Diels-Alder reaction or a Michael addition reaction to form three-dimensional crosslinks.

[0069] When heating is performed in three stages, it is preferable that the first heating stage be performed in the range of 40°C to 100°C for 1 to 2 hours, the second heating stage be performed in the range of 80°C to 130°C for 1 to 2 hours, and the third heating stage be performed in the range of 120°C to 180°C for 1 to 2 hours. In one embodiment when heating is performed in three stages, the first heating stage is performed for the purpose of removing volatile components (e.g., water) if they are contained in the raw material composition, the second heating stage is performed for the purpose of causing a chain polymerization reaction of the furfuryl alcohol units or epoxy units of the furan resin, and the third heating stage is performed for the purpose of causing a Diels-Alder reaction or a Michael addition reaction to form three-dimensional crosslinks. Heating may be performed in four or more stages, and for a long period of time. [Example]

[0070] The present embodiment will be described below with reference to examples, but the present disclosure is not limited to these examples.

[0071] The following materials were used as raw materials: Furan resin-1: Polyfurfuryl alcohol (FA) type furan resin (a mixture in which the average molecular weight of furan oligomer is 1,000 and which contains less than 30% by weight of furfuryl alcohol and furfural) Furan resin-2: FA·HCHO copolymer furan resin (Hitachi Chemical Co., Ltd., Hitafran VF-303) Furan resin-3: FA-urea-HCHO copolymer furan resin (a mixture in which the average molecular weight of the furan oligomer is 1,000, the ratio of the amount of copolymerized FA-urea-HCHO substances is 1:1:1, and furfuryl alcohol and furfural are less than 30 weight percent) PTSA: Paratoluenesulfonic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) TFA: Trifluoroacetic acid (Fujifilm Wako Pure Chemical Industries, Ltd.) Borane Acid: Tetrakispentafluorophenylboronic acid Antimony acids: Hexafluoroantimonic acid Amine: N-methylmorpholine (Tokyo Chemical Industry Co., Ltd.) [ka] Oxetane: 3-ethyl-3-(4-hydroxybutylmethyl)oxetane (UBE) [ka] Epoxy resin: Epoxy resin listed in Table 4

[0072] [Table 4]

[0073] [Experimental Example 1] (Preparation of one-component composition) The components were blended, dispersed, and mixed in the proportions shown in Tables 5 and 6. Specifically, the acid was dispersed in the epoxy resin, and the mixture of the acid and the epoxy resin was mixed with the furan resin to prepare a one-component composition.

[0074] Mixing was carried out under atmospheric pressure using a Thinky Mixer, with appropriate cooling to maintain the temperature within the range of 20 to 40°C. The mixing time to obtain the mixture of acid and epoxy resin was 10 minutes in total, excluding cooling time, and the mixing time after blending the furan resin into the mixture was 10 minutes in total, excluding cooling time. The types and amounts of each raw material are shown in Tables 5 and 6.

[0075] [Table 5]

[0076] [Table 6]

[0077] (Measurement of viscosity increase rate) The viscosity of the one-component composition was measured immediately after preparation (within 1 hour). A Brookfield E-type viscometer (product name LVDV2T) was used for the viscosity measurement. The viscometer was prepared in advance so that measurements could be made at 25°C.

[0078] The viscosity of the one-component composition was measured immediately after preparation, and then a portion of the composition was placed in a thermostatic bath set at 25°C. After 24 hours, the composition was removed from the thermostatic bath and the viscosity was measured in the same manner.

[0079] In addition, the viscosity of the one-component composition was measured immediately after preparation, and then a portion of the composition was placed in a thermostatic bath set at 40°C. After 24 hours, the composition was removed from the thermostatic bath and cooled to 25°C, and the viscosity was measured in the same manner.

[0080] The viscosity increase rate after 24 hours when the composition was stored at 25°C after preparation and the viscosity increase rate after 24 hours when the composition was stored at 40°C after preparation were calculated. The viscosity increase rates are shown in Table 7. In Table 7, compositions in which the viscosity could not be measured due to curing after 24 hours were recorded as "cured." Furthermore, compositions in which rapid curing was visually confirmed after preparation of a one-component composition were recorded as "runaway curing."

[0081] [Table 7]

[0082] (Preparation of cured furan resin) The one-component composition was cured by the following method to produce a furan resin cured product measuring 2 mm thick x 10 cm x 10 cm.

[0083] The one-component composition was poured into a mold made of a stainless steel plate with inner dimensions of 2 mm thick x 10 cm x 10 cm, and heated as follows to cure the one-component composition. After heating, the composition was removed to obtain a cured furan resin. First stage: Temperature controlled at 80℃~100℃ for 2 hours Second stage: Control the temperature to 100℃~120℃ for 2 hours Third stage: Control the temperature to 120℃~140℃ for 2 hours

[0084] (Evaluation of cured furan resin) The physical properties of the cured furan resin were evaluated by the following methods. When measuring the physical properties, a 2 mm thick x 10 cm x 10 cm piece of the cured furan resin was cut into appropriate pieces and used.

[0085] [Glass transition temperature measurement] The average linear expansion coefficient was measured using a thermomechanical analyzer (TMA), and the inflection point of the average linear expansion coefficient was regarded as the glass transition temperature of the cured furan resin, which was evaluated as an index of heat resistance.

[0086] Test method: Compliant with ISO 11359-2 Analysis item: Average linear expansion coefficient Sample dimensions: 5 x 2 x 10 mm (height) Test conditions: Measurement temperature: Room temperature to 300°C Temperature rise: 5℃ / min Atmosphere: Nitrogen flow (150 mL / min) Test load: 32mN Number of measurements: n=1

[0087] Based on the evaluation results of the glass transition temperature, the heat resistance was evaluated according to the following criteria, and the results are shown in Table 8. Excellent: 240℃ or more Good: 175℃ or higher Bad: Less than 175°C

[0088] [Table 8]

[0089] [Dielectric constant and dielectric loss tangent] The relative dielectric constant and dielectric loss tangent were measured under the following conditions. Test method: IEC 62631-2-1 (automatic balancing bridge method) Sample dimensions: 60 x 60 x 2.0 mm (thickness) Test conditions: Frequency: 1MHz Electrode dimensions: Main electrode diameter φ36mm, ring electrode inner diameter φ38mm Electrode material: tin foil Test environment: 23°C ± 2°C, 50% RH ± 5% RH Measurement equipment: Precision LCR meter E4980A (Agilent Technologies)

[0090] [Volume resistivity] The volume resistivity was measured under the following conditions. Test method: IEC 62631-3-1, JIS C 2139-3-1 compliant Test conditions: Applied voltage: DC 100V x 60s Measurement temperature: 23℃ Electrode dimensions: Main electrode diameter φ26mm, ring electrode inner diameter φ38mm Electrode material: tin foil Conditioning: 23°C ± 2°C, 50% RH ± 5% RH x 24 hours or more Test room environment: 23°C ± 2°C, 50% ± 5% RH Measurement equipment: High Resistance Meter 4339B (Agilent Technologies)

[0091] [Breakdown voltage and breakdown strength] The dielectric breakdown voltage and dielectric breakdown strength were measured under the following conditions. Test method: Compliant with IEC60243-1, -2, JIS C 2110-1, -2 Test conditions: Boost method; Short-time method (AC, 50Hz) Surrounding medium: Insulating oil Measurement temperature: 23℃ Electrode: φ6 cylinder / φ6 cylinder Boost speed: 3kV / s Test environment: 23°C ± 2°C, 50% RH ± 5% RH Measurement equipment: Dielectric breakdown test equipment YST-243-100RHO (manufactured by Yamayo Test Instruments Co., Ltd.) Table 9 shows the evaluation results of the relative dielectric constant, dielectric loss tangent, volume resistivity, breakdown voltage and breakdown strength of the cured furan resin.

[0092] [Table 9]

[0093] The electrical properties of the cured furan resin were evaluated based on the relative permittivity, dielectric loss tangent, volume resistivity, breakdown voltage, and breakdown strength, and are shown in Table 10, which is based on the following criteria.

[0094] <Electrical characteristics standards> Relative dielectric constant: 5.0 (εr) or less Dielectric tangent: 0.10 or less Volume resistivity: 1.0 x 10 13 (Ω cm) or more Breakdown voltage: 7 kV or more Dielectric breakdown strength: 4 (kV / mm) or more Of the five types of evaluation above, Those that meet the five criteria: Excellent 4 types or less: poor The results are shown in Table 10.

[0095] [Table 10]

[0096] The above-described experimental examples suggest that the one-component composition of the present disclosure has a low viscosity increase rate and a long usable life. Furthermore, the cured furan resin of the present disclosure has excellent heat resistance and electrical properties, suggesting that it can be used in various applications such as electronic components.

[0097] Furthermore, in Test No. 14, an experiment was also conducted in which the epoxy resin of Compound No. 92, 99, 100, or 101 in Table 1 was used instead of the epoxy resin of Compound No. 91 (alicyclic epoxy resin), and the results were similar to those obtained when the epoxy resin of Compound No. 91 was used.

[0098] In addition, in Test No. 20, an experiment was also conducted in which the epoxy resin of Compound No. 41 (glycidyl ether type epoxy resin) was replaced with the epoxy resin of Compound No. 4, 18, 20, 24, 26, 27, 37, 58 or 60 in Table 1, and the results were similar to those obtained when the epoxy resin of Compound No. 41 was used.

[0099] In addition, in Test No. 21, an experiment was also conducted in which the epoxy resin of Compound No. 85 or 86 in Table 1 was used instead of the epoxy resin of Compound No. 88 (glycidylamine type epoxy resin), and the same results as those obtained when the epoxy resin of Compound No. 88 was used were obtained.

[0100] In addition, in Test No. 22, an experiment was also conducted in which the epoxy resin of Compound No. 62, 65, or 67 in Table 1 was used instead of the epoxy resin of Compound No. 63 (bisphenol A type epoxy resin), and the results were similar to those obtained when the epoxy resin of Compound No. 63 was used.

[0101] In addition, in Test No. 23, an experiment was also conducted in which the epoxy resin of Compound No. 8, 28, 53, or 59 in Table 1 was used instead of the epoxy resin of Compound No. 72 (glycidyl ester type epoxy resin). Results similar to those obtained when the epoxy resin of Compound No. 72 was used were obtained.

[0102] In addition, in Test No. 24, an experiment was also conducted in which the epoxy resin of Compound No. 74, 76, or 77 in Table 1 was used instead of the epoxy resin of Compound No. 75 (olefin oxidation type epoxy resin). The results were similar to those obtained when the epoxy resin of Compound No. 75 was used.

[0103] In addition, in Test No. 25, an experiment was also conducted in which the epoxy resin of Compound No. 93, 95, 96, 97, 98, 102, or 103 in Table 1 was used instead of the epoxy resin of Compound No. 94 (alicyclic epoxy resin). Results similar to those obtained when the epoxy resin of Compound No. 94 was used were obtained.

[0104] In addition, in Test No. 26, an experiment was also conducted in which the epoxy resin of Compound No. 56, 57, or 61 in Table 1 was used instead of the epoxy resin of Compound No. 55 (hydrogenated bisphenol type epoxy resin). As a result, the same results as those obtained when the epoxy resin of Compound No. 55 was used were obtained.

[0105] The upper and / or lower limits of the numerical ranges described herein can be arbitrarily combined to define a preferred range. For example, the upper and lower limits of the numerical ranges can be arbitrarily combined to define a preferred range, the upper limits of the numerical ranges can be arbitrarily combined to define a preferred range, and the lower limits of the numerical ranges can be arbitrarily combined to define a preferred range. Furthermore, in this application, numerical ranges expressed using the symbol "to" include the numerical values ​​written before and after the symbol "to" as the upper and lower limits, respectively.

[0106] Although the present embodiment has been described in detail above, the specific configuration is not limited to this embodiment, and even if there are design changes within the scope that do not deviate from the gist of this disclosure, they are included in this disclosure.

Claims

1. comprising a furan resin, an acid scavenger, and an acid catalyst; A one-part composition, wherein the acid scavenger comprises an epoxy resin.

2. The one-component composition according to claim 1 , wherein the amount of cations derived from the acid catalyst is equal to or less than the amount of acid-capturing moieties contained in the acid-capturing agent.

3. 2. The one-component composition according to claim 1, which exhibits a viscosity increase rate of 100% or less after 24 hours of storage at 25°C after preparation.

4. 2. The one-component composition according to claim 1, which exhibits a viscosity increase rate of 100% or less after 24 hours when stored at 40°C after preparation.

5. A cured product of a raw material composition including a furan resin, an acid scavenger, and an acid catalyst, A cured furan resin, wherein the acid scavenger comprises an epoxy resin.

6. 6. The cured furan resin according to claim 5, wherein in the raw material composition, the amount of cations derived from the acid catalyst is equal to or less than the amount of acid-capturing moieties contained in the acid scavenger.

7. 6. The cured furan resin according to claim 5, having a relative dielectric constant of 5.0 εr or less and a dielectric dissipation factor of 0.10 or less at 1 MHz.

8. Volume resistivity is 1.0 x 10 １３ The cured furan resin according to claim 5, having a resistivity of Ω·cm or more.

9. 6. The cured furan resin according to claim 5, which has a dielectric breakdown voltage of 7 kV or more and a dielectric breakdown strength of 3 kv / mm or more.

10. a first agent containing a furan resin; a second agent containing an acid scavenger and an acid catalyst; A kit comprising:

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