Curable epoxy resin composition, cured product, and method for producing cured product

Abstract

To provide a curable epoxy resin composition in which biomass is utilized and with which a cured product having excellent heat resistance is given; a cured product; and a method for producing a cured product.SOLUTION: A curable epoxy resin composition comprising a biomass-derived non-aromatic epoxy compound and a biomass-derived curing agent, wherein the non-aromatic epoxy compound has a ring structure other than an epoxy group, and the curing agent is at least one selected from the group consisting of thiols and phenolic compounds.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a curable epoxy resin composition, a cured product, and a method for producing the cured product. [Background technology]

[0002] In recent years, the use of biomass has been attracting attention in the materials sector as well, with the aim of promoting a recycling-oriented society.

[0003] It is known that a diamine compound is used as a curing agent in a curable epoxy resin composition using a biomass material (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2020-037649 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present disclosure is to provide a curable epoxy resin composition that utilizes biomass and gives a cured product that has excellent heat resistance, a cured product, and a method for producing the cured product. [Means for solving the problem]

[0006] The present disclosure (1) includes a biomass-derived non-aromatic epoxy compound and a biomass-derived curing agent, In the curable epoxy resin composition, the curing agent is at least one selected from the group consisting of acid anhydrides, thiols, and phenolic compounds.

[0007] The present disclosure (2) is the curable epoxy resin composition according to the present disclosure (1), in which the non-aromatic epoxy compound and the curing agent have a biomass degree of 50% or more.

[0008] The present disclosure (3) is the curable epoxy resin composition according to the present disclosure (1) or (2), in which the biomass content of the non-aromatic epoxy compound and the curing agent is 100%.

[0009] The present disclosure (4) is the curable epoxy resin composition according to any one of the present disclosures (1) to (3), wherein the non-aromatic epoxy compound has a ring structure other than an epoxy group.

[0010] The present disclosure (5) is the curable epoxy resin composition according to any one of the present disclosures (1) to (4), wherein the non-aromatic epoxy compound contains two or more epoxy groups.

[0011] The present disclosure (6) is the curable epoxy resin composition according to any one of the present disclosures (1) to (5), wherein the non-aromatic epoxy compound is a non-aromatic diepoxy compound.

[0012] The present disclosure (7) is the curable epoxy resin composition according to any one of the present disclosures (1) to (6), wherein the non-aromatic epoxy compound has an isosorbide structure.

[0013] The present disclosure (8) is the curable epoxy resin composition according to any one of the present disclosures (1) to (7), wherein the non-aromatic epoxy compound is at least one selected from the group consisting of isosorbide diglycidyl ether, ethylene glycol diglycidyl ether, and poly(propylene glycol) diglycidyl ether.

[0014] The present disclosure (9) is the curable epoxy resin composition according to any one of the present disclosures (1) to (8), wherein the non-aromatic epoxy compound is isosorbide diglycidyl ether.

[0015] The present disclosure (10) is the curable epoxy resin composition according to any one of the present disclosures (1) to (9), wherein the curing agent is at least one selected from the group consisting of thiol and phenolic compounds.

[0016] The present disclosure (11) is the curable epoxy resin composition according to any one of the present disclosures (1) to (10), wherein the acid anhydride has a ring structure other than an acid anhydride ring.

[0017] The present disclosure (12) is the curable epoxy resin composition according to any one of the present disclosures (1) to (11), wherein the acid anhydride is at least one selected from the group consisting of maleic anhydride, phthalic anhydride, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

[0018] The present disclosure (13) is the curable epoxy resin composition according to any one of the present disclosures (1) to (12), wherein the thiol is an aliphatic thiol.

[0019] The present disclosure (14) is the curable epoxy resin composition according to any one of the present disclosures (1) to (13), wherein the thiol is at least one selected from the group consisting of pentaerythritol tetrakis(3-mercaptobutyrate) and L-cysteine.

[0020] The present disclosure (15) is the curable epoxy resin composition according to any one of the present disclosures (1) to (14), wherein the phenolic compound contains two or more hydroxy groups.

[0021] The present disclosure (16) is the curable epoxy resin composition according to any one of the present disclosures (1) to (15), wherein the phenolic compound is (+)-catechin hydrate.

[0022] The present disclosure (17) is a cured product obtained by curing the curable epoxy resin composition according to any one of the present disclosures (1) to (16).

[0023] The present disclosure (18) is the cured product according to the present disclosure (17), which has a relative dielectric constant of 6.0 or less at 10 GHz.

[0024] The present disclosure (19) is an insulating material using the curable epoxy resin composition according to any one of the present disclosures (1) to (16).

[0025] The present disclosure (20) is an encapsulating material using the curable epoxy resin composition according to any one of the present disclosures (1) to (16).

[0026] The present disclosure (21) is an optical material using the curable epoxy resin composition according to any one of the present disclosures (1) to (16).

[0027] The present disclosure (22) is a printed circuit board material using the curable epoxy resin composition according to any one of the present disclosures (1) to (16).

[0028] The present disclosure (23) is a method for producing a cured product, comprising a step of curing the curable epoxy resin composition according to any one of the present disclosures (1) to (16). [Effects of the Invention]

[0029] According to the present disclosure, it is possible to provide a curable epoxy resin composition that utilizes biomass and gives a cured product that has excellent heat resistance, a cured product, and a method for producing the cured product. DETAILED DESCRIPTION OF THE INVENTION

[0030] The present disclosure will be specifically described below.

[0031] The curable epoxy resin composition of the present disclosure comprises a biomass-derived non-aromatic epoxy compound and a biomass-derived curing agent, wherein the curing agent is at least one selected from the group consisting of acid anhydrides, thiols, and phenolic compounds.

[0032] The curable epoxy resin composition of the present disclosure comprises a biomass-derived non-aromatic epoxy compound and a biomass-derived curing agent, and the curing agent is at least one selected from the group consisting of acid anhydrides, thiols, and phenolic compounds, thereby providing a cured product with excellent heat resistance and electrical properties. Furthermore, sustainability is improved, and the environmental impact can be reduced.

[0033] The curable epoxy resin composition of the present disclosure can also provide a cured product that has excellent transparency and weather resistance.

[0034] The non-aromatic epoxy compound is derived from biomass. Note that the phrase "the non-aromatic epoxy compound is derived from biomass" means that the biomass content of the non-aromatic epoxy compound is 10% or more. The non-aromatic epoxy compound preferably has a biomass degree of 50% or more, more preferably 70% or more, more preferably 90% or more, and particularly preferably 100%. The biomass degree is measured in accordance with ASTM D 6866. By using non-aromatic epoxy compounds derived from biomass, the carbon-neutral concept can be achieved, reducing the actual amount of carbon dioxide emitted during combustion, improving sustainability and reducing the environmental burden.

[0035] Examples of the non-aromatic epoxy compound include aliphatic epoxy compounds, which may have no ring structure other than the epoxy group, or may have a ring structure other than the epoxy group. The non-aromatic epoxy compound may have at least one structure selected from the group consisting of an ether bond, an ester bond, and an amide bond in its structure.

[0036] Examples of non-aromatic epoxy compounds that do not have a ring structure other than an epoxy group include glycidyl ether-type epoxy compounds such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, glycerin triglycidyl ether, and poly(propylene glycol) diglycidyl ether; glycidyl ester-type epoxy compounds made from polycarboxylic acids such as dimer acids and their anhydrides; and glycidyl amine-type epoxy compounds made from aliphatic amines.

[0037] Examples of non-aromatic epoxy compounds having a ring structure other than an epoxy group include hydrogenated bisphenol A epoxy resins, hydrogenated bisphenol F epoxy resins, hydrogenated bisphenol AD ​​epoxy resins, hydrogenated bisphenol S epoxy resins, hydrogenated phenol novolac epoxy resins, hydrogenated cresol novolac epoxy resins, glycidyl ether epoxy compounds such as tetrakis(glycidyloxycyclohexyl)ethane, 1,2-diglycidyloxycyclohexane, 1,3-diglycidyloxycyclohexane, 1,4-diglycidyloxycyclohexane, and isosorbide diglycidyl ether; diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, and dimethylglycidyl hexahydrophthalate. glycidyl ester-type epoxy compounds such as glycidyl ester; glycidyl amine-type epoxy compounds such as N,N-diglycidylaminocyclohexane, 2-methyl-N,N-diglycidylaminocyclohexane, N,N-diglycidyl-4-glycidyloxycyclohexane, 1,1-bis(4-N,N-diglycidylaminocyclohexyl)methane, 1,2-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane; and alicyclic epoxy compounds in which the double bond of the cyclohexene ring is oxidized, such as alicyclic diepoxy acetal and alicyclic diepoxy adipate.

[0038] The non-aromatic epoxy compound preferably has a ring structure other than an epoxy group. The ring structure other than the epoxy group is preferably a non-aromatic ring, more preferably a saturated non-aromatic ring. The ring structure other than the epoxy group may contain a heteroatom, such as an oxygen atom, a nitrogen atom, or a sulfur atom, with an oxygen atom being preferred. The ring structure other than the epoxy group may be monocyclic or polycyclic, preferably polycyclic, and more preferably bicyclic.

[0039] The non-aromatic epoxy compound preferably has a structure capable of forming a ring structure upon curing. The ring structure capable of forming upon curing may be a non-aromatic ring, and is preferably a saturated non-aromatic ring. The ring structure that can be formed by the curing may contain a heteroatom, such as an oxygen atom, a nitrogen atom, or a sulfur atom, with an oxygen atom being preferred. The ring structure that can be formed by the above curing may be monocyclic or polycyclic.

[0040] The non-aromatic epoxy compound preferably contains two or more epoxy groups in the molecule, more preferably six or less epoxy groups in the molecule, and even more preferably three or less epoxy groups in the molecule. The non-aromatic epoxy compound more preferably contains two epoxy groups, i.e., is a non-aromatic diepoxy compound.

[0041] The non-aromatic epoxy compound is preferably a glycidyl ether type epoxy resin, more preferably at least one selected from the group consisting of isosorbide diglycidyl ether, ethylene glycol diglycidyl ether, and poly(propylene glycol) diglycidyl ether, and even more preferably isosorbide diglycidyl ether. The non-aromatic epoxy compound is preferably a glycidyl ether type epoxy resin having an aliphatic ring other than an epoxy group, and isosorbide diglycidyl ether is more preferred.

[0042] The non-aromatic epoxy compound preferably has an isosorbide structure.

[0043] The non-aromatic epoxy compound is preferably derived from a plant. Use of a plant-derived non-aromatic epoxy compound can improve sustainability and reduce the environmental impact. Examples of plant-derived non-aromatic epoxy compounds include isosorbide diglycidyl ether, ethylene glycol diglycidyl ether, and poly(propylene glycol) diglycidyl ether.

[0044] The curing agent is derived from biomass. Note that "the curing agent is derived from biomass" means that the biomass content of the curing agent is 10% or more. The curing agent preferably has a biomass degree of 50% or more, more preferably 70% or more, even more preferably 90% or more, and particularly preferably 100%. The biomass degree is measured in accordance with ASTM D 6866. By using a biomass-derived hardener, the carbon neutral concept can be achieved, reducing the actual amount of carbon dioxide emitted during combustion, improving sustainability and reducing the environmental burden.

[0045] The curing agent is at least one selected from the group consisting of acid anhydrides, thiols, and phenolic compounds. One or more of the curing agents may be used alone or in combination.

[0046] Examples of acid anhydrides include maleic anhydride, dodecenylsuccinic anhydride, chlorendic anhydride, sebacic anhydride, phthalic anhydride, succinic anhydride, pyromellitic anhydride, trimellitic anhydride, cyclopentane tetracarboxylic dihydrate, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, oxabicyclodicarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, mellophanic dianhydride, 5-(2,5-dioxotetrahydroxyfuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, and methylnadic anhydride.

[0047] The acid anhydride preferably has a ring structure other than the acid anhydride ring in the molecule.

[0048] The acid anhydride is preferably at least one selected from the group consisting of maleic anhydride, phthalic anhydride, succinic anhydride, oxabicyclodicarboxylic anhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and mellophanic dianhydride, and more preferably at least one selected from the group consisting of maleic anhydride, phthalic anhydride, and 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

[0049] Examples of thiols include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, 4-mercaptobutanoic acid, mercaptosuccinic acid, mercaptostearic acid, mercaptooctanoic acid, 4-mercaptobenzoic acid, 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid, L-cysteine, N-acetyl-L-cysteine, 3-methoxybutyl 3-mercaptopropionate, and 3-mercapto-2-methylpropionate. Pionic acid, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate ester, pentaerythritol tetrakis(thiopropionate), trimercaptopropionic acid tris(2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, tetraethylene glycol bis-3-mercaptopropionate, trimethylolpropane tris-3-mercaptopropionate, tris(3-mercapto Examples of suitable esters include pentaerythritol tetrakis(3-mercaptopropionyloxyethyl)isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol tetrakis(3-mercaptopropionate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and pentaerythritol tetrakis(3-mercaptobutyrate).

[0050] The thiol may be an aliphatic thiol or an aromatic thiol, but is preferably an aliphatic thiol.

[0051] The thiol may be a compound in which an OH group or a COOH group of a biomass-derived compound is converted into an SH group.

[0052] The thiol is preferably at least one selected from the group consisting of pentaerythritol tetrakis(3-mercaptobutyrate) and L-cysteine.

[0053] Examples of phenolic compounds include polyhydric phenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcinol, methylresorcinol, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, catechin hydrate, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, bisphenol A novolac resin, trisphenolmethane type resin, naphthol novolac resin, brominated bisphenol A, and brominated phenol novolac resin; lignin-modified phenolic resin; and lignin decomposition products such as catechol, cresol, and creosol. These include cashew nut shell liquids such as anacardic acid, cardanol, cardol, and 2-methyl cardol; resins in which biomass-derived active groups have been added to bisphenols; polyhydric phenol resins obtained by the condensation reaction of phenols with aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, and glyoxal; polyhydric phenol resins obtained by the condensation reaction of xylene resin with phenols; co-condensation resins of heavy oils or pitches with phenols and formaldehydes; and phenolic resins such as phenol-benzaldehyde-xylylene dimethoxide polycondensates, phenol-benzaldehyde-xylylene dihalide polycondensates, phenol-benzaldehyde-4,4'-dimethoxide biphenyl polycondensates, and phenol-benzaldehyde-4,4'-dihalide biphenyl polycondensates.

[0054] The phenolic compound preferably contains two or more hydroxy groups, and more preferably contains two or more hydroxy groups in each of one or more aromatic rings.

[0055] The phenolic compound is preferably at least one selected from the group consisting of catechin hydrate, lignin-modified phenolic resin, catechol, curd, 2-methylcurd, and a resin in which a biomass-derived active group is added to bisphenol, more preferably catechin hydrate, and even more preferably (+)-catechin hydrate.

[0056] The curing agent may be at least one selected from the group consisting of thiols and phenolic compounds.

[0057] The curing agent is preferably plant-derived, which improves sustainability and reduces the environmental impact. Examples of plant-derived hardening agents include phthalic anhydride, maleic anhydride, pentaerythritol tetrakis(3-mercaptobutyrate), and catechin hydrate (preferably (+)-catechin hydrate).

[0058] In the curable epoxy resin composition of the present disclosure, the equivalent ratio of the epoxy groups of the non-aromatic epoxy compound to the functional groups of the curing agent (epoxy groups / functional groups) may be 0.75 or more, and preferably 0.85 or more, and may be 1.50 or less, and preferably 1.25 or less.

[0059] The curable epoxy resin composition of the present disclosure may contain an organic solvent. The content of the organic solvent may be 75% by mass or less, preferably 65% ​​by mass or less, and may be 10% by mass or more, based on the curable epoxy resin composition. Examples of the organic solvent include toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, dimethylformamide, and N-methylpyrrolidone, which can be used alone or in combination of two or more.

[0060] The curable epoxy resin composition of the present disclosure may contain a curing accelerator. The content of the curing accelerator may be 20% by mass or less, preferably 15% by mass or less, and may be 0.5% by mass or more, based on the curable epoxy resin composition. Examples of the curing accelerator include 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5,4,0]-7-undecene, triphenylphosphine, and methyldiphenylphosphine, which can be used alone or in combination of two or more.

[0061] The curable epoxy resin composition of the present disclosure may contain additives commonly used in the art, as needed. Examples of such additives include flame retardants, storage stability improvers, fillers, diluents, pigments, flexibility-imparting agents, coupling agents, antioxidants, anti-settling agents, and dispersants. The content of such additives may be 0.01 to 10% by mass of the curable epoxy resin composition.

[0062] The present disclosure also provides a cured product obtained by curing the curable epoxy resin composition of the present disclosure. Since the cured product of the present disclosure is obtained by curing the curable epoxy resin composition, the cured product has excellent heat resistance and electrical properties, as well as excellent transparency and weather resistance. Furthermore, sustainability is improved, and the environmental load can be reduced. The curable epoxy resin composition can be cured by the methods described below.

[0063] The glass transition temperature (Tg) of the cured product of the present disclosure is preferably 22°C or higher, more preferably 50°C or higher, even more preferably 80°C or higher, and even more preferably 100°C or higher, and may be 400°C or lower. The glass transition temperature can be determined by measuring a DSC curve using a differential scanning calorimeter (Q1000 manufactured by TA Instruments) by a temperature-modulated DSC measurement method in which a 5 mg sample is repeatedly heated and cooled at a constant cycle and amplitude while the temperature is raised on average, and the temperature is measured.The glass transition temperature can be determined as the temperature indicating the midpoint between the two intersections of an extension of the baseline before and after the second-order transition of the DSC curve and a tangent to the inflection point of the DSC curve.

[0064] The thermal decomposition temperature (Td) of the cured product of the present disclosure is preferably 125°C or higher, more preferably 150°C or higher, and even more preferably 200°C or higher, and may be 450°C or lower. The thermal decomposition temperature was measured using a thermal analyzer, TG-DTA 2000SA, manufactured by Bruker AXS. Measurements were performed under a nitrogen purge atmosphere at 150 mL / min. 10 mg of sample was placed in a platinum pan, held at 25°C for 10 minutes, and then heated to 600°C at a rate of 10°C / min. The temperature at which the mass decreased by 1% from the initial mass (Td1) was evaluated as the thermal decomposition temperature.

[0065] The cured product of the present disclosure preferably has a relative dielectric constant at 10 GHz of 6.0 or less, more preferably 4.0 or less, even more preferably 3.0 or less, particularly preferably 2.5 or less, and may be 2.0 or more. Furthermore, the dielectric loss tangent at 10 GHz of the cured product of the present disclosure is preferably 0.1 or less, more preferably 0.05 or less, even more preferably 0.025 or less, even more preferably 0.02 or less, particularly preferably 0.01 or less, and may be 0.0001 or more. The dielectric constant and dielectric loss tangent are measured at a frequency of 10 GHz for the cured product using a cavity resonator dielectric constant measuring device (manufactured by AET Corporation).

[0066] The dielectric constant and dielectric loss tangent are measured at a frequency of 10 GHz for a powdered sample using a cavity resonator dielectric constant measuring device (manufactured by AET Co., Ltd.) for the cured product. The specific gravity of the sample is measured using a specific gravity measuring device AUW120D (manufactured by Shimadzu Corporation). Materials with low relative dielectric constants and dielectric loss tangents are useful as materials for electronic and electric devices with low transmission loss in the high frequency range. Here, the transmission loss αd satisfies the following relationship (Equation (1)) with the frequency f, the relative permittivity εr of the dielectric layer, and the dielectric loss tangent tanδ. Since the transmission loss is proportional to the square root of the relative permittivity and the dielectric loss tangent, a small dielectric loss tangent is more important in reducing the transmission loss.

number

[0067] The cured product of the present disclosure has a thickness of 100 μm and a transmittance at a wavelength of 550 nm of preferably 70% or more, more preferably 80% or more, and may even have a transmittance of 100%. The transmittance is a value measured using an ultraviolet spectrophotometer. The material with high transmittance is useful as an encapsulant for UV-LEDs. When the cured product does not contain a compound with an aromatic ring, it exhibits high transmittance.

[0068] The refractive index of the cured product of the present disclosure is preferably 1.35 to 1.60. It is more preferably 1.57 or less, and even more preferably 1.55 or less, and may be 1.40 or more, or 1.42 or more. The refractive index is a value measured with an Abbe refractometer.

[0069] The cured product of the present disclosure also has excellent weather resistance. Weatherability refers to the change in appearance and mechanical strength when exposed under certain conditions, and can be measured, for example, using a Q-Lab ultraviolet fluorescent lamp accelerated weathering tester.

[0070] Substituting the cured products of the present disclosure for conventional cured products can improve sustainability and reduce environmental impact. One indicator of environmental impact is the amount of carbon dioxide emitted when the hardened material is burned and disposed of. The amount of carbon dioxide emitted when burned and disposed of is calculated assuming that all of the biomass-derived carbon contained in the hardened material is converted to carbon dioxide through combustion. Carbon derived from biomass raw materials is carbon neutral, so carbon dioxide emissions during combustion are considered to be zero. The amount of carbon dioxide emitted per 1 kg of the cured product disposed of by combustion is preferably 1 kg or less, more preferably 0.8 kg or less, even more preferably 0.6 kg or less, even more preferably 0.4 kg or less, and particularly preferably 0.2 kg or less.

[0071] The curable epoxy resin composition of the present disclosure and the cured product of the present disclosure have excellent heat resistance and electrical properties, as well as excellent transparency and weather resistance, and therefore can be suitably used for insulating materials; sealing materials for LEDs, solar cells, electronic components, etc.; optical materials such as optical lenses, optical elements, optical connectors, optical waveguides, and optical shaping resins; printed circuit board materials; semiconductor package substrate materials; communication cover antennas; drone housings; transparent heater substrates, etc. Among these, they can be suitably used for insulating materials, sealing materials, optical materials, and printed circuit board materials, and are particularly suitable for use in insulating materials.

[0072] The present disclosure also provides insulating materials, sealing materials, optical materials, and printed circuit board materials using the curable epoxy resin composition of the present disclosure. The insulating materials, sealing materials, optical materials, and printed circuit board materials of the present disclosure have excellent heat resistance and electrical properties, as well as excellent transparency and weather resistance. In addition, sustainability is improved, and environmental impact can be reduced. The insulating material, sealing material, optical material, and printed circuit board material of the present disclosure may contain the curable epoxy resin composition of the present disclosure, or may contain the cured product of the present disclosure.

[0073] The present disclosure also provides a method for producing a cured product, comprising the step of curing the curable epoxy resin composition of the present disclosure.

[0074] The method for curing the curable epoxy resin composition is not particularly limited, and may involve heating in an oven or the like, or blowing hot air, etc. The temperature may be constant, or a temperature gradient may be applied. The curing temperature may be in a temperature range of 100°C or less, but because the curable epoxy resin composition of the present disclosure has excellent heat resistance, it can also be used for treatment in a high temperature range of 120 to 200°C. The curing time is not particularly limited, but is, for example, 1 to 15 hours. The curing temperature is preferably 200°C or less, and the drying time in a high temperature range of 160 to 200°C is preferably 5 hours or less, more preferably 3 hours or less.

[0075] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims. [Example]

[0076] The present disclosure will now be described in more detail with reference to examples, but the present disclosure is not limited to these examples.

[0077] The various properties in this specification were measured by the following methods.

[0078] (glass transition temperature) The glass transition temperature was evaluated by measuring a 5 mg sample by a temperature-modulated DSC measurement method using a differential scanning calorimeter (Q1000 manufactured by TA Instruments) by repeatedly heating and cooling a 5 mg sample at a constant cycle and amplitude while raising the temperature on average to obtain a DSC curve, and the peak-top temperature of the differential curve specified in JIS K6240 was taken as the glass transition temperature.

[0079] (pyrolysis temperature) Measurements were performed using a thermal analyzer, TG-DTA 2000SA, manufactured by Bruker AXS. Measurements were performed under a nitrogen purge atmosphere at 150 mL / min. 10 mg of sample was placed in a platinum pan, held at 25°C for 10 minutes, and then heated to 600°C at a rate of 10°C / min. The temperature at which the mass decreased by 1% from the initial mass (Td1) was defined as the thermal decomposition temperature and evaluated.

[0080] (Method for measuring relative permittivity and dielectric loss tangent) The dielectric constant and dielectric loss tangent of the cured product at a frequency of 10 GHz were measured and evaluated using a powder cavity resonator dielectric constant measuring device (manufactured by AET Co., Ltd.) The specific gravity of the sample was measured using a specific gravity measuring device AUW120D (manufactured by Shimadzu Corporation).

[0081] The following materials were used in the examples and comparative examples. Isosorbide diglycidyl ether (A: 100% biomass, B: 50% biomass) [ka] Ethylene glycol diglycidyl ether (biomass content 100%) [ka] Poly(propylene glycol) diglycidyl ether (biomass content 100%, Mn 380 or less) [ka] Phthalic anhydride (biomass content 100%) [ka] Maleic anhydride (biomass content 100%) [ka] Pentaerythritol tetrakis(3-mercaptobutyrate) (biomass content 100%) [ka] (+)-Catechin hydrate (biomass content 100%) [ka] Pentamethylenediamine (biomass content 100%) [ka]

[0082] Example 1 Phthalic anhydride (2.06 g) and ethyl acetate (5.0 mL) were placed in a 20 mL glass container and heated and stirred on a hot plate heated to 70°C. The phthalic anhydride gradually dissolved to form a colorless, transparent solution. Next, isosorbide diglycidyl ether A (2.0 g) was gradually added dropwise. The hot plate was removed and the mixture was stirred at room temperature for approximately 5 minutes, after which 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) (20 mg) was added. After stirring for 5 minutes, the mixture was cast onto a Teflon (registered trademark) sheet. The mixture was then cured in a constant temperature oven (120°C for 5 hours, then 150°C for 10 hours) to yield 3.7 g of cured material. The cured product was subjected to various tests, and the obtained properties are shown in Table 1.

[0083] Example 2 Maleic anhydride (2.1 g) and ethyl acetate (10 mL) were placed in a 20 mL glass container and heated and stirred on a hot plate heated to 70°C. The maleic anhydride gradually dissolved to form a colorless, transparent solution. Next, isosorbide diglycidyl ether A (3.0 g) was gradually added dropwise. The hot plate was removed and the mixture was stirred at room temperature for approximately 5 minutes, after which DMP-30 (24 mg) was added. After stirring for 5 minutes, the mixture was cast onto a Teflon (registered trademark) sheet. The mixture was then cured in a constant temperature oven (120°C for 5 hours, then 150°C for 10 hours) to yield 4.5 g of cured product. The cured product was subjected to various tests, and the obtained properties are shown in Table 2.

[0084] Example 3 Isosorbide diglycidyl ether A (1.9 g) and pentaerythritol tetrakis(3-mercaptobutyrate) (2.0 g) were placed in a 10 mL glass container and stirred at room temperature for approximately 10 minutes. Next, 2-ethyl-4-methylimidazole (2E4MZ) (19.5 mg) was added. After stirring for 10 minutes, the mixture was cast onto a Teflon (registered trademark) sheet. The mixture was then cured (100°C for 1 hour) to yield 3.5 g of a cured product. The cured product was subjected to various tests, and the obtained properties are shown in Table 2.

[0085] Example 4 (+)-Catechin hydrate (2.1 g) and ethyl acetate (8.0 mL) were placed in a 20 mL glass container and heated and stirred on a hot plate heated to 70°C. The (+)-catechin hydrate gradually dissolved, forming an orange solution. Next, isosorbide diglycidyl ether A (3.5 g) was gradually added dropwise. The hot plate was removed, and the mixture was stirred at room temperature for approximately 5 minutes, after which 2E4MZ (28 mg) was added. After stirring for 5 minutes, the mixture was cast onto a Teflon (registered trademark) sheet. The mixture was then cured in a constant temperature oven (160°C for 1.5 hours, then 200°C for 1.5 hours) to yield 5.5 g of a cured product. The cured product was subjected to various tests, and the obtained properties are shown in Table 2.

[0086] Example 5 Phthalic anhydride (3.06 g) and ethyl acetate (8.0 mL) were placed in a 20 mL glass container and heated and stirred on a hot plate heated to 70°C. The phthalic anhydride gradually dissolved to form a colorless, transparent solution. Next, ethylene glycol diglycidyl ether (2.0 g) was gradually added dropwise. The hot plate was removed and the mixture was stirred at room temperature for approximately 5 minutes, after which DMP-30 (20 mg) was added. After stirring for 5 minutes, the mixture was cast onto a Teflon (registered trademark) sheet. The mixture was then cured in a constant temperature dryer (120°C for 5 hours, then 150°C for 10 hours) to yield 4.6 g of cured product. The cured product was subjected to various tests, and the obtained properties are shown in Table 2.

[0087] Example 6 Phthalic anhydride (1.89 g) and ethyl acetate (8.0 mL) were placed in a 20 mL glass container and heated and stirred on a hot plate heated to 70°C. The phthalic anhydride gradually dissolved to form a colorless, transparent solution. Next, poly(propylene glycol) diglycidyl ether (2.7 g) was gradually added dropwise. The hot plate was removed and the mixture was stirred at room temperature for approximately 5 minutes, after which DMP-30 (20 mg) was added. After stirring for 5 minutes, the mixture was cast onto a Teflon (registered trademark) sheet. The mixture was then cured in a constant temperature oven (120°C for 5 hours, then 150°C for 10 hours) to yield 4.2 g of cured material. The cured product was subjected to various tests, and the obtained properties are shown in Table 2.

[0088] Example 7 The same procedure as in Example 1 was carried out except that isosorbide diglycidyl ether B was used instead of isosorbide diglycidyl ether A, to obtain 3.7 g of a cured product. The cured product was subjected to various tests, and the obtained properties are shown in Table 3.

[0089] Comparative Example 1 Isosorbide diglycidyl ether A (5.0 g) was placed in a 10 mL glass container and stirred at room temperature. Subsequently, pentamethylenediamine (1.98 g) was slowly added dropwise. The isosorbide diglycidyl ether gradually dissolved to form a colorless, transparent solution. After stirring at room temperature for approximately 15 minutes, the mixture was cast onto an aluminum cup and Kapton film. This was then cured in a constant temperature oven (120°C for 5 hours, then 150°C for 10 hours) to yield 3.7 g of cured material. The cured product was subjected to various tests, and the obtained properties are shown in Table 1.

[0090] [Table 1]

[0091] [Table 2]

[0092] [Table 3]

[0093] (carbon dioxide emissions) The carbon dioxide emissions of the cured products obtained in the examples were calculated as follows. Of the carbon contained in the epoxy compound, curing agent, and catalyst, the amount of non-biomass-derived carbon (kg / 1 kg (amount of non-biomass-derived carbon contained in 1 kg of cured material)) is calculated for each example. Carbon dioxide derived from biomass carbon is excluded from carbon dioxide emissions under the concept of carbon neutrality, so the amount of carbon dioxide emitted when 1 kg of hardened material is burned refers to the amount of carbon dioxide derived from non-biomass carbon, and can be calculated using the following formula. Carbon dioxide emissions (kg / 1kg) = Amount of carbon derived from non-biomass (kg / 1kg) x 44 / 12

[0094] The carbon dioxide emissions for Example 1 are calculated. The materials used in Example 1 are as follows. Isosorbide diglycidyl ether A (biomass-derived, molecular weight: 258.2, carbon content: 55.81% by mass): 2.0 g (49.02% by mass of the total cured material) Phthalic anhydride (biomass-derived, molecular weight: 148.12, carbon content: 64.82% by mass): 2.06 g (50.49% by mass of the entire cured material) 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30) (non-biomass-derived, molecular weight: 265.4, carbon content: 67.88% by mass): 0.02 g (0.49% by mass of the total cured material) Therefore, the amount of non-biomass-derived carbon in 1 kg of the hardened material of Example 1 (kg / 1 kg) is 67.83 / 100×0.49 / 100=0.00332(kg / 1kg) The carbon dioxide emissions of the cured product of Example 1 are: 0.00332×44 / 12=0.012(kg / 1kg) It can be found that:

[0095] When the amount of carbon dioxide emitted in Example 7 was calculated in the same manner as in Example 1, the amount of carbon dioxide emitted was 1.0 kg / 1 kg. For reference, when the carbon dioxide emissions when non-biomass-derived isosorbide diglycidyl ether, non-biomass-derived phthalic anhydride, and non-biomass-derived DMP-30 were used, the amount was calculated in the same manner as in Example 1 and was found to be 2.2 kg / 1 kg. From the above, it can be seen that the cured product of the present disclosure has an extremely small environmental impact.

Claims

1. Contains a biomass-derived non-aromatic epoxy compound and a biomass-derived curing agent, the non-aromatic epoxy compound has a ring structure other than an epoxy group, The curable epoxy resin composition, wherein the curing agent is at least one selected from the group consisting of thiols and phenolic compounds.

2. 2. The curable epoxy resin composition according to claim 1, wherein the non-aromatic epoxy compound and the curing agent have a biomass content of 50% or more.

3. 3. The curable epoxy resin composition according to claim 1, wherein the non-aromatic epoxy compound and the curing agent have a biomass content of 100%.

4. 3. The curable epoxy resin composition according to claim 1, wherein the non-aromatic epoxy compound contains two or more epoxy groups.

5. 3. The curable epoxy resin composition according to claim 1, wherein the non-aromatic epoxy compound is a non-aromatic diepoxy compound.

6. 3. The curable epoxy resin composition according to claim 1, wherein the non-aromatic epoxy compound has an isosorbide structure.

7. 3. The curable epoxy resin composition according to claim 1, wherein the non-aromatic epoxy compound is at least one selected from the group consisting of isosorbide diglycidyl ether, ethylene glycol diglycidyl ether, and poly(propylene glycol) diglycidyl ether.

8. 3. The curable epoxy resin composition according to claim 1, wherein the non-aromatic epoxy compound is isosorbide diglycidyl ether.

9. 3. The curable epoxy resin composition according to claim 1, wherein the thiol is an aliphatic thiol.

10. 3. The curable epoxy resin composition according to claim 1, wherein the thiol is at least one selected from the group consisting of pentaerythritol tetrakis(3-mercaptobutyrate) and L-cysteine.

11. 3. The curable epoxy resin composition according to claim 1, wherein the phenolic compound contains two or more hydroxy groups.

12. 3. The curable epoxy resin composition according to claim 1, wherein the phenolic compound is (+)-catechin hydrate.

13. A cured product obtained by curing the curable epoxy resin composition according to claim 1 or 2.

14. An insulating material using the curable epoxy resin composition according to claim 1 or 2.

15. A sealing material using the curable epoxy resin composition according to claim 1 or 2.

16. An optical material using the curable epoxy resin composition according to claim 1 or 2.

17. A printed circuit board material using the curable epoxy resin composition according to claim 1 or 2.

18. A method for producing a cured product, comprising a step of curing the curable epoxy resin composition according to claim 1 or 2.

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