Composition, resin composition, and cured product

Abstract

The invention provides a composition, and a resin composition and a cured product using the composition. The composition contains: a compound that contains an amino group and a cyclic ether structure and has a molecular weight of 1000 or less; and a low hindered phenol-based antioxidant.

Description

Technical Field

[0001] The present invention relates to a composition, a resin composition, and a cured product. Background Art

[0002] Low molecular weight compounds containing an amino group and a cyclic ether structure, such as 2,5-bis(aminomethyl)tetrahydrofuran, are widely used as curing agents for thermosetting resins such as epoxy resins, raw materials for polyamide resins, and the like (Patent Documents 1 and 2).

[0003] On the other hand, it is known that low molecular weight diamine compounds are easily colored by air oxidation, and have disadvantages such as coloration during production and coloration progressing during storage, and limitations on materials requiring transparency (Patent Document 3).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2020 / 153280

[0007] Patent Document 2: Japanese Patent Application Publication No. 2021-091816

[0008] Patent Document 3: Japanese Patent Application Publication No. 2015-010080 Summary of the invention

[0009] Problem that the invention aims to solve

[0010] Here, the present inventors have conducted studies and found that, when pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], a general-purpose hindered phenol antioxidant, is blended with a low molecular weight compound containing an amino group and a cyclic ether structure and then heat-treated, the compound turns yellow and fails to achieve a sufficient anti-oxidation effect.

[0011] The present invention aims to solve the above problems and provides a composition comprising a low molecular weight compound containing an amino group and a cyclic ether structure and an antioxidant, wherein yellowing after heat treatment is suppressed; and a resin composition and a cured product using the composition.

[0012] Solutions for solving problems

[0013] The inventors of the present invention have conducted studies based on the above problems and have found that the above problems can be solved by blending a low-hindered phenol-based antioxidant into a low-molecular compound containing an amino group and a cyclic ether structure.

[0014] Specifically, the above-mentioned problems are solved by the following means.

[0015] <1> A composition comprises: a compound containing an amino group and a cyclic ether structure and having a molecular weight of 1000 or less, and a low hindered phenol antioxidant.

[0016] <2> according to <1> The composition, wherein the compound containing an amino group and a cyclic ether structure and having a molecular weight of 1000 or less is represented by formula (F),

[0017]

[0018] In formula (F), n1 represents an integer of 0-3, and n2 represents an integer of 1-4.

[0019] <3> according to <1> or <2> The composition further comprises a phosphorus antioxidant.

[0020] <4> according to <3> In the composition, the mass ratio of the low hindered phenol antioxidant to the phosphorus antioxidant (low hindered phenol antioxidant / phosphorus antioxidant) is 0.6 to 1.4.

[0021] <5> according to <1> to <4> The composition according to any one of the preceding claims, wherein the content of the low hindered phenol-based antioxidant is 100 to 5000 ppm by mass.

[0022] <6> according to <1> The composition further comprises a phosphorus antioxidant,

[0023] The mass ratio of the low hindered phenol antioxidant to the phosphorus antioxidant (low hindered phenol antioxidant / phosphorus antioxidant) is 0.6 to 1.4,

[0024] The content of the low hindered phenol antioxidant is 100 to 5000 ppm by mass.

[0025] <7> A resin composition comprising <1> to <6> The composition and thermosetting resin described above.

[0026] <8> according to <7> The resin composition, wherein the thermosetting resin comprises epoxy resin.

[0027] <9> A solidified material, which is <7> or <8> A cured product of the resin composition.

[0028] Effects of the Invention

[0029] According to the present invention, there can be provided a composition comprising a low molecular weight compound containing an amino group and a cyclic ether structure and an antioxidant, wherein yellowing after heat treatment is suppressed; and a resin composition and a cured product using the composition. DETAILED DESCRIPTION

[0030] A mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail below. It should be noted that the following this embodiment is an example for explaining the present invention, and the present invention is not limited to this embodiment.

[0031] In addition, "to" in this specification is used in the meaning which includes the numerical value described before and after it as a lower limit and an upper limit.

[0032] In this specification, various physical property values ​​and characteristic values ​​are defined as values ​​at 23°C unless otherwise specified.

[0033] In the description of the group (atomic group) in this specification, the description that does not record substitution and unsubstituted also includes the group (atomic group) without substitution and the group (atomic group) with substitution. For example, "alkyl" is not only an alkyl group without substitution (unsubstituted alkyl), but also includes an alkyl group with substitution (substituted alkyl). In this specification, the description that does not record substitution and unsubstituted is preferably unsubstituted.

[0034] In this specification, the weight average molecular weight and the number average molecular weight are polystyrene-equivalent values ​​measured by GPC (gel permeation chromatography) unless otherwise specified.

[0035] When the measurement methods and the like described in the standards shown in this specification differ by year, unless otherwise specified, they are based on the standards as of January 1, 2022.

[0036] The composition of this embodiment is characterized by comprising: a compound containing an amino group and a cyclic ether structure and having a molecular weight of 1000 or less (sometimes referred to as a "low molecular weight compound containing an amino group and a cyclic ether structure" in this specification) and a low hindered phenol antioxidant. With such a composition, yellowing after heat treatment can be effectively suppressed.

[0037] In order to prevent the oxidation of amine compounds, antioxidants have been blended. Therefore, when the inventors studied antioxidants that are effective in inhibiting the yellowing of low molecular weight compounds containing amino groups and cyclic ether structures, they focused on antioxidants that are effective for 1,3-bis(aminomethyl)cyclohexane (1,3-BAC). However, the expected results were not obtained. After in-depth research on the reasons, it was speculated that the reason is that "low molecular weight compounds containing amino groups and cyclic ether structures" are more likely to generate free radicals than 1,3-BAC and are more likely to be colored. In addition, as a result of further research, it was found that the yellowing of "low molecular weight compounds containing amino groups and cyclic ether structures" can be effectively inhibited by using low hindered phenol antioxidants. In particular, as shown in the examples described below, low hindered phenol antioxidants have no effect on 1,3-BAC, but surprisingly, they can significantly inhibit the yellowing of "low molecular weight compounds containing amino groups and cyclic ether structures".

[0038] <Compounds containing an amino group and a cyclic ether structure and having a molecular weight of 1000 or less>

[0039] The composition of the present embodiment contains a compound having an amino group and a cyclic ether structure and having a molecular weight of 1000 or less (a low-molecular compound having an amino group and a cyclic ether structure).

[0040] In the present embodiment, the molecular weight of the low molecular weight compound containing an amino group and a cyclic ether structure is preferably 80 or more, more preferably 90 or more, further preferably 100 or more, further preferably 110 or more, and further preferably 120 or more. In addition, it is preferably 800 or less, more preferably 600 or less, further preferably 400 or less, further preferably 300 or less, further preferably 200 or less, further preferably 180 or less, and particularly preferably 150 or less.

[0041] In the present embodiment, the low molecular weight compound containing an amino group and a cyclic ether structure preferably has 1 to 4 amino groups in one molecule, more preferably 2 to 4 amino groups, further preferably 2 or 4 amino groups, and further preferably 2 amino groups.

[0042] In the low molecular weight compound containing an amino group and a cyclic ether structure, the amino group may be directly bonded to the cyclic ether structure or bonded via a connecting group. In the present embodiment, in the low molecular weight compound containing an amino group and a cyclic ether structure, the amino group is preferably bonded to the cyclic ether structure via a connecting group, more preferably bonded via an aliphatic hydrocarbon group (preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms), and further preferably bonded via an alkylene group (preferably an alkylene group having 1 to 5 carbon atoms). In addition, in the low molecular weight compound containing an amino group and a cyclic ether structure, a group other than a group having an amino group may also be bonded to the cyclic ether structure. As a group other than such a group having an amino group, a hydroxyl group, an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), a halogen atom, etc. may be exemplified.

[0043] The cyclic ether structure possessed by the low molecular compound containing an amino group and a cyclic ether structure is preferably a 3-membered ring, a 4-membered ring, a 5-membered ring or a 6-membered ring, more preferably a 5-membered ring or a 6-membered ring, and further preferably a 5-membered ring. Specific examples of the cyclic ether structure possessed by the low molecular compound containing an amino group and a cyclic ether structure include a pyran ring, a furan ring, an oxirane ring, an oxetane ring, a tetrahydropyran ring, and a tetrahydrofuran ring, preferably a tetrahydrofuran ring.

[0044] In the present embodiment, the low molecular weight compound containing an amino group and a cyclic ether structure is preferably represented by formula (F).

[0045] [Chemistry 2]

[0046]

[0047] In formula (F), n1 represents an integer of 0-3, and n2 represents an integer of 1-4.

[0048] n1 is preferably an integer of 1 to 3, more preferably 1 or 2, and further preferably 1.

[0049] n2 is preferably an integer of 2 to 4, more preferably 2 or 4, and further preferably 2.

[0050] When n2 is an integer of 2 to 4, respective n1s may be the same or different, but are preferably the same.

[0051] Preferably -((CH2) n1 NH2) n2 The group represented by is bonded to at least one of the 2-position and the 5-position.

[0052] The compound represented by formula (F) is preferably a compound represented by formula (F1) (H-AMF).

[0053] [Chemistry 3]

[0054]

[0055] The composition of the present embodiment usually contains low molecular weight compounds containing amino groups and cyclic ether structures as main components, and its content in the composition is preferably 95% by mass or more, more preferably 98% by mass or more, and further preferably 99% by mass or more. The upper limit of the low molecular weight compounds containing amino groups and cyclic ether structures in the composition of the present embodiment means that all components other than the low hindered phenol-based antioxidant are low molecular weight compounds containing amino groups and cyclic ether structures.

[0056] In addition, the composition of the present embodiment may include only one low molecular weight compound containing an amino group and a cyclic ether structure, or may include more than two. When including more than two, the preferred total amount is the above range. In the present embodiment, more than 99% by mass of the low molecular weight compound containing an amino group and a cyclic ether structure included in the preferred composition is the same compound.

[0057] <Low hindered phenol antioxidant>

[0058] The composition of the present embodiment contains a low hindered phenol-based antioxidant.

[0059] Phenolic antioxidants are known to include, for example, hindered phenolic antioxidants in which two hydrogen atoms at the ortho positions of the phenolic hydroxyl group are replaced by groups with large steric hindrance, semi-hindered phenolic antioxidants in which one hydrogen atom at the ortho position of the phenolic hydroxyl group is replaced by a group with large steric hindrance and the other hydrogen atom at the ortho position is replaced by a methyl group, and low-hindered phenolic antioxidants in which one hydrogen atom at the ortho position of the phenolic hydroxyl group is replaced by a group with large steric hindrance and the other hydrogen atom at the ortho position is not replaced. Among these, in the present embodiment, by using a low-hindered phenolic antioxidant, the increase in the YI value of low molecular weight compounds containing an amino group and a cyclic ether structure can be effectively suppressed.

[0060] The group with large steric hindrance refers to, for example, a branched alkyl group or an aromatic ring group other than a straight-chain alkyl group. Specifically, tertiary alkyl groups such as tert-butyl, tert-pentyl, and tert-hexyl; secondary alkyl groups such as isopropyl, sec-butyl, and sec-pentyl; branched primary alkyl groups such as isobutyl and isopentyl; cycloalkyl groups such as cyclohexyl and cyclopentyl; and aromatic ring groups such as phenyl, benzyl, and naphthyl.

[0061] In this embodiment, the low hindered phenol antioxidant is preferably a compound having the following partial structure, more preferably a compound having 2 to 5 of the following partial structures, further preferably a compound having 2 to 4 of the following partial structures, and further preferably a compound having 2 to 3 of the following partial structures.

[0062] [Chemistry 4]

[0063]

[0064] In the above partial structures, the wavy lines are the bonding sites with other parts.

[0065] In the present embodiment, the molecular weight of the low hindered phenol-based antioxidant is preferably 300 or more, and is preferably 1000 or less, and more preferably 800 or less.

[0066] Specific examples of low hindered phenol antioxidants include 4,4'-thiobis(3-methyl-6-tert-butyl)phenol (e.g., NOCRAC 300 manufactured by Ouchi Shinko Chemical Industry Co., Ltd.), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (e.g., ADK STAB AO-30 manufactured by ADEKA Corporation), and 4,4'-butylidenebis(3-methyl-6-tert-butyl)phenol (e.g., ADK STAB AO-40 manufactured by ADEKA Corporation).

[0067] For the content of the low hindered phenol antioxidant in the composition of the present embodiment, when the composition is set to 100 parts by mass, it is preferably 100 mass ppm or more, more preferably 200 mass ppm or more, further preferably 300 mass ppm or more, further preferably 400 mass ppm or more, further preferably 600 mass ppm or more, and further more preferably 800 mass ppm or more. By being above the aforementioned lower limit, there is a tendency to further reduce the YI value of the composition or the cured product using the composition. In addition, for the content of the low hindered phenol antioxidant in the composition of the present embodiment, when the composition is set to 100 parts by mass, it is preferably 5000 mass ppm or less, more preferably 4000 mass ppm or less, further preferably 3000 mass ppm or less, further preferably 2500 mass ppm or less, further preferably 1900 mass ppm or less, and further more preferably 1600 mass ppm or less. By being below the aforementioned upper limit, a composition having excellent economic performance and sufficient YI value rising effect can be obtained. Furthermore, there is a tendency that the YI value of the composition or a cured product using the composition can be further reduced.

[0068] The resin composition of the present embodiment may contain only one low hindered phenol antioxidant, or may contain two or more. When containing two or more, the total amount is preferably within the above range.

[0069] The composition of the present embodiment may or may not contain a hindered phenol-based antioxidant other than the low hindered phenol-based antioxidant.

[0070] The composition of the present embodiment preferably does not substantially contain hindered phenolic antioxidants other than low hindered phenolic antioxidants. Substantially containing means that the content of hindered phenolic antioxidants other than low hindered phenolic antioxidants contained in the composition is 10% by mass or less of the content of the low hindered phenolic antioxidant, preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less.

[0071] <Phosphorus antioxidant>

[0072] The composition of the present embodiment may contain a phosphorus-based antioxidant. By containing a phosphorus-based antioxidant, an increase in the YI value of a low-molecular compound containing an amino group and a cyclic ether structure can be effectively suppressed.

[0073] The phosphorus-based antioxidant is not particularly limited as long as it is an antioxidant containing a phosphorus atom.

[0074] If specific examples of phosphorus antioxidants are listed, phosphorus oxygen acids such as phosphoric acid, phosphonic acid, phosphorous acid, hypophosphorous acid, and polyphosphoric acid can be listed; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphates of Group 1 or Group 2B metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; phosphate compounds, phosphite compounds, and phosphite compounds are particularly preferred. By selecting phosphite compounds, a resin sheet with higher color resistance and continuous productivity can be obtained.

[0075] The phosphorus-based antioxidants can refer to the descriptions in paragraphs 0058 to 0064 of JP-A-2018-090677, and these contents are incorporated into the present specification.

[0076] The phosphorus-based antioxidant used in the present embodiment preferably has an aromatic ring, more preferably has a diarylphosphite structure or a triarylphosphite structure, and further preferably is represented by the formula (P).

[0077] Formula (P)

[0078] [Chemistry 5]

[0079]

[0080] (In formula (P), R p Each independently represents an aryl group having 6 or more and 30 or less carbon atoms. )

[0081] R p It may be an aryl group having a substituent, and is preferably an aryl group substituted with an alkyl group. The aryl group is preferably a phenyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a butyl group, and further preferably a tert-butyl group.

[0082] Examples of the phosphorus antioxidant represented by formula (P) include ADK STAB 2112, ADK STAB 1178, and ADK STAB TPP manufactured by ADEKA. In addition, in the present embodiment, a phosphorus antioxidant having a pentaerythritol diphosphite structure can also be preferably used, and the details thereof can be exemplified by compounds described in International Publication No. 2013 / 088796.

[0083] When the composition of the present embodiment contains a phosphorus antioxidant, its content is preferably more than 100 mass ppm relative to 100 mass parts of the composition, more preferably more than 300 mass ppm, further preferably more than 700 mass ppm, and also more than 1200 mass ppm. By being above the aforementioned lower limit, there is a tendency that the YI value of the cured product of the composition or resin combination can be more effectively suppressed to rise. In addition, the upper limit of the content of the aforementioned phosphorus antioxidant is preferably less than 5000 mass ppm relative to 100 mass parts of the composition, more preferably less than 3000 mass ppm, further preferably less than 2500 mass ppm, and further preferably less than 1800 mass ppm. By being below the aforementioned upper limit, there is a tendency that the YI value of the cured product of the composition or resin combination can be more effectively suppressed to rise.

[0084] The composition of the present embodiment may contain only one phosphorus-based antioxidant, or may contain two or more thereof. When containing two or more thereof, the total amount is preferably within the above range.

[0085] In addition, in the composition of the present embodiment, the mass ratio of the low hindered phenol antioxidant to the phosphorus antioxidant (low hindered phenol antioxidant / phosphorus antioxidant) is preferably 0.2 or more, more preferably 0.3 or more, further preferably 0.4 or more, further preferably 0.6 or more, and further preferably 0.8 or more, and preferably 3.0 or less, more preferably 1.8 or less, further preferably 1.4 or less, and further preferably 1.2 or less. By being above the lower limit and below the upper limit, there is a tendency to more effectively suppress the increase in the YI value of the cured product of the composition or resin composition.

[0086] In addition, in the composition of the present embodiment, the total amount of low hindered phenol antioxidant and phosphorus antioxidant is preferably more than 500 mass ppm relative to 100 mass parts of the composition, more preferably more than 900 mass ppm, further preferably more than 1100 mass ppm, and also more than 1600 mass ppm. By above the aforementioned lower limit, there is a tendency that the YI value of the cured product of the composition or resin combination can be more effectively suppressed to rise. In addition, the upper limit of the content of the aforementioned phosphorus antioxidant is preferably less than 3000 mass ppm relative to 100 mass parts of the composition, more preferably less than 2800 mass ppm, and also less than 2400 mass ppm. By being below the aforementioned upper limit, there is a tendency that the YI value of the cured product of the composition or resin combination can be more effectively suppressed to rise.

[0087] <Other ingredients>

[0088] The composition of this embodiment may consist only of a low molecular weight compound containing an amino group and a cyclic ether structure and a low hindered phenol antioxidant, or may contain other components. Other components may include modifying components such as plasticizers, reactive or non-reactive diluents, flow regulating components such as thixotropy imparting agents, pigments, thickeners, anti-shrinkage agents, flow-spreading agents, defoaming agents, ultraviolet absorbers, light stabilizers, curing accelerators, etc.

[0089] The composition of the present embodiment can be effectively used for various purposes using low molecular weight amine compounds. Specifically, it can be widely used in curing agents for thermosetting resins, raw materials for polyamide resins and other resins, raw materials for adhesives, etc. As an example of the use of curing agents for thermosetting resins, the composition of the present embodiment can be used in place of the curing agents described in International Publication No. 2016 / 158871 and Japanese Patent Publication No. 2012-153857.

[0090] As an example of the composition of the present embodiment, it is a composition consisting essentially only of low molecular weight compounds containing amino groups and cyclic ether structures and low hindered phenol antioxidants. It essentially means that the components other than low molecular weight compounds containing amino groups and cyclic ether structures and low hindered phenol antioxidants are less than 5% by mass of the total amount of low molecular weight compounds containing amino groups and cyclic ether structures and low hindered phenol antioxidants, preferably less than 3% by mass, more preferably less than 1% by mass, further preferably less than 0.1% by mass, further preferably less than 0.01% by mass, and further preferably less than 0.001% by mass, preferably not actively mixed. It is preferred that the composition consisting essentially only of low molecular weight compounds containing amino groups and cyclic ether structures and low hindered phenol antioxidants is directly sealed in a container. Such a composition can be sold, for example, as a reagent for low molecular weight compounds containing amino groups and cyclic ether structures.

[0091] <Resin composition>

[0092] The resin composition of the present embodiment includes the composition of the present embodiment and a thermosetting resin.

[0093] As the thermosetting resin, it is preferred to include at least one selected from the group consisting of epoxy resin, benzoxazine resin, phenolic resin, unsaturated polyester resin, maleimide resin, thermosetting polyimide resin, and silicone resin, and more preferably epoxy resin. As the epoxy resin, reference can be made to the description of paragraph 0036 of International Publication No. 2016 / 158871, which is incorporated into this specification.

[0094] In addition, the resin composition of the present embodiment can use fillers, plasticizers and other modifying components, reactive or non-reactive diluents, thixotropy-imparting agents and other flow regulating components, pigments, thickeners and other components, anti-shrinkage agents, flow-spreading agents, defoaming agents, ultraviolet absorbers, light stabilizers, curing accelerators and other additives according to the application within the range that does not impair the effects of the present invention.

[0095] The resin composition of this embodiment can be used in a wide range of applications, for example: coatings or adhesives for concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, etc.; adhesive tapes for packaging, adhesive labels, frozen food labels, removable labels, POS labels, adhesives for bonding wallpaper, adhesives for bonding floor materials; processed papers such as coated paper, lightweight coated paper, cast-coated paper, coated board paper, carbonless copy paper, impregnated paper, etc.; fiber treatment agents such as sizing agents, anti-scattering agents, and processing agents for natural fibers, synthetic fibers, glass fibers, carbon fibers, metal fibers, etc.; building materials such as sealing materials, cement admixtures, and waterproof materials, etc.

[0096] <Cured product>

[0097] The cured product of the present embodiment is a cured product of the resin composition of the present embodiment.

[0098] The cured product may be in the form of a film, a sheet, or any other shape.

[0099] Example

[0100] The present invention is further described in detail by enumerating examples below. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples may be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0101] If the measuring equipment used in the examples is difficult to obtain due to discontinuation of production, etc., other equipment with equivalent performance may be used for measurement.

[0102] In addition, t-Bu represents a tert-butyl group.

[0103] 1. Raw materials

[0104] <Synthesis Example 1 Synthesis of the compound represented by formula (F1) (H-AMF)>

[0105] After 20 g of 2,5-bis(aminomethyl)furan (AMF), 8 g of Ru / alumina (Al2O3) (the amount of Ru catalyst is 5 mass%) and 120 mL of THF (tetrahydrofuran) as a solvent were added to a pressure autoclave, the hydrogen pressure was increased to 6 MPaG, and the temperature was maintained at 90°C for 1 hour to react, and the pressure autoclave was cooled with ice water to stop the reaction. Under the circulation of argon gas, the catalyst was removed by filtering the catalyst and the reaction solution to obtain a filtrate containing the product. The filtrate was post-concentrated, vacuum dried, and purified by reduced pressure distillation at a temperature of 120°C and a pressure of 1 mbar.

[0106] [Chemistry 6]

[0107]

[0108] <Comparative diamine>

[0109] 1,3-BAC: 1,3-bis(aminomethyl)cyclohexane, manufactured by Mitsubishi Gas Chemical Co., Ltd. <Antioxidant>

[0110] AO-30: Made by ADEKA, ADK STAB, low hindered phenol antioxidant

[0111] [Chemistry 7]

[0112]

[0113] AO-40: Made by ADEKA, ADK STAB, low hindered phenol antioxidant

[0114] [Chemistry 8]

[0115]

[0116] AO-50: Made by ADEKA, ADK STAB AO-50, hindered phenol antioxidant

[0117] [Chemistry 9]

[0118]

[0119] AO-60: Made by ADEKA, ADK STAB AO-60, hindered phenol antioxidant

[0120] [Chemistry 10]

[0121]

[0122] Phosphorus oxidant: ADK STAB 2112 manufactured by ADEKA

[0123] [Chemistry 11]

[0124]

[0125] Example 1

[0126] Composition 1 was obtained by blending 100 parts by mass of the H-AMF as a diamine without blending a phosphorus-based antioxidant and blending 1000 parts by mass of a low hindered amine-based antioxidant (A-30).

[0127] The obtained composition was heated at 160° C. for 30 minutes, and the YI value of the composition was measured after being cooled to room temperature by air cooling after heating. The YI value was measured using a spectroscopic haze meter SH-7000 manufactured by Nippon Denshoku Industries Co., Ltd.

[0128] Furthermore, the composition of Reference Example 1 (a composition containing only H-AMF without adding a phosphorus-based antioxidant and a low hindered amine-based antioxidant) was also heated at 160° C. for 30 minutes in the same manner, and the YI value after heating was measured.

[0129] The difference (ΔYI) between the YI value of the composition 1 and the YI value of the composition of Reference Example 1 was −5.3, which was significantly lower than that of the composition of Reference Example 1.

[0130] Example 2

[0131] In Example 1, a composition 2 was obtained in the same manner as in Example 1 except that the content of the low hindered amine antioxidant (A-30) was changed to 1500 mass ppm.

[0132] Composition 1 in Example 1 was replaced by Composition 2, and the other procedures were carried out in the same manner. The obtained ΔYI value was -4.3, which was significantly lower than the YI value of the composition in Reference Example 1.

[0133] Example 3

[0134] In Example 1, a composition 3 was obtained in the same manner as in Example 1 except that the content of the low hindered amine antioxidant (A-30) was changed to 2000 mass ppm.

[0135] Composition 1 in Example 1 was replaced by Composition 3, and the other procedures were carried out in the same manner. The obtained ΔYI value was -2.6, which was significantly lower than the YI value of the composition in Reference Example 1.

[0136] Example 4

[0137] In Example 1, composition 4 was obtained in the same manner as in Example 1 except that the type of the low hindered amine antioxidant was changed from ADK STAB A-30 to ADK STAB AO-40.

[0138] Composition 1 in Example 1 was changed to Composition 4, and the other procedures were carried out in the same manner. The obtained ΔYI value was -5.0, which was significantly lower than the YI value of the composition in Reference Example 1.

[0139] Example 5

[0140] In Example 4, a composition 5 was obtained in the same manner as in Example 4 except that the content of the low hindered amine antioxidant (A-40) was changed to 1500 mass ppm.

[0141] Composition 4 in Example 4 was changed to Composition 5, and the other procedures were carried out in the same manner. The obtained ΔYI value was -3.5, which was significantly lower than the YI value of the composition in Reference Example 1.

[0142] Example 6

[0143] In Example 4, a composition 6 was obtained in the same manner as in Example 4 except that the content of the low hindered amine antioxidant (A-40) was changed to 2000 mass ppm.

[0144] Composition 4 in Example 4 was changed to Composition 6, and the other procedures were carried out in the same manner. The obtained ΔYI value was -3.0, which was significantly lower than the YI value of the composition in Reference Example 1.

[0145] Example 7

[0146] Composition 7 was obtained by further blending 500 mass ppm of a phosphorus antioxidant into Composition 1 of Example 1 and performing the same procedure as above.

[0147] Composition 1 in Example 1 was replaced by Composition 7, and the other procedures were carried out in the same manner. The obtained ΔYI value was -5.7, which was significantly lower than the YI value of the composition in Reference Example 1.

[0148] Example 8

[0149] Composition 8 was obtained in the same manner as in Composition 2 of Example 2 except that 500 ppm by mass of a phosphorus-based antioxidant was further blended.

[0150] Composition 2 in Example 2 was replaced by Composition 8, and the other procedures were carried out in the same manner. The obtained ΔYI value was -4.9, which was significantly lower than the YI value of the composition in Reference Example 1.

[0151] Example 9

[0152] Composition 9 was obtained in the same manner as in Composition 4 of Example 4 except that 500 mass ppm of a phosphorus-based antioxidant was further blended.

[0153] Composition 4 in Example 4 was changed to Composition 9, and the other procedures were carried out in the same manner. The obtained ΔYI value was -5.0, which was significantly lower than the YI value of the composition in Reference Example 1.

[0154] Example 10

[0155] Composition 10 was obtained in the same manner as in Composition 5 of Example 5 except that 500 ppm by mass of a phosphorus-based antioxidant was further blended therein.

[0156] Composition 5 in Example 5 was changed to Composition 10, and the other procedures were carried out in the same manner. The obtained ΔYI value was -5.5, which was significantly lower than the YI value of the composition in Reference Example 1.

[0157] Embodiment 11

[0158] In Example 1, the composition 11 was obtained in the same manner as in Example 1 except that the content of the low hindered amine antioxidant (A-30) was changed to 500 mass ppm and 1000 mass ppm of a phosphorus antioxidant was further added.

[0159] Composition 1 in Example 1 was changed to Composition 11, and the other procedures were carried out in the same manner. The obtained ΔYI value was -5.2, which was significantly lower than the YI value of the composition in Reference Example 1.

[0160] Example 12

[0161] In Example 1, 1000 mass ppm of a phosphorus-based antioxidant was further blended, and the same procedures were followed as in Example 1 to obtain Composition 12.

[0162] Composition 1 in Example 1 was changed to Composition 12, and the other procedures were carried out in the same manner. The obtained ΔYI value was -7.4, which was significantly lower than the YI value of the composition in Reference Example 1.

[0163] Example 13

[0164] Composition 13 was obtained in the same manner as in Composition 4 of Example 4 except that the content of the low hindered amine antioxidant (A-40) was changed to 500 mass ppm and 1000 mass ppm of a phosphorus antioxidant was further added.

[0165] Composition 4 in Example 4 was changed to Composition 13, and the other procedures were carried out in the same manner. The obtained ΔYI value was -6.3, which was significantly lower than the YI value of the composition in Reference Example 1.

[0166] Embodiment 14

[0167] In Composition 4 of Example 4, Composition 14 was obtained in the same manner except that the content of the phosphorus antioxidant was further changed to 1000 mass ppm.

[0168] Composition 4 in Example 4 was changed to Composition 14, and the other procedures were carried out in the same manner. The obtained ΔYI value was -7.6, which was significantly lower than the YI value of the composition in Reference Example 1.

[0169] Embodiment 15

[0170] In Example 11, a composition 15 was obtained in the same manner as in Example 11 except that the content of the phosphorus-based antioxidant was changed to 1500 mass ppm.

[0171] Composition 14 in Example 11 was replaced by Composition 15, and the other procedures were carried out in the same manner. The obtained ΔYI value was -6.2, which was significantly lower than the YI value of the composition in Reference Example 1.

[0172] Example 16

[0173] In Example 13, a composition 16 was obtained in the same manner as in Example 13 except that the content of the phosphorus antioxidant was changed to 1500 mass ppm.

[0174] Composition 13 in Example 13 was changed to Composition 16, and the other procedures were carried out in the same manner. The obtained ΔYI value was -6.5, which was significantly lower than the YI value of the composition in Reference Example 1.

[0175] Comparative Example 1

[0176] Comparative composition 1 was obtained by mixing 100 parts by mass of the 1,3-BAC as a diamine without mixing a phosphorus-based antioxidant and mixing a low hindered amine-based antioxidant (A-30, 2000 ppm by mass).

[0177] The obtained comparative composition 1 was heated at 160° C. for 30 minutes, and the YI value after heating was measured.

[0178] Furthermore, the composition of Reference Example 2 (a composition containing only 1,3-BAC without adding a phosphorus-based antioxidant and a low hindered amine-based antioxidant) was also heated at 160° C. for 30 minutes in the same manner, and the YI value after heating was measured.

[0179] The difference (ΔYI) between the YI value of the comparative composition 1 and the YI value of the composition of reference example 2 was 1.9, and the YI value of the composition of reference example 2 was higher.

[0180] Comparative Example 2

[0181] In Comparative Example 1, the low hindered amine antioxidant (A-30, 2000 mass ppm) was replaced with a low hindered amine antioxidant (A-40, 2000 mass ppm), and Comparative Composition 2 was obtained.

[0182] The comparative composition 1 in Comparative Example 1 was changed to the comparative composition 2, and the other procedures were carried out in the same manner. The obtained ΔYI value was 4.8, which was significantly higher than the YI value of the composition of Reference Example 2.

[0183] The following Tables 1 and 2 summarize the Examples, Comparative Examples, and Reference Examples.

[0184] [Table 1]

[0185]

[0186] [Table 2]

[0187]

[0188] From the above results, it is understood that in the present invention, yellowing of the composition can be effectively suppressed by blending a low-hindered phenol-based antioxidant with a low-molecular compound containing an amino group and a cyclic ether structure.

[0189] On the other hand, as shown in Comparative Examples 1 and 2, even if a low-hindered phenol-based antioxidant is added to a low-molecular compound containing an amino group and a cyclic alkane structure, yellowing of the composition cannot be suppressed at all.

[0190] Furthermore, in Example 1, the low hindered phenol antioxidant was changed to AO-60 (ADK STAB AO-60, manufactured by ADEKA) which is also a widely used hindered phenol antioxidant, and the yellowing of the composition was not suppressed at all when the other procedures were the same. In addition, in Example 1, AO-50 (ADK STAB AO-50, manufactured by ADEKA) was changed as the hindered phenol antioxidant, and the other procedures were the same, and the yellowing of the composition was not suppressed at all.

[0191] That is, it is understood that low hindered phenol-based antioxidants are particularly useful in suppressing the oxidation of low molecular weight compounds containing an amino group and a cyclic ether structure.

Claims

1. A composition comprising: a compound having an amino group and a cyclic ether structure and having a molecular weight of 1000 or less, and a low hindered phenol antioxidant.

2. The composition according to claim 1, wherein The compound containing an amino group and a cyclic ether structure and having a molecular weight of 1000 or less is represented by formula (F), In formula (F), n1 represents an integer of 0-3, and n2 represents an integer of 1-4. The composition according to claim 1 or 2, further comprising a phosphorus-based antioxidant.

4. The composition according to claim 3, wherein The mass ratio of the low hindered phenol antioxidant to the phosphorus antioxidant, ie, low hindered phenol antioxidant / phosphorus antioxidant, is 0.6 to 1.

4.

5. The composition according to any one of claims 1 to 4, wherein The content of the low hindered phenol antioxidant is 100 to 5000 ppm by mass.

6. The composition according to claim 1, further comprising a phosphorus antioxidant, The mass ratio of the low hindered phenol antioxidant to the phosphorus antioxidant, i.e., the low hindered phenol antioxidant / phosphorus antioxidant, is 0.6 to 1.

4. The content of the low hindered phenol antioxidant is 100 to 5000 ppm by mass. 7 . A resin composition comprising the composition according to claim 1 and a thermosetting resin.

8. The resin composition according to claim 7, wherein The thermosetting resin includes an epoxy resin. 9 . A cured product, which is a cured product of the resin composition according to claim 7 or 8 .

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