Epoxy resin composition and epoxy resin composition product

Abstract

To provide a one-liquid type epoxy resin composition having low viscosity property, short time curing property, and high storage stability, and excellent in normal temperature transportation adequacy, environmental load reduction when transporting, and reduction of waste generating after transportation.SOLUTION: An epoxy resin composition contains constituent (A): a bisphenol A-type epoxy resin having a percentage of a peak area Sα derived from α-glycol represented by formula (1) calculated by liquid chromatography measurement to an all peak area total sum STotal of 0.4% or more and 1.4% or less; constituent (B): a bisphenol F-type epoxy resin; constituent (C): an acid anhydride; and constituent (D): a microcapsule-type curing accelerator.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an epoxy resin composition and an epoxy resin composition product. [Background technology]

[0002] Epoxy resins have traditionally been used in a wide range of applications, such as insulating materials for electric and electronic components, sealing materials, adhesives, conductive materials, matrix resins for fiber-reinforced plastics, and impregnating adhesives for motor coils.

[0003] Recent demands for electronic devices are diverse, including miniaturization, high performance, lightweight design, and multi-functionality, and semiconductor chip mounting technology is also advancing, with electrode pads being spaced at finer pitches, resulting in further miniaturization, miniaturization, and higher density. An underfill material made of a thermosetting resin composition that protects the bump connections and the circuit surface of the chip is used in the gap between the semiconductor chip and the substrate, and an epoxy resin composition is used as such an underfill material.

[0004] Fiber-reinforced plastics are manufactured using reinforcing fibers and a matrix resin. The matrix resin is often a thermosetting resin using an epoxy resin, and fiber-reinforced plastics are obtained by impregnating reinforcing fibers with a resin composition containing the epoxy resin and curing the resin composition.

[0005] Furthermore, motor coils are protected from deterioration due to moisture and environmental waste by impregnating the spaces between the coils with an epoxy resin composition and curing it. For example, Patent Document 1 discloses an example of such an epoxy resin composition, a one-component epoxy resin composition for electrical insulation that has excellent storage stability and short curing time. Patent Document 2 also discloses an epoxy resin composition for impregnation and fixing that has excellent storage stability and is easy to process. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-220306 [Patent Document 2] Patent No. 5400383 Summary of the Invention [Problem to be solved by the invention]

[0007] In recent years, the automotive industry has been working to address environmental issues, leading to an increase in the production of hybrid and electric vehicles, and demand for motor coils is on the rise. Furthermore, from the perspective of improving fuel efficiency, vehicle weight reduction technology is important, and the use of lightweight, high-strength fiber-reinforced plastics is expanding.

[0008] In response to the increasing demand for motor coils and fiber-reinforced plastics, improving productivity by shortening production takt time and reducing environmental impact are becoming issues. To solve these issues, there is a need for a one-component epoxy resin composition that can shorten impregnation and curing times, has high storage stability, and eliminates the need for a mixing step during use. However, in one-component epoxy resin compositions, there is a trade-off between high storage stability and shortened curing time, and it is extremely difficult to achieve both at a high level. Furthermore, when transporting one-component epoxy resin products, coolants, refrigeration equipment, and special packaging materials suitable for these are required to maintain quality. Refrigeration equipment has the problem of placing a heavy burden on the environment, and the coolants and special packaging materials used become waste. To address these issues, the one-component epoxy resin compositions described in Patent Documents 1 and 2 have the problem that there is still room for improvement in terms of low viscosity, short-time curing, high storage stability, suitability for transportation at room temperature, reduction of the environmental load during transportation, and reduction of waste generated after transportation.

[0009] In view of the above-mentioned problems of the conventional art, the present invention aims to provide a one-component epoxy resin composition which has low viscosity, short-time curing properties, high storage stability, and is suitable for transportation at room temperature, reduces the environmental load during transportation, and is excellent in reducing waste generated after transportation, as well as a product packaged with the same. [Means for solving the problem]

[0010] As a result of extensive research, the present inventors have found that the above object can be achieved by the following technical means, and have arrived at the present invention. That is, the present invention is as follows.

[0011] [1] Component (A): The ratio of the peak area Sα derived from α-glycol represented by formula (1), calculated by liquid chromatography, to the sum of all peak areas S Total Bisphenol A type epoxy resin, which is 0.4% or more and less than 1.4% of

[0012] [ka]

[0013] Component (B): bisphenol F type epoxy resin, Component (C): an acid anhydride, Component (D): a microcapsule-type hardening accelerator; An epoxy resin composition comprising:

[0014] [2] The epoxy resin composition according to [1] above, wherein the content of the component (B): bisphenol F type epoxy resin is 10 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the total amount of the epoxy compounds. [3] The epoxy resin composition according to [1] or [2] above, further comprising a component (E) reactive diluent. [4] The epoxy resin composition according to any one of [1] to [3] above, wherein the component (C) is an acid anhydride having a structure of the following formula (2) or formula (3):

[0015] [ka]

[0016] In formula (2), carbon atoms C1 to C6 may be saturated or unsaturated. In the case of unsaturated carbon atoms, adjacent carbon atoms may form an unsaturated bond. R1~R 14 are each one selected from the group consisting of hydrogen, an alkyl group, an aromatic group, a substituent containing a hetero atom, and a substituent containing a halogen atom. R1~R 14 may be the same or different. Also, R1~R 14 It may also be a fused ring compound in which any one selected from the following is present in the same ring.)

[0017] [ka]

[0018] In formula (3), carbon atoms C1 to C6 may be saturated or unsaturated. In the case of unsaturated carbon atoms, adjacent carbon atoms may form an unsaturated bond. R1~R 12 are each one selected from the group consisting of hydrogen, an alkyl group, an aromatic group, a substituent containing a hetero atom, and a substituent containing a halogen atom. R1~R 12 may be the same or different. Also, R1~R 12 It may also be a fused ring compound in which any one selected from the following is present in the same ring.)

[0019] [5] The epoxy resin composition according to any one of [1] to [4] above, a resin or metal container containing the epoxy resin composition; and a renewable or reusable paper or plastic outer packaging material for packaging the container. [Effects of the Invention]

[0020] According to the present invention, it is possible to provide a one-component epoxy resin composition that has low viscosity, short-time curing properties, high storage stability, is suitable for transportation at room temperature, reduces the environmental load during transportation, and is excellent in reducing waste generated after transportation. DETAILED DESCRIPTION OF THE INVENTION

[0021] Hereinafter, an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following embodiments are merely examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be practiced with appropriate modifications within the scope of its gist.

[0022] [Epoxy resin composition] The epoxy resin composition of the present embodiment comprises: Component (A): The ratio of the peak area Sα derived from α-glycol represented by formula (1), calculated by liquid chromatography (hereinafter sometimes referred to as LC), to the sum of all peak areas S Total Bisphenol A type epoxy resin, which is 0.4% or more and less than 1.4% of

[0023] [ka]

[0024] Component (B): bisphenol F type epoxy resin, Component (C): an acid anhydride, Component (D): a microcapsule-type hardening accelerator; Contains: The epoxy resin composition of the present embodiment contains components (A) to (D), and thus exhibits low viscosity, short-time curing properties, and high storage stability, even though it is a one-component epoxy resin composition.

[0025] (Component (A)) The epoxy resin composition of the present embodiment contains, as component (A), a compound having a peak area Sα derived from α-glycol represented by the above formula (1), which is calculated by LC measurement, and ... Total It contains bisphenol A type epoxy resin, which is 0.4% or more but less than 1.4% of the total. By including component (A), high storage stability, sufficient reactivity, and appropriate viscosity are achieved. Examples of component (A) include, but are not limited to, BE-186EL (trade name, manufactured by Changchun Co., Ltd.) and DER383J (trade name, manufactured by Olin). The component (A) may be used alone or in combination of two or more types.

[0026] The α-glycol represented by formula (1) contained in component (A) is a compound having a hydroxyl group at the molecular end. From the viewpoint of storage stability, the ratio of the peak area Sα derived from the α-glycol calculated by LC measurement is set to be less than the sum of all peak areas S Total It is to be less than 1.4%, preferably 1.3% or less, more preferably 1.1% or less, and even more preferably 1.0% or less. On the other hand, in the epoxy resin composition of the present embodiment, from the viewpoint of maintaining high storage stability and sufficient reactivity, the content is 0.40% or more, preferably 0.41% or more, and more preferably 0.42% or more.

[0027] The ratio of the peak area Sα derived from α-glycol, as calculated by the above formula (1), to the sum of all peak areas S Total The mechanism by which a content of 0.4% or more and less than 1.4% of the total amount of HCl is effective in achieving high storage stability and sufficient reactivity is thought to be as follows, although it is not limited thereto. The hydroxyl groups in the structure of α-glycol coordinate to the acid anhydride (component (C) described below), thereby accelerating the ring-opening reaction of the acid anhydride, which deteriorates the storage stability of the epoxy resin composition and increases the water absorption of the epoxy resin composition. When the water absorption of the epoxy resin composition is thus increased, the water that has entered the epoxy resin composition further accelerates the ring-opening reaction of the acid anhydride (component (C) described below), further deteriorating the storage stability of the epoxy resin composition. Therefore, reducing the amount of α-glycol can improve storage stability. On the other hand, including α-glycol within a range that does not impair storage stability can effectively improve the reactivity of the acid anhydride (component (C)), which will be described later. From the above, the epoxy resin composition of the present embodiment has a peak area Sα derived from α-glycol represented by the above formula (1), which is calculated by LC measurement, and is smaller than the sum of all peak areas S Total It contains bisphenol A type epoxy resin in an amount of 0.4% or more and less than 1.4% of the total. The proportion of the peak area of α-glycol represented by the formula (1) in component (A), calculated by LC measurement, can be controlled to fall within the above-mentioned range by controlling the water content in the production process or by purifying the product by distillation or the like after production.

[0028] From the viewpoint of imparting an appropriate viscosity to the epoxy resin composition of this embodiment, the content of component (A) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 40 parts by mass or more, and even more preferably 45 parts by mass or more, relative to 100 parts by mass of the total amount of epoxy compounds. Furthermore, component (B), which will be described later, is added to achieve low viscosity, high storage stability, and short-time curing properties. The content of component (A) need only be an amount sufficient to achieve these effects, and from the viewpoint of preventing excessive addition, the content is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and even more preferably 75 parts by mass or less. Here, the appropriate viscosity refers to a viscosity that allows the one-component epoxy resin composition of the present embodiment to sufficiently penetrate into coils, carbon fibers, and narrow gaps in a short time, and also prevents dripping and spreading to unwanted areas after application. The total amount of epoxy compounds refers to an amount that includes at least the epoxy resins of component (A) and component (B), and further refers to an amount that also includes component (E), which will be described later, when the component (E) is an epoxy compound.

[0029] (Component (B)) The epoxy resin composition of the present embodiment contains a bisphenol F epoxy resin as component (B). By including component (B), the composition has low viscosity, short curing time, and high storage stability. Examples of liquid bisphenol F epoxy resins include, but are not limited to, jER806, jER806H, jER807, jER1750, YL983U (trade names manufactured by Mitsubishi Chemical), 830, 830-S, EXA-830CRP, EXA-830LVP, 835, EXA-835LV (trade names manufactured by DIC), EP-4901, EP-4901E (trade names manufactured by ADEKA), YDF-8170C, YDF-170, YDF-170N (trade names manufactured by Nippon Steel Chemical), and the like. Examples of solid bisphenol F epoxy resins include, but are not limited to, jER4005PP, jER4007P, jER4010P (trade names manufactured by Mitsubishi Chemical), YDF-2001, YDF-2004, and YDF-2005RD (trade names manufactured by Nippon Steel Chemical). These may be used alone or in combination of two or more. In this embodiment, liquid bisphenol F epoxy resin is preferred from the viewpoint of low viscosity and ease of handling.

[0030] The mechanism by which the inclusion of component (B): bisphenol F type epoxy resin is effective in achieving low viscosity, short curing time, and high storage stability is thought to be, but is not intended to be limiting, as follows. The inclusion of the bisphenol F epoxy resin suppresses aggregation of the bisphenol A epoxy resins, improving the uniformity of the epoxy resin composition of the present embodiment and increasing the molecular diffusivity at the curing temperature, thereby exhibiting low viscosity, high storage stability, and short-term reactivity.

[0031] The content of component (B), bisphenol F epoxy resin, is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more, from the viewpoint of exhibiting low viscosity, short-time curing property, and high storage stability, when the total amount of epoxy compounds is 100 parts by mass. Furthermore, since component (A) is added to impart sufficient viscosity, the content of component (B) need only be an amount sufficient to realize such effects, and from the viewpoint of preventing excessive addition, the content is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 50 parts by mass or less. The total amount of epoxy compounds refers to an amount that includes at least the epoxy resins of component (A) and component (B), and further refers to an amount that also includes component (E), which will be described later, when the component (E) is an epoxy compound.

[0032] (Component (C)) The epoxy resin composition of the present embodiment contains an acid anhydride as component (C). The acid anhydride functions as a curing agent. Component (C): Acid anhydride is not limited to the following, but examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhimic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0033] In the epoxy resin composition of the present embodiment, from the viewpoints of storage stability and reactivity, component (C) is preferably an acid anhydride having a phthalic anhydride structure or an acid anhydride having a structure represented by the following formula (2) or formula (3), and from the viewpoint of storage stability, an acid anhydride having the structure represented by formula (2) is more preferred.

[0034] [ka]

[0035] In formula (2), carbon atoms C1 to C6 may be saturated or unsaturated. In the case of unsaturated carbon atoms, adjacent carbon atoms may form an unsaturated bond. R1~R 14 are each one selected from the group consisting of hydrogen, an alkyl group, an aromatic group, a substituent containing a hetero atom, and a substituent containing a halogen atom. R1~R 14 may be the same or different. Also, R1~R 14 It may also be a fused ring compound in which any one selected from the following is present in the same ring.)

[0036] [ka]

[0037] In formula (3), carbon atoms C1 to C6 may be saturated or unsaturated. In the case of unsaturated carbon atoms, adjacent carbon atoms may form an unsaturated bond. R1~R 12 are each one selected from the group consisting of hydrogen, an alkyl group, an aromatic group, a substituent containing a hetero atom, and a substituent containing a halogen atom. R1~R 12 may be the same or different. Also, R1~R 12 It may also be a fused ring compound in which any one selected from the following is present in the same ring.)

[0038] Examples of acid anhydrides having the structure of general formula (2) include, but are not limited to, nadic anhydrides such as methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, hydrogenated methyl nadic anhydride, and chlorendic anhydride. Examples of acid anhydrides having the structure of general formula (3) include, but are not limited to, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. These acid anhydrides as component (C) may be used alone or in combination of two or more.

[0039] The content of component (C) is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 60 parts by mass or more, from the viewpoint of appropriate viscosity, reactivity, strength, and heat resistance, when the total amount of component (A), component (B), and component (E) described below is taken as 100 parts by mass. From the viewpoint of storage stability, the amount is preferably 150 parts by mass or less, more preferably 130 parts by mass or less, and even more preferably 120 parts by mass or less.

[0040] (Component (D)) The epoxy resin composition of the present embodiment contains component (D): a microcapsule-type curing accelerator. Component (D) has excellent storage stability because the hardening accelerator component is physically isolated from components (A), (B), and (C) by the capsule membrane.

[0041] In order to ensure sufficient reactivity, the content of component (D), a microcapsule-type curing accelerator, is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, and even more preferably 4 parts by mass or more, when the total of components (A), (B), and (E) described below is 100 parts by mass. Furthermore, from the viewpoint of appropriate viscosity, the amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 12 parts by mass or less, and even more preferably 11 parts by mass or less.

[0042] Examples of the hardening accelerator component in the microcapsules of component (D) include amine-based compounds, amide-based compounds, and phenol-based compounds.

[0043] Examples of the amine compounds include, but are not limited to, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, diaminodiphenylmethane, m-phenylenediamine, and diaminodiphenylsulfonyl. HO, diethyltoluenediamine, trimethylenebis(4-aminobenzoate), polytetramethyleneoxide-di-p-aminobenzoate, trimethylamine, triethylamine, benzyldimethylamine, N,N-dimethyl-ethylamine, N,N-dimethyl-butylamine, N,N-dimethyldecylamine, N,N-dimethyl-m-toluidine, N,N-dimethyl-p-toluidine, 2,6,10-trimethyl-2,6,10-triazaundecane, N,N'-dimethylpiperazine, 1 Tertiary amines such as 4-diazabicyclo[2.2.2]octane, 1-azabicyclo[2.2.2]octan-3-one, 1,8-diazabicyclo(5,4,0)-undecene-7, 1,5-diazabicyclo(4,3,0)-nonene-5, and hexamethylenetetramine; imidazoles such as 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 1-vinylimidazole, 1-allylimidazole, 2-methyl-1-vinylimidazole, and N-acetylimidazole; Examples of the aromatic tertiary amines include dimethylaminobenzhydrol, bis[4-(dimethylamino)phenyl]methane, 4,4'-bis(dimethylamino)benzophenone, and 2-diethylamino-N-(2,6-dimethylphenyl)acetamide; aminopyridines having a tertiary amino group, such as 2-dimethylaminopyridine and 4-dimethylaminopyridine; and products obtained by reacting an amine compound with a carboxylic acid compound, a sulfonic acid compound, a urea compound, an isocyanate compound, or an epoxy compound. These amine compounds may be used alone or in combination of two or more. In this embodiment, imidazole compounds are preferred because they have high reactivity and can be cured in a short time.

[0044] Examples of amide compounds include, but are not limited to, succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, p-oxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic acid hydrazide, maleic acid dihydrazide, dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, toluoylguanidine, and compounds obtained by reacting an amine compound with an acid anhydride. These amide compounds may be used alone or in combination of two or more.

[0045] Examples of phenolic compounds include, but are not limited to, phenol novolac resin, cresol novolac resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenol resin, biphenyl-modified phenol aralkyl resin, dicyclopentadiene-modified phenol resin, aminotriazine-modified phenol resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, and allyl acrylic phenol resin. These phenolic compounds may be used alone or in combination of two or more.

[0046] These curing accelerator components in the microcapsules may be used alone or in combination of two or more.

[0047] From the viewpoint of storage stability, it is preferable that the hardening accelerator component in the microcapsules contains a hardener that is solid at 25°C and 1013 hPa. This prevents the hardener from leaching out of the capsule even if the capsule is damaged when the components are mixed, thereby maintaining storage stability.

[0048] Examples of microcapsule-type curing accelerators containing a curing agent that is solid at 25°C and 1013 hPa include Novacure HX-3721, HX-3722, HX-3742, HX-3088, HX-3792, HX-3921HP, HXA3922HP, HXA3932HP, HXA9322HP, and HXA9382HP, as well as AER Hardener D1301 (manufactured by Asahi Kasei). These microcapsule type hardening accelerators may be used alone or in combination of two or more.

[0049] (Component (E)) The epoxy resin composition of the present embodiment may contain component (E), a reactive diluent (hereinafter sometimes referred to as component (E)), as needed.

[0050] Examples of the component (E), the reactive diluent, include, but are not limited to, polyfunctional acrylate compounds containing acrylic groups, and epoxy compounds that can reduce viscosity without impairing reactivity. Epoxy compounds that do not belong to the bisphenol type epoxy resins and have a lower viscosity than the bisphenol A type epoxy resin of component (A) are sometimes called epoxy type reactive diluents.

[0051] Examples of polyfunctional acrylates containing an acrylic group include, but are not limited to, compounds having (meth)acryloyl groups at both ends of a polyalkylene oxide, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, trimethylolpropane-type polyfunctional (meth)acrylate, pentaerythritol-type polyfunctional (meth)acrylate, and dipentaerythritol-type polyfunctional (meth)acrylate.

[0052] The epoxy-type reactive diluent is not particularly limited, but includes the following: Examples of nitrogen-free epoxy-type reactive diluents include ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, (o-, m-, or p-)cresyl glycidyl ether, 2-biphenyl glycidyl ether, p-tert-butoxyphenyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol (400) diglycidyl ether, polyethylene glycol diglycidyl ether, dimer acid glycidyl ester, 1,4-cyclohexanedimethanol diglycidyl ether, and hydrogenated bisphenol A diglycidyl ether. Examples of the epoxy-type reactive diluent containing a nitrogen atom include glycidyl aniline and glycidyl toluidine. The epoxy resin composition of the present embodiment contains component (C) an acid anhydride, and therefore preferably contains, as component (E), an epoxy-type reactive diluent containing no nitrogen atoms, from the viewpoint of achieving high storage stability and low viscosity, and more preferably contains an epoxy-type reactive diluent containing no nitrogen atoms and having a linear structure with 4 or more carbon atoms, from the viewpoint of increasing the tensile strength of the cured product.

[0053] The component (E), reactive diluent, may be used alone or in combination of two or more.

[0054] The content of component (E) is preferably 0.5 parts by mass or more, more preferably 2 parts by mass or more, and even more preferably 3 parts by mass or more, from the viewpoint of exhibiting an appropriate viscosity and sufficient mechanical properties, when the total of components (A), (B), and (E) is taken as 100 parts by mass. In addition, from the viewpoint of preventing excessive viscosity reduction and deterioration of mechanical properties, the amount is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less.

[0055] (Other additives) In addition to the components described above, the epoxy resin composition of the present embodiment may further contain additives, as needed, such as epoxy resins other than components (A) and (B), organic fillers, inorganic fillers, pigments, dyes, flow modifiers, thickeners, release agents, wetting agents, flame retardants, surfactants, resins, and the like.

[0056] Epoxy resins other than components (A) and (B) include, but are not limited to, bisphenol AD type epoxy resins, bisphenol M type epoxy resins, bisphenol P type epoxy resins, tetrabromobisphenol A type epoxy resins, biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, tetrabromobiphenyl type epoxy resins, diphenyl ether type epoxy resins, benzophenone type epoxy resins, phenyl benzoate type epoxy resins, diphenyl sulfide type epoxy resins, diphenyl sulfoxide type epoxy resins, diphenyl sulfone type epoxy resins, diphenyl disulfide type epoxy resins, naphthalene type epoxy resins, anthracene type epoxy resins, hydroquinone type epoxy resins, methylhydroquinone type epoxy resins, dibutylhydroquinone type epoxy resins, resorcinol type epoxy resins, bifunctional epoxy resins such as alkoxy resin, methylresorcinol-type epoxy resin, catechol-type epoxy resin, and N,N-diglycidylaniline-type epoxy resin; trifunctional epoxy resins such as N,N-diglycidylaminobenzene-type epoxy resin, o-(N,N-diglycidylamino)toluene-type epoxy resin, and triazine-type epoxy resin; tetrafunctional epoxy resins such as tetraglycidyldiaminodiphenylmethane-type epoxy resin and diaminobenzene-type epoxy resin; multifunctional epoxy resins such as phenol novolac-type epoxy resin, cresol novolac-type epoxy resin, triphenylmethane-type epoxy resin, tetraphenylethane-type epoxy resin, dicyclopentadiene-type epoxy resin, naphthol aralkyl-type epoxy resin, and brominated phenol novolac-type epoxy resin; and alicyclic epoxy resins. These epoxy resins other than components (A) and (B) may be used alone or in combination of two or more.

[0057] The organic filler functions as a shock absorber, capable of mitigating stress generated by impact. By including an organic filler, the epoxy resin composition of the present embodiment can further improve adhesion to various connecting members and also tends to suppress the occurrence and propagation of fillet cracks. Examples of organic fillers include, but are not limited to, organic fine particles of acrylic resin, silicone resin, butadiene rubber, polyester, polyurethane, polyvinyl butyral, polyarylate, polymethyl methacrylate, acrylic rubber, polystyrene, NBR, SBR, silicone-modified resin, and copolymers containing any of these as components. From the viewpoint of improving adhesiveness, examples of organic fine particles include alkyl (meth)acrylate-butadiene-styrene copolymers, alkyl (meth)acrylate-silicone copolymers, silicone-(meth)acrylic copolymers, complexes of silicone and (meth)acrylic acid, complexes of alkyl (meth)acrylate-butadiene-styrene and silicone, and complexes of alkyl (meth)acrylate and silicone. Alternatively, organic fine particles having a core-shell structure with different compositions between the core layer and the shell layer may be used. Examples of core-shell organic fine particles include particles having a silicone-acrylic rubber core to which an acrylic resin is grafted, and particles having an acrylic resin grafted to an acrylic copolymer. These organic fillers may be used alone or in combination of two or more.

[0058] When an inorganic filler is contained, adjusting the thermal expansion coefficient of the epoxy resin composition of the present embodiment tends to contribute to improving the heat resistance and moisture resistance when used as an underfill material. Examples of inorganic fillers include, but are not limited to, silicates such as talc, calcined clay, uncalcined clay, mica, and glass; oxides such as silica oxides such as titanium oxide, aluminum oxide (alumina), fused silica (fused spherical silica, fused crushed silica), synthetic silica, and crystalline silica; carbonates such as calcium carbonate, magnesium carbonate, and hydrotalcite; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; sulfates such as barium sulfate and calcium sulfate; sulfites such as calcium sulfite; borates such as zinc borate, barium metaborate, aluminum borate, calcium borate, and sodium borate; and nitrides such as aluminum nitride, boron nitride, and silicon nitride. Among these, fused silica, crystalline silica, and synthetic silica powder are preferred from the viewpoint of improving heat resistance, moisture resistance, and strength, and silicon oxide, aluminum oxide, and boron nitride are also preferred. Use of these materials can suppress the coefficient of linear thermal expansion, which is expected to improve performance in thermal cycle tests. The shape of the inorganic filler is not particularly limited and may be, for example, any of amorphous, spherical, and scale-like shapes. These inorganic fillers may be used alone or in combination of two or more.

[0059] Examples of pigments include, but are not limited to, kaolin, aluminum oxide trihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, pentone, silica, aerosol, lithopone, baryte, and titanium dioxide.

[0060] Examples of dyes include, but are not limited to, natural dyes such as plant-derived dyes such as madder and indigo, and mineral-derived dyes such as yellow ochre and red clay, synthetic dyes such as alizarin and indigo, and fluorescent dyes.

[0061] Examples of flow control agents include, but are not limited to, silane coupling agents; organic titanium compounds such as titanium tetraisopropoxide and titanium diisopropoxybis(acetylacetonate); and organic zirconium compounds such as zirconium tetra-n-butoxide and zirconium tetraacetylacetonate.

[0062] Examples of thickeners include, but are not limited to, animal-based thickeners such as gelatin; plant-based thickeners such as polysaccharides and cellulose; and chemically synthesized thickeners such as polyacrylics, modified polyacrylics, polyethers, urethane-modified polyethers, and carboxymethyl cellulose.

[0063] Examples of the release agent include, but are not limited to, fluorine-based release agents, silicone-based release agents, and acrylic release agents made of a copolymer of glycidyl (meth)acrylate and a linear alkyl (meth)acrylate ester having 16 to 22 carbon atoms.

[0064] Examples of wetting agents include, but are not limited to, unsaturated polyester copolymer wetting agents having acidic groups, such as acrylic polyphosphate esters.

[0065] Examples of flame retardants include, but are not limited to, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, halogen-based flame retardants such as chlorine compounds and bromine compounds, phosphorus-based flame retardants such as condensed phosphate esters, antimony-based flame retardants such as antimony trioxide and antimony pentoxide, and inorganic oxides such as silica fillers.

[0066] Examples of surfactants include, but are not limited to, anionic surfactants such as alkylbenzenesulfonates and alkylpolyoxyethylenesulfates, cationic surfactants such as alkyldimethylammonium salts, amphoteric surfactants such as alkyldimethylamine oxides and alkylcarboxybetaines, and nonionic surfactants such as linear alcohols and fatty acid esters having 25 or more carbon atoms.

[0067] [Epoxy resin composition products] The epoxy resin composition product of the present embodiment includes the epoxy resin composition of the present embodiment, a resin or metal container containing the epoxy resin composition therein, and a recyclable or reusable paper or plastic exterior packaging material for packaging the container. Because the epoxy resin composition of this embodiment has high storage stability, even when stored at room temperature without the use of coolants, refrigeration, or special packaging to maintain quality, changes in viscosity characteristics and curing properties are minimal, allowing for transportation at room temperature. Therefore, there is no need to consider the effects of condensation, the ease of installing coolants, or changes in internal temperature when packaging the product, and renewable or reusable paper or plastic materials can be used. Furthermore, the elimination of the need for coolants or special packaging materials such as polystyrene foam reduces post-transport waste. Furthermore, the elimination of the need for refrigeration contributes to the reduction of greenhouse gas emissions. Examples of renewable or reusable paper or plastic materials include, but are not limited to, cardboard and recyclable and reusable plastic packaging materials.

[0068] [Method for producing epoxy resin composition] The epoxy resin composition of the present embodiment is obtained by mixing the above-mentioned components (A), (B), (C), and (D). The method for mixing the components is not particularly limited, and general mixing equipment and processing conditions can be applied. Specifically, although not particularly limited, an example of a method for obtaining an epoxy resin composition includes thoroughly mixing the above-mentioned components (A) to (D) and, if necessary, component (E) and other additive components, etc., until a homogeneous mixture is obtained using a mixing roll such as a three-roll mill, a dissolver, a planetary mixer, a kneader, an extruder, etc. [Example]

[0069] Hereinafter, the present embodiment will be described with reference to specific examples and comparative examples, but the present embodiment is not limited to the following examples and comparative examples. In the following, "parts" and "%" are by mass unless otherwise specified.

[0070] [Preparation of Epoxy Resin Composition] Components (A) to (E) described below were weighed out in the blending ratios shown in Table 1 below, and then these components were mixed in a non-bubbling kneader, stirring for 2 minutes and degassing for 3 minutes, to prepare an epoxy resin composition. The amount of each component in Table 1 below is shown in parts by mass, where the total amount of component (A), component (B), component (E), or epoxy resins other than component (A), component (B), and component (E) is taken as 100 parts by mass.

[0071] [Methods for measuring physical properties] (Percentage of peak area derived from α-glycol in bisphenol A epoxy resin, measured by LC) Bisphenol A type epoxy resin was dissolved in acetonitrile to prepare a 0.5% by mass solution, and then measurement was carried out using a UPLC manufactured by Waters Corporation under the following conditions. Equipment: UPLC H-Class / QDa (Waters Corporation) Column: Waters ACQUITY UPLC BEH C18 1.7 μm (2.1 mm I.D. x 50 mm) Column temperature: 40℃ Flow rate: 0.2mL / min Detection: Photodiode Array 280.4nm Mobile phase A: Water / methanol (80% / 20%) B: Acetonitrile (100%) Gradient 0 minutes = A:70% / B:30% 30 minutes = A:0% / B:100% 36 minutes = A:70% / B:30% 40 minutes = A:80% / B:20% Injection volume 1μL Measurement was carried out under the above conditions, and the peak appearing at 4.5 minutes corresponds to the α-glycol represented by formula (1). The area value corresponding to α-glycol is Sα, and the sum of all peak areas detected by liquid chromatography is S Total The sum of all peak areas S Total The ratio of the peak area Sα derived from α-glycol to the total peak area Sα was calculated using the following formula (1). Sα / S Total ×100 (%)...Formula (1)

[0072] [Method of measuring characteristics] (Low viscosity: Initial viscosity measurement of epoxy resin composition) The viscosity (initial viscosity) of the epoxy resin composition immediately after preparation was measured at room temperature (25°C) using an E-type viscometer (TVE-35H, manufactured by Toki Sangyo Co., Ltd.). The initial viscosity was evaluated as being preferably 1700 mPa·s or less from the viewpoint of impregnation into coils and carbon fibers in a short time and penetration into narrow gaps. On the other hand, from the viewpoint of reducing dripping and spreading to unwanted areas after application, a viscosity of 750 mPa·s or more was evaluated as preferable, and 1000 mPa or more was evaluated as more preferable.

[0073] (Storage stability: Storage stability viscosity magnification) The initial viscosity immediately after the preparation of the epoxy resin composition and the viscosity after leaving the epoxy resin composition at 40°C for 7 days were measured at room temperature (25°C) using an E-type viscometer, and the storage stability viscosity ratio was calculated using the following formula (2). Storage stability viscosity ratio = viscosity after 7 days at 40°C / initial viscosity Formula (2) The storage stability viscosity factor was evaluated as preferably 2 or less, more preferably 1.6 or less, and even more preferably 1.3 or less.

[0074] (Short-time curing: 150°C curastometer torque rise time) Using a Curastometer (Curastometer V, manufactured by TS Engineering Co., Ltd.), a torque-vulcanization time chart was obtained for the epoxy resin composition at a set temperature of 150°C. For the obtained chart, the time when the torque value started to increase slightly was taken as the torque rise time. The faster the torque rise time, the faster the gelation rate of the epoxy resin composition, indicating that it is suitable for short-time curing. A torque rise time of less than 200 seconds was evaluated as preferable, and 190 seconds or less was evaluated as particularly preferable.

[0075] (Tensile elongation measurement) The epoxy resin composition was poured fully into a Teflon (registered trademark) mold measuring 550 mm in length, 350 mm in width, and 2 mm in thickness, up to the opening, and heated in a heating furnace at a set temperature of 100°C for 30 minutes, and then at 150°C for 60 minutes. After heating was completed, the composition was removed from the Teflon (registered trademark) mold, and the resulting cured piece was cut into a size of 40 mm in length, 5 mm in width, and 2 mm in thickness to obtain a cured product sample as a test piece for measuring tensile strength. The obtained test pieces were subjected to a tensile test in a constant temperature and humidity chamber at 23°C and 50% RH using an AUTOGRAPH AGS-X 5kN (manufactured by SHIMADZU) at a unit moving speed of 5 mm / min to obtain the tensile elongation (%). The tensile test was carried out five times in total, and the median value of the obtained results was taken as the positive tensile elongation (%).

[0076] (Suitable for room temperature transportation: room temperature storage) 50 g of the epoxy resin composition was weighed into a resin container, which was then sealed and placed in a cardboard packaging material or a plastic packaging material to obtain an evaluation sample. This evaluation sample was stored in a metal container exposed to the open air for 10 days in May 2021 at a location of 35.14 north latitude and 138.68 east longitude, and the changes in the viscosity increase ratio of the epoxy resin composition and the 150°C curastometer torque rise time after 10 days were evaluated. <Criteria for determining the viscosity increase ratio in this evaluation> 1x or more and less than 1.3x ◎ 1.3 times or more but less than 1.6 times... 〇 1.6 times or more but less than 2 times △ More than twice as large × <Criteria for determining change in torque rise time at 150°C using a curastometer in this evaluation> 5% or less... More than 5% and less than 50% △ Greater than 50% ×

[0077] [Ingredients] The components are shown below in Table 1. The viscosity of each epoxy resin was measured in the same manner as in measuring the initial viscosity of the epoxy resin composition. (Bisphenol A epoxy resin corresponding to component (A)) BE-186EL (product name manufactured by Choshunsha) Epoxy equivalent 178g / eq., viscosity 9410mPa·s, Sα / Stotal×100=1.03% DER383J (Olin product name) Epoxy equivalent weight 178g / eq., viscosity 9780mPa·s, Sα / Stotal×100=0.42% (Bisphenol A epoxy resin not corresponding to component (A)) jER828 (product name manufactured by Mitsubishi Chemical Corporation) Epoxy equivalent 184g / eq., viscosity 13385mPa·s, Sα / Stotal×100=1.40% (Component (B) Bisphenol F type epoxy resin) EXA-830CRP (product name manufactured by DIC) Epoxy equivalent weight 161g / eq. (Component (C) acid anhydride) MHAC-P (product name manufactured by Showa Denko Materials) Methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride (methyl nadic anhydride) HN-5500 (product name manufactured by Showa Denko Materials) 3 or 4-Methyl-hexahydrophthalic anhydride (Component (D) Microcapsule-type curing accelerator) Novacure HX-3742 (product name, manufactured by Asahi Kasei) Masterbatch type curing agent containing an imidazole-based curing agent that is solid at 25°C and 1013 hPa (Component (E) Reactive Diluent) YED216D (Mitsubishi Chemical product name) 1,6-Hexanediol diglycidyl ether, viscosity 121 mPa·s

[0078] Example 1 , Reference Example 2, Example 3 ~6] and [Comparative Examples 1 to 3] The components were blended in the proportions shown in Table 1, and epoxy resin compositions were prepared by the method described above. The properties of the prepared epoxy resin compositions were measured by the above-mentioned methods.

[0079] [Table 1]

[0080] Comparing Example 1 and Comparative Example 1, it is clear that the epoxy resin is obtained by combining component (A) and component (B). The resin composition contains bisphenol A epoxy resin and bisphenol F epoxy resin. By incorporating the above, it has been possible to achieve low viscosity, improved storage stability, and improved short-time curing properties. In all these respects, the epoxy resin composition exhibits excellent effects and has an excellent balance of properties. It was found that it can be obtained. Also, Reference example 2 When comparing Comparative Example 2 with Comparative Example 2, the bisphenol A type epoxy resin (component (A )) was found to have the effects of lowering viscosity and improving storage stability. Furthermore, when Example 1 is compared with Comparative Example 3, by including component (A) and component (B), It was found that the effects of lowering viscosity, improving storage stability, and improving reactivity were obtained.

[0081] Reference example 2When comparing Example 1 with Example 3, it was found that the inclusion of the component (C) having the structure of formula (2): an acid anhydride, had the effect of improving storage stability.

[0082] Comparing Examples 3, 4, and 5, it was found that increasing the amount of component (B), the bisphenol F epoxy resin, improved storage stability but also reduced viscosity. Examples 3 and 4 were found to have particularly favorable viscosity ranges.

[0083] The tensile test results for Examples 4 and 6 are shown in Table 2 below.

[0084] [Table 2]

[0085] Comparing Example 4 with Example 6, it was found that the inclusion of an epoxy-type reactive diluent (component (E)) that does not contain nitrogen atoms and has a linear structure with 4 or more carbon atoms provides the effect of improving tensile elongation while maintaining appropriate viscosity, good storage stability, and short-time curing properties.

[0086] The test results for room temperature transport suitability (room temperature storage stability) using Examples 1 to 6 are shown in Table 3 below.

[0087] [Table 3]

[0088] The results of Examples 7 to 18 show that when Examples 1 to 6 are placed in a resin container and stored at room temperature for 10 days without using a coolant, refrigeration equipment, or special packaging materials, and packaged using cardboard or plastic packaging materials, they still exhibit good viscosity and reactivity. Although the present embodiment has been described above, the present invention is not limited to this embodiment, and can be modified as appropriate within the scope of the invention. [Industrial Applicability]

[0089] The epoxy resin composition of the present invention has industrial applicability as an insulating material for electronic components, a sealing material, an adhesive, a conductive material, a matrix resin for fiber-reinforced plastics, an impregnating adhesive for motor coils, and the like.

Claims

1. Component (A): The ratio of the peak area Sα derived from α-glycol represented by formula (1), calculated by liquid chromatography, to the sum of all peak areas S Total a bisphenol A type epoxy resin in an amount of 0.4% or more and less than 1.4% relative to the total weight of the epoxy resin; 【Chemical 1】 Component (B): bisphenol F type epoxy resin, Component (C): an acid anhydride, Component (D): a microcapsule-type curing accelerator; An epoxy resin composition comprising: The component (C) is an acid anhydride having a structure of the following formula (2): the content of the component (D) is 1 part by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total amount of the epoxy compounds in the epoxy resin composition; Epoxy resin composition. 【Chemistry 2】 In formula (2), the carbon atoms C 1 to C 6 may be saturated or unsaturated. In the case of unsaturated carbon atoms, adjacent carbon atoms may form an unsaturated bond. R 1 to R 14 are each one selected from the group consisting of hydrogen, an alkyl group, an aromatic group, a substituent containing a hetero atom, and a substituent containing a halogen atom. R 1 to R 14 may be the same or different. It may also be a fused ring compound in which any one selected from R 1 to R 14 is present in the same ring.

2. the content of the component (B): bisphenol F epoxy resin is 10 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the total amount of the epoxy compounds; The epoxy resin composition according to claim 1.

3. Further comprising component (E) a reactive diluent; The epoxy resin composition according to claim 1 or 2.

4. The epoxy resin composition according to any one of claims 1 to 3, a resin or metal container containing the epoxy resin composition; and a renewable or reusable paper or plastic outer packaging material for packaging the container.

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