JPWO2015163287A1 - Bisphenol resin, electrode and lead acid battery - Google Patents

Abstract

(A) a bisphenol compound, (b1) at least one selected from the group consisting of aminoalkylsulfonic acid, aminoalkylsulfonic acid derivatives, aminonaphthalenesulfonic acid and aminonaphthalenesulfonic acid derivatives, and (c) formaldehyde and formaldehyde derivatives A bisphenol-based resin obtained by reacting at least one selected from the group consisting of:

Description

  The present invention relates to a bisphenol-based resin, an electrode, and a lead storage battery.

  In recent years, various measures for improving fuel efficiency have been studied for automobiles in order to prevent air pollution or global warming. Automobiles that have taken measures to improve fuel efficiency include, for example, idling stop vehicles (hereinafter referred to as “ISS vehicles”) that reduce engine operation time, and micro hybrid vehicles (power generation control) that use engine rotation without waste. Car etc.) is under consideration.

  In an ISS vehicle, the number of engine starts increases, so that a large current discharge of the lead storage battery is repeated. Further, in an ISS vehicle and a micro hybrid vehicle (such as a power generation control vehicle), the amount of power generated by the alternator is reduced, and charging of the lead storage battery is performed intermittently, resulting in insufficient charging.

  The lead storage battery which is used as described above is used in a partially charged state called PSOC (Partial State Of Charge). Lead acid batteries have a shorter life when used under PSOC than when used in a fully charged state.

  In recent years, in Europe, the chargeability of lead-acid batteries during charge / discharge cycles in accordance with the control of micro hybrid vehicles has been regarded as important, and DCA (Dynamic Charge Acceptance) evaluation in this form is being standardized. is there. In other words, the use of the lead storage battery as described above has been regarded as important.

  On the other hand, Patent Document 1 below discloses a technique using an electrolytic solution containing a specific concentration of aluminum ions or the like in order to improve the charging efficiency and life characteristics of a battery when used under PSOC. Yes.

  Patent Document 2 below discloses a technique that uses a negative electrode including a specific negative electrode additive in order to improve charging performance and life characteristics.

International Publication No. 2007/036979 International Publication No. 1997/37393

  By the way, when a lead storage battery is used in a state where charging is not complete and charging is insufficient, the difference in concentration of dilute sulfuric acid, which is an electrolyte, between the upper part and the lower part of the electrode (electrode plate, etc.) in the battery A stratification phenomenon occurs. In this case, the concentration of dilute sulfuric acid in the lower part of the electrode becomes high and sulfation occurs. Therefore, the reactivity of the lower part of the electrode is lowered, and only the upper part of the electrode reacts intensively. As a result, the deterioration such as weakening of the connection between the active materials proceeds, and the active material is peeled from the lattice at the upper part of the electrode, leading to a decrease in battery performance and an early life.

  Therefore, in recent lead acid batteries for automobiles, it is an extremely important issue to improve the charge acceptability and cycle characteristics (life characteristics) of the batteries when used under PSOC. However, with the technologies described in Patent Document 1 and Patent Document 2, it has been difficult to obtain sufficient charge acceptance and cycle characteristics.

  This invention is made | formed in view of the said situation, and it aims at providing the bisphenol-type resin, electrode, and lead acid battery which can acquire the outstanding charge acceptance property and cycling characteristics.

  As a result of intensive studies by the present inventors, it has been clarified that the techniques of Patent Document 1 and Patent Document 2 are not sufficient in charge acceptance and cycle characteristics. On the other hand, the present inventors use the bisphenol-based resin obtained by reacting a bisphenol-based compound, a specific sulfonic acid compound, and at least one selected from the group consisting of formaldehyde and a formaldehyde derivative. I found out that it could be solved.

  That is, the bisphenol-based resin according to the first embodiment of the present invention comprises (a) a bisphenol-based compound and (b1) an aminoalkylsulfonic acid, an aminoalkylsulfonic acid derivative, an aminonaphthalenesulfonic acid, and an aminonaphthalenesulfonic acid derivative. It is obtained by reacting at least one selected from the group with at least one selected from the group consisting of (c) formaldehyde and formaldehyde derivatives.

  According to the bisphenol-based resin according to the first embodiment of the present invention, excellent charge acceptance and cycle characteristics can be obtained in a lead-acid battery. In addition, according to the bisphenol-based resin according to the first embodiment of the present invention, it is possible to achieve both battery performance such as excellent charge acceptance, discharge characteristics, and cycle characteristics.

  As described above, in the lead storage battery obtained by using the bisphenol-based resin according to the first embodiment of the present invention, the reaction product generated in the electrode reaction of the lead storage battery is coarsened with respect to the factor that provides excellent cycle characteristics as described above. It is presumed that this is because the specific surface area of the electrode is kept high by suppressing the above. However, the factor is not limited to this.

The component (b1) preferably contains a compound represented by the following general formula (I). In this case, charge acceptability, discharge characteristics, and cycle characteristics can be improved in a balanced manner.
[In Formula (I), R ¹ represents a hydrogen atom or a hydrocarbon group, X ¹ represents an alkali metal or a hydrogen atom, and n 1 represents an integer of 0 to 3. ]

The component (b1) preferably contains a compound represented by the following general formula (II). In this case, charge acceptability, discharge characteristics, and cycle characteristics can be improved in a balanced manner.
[In Formula (II), R ² represents an alkali metal or a hydrogen atom, and n ² represents an integer of 1 to 3. ]

  The electrode according to the first embodiment of the present invention is manufactured using an electrode active material and the bisphenol-based resin. Moreover, the lead acid battery which concerns on 1st Embodiment of this invention is equipped with the said electrode. Even in these, excellent charge acceptance and cycle characteristics can be obtained.

  In addition, the present inventors, in a lead storage battery including a positive electrode, a negative electrode, and an electrolytic solution, the negative electrode includes a specific bisphenol-based resin and a negative electrode active material, and the electrolytic solution includes aluminum ions, thereby causing the above problem. I found that it could be solved.

  That is, the lead storage battery according to the second embodiment of the present invention is a lead storage battery including a positive electrode, a negative electrode, and an electrolytic solution, and the negative electrode includes a bisphenol-based resin and a negative electrode active material, and the bisphenol-based resin. (A) a bisphenol compound and (b2) at least one selected from the group consisting of amino acids, amino acid derivatives, aminoalkyl sulfonic acids, aminoalkyl sulfonic acid derivatives, aminoaryl sulfonic acids and aminoaryl sulfonic acid derivatives; c) A resin obtained by reacting at least one selected from the group consisting of formaldehyde and a formaldehyde derivative, and the electrolytic solution contains aluminum ions.

  According to the lead storage battery according to the second embodiment, it is possible to obtain excellent charge acceptability. Therefore, in particular, after the charge and discharge are repeated to some extent from the initial state and the active material is sufficiently activated, the SOC that tends to be low in the ISS vehicle and the micro hybrid vehicle can be maintained at an appropriate level.

  Moreover, according to the lead acid battery which concerns on 2nd Embodiment, it is possible to suppress that the lifetime of the lead acid battery used under PSOC becomes short, and the outstanding cycling characteristics can be acquired. Moreover, according to the lead storage battery which concerns on 2nd Embodiment, the outstanding charge acceptance property and cycling characteristics, and other outstanding battery performance (discharge characteristics etc.) can be made compatible. Regarding the reason why the life of lead-acid batteries used under PSOC is shortened, if charging and discharging are repeated in a state where charging is insufficient, lead sulfate produced on the negative electrode (negative electrode plate, etc.) becomes coarse during discharge. This is thought to be because lead sulfate is difficult to return to lead metal as a charge product.

  In the lead acid battery according to the second embodiment, the specific gravity of the electrolytic solution is preferably 1.25 to 1.35. In this case, charge acceptability, discharge characteristics, and cycle characteristics can be improved in a balanced manner. In addition, since specific gravity changes with temperature, in this specification, it defines as specific gravity converted at 20 degreeC. The same applies hereinafter.

  According to the present invention, it is possible to obtain excellent charge acceptance and cycle characteristics. In addition, according to the present invention, both excellent charge acceptance and cycle characteristics and other excellent battery performance (discharge characteristics and the like) can be achieved. The lead storage battery according to the present invention can be suitably used in an ISS vehicle, a micro hybrid vehicle, or the like as a liquid lead storage battery in which charging is performed intermittently and high-rate discharge to a load is performed under PSOC.

  ADVANTAGE OF THE INVENTION According to this invention, the application to the lead acid battery of bisphenol-type resin can be provided. ADVANTAGE OF THE INVENTION According to this invention, the application to the negative electrode of the lead storage battery of a bisphenol-type resin can be provided. ADVANTAGE OF THE INVENTION According to this invention, the application to the lead storage battery in the motor vehicle of a bisphenol-type resin can be provided. ADVANTAGE OF THE INVENTION According to this invention, the application to the lead storage battery in the ISS vehicle of a bisphenol-type resin can be provided. ADVANTAGE OF THE INVENTION According to this invention, the application to the ISS vehicle of a lead storage battery can be provided. ADVANTAGE OF THE INVENTION According to this invention, the application to the micro hybrid vehicle of a lead storage battery can be provided.

FIG. 1 is a drawing showing measurement results of ¹ H-NMR spectrum. FIG. 2 is a drawing showing measurement results of ¹ H-NMR spectrum. FIG. 3 is a drawing for explaining a method for evaluating charge acceptance in the embodiment. FIG. 4 is a drawing showing evaluation results of charge acceptability in Examples.

  Hereinafter, embodiments of the present invention will be described in detail.

  A lead storage battery according to this embodiment (including the first embodiment and the second embodiment; the same applies hereinafter) includes a battery case, an electrode plate group having a positive electrode and a negative electrode, and an electrolytic solution. The plate group and the electrolytic solution are accommodated in the battery case. The electrode plate group is configured by laminating a positive electrode and a negative electrode via a separator. The negative electrode is, for example, a negative electrode plate having a negative electrode current collector and a negative electrode active material filled in the negative electrode current collector. The positive electrode is, for example, a positive electrode plate having a positive electrode current collector and a positive electrode active material filled in the positive electrode current collector. The electrolytic solution can include sulfuric acid. In the first embodiment, the electrolytic solution may contain aluminum ions. In the second embodiment, the electrolytic solution contains aluminum ions. As a basic configuration of the lead storage battery, the same configuration as that of a conventional lead storage battery can be used.

  In the lead storage battery according to the present embodiment, the negative electrode can include (A) a bisphenol-based resin and (B) a negative electrode active material. In the first embodiment, the (A) bisphenol-based resin comprises (a) a bisphenol-based compound (hereinafter referred to as “component (a)” in some cases), (b1) an aminoalkylsulfonic acid, an aminoalkylsulfonic acid derivative, amino At least one selected from the group consisting of naphthalenesulfonic acid and aminonaphthalenesulfonic acid derivatives (hereinafter sometimes referred to as “component (b1)”), and (c) at least one selected from the group consisting of formaldehyde and formaldehyde derivatives (hereinafter, In some cases, the resin is obtained by reacting “component (c)”. In the second embodiment, (A) bisphenol-based resin includes (a) bisphenol-based compound, (b2) amino acid, amino acid derivative, aminoalkyl sulfonic acid, aminoalkyl sulfonic acid derivative, aminoaryl sulfonic acid, and aminoaryl sulfonic acid. A resin obtained by reacting at least one selected from the group consisting of derivatives (hereinafter sometimes referred to as “component (b2)”) and at least one selected from the group consisting of (c) formaldehyde and formaldehyde derivatives. . Hereinafter, the component (b1) and the component (b2) are collectively referred to as “component (b)”.

<(A) Bisphenol resin>
((A) component: bisphenol compound)
A bisphenol-based compound is a compound having two hydroxyphenyl groups. Examples of bisphenol compounds include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as “bisphenol A”), bis (4-hydroxyphenyl) methane, and 1,1-bis (4-hydroxyphenyl). Ethane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) butane, bis (4 -Hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, and bis (4-hydroxyphenyl) sulfone (Hereinafter referred to as “bisphenol S”).

  A bisphenol-type compound can be used individually by 1 type or in combination of 2 or more types. As the bisphenol compound, bisphenol A is preferable from the viewpoint of further excellent charge acceptance, and bisphenol S is preferable from the viewpoint of further excellent discharge characteristics.

  As the bisphenol-based compound, it is preferable to use bisphenol A and bisphenol S in combination from the viewpoint of improving charge acceptability, discharge characteristics, and cycle characteristics in a well-balanced manner. In this case, the blending amount of bisphenol A for obtaining (A) bisphenol-based resin is 70 mol on the basis of the total amount of bisphenol A and bisphenol S, from the viewpoint of improving charge acceptance, discharging characteristics and cycle characteristics in a balanced manner. % Or more is preferable, 75 mol% or more is more preferable, and 80 mol% or more is still more preferable. The blending amount of bisphenol A is preferably 99 mol% or less, more preferably 98 mol% or less, more preferably 97 mol%, based on the total amount of bisphenol A and bisphenol S, from the viewpoint of improving charge acceptance, discharge characteristics and cycle characteristics in a balanced manner. % Or less is more preferable.

((B) component)
[Aminoalkylsulfonic acid and aminoalkylsulfonic acid derivatives]
Examples of the aminoalkylsulfonic acid and aminoalkylsulfonic acid derivatives include compounds represented by the following general formula (I). The aminoalkyl sulphonic acids, for example, compound X ¹ is a hydrogen atom in the following general formula (I). Examples of the aminoalkylsulfonic acid derivative include alkali metal salts in which X ¹ is an alkali metal in the following general formula (I).
[In Formula (I), R ¹ represents a hydrogen atom or a hydrocarbon group, X ¹ represents an alkali metal or a hydrogen atom, and n 1 represents an integer of 0 to 3. ]

Examples of the hydrocarbon group for R ¹ in formula (I) include linear, branched, or cyclic hydrocarbon groups. Examples of the linear or branched hydrocarbon group include a linear or branched alkyl group. Examples of the cyclic hydrocarbon group include an alicyclic hydrocarbon group. The number of carbon atoms of the hydrocarbon group is preferably 1 or more from the viewpoint of improving charge acceptability, discharge characteristics, and cycle characteristics in a well-balanced manner. The number of carbon atoms of the hydrocarbon group is preferably 6 or less, more preferably 5 or less, and even more preferably 3 or less, from the viewpoint of improving charge acceptability, discharge characteristics, and cycle characteristics in a balanced manner.

Examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, n-pentyl, and isopentyl. Group, t-pentyl group, n-hexyl group, isohexyl group, s-hexyl group and t-hexyl group. Examples of the alicyclic hydrocarbon group include alicyclic alkyl groups, and specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. R ¹ is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms from the viewpoint of improving charge acceptance, discharge characteristics, and cycle characteristics in a well-balanced manner, and a hydrogen atom and a methyl group Is more preferable.

Examples of the alkali metal of X ¹ in the formula (I) include sodium and potassium. X ¹ is preferably sodium from the viewpoint of improving charge acceptance, discharge characteristics, and cycle characteristics in a well-balanced manner. In the first embodiment, n1 is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1 from the viewpoint of improving charge acceptance, discharge characteristics, and cycle characteristics in a well-balanced manner. In the second embodiment, n1 is preferably 0 to 2 and more preferably 0 or 1 from the viewpoint of improving charge acceptance, discharge characteristics, and cycle characteristics in a well-balanced manner.

Examples of the compound represented by the formula (I) include compounds represented by the following general formulas (Ia) to (Ih). However, the compound represented by Formula (I) is not limited to these. In addition, each X < ¹ > of Formula (Ia)-(Ih) is the same as that of X < ¹ > of Formula (I), and shows an alkali metal or a hydrogen atom. The compound represented by the formula (I) is represented by the compound represented by the formula (Ia) and the formula (Id) from the viewpoint of improving the charge acceptability, the discharge characteristics, and the cycle characteristics in a balanced manner. And a compound represented by formula (Ia) (X ¹ : hydrogen atom) and a compound represented by formula (Id) (X ¹ : hydrogen atom) are more preferred.

  Examples of the aminoalkylsulfonic acid include aminomethanesulfonic acid, 2-aminoethanesulfonic acid, 3-aminopropanesulfonic acid, and 2-methylaminoethanesulfonic acid, and 2-aminoethanesulfonic acid is preferable.

[Aminoarylsulfonic acid and aminoarylsulfonic acid derivative]
Examples of aminoarylsulfonic acid include aminobenzenesulfonic acid and aminonaphthalenesulfonic acid. Examples of aminoarylsulfonic acid derivatives include aminobenzenesulfonic acid derivatives and aminonaphthalenesulfonic acid derivatives.

  Examples of aminobenzene sulfonic acid include 2-aminobenzene sulfonic acid (also known as alternilic acid), 3-aminobenzene sulfonic acid (also known as metanylic acid), and 4-aminobenzene sulfonic acid (also known as sulfanilic acid).

Examples of the aminobenzene sulfonic acid derivative include a compound in which a part of hydrogen atoms of aminobenzene sulfonic acid is substituted with an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms), and the sulfo group of aminobenzene sulfonic acid. Examples include alkali metal salts in which a hydrogen atom of (—SO ₃ H) is substituted with an alkali metal (for example, sodium or potassium). Examples of the compound in which some hydrogen atoms of aminobenzenesulfonic acid are substituted with an alkyl group include 4- (methylamino) benzenesulfonic acid, 3-methyl-4-aminobenzenesulfonic acid, 3-amino-4- Examples include methylbenzenesulfonic acid, 4- (ethylamino) benzenesulfonic acid, and 3- (ethylamino) -4-methylbenzenesulfonic acid. Examples of the alkali metal salt in which the hydrogen atom of the sulfo group of aminobenzenesulfonic acid is substituted with an alkali metal include sodium 2-aminobenzenesulfonate, sodium 3-aminobenzenesulfonate, sodium 4-aminobenzenesulfonate, 2 -Potassium aminobenzenesulfonate, potassium 3-aminobenzenesulfonate, and potassium 4-aminobenzenesulfonate.

  Examples of aminonaphthalenesulfonic acid include 4-amino-1-naphthalenesulfonic acid (p-form), 5-amino-1-naphthalenesulfonic acid (ana-form), 1-amino-6-naphthalenesulfonic acid (ε -Form, 5-amino-2-naphthalenesulfonic acid), 6-amino-1-naphthalenesulfonic acid (ε-form), 6-amino-2-naphthalenesulfonic acid (amphi-form), 7-amino-2- Aminonaphthalene monosulfonic acid such as naphthalenesulfonic acid, 8-amino-1-naphthalenesulfonic acid (peri-form), 1-amino-7-naphthalenesulfonic acid (kata-form, 8-amino-2-naphthalenesulfonic acid) 1-amino-3,8-naphthalenedisulfonic acid, 3-amino-2,7-naphthalenedisulfonic acid, 7-amino-1,5-naphthalene Aminosulfonic acid, 6-amino-1,3-naphthalene disulfonic acid, amino naphthalene disulfonic acid such as 7-amino-1,3-naphthalene disulfonic acid; 7-amino-1,3,6-naphthalene trisulfonic acid, 8- Examples include aminonaphthalene trisulfonic acid such as amino-1,3,6-naphthalene trisulfonic acid.

Examples of the aminonaphthalene sulfonic acid derivative include compounds in which a part of hydrogen atoms of aminonaphthalene sulfonic acid is substituted with an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms), and the sulfo group of aminonaphthalene sulfonic acid. An alkali metal salt in which a hydrogen atom of (—SO ₃ H) is substituted with an alkali metal can be mentioned. Examples of the alkali metal salt include a monoalkali metal salt and a dialkali metal salt. As the alkali metal salt, a sodium salt and a potassium salt are preferable, and a sodium salt is more preferable from the viewpoint of improving charge acceptability, discharge characteristics, and cycle characteristics in a well-balanced manner.

As the aminonaphthalenesulfonic acid and the aminonaphthalenesulfonic acid derivative, a compound represented by the following general formula (II) is preferable from the viewpoint of improving charge acceptance, discharge characteristics, and cycle characteristics in a well-balanced manner. Examples of the alkali metal for R ² include sodium and potassium. n2 is preferably 1 or 2, and more preferably 1, from the viewpoint of improving the charge acceptance, discharge characteristics, and cycle characteristics in a well-balanced manner. When n2 is 2 or 3, R ² may be the same as or different from each other.
[In Formula (II), R ² represents an alkali metal or a hydrogen atom, and n ² represents an integer of 1 to 3. ]

  As aminonaphthalenesulfonic acid and aminonaphthalenesulfonic acid derivative, from the viewpoint of improving the balance between charge acceptance, discharge characteristics and cycle characteristics, 5-amino-1-naphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 7-amino-2-naphthalenesulfonic acid, 7-amino-1,5-naphthalenedisulfonic acid, 7-amino-1,3-naphthalenedisulfonic acid and derivatives thereof are more preferred, and 5-amino-1-naphthalenesulfonic acid 7-amino-2-naphthalenesulfonic acid is more preferable, and 5-amino-1-naphthalenesulfonic acid is particularly preferable.

[Amino acids and amino acid derivatives]
Examples of amino acids include glycine, alanine, phenylalanine, aspartic acid and glutamic acid. Examples of amino acid derivatives include alkali metal salts in which the hydrogen atom of the carboxyl group of the amino acid is substituted with an alkali metal. Of the amino acids and amino acid derivatives, glutamic acid and alkali metal salts thereof are particularly preferable. Examples of the alkali metal salt include sodium salt and potassium salt.

  (B) A component can be used individually by 1 type or in combination of 2 or more types. As the component (b), aminoalkylsulfonic acid, aminoalkylsulfonic acid derivative, aminoarylsulfonic acid and aminoarylsulfonic acid derivative are preferable from the viewpoint of further improving charge acceptability and cycle characteristics, and 2-aminoethanesulfonic acid. 4-aminobenzenesulfonic acid and sodium 7-amino-2-naphthalenesulfonate are more preferable.

  In 1st Embodiment, the compounding quantity of (b1) component for obtaining (A) bisphenol-type resin is 0.2 mol or more with respect to 1 mol of (a) component from a viewpoint which discharge characteristics further improve, 0.3 mol or more is more preferable, 0.4 mol or more is further preferable, 0.5 mol or more is particularly preferable, 0.6 mol or more is very preferable, and 0.8 mol or more is very preferable. The amount of the component (b1) is preferably 2.5 mol or less, more preferably 2.2 mol or less, still more preferably 2 mol or less, with respect to 1 mol of the component (a) from the viewpoint that the cycle characteristics are further improved. 1.3 mol or less is particularly preferable, 1.2 mol or less is extremely preferable, and 1.1 mol or less is very preferable.

  When the component (b1) contains the compound represented by the formula (I), the blending amount of the component (b1) for obtaining the (A) bisphenol-based resin is the component (a) from the viewpoint of further improving the discharge characteristics. 0.2 mol or more is preferable with respect to 1 mol, 0.3 mol or more is more preferable, 0.4 mol or more is more preferable, and 0.5 mol or more is particularly preferable. The amount of the component (b1) is preferably 2.5 mol or less, more preferably 2.2 mol or less, and further preferably 2 mol or less with respect to 1 mol of the component (a) from the viewpoint that the cycle characteristics can be further improved.

  When the component (b1) contains the compound represented by the formula (II), the amount of the component (b1) for obtaining the (A) bisphenol-based resin improves the charge acceptance, discharge characteristics and cycle characteristics in a well-balanced manner. In view of this, 0.5 mol or more is preferable, 0.6 mol or more is more preferable, and 0.8 mol or more is more preferable with respect to 1 mol of component (a). The amount of component (b1) is preferably 2 mol or less, more preferably 1.3 mol or less, and 1 mol or less with respect to 1 mol of component (a) from the viewpoint of improving the balance between charge acceptance, discharge characteristics and cycle characteristics. 2 mol or less is more preferable, and 1.1 mol or less is particularly preferable.

  In 2nd Embodiment, the compounding quantity of (b2) component for obtaining (A) bisphenol-type resin is 0.5 mol or more with respect to 1 mol of (a) component from a viewpoint which discharge characteristics further improve, 0.6 mol or more is more preferable, 0.8 mol or more is still more preferable, and 0.9 mol or more is particularly preferable. The amount of the component (b2) is preferably 1.3 mol or less, more preferably 1.2 mol or less, and more preferably 1.1 mol with respect to 1 mol of the component (a), from the viewpoint that the discharge characteristics and cycle characteristics can be further improved. The following is more preferable.

((C) component: formaldehyde and formaldehyde derivatives)
As formaldehyde, formaldehyde in formalin (for example, an aqueous solution of 37% by mass of formaldehyde) may be used. Examples of formaldehyde derivatives include paraformaldehyde, hexamethylenetetramine, and trioxane. (C) A component can be used individually by 1 type or in combination of 2 or more types. You may use formaldehyde and a formaldehyde derivative together.

As the component (c), a formaldehyde derivative is preferable and paraformaldehyde is more preferable from the viewpoint that excellent cycle characteristics are easily obtained. Paraformaldehyde has, for example, a structure represented by the following general formula (III).
HO (CH ₂ O) _n3 H (III)
[In Formula (III), n3 shows the integer of 2-100. ]

  In 1st Embodiment, the compounding quantity of the (c) component for obtaining (A) bisphenol-type resin in the formaldehyde conversion is a viewpoint with which the reactivity of (b1) component improves, (a) With respect to 1 mol of component, The amount is preferably 1.5 mol or more, more preferably 2 mol or more, further preferably 2.2 mol or more, and particularly preferably 2.4 mol or more. (C) From the viewpoint of excellent solubility of the (A) bisphenol-based resin in the solvent, the amount of component (c) in terms of formaldehyde is preferably 5.5 mol or less, and 4.5 mol or less with respect to 1 mol of component (a). More preferably, it is more preferably 3.5 mol or less, particularly preferably 3.2 mol or less, and particularly preferably 3 mol or less.

  In the case where the component (b1) contains the compound represented by the formula (I), the formaldehyde conversion amount of the component (c) for obtaining the (A) bisphenol resin improves the reactivity of the component (b1). From the viewpoint, with respect to 1 mol of component (a), 1.5 mol or more is preferable, 2 mol or more is more preferable, and 2.2 mol or more is more preferable. (C) From the viewpoint of excellent solubility of the (A) bisphenol-based resin in the solvent, the amount of component (c) in terms of formaldehyde is preferably 5.5 mol or less, and 4.5 mol or less with respect to 1 mol of component (a). More preferred is 3.5 mol or less.

  When the compound represented by formula (II) includes the component (b1), the amount of the (c) component in formaldehyde conversion for obtaining the (A) bisphenol resin improves the reactivity of the component (b1). From a viewpoint, 2 mol or more is preferable with respect to 1 mol of (a) component, 2.2 mol or more is more preferable, and 2.4 mol or more is still more preferable. From the viewpoint of excellent solubility of the component (c) in terms of formaldehyde in the solvent of the (A) bisphenol resin, it is preferably 3.5 mol or less, preferably 3.2 mol or less with respect to 1 mol of the component (a). More preferred is 3 mol or less.

  In 2nd Embodiment, the compounding quantity of the (c) component for obtaining (A) bisphenol-type resin is equivalent to the 1 mol of (a) component from a viewpoint that the reactivity of (b2) component improves. 2 mol or more is preferable, 2.2 mol or more is more preferable, and 2.4 mol or more is more preferable. From the viewpoint of excellent solubility of the component (c) in terms of formaldehyde in the solvent of the (A) bisphenol resin, it is preferably 3.5 mol or less, preferably 3.2 mol or less with respect to 1 mol of the component (a). More preferred is 3 mol or less.

  When (b) aminoalkyl sulfonic acid, aminoalkyl sulfonic acid derivative, aminoaryl sulfonic acid or aminoaryl sulfonic acid derivative is used as component, (A) bisphenol-based resin is a structural unit represented by the following formula (IV): And it is preferable to have at least 1 type chosen from the group which consists of a structural unit represented by following formula (V). The ratio of the structural unit represented by the formula (IV) and the structural unit represented by the formula (V) is not particularly limited, and may vary depending on synthesis conditions and the like. (A) As a bisphenol-type resin, you may use resin which has only any one of the structural unit represented by Formula (IV), and the structural unit represented by Formula (V).

[In the formula (IV), X ⁴ represents a divalent group, A ⁴ represents an alkylene group or an arylene group, R ⁴¹ represents an alkali metal or a hydrogen atom, and R ⁴² represents a methylol group (- CH ₂ OH), R ⁴³ and R ⁴⁴ each independently represents an alkali metal or a hydrogen atom, R ⁴⁵ represents a hydrogen atom or a hydrocarbon group, n41 represents an integer of 1 to 600, n42 Represents an integer of 1 to 3, and n43 represents 0 or 1. ]

[In the formula (V), X ⁵ represents a divalent group, A ⁵ represents an alkylene group or an arylene group, R ⁵¹ represents an alkali metal or a hydrogen atom, and R ⁵² represents a methylol group (- CH ₂ OH), R ⁵³ and R ⁵⁴ each independently represent an alkali metal or a hydrogen atom, R ⁵⁵ represents a hydrogen atom or a hydrocarbon group, n51 represents an integer of 1 to 600, n52 Represents an integer of 1 to 3, and n53 represents 0 or 1. ]

  When (b) an aminoalkyl sulfonic acid, an aminoalkyl sulfonic acid derivative, an aminoaryl sulfonic acid or an aminoaryl sulfonic acid derivative is used as the component, (A) the bisphenol-based resin is a structural unit represented by the following formula (VI): And it is preferable to have at least 1 type chosen from the group which consists of a structural unit represented by a following formula (VII). The ratio of the structural unit represented by the formula (VI) and the structural unit represented by the formula (VII) is not particularly limited, and may vary depending on synthesis conditions and the like. (A) As a bisphenol-type resin, you may use resin which has only any one of the structural unit represented by Formula (VI), and the structural unit represented by Formula (VII).

[In formula (VI), X ⁶ represents a divalent group, A ⁶ represents an alkylene group or an arylene group, R ⁶¹ represents an alkali metal or a hydrogen atom, and R ⁶² represents a methylol group (- CH ₂ OH), R ⁶³ and R ⁶⁴ each independently represents an alkali metal or a hydrogen atom, n61 represents an integer of 1 to 600, n62 represents an integer of 1 to 3, and n63 represents 0 or 1 is shown. ]

[In Formula (VII), X ⁷ represents a divalent group, A ⁷ represents an alkylene group or an arylene group, R ⁷¹ represents an alkali metal or a hydrogen atom, and R ⁷² represents a methylol group (- CH ₂ OH), R ⁷³ and R ⁷⁴ each independently represent an alkali metal or a hydrogen atom, n71 represents an integer of 1 to 600, n72 represents an integer of 1 to 3, and n73 represents 0 or 1 is shown. ]

  In the first embodiment, when the compound represented by the formula (I) is used as the component (b1), the (A) bisphenol-based resin includes, for example, a structural unit represented by the following general formula (VIII) and It preferably has at least one of the structural units represented by the general formula (IX). The ratio of the structural unit represented by the formula (VIII) and the structural unit represented by the formula (IX) is not particularly limited, and may vary depending on synthesis conditions and the like. (A) As a bisphenol-type resin, you may use resin which has only any one of the structural unit represented by Formula (VIII), and the structural unit represented by Formula (IX).

[In Formula (VIII), X ⁸ represents a divalent group, R ⁸¹ represents an alkali metal or a hydrogen atom, R ⁸² represents a methylol group (—CH ₂ OH), R ⁸³ and R ⁸⁴ Each independently represents an alkali metal or a hydrogen atom, R ⁸⁵ represents a hydrogen atom or a hydrocarbon group, n81 represents an integer of 1 to 200, n82 represents an integer of 1 to 3, and n83 represents , 0 or 1 is shown. ]

[In Formula (IX), X ⁹ represents a divalent group, R ⁹¹ represents an alkali metal or a hydrogen atom, R ⁹² represents a methylol group (—CH ₂ OH), R ⁹³ and R ⁹⁴ Each independently represents an alkali metal or a hydrogen atom, R ⁹⁵ represents a hydrogen atom or a hydrocarbon group, n91 represents an integer of 1 to 200, n92 represents an integer of 1 to 3, and n93 represents , 0 or 1 is shown. ]

  In the first embodiment, when the compound represented by the formula (II) is used as the component (b1), the (A) bisphenol-based resin includes, for example, a structural unit represented by the following general formula (X) and It is preferable to have at least one of the structural units represented by the general formula (XI). The ratio of the structural unit represented by the formula (X) and the structural unit represented by the formula (XI) is not particularly limited, and may vary depending on synthesis conditions and the like. (A) As a bisphenol-type resin, you may use resin which has only any one of the structural unit represented by Formula (X), and the structural unit represented by Formula (XI).

[In formula (X), X ¹⁰ represents a divalent group, R ¹⁰¹ represents an alkali metal or a hydrogen atom, R ¹⁰² represents a methylol group (—CH ₂ OH), R ¹⁰³ and R ¹⁰⁴ Each independently represents an alkali metal or a hydrogen atom, n101 represents an integer of 1 to 600, n102 represents an integer of 1 to 3, and n103 represents 0 or 1. ]

[In the formula (XI), X ¹¹ represents a divalent group, R ¹¹¹ represents an alkali metal or a hydrogen atom, R ¹¹² represents a methylol group (—CH ₂ OH), R ¹¹³ and R ¹¹⁴ Each independently represents an alkali metal or a hydrogen atom, n111 represents an integer of 1 to 600, n112 represents an integer of 1 to 3, and n113 represents 0 or 1. ]

  When an amino acid or an amino acid derivative is used as the component (b), the (A) bisphenol-based resin is selected from the group consisting of a structural unit represented by the following formula (XII) and a structural unit represented by the following formula (XIII). It is preferable to have at least one selected. The ratio of the structural unit represented by the formula (XII) and the structural unit represented by the formula (XIII) is not particularly limited, and may vary depending on synthesis conditions and the like. (A) As a bisphenol-type resin, you may use resin which has only any one of the structural unit represented by Formula (XII), and the structural unit represented by Formula (XIII).

[In the formula (XII), X ¹² represents a divalent group, A ¹² represents an alkylene group or an arylene group, R ¹²¹ represents an alkali metal or a hydrogen atom, and R ¹²² represents a methylol group (- CH ₂ OH), R ¹²³ and R ¹²⁴ each independently represent an alkali metal or a hydrogen atom, n121 represents an integer of 1 to 600, n122 represents an integer of 1 to 3, and n123 represents 0 or 1 is shown. ]

[In Formula (XIII), X ¹³ represents a divalent group, A ¹³ represents an alkylene group or an arylene group, R ¹³¹ represents an alkali metal or a hydrogen atom, and R ¹³² represents a methylol group (- CH ₂ OH), R ¹³³ and R ¹³⁴ each independently represent an alkali metal or a hydrogen atom, n131 represents an integer of 1 to 600, n132 represents an integer of 1 to 3, and n133 represents 0 or 1 is shown. ]

Examples of X ^{4 to} X ¹³ (X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ⁹ , X ¹⁰ , X ¹¹ , X ¹² and X ¹³ ) include alkylidene groups (methylidene groups, ethylidene groups, Isopropylidene group, sec-butylidene group, etc.), cycloalkylidene group (cyclohexylidene group, etc.), phenylalkylidene group (diphenylmethylidene group, phenylethylidene group, etc.) and the like; From the viewpoint of further superiority, an isopropylidene group (—C (CH ₃ ) ₂ —) group is preferred, and from the viewpoint of further superior discharge characteristics, a sulfonyl group (—SO ₂ —) is preferred. X ^{4 to} X ¹³ may be substituted with a halogen atom such as a fluorine atom. When X ^{4 to} X ¹³ are cycloalkylidene groups, the hydrocarbon ring may be substituted with an alkyl group or the like.

Examples of A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ¹² and A ¹³ include alkylene groups having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group and a butylene group; a phenylene group and a naphthylene group. Of the divalent arylene group. The arylene group may be substituted with an alkyl group or the like.

^R41 , ^R43 , ^R44 , ^R51 , ^R53 , ^R54 , ^R61 , ^R63 , ^R64 , ^R71 , ^R73 , ^R74 , ^R81 , ^R83 , ^R84 , ^R91 , ^R93 R ⁹⁴ , R ¹⁰¹ , R ¹⁰³ , R ¹⁰⁴ , R ¹¹¹ , R ¹¹³ , R ¹¹⁴ , R ¹²¹ , R ¹²³ , R ¹²⁴ , R ¹³¹ , R ^133, and R ¹³⁴ include, for example, sodium and potassium Is mentioned. As the hydrocarbon groups for R ⁴⁵ , R ⁵⁵ , R ⁸⁵ and R ⁹⁵ , the same hydrocarbon groups as those for R ^{1 in} formula (I) can be used.

  n41, n51, n61, n71, n121 and n131 are preferably 5 to 300 from the viewpoint of further excellent cycle characteristics and solubility in a solvent. n81, n91, n101 and n111 are preferably 1 to 150 from the viewpoint of further excellent cycle characteristics and solubility in a solvent. n42, n52, n62, and n72 are preferably 1 or 2, and more preferably 1, from the viewpoint of improving charge acceptability, discharge characteristics, and cycle characteristics in a balanced manner. n43, n53, n63 and n73 vary depending on the production conditions, but 0 is preferable from the viewpoint of further excellent cycle characteristics and excellent storage stability of the (A) bisphenol-based resin.

  In the first embodiment, the weight average molecular weight of the (A) bisphenol-based resin is from the viewpoint that the cycle characteristics are easily improved by suppressing the (A) bisphenol-based resin from eluting from the electrode to the electrolyte in the lead storage battery. 1000 or more, 2000 or more is more preferable, 3000 or more is more preferable, 5000 or more is particularly preferable, 10,000 or more is very preferable, and 20000 or more is very preferable. (A) The weight average molecular weight of the bisphenol-based resin is preferably 300000 or less, more preferably 250,000 or less, and more preferably 200000 or less, from the viewpoint that the cycle characteristics are easily improved by suppressing the decrease in the adsorptivity to the electrode active material. Is more preferably 150,000 or less, and particularly preferably 120,000 or less.

  When component (b1) contains the compound represented by formula (I), the weight average molecular weight of (A) bisphenol-based resin suppresses the dissolution of (A) bisphenol-based resin from the electrode in the lead storage battery into the electrolyte. From the viewpoint of improving the cycle characteristics easily, it is preferably 5000 or more, more preferably 10,000 or more, and still more preferably 20000 or more. (A) The weight average molecular weight of the bisphenol-based resin is preferably 300,000 or less, more preferably 200000 or less, and more preferably 150,000 or less from the viewpoint that the cycle characteristics are easily improved by suppressing the decrease in the adsorptivity to the electrode active material. Is more preferable, and 120,000 or less is particularly preferable.

  When component (b1) contains the compound represented by formula (II), the weight average molecular weight of (A) bisphenol-based resin inhibits (A) bisphenol-based resin from eluting from the electrode to the electrolyte in the lead-acid battery. From the viewpoint of improving the cycle characteristics, it is preferably 1000 or more, more preferably 2000 or more, and still more preferably 3000 or more. (A) The weight average molecular weight of the bisphenol-based resin is preferably 300000 or less, more preferably 250,000 or less, and more preferably 200000 or less, from the viewpoint that the cycle characteristics are easily improved by suppressing the decrease in the adsorptivity to the electrode active material. Is more preferable.

  In 2nd Embodiment, the weight average molecular weight of (A) bisphenol-type resin is from a viewpoint which cycling characteristics improve easily by suppressing that (A) bisphenol-type resin elutes from an electrode in electrolyte in a lead acid battery. 3000 or more are preferable, 10,000 or more are more preferable, 20000 or more are still more preferable, and 30000 or more are especially preferable. (A) The weight average molecular weight of the bisphenol-based resin is preferably 200000 or less, and preferably 150,000 or less, from the viewpoint that the cycle characteristics are easily improved by suppressing the adsorptivity to the electrode active material and the dispersibility. Is more preferable and 100,000 or less is still more preferable.

(A) The weight average molecular weight of a bisphenol-type resin can be measured by the gel permeation chromatography (henceforth "GPC") of the following conditions, for example.
(GPC conditions)
Apparatus: High performance liquid chromatograph LC-2200 Plus (manufactured by JASCO Corporation)
Pump: PU-2080
Differential refractometer: RI-2031
Detector: UV-visible spectrophotometer UV-2075 (λ: 254 nm)
Column oven: CO-2065
Column: TSKgel SuperAW (4000), TSKgel SuperAW (3000), TSKgel SuperAW (2500) (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Eluent: methanol solution containing LiBr (10 mM) and triethylamine (200 mM) Flow rate: 0.6 mL / min Molecular weight standard sample: Polyethylene glycol (molecular weight: 1.10 × 10 ⁶ , 5.80 × 10 ⁵ , 2.55 × 10 ⁵ , 1.46 × 10 ⁵ , 1.01 × 10 ⁵ , 4.49 × 10 ⁴ , 2.70 × 10 ⁴ , 2.10 × 10 ⁴ ; manufactured by Tosoh Corporation), diethylene glycol (molecular weight: 1 .06 × 10 ² ; manufactured by Kishida Chemical Co., Ltd.), dibutylhydroxytoluene (molecular weight: 2.20 × 10 ² ; manufactured by Kishida Chemical Co., Ltd.)

  The manufacturing method of the bisphenol-type resin which concerns on this embodiment is equipped with the resin manufacturing process which makes (a) component, (b) component, and (c) component react, and obtains (A) bisphenol-type resin.

  (A) A bisphenol-type resin can be obtained by making (a) component, (b) component, and (c) component react in a reaction solvent, for example. The reaction solvent is preferably water (for example, ion exchange water). In order to promote the reaction, an organic solvent, a catalyst, an additive, or the like may be used.

  In the first embodiment, when the component (b1) contains the compound represented by the formula (I), the blending amount of the component (b1) is the component (a) from the viewpoint of further improving the cycle characteristics. It is preferable that the amount is 0.2 to 2.5 mol with respect to 1 mol, and the amount of component (c) is 1.5 to 5.5 mol in terms of formaldehyde with respect to 1 mol of component (a). (B1) The preferable compounding quantity of a component and (c) component is the range mentioned above about each of the compounding quantity of (b1) component and (c) component.

  In 1st Embodiment, when (b1) component contains the compound represented by Formula (II), the compounding quantity of (b1) component is (a) component from a viewpoint that cycling characteristics further improve a resin manufacturing process. It is preferably 0.5 to 2 mol with respect to 1 mol, and the amount of component (c) is 2 to 3.5 mol in terms of formaldehyde with respect to 1 mol of component (a). (B1) The preferable compounding quantity of a component and (c) component is the range mentioned above about each of the compounding quantity of (b1) component and (c) component.

  In 2nd Embodiment, the resin manufacturing process which obtains (A) bisphenol-type resin has the compounding quantity of (b2) component with respect to 1 mol of (a) component 0.5-1. It is preferable that the amount of the component (c) is 2 to 3.5 mol in terms of formaldehyde with respect to 1 mol of the component (a). (B2) The preferable compounding quantity of a component and (c) component is the range mentioned above about each of the compounding quantity of (b2) component and (c) component.

  The (A) bisphenol resin is obtained by reacting the component (a), the component (b) and the component (c) under basic conditions (alkaline conditions) from the viewpoint that a sufficient amount of the (A) bisphenol resin is easily obtained. Is preferably obtained. In order to adjust to basic conditions, you may use a basic compound. Examples of the basic compound include sodium hydroxide, potassium hydroxide, and sodium carbonate. A basic compound can be used individually by 1 type or in combination of 2 or more types. Among the basic compounds, sodium hydroxide and potassium hydroxide are preferable from the viewpoint of excellent reactivity.

  In the first embodiment, when the reaction solution containing the component (a), the component (b1), and the component (c) is neutral (pH = 7) at the start of the reaction, (A) the formation reaction of the bisphenol-based resin May not proceed easily, and when the reaction solution is acidic (pH <7), side reactions may proceed. Therefore, the pH of the reaction solution at the start of the reaction is preferably alkaline (more than 7) from the viewpoint of suppressing the side reaction from proceeding while the (A) bisphenol-based resin formation reaction proceeds. Is preferably 1 or more, more preferably 7.2 or more, particularly preferably 8 or more, and extremely preferably 8.5 or more. The pH of the reaction solution is preferably 14 or less, more preferably 13.5 or less, and more preferably 13 or less from the viewpoint of suppressing the hydrolysis of the group derived from the component (b1) of the (A) bisphenol resin. Further preferred. When the component (b1) contains the compound represented by the formula (I), the pH of the reaction solution at the start of the reaction is such that hydrolysis of the group derived from the component (b1) of the (A) bisphenol resin proceeds. 11 or less is particularly preferable, and 9.5 or less is extremely preferable.

  In the second embodiment, when the reaction solution containing the component (a), the component (b2), and the component (c) is neutral (pH = 7) at the start of the reaction, (A) the formation reaction of the bisphenol-based resin May not proceed easily, and when the reaction solution is acidic (pH <7), side reactions may proceed. Therefore, the pH of the reaction solution at the start of the reaction is preferably alkaline (more than 7) from the viewpoint of suppressing the side reaction from proceeding while the (A) bisphenol-based resin formation reaction proceeds. .1 or more is more preferable, and 7.2 or more is more preferable. The pH of the reaction solution is preferably 13 or less, more preferably 10 or less, and even more preferably 9 or less, from the viewpoint of suppressing the hydrolysis of the group derived from the component (b2) of the (A) bisphenol resin. .

  The pH of the reaction solution can be measured by, for example, Twin pH manufactured by AS ONE Corporation. The pH is defined as the pH at 25 ° C.

  In 1st Embodiment, since it is easy to adjust to pH as mentioned above, the compounding quantity of a strong basic compound is 1.01 mol or more with respect to 1 mol of sulfo groups contained in (b1) component. 02 mol or more is more preferable, 1.03 mol or more is further more preferable, and 1.05 mol or more is particularly preferable. From the same viewpoint, the compounding amount of the strongly basic compound is preferably 1.6 mol or less, more preferably 1.5 mol or less, still more preferably 1.3 mol or less, relative to 1 mol of the sulfo group contained in the component (b1). 1.2 mol or less is particularly preferable, and 1.1 mol or less is extremely preferable. Examples of the strongly basic compound include sodium hydroxide and potassium hydroxide.

  In the second embodiment, since it is easy to adjust the pH as described above, the blending amount of the strongly basic compound is preferably 1.01 mol or more, more preferably 1.02 mol or more with respect to 1 mol of the component (b2). 1.03 mol or more is more preferable. From the same viewpoint, the compounding amount of the strongly basic compound is preferably 1.1 mol or less, more preferably 1.08 mol or less, and still more preferably 1.07 mol or less with respect to 1 mol of component (b2). Examples of the strongly basic compound include sodium hydroxide and potassium hydroxide.

  In the present embodiment, (A) a reaction product (reaction solution) obtained when producing a bisphenol-based resin may be used as it is in the production of an electrode described later, or obtained by drying the reaction product (A). A bisphenol-based resin may be dissolved in a solvent (water or the like) and used for manufacturing an electrode to be described later.

  The synthesis reaction of (A) bisphenol-based resin is sufficient as long as (a) component, (b) component, and (c) component react to obtain (A) bisphenol-based resin. For example, (a) component, (b ) Component and (c) component may be reacted simultaneously, or the remaining one component may be reacted after reacting two of component (a), component (b) and component (c).

  In 1st Embodiment, when (b1) component contains the compound represented by Formula (I), it is preferable to perform the synthesis reaction of (A) bisphenol-type resin in two steps as follows. In the first stage reaction, for example, the component (b1), a solvent (such as water), and a basic compound (for example, a strongly basic compound) are charged and stirred, and the hydrogen atom of the sulfo group in the component (b1) is alkali metal. To obtain an alkali metal salt of the component (b1). Thereby, it becomes easy to suppress a side reaction in the below-mentioned condensation reaction. The temperature of the reaction system is preferably 0 ° C. or higher, more preferably 25 ° C. or higher, from the viewpoint of excellent solubility of the component (b1) in a solvent (such as water). The temperature of the reaction system is preferably 80 ° C. or less, more preferably 70 ° C. or less, and still more preferably 65 ° C. or less from the viewpoint of suppressing side reactions. The reaction time is, for example, 30 minutes.

  In the first embodiment, when the component (b1) contains the compound represented by the formula (I), in the second stage reaction, for example, the reaction product obtained in the first stage includes the (a) component and (c ) Component is added and subjected to a condensation reaction to obtain (A) a bisphenol-based resin. The temperature of the reaction system is preferably 75 ° C. or higher, more preferably 85 ° C. or higher, and still more preferably 87 ° C. or higher, from the viewpoint of excellent reactivity of the components (a), (b1) and (c). The temperature of the reaction system is preferably 100 ° C. or less from the viewpoint of suppressing side reactions. The reaction time is, for example, 3 to 20 hours.

  In 1st Embodiment, when (b1) component contains the compound represented by Formula (II), it is preferable to perform the synthetic reaction of (A) bisphenol-type resin in two steps as follows. In the first stage reaction, for example, the component (b1), a solvent (such as water), and a basic compound (for example, a strongly basic compound) are charged and stirred, and the hydrogen atom of the sulfo group in the component (b1) is alkali metal. To obtain an alkali metal salt of the component (b1). Thereby, it becomes easy to suppress a side reaction in the below-mentioned condensation reaction. The temperature of the reaction system is preferably 0 ° C. or higher, more preferably 25 ° C. or higher, from the viewpoint of excellent solubility of the component (b1) in a solvent (such as water). The temperature of the reaction system is preferably 80 ° C. or less, more preferably 70 ° C. or less, and still more preferably 65 ° C. or less from the viewpoint of suppressing side reactions. The reaction time is, for example, 5 to 30 minutes.

  In the first embodiment, when the component (b1) contains the compound represented by the formula (II), in the second step reaction, for example, the component (c) is added to the reaction product obtained in the first step, After stirring for 5 to 30 minutes until the mixture becomes a transparent homogeneous system, component (a) is added to the mixture and subjected to a condensation reaction to obtain (A) a bisphenol-based resin. The temperature of the reaction system is preferably 80 ° C. or higher, more preferably 85 ° C. or higher, and still more preferably 95 ° C. or higher, from the viewpoint of excellent reactivity of the components (a), (b1) and (c). The temperature of the reaction system is preferably 120 ° C. or lower, more preferably 115 ° C. or lower, from the viewpoint of suppressing evaporation of the reaction solvent (for example, water). The reaction time is, for example, 1 to 5 hours.

  In 2nd Embodiment, it is preferable to perform the synthesis reaction of (A) bisphenol-type resin in two steps as follows. In the first stage reaction, for example, the component (b2), the solvent (water, etc.) and the basic compound are charged and stirred, and the hydrogen atom of the sulfo group in the component (b2) is replaced with an alkali metal or the like (b2 ) An alkali metal salt of the component is obtained. Thereby, it becomes easy to suppress a side reaction in the below-mentioned condensation reaction. The temperature of the reaction system is preferably 0 ° C. or higher, more preferably 25 ° C. or higher, from the viewpoint of excellent solubility of the component (b2) in a solvent (water or the like). The temperature of the reaction system is preferably 80 ° C. or less, more preferably 70 ° C. or less, and still more preferably 65 ° C. or less from the viewpoint of suppressing side reactions. The reaction time is, for example, 30 minutes.

  In the second stage reaction in the second embodiment, for example, the (a) bisphenol resin is obtained by adding the (a) component and the (c) component to the reaction product obtained in the first stage to cause a condensation reaction. The temperature of the reaction system is preferably 75 ° C. or higher, more preferably 85 ° C. or higher, and still more preferably 87 ° C. or higher, from the viewpoint of excellent reactivity of the components (a), (b2) and (c). The temperature of the reaction system is preferably 100 ° C. or lower, more preferably 95 ° C. or lower, and still more preferably 93 ° C. or lower, from the viewpoint of suppressing side reactions. The reaction time is, for example, 5 to 20 hours.

  The reaction product thus obtained is dried to remove the solvent (such as water) and the unreacted component (c), thereby obtaining (A) a bisphenol-based resin. Although it does not specifically limit as a drying method, From the viewpoint of preventing the self-curing reaction of (A) bisphenol-type resin, the method by which the temperature of (A) bisphenol-type resin will be 100 degrees C or less is preferable. Examples of the drying method include vacuum drying, freeze drying, and spray drying.

  According to this embodiment, (A) the resin composition containing a bisphenol-type resin can be provided. According to this embodiment, the application to the lead acid battery of the resin composition containing a bisphenol-type resin can be provided. According to this embodiment, the application to the negative electrode of the lead storage battery of the resin composition containing a bisphenol-type resin can be provided. According to this embodiment, the application to the lead storage battery in the motor vehicle of the resin composition containing a bisphenol-type resin can be provided. According to this embodiment, the application to the lead storage battery in the ISS vehicle of the resin composition containing a bisphenol-type resin can be provided. According to this embodiment, the application to the ISS car of a lead storage battery can be provided. According to this embodiment, the application to the micro hybrid vehicle of a lead storage battery can be provided.

  The resin composition according to this embodiment is, for example, a composition containing (A) a bisphenol-based resin and a solvent, and is a liquid resin solution at 25 ° C. Examples of the solvent include water (for example, ion exchange water) and an organic solvent. The solvent contained in the resin composition may be a reaction solvent used to obtain (A) a bisphenol-based resin. The resin composition according to this embodiment may further contain a natural resin or a synthetic resin other than (A) a bisphenol-based resin.

  The resin composition according to the present embodiment may be a composition obtained in the resin production process, and is a composition obtained by mixing (A) a bisphenol-based resin and other components after the resin production process. Also good.

  The content of the (A) bisphenol-based resin in the resin composition according to the present embodiment is based on the total mass of non-volatile components in the resin composition from the viewpoint of improving charge acceptance, discharge characteristics, and cycle characteristics in a balanced manner. 70 mass% or more is preferable, 80 mass% or more is more preferable, and 90 mass% or more is still more preferable.

  The content of the unreacted component (c) (residual component (c)) in the resin composition according to this embodiment is 1% by mass based on the total mass of the resin composition from the viewpoint of further improving cycle characteristics. The following is preferable, 0.9 mass% or less is more preferable, and 0.8 mass% or less is still more preferable. The content of the unreacted component (c) can be reduced, for example, by drying the resin composition. The content of the unreacted component (c) can be measured, for example, by gas chromatography.

  The water content in the resin composition according to the present embodiment is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more from the viewpoint of excellent quality control and operability. From the same viewpoint, the water content is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less. The amount of water can be measured, for example, by Karl Fischer titration.

  When the component represented by formula (I) includes the component (b1), the pH of the resin composition according to the first embodiment (for example, a resin solution that is liquid at 25 ° C.) is (A) a solvent of a bisphenol-based resin ( From the viewpoint of excellent solubility in water, etc., it is preferably alkaline (exceeding 7), more preferably 7.1 or more. The pH of the resin composition is preferably 14 or less, more preferably 12 or less, still more preferably 11 or less, from the viewpoint of further improving the wettability of the resin composition to an electrode active material (lead, lead oxide, etc.). The following are particularly preferred: Moreover, when using the reaction material obtained in a resin manufacturing process as a resin composition, it is preferable that pH of a resin composition is the said range.

  When the component (b1) contains the compound represented by the formula (II), the pH of the resin composition according to the first embodiment (for example, a resin solution that is liquid at 25 ° C.) is (A ) Alkaline (greater than 7) from the viewpoint of excellent solubility of the bisphenol-based resin in a solvent (water, etc.) and excellent wettability of the resin composition to an electrode active material (lead, lead oxide, etc.) Is preferably 7.1 or more. The pH of the resin composition is preferably 7.5 or more from the viewpoint of further excellent solubility of the (A) bisphenol-based resin in a solvent (such as water). The pH of the resin composition is preferably 8 or more from the viewpoint of further improving the wettability of the resin composition to an electrode active material (lead, lead oxide, etc.). The pH of the resin composition is preferably 14 or less, more preferably 13.5 or less, and still more preferably 13 or less, from the viewpoint of reducing hydrolysis of the group derived from the component (b1) of the (A) bisphenol resin. The pH of the resin composition is preferably 11 or less from the viewpoint of further improving the wettability of the resin composition to an electrode active material (lead, lead oxide, etc.). In particular, the pH when the (A) bisphenol-based resin is adjusted to a 5% by mass aqueous solution (for example, an aqueous solution containing ion-exchanged water) is preferably in the above range. Moreover, when using the reaction material obtained in a resin manufacturing process as a resin composition, it is preferable that pH of a resin composition is the said range.

  The pH of the resin composition according to the second embodiment (for example, a resin solution that is liquid at 25 ° C.) is alkaline (7) from the viewpoint of excellent solubility of the bisphenol-based resin in a solvent (such as water). More preferably 7.1 or more. From the viewpoint of improving the storage stability of the resin composition, the pH of the resin composition is preferably 10 or less, more preferably 9 or less, and even more preferably 8.5 or less. In particular, when the reaction product obtained in the resin production process is used as a resin composition, the pH of the resin composition is preferably in the above range.

  The pH of the resin composition can be measured by, for example, Twin pH manufactured by AS ONE Corporation. The pH is defined as the pH at 25 ° C. The pH of the resin composition can be adjusted using, for example, a 10% by mass aqueous sodium hydroxide solution.

<(B) Negative electrode active material>
As described later, the negative electrode active material can be obtained by chemical conversion after obtaining an unformed active material by aging and drying a negative electrode active material paste containing a raw material of the negative electrode active material. It is preferable that the negative electrode active material after chemical conversion contains porous sponge-like lead (Spongy Lead). There is no restriction | limiting in particular as a raw material of a negative electrode active material, For example, lead powder is mentioned. As the lead powder, for example, lead powder manufactured by a ball mill type lead powder manufacturing machine or a barton pot type lead powder manufacturing machine (in the ball mill type lead powder manufacturing machine, a mixture of powder of main component PbO and scale-like metal lead) ).

  The average particle diameter of the negative electrode active material is preferably 0.3 μm or more, more preferably 0.5 μm or more, and even more preferably 0.7 μm or more, from the viewpoint of further improving charge acceptance and cycle characteristics. The average particle diameter of the negative electrode active material is preferably 2.5 μm or less, more preferably 2 μm or less, and even more preferably 1.5 μm or less from the viewpoint of further improving cycle characteristics. As an average particle diameter of the negative electrode active material, for example, after obtaining a transmission electron micrograph (1000 times) in the range of 10 μm in length × 10 μm in the center of the negative electrode after chemical conversion, the length of all particles in the image A numerical value obtained by arithmetically averaging the side length values can be used.

The specific surface area of the negative electrode active material is preferably 0.4 m ² / g or more, more preferably 0.5 m ² / g or more, and 0.6 m ² / g from the viewpoint of increasing the reactivity between the electrolytic solution and the negative electrode active material. The above is more preferable. The specific surface area of the negative electrode active material, a further inhibition of the contraction of the negative electrode at the time of the cycle, preferably ^2m 2 / g or less, more preferably 1.8 m ² / g, more preferably 1.5 m ² / g or less . The specific surface area of the negative electrode active material can be adjusted by, for example, a method of refining the active material at the stage of the unformed active material.

  The specific surface area of the negative electrode active material can be measured, for example, by the BET method. The BET method is a method in which an inert gas (for example, nitrogen gas) having a known molecular size is adsorbed on the surface of a measurement sample, and the surface area is obtained from the adsorption amount and the area occupied by the inert gas. This is a general method for measuring the surface area. Specifically, it is measured based on the following BET equation.

Relationship of the following formula (1), _P / P _o is established well in the range of 0.05 to 0.35. In addition, in Formula (1), the detail of each code | symbol is as follows.
P: Adsorption equilibrium pressure when in an adsorption equilibrium state at a constant temperature P _o : Saturated vapor pressure at the adsorption temperature V: Adsorption amount at the adsorption equilibrium pressure P V _m : Monomolecular layer adsorption amount (a gas molecule is a single molecule on a solid surface) Adsorption amount when layer is formed)
C: BET constant (parameter relating to the interaction between the solid surface and the adsorbent)

By transforming equation (1) (dividing the numerator denominator on the left side by P), the following equation (2) is obtained. In the specific surface area meter used for the measurement, gas molecules having a known adsorption occupation area are adsorbed on the sample, and the relationship between the adsorption amount (V) and the relative pressure (P / P _o ) is measured. From the measured V and P / _Po , the left side of Equation (2) and P / _Po are plotted. Here, assuming that the gradient is s, the following formula (3) is derived from the formula (2). Assuming that the intercept is i, the intercept i and the gradient s are expressed by the following formula (4) and the following formula (5), respectively.

When Expression (4) and Expression (5) are modified, the following Expression (6) and Expression (7) are obtained, respectively, and the following Expression (8) for obtaining the monomolecular layer adsorption amount V _m is obtained. That is, when the adsorption amount V at a certain relative pressure P / _Po is measured at several points and the slope and intercept of the plot are obtained, the monomolecular layer adsorption amount V _m is obtained.

The total surface area S _total (m ² ) of the sample is obtained by the following formula (9), and the specific surface area S (m ² / g) is obtained by the following formula (10) from the total surface area S _total . In the formula (9), N denotes the Avogadro's _{number, A CS} shows the adsorption cross sectional area ^{(m 2),} M indicates the molecular weight. Moreover, in Formula (10), w shows a sample amount (g).

<Electrode, lead acid battery, and manufacturing method thereof>
The electrode according to the present embodiment is manufactured using an electrode active material and the bisphenol resin according to the present embodiment or a resin composition containing the bisphenol resin. The manufacturing method of the electrode which concerns on this embodiment is equipped with the process of manufacturing an electrode using the bisphenol-type resin obtained by the manufacturing method of the bisphenol-type resin which concerns on this embodiment. The electrode includes, for example, an electrode layer containing an electrode active material and a current collector that supports the electrode layer. The electrode is, for example, a negative electrode (a negative electrode plate or the like) for a lead storage battery.

  The lead storage battery according to the present embodiment includes the electrode according to the present embodiment. As a lead acid battery concerning this embodiment, a liquid lead acid battery and a sealed lead acid battery are mentioned, for example, and a liquid lead acid battery is preferred. The method for manufacturing a lead storage battery according to the present embodiment includes, for example, an electrode manufacturing process for obtaining electrodes (positive electrode and negative electrode) and an assembly process for obtaining a lead storage battery by assembling constituent members including the electrodes. When the electrode is not formed, the electrode includes, for example, an electrode layer containing a raw material for the electrode active material, and a current collector that supports the electrode layer. The electrode after the formation includes, for example, an electrode layer containing an electrode active material and the like, and a current collector that serves as a current conduction path from the electrode layer and supports the electrode layer.

  In the electrode manufacturing process, for example, after filling an active material paste into a current collector (for example, current collector grid), aging and drying are performed to obtain an unformed electrode. The unformed electrode preferably contains an unformed active material containing tribasic lead sulfate as a main component. The active material paste includes, for example, a raw material of the active material, and may further include other predetermined additives. When the electrode is a negative electrode, the active material paste includes (A) a bisphenol-based resin and (B) a raw material for the negative electrode active material.

  The active material paste may further contain a solvent and sulfuric acid. As a solvent, water (for example, ion-exchange water) and an organic solvent are mentioned, for example. The solvent may be a reaction solvent used to obtain (A) a bisphenol-based resin. The active material paste may further contain (A) a natural resin or a synthetic resin other than the bisphenol-based resin.

  Examples of the additive contained in the active material paste include barium sulfate, a carbon material, and reinforcing short fibers (acrylic fiber, polyethylene fiber, polypropylene fiber, polyethylene terephthalate fiber, carbon fiber, and the like). Examples of the carbon material include carbon black and graphite. Examples of carbon black include furnace black, channel black, acetylene black, thermal black, and ketjen black.

  The negative electrode active material paste for obtaining the negative electrode (negative electrode plate or the like) of the lead storage battery according to this embodiment can be obtained, for example, by the following method. First, (A) bisphenol-based resin or (A) a resin composition containing a bisphenol-based resin (resin solution, etc.) and an additive added as necessary are mixed with lead powder. Get. Next, a negative electrode active material paste is obtained by adding sulfuric acid (dilute sulfuric acid, etc.) and a solvent (water, etc.) to this mixture and kneading them.

  When barium sulfate is used in the negative electrode active material paste, the compounding amount of barium sulfate is preferably 0.01 to 1% by mass based on the total mass of the raw material of the negative electrode active material. Moreover, when using a carbon material, the compounding quantity of a carbon material has preferable 0.2-1.4 mass% on the basis of the total mass of the raw material of a negative electrode active material. Moreover, when using the short fiber for a reinforcement, the compounding quantity of the short fiber for a reinforcement has preferable 0.05-0.3 mass% on the basis of the total mass of the raw material of a negative electrode active material. The blending amount of (A) bisphenol-based resin or resin composition (resin solution, etc.) containing (A) bisphenol-based resin is 0 in terms of resin solid content, based on the total mass of the negative electrode active material. 0.01-2 mass% is preferable, 0.05-1 mass% is more preferable, and 0.1-0.5 mass% is still more preferable.

  Examples of the composition of the current collector include lead alloys such as a lead-calcium-tin alloy, a lead-calcium alloy, and a lead-antimony-arsenic alloy. Depending on the application, selenium, silver, bismuth or the like may be added to the current collector. A current collector can be obtained by forming these lead alloys in a lattice shape by a gravity casting method, an expanding method, a punching method, or the like.

  The aging conditions are preferably 15 to 60 hours in an atmosphere at a temperature of 35 to 85 ° C. and a humidity of 50 to 98 RH%. The drying conditions are preferably 45 to 80 ° C. and 15 to 30 hours.

The positive electrode (positive electrode plate or the like) in the lead storage battery can be obtained by the following method, for example. First, a reinforcing short fiber is added to the raw material of the positive electrode active material and dry mixed. Next, water and dilute sulfuric acid are added and then kneaded to prepare a positive electrode active material paste. In producing the positive electrode active material paste, lead powder can be used as a raw material of the positive electrode active material. From the viewpoint of shortening the chemical conversion time, lead (Pb ₃ O ₄ ) may be added as a raw material for the positive electrode active material. After filling this positive electrode active material paste into a current collector (for example, current collector grid), aging and drying are performed to obtain an unformed positive electrode. In the positive electrode active material paste, the blending amount of the reinforcing short fibers is preferably 0.005 to 0.3% by mass based on the total mass of the raw material of the positive electrode active material. The type of current collector, aging conditions, and drying conditions are almost the same as in the case of the negative electrode.

  The positive electrode active material can be obtained by chemical conversion after obtaining an unformed active material by aging and drying a positive electrode active material paste containing a raw material of the positive electrode active material. The positive electrode active material after conversion contains, for example, lead dioxide.

  The average particle diameter of the positive electrode active material is preferably 0.3 μm or more, more preferably 0.5 μm or more, and even more preferably 0.7 μm or more, from the viewpoint of further improving charge acceptance and cycle characteristics. The average particle diameter of the positive electrode active material is preferably 2.5 μm or less, more preferably 2 μm or less, and even more preferably 1.5 μm or less from the viewpoint of further improving the cycle characteristics. As the average particle diameter of the positive electrode active material, for example, after obtaining a transmission electron micrograph (1000 times) in the range of 10 μm in length × 10 μm in the center of the positive electrode after chemical conversion, the length of all particles in the image A numerical value obtained by arithmetically averaging the side length values can be used.

The specific surface area of the positive electrode active material, from the viewpoint of enhancing the reactivity with a liquid electrolyte and the positive electrode active material, preferably at least ^2m 2 / g, more preferably at least ^3m 2 / g, more ^4m 2 / g is more preferable. The specific surface area of the positive electrode active material, from the viewpoint of excellent utilization, is preferably from ^{10 m} 2 / g, more preferably not more than ^8m 2 / g, more preferably not more than ^{6 m} 2 / g. The specific surface area of the positive electrode active material can be adjusted by, for example, a method of refining the active material at the stage of the unformed active material or a method of changing the conversion conditions. The specific surface area of the positive electrode active material can be measured, for example, by the BET method based on nitrogen gas adsorption, similarly to the negative electrode active material.

  In the assembly process, for example, the unformed negative electrode and positive electrode produced as described above are alternately stacked via separators, and the same polarity plates are connected to a strap (welding or the like) to obtain a plate group. . This electrode group is arranged in a battery case to produce an unformed battery. Next, after injecting dilute sulfuric acid or the like into the unformed battery, a lead-acid battery is obtained by applying a direct current to perform formation. Normally, a lead-acid battery having a specific gravity can be obtained only by energization. However, for the purpose of shortening the energization time, after dilute sulfuric acid is once extracted after chemical conversion, an electrolytic solution may be injected.

  Examples of the material of the separator include polyethylene and glass fiber. The chemical conversion conditions and the specific gravity of the electrolytic solution can be adjusted according to the properties of the electrode active material. The chemical conversion treatment is not limited to being performed in the assembly process, and may be performed in the electrode manufacturing process.

  The electrolytic solution in the present embodiment contains, for example, sulfuric acid. The electrolytic solution in the second embodiment further contains aluminum ions, and can be obtained by mixing sulfuric acid and aluminum sulfate powder. Aluminum sulfate to be dissolved in the electrolytic solution can be added as an anhydride or a hydrate. The electrolytic solution in the first embodiment may not contain aluminum ions.

  The specific gravity (converted to 20 ° C.) of the electrolytic solution after chemical conversion is preferably in the following range. The specific gravity (converted to 20 ° C.) of the electrolytic solution in the first embodiment is preferably 1.25 to 1.35, and more preferably 1.25 to 1.33. The specific gravity of the electrolytic solution in the second embodiment is preferably 1.25 or more, more preferably 1.28 or more, still more preferably 1.285 or more, from the viewpoint of suppressing osmotic short-circuiting or freezing and further improving discharge characteristics. 1.29 or more is particularly preferable. The specific gravity of the electrolytic solution is preferably 1.35 or less, more preferably 1.33 or less, still more preferably 1.32 or less, and particularly preferably 1.315 or less, from the viewpoint of further improving charge acceptance and cycle characteristics. 1.31 or less is very preferable. The specific gravity of the electrolytic solution is, for example, the specific gravity of the electrolytic solution (such as sulfuric acid) after chemical conversion. The value of the specific gravity of the electrolytic solution can be measured by, for example, a floating hydrometer or a digital hydrometer manufactured by Kyoto Electronics Industry Co., Ltd.

  The aluminum ion concentration of the electrolytic solution in the case where the electrolytic solution contains aluminum ions is preferably 0.01 mol / L or more, more preferably 0.02 mol / L or more, from the viewpoint of further improving charge acceptance and cycle characteristics. 0.03 mol / L or more is more preferable. The aluminum ion concentration of the electrolytic solution is preferably 0.2 mol / L or less, more preferably 0.15 mol / L or less, and still more preferably 0.13 mol / L or less, from the viewpoint of further improving charge acceptance and cycle characteristics. The aluminum ion concentration of the electrolytic solution can be measured by, for example, ICP emission spectroscopy (high frequency inductively coupled plasma emission spectroscopy).

  Although the details of the mechanism for improving the charge acceptability when the aluminum ion concentration of the electrolytic solution is within the predetermined range are not clear, in any electrolytic solution of crystalline lead sulfate as a discharge product under any low SOC This is considered to be because the solubility in the electrode active material increases or the diffusibility of the electrolytic solution into the electrode active material improves due to the high ion conductivity of aluminum ions.

  The mechanism by which the cycle characteristics are improved when the aluminum ion concentration of the electrolytic solution is within the predetermined range is estimated as follows. First, when a normal electrolyte solution that does not contain aluminum ions is used, sulfate ions (for example, sulfate ions generated from lead sulfate) supplied to the electrolyte solution at the time of charging travel downward along the surface of the electrode (electrode plate, etc.). Move to. Under PSOC, the battery will not be fully charged, so the electrolyte is not agitated by gas generation. As a result, non-uniformity of the electrolyte concentration called “stratification” occurs in which the electrolyte specific gravity at the lower part of the battery increases while the electrolyte specific gravity at the upper part of the battery decreases. When such a phenomenon occurs, crystalline lead sulfate that does not easily return to the original state is generated even when charged, and the reaction area of the active material decreases. Thereby, performance deterioration occurs in a life test in which charge and discharge are repeated. On the other hand, when the aluminum ion concentration of the electrolytic solution is within the predetermined range, sulfate ions are strongly attracted by the electrostatic attraction of aluminum ions, so that stratification is unlikely to occur.

  Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to the following examples.

<Preparation of bisphenol resin>
[Synthesis Example 1 (bisphenol / aminobenzenesulfonic acid / formaldehyde condensate)]
After adding 4.2 parts by mass (0.105 mol) of sodium hydroxide and 79.26 parts by mass (4.4 mol) of ion-exchanged water to a 500 mL separable flask equipped with a Dimroth, mechanical stirrer and thermometer, 150 rpm (= The mixture was stirred for 5 minutes at min ⁻¹ ) to prepare an aqueous sodium hydroxide solution. To this sodium hydroxide aqueous solution, 17.32 parts by mass (0.1 mol) of 4-aminobenzenesulfonic acid was added and stirred at 25 ° C. for 30 minutes to obtain a uniform aqueous solution. After adding 9.01 parts by mass of paraformaldehyde (formaldehyde conversion, 0.3 mol, manufactured by Mitsui Chemicals, Inc.) to this aqueous solution, the mixture was stirred for 5 minutes to dissolve paraformaldehyde to obtain a uniform aqueous solution. After adding 21.92 parts by mass (0.096 mol) of bisphenol A and 1.04 parts by mass (0.004 mol) of bisphenol S to this aqueous solution, the solution was stirred for 10 hours while heating using an oil bath set at 90 ° C. Got. As a result of measuring the pH of the aqueous solution at the start of the reaction immediately after adding bisphenol A and bisphenol S under the following pH measurement conditions, the pH was 8.6.

  After the obtained aqueous solution was transferred to a heat-resistant container, this aqueous solution was put into a vacuum dryer set at 60 ° C. Next, bisphenol-based resin powder (bisphenol / aminobenzenesulfonic acid / formaldehyde condensate) was obtained by drying for 10 hours under a reduced pressure of 1 kPa or less. As a result of measuring the weight average molecular weight of the bisphenol-based resin obtained in Synthesis Example 1 by GPC under the following conditions, the weight average molecular weight was 53900.

[Synthesis Example 2 (Bisphenol / aminonaphthalenesulfonic acid / formaldehyde condensate)]
After adding 4.2 parts by mass (0.105 mol) of sodium hydroxide and 137.4 parts by mass (7.6 mol) of ion-exchanged water to a 500 mL separable flask equipped with a Dimroth, mechanical stirrer and thermometer, 5 at 150 rpm. An aqueous sodium hydroxide solution was prepared by stirring for a minute. To this sodium hydroxide aqueous solution, 24.5 parts by mass (0.1 mol) of sodium 7-amino-2-naphthalenesulfonate was added and stirred at 25 ° C. for 10 minutes to obtain a uniform aqueous solution. After adding 9.01 parts by mass of paraformaldehyde (formaldehyde conversion, 0.3 mol, manufactured by Mitsui Chemicals, Inc.) to this aqueous solution, the mixture was stirred for 5 minutes to dissolve paraformaldehyde to obtain a uniform aqueous solution. After adding 22.8 mass parts (0.1 mol) of bisphenol A to this aqueous solution, it stirred for 3 hours, heating using the oil bath set to 115 degreeC, and obtained aqueous solution. As a result of measuring the pH of the aqueous solution at the start of the reaction immediately after the addition of bisphenol A under the following pH measurement conditions, the pH was 12.9.

  After the obtained aqueous solution was transferred to a heat-resistant container, a 10% by mass aqueous sodium hydroxide solution was added to obtain an aqueous solution having a pH of 10.0. Subsequently, this aqueous solution was put into a vacuum dryer set to 60 ° C. Next, bisphenol-based resin powder (bisphenol / aminonaphthalenesulfonic acid / formaldehyde condensate) was obtained by drying for 10 hours under a reduced pressure of 1 kPa or less. As a result of measuring the weight average molecular weight of the bisphenol-based resin obtained in Synthesis Example 2 by GPC under the following conditions, the weight average molecular weight was 97,000.

[Synthesis Example 3 (Bisphenol / aminoethanesulfonic acid / formaldehyde condensate)]
After adding 4.2 parts by mass (0.105 mol) of sodium hydroxide and 100 parts by mass (5.56 mol) of ion-exchanged water to a 500 mL separable flask equipped with a Dimroth, mechanical stirrer and thermometer, the mixture was stirred at 150 rpm for 5 minutes. Thus, an aqueous sodium hydroxide solution was prepared. To this aqueous sodium hydroxide solution, 12.52 parts by mass (0.1 mol) of 2-aminoethanesulfonic acid was added and stirred at 25 ° C. for 30 minutes to obtain a uniform aqueous solution. After adding 9.01 parts by mass of paraformaldehyde (formaldehyde conversion, 0.3 mol, manufactured by Mitsui Chemicals, Inc.) to this aqueous solution, the mixture was stirred for 5 minutes to dissolve paraformaldehyde to obtain a uniform aqueous solution. After adding 22.83 parts by mass (0.1 mol) of bisphenol A to this aqueous solution, it was stirred for 4 hours while heating using an oil bath set at 90 ° C. to obtain an aqueous solution. As a result of measuring the pH of the aqueous solution at the start of the reaction immediately after the addition of bisphenol A under the following pH measurement conditions, the pH was 9.1.

  After the obtained aqueous solution was transferred to a heat-resistant container, this aqueous solution was put into a vacuum dryer set at 60 ° C. Next, bisphenol-based resin powder (bisphenol / aminoethanesulfonic acid / formaldehyde condensate) was obtained by drying for 10 hours under a reduced pressure of 1 kPa or less. As a result of measuring the weight average molecular weight of the bisphenol-based resin obtained in Synthesis Example 3 by GPC under the following conditions, the weight average molecular weight was 76,000.

The ¹ H-NMR spectrum of the bisphenol-based resin powder obtained in Synthesis Example 3 was measured under the following conditions. The measurement result of ¹ H-NMR spectrum is shown in FIG.
Device: AVANCE300 (manufactured by Nippon Bruker Co., Ltd.)
Heavy solvent: DMSO-d ₆

(PH measurement conditions)
Testing machine: Twin pH (manufactured by ASONE Corporation)
Calibration solution: pH 6.86 (25 ° C.), pH 4.01 (25 ° C.)
Measurement temperature: 25 ° C
Measurement procedure: Two-point calibration was performed using a calibration solution. After washing the sensor part of the testing machine, the measurement solution was sucked with a dropper, and 0.1 to 0.3 mL was dropped onto the sensor part. The pH at the end of measurement on the screen was taken as the measured value.

(GPC conditions)
Apparatus: High performance liquid chromatograph LC-2200 Plus (manufactured by JASCO Corporation)
Pump: PU-2080
Differential refractometer: RI-2031
Detector: UV-visible spectrophotometer UV-2075 (λ: 254 nm)
Column oven: CO-2065
Column: TSKgel SuperAW (4000), TSKgel SuperAW (3000), TSKgel SuperAW (2500) (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Eluent: methanol solution containing LiBr (10 mM) and triethylamine (200 mM) Flow rate: 0.6 mL / min Molecular weight standard sample: Polyethylene glycol (molecular weight: 1.10 × 10 ⁶ , 5.80 × 10 ⁵ , 2.55 × 10 ⁵ , 1.46 × 10 ⁵ , 1.01 × 10 ⁵ , 4.49 × 10 ⁴ , 2.70 × 10 ⁴ , 2.10 × 10 ⁴ ; manufactured by Tosoh Corporation), diethylene glycol (molecular weight: 1 .06 × 10 ² ; manufactured by Kishida Chemical Co., Ltd.), dibutylhydroxytoluene (molecular weight: 2.20 × 10 ² ; manufactured by Kishida Chemical Co., Ltd.)

{Experiment A}
<Preparation of negative electrode plate>
[Example A1]
Based on the total mass of the lead powder, 0.2 mass% of the bisphenol resin obtained in Synthesis Example 3 in terms of solid content, 0.2 mass% of furnace black, and 1.0 mass% of barium sulfate are lead. Dry added after adding to flour. Next, it knead | mixes, adding dilute sulfuric acid (specific gravity 1.26 (20 degreeC conversion)) and water, and produced the negative electrode active material paste. The negative electrode active material paste was filled into an expanded current collector (lead-calcium-tin alloy) having a thickness of 0.6 mm to produce a negative electrode plate. The negative electrode plate was aged for 18 hours in an atmosphere of a temperature of 50 ° C. and a humidity of 95% according to a normal method, and then dried in an atmosphere of a temperature of 50 ° C. to obtain an unformed negative electrode plate.

[Examples A2 to A3]
A bisphenol resin was obtained in the same manner as in Synthesis Example 3 except that the components for obtaining the bisphenol resin were changed to the components shown in Table 1. In Table 1, the blending amount of paraformaldehyde is a blending amount in terms of formaldehyde. In the same manner as in Synthesis Example 3, the weight average molecular weight of the bisphenol-based resin was measured. The measurement results are shown in Table 1. And using this bisphenol-type resin, the unchemically formed negative electrode plate was obtained by the method similar to Example A1.

[Comparative Example A1]
An unformed negative electrode plate was obtained in the same manner as in Example A1 except that the bisphenol-based resin was not used.

[Comparative Example A2]
A bisphenol resin was obtained in the same manner as in Synthesis Example 3 except that the components for obtaining the bisphenol resin were changed to the components shown in Table 1. In Table 1, the blending amount of 37 mass% formalin is a blending amount in terms of formaldehyde. In the same manner as in Synthesis Example 3, the weight average molecular weight of the bisphenol-based resin was measured. The measurement results are shown in Table 1. And using this bisphenol-type resin, the unchemically formed negative electrode plate was obtained by the method similar to Example A1.

<PH after completion of reaction>
After the reaction of the bisphenol resin, the pH of the resin solution containing the bisphenol resin was measured under the same measurement conditions as those for the pH at the start of the reaction. The results are shown in Table 1.

<Preparation of positive electrode plate>
After adding 0.01% by mass of cut fibers (reinforcing short fibers, polyethylene fibers) to the lead powder based on the total mass of the lead powder, dry mixing was performed. Next, dilute sulfuric acid (specific gravity 1.26 (converted at 20 ° C.)) and water were added and kneaded to prepare a positive electrode active material paste. A positive electrode current collector (lead-calcium-tin alloy) made of a cast grid is filled with a positive electrode active material paste, left to stand for 18 hours in an atmosphere having a temperature of 50 ° C. and a humidity of 95%, and then a temperature of 50 ° C. Was dried under an atmosphere of 2 to obtain an unchemically formed positive electrode plate.

<Battery assembly>
After laminating 6 unformed negative plates and 5 unformed positive plates through a polyethylene separator so that unformed negative plates and unformed positive plates are alternately laminated, the same Polar plates were connected with a strap to produce a group of plates. The electrode plate group was inserted into the battery case to assemble a 2V single cell battery. After dilute sulfuric acid (specific gravity 1.28 (converted at 20 ° C.)) was poured into this battery, it was formed in a 50 ° C. water bath under an electric current of 1.0 A for 15 hours. And after discharging | emitting dilute sulfuric acid, the dilute sulfuric acid of specific gravity 1.28 (20 degreeC conversion) was inject | poured again and the lead acid battery was obtained. In addition, the electrolyte solution (dilute sulfuric acid) of this lead acid battery does not contain aluminum ions.

<Evaluation of battery characteristics>
About said 2V single cell battery, charge acceptance, a discharge characteristic, and cycling characteristics were measured as follows. The measurement results of charge acceptance, discharge characteristics, and cycle characteristics of Comparative Example A2 were set to 100, and each characteristic was relatively evaluated. The results are shown in Table 1.

(Charge acceptance)
5 seconds after the state of charge of the battery has reached 90%, that is, 10% of the battery capacity is discharged from the fully charged state and charged at a constant voltage of 2.33 V. The current value of was measured. The larger the current value after 5 seconds, the better the initial charge acceptance.

(Discharge characteristics)
As discharge characteristics, a constant current discharge was performed at −15 ° C. at 5 C, and the discharge duration until the battery voltage reached 1.0 V was measured. The longer the discharge duration, the better the battery.

(Cycle characteristics)
The cycle characteristics were evaluated by a method according to a Japanese Industrial Standard light load life test (JIS D 5301). The larger the number of cycles, the higher the durability.

  In the example, it can be confirmed that the cycle characteristics are greatly improved as compared with the comparative example. Further, the charge acceptability and the discharge characteristics remain at substantially the same level as in Comparative Example A2, and it can be confirmed that, for example, the performance as an ISS vehicle application can be sufficiently satisfied. Thus, in the Examples, it can be confirmed that excellent charge acceptance, discharge characteristics, and cycle characteristics are compatible.

{Experiment B}
<Preparation of negative electrode plate>
[Examples B1 to B6]
A bisphenol resin was obtained in the same manner as in Synthesis Example 2 except that the components for obtaining the bisphenol resin were changed to the components shown in Table 2. In Table 2, the blending amount of paraformaldehyde is a blending amount in terms of formaldehyde. The bisphenol resin of Example B3 is the bisphenol resin obtained in Synthesis Example 2. And using this bisphenol-type resin, the unchemically formed negative electrode plate was obtained by the method similar to Example A1.

  In the same manner as in Synthesis Example 2, the weight average molecular weight of the bisphenol-based resin and the pH at the start of the reaction were measured. Further, the pH of the aqueous solution containing 5% by mass of the obtained bisphenol-based resin was measured under the same measurement conditions as the pH measurement conditions at the start of the reaction. The measurement results are shown in Table 2.

Further, in the embodiment B1, after obtaining the bisphenol-based resin powder in the same manner as in Synthesis Example 2, it was analyzed by ^{1 H-NMR} spectrum of the bisphenol-based resin powder under the following conditions. The measurement result of ¹ H-NMR spectrum is shown in FIG.
Device: AVANCE300 (manufactured by Nippon Bruker Co., Ltd.)
Heavy solvent: DMSO-d ₆

[Comparative Example B1]
An unformed negative electrode plate was obtained by the same method as in Example B1 except that the bisphenol-based resin was not used.

[Comparative Example B2]
A bisphenol resin was obtained in the same manner as in Synthesis Example 2 except that the components for obtaining the bisphenol resin were changed to the components shown in Table 2. In Table 2, the blending amount of 37% by mass formalin is a blending amount in terms of formaldehyde. In the same manner as in Example B1, the weight average molecular weight of the bisphenol resin, the pH at the start of the reaction, and the pH of the aqueous solution containing 5% by mass of the bisphenol resin were measured. The measurement results are shown in Table 2. And using this bisphenol-type resin, the unchemically formed negative electrode plate was obtained by the method similar to Example A1.

<Evaluation of battery characteristics>
A non-chemically formed positive electrode plate was produced in the same manner as in Experiment A. And the lead acid battery was obtained similarly to the experiment A using the unchemically formed negative electrode plate and the unformed positive electrode plate. Charge acceptance, discharge characteristics and cycle characteristics were measured and evaluated in the same manner as in Experiment A. The results are shown in Table 2.

  In the example, it can be confirmed that the charge acceptance and the cycle characteristics are greatly improved as compared with the comparative example. Also, the discharge characteristics remain almost the same level as in Comparative Example B2, and it can be confirmed that the performance as, for example, an ISS vehicle application can be sufficiently satisfied. Thus, in the Examples, it can be confirmed that excellent charge acceptance, discharge characteristics, and cycle characteristics are compatible.

{Experiment C}
<Production of lead acid battery>
[Example C1]
(Preparation of positive electrode plate)
Lead powder and red lead (Pb ₃ O ₄ ) were used as raw materials for the positive electrode active material (lead powder: red lead = 96: 4 (mass ratio)). 0.07% by mass of reinforcing short fibers (acrylic fibers) based on the total mass of the positive electrode active material, the total mass of the positive electrode active material, and water were added and kneaded. Subsequently, the mixture was kneaded while adding dilute sulfuric acid having a specific gravity of 1.280 (converted to 20 ° C., the same applies hereinafter) little by little to prepare a positive electrode active material paste. The positive electrode active material paste was filled in an expandable current collector produced by subjecting a rolled sheet made of a lead alloy to an expanding process, and then aged for 24 hours in an atmosphere at a temperature of 50 ° C. and a humidity of 98%. Thereafter, it was dried to produce an unformed positive electrode plate.

(Preparation of negative electrode plate)
Lead powder was used as a raw material for the negative electrode active material. 0.2% by mass of resin (bisphenol-based resin) shown in Table 3, 0.1% by mass of reinforcing short fibers (acrylic fibers), 1.0% by mass of barium sulfate, and carbonaceous conductive material (furnace black) A 2 mass% mixture was added to the lead powder and then dry-mixed (the blending amount is based on the total mass of the negative electrode active material). Next, the mixture was kneaded after adding water. Subsequently, the mixture was kneaded while dilute sulfuric acid having a specific gravity of 1.280 was added little by little to prepare a negative electrode active material paste. The negative electrode active material paste was filled in an expandable current collector produced by subjecting a rolled sheet made of a lead alloy to an expanding process, and then aged for 24 hours in an atmosphere of a temperature of 50 ° C. and a humidity of 98%. Thereafter, it was dried to produce an unformed negative electrode plate.

(Battery assembly)
An unformed negative electrode plate was inserted into a polyethylene separator processed into a bag shape. Next, five unchemically formed positive electrode plates and six unchemically formed negative electrode plates inserted in the bag-like separator were alternately laminated. Then, the electrode plate group was prepared by welding the ears of the same polarity electrode plates by a cast on strap (COS) method. The electrode plate group was inserted into a battery case to assemble a 2V single cell battery (corresponding to a B19 size single cell defined in JIS 50301). Dilute sulfuric acid in which aluminum sulfate anhydride was dissolved so that the aluminum ion concentration was 0.04 mol / L (adjusted so that the specific gravity of the electrolytic solution after the formation was 1.290) was poured into this battery. Then, it formed in a 50 degreeC water tank with the energizing current 10A on conditions for 16 hours, and obtained the lead acid battery. The electrolyte specific gravity after conversion (at 20 ° C.) was 1.290.

The specific surface areas of the positive electrode active material and the negative electrode active material after the chemical conversion were calculated according to the BET method by measuring the nitrogen gas adsorption amount at a liquid nitrogen temperature by a multipoint method while cooling the sample with liquid nitrogen. The measurement conditions are as follows. As a result of measurement in this manner, the specific surface area of the positive electrode active material was 5 m ² / g. The specific surface area of the negative electrode active material was 0.6 m ² / g.
(Specific surface area measurement conditions)
Apparatus: HM-2201FS (manufactured by Macsorb)
Degassing time: 10 minutes at 130 ° C. Cooling: 4 minutes with liquid nitrogen Adsorbed gas flow rate: 25 mL / m

[Examples C2 to C8, Comparative Examples C1 to C2]
A lead-acid battery was produced in the same manner as in Example C1, except that the type of resin used for the negative electrode plate, the aluminum ion concentration, and the specific gravity (converted to 20 ° C.) of the electrolytic solution after conversion were changed as shown in Table 3. . In Comparative Example C1, a commercially available sodium lignin sulfonate (trade name: Vanillex N, manufactured by Nippon Paper Industries Co., Ltd.) was used instead of the bisphenol-based resin. In Comparative Example C2, the negative electrode plate obtained using the bisphenol-based resin of Synthesis Example 1 was used, an electrolytic solution containing no aluminum ions was used, and the specific gravity of the electrolytic solution after formation was 1.280.

<Evaluation of battery characteristics>
The lead storage battery was measured for charge acceptance, discharge characteristics, and cycle characteristics as follows. The discharge characteristics and the cycle characteristics were relatively evaluated with the measurement result of Comparative Example C2 as 100. By these tests, the charge acceptability at the time of constant voltage charge and the durability when used under PSOC can be evaluated. The results are shown in Table 3.

(Charge acceptance)
For a lead-acid battery in a fully charged state, while adjusting the temperature in a constant temperature bath at 25 ° C., a predetermined charging / discharging pattern composed of constant voltage charging and constant current discharging is repeated, and the SOC value at the end is set. It was evaluated as charge acceptance. Hereinafter, the evaluation method will be further described with reference to FIG. 3 showing a charge / discharge current pattern. The vertical axis of FIG. 3 shows the behavior of the current of the lead storage battery, the upper part of the X axis shows the behavior of the charging current, and the lower part of the X axis shows the behavior of the discharging current. First, discharge was performed at 0.6 C for x seconds (step S1, x in the first cycle was 25 seconds), then discharge was performed at 5 C for 1 second (step S2), and then discharge was performed at 0.3 C for 35 seconds (step S3). Thereafter, constant voltage charging (step S4) was performed for 12 seconds at 2.4V (limit current 1.5C), and then constant voltage charging (step S5) was performed for 14 seconds at 2.5V (limit current 2C). Subsequently, the above charge / discharge pattern was repeated a total of 11 times, replacing x with the numerical values shown in Table 4, and this was taken as one cycle. This charge / discharge pattern assuming use in an ISS vehicle was repeated 30 cycles, and the SOC value at the end of 30 cycles was evaluated as charge acceptance. The C is a relative representation of the magnitude of current when the rated capacity is discharged at a constant current from a fully charged state. For example, a current that can discharge a rated capacity in 1 hour is expressed as 1C, and a current that can discharge a rated capacity in 2 hours is expressed as 0.5C.

  FIG. 4 shows the results of evaluating the SOC values at the end of each cycle for Example C2, Comparative Example C1, and Comparative Example C2. In the lead storage batteries obtained in Examples C1 to C8, the SOC decreased until 5 to 10 cycles, but thereafter, the SOC increased, and it was confirmed that high charge acceptance was exhibited. The period in which the SOC decreases until 5 to 10 cycles is considered to be a run-up period until the active material is sufficiently activated by repeating a certain amount of charge / discharge from the initial state.

In this evaluation test, the balance between the discharge amount and the charge amount is important. In the evaluation started from the fully charged state, the initial state of the evaluation is a state in which the battery is close to the fully charged state, that is, the SOC (State of charge) is high. In such an initial stage of evaluation, since the active material is not sufficiently activated, the charge amount is originally reduced with respect to the discharge amount. Since the number of evaluation cycles increases in a state where the amount of charge is insufficient, the SOC rapidly decreases. This evaluation test sets strict conditions from the viewpoint of sufficiently charging. Therefore, after the active material is sufficiently activated through the initial state, a higher SOC at the same cycle time means higher charge acceptability. The SOC was calculated from the following equation based on the charge / discharge amount balance by the current integration method. The fully charged battery capacity (rated capacity) was the capacity when the fully charged battery was discharged at 0.2C.
SOC (%) = 100 × (battery capacity in a fully charged state−accumulated value of charge / discharge amount balance) / battery capacity in a fully charged state

(Discharge characteristics)
The measurement of the low-temperature high-rate discharge characteristics was performed as follows. A 150 A (5 C) constant current discharge was performed with the battery temperature adjusted to −15 ° C., and the discharge duration until the battery voltage dropped below 1.0 V was evaluated. The longer the discharge duration, the better the battery.

(Cycle characteristics)
A cycle test was performed based on the charge / discharge pattern used in the evaluation of charge acceptance. The battery life was determined when the voltage during discharge during cycle evaluation was lower than 1.25 V, and the number of cycles at that time was evaluated.

*: Means that aluminum sulfate was not blended.

  In the Examples, it can be seen that excellent charge acceptability and cycle characteristics can be obtained as compared with the Comparative Examples. The charge acceptance of Comparative Example C2 is 89%, while in Examples C1 to C8, it is 93 to 95%, and the difference is 4 to 6%. Even if the charge acceptability is 1%, it is not easy to improve, so even if the charge acceptability can be improved by 1%, it is a significant difference.

  Further, according to the comparison between Example C3 and Example C5 and the comparison between Example C3 and Example C6, when the bisphenol-based resin of Synthesis Example 2 or Synthesis Example 3 is used, the bisphenol-based resin of Synthesis Example 1 It can be seen that the charge-accepting property is equivalent to that of, and the cycle characteristics can be improved although the discharge characteristics are slightly inferior.

  According to Examples C1 to C4, when the aluminum ion concentration of the electrolytic solution is within a predetermined range, by using the bisphenol-based resin of Synthesis Example 1, charging is performed while suppressing a decrease in discharge performance due to these synergistic effects. It can be seen that the acceptability and cycle characteristics are improved.

  In Example C7 and Example C8, the discharge characteristics are slightly lower than those in Examples C1 to C6, but this is a level that causes no problem in practical use. The reason why the discharge characteristics slightly decrease is considered to be due to the low specific gravity of the electrolyte.

  From the comparison between Example C3 and Example C4, when the aluminum ion concentration of the electrolyte was changed from 0.10 mol / L to 0.12 mol / L, excellent charge acceptability and cycle characteristics were obtained. It can be seen that the charge acceptance and cycle characteristics are not further improved with the increase. This is presumably because when the concentration of aluminum ions becomes high, the influence of electrostatic interaction between ions increases, and the decrease in ion conductivity, that is, the improvement in charge acceptance performance reaches its peak. Therefore, it is desirable to provide an upper limit for the aluminum ion concentration of the electrolytic solution from the viewpoint of efficiently obtaining an effect according to the amount of the compound that supplies aluminum ions (for example, aluminum sulfate).

  ADVANTAGE OF THE INVENTION According to this invention, the bisphenol-type resin which can acquire the outstanding charge acceptance property and cycling characteristics, and its manufacturing method can be provided. Moreover, according to this invention, the resin composition containing the said bisphenol-type resin can be provided. Furthermore, according to this invention, the electrode manufactured using an electrode active material and the said bisphenol-type resin, lead acid battery, and these manufacturing methods can be provided.

  INDUSTRIAL APPLICABILITY The present invention can provide a lead storage battery (for example, a liquid lead storage battery) that can improve charge acceptability and life characteristics under PSOC as compared with the conventional one. The present invention contributes to the spread of ISS vehicles, micro hybrid vehicles (power generation control vehicles, etc.) and the like. Therefore, the present invention is useful for solving the global problem of reducing carbon dioxide emissions by suppressing the fuel consumption of automobiles and suppressing global warming, and has high industrial applicability.

Claims (7)

  (A) a bisphenol compound, (b1) at least one selected from the group consisting of aminoalkylsulfonic acid, aminoalkylsulfonic acid derivatives, aminonaphthalenesulfonic acid and aminonaphthalenesulfonic acid derivatives, and (c) formaldehyde and formaldehyde derivatives A bisphenol-based resin obtained by reacting at least one selected from the group consisting of: The bisphenol-type resin of Claim 1 in which the said (b1) component contains the compound represented by the following general formula (I).
[In Formula (I), R ¹ represents a hydrogen atom or a hydrocarbon group, X ¹ represents an alkali metal or a hydrogen atom, and n 1 represents an integer of 0 to 3. ] The bisphenol-based resin according to claim 1 or 2, wherein the component (b1) includes a compound represented by the following general formula (II).
[In Formula (II), R ² represents an alkali metal or a hydrogen atom, and n ² represents an integer of 1 to 3. ]   The electrode manufactured using an electrode active material and the bisphenol-type resin as described in any one of Claims 1-3.   A lead acid battery comprising the electrode according to claim 4. A lead acid battery comprising a positive electrode, a negative electrode and an electrolyte solution,
The negative electrode includes a bisphenol-based resin and a negative electrode active material,
The bisphenol-based resin is at least selected from the group consisting of (a) a bisphenol-based compound and (b2) an amino acid, an amino acid derivative, an aminoalkyl sulfonic acid, an aminoalkyl sulfonic acid derivative, an aminoaryl sulfonic acid, and an aminoaryl sulfonic acid derivative. A resin obtained by reacting one type with (c) at least one selected from the group consisting of formaldehyde and a formaldehyde derivative;
A lead acid battery in which the electrolyte contains aluminum ions.   The lead acid battery of Claim 6 whose specific gravity of the said electrolyte solution is 1.25-1.35.