JP2016102079A - Saturated heterocycle-containing compound, secondary battery electrode and secondary battery using the same, binder, and fluorescent substance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a saturated heterocycle-containing compound capable of emitting fluorescence, a fluorescent substance, and a binder, and to provide a secondary battery electrode and a secondary battery using the saturated heterocycle-containing compound.SOLUTION: The saturated heterocycle-containing compound of the present invention has a chemical structure represented by formula (1) (where n is an integer from 0 to 5 inclusive; m is an integer from 0 to 2 inclusive; E is, for example, O, S or N; R, Rand Rare each independently a hydrogen group or a substituent; and Rand Rare each independently a hydrocarbon group which may be substituted with a substituent, or a hydrogen group).SELECTED DRAWING: None

Description

  The present invention relates to a saturated heterocycle-containing compound, a secondary battery electrode using the same, a secondary battery, a binder, and a fluorescent material.

  Examples of the fluorescent polymer material include those described in Patent Documents 1 to 4. Patent Document 1 discloses polymer nanoparticles containing a cationic polymer and a fluorescent dye. Patent Document 2 discloses a molecule having a hydrophilic side chain unit in the molecule and a hydrophobic and fluorescent skeleton unit. Patent Document 3 discloses a fluorescent material containing a fluorescent dye molecule-containing silica sphere, a polymer, and an X-ray phosphor-containing silica sphere. Patent Document 4 discloses a polymer dye exhibiting fluorescence.

Special table 2009-539793 Special table 2011-500916 gazette JP 2006-300930 A Japanese Patent Laid-Open No. 5-230393

  However, in Patent Document 1, a polymer nanoparticle is made fluorescent by containing a water-soluble polymer and a fluorescent dye in the polymer nanoparticle, and the polymer itself does not emit fluorescence.

  In the fluorescent particles described in Patent Document 2, the fluorescence generation site that emits fluorescence is sparingly water-soluble. For this reason, in order to make the fluorescent particles water-soluble, there is a limitation on the amount of the fluorescence generation site.

  In Patent Document 3, a fluorescent material is made by adding a fluorescent dye to a silica sphere, and the polymer itself does not express fluorescence.

In the polymer dye described in Patent Document 4, the fluorescent site has a conjugated structure based on aromatic carbon. For this reason, the presence of carbon-carbon bonds having an sp ² structure is necessary at the fluorescent site.

  Conventionally, fluorescent materials have been developed as exemplified above, but in recent years, new fluorescent materials have been increasingly developed.

  This invention is made | formed in view of this situation, and makes it a subject to provide the compound which can emit fluorescence, the electrode for secondary batteries using this, a secondary battery, a binder, and a fluorescent substance.

  The present inventor has sought a novel fluorescent material having a structure that does not have an unsaturated bond between carbon atoms, and has also sought the use of the fluorescent material as a battery material. As a result, the inventors completed the present invention.

  The saturated heterocyclic ring-containing compound of the present invention has a chemical structure represented by the following formula (1).

（式（１）中、ｎは０以上５以下の整数、ｍは０以上２以下の整数である。
Ｅは、Ｂ、Ｎ、Ｏ、Ａl、Ｓｉ、Ｐ、Ｓ、Ｇａ、Ｇｅ、Ａｓ、又はＳｅからなる。
Ｒ^１は、互いに独立して、炭化水素基、複素環基、水酸基、アルコキシ基、アルデヒド基、カルボニル基、カルボキシル基、エステル基、アミノ基、アミド基、イミド基、イソシアン酸基、ニトロ基、ニトロソ基、イソニトリル基、ハロゲン基、ホスフィノ基、ホスファゼン基、チオ基、チオキシ基、シリル基の群から選ばれる１種以上をもつ構造を有する置換基、水素基、又は不対電子からなる。
Ｒ^２は、互いに独立して、炭化水素基、複素環基、水酸基、アルコキシ基、アルデヒド基、カルボニル基、カルボキシル基、エステル基、アミノ基、アミド基、イミド基、イソシアン酸基、ニトロ基、ニトロソ基、イソニトリル基、ハロゲン基、ホスフィノ基、ホスファゼン基、チオ基、チオキシ基、シリル基の群から選ばれる１種以上をもつ構造を有する置換基、又は、水素基からなる。
Ｒ^３は、互いに独立して、炭化水素基、複素環基、水酸基、アルコキシ基、アルデヒド基、カルボニル基、カルボキシル基、エステル基、アミノ基、アミド基、イミド基、イソシアン酸基、ニトロ基、ニトロソ基、イソニトリル基、ハロゲン基、ホスフィノ基、ホスファゼン基、チオ基、チオキシ基、シリル基の群から選ばれる１種以上をもつ構造を有する置換基、又は、水素基からなる。
Ｒ^４は、互いに独立して、置換基で置換されていてもよい炭化水素基、又は水素基からなる。
Ｒ^５は、互いに独立して、置換基で置換されていてもよい炭化水素基、又は水素基からなる。
前記炭化水素基の炭素の一部はＯ，Ｎ、又はＳで置換されていてもよい。
また、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、及びＲ^５の中から選ばれる２つは、互いに結合して環を形成しても良い。）
本発明の結着剤は、上記の飽和ヘテロ環含有化合物を有する。

(In Formula (1), n is an integer of 0 or more and 5 or less, and m is an integer of 0 or more and 2 or less.
E consists of B, N, O, Al, Si, P, S, Ga, Ge, As, or Se.
R ¹ is independently of each other a hydrocarbon group, heterocyclic group, hydroxyl group, alkoxy group, aldehyde group, carbonyl group, carboxyl group, ester group, amino group, amide group, imide group, isocyanate group, nitro group, It consists of a substituent having a structure having at least one selected from the group consisting of a nitroso group, an isonitrile group, a halogen group, a phosphino group, a phosphazene group, a thio group, a thioxy group and a silyl group, a hydrogen group, or an unpaired electron.
R ² is independently of each other a hydrocarbon group, heterocyclic group, hydroxyl group, alkoxy group, aldehyde group, carbonyl group, carboxyl group, ester group, amino group, amide group, imide group, isocyanate group, nitro group, It consists of a substituent having a structure having at least one selected from the group consisting of a nitroso group, an isonitrile group, a halogen group, a phosphino group, a phosphazene group, a thio group, a thioxy group and a silyl group, or a hydrogen group.
R ³ is independently of each other a hydrocarbon group, heterocyclic group, hydroxyl group, alkoxy group, aldehyde group, carbonyl group, carboxyl group, ester group, amino group, amide group, imide group, isocyanate group, nitro group, It consists of a substituent having a structure having at least one selected from the group consisting of a nitroso group, an isonitrile group, a halogen group, a phosphino group, a phosphazene group, a thio group, a thioxy group and a silyl group, or a hydrogen group.
R ⁴ is independently of each other a hydrocarbon group which may be substituted with a substituent, or a hydrogen group.
R ⁵ is independently of each other a hydrocarbon group which may be substituted with a substituent, or a hydrogen group.
A part of carbon of the hydrocarbon group may be substituted with O, N, or S.
^Two selected from R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring. )
The binder of the present invention has the above saturated heterocyclic ring-containing compound.

  An electrode for a secondary battery according to the present invention includes a current collector and an active material layer covering a surface of the current collector, and the active material layer includes the saturated heterocyclic ring-containing compound and the active material described above. Including.

  The secondary battery of the present invention has the saturated heterocyclic ring-containing compound described above.

  The fluorescent substance of the present invention comprises the above-described saturated heterocyclic ring-containing compound.

  Since the present invention has the above-described structure, it is possible to provide a compound capable of emitting fluorescence, a secondary battery electrode and a secondary battery, a binder, and a fluorescent material using the compound.

The IR (infrared spectroscopy) spectrum of the viscous liquid obtained in Example 1 is shown. The ¹ H-NMR spectrum of the mixture of Comparative Example 1 is shown. 1 shows the ¹ H-NMR spectrum of the viscous liquid of Example 1. The ¹³ C-NMR spectrum of the mixture of Comparative Example 1 is shown. The ¹³ C-NMR spectrum of the viscous liquid of Example 1 is shown. The fluorescence spectrum emitted from the reaction product of Example 1 when two types of excitation light with a wavelength of 320 nm and a wavelength of 365 nm are irradiated is shown. The fluorescence spectrum emitted from the reaction product of Example 1 and the chelate compound of Reference Example 1 when irradiated with two types of excitation light having a wavelength of 320 nm and a wavelength of 365 nm is shown.

  The electrode for a secondary battery and the secondary battery using the saturated heterocyclic ring-containing compound, the binder, the fluorescent material, and the saturated heterocyclic ring-containing compound according to the embodiment of the present invention will be described in detail.

(Saturated heterocycle-containing compound)
The saturated heterocyclic ring-containing compound of the present invention has a structure represented by the following formula (1).

Here, in Formula (1), n is an integer of 0 or more and 5 or less.
E consists of B, N, O, Al, Si, P, S, Ga, Ge, As, or Se. Further, E is preferably O, S, or N.
E is a hetero element that forms a skeleton of a cyclic structure together with a carbon atom. Since the cyclic structure shown in Formula (1) forms a skeleton with carbon and the heteroelement E, it is referred to as a heteroatom-containing cyclic structure.

M in the formula (1) is an integer of 0 or more and 2 or less. m is the number of R ¹ in the formula (1). m varies depending on the valence of E. When the valence of E is divalent, m is zero. When the valence of E is trivalent or tetravalent, m is 1 or 2. When m is 1 or 2, R ¹ is a hydrocarbon group (a part of carbon of the hydrocarbon group may be substituted with O, N, or S), a heterocyclic group, a hydroxyl group, an alkoxy group. Group, aldehyde group, carbonyl group, carboxyl group, ester group, amino group, amide group, imide group, isocyanate group, nitro group, nitroso group, isonitrile group, halogen group, phosphino group, phosphazene group, thio group, thio group And a substituent having a structure having at least one selected from the group of silyl groups, a hydrogen group, or an unpaired electron.

R ² is independently of each other a hydrocarbon group (some carbons of the hydrocarbon group may be substituted with O, N, or S), a heterocyclic group, a hydroxyl group, an alkoxy group, an aldehyde. Group, carbonyl group, carboxyl group, ester group, amino group, amide group, imide group, isocyanate group, nitro group, nitroso group, isonitrile group, halogen group, phosphino group, phosphazene group, thio group, thioxy group, silyl group It consists of a substituent having a structure having one or more selected from the group consisting of: or a hydrogen group.

R ³ is independently of each other a hydrocarbon group (some carbons of the hydrocarbon group may be substituted with O, N, or S), a heterocyclic group, a hydroxyl group, an alkoxy group, an aldehyde. Group, carbonyl group, carboxyl group, ester group, amino group, amide group, imide group, isocyanate group, nitro group, nitroso group, isonitrile group, halogen group, phosphino group, phosphazene group, thio group, thioxy group, silyl group It consists of a substituent having a structure having one or more selected from the group consisting of: or a hydrogen group.

The hydrocarbon group that may be contained in R ¹ , R ² , and R ³ may include one or more selected from the group consisting of a chain alkyl group, a cyclic alkyl group, a saturated alkyl group, and an unsaturated alkyl group. .

  Examples of the hydrocarbon group include a polyalkyleneimine residue, a polyalkylene oxide residue, and a polyalkylenethioxide residue. Examples of the polyalkyleneimine group include a polyethyleneimine residue, a polypropyleneimine residue, and a polybutyleneimine residue. Examples of the polyalkylene oxide residue include a polyethylene oxide residue, a polypropylene oxide residue, and a polybutylene oxide residue. Examples of the polyalkylene thioxide residue include a polyethylene thioxide residue, a polypropylene thioxide residue, a polybutyrene oxide residue, and the like.

R ¹ , R ² , and / or R ³ may be an amide group to which a hydrocarbon group is bonded. In particular, R ² and / or R ³ are preferably an amide group to which a hydrocarbon group is bonded.

R ¹ , R ² , and / or R ³ may be independently composed of an amide group to which a water-soluble polymer residue is bonded. In this case, the saturated heterocyclic ring-containing compound can be made water-soluble. Among these, examples of the water-soluble polymer residue include a polyalkyleneimine residue, a polyalkylene oxide residue, and a polyalkylenethioxide residue. In addition, as the water-soluble polymer residue, biopolymer residues such as sugar, protein, nucleic acid and the like can be used.

In the case where R ¹ , R ² and R ³ are each composed of an amide group to which a water-soluble polymer residue is bonded, the mass average molecular weight of each water-soluble polymer residue is preferably 300 to 70000. In this case, the saturated heterocycle-containing compound can suitably exhibit adhesiveness.

R ⁴ is independently of each other a hydrocarbon group that may be substituted with a substituent (a part of carbon of the hydrocarbon group may be substituted with O, N, or S), or Consists of a hydrogen group. R ⁵ is independently of each other a hydrocarbon group that may be substituted with a substituent (a part of carbon of the hydrocarbon group may be substituted with O, N, or S), or Consists of a hydrogen group.

The hydrocarbon group that can be R ⁴ and R ⁵ can contain, independently of each other, one or more selected from the group consisting of a chain alkyl group, a cyclic alkyl group, a saturated alkyl group, and an unsaturated alkyl group.

Examples of the substituent that may be substituted with a hydrocarbon group that can be R ⁴ and R ⁵ include a hydroxyl group, an alkoxy group, an aldehyde group, a carbonyl group, a carboxyl group, an ester group, an amino group, an amide group, an imide group, and isocyanate. It has a structure having at least one selected from the group consisting of acid groups, nitro groups, nitroso groups, isonitrile groups, halogen groups, phosphino groups, phosphazene groups, thio groups, thioxy groups, and silyl groups.

Examples of the hydrocarbon group that can be R ⁴ and R ⁵ include a polyalkyleneimine residue, a polyalkylene oxide residue, and a polyalkylenethioxide residue. Examples of the polyalkyleneimine group include a polyethyleneimine residue, a polypropyleneimine residue, and a polybutyleneimine residue. Examples of the polyalkylene oxide residue include a polyethylene oxide residue, a polypropylene oxide residue, and a polybutylene oxide residue. Examples of the polyalkylene thioxide residue include a polyethylene thioxide residue, a polypropylene thioxide residue, a polybutyrene oxide residue, and the like.

R ⁴ and / or R ⁵ are preferably independently of each other a hydrocarbon group comprising a water-soluble polymer residue. In this case, the saturated heterocyclic ring-containing compound can be made water-soluble. Examples of the water-soluble polymer residue include a polyalkyleneimine residue, a polyalkylene oxide residue, and a polyalkylenethioxide residue. As the water-soluble polymer residue, biopolymer residues such as sugars, proteins, and nucleic acids can be used. The mass average molecular weight of the water-soluble polymer residue as R ⁴ and R ⁵ is preferably 300 to 70000. In this case, the saturated heterocycle-containing compound can suitably exhibit adhesiveness.

The number of R ^{1 and} the number of R ² , R ³ , R ⁴ , and R ⁵ when m in the formula (1) showing the structure of the saturated heterocycle-containing compound of the present invention is 2, is there. Two each of R ¹ , R ² , R ³ , R ⁴ , and R ⁵ may have different structures independently of each other, or may have the same structure.

At least two of R ⁴ and R ^{5 in} the formula (1) showing the structure of the saturated heterocyclic ring-containing compound of the present invention may be a hydrocarbon group composed of a water-soluble polymer residue. At least two of R ¹ , R ² and R ³ may be composed of a substituent containing a water-soluble polymer residue. In this case, the adhesiveness of the saturated heterocycle-containing compound is increased, and the saturated heterocycle-containing compound can be suitably used as an adhesive or a binder.

^Two selected from R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring.

  The saturated heterocyclic ring-containing compound preferably has a structure represented by the following formula (4), and for example, a structure represented by the following formula (2) or formula (3) is preferable.

（式（４）中、ｒ及びｓは、互いに独立して、０〜２の整数であり、ｒ+ｓ＝２の関係をもつ。
Ｒ^４、Ｒ^５、及びＲ^６は、それぞれ独立して、置換基で置換されていてもよい炭化水素基（炭化水素基の炭素の一部がＯ，Ｎ、又はＳで置換されていてもよい。）、又は水素基からなる。）

(In Formula (4), r and s are the integers of 0-2 independently of each other, and have a relationship of r + s = 2.
R ⁴ , R ⁵ , and R ⁶ are each independently a hydrocarbon group that may be substituted with a substituent (even if a part of the carbon of the hydrocarbon group is substituted with O, N, or S). Or a hydrogen group. )

R ⁴ and R ⁵ in Formula (2) and Formula (3), and R ⁶ and R ^{7 in} Formula (2) are each a hydrocarbon group that may be substituted with a substituent (carbon of the hydrocarbon group). Some may be substituted with O, N, or S.), or a hydrogen group.

The substituents that may be substituted with the hydrocarbon groups as R ⁴ , R ⁵ , R ⁶ , and R ⁷ are, for example, independently of each other, a hydroxyl group, an alkoxy group, an aldehyde group, a carbonyl group, a carboxyl group, and an ester group. One or more selected from the group consisting of amino group, amide group, imide group, isocyanate group, nitro group, nitroso group, isonitrile group, halogen group, phosphino group, phosphazene group, thio group, thioxy group, and silyl group It has a structure with

  The mass average molecular weight of the saturated heterocyclic ring-containing compound of the present invention is preferably 300 or more and 15000 or less.

In the saturated heterocycle-containing compound of the present invention, R ⁴ and R ⁵ are bonded to a heteroatom-containing cyclic structure having a heteroatom-carbon bond through an amide bond. It is considered that fluorescence is generated by an orbital interaction (σ conjugation) between a heteroatom-carbon antibonding orbital and an amide bond N (nitrogen) rompair. The saturated heterocycle-containing compound of the present invention emits fluorescence even in a state in which the heteroatom-containing cyclic structure has no C═C bond.

  As shown in the following formula (5), when the heteroatom-containing cyclic structure in the saturated heterocycle-containing compound is a furan ring, there are two α-position carbons adjacent to O (oxygen) of the furan ring. The two α-position carbons each have an antibonding orbit of a C—O bond. Each of the two α-position carbons causes σ-conjugation with the amide bond N lone pair bonded to the α-position carbon. Therefore, a new conjugate orbital is formed on the partial structure of the polymer [-NH-CO-CH-O-CH-CO-NH] in the furan ring and the amide bond in the saturated heterocycle-containing compound, Electron excitation is likely to occur. Therefore, it is considered that the saturated heterocyclic ring-containing compound of the present invention emits fluorescence without passing through an unsaturated bond between carbons.

（式（５）中のＲ^２、Ｒ^３、Ｒ^４は、式（１）中のＲ^２、Ｒ^３、Ｒ^４と同様である。）

^{(R 2,} R 3, ^{R 4} in the formula (5) are the same as ^{R 2,} R 3, ^{R 4} in the formula (1).)

  As shown in formula (5), in order to make the orbital interaction between the heteroatom-carbon antibonding orbital and the amide N rompair efficient, the heteroatom-carbon has a part of the cyclic structure. It is desirable to configure. In a compound in which the heteroatom-carbon structure is included in the chain structure as in the formula (6), the antibonding orbital of the heteroatom-carbon is not stable, and the orbital interaction with the N rompair of the amide bond It is considered that fluorescence is difficult to be exhibited.

（式（６）中のＲ^４は、式（１）中のＲ^４と同様である。）

^{(R 4} in the formula (6) is the same as ^{R 4} in the formula (1).)

In the heteroatom-containing cyclic structure represented by the formula (5), a hydrocarbon group or a hydrogen group (R ⁴ ) is bonded to two α-position carbons of the furan ring via an amide bond. An amide bond to which a hydrogen group or a hydrogen group (R ⁵ ) is bonded is omitted. The chain structure shown in Formula (6) has two carbon atoms adjacent to the heteroatom (O), but one carbon atom is omitted.

  As described above, the case where the heterocycle is a furan ring has been shown as an example. However, in the other heterocycle represented by the formula (1), the α-position carbon in the heterocycle and the N of the amide bond bonded thereto are also shown. It is considered that sigma conjugation occurs between the pair and fluorescence is expressed.

  In the formula (1) showing the saturated heterocyclic ring-containing compound of the present invention, n is an integer of 0 or more and 5 or less. The number of carbon atoms forming the ring skeleton of the saturated heterocyclic ring-containing compound is 3 or more and 8 or less. When the number of carbon atoms forming the ring skeleton is 2, a ring structure cannot be constructed, and thus fluorescence based on the desired conjugation cannot be expressed. If the number of carbon atoms forming the cyclic skeleton is 9 (n = 6) or more, the cyclic motion of the cyclic structure increases, and therefore the α-position carbon is less likely to exhibit σ conjugation, and there is a possibility that fluorescence will not be expressed. N in the formula (1) is preferably an integer of 0 to 2. In this case, the ring motion of the cyclic structure is further suppressed, and the α-position carbon is likely to exhibit σ conjugation, and easily emits fluorescence.

An example of the method for producing the saturated heterocyclic ring-containing compound of the present invention will be described. In order to produce the saturated heterocyclic ring-containing compound of the present invention, a heteroatom-containing cyclic structure in which a carboxyl group is introduced into the α-position carbon, and an amino group corresponding to R ⁴ or / and R ⁵ in formula (1) And having a substituent precursor. By condensing the amino group of the substituent precursor to the carboxyl group of the heteroatom-containing cyclic structure, a saturated heterocyclic-containing compound in which the substituent is introduced into the heteroatom-containing cyclic structure via an amide bond is generated. The condensation reaction is preferably performed at 100 ° C to 200 ° C. If the condensation reaction temperature is too low, the reaction may not proceed. If the reaction temperature is too high, the heteroatom-containing cyclic structure and the substituent precursor may be thermally decomposed. The time for the condensation reaction is preferably 1 to 10 hours.

R ¹ , R ² , and R ³ can be bonded to the heteroatom-containing cyclic structure by a general method. In addition, a carboxyl group is introduced into the α-position carbon of the heteroatom-containing cyclic structure in which R ¹ , R ² , and / or R ³ is bonded in advance, and this carboxyl group is substituted corresponding to the above R ⁴ and R ⁵ The amino group of the group precursor may be subjected to a condensation reaction.

  The molar ratio of the heteroatom-containing cyclic structure to the substituent precursor is preferably 0.001-1, and more preferably 0.01-0.5. When this molar ratio is excessive, the amide group is not sufficiently bonded to the α-position carbon of the heteroatom-containing cyclic structure, and the reaction product may not exhibit sufficient fluorescence. When the molar ratio of the heteroatom-containing cyclic structure to the substituent precursor is too small, the substituent is bonded to the site that binds to the heteroatom-containing cyclic structure, but there are too many substituent precursors and involved in the condensation reaction. A large amount of substituent precursors remain, and the reaction efficiency may be reduced.

Since the saturated heterocycle-containing compound of the present invention is a fluorescent substance, it can be used as a fluorescent labeling substance or a fluorescent paint. At least one of R ¹ , R ² , and R ^{3 in} the formula (1) may be an amide group to which a water-soluble polymer residue is bonded. Further, at least one of R ⁴ and R ⁵ is preferably composed of a water-soluble polymer residue. In this case, the saturated heterocycle-containing compound of the present invention becomes a water-soluble fluorescent material, and can be used as a fluorescent biomarker or water-based paint.

Moreover, it is also possible to use a saturated heterocyclic ring-containing compound for an oil-based paint. In this case, at least one of R ¹ , R ² , and R ^{3 in} the formula (1) may be composed of an amide group to which a water-insoluble polymer residue is bonded. Moreover, it is preferable that at least one of R ⁴ and R ⁵ is composed of a water-insoluble polymer residue. Examples of the water-insoluble polymer residue include a polyethylene residue.

In addition, the heteroatom-containing cyclic structure of the saturated heterocycle-containing compound has a large number of substituent introduction sites, as indicated by R ¹ , R ² , R ³ , R ⁴ , and R ⁵ in formula (1). For this reason, by introducing a polymer chain or the like into the substituent introduction site, the heteroatom-containing cyclic structure becomes a crosslinking point of the polymer chain. Thereby, the saturated heterocycle-containing compound of the present invention can form a three-dimensional network.

  The saturated heterocyclic ring-containing compound of the present invention can be used for electronic devices such as chemical sensors.

  In addition, various functional groups can be introduced as substituents into the saturated heterocyclic ring-containing compound of the present invention. For example, a saturated heterocycle-containing compound into which a functional group capable of binding to the test object is introduced is generated, and the saturated heterocycle-containing compound is fixed to the substrate. Then, the test object is fixed to the saturated heterocyclic ring-containing compound by bringing the substrate into contact with a solution containing the test object. Thereby, the presence or absence of the inspection object can be detected.

  In addition, the saturated heterocyclic ring-containing compound of the present invention can be used as a chelate compound by utilizing the coordinating properties of substituents.

  The saturated heterocyclic ring-containing compound of the present invention can be used as a fluorescent labeling substance.

  For example, the saturated heterocyclic ring-containing compound of the present invention is included in a secondary battery electrode or a secondary battery. In this case, the saturated heterocyclic ring-containing compound takes in the transition metal eluted inside the battery and changes the fluorescence characteristics. For this reason, according to the saturated heterocycle-containing compound of the present invention, it is possible to detect the presence or absence of metal elution in the battery.

In addition, the saturated heterocycle-containing compound of the present invention can be obtained by selecting an amide group to which a water-soluble polymer residue such as a polyethyleneimine residue is bonded as substituents R ¹ , R ² , and R ³ bonded to the ring skeleton, Adhesiveness is suitably expressed. In this case, the saturated heterocyclic ring-containing compound of the present invention can be suitably used as a pressure-sensitive adhesive or a binder. The pressure-sensitive adhesive is one that develops the viscosity of a saturated heterocyclic ring-containing compound.

  The binder of the present invention has the above saturated heterocyclic ring-containing compound. The binder plays a role of holding materials together.

The binder of this invention is good in it being a binder used for the electrode for secondary batteries. The binder serves to bind the active material and the conductive additive to the surface of the current collector. The binder of the present invention includes, in addition to the above saturated heterocyclic ring-containing compound, thermoplastic resins such as polyvinylidene fluoride, polytetrafluoroethylene, fluororubber, fluororesin, polypropylene and polyethylene, polyimide, polyamideimide and the like. An imide-based resin and an alkoxysilyl group-containing resin may be included. When a saturated heterocyclic ring-containing compound is used as a binder in an electrode, the saturated heterocyclic ring-containing compound of the present invention is a water-insoluble polymer residue as R ¹ , R ² , or R ³ in formula (1). ^May have an amide group bonded thereto, and R ⁴ and / or R ⁵ in the formula (1) may have a water-insoluble polymer residue. The water-insoluble polymer residue may be included in a part of the structure of R ¹ , R ² , R ³ , R ⁴ , and / or R ⁵ . Examples of the water-insoluble polymer residue include, for example, a polyvinylidene fluoride residue, a polytetrafluoroethylene residue, a polyolefin residue such as a polypropylene residue and a polyethylene residue, an imide polymer residue such as a polyimide residue and a polyamideimide , Fluororubber residues, fluorine-containing polymer residues, and alkoxysilyl group-containing polymer residues.

(Electrode for secondary battery)
An electrode for a secondary battery of the present invention comprises a current collector and an active material layer covering the surface of the current collector, and the active material layer comprises the saturated heterocyclic ring-containing compound and the active material described above. Including. The saturated heterocyclic ring-containing compound exhibits adhesiveness, and thus acts as a binder that connects the active materials or the active material and the current collector.

  The secondary battery electrode using the saturated heterocycle-containing compound of the present invention may be either a secondary battery positive electrode or a secondary battery negative electrode. Here, the blending ratio of the active material and the saturated heterocycle-containing compound in the active material layer is preferably a mass ratio of active material: saturated heterocycle-containing compound = 1: 0.005 to 1: 0.3. . This is because when the amount of the saturated heterocyclic ring-containing compound is too small, the moldability of the electrode is lowered, and when the amount of the saturated heterocyclic ring-containing compound is too large, the energy density of the electrode is lowered.

  When the secondary battery electrode is a secondary battery positive electrode, a positive electrode active material is used as the active material.

  The positive electrode active material is a material that can occlude and release metal ions. When the metal ions are lithium ions, the positive electrode active material may be a material that can occlude and release lithium ions. Such a positive electrode active material is preferably made of a lithium composite metal oxide having lithium and a transition metal.

As the lithium composite metal oxide represented by the general _{formula: Li a Ni b Co c Mn} d D e O f (0.2 ≦ a ≦ 1.2, b + c + d + e = 1,0 ≦ e <1, D is Li, Fe, At least one element selected from Cr, Cu, Zn, Ca, Mg, S, Si, Na, K, Al, Zr, Ti, P, Ga, Ge, V, Mo, Nb, W, La, 1.7 ≦ f ≦ 2.1), Li ₂ MnO ₃ can be mentioned. The lithium composite metal oxide has a general formula: Li _x A _y Mn _{2 -y} O ₄ (A is a transition metal element, Ca, Mg, S, Si, Na, K, Al, P, Ga, and Ge. At least one element selected from the group consisting of: a spinel compound represented by 0 <x <2, 0 ≦ y ≦ 1), and a solid solution composed of a mixture of a spinel compound and a layered compound, LiMPO ₄ , LiMVO ₄ or A polyanionic compound represented by Li ₂ MSiO ₄ (wherein M is selected from at least one of Co, Ni, Mn, and Fe) may be used.

For example, as the layered compound, LiNi _0.5 Co _0.2 Mn _0.3 O ₂ , LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiNi _0.5 Mn _0.5 O ₂ , LiNi _{0 And} at least one selected from _.75 Co _0.1 Mn _0.15 O ₂ , LiMnO ₂ , LiNiO ₂ , and LiCoO ₂ . Examples of the spinel compound include LiNi _0.5 Mn _1.5 O ₄ and LiMn ₂ O ₄ . Examples of the polyanion compound include LiFePO ₄ , LiCoPO ₄ , Li ₂ CoPO ₄ F, Li ₂ MnSiO ₄ , and Li ₂ FeSiO ₄ . When the secondary battery electrode is a secondary battery negative electrode, a negative electrode active material is used as the active material.

The negative electrode active material is a material that can occlude and release metal ions. When the metal ion is lithium ion, a material capable of inserting and extracting lithium ions can be used as the negative electrode active material, particularly if it is a simple substance, alloy or compound capable of inserting and extracting lithium ions. There is no limitation. For example, Li, group 14 elements such as carbon, silicon, germanium and tin, group 13 elements such as aluminum and indium, group 12 elements such as zinc and cadmium, group 15 elements such as antimony and bismuth, magnesium as the negative electrode active material , Alkaline earth metals such as calcium, and group 11 elements such as silver and gold may be employed alone. When silicon or the like is used for the negative electrode active material, a silicon atom reacts with a plurality of lithiums, so that it becomes a high-capacity active material. However, there is a problem that volume expansion and contraction due to insertion and extraction of lithium becomes significant. In order to reduce the fear, it is also preferable to employ a material such as silicon combined with another element such as a transition metal as the negative electrode active material. Specific examples of the single substance include various carbon-based materials such as graphite. Specific examples of the alloy or the compound include a tin-based material such as an Ag—Sn alloy, a Cu—Sn alloy, and a Co—Sn alloy, SiO _{x that} disproportionates into silicon and silicon dioxide (0.3 ≦ x ≦ 1. Examples thereof include silicon-based materials such as 6), silicon alone, or a composite of a silicon-based material and a carbon-based material. In addition, as the negative electrode active material, oxides such as Nb ₂ O ₅ , TiO ₂ , Li ₄ Ti ₅ O ₁₂ , WO ₂ , MoO ₂ , Fe ₂ O ₃ , or Li _3-x M _x N (M = A nitride represented by (Co, Ni, Cu) may be employed. One or more of these materials can be used as the negative electrode active material.

  In addition to the active material and the above-described saturated heterocyclic ring-containing compound, the active material layer may contain a conductive additive as necessary. The conductive assistant is added to increase the conductivity of the electrode. Therefore, the conductive auxiliary agent may be added arbitrarily when the electrode conductivity is insufficient, and may not be added when the electrode conductivity is sufficiently excellent. The conductive auxiliary agent may be any chemically inert electronic high conductor, such as carbon black, graphite, acetylene black, ketjen black (registered trademark), vapor grown carbon fiber (Vapor Grown Carbon). Fiber: VGCF) and various metal particles are exemplified. These conductive assistants can be added to the active material layer alone or in combination of two or more.

  The current collector refers to a chemically inert electronic high conductor that keeps a current flowing through an electrode during discharging or charging of a non-aqueous secondary battery. The current collector is not particularly limited as long as it is a metal that can withstand a voltage suitable for the active material to be used. For example, silver, copper, gold, aluminum, tungsten, cobalt, zinc, nickel, iron, platinum, tin, indium Examples thereof include at least one selected from titanium, ruthenium, tantalum, chromium and molybdenum, and metal materials such as stainless steel.

  The current collector can take the form of a foil, a sheet, a film, a linear shape, a rod shape, a mesh, or the like. Therefore, for example, a metal foil such as a copper foil, a nickel foil, an aluminum foil, and a stainless steel foil can be suitably used as the current collector.

(Secondary battery)
The secondary battery of this invention comprises said electrode for secondary batteries. The secondary battery of this invention comprises electrolyte solution other than said secondary battery electrode.

  In the secondary battery of the present invention, the electrolytic solution may be a nonaqueous electrolytic solution. The nonaqueous electrolytic solution has an electrolyte salt and a nonaqueous solvent. The electrolyte salt is a salt having a metal ion serving as a charge carrier.

  The salt having a metal ion serving as a charge carrier is preferably, for example, a lithium salt or a sodium salt. The electrolyte salt is preferably a fluoride salt, and more preferably an alkali metal fluoride salt.

Examples of the lithium salt include LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiCF ₃ SO ₃ , and lithium perchlorate. Examples of sodium salts include NaPF ₆ , NaBF ₄ , and NaAsF ₆ .

  The non-aqueous solvent may be an organic solvent. Examples of the organic solvent include cyclic carbonates such as ethylene carbonate and propylene carbonate; chain carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate; aliphatic carboxylic acid esters such as methyl formate, ethyl acetate, and methyl propionate; γ-lactones such as γ-butyrolactone; chain ethers such as 1,2-dimethoxyethane and 1,2-diethoxyethane; cyclic ethers such as tetrahydrofuran, dimethyl sulfoxide, dioxolanes, dimethylformamide, dimethylacetamide 1 type, or 2 or more types of various aprotic solvents, such as amides, such as sulfolanes, nitriles, such as acetonitrile, can be used.

  A separator is used for the secondary battery as necessary. As separators, natural resins such as polytetrafluoroethylene, polypropylene, polyethylene, polyimide, polyamide, polyaramid (Aromatic polymer), polyester, polyacrylonitrile, and other polysaccharides, cellulose, amylose and other polysaccharides, fibroin, keratin, lignin, suberin, etc. Examples thereof include porous bodies, nonwoven fabrics, and woven fabrics using one or more electrically insulating materials such as polymers and ceramics.

  A method for producing the secondary battery of the present invention will be described. If necessary, a separator is sandwiched between the positive electrode and the negative electrode to form an electrode body. The electrode body may be either a stacked type in which the positive electrode, the separator and the negative electrode are stacked, or a wound type in which the positive electrode, the separator and the negative electrode are sandwiched. After connecting between the positive electrode current collector and the negative electrode current collector to the positive electrode terminal and the negative electrode terminal connected to the outside using a current collecting lead or the like, an electrolyte is added to the electrode body to form a secondary battery. Good. Moreover, the secondary battery of this invention should just be charged / discharged in the voltage range suitable for the kind of active material contained in an electrode.

  The secondary battery of the present invention may be mounted on a vehicle. The vehicle may be a vehicle that uses electric energy from the secondary battery for all or part of its power source, and may be, for example, an electric vehicle, a hybrid vehicle, or the like. Examples of devices equipped with secondary batteries include various home appliances driven by batteries, office devices, industrial devices, and the like, such as personal computers and portable communication devices, in addition to vehicles. Further, the secondary battery according to the present invention includes wind power generation, solar power generation, hydroelectric power generation and other power system power storage devices and power smoothing devices, power of power sources for ships, etc. and / or power supply sources for auxiliary equipment, aircraft, spacecraft Power supply for auxiliary power and / or auxiliary equipment, auxiliary power source for vehicles that do not use electricity as a power source, power source for mobile home robots, power source for system backup, power source for uninterruptible power supply, electric vehicle You may use for the electrical storage apparatus which temporarily stores the electric power required for charge in the charging station for a vehicle.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment. The present invention can be implemented in various forms without departing from the gist of the present invention, with modifications and improvements that can be made by those skilled in the art.

(Comparative Example 1)
To 1 g of polyethyleneimine (PEI, manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 1800) was added tetrahydrofuran-2,3,4,5-tetracarboxylic acid aqueous solution (250 mg, manufactured by Tokyo Chemical Industry Co., Ltd./1 ml H ₂ O), and at room temperature. The mixture was stirred for 20 minutes to obtain a mixed solution. The molar ratio of tetrahydrofuran-2,3,4,5-tetracarboxylic acid (THT) to polyethyleneimine (PEI) in the mixed solution is 0.1. Water remaining in the mixed solution was distilled off under reduced pressure to obtain a mixture. The mixture contains tetrahydrofuran-2,3,4,5-tetracarboxylic acid and polyethyleneimine represented by the formula (7) before the reaction, and does not contain a reaction product.

Example 1
Tetrahydrofuran-2,3,4,5-tetracarboxylic acid aqueous solution (250 mg / 1 ml H ₂ O) was added to 1 g of polyethyleneimine and stirred at room temperature for 20 minutes to obtain a mixed solution. The mixing ratio of polyethyleneimine and tetrahydrofuran-2,3,4,5-tetracarboxylic acid in the mixed solution is 1: 0.1 in terms of molar ratio. The mixed solution was subjected to dehydration condensation at 130 ° C. for 3 hours using a Dean-Stark apparatus to obtain 1.10 g of a viscous liquid. The reaction product contained in the viscous liquid was a water-soluble amide-fused polyethylenimine derivative amide-bonded to the tetrahydrofuran skeleton, and was a saturated heterocycle-containing compound having a structure represented by the formula (8). Specific examples of the structure represented by Formula (8) include Formula (9) or Formula (10).

（式（８）、式（９）、及び（１０）中、ＰＥＩは、ポリエチレンイミン残基を示す。式（８）中、ｒ及びｓは、互いに独立して、０〜２の整数であり、ｒ+ｓ＝２の関係をもつ。）

(In Formula (8), Formula (9), and (10), PEI represents a polyethyleneimine residue. In Formula (8), r and s are each independently an integer of 0 to 2. , R + s = 2.)

<Analysis>
The IR (infrared spectroscopy) spectrum of the reaction product obtained in Example 1 was measured. The measurement results are shown in FIG. As shown in FIG. 1, a peak at 1653 cm ⁻¹ was observed in the IR spectrum of the reaction product. This peak is considered to be derived from stretching vibration corresponding to the amide bond obtained by dehydration condensation of NH bond of polyethyleneimine and COOH of carboxylic acid.

Further, the mixture of Comparative Example 1 and the reaction product of Example 1 were dissolved in heavy water (D ₂ O), and a ¹ H-NMR (nuclear magnetic resonance) spectrum in the heavy water was measured. The ¹ H-NMR spectrum of the mixture of Comparative Example 1 is shown in FIG. 2, and the ¹ H-NMR spectrum of the reaction product of Example 1 is shown in FIG.

When the ¹ H-NMR spectrum (FIG. 2) of the mixture of Comparative Example 1 and the ¹ H-NMR spectrum (FIG. 3) of the reaction product of Example 1 were compared, in Comparative Example 1, the α-position of the main skeleton of tetrahydrofuran was compared. peak due to protons ^{H a} was observed at about 4.42Ppm. In Example 1, a peak attributable to protons H ^a of α-position of the main skeleton of tetrahydrofuran was observed at about 3.29 ppm, it was shifted to the higher magnetic field side. This suggests the following. The α-position carbon of the heteroatom-containing cyclic structure is electron-rich, the antibonding orbital of the C—O σ bond is increased, and σ conjugation is likely to occur. Σ conjugation in which nitrogen electrons flow into the antibonding orbitals of the α-position carbon of the heteroatom-containing cyclic structure is expressed.

  It was observed from the NMR spectrum that all carboxylic acid groups bonded to the α-position of tetrahydrofuran-2,3,4,5-tetracarboxylic acid used in the reaction were terminated with amide.

  From the above results, it is considered that the PEI residue was successfully bonded to the α-position carbon of the heteroatom-containing cyclic structure via an amide bond.

Further, ¹³ C-NMR (nuclear magnetic resonance) spectra of the mixture of Comparative Example 1 and the reaction product of Example 1 were measured. The ¹³ C-NMR spectrum of the mixture of Comparative Example 1 is shown in FIG. 4, and the ¹³ C-NMR spectrum of the reaction product of Example 1 is shown in FIG.

Comparing the ¹³ C-NMR spectrum of ¹³ C-NMR spectrum of a mixture of unreacted (Figure 4) and a viscous liquid (reaction product) after the reaction (FIG. 5), alpha-position of the main skeleton of tetrahydrofuran carbon C ^a For the peak due to, no large magnetic field shift due to the change in chemical structure was observed before and after the reaction. Further, in FIG. 5, since no peak is observed at 100 to 160 ppm, which is characteristic of C═C bond, all the C—C bonds of the saturated heterocyclic ring-containing compound of Example 1 have single bond properties. It was shown that

<Fluorescence observation>
The reaction product of Example 1 and the mixture of Comparative Example 1 were irradiated with excitation light having a wavelength of 365 nm. The reaction product of Example 1 emitted fluorescence. On the other hand, the mixture of Comparative Example 1 did not emit fluorescence.

  Next, when the reaction product of Example 1 was irradiated with two types of excitation light having a wavelength of 320 nm and a wavelength of 365 nm, fluorescence spectra emitted from the reaction product were measured. The results are shown in FIG. The fluorescence spectrum was changed by the excitation wavelengths of 320 nm and 365 nm. When irradiated with an excitation wavelength of 320 nm, two main peaks were observed in the fluorescence spectrum, as indicated by ↓ in FIG.

(Reference Example 1)
By adding dropwise to 5 ml of 44 mg of copper acetate monohydrate in a 10 ml aqueous solution of 100 mg of the reaction product of Example 1, copper ions are coordinated with the saturated heterocyclic ring-containing compound of Example 1 to form Formula (11). The chelate compounds shown were prepared.

（式（１１）中、Ｇはフラン環部分を示す。ＰＥＩは、ポリエチレンイミン残基を示す。）

(In formula (11), G represents a furan ring moiety. PEI represents a polyethyleneimine residue.)

The fluorescence spectrum was measured when the reaction product of Example 1 and the chelate compound of Reference Example 1 were irradiated with excitation light. The measurement results are shown in FIG. As indicated by ↓ in FIG. 7, the fluorescence intensity when the excitation light with a wavelength of 320 nm was irradiated significantly decreased due to the coordination of copper ions to the reaction product of Example 1. From this, it was found that the excitation at 320 nm is the main of σ conjugate. This is because, as shown in the formula (12), the copper ion is coordinated to the saturated heterocyclic ring-containing compound that is the reaction product of Example 1, so that the N ion of the amide bond is coordinated to the copper ion. It is considered that the fluorescence waveform changed due to the collapse of the superconjugation with the α-position carbon. In the heteroatom-containing cyclic structure represented by the formula (12), a hydrocarbon group is bonded to each of the two α-position carbons via an amide bond, but an amide having one hydrocarbon group R ⁵ bonded thereto. Bonding was omitted.

（式（１２）中、ＰＥＩは、ポリエチレンイミン残基を示す。）

(In formula (12), PEI represents a polyethyleneimine residue.)

  The reaction product of Example 1 has a heteroatom-containing cyclic structure (heterocycle). In order to confirm that the heteroatom-containing cyclic structure contributes to fluorescence, a cyclopentane ring compound in which oxygen in the tetrahydrofuran of the heteroatom-containing cyclic structure is replaced with carbon, and diglycolic acid that is a ring-opened structure Each was reacted with polyethyleneimine.

(Comparative Example 2)
A cyclopentane-1,2,3,4-tetracarboxylic acid aqueous solution (250 mg / 1 ml H ₂ O) was added to 1 g of polyethyleneimine, and the mixture was stirred at room temperature for 20 minutes to obtain a mixed solution. The mixed solution was subjected to dehydration condensation at 130 ° C. for 3 hours using a Dean-Stark apparatus to obtain 1.07 g of a viscous liquid having a reaction product. The reaction product contained in the viscous liquid is a product in which a water-soluble polyethyleneimine residue is bonded to a cyclopentane skeleton via an amide bond as represented by the formula (13).

（式（１３）中、ＰＥＩは、ポリエチレンイミン残基を示す。）

(In formula (13), PEI represents a polyethyleneimine residue.)

(Comparative Example 3)
A diglycolic acid aqueous solution (260 mg / 1 ml H ₂ O) was added to 1 g of polyethyleneimine, and the mixture was stirred at room temperature for 20 minutes to obtain a mixed solution. The mixed solution was subjected to dehydration condensation at 130 ° C. for 3 hours using a Dean-Stark apparatus to obtain 1.07 g of a viscous liquid having a reaction product. The reaction product contained in the viscous liquid is a product in which a water-soluble polyethyleneimine residue is bonded to diglycolic acid via an amide bond, as shown in Formula (14).

（式（１４）中、ＰＥＩは、ポリエチレンイミン残基を示す。）

(In formula (14), PEI represents a polyethyleneimine residue.)

<Fluorescence observation>
When the reaction products of Comparative Examples 2 and 3 were irradiated with excitation light having a wavelength of 365 nm, none of them emitted fluorescence.

From this, it was found that it is necessary to have the following structure in order to emit fluorescence.
In order to interact with the N rom pair of the amide bond, a hetero atom E is bonded to the α-position carbon in the cyclic structure bonded to the carbonyl group of the amide bond.
In order to efficiently cause σ conjugation, the α-position carbon and the heteroatom E form part of a cyclic structure.

(Battery 1)
Using the reaction product of Example 1, a lithium ion secondary battery was produced by the following method.

  45 parts by mass of SiO (manufactured by Aldrich), 40 parts by mass of natural graphite, 5 parts by mass of acetylene black, and 10 parts by mass of the reaction product (saturated heterocycle-containing compound) of Example 1 were mixed with N-methyl-2-pyrrolidone (NMP). ) To prepare a slurry for forming a negative electrode active material layer. This slurry was applied to the surface of a 30 μm thick copper foil (current collector) using a doctor blade and dried to form a negative electrode active material layer on the copper foil. Thereafter, the current collector and the negative electrode active material layer were firmly adhered and fixed by a roll press so that the thickness of the negative electrode active material layer was 20 μm. This was vacuum-dried at 120 ° C. for 6 hours to obtain a negative electrode.

  Using the obtained negative electrode as an evaluation electrode, a lithium ion secondary battery (half cell) was produced. The counter electrode was a metal lithium foil having a thickness of 500 μm.

The counter electrode was cut to a diameter of 13 mm and the evaluation electrode was cut to a diameter of 11 mm, and a separator (Hoechst Celanese glass filter and celgard 2400) was sandwiched between them to produce an electrode body. The electrode body was accommodated in a battery case (CR2032 coin cell manufactured by Hosen Co., Ltd.). In addition, a non-aqueous electrolyte solution in which the electrolyte salt LiPF ₆ was dissolved at a concentration of 1 mol / L was injected into the battery case in a mixed solution in which ethylene carbonate and diethyl carbonate were mixed at a ratio of 1: 1 (volume ratio). The battery case was sealed to obtain a lithium ion secondary battery of battery 1.

(Battery C1)
The lithium ion secondary battery of the battery C1 is the same as the battery 1 except that PEI is mixed with the slurry for forming the negative electrode active material layer instead of the reaction product (saturated heterocycle-containing compound) of Example 1. is there.

<Battery characteristics measurement>
Battery 1 and battery C1 were discharged and charged. The test conditions were a constant current discharge at 0.5 mA to a final voltage of 0.01 V, and after 10 minutes after reaching the final voltage, a constant current charge was performed to 0.5 mA to a final voltage of 1 V. The initial efficiency was calculated by 100 × initial charge capacity / initial discharge capacity. In this measurement, discharging refers to the case where electrons are occluded in the evaluation electrode, and charging refers to the case where electrons are emitted from the evaluation electrode. The measurement results are shown in Table 1.

  Battery 1 using the reaction product of Example 1 (saturated heterocycle-containing compound) had higher initial charge capacity and higher initial efficiency than battery C1 using PEI.

(Example 2)
The saturated heterocycle-containing compound of Example 2 was produced in the same manner as the saturated heterocycle-containing compound of Example 1 except that the dehydration condensation was performed at 160 ° C. for 30 minutes. The saturated heterocyclic ring-containing compound of Example 2 was rubbery.

  When the saturated heterocyclic ring-containing compound of Example 2 was irradiated with excitation light having a wavelength of 365 nm, fluorescence was generated.

(Battery 2)
The lithium ion secondary battery of Battery 2 is Battery 1 except that the saturated heterocyclic ring-containing compound of Example 2 was mixed with the slurry for forming the negative electrode active material layer instead of the saturated heterocyclic ring-containing compound of Example 1. It is the same. Even when NMP was added to the saturated heterocyclic ring-containing compound of Example 2 when forming the negative electrode active material layer, it was difficult to produce a slurry.

  About the lithium ion secondary battery of the battery 2, discharge and charge were performed similarly to said <battery characteristic measurement>. The results are shown in Table 1. Battery 2 using the saturated heterocyclic ring-containing compound of Example 2 had a higher initial charge capacity and higher initial efficiency than battery C1 using PEI of Comparative Example 1.

(Example 3)
The saturated heterocycle-containing compound of Example 3 was produced in the same manner as the saturated heterocycle-containing compound of Example 2, except that the molar ratio of THT to PEI in the reaction solution was 0.05.

Example 4
The saturated heterocycle-containing compound of Example 4 was produced in the same manner as the saturated heterocycle-containing compound of Example 2, except that the molar ratio of THT to PEI in the reaction solution was 0.033.

(Example 5)
The saturated heterocycle-containing compound of Example 5 was produced in the same manner as the saturated heterocycle-containing compound of Example 2, except that the molar ratio of THT to PEI in the reaction solution was 0.015.

  The saturated heterocyclic ring-containing compounds of Examples 2 to 5 emitted fluorescence when irradiated with excitation light having wavelengths of 320 nm and 365 nm. The colors and properties of the saturated heterocyclic ring-containing compounds of Examples 2 to 5 are shown in Table 2.

<Concentration study>
The color of the reaction product was yellow when the molar ratio of THT to PEI was 0.05 or more. When the molar ratio of THT to PEI was 0.033, it became slightly yellow and became sticky. When the molar ratio of THT to PEI was 0.015, the reaction product was not rubberized and became a viscous liquid. From this, it was found that the reaction product became harder as the molar ratio of THT to PEI in the reaction solution increased.

  Further, comparing Examples 1 and 2, in Example 1, the condensation reaction temperature was 130 ° C., and the reaction product became a viscous liquid. In Example 2, the condensation reaction temperature was set to 160 ° C. in the reaction solution having the same composition as in Example 1. In this case, the reaction product became a rubbery solid. From this, it was found that the reaction product became harder as the reaction temperature increased, depending on the molar ratio of THT to PEI in the reaction solution.

  Moreover, in any case of THT / PEI, the maximum value of the fluorescence intensity was shown in the same fluorescence wavelength region. This suggests that the fluorescence is derived from [—NH—CO—CH—O—CH—CO—NH—], which is a partial structure of the saturated heterocyclic compound represented by the formulas (8) and (9). doing. If the conjugation mechanism is different from this partial structure, conjugation further spreads according to THT / PEI, and the wavelength region showing the maximum value of fluorescence intensity is considered to change.

Claims (12)

A saturated heterocyclic ring-containing compound having a chemical structure represented by the following formula (1).

(In Formula (1), n is an integer of 0 or more and 5 or less, and m is an integer of 0 or more and 2 or less.
E consists of B, N, O, Al, Si, P, S, Ga, Ge, As, or Se.
R ¹ is independently of each other a hydrocarbon group, heterocyclic group, hydroxyl group, alkoxy group, aldehyde group, carbonyl group, carboxyl group, ester group, amino group, amide group, imide group, isocyanate group, nitro group, It consists of a substituent having a structure having at least one selected from the group consisting of a nitroso group, an isonitrile group, a halogen group, a phosphino group, a phosphazene group, a thio group, a thioxy group and a silyl group, a hydrogen group, or an unpaired electron.
R ² is independently of each other a hydrocarbon group, heterocyclic group, hydroxyl group, alkoxy group, aldehyde group, carbonyl group, carboxyl group, ester group, amino group, amide group, imide group, isocyanate group, nitro group, It consists of a substituent having a structure having at least one selected from the group consisting of a nitroso group, an isonitrile group, a halogen group, a phosphino group, a phosphazene group, a thio group, a thioxy group and a silyl group, or a hydrogen group.
R ³ is independently of each other a hydrocarbon group, heterocyclic group, hydroxyl group, alkoxy group, aldehyde group, carbonyl group, carboxyl group, ester group, amino group, amide group, imide group, isocyanate group, nitro group, It consists of a substituent having a structure having at least one selected from the group consisting of a nitroso group, an isonitrile group, a halogen group, a phosphino group, a phosphazene group, a thio group, a thioxy group and a silyl group, or a hydrogen group.
R ⁴ is independently of each other a hydrocarbon group which may be substituted with a substituent, or a hydrogen group.
R ⁵ is independently of each other a hydrocarbon group which may be substituted with a substituent, or a hydrogen group.
A part of carbon of the hydrocarbon group may be substituted with O, N, or S.
^Two selected from R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be bonded to each other to form a ring. )   The saturated heterocycle-containing compound according to claim 1, wherein E consists of O, S, or N. The saturated heterocycle-containing compound according to claim 1 or 2, wherein R ² and / or R ³ is an amide group to which the hydrocarbon group is bonded.   The saturated heterocyclic ring-containing compound according to claim 1, wherein the hydrocarbon group is a water-soluble polymer residue. The saturated telocycle-containing compound according to claim 4, wherein the water-soluble polymer residue is a polyethyleneimine residue.   N in said Formula (1) is 1 or 2, The saturated heterocyclic containing compound of any one of Claims 1-5. It is a chemical structure shown in following formula (2) or formula (3), The saturated heterocyclic containing compound of any one of Claims 1-6.

(R ⁴ and R ⁵ in Formula (2) and Formula (3), and R ⁶ and R ^{7 in} Formula (2) are each a hydrocarbon group that may be substituted with a substituent, or a hydrogen group. .)   A binder having the saturated heterocyclic ring-containing compound according to any one of claims 1 to 7. A current collector, and an active material layer covering a surface of the current collector,
The said active material layer contains the saturated heterocyclic ring-containing compound and active material of any one of Claims 1-7, The electrode for secondary batteries characterized by the above-mentioned.   A secondary battery comprising the saturated heterocyclic ring-containing compound according to claim 1.   The fluorescent substance which consists of a saturated heterocycle containing compound of any one of Claims 1-7.   The fluorescent substance which consists of a saturated heterocycle containing compound of any one of Claims 1-7 in which the maximum value of a fluorescence wavelength shows 400-600 nm in excitation wavelength 300-400 nm.

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