Amine compounds or their salts, as well as methods for producing the same and their uses.

Abstract

Provided is a novel amine compound or a salt thereof having excellent heat resistance. 【Solution means】The following formula (1) TIFF2026046811000008.tif58154 (In the formula, R 1 represents a substituent, n represents an integer from 0 to 8, R 2a ~R 2 d each independently represents a hydrogen atom or a substituent, R 3a and R 3b each independently represents a hydrogen atom or a substituent, A 1a and A 1b each independently represents an alkylene group, R 4a ~R 4 d each independently represents a hydrogen atom, an alkyl group or an acyl group) to prepare an amine compound or a salt thereof.

Description

[Technical Field]

[0001] This disclosure relates to novel amine compounds having a fluorene skeleton or salts thereof, as well as methods for producing the same and uses thereof. [Background technology]

[0002] Fluorene compounds, leveraging their excellent properties based on their unique chemical structure, are used in various fields as materials for forming organic semiconductors and optical components, and are often used in resins as monomer components or additives. U.S. Patent No. 2,299,948 (Patent Document 1) describes the usefulness of 9,9-di-(β-carbamoyl-ethyl)fluorene as an intermediate for preparing synthetic resins. Furthermore, Japanese Patent No. 7044,955 (Patent Document 2) describes the use of fluorene derivatives in which the nitrogen atom constituting the carbamoyl group of 9,9-di-(β-carbamoyl-ethyl)fluorene is replaced with an aliphatic hydrocarbon group as an additive to improve the properties of resins. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] U.S. Patent No. 2,299,948 [Patent Document 2] Patent No. 7044955 [Overview of the project] [Problems that the invention aims to solve]

[0004] Patent documents 1 and 2 describe the use of fluorene compounds as intermediates or additives in resins, and it is expected that the excellent properties of fluorene compounds, such as heat resistance and optical properties, can be imparted to resins. However, the fluorene compounds in patent documents 1 and 2 are compounds having an amide bond (amide group) as a reactive group or functional group at the end of the side chain, and depending on the application, there is a need for fluorene compounds with different reactivity than those in patent documents 1 and 2, such as affinity with resins.

[0005] Therefore, the object of this disclosure is to provide novel amine compounds or salts thereof with excellent heat resistance, as well as methods for producing the same and their uses. [Means for solving the problem]

[0006] As a result of diligent research to achieve the above objectives, the present inventors have discovered that by reacting fluorene with an amine compound having a (meth)acrylamide group, they can provide a novel amine compound or a salt thereof with excellent heat resistance and optical properties, and have completed the present invention (or present disclosure).

[0007] In other words, this disclosure includes the following aspects:

[0008] Appearance [1]: Formula (1)

[0009] [ka]

[0010] (In the formula, R 1 represents a substituent, and n represents an integer from 0 to 8. R 2a , R 2b , R 2c and R 2d These independently represent a hydrogen atom or a substituent. R 3a and R 3b These independently represent a hydrogen atom or a substituent. A 1a and A1b independently represents an alkylene group, R 4a , R 4b , R 4c and R 4d each independently represents a hydrogen atom, an alkyl group or an acyl group) an amine compound represented by or a salt thereof.

[0011] Aspect [2]: In the above formula (1), R 4a , R 4b , R 4c and R 4d each independently represents a C 1-3 alkyl group, the amine compound or a salt thereof according to the above Aspect [1].

[0012] Aspect [3]: In the above formula (1), A 1a and A 1b each independently represents a C 1-6 alkylene group, the amine compound or a salt thereof according to the above Aspect [1] or [2].

[0013] Aspect [4]: The following formula (2)

[0014]

Chemical formula

[0015] [In the formula, R 1 and n are the same as those in the above formula (1) respectively] a compound represented by and the following formulas (3a) and (3b)

[0016]

Chemical formula

[0017] [In the formula, R 2a , R 2b , R 2c and R 2d , R 3a and R 3b , A 1a and A 1b , R 4a, R 4b , R 4c and R 4d [Each of these is the same as in formula (1) above] A method for producing an amine compound or a salt thereof according to any one of the embodiments [1] to [3], comprising the step of reacting it with a compound represented by .

[0018] Embodiment [5]: A resin composition comprising a resin and an amine compound or a salt thereof as described in any of Embodiments [1] to [3].

[0019] Embodiment [6]: A molded article formed from the resin composition described in Embodiment [5].

[0020] Furthermore, this disclosure may achieve the following secondary objectives (solve the following problems).

[0021] Another object of this disclosure is to provide novel amine compounds or salts thereof with excellent optical properties, as well as methods for producing the same and applications.

[0022] In this specification and in the claims, the number of carbon atoms in substituents, etc., is defined as C1, C6, C 10 It is sometimes indicated in these ways. For example, "C1 alkyl group" means an alkyl group with 1 carbon atom, and "C 6-10 The term "aryl group" refers to an aryl group with 6 to 10 carbon atoms.

[0023] In this specification and in the claims, “independently” means that the two components are independent components, for example, alkylene group A 1a and A 1b In the case of A 1a and A 1b This means that the alkylene groups do not need to be the same; they may be different alkylene groups.

[0024] In this specification and in the claims, when a numerical range is indicated using "X~Y", it may include the end numbers X and Y. [Effects of the Invention]

[0025] This disclosure provides novel amine compounds or salts thereof that exhibit excellent heat resistance. [Brief explanation of the drawing]

[0026] [Figure 1] Figure 1 shows the 1H-NMR spectrum of the amine compound (1a) obtained in Example 1. [Modes for carrying out the invention]

[0027] [Amine compounds represented by formula (1) or their salts] The amine compound represented by formula (1) in this disclosure or its salt (hereinafter referred to as "amine compound or salt (1)") has excellent heat resistance and optical properties, possibly due to having a fluorene skeleton. For this reason, the novel amine compound or salt (1) in this disclosure is useful as an additive or raw material for resins, and because it has an amino group or a substituted amino group at the end of its side chain, it can also be used as a curing agent or crosslinking agent for resins.

[0028] In formula (1) above, base R 1 The substituents represented as may be non-reactive substituents that are inert to the reaction. Examples of non-reactive substituents include cyano groups; halogen atoms such as fluorine, chlorine, and bromine atoms; and hydrocarbon groups such as alkyl and aryl groups.

[0029] Examples of alkyl groups (linear or branched alkyl groups) include methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups. 1-12 Examples include alkyl groups.

[0030] Examples of aryl groups include phenyl groups and other C groups. 6-10 Examples include aryl groups.

[0031] Of these, cyano groups, halogen atoms, and alkyl groups are preferred, C 1-8 Alkyl groups are even more preferred, such as C(methyl) groups.1-4 Alkyl alkyl groups are more preferred.

[0032] Note that the base R 1 If the number of substitutions n is multiple (2 or more), then of the two benzene rings constituting the fluorene ring, two or more groups R substituted on the same benzene ring. 1 The types may be the same or different, and may consist of two or more groups R substituted on different benzene rings. 1 The types may be the same or different. Also, base R 1 The bonding position (substitution position) is not particularly restricted as long as it is between positions 1 and 8 of the fluorene ring, for example, positions 2, 7, and 2,7 of the fluorene ring.

[0033] The number of substitutions n can be an integer from 0 to 8, and preferred ranges are, in order, integers from 0 to 6, integers from 0 to 4, integers from 0 to 3, and integers from 0 to 2, and more preferably 0 or 1, particularly 0. Note that in the two benzene rings constituting the fluorene ring, the group R 1 The number of each substitution may be different from one another, but it is preferable that they be the same.

[0034] R 2a , R 2b , R 2c and R 2d The substituent represented by may also be an inactive substituent that is inert to the reaction. Examples of inactive substituents include hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups.

[0035] Examples of alkyl groups (linear or branched alkyl groups) include substituent R 1 C is an example of 1-12 Examples include alkyl groups.

[0036] Examples of cycloalkyl groups include cyclopentyl groups, cyclohexyl groups, and other C groups. 5-10 Examples include cycloalkyl groups.

[0037] Examples of aryl groups include phenyl groups, alkylphenyl groups, biphenylyl groups, naphthyl groups, etc. 6-12 Examples include aryl groups. Alkylphenyl groups include mono- or tri-C groups such as methylphenyl (or tolyl) and dimethylphenyl (or xylyl) groups. 1-4 Examples include alkylphenyl groups.

[0038] Aralkyl groups include C groups such as benzyl and phenethyl. 6-10 Aryl-C 1-4 Examples include alkyl groups.

[0039] Preferred R 2a , R 2b , R 2c and R 2d is a hydrogen atom or a hydrocarbon group, particularly preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or C 1-6 It is an alkyl group, more preferably a hydrogen atom or C 1-3 It is an alkyl group, most preferably a hydrogen atom (i.e., R 2a , R 2b , R 2c and R 2d (These are all hydrogen atoms.)

[0040] Also, R 2a , R 2b , R 2c and R 2d The types may be different from each other, R 2a and R 2b They are identical and R 2c and R 2d It is preferable that they are identical.

[0041] R 3a and R 3b The substituent represented by R may also be an inactive substituent that is inert to the reaction. Examples of inactive substituents include hydrocarbon groups such as alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. 2a ~R 2dExamples thereof include hydrocarbon groups exemplified as the substituent represented by .

[0042] Preferred R 3a and R 3b are a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a C 1-3 alkyl group, more preferably a hydrogen atom or a C 1-2 alkyl group, still more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.

[0043] A[[ID=z17]] 1a and A 1b Examples of the alkylene group (linear or branched alkylene group) represented by include C 1-12 alkylene groups such as a methylene group, an ethylene group, a propylene group (1,2-propanediyl group), a trimethylene group, a 1,2-butanediyl group, a tetramethylene group, a hexamethylene group, an isohexylene group, an octamethylene group, and a decamethylene group. Among these, a C 1-6 alkylene group is preferred, a C 2-4 alkylene group is more preferred, and a C 2-3 alkylene group such as a trimethylene group is even more preferred.

[0044] R 4a R 4b R 4c and R 4d Examples of the alkyl group (linear or branched alkyl group) represented by include the C 1 alkyl groups exemplified as the substituent R 1-12 .

[0045] R 4a R 4b R 4c and R 4d Examples of the acyl group represented by include C 1-10 alkyl-carbonyl groups such as an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a t-butyryl group, a pentanoyl group (valeryl group), and a hexanoyl group.

[0046] Preferred R4a , R 4b , R 4c and R 4d C is a hydrogen atom. 1-6 Alkyl or C 2-6 It is an acyl group, and particularly preferably C 1-4 Alkyl or C 2-4 It is an acyl group, and more preferably C 1-3 It is an alkyl group, more preferably C 1-2 It is an alkyl group, most preferably a methyl group (i.e., R 4a , R 4b , R 4c and R 4d (All of these are methyl groups)

[0047] Also, R 4a , R 4b , R 4c and R 4d The types may be different from each other, R 4a and R 4b They are identical and R 4c and R 4d It is preferable that they are identical.

[0048] The amine compound represented by formula (1) is, specifically, R 1 R is a cyano group, a halogen atom, or an alkyl group, and n is an integer from 0 to 6. 2a , R 2b , R 2c and R 2d is a hydrogen atom or an alkyl group, and R 3a and R 3b is a hydrogen atom or an alkyl group, A 1a and A 1b C 1-6 It is an alkylene group and R 4a , R 4b , R 4c and R 4d is a hydrogen atom or C 1-6 A amine compound that is an alkyl group is preferred. R 1 is an alkyl group, n is an integer from 0 to 3, and R 2a , R2b , R 2c and R 2d is a hydrogen atom or C 1-3 It is an alkyl group, R 3a and R 3b is a hydrogen atom or C 1-3 It is an alkyl group, A 1a and A 1b C 2-4 It is an alkylene group and R 4a , R 4b , R 4c and R 4d is a hydrogen atom or C 1-4 Amine compounds that are alkyl groups are even more preferred. n is 0, R 2a , R 2b , R 2c and R 2d is a hydrogen atom, and R 3a and R 3b A is a hydrogen atom, 1a and A 1b C 2-3 It is an alkylene group and R 4a , R 4b , R 4c and R 4d is a hydrogen atom or C 1-2 Amine compounds that are alkyl groups are more preferred.

[0049] Typical amine compounds represented by formula (1) include, R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, A 1a and A 1b C 2-4 Alkylene group, R 4a , R 4b , R 4c and R 4dCompounds in which the atom is a hydrogen atom, such as 9,9-bis{2-[N-(2-aminoethyl)carbamoyl]ethyl}fluorene, 9,9-bis{2-[N-(3-aminopropyl)carbamoyl]ethyl}fluorene, 9,9-bis{2-[N-(4-aminobutyl)carbamoyl]ethyl}fluorene, 9,9-bis{2-[N-(2-aminoethyl)carbamoyl]propyl}fluorene, 9,9-bis{2-[N-(3-aminopropyl)carbamoyl]propyl}fluorene, and 9,9-bis{2-[N-(4-aminobutyl)carbamoyl]propyl}fluorene, etc. 2-4 (Alkyl-carbamoyl)C 2-3 Alkyl fluorene; R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, A 1a and A 1b C 2-4 Alkylene group, R 4a , R 4b , R 4c and R 4d C 1-3 Compounds that are alkyl groups, such as 9,9-bis{2-[N-(2-(N,N-dimethylamino)ethyl)carbamoyl]ethyl}fluorene, 9,9-bis{2-[N-(3-(N,N-dimethylamino)propyl)carbamoyl]ethyl}fluorene, 9,9-bis{2-[N-(4-(N,N-dimethylamino)butyl)carbamoyl]ethyl}fluorene, 9,9-bis{2-[N-(2-(N,N-dimethylamino)ethyl)carbamoyl]propyl}fluorene, 9,9-bis{2-[N-(3-(N,N-dimethylamino)propyl)carbamoyl]propyl}fluorene, 9,9-bis{2-[N-(4-(N,N-dimethylamino)butyl)carbamoyl]propyl}fluorene, etc. 1-3 Alkylamino C 2-4 [Alkyl)Carbamoyl]C 2-3 Examples include alkyl fluorene.

[0050] In the amine compound or its salt (1), examples of salts include inorganic acid salts such as hydrochloride, sulfate, nitrate, hydrobromide, and phosphate; and organic acid salts such as acetate, oxalate, lactate, methanesulfonate, carbonate, and bicarbonate.

[0051] These amine compounds or their salts (1) can be used individually or in combination of two or more. Among these amine compounds or their salts, R in formula (1) 4a , R 4b , R 4c and R 4d A preferred amine compound or salt thereof, in which the alkyl group is 9,9-bis{2-[N-(N,N-diC 1-3 Alkylamino C 2-4 [Alkyl)Carbamoyl]C 2-3 Alkyl fluorene is particularly preferred.

[0052] [Method for producing amine compounds or their salts (1)] The method for producing the amine compound or its salt (1) is not particularly limited, but for example, it may be prepared by reacting the compound represented by formula (2) with the compounds represented by formulas (3a) and (3b) (Michael addition reaction).

[0053] Representative compounds represented by formula (2) include fluorene compounds with an unsubstituted 9-position, such as 9H-fluorene.

[0054] Furthermore, the compounds represented by formulas (3a) and (3b) are R 2a , R 2b , R 2c and R 2d , R 3a and R 3b , A 1a and A 1 , and R 4a , R 4b , R 4c and R 4dDepending on the type, either the E-form or the Z-form may be used.

[0055] Representative compounds represented by formulas (3a) and (3b) include, for example, the compounds specifically exemplified as compounds represented by formula (1), in which formulas (3a) and (3b) are: R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, A 1a and A 1b C 2-4 Alkylene group, R 4a , R 4b , R 4c and R 4d Compounds in which the atom is a hydrogen atom, such as N-(2-aminoethyl)(meth)acrylamide, N-(3-aminopropyl)(meth)acrylamide, N-(4-aminobutyl)(meth)acrylamide, etc. 2-4 Alkyl-(meth)acrylamide; R 2a , R 2b , R 2c and R 2d is a hydrogen atom, R 3a and R 3b is a hydrogen atom or a methyl group, A 1a and A 1b C 2-4 Alkylene group, R 4a , R 4b , R 4c and R 4d C 1-3 Compounds that are alkyl groups, such as N-[2-(N,N-dimethylamino)ethyl](meth)acrylamide, N-[3-(N,N-dimethylamino)propyl](meth)acrylamide, N-[4-(N,N-dimethylamino)butyl](meth)acrylamide, etc. 1-3 Alkylamino C 2-4Examples include alkyl(meth)acrylamide. It is preferable that the compounds represented by formulas (3a) and (3b) are the same compound.

[0056] The ratio of the amount of compound represented by formula (2) to the total amount of compounds represented by formulas (3a) and (3b) may be, for example, the former / latter (molar ratio) = 1 / 2 to 1 / 10, and preferred ranges are, in order, 1 / 2 to 1 / 5, 1 / 2.05 to 1 / 3, and 1 / 2.1 to 1 / 2.3.

[0057] The reaction may be carried out in the presence of a base. Examples of bases include metal hydroxides, metal carbonates or bicarbonates, and metal alkoxides.

[0058] Examples of metal hydroxides include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as barium hydroxide.

[0059] Examples of metal carbonates or bicarbonates include alkali metal carbonates or bicarbonates such as sodium carbonate, potassium carbonate, and sodium bicarbonate.

[0060] Examples of metal alkoxides include alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.

[0061] These bases can be used individually or in combination of two or more. Of these bases, metal hydroxides are preferred, and alkali metal hydroxides such as potassium hydroxide are even more preferred.

[0062] The proportion of the base may be, for example, about 0.001 to 0.1 moles per mole of the compound represented by formula (2), and preferably 0.01 to 0.05 moles.

[0063] The reaction may be carried out in or without a phase transfer catalyst. Examples of phase transfer catalysts include tetrabutylammonium bromide (TBAB) and tetraalkylammonium halides such as trioctylmethylammonium chloride. These phase transfer catalysts can be used individually or in combination of two or more. Of these phase transfer catalysts, TBAB is preferred.

[0064] The proportion of the phase transfer catalyst may be, for example, about 0.001 to 0.1 moles per mole of the compound represented by formula (2), and preferably 0.01 to 0.05 moles.

[0065] The reaction may be carried out in the absence or presence of a solvent that is inert to the reaction. Examples of solvents include water; alcohols such as methanol and ethanol; ethers such as cyclic ethers and chain ethers; sulfoxides such as dimethyl sulfoxide (DMSO); and hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons.

[0066] Examples of cyclic ethers include 1,4-dioxane and tetrahydrofuran (THF). Examples of linear ethers include diethyl ether, diisopropyl ether and other dialkyl ethers, and glycol ethers. Examples of the aforementioned glycol ethers include (poly)alkylene glycol monoalkyl ethers such as methyl cellosolve and methyl carbitol, and (poly)alkylene glycol dialkyl ethers such as dimethoxyethane.

[0067] Examples of aliphatic hydrocarbons include hexane and dodecane. Examples of alicyclic hydrocarbons include cyclohexane. Examples of aromatic hydrocarbons include toluene and xylene.

[0068] These solvents can be used individually or in combination of two or more. Of these solvents, a mixed solvent of water, sulfoxides such as DMSO, and aromatic hydrocarbons such as toluene is preferred. Water may also be added in the form of an aqueous solution of the aforementioned base. The amount of solvent used is not particularly limited as long as it does not hinder the progress of the reaction, and is, for example, 10 to 1000 mL, preferably 100 to 500 mL, and more preferably 200 to 400 mL, per 100 g of the total amount of the compounds represented by formulas (2), (3a), and (3b).

[0069] The reaction may be carried out under an inert gas atmosphere, such as nitrogen; or under an atmosphere of a noble gas such as helium or argon. The reaction temperature is, for example, 50 to 200°C, preferably 70 to 150°C, and more preferably 80 to 100°C. The reaction time is not particularly limited, for example, 0.5 to 10 hours, preferably 1 to 5 hours.

[0070] After the reaction is complete, the reaction mixture may be separated and purified as needed by conventional separation and purification methods, such as neutralization, washing, extraction, filtration, decantation, concentration, dehydration, drying, crystallization, chromatography, or a combination thereof. In particular, after neutralization, the amine compound may be extracted using aromatic hydrocarbons such as toluene, cyclic ethers such as THF, and water, and then crystallized. As a crystallization method, the amine compound may be dissolved in a crystallization solvent (such as aromatic hydrocarbons such as toluene) by heating at 50-100°C, and then crystals may be precipitated by cooling at 10-30°C and allowing to stand.

[0071] [Properties of amine compounds or their salts (1)] The amine compound or salt(1) of the present disclosure may be in crystalline or amorphous form. If in crystalline form, the melting point is, for example, 80 to 200°C, preferably 90 to 170°C, more preferably 100 to 150°C, more preferably 110 to 140°C, and most preferably 120 to 130°C.

[0072] The amine compound or its salt (1) of the present disclosure has high heat resistance, and its 5% weight loss temperature may be 200°C or higher, for example, 200 to 350°C, preferably 250 to 340°C, more preferably 280 to 330°C, and more preferably 300 to 320°C. Therefore, the amine compound of the present disclosure can be effectively used as a resin additive or the like even in high-temperature environments.

[0073] The refractive index of the amine compound or its salt (1) of this disclosure is, for example, 1.45 to 1.6, preferably 1.47 to 1.55, more preferably 1.48 to 1.53, more preferably 1.49 to 1.52, and most preferably 1.5 to 1.51 at a temperature of 25°C and a wavelength of 589 nm.

[0074] In this specification and in the claims, the melting point, 5% weight loss temperature, and refractive index can be measured by the methods described in the examples below.

[0075] [Resin composition] The amine compound or its salt (1) of this disclosure has excellent heat resistance and can be incorporated into resins even at high temperatures, such as during melt kneading, and can therefore be effectively used as a resin additive to modify the optical properties of the resin.

[0076] The resin may be a curable resin (thermo-curable or photocurable resin) or a thermoplastic resin.

[0077] Examples of curable resins include phenolic resins such as resol-type phenolic resins and novolac-type phenolic resins; amino resins such as urea resins, melamine resins, and guanamine resins; furan resins; unsaturated polyester resins; diallyl phthalate resins; vinyl ester resins (or epoxy (meth)acrylate resins); polyfunctional (meth)acrylate resins; epoxy resins; urethane resins; polyimide resins such as bismaleimide resins; and silicone resins.

[0078] Examples of thermoplastic resins include polyolefin resins, styrene resins, (meth)acrylic resins, vinyl acetate resins, vinyl chloride resins, fluororesins, polyester resins; polycarbonate resins (PC), polyamide resins (PA), polyacetal resins (POM), polyphenylene ether resins (PPE), polyetherketone resins, phenoxy resins, polyketone resins, polyphenylene sulfide resins (PPS), polysulfone resins, cellulose derivatives, thermoplastic polyimide resins, polyethernitrile resins, and thermoplastic elastomers (TPE).

[0079] Furthermore, if the resin is an epoxy resin, the amine compound or its salt (1) of the present disclosure may act as a curing agent and / or curing catalyst.

[0080] In the resin composition of this disclosure, the ratio of the amine compound or its salt (1) to the resin may be selected from, for example, a range of former / latter (mass ratio) = 0.01 / 99.99 to 50 / 50, preferably in the following increments: 0.1 / 99.9 to 30 / 70, 0.5 / 99.5 to 20 / 80, 1 / 99 to 15 / 85, 1 / 99 to 10 / 90, 2 / 98 to 8 / 92, 3 / 97 to 7 / 93, and 4 / 96 to 6 / 94. When the ratio of the amine compound or its salt (1) is above the lower limit, the resin tends to be easily modified, and when it is below the upper limit, the mechanical properties tend to improve.

[0081] The resin composition of this disclosure may optionally contain various additives, such as fillers or reinforcing agents, colorants such as dyes and pigments, conductive agents, flame retardants, plasticizers, lubricants, stabilizers, mold release agents, antistatic agents, dispersants, flow regulators, leveling agents, defoaming agents, surface modifiers, stress reducers, carbon materials, curing agents, and curing accelerators. Examples of stabilizers include antioxidants, ultraviolet absorbers, and heat stabilizers. These additives may be used individually or in combination of two or more.

[0082] The resin composition of this disclosure can be prepared by mixing an amine compound or a salt thereof (1), a resin, and other components such as additives as needed, by conventional methods such as dry mixing or melt kneading, and the resin composition may be in the form of pellets or the like.

[0083] [Molded body] The molded articles of this disclosure are formed from the resin composition. The shape of the molded articles is not particularly limited and can be selected according to the application, and may be one-dimensional structures such as linear or thread-like structures, two-dimensional structures such as film-like, sheet-like, or plate-like structures, or three-dimensional structures such as block-like, rod-like, tubular, or hollow structures.

[0084] Molded articles can be manufactured using conventional molding methods such as injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, and casting molding. [Examples]

[0085] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples. The raw materials, equipment, and evaluation methods used in the examples are as follows.

[0086] [Raw materials] N-[3-(dimethylaminopropyl)]acrylamide: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. DMSO: Dimethyl sulfoxide, manufactured by Kanto Chemical Co., Ltd. Toluene: Manufactured by Kanto Chemical Co., Ltd. TBAB: Tetrabutylammonium bromide, manufactured by Tokyo Chemical Industry Co., Ltd. KOH: Potassium hydroxide, manufactured by Kanto Chemical Co., Ltd. THF: Manufactured by Fujifilm Wako Pure Chemical Corporation

[0087] [HPLC] Using a Shimadzu LC-2030 HPLC (High Performance Liquid Chromatography) instrument and a Tosoh ODS-80TM column, samples were dissolved in acetonitrile and measured to calculate HPLC purity [area %].

[0088] [ 1 [H-NMR] The sample is dissolved in a deuterated solvent (CDCl3) containing tetramethylsilane as an internal standard, and then analyzed using a nuclear magnetic resonance spectrometer (BRUKER AVANCE III HD). 1 The 1H-NMR spectrum was measured.

[0089] [Melting point] A differential scanning calorimeter (DSC) (TA Instruments "Discovery DSC25") was used to perform measurements under a nitrogen atmosphere, with measurement temperatures ranging from 30 to 350°C and a heating rate of 10°C / min. The peak top temperature of the endothermic peak was read from the obtained DSC chart.

[0090] [5% weight loss temperature] Thermogravimetric analysis - Using a differential thermal analyzer (TG-DTA) (Rigaku Corporation "TG-DTA8122"), the temperature at which the mass of the sample decreased by 5% (5% weight loss temperature Td5) was measured under conditions of a nitrogen atmosphere, a heating rate of 10°C / min, and a temperature range of 30 to 400°C.

[0091] [Refractive index nD] The refractive index of the amine compound was measured using a refractometer (ATAGO RX-7000i) at a temperature of 25°C and a wavelength of 589 nm (D line). Furthermore, the refractive index was calculated by dissolving the sample in methanol to prepare solutions with concentrations (mass%) of 10 mass%, 15 mass%, and 20 mass%, and then extrapolating the concentration to 100 mass% in a calibration curve (approximate straight line) created by measuring the refractive index of the obtained solutions and 0 mass% (methanol only).

[0092] Example 1 As shown in the formula below, 9H-fluorene was reacted with N-[3-(N,N-dimethylamino)propyl]acrylamide to produce the amine compound (1a), 9,9-bis{2-[N-(3-(N,N-dimethylamino)propyl)carbamoyl]ethyl}fluorene.

[0093] [ka]

[0094] In detail, 9H-fluorene (49.9 g; 0.30 mol), DMSO (77.5 mL), toluene (67.1 g, 77.5 mL), TBAB (1.55 g; 0.0048 mol), and N-[3-(N,N-dimethylamino)propyl]acrylamide (103.1 g; 0.66 mol) were charged into a reaction vessel, and after purging with nitrogen, the temperature was raised to 65°C and it was confirmed that the substances were completely dissolved. To the resulting solution, 50% by mass aqueous KOH solution (1.35 g; equivalent to 0.012 mol of KOH) was added, and the temperature was raised to 90°C and stirred for 2 hours. The reaction was terminated by confirming the disappearance of 9H-fluorene using HPLC. The resulting reaction solution was cooled to 50°C, and neutralization treatment was performed by adding 10% by mass HCl aqueous solution (2.18 g; 0.0060 mol in terms of HCl) and deionized water (51 g) and stirring. Then, toluene (47 g) and THF (151 g) were added, and the mixture was washed three times with saturated brine (100 g) (liquid-liquid separation). The resulting organic layer was concentrated to obtain a solid, and then toluene (95 g) was added and the temperature was raised to 80°C to completely dissolve it. After that, it was cooled to 25°C, and crystalline material precipitated. The crystalline material was filtered off and washed with toluene (60 g), and the target amine compound (1a) was obtained in a yield of 51.7%. 1 The results of the 1H-NMR spectrum are shown in Figure 1 and below. The refractive index of amine compound (1a) was 1.5068, the 5% weight loss temperature was 311.25°C, and the melting point was 122.08°C.

[0095] 1H NMR(300MHz,CDCl3):1.34-1.40(4H,m), 1.47(4H,quin), 2.12(12H,s), 2.22(4H,t) , 2.37-2.43(4H,m), 3.08(4H,q), 6.24(2H,s), 7.27-7.40(6H,m), 7.68-7.69(2H,m) [Industrial applicability]

[0096] The amine compounds or salts thereof disclosed herein can be effectively used as additives (or resin modifiers) for modifying the optical properties of resins, as well as as resin raw materials (especially monomers such as polyamides, polyimides, and polyurethanes), as curing agents (or crosslinking agents) or curing catalysts for resins such as epoxy resins.

Claims

1. The following formula (1) 【Chemistry 1】 (In the formula, R １ represents a substituent, and n represents an integer from 0 to 8. R ２ａ , R ２ｂ , R ２ｃ and R ２ｄ These independently represent a hydrogen atom or a substituent. R ３ａ and R ３ｂ These independently represent a hydrogen atom or a substituent. A １ａ and A １ｂ each independently represents an alkylene group, R ４ａ , R ４ｂ , R ４ｃ and R ４ｄ (Each represents a hydrogen atom, an alkyl group, or an acyl group independently.) An amine compound represented by the same compound or a salt thereof.

2. In the above formula (1), R ４ａ , R ４ｂ , R ４ｃ and R ４ｄ C １－３ The amine compound or a salt thereof according to claim 1, which represents an alkyl group.

3. In the above formula (1), A １ａ and A １ｂ C １－６ The amine compound or a salt thereof according to claim 1 or 2, which exhibits an alkylene group.

4. The following formula (2) 【Chemistry 2】 [In the formula, R １ and n are the same as in formula (1) above. Compounds represented by the following formulas (3a) and (3b) 【Transformation 3】 [In the formula, R ２ａ , R ２ｂ , R ２ｃ and R ２ｄ , R ３ａ and R ３ｂ A １ａ and A １ｂ , R ４ａ , R ４ｂ , R ４ｃ and R ４ｄ [These are the same as in formula (1) above] A method for producing an amine compound or a salt thereof according to claim 1 or 2, comprising the step of reacting it with a compound represented by .

5. A resin composition comprising a resin and an amine compound or a salt thereof according to claim 1 or 2.

6. A molded article formed from the resin composition described in claim 5.

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