JP6222239B2 - Resin composition, electrode, lead-acid battery, and production method thereof - Google Patents

Description

  The present invention relates to a resin composition, an electrode, a lead storage battery, and a method for producing them.

  BACKGROUND ART Lead-acid batteries for automobiles are widely used for engine starting and power supply for electrical components. In recent years, an idling stop system (hereinafter referred to as “ISS”) that stops the engine when the vehicle is temporarily stopped and restarts when the vehicle starts is being implemented as an effort to protect the environment and improve fuel efficiency. In the lead storage battery used in ISS, the engine is frequently started and stopped repeatedly, so that the number of large current discharges at the start of the engine increases, and the use of electrical components overlaps with the discharge load.

Charging of the lead acid battery for automobiles is constant voltage charging by an alternator. In recent years, the set value of the alternator voltage has been lowered for the purpose of suppressing a decrease in the electrolyte due to water decomposition during charging. Further, in recent years, in addition to adopting such a low charging voltage, a power generation control system called “charging by an alternator during traveling is controlled according to the traveling state of the vehicle and the charged state of the lead storage battery. The system that reduces engine load, improves fuel consumption, and reduces CO ₂ is also employed. In such a system, it is difficult to charge the lead storage battery, and it is difficult to achieve a fully charged state. Under such conditions of use, lead-acid batteries are often not fully charged and used due to excessive discharge.

  If the lead storage battery is not fully charged and the state of low charge continues, a phenomenon (sulfation) in which lead sulfate as an inactive discharge product accumulates on the electrode plate may occur. In such a situation, it is known that battery performance such as cycle characteristics deteriorates because the active material is difficult to be reduced (it is difficult to be charged).

  Moreover, when it is difficult to perform complete charging, a stratification phenomenon occurs in which a difference in concentration of dilute sulfuric acid, which is an electrolytic solution, occurs between the upper and lower portions of the electrode plate in the lead acid battery. In this case, the concentration of dilute sulfuric acid in the lower part of the electrode plate increases and sulfation occurs. For this reason, the reactivity of the lower part of the electrode plate is reduced, and only the upper part of the electrode plate reacts intensively. As a result, deterioration such as weakening of the connection between the active materials progresses, and the active material peels off from the current collector supporting the active material (for example, current collector grid) at the upper part of the electrode plate, so that the battery having cycle characteristics and the like Performance decreases.

  On the other hand, as a means for improving cycle characteristics and the like, the following Patent Document 1 discloses a technique relating to a negative electrode for a lead storage battery obtained by using a negative electrode active material and a condensate of phenols, aminobenzenesulfonic acid and formaldehyde. It is disclosed.

International Publication No. 1997/37393

  By the way, for lead-acid batteries, it is required to further improve battery performance such as cycle characteristics.

  This invention is made | formed in view of the said situation, and it aims at providing the resin composition which can acquire the cycling characteristics outstanding in the lead acid battery, and its manufacturing method. Moreover, an object of this invention is to provide the electrode and lead acid battery which are manufactured using the said resin composition, and these manufacturing methods.

  As a result of intensive studies by the present inventors, it has become clear that sufficient cycle characteristics cannot be obtained when the lead-acid battery negative electrode described in Patent Document 1 is used. On the other hand, the present inventors reacted a bisphenol compound with at least one selected from the group consisting of aminobenzenesulfonic acid and aminobenzenesulfonic acid derivatives and at least one selected from the group consisting of formaldehyde and formaldehyde derivatives. It has been found that the above-described problems can be solved by using a resin composition that contains a resin obtained by using the resin composition and has an alcohol content of 0.5% by mass or less.

  That is, the resin composition according to the present invention comprises (a) a bisphenol compound, (b) at least one selected from the group consisting of aminobenzenesulfonic acid and aminobenzenesulfonic acid derivatives, and (c) formaldehyde and formaldehyde derivatives. A resin obtained by reacting at least one selected from the group consisting of the above and the alcohol content is 0.5% by mass or less.

  According to the resin composition according to the present invention, excellent cycle characteristics can be obtained in a lead storage battery. Moreover, according to the resin composition which concerns on this invention, battery performance, such as the outstanding charge acceptance property, discharge characteristic, and cycling characteristics, can be made compatible.

  As described above, in the lead storage battery obtained using the resin composition having a low alcohol content, the reaction product generated in the electrode reaction of the lead storage battery may be coarsened. It is presumed that the specific surface area of the electrode is kept high by being suppressed. However, the factor is not limited to this.

  The resin preferably has a weight average molecular weight of 30,000 to 70,000. In this case, further excellent cycle characteristics can be obtained.

  In the resin composition according to the present invention, the content of the unreacted component (b) is preferably 6% by mass or less. In this case, further excellent cycle characteristics can be obtained.

  The nonvolatile content of the resin composition according to the present invention is preferably 10 to 50% by mass. In this case, the solubility of the resin is excellent, and further excellent battery performance can be obtained.

  The electrode according to the present invention is manufactured using the resin composition according to the present invention. The lead acid battery according to the present invention includes the electrode according to the present invention. Even in these, excellent cycle characteristics can be obtained.

  The method for producing a resin composition according to the present invention comprises (a) a bisphenol compound, (b) at least one selected from the group consisting of aminobenzenesulfonic acid and aminobenzenesulfonic acid derivatives, and (c) formaldehyde and formaldehyde derivatives. A process of obtaining a resin by reacting at least one selected from the group consisting of: wherein the alcohol content in the resin composition containing the resin is 0.5% by mass or less.

  According to the method for producing a resin composition according to the present invention, excellent cycle characteristics can be obtained in a lead storage battery. Moreover, according to the manufacturing method of the resin composition which concerns on this invention, battery performance, such as the outstanding charge acceptance property, discharge characteristic, and cycling characteristics, can be made compatible.

  In the method for producing a resin composition according to the present invention, the amount of component (b) is 0.50 to 1.30 mol with respect to 1.00 mol of component (a), and the amount of component (c) is (A) The aspect which is 2.00-3.50 mol in conversion of formaldehyde with respect to 1.00 mol of components is preferable. In this case, further excellent cycle characteristics can be obtained.

  The manufacturing method of the electrode which concerns on this invention is equipped with the process of manufacturing an electrode using the resin composition obtained by the manufacturing method of the resin composition which concerns on this invention. The manufacturing method of the lead acid battery which concerns on this invention comprises the process of obtaining an electrode with the manufacturing method of the electrode which concerns on this invention. Even in these, excellent cycle characteristics can be obtained.

  According to the present invention, excellent cycle characteristics can be obtained in a lead storage battery. Further, according to the present invention, it is possible to achieve both battery performance such as excellent charge acceptability, discharge characteristics, and cycle characteristics. ADVANTAGE OF THE INVENTION According to this invention, the application of the resin composition to a lead acid battery can be provided.

  In particular, according to the present invention, excellent characteristics can be obtained in a lead-acid battery having a negative electrode produced using the resin composition. ADVANTAGE OF THE INVENTION According to this invention, the application of the resin composition to the negative electrode of lead acid battery can be provided.

  ADVANTAGE OF THE INVENTION According to this invention, the application of the resin composition to the lead storage battery in a motor vehicle can be provided. In addition, according to the present invention, since the decrease in charge capacity is extremely small, it is possible to provide a lead storage battery that can be sufficiently satisfied as an ISS vehicle application used in a harsh environment. ADVANTAGE OF THE INVENTION According to this invention, the application of the resin composition to the lead acid battery in an ISS vehicle can be provided.

FIG. 1 is a drawing showing measurement results of ¹ H-NMR spectrum. FIG. 2 is a drawing showing a calibration curve in the measurement of the weight average molecular weight.

  Hereinafter, embodiments of the present invention will be described in detail. In addition, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. .

<Resin composition and production method thereof>
The resin composition according to this embodiment is selected from the group consisting of (a) a bisphenol-based compound (hereinafter sometimes referred to as “(a) component”) and (b) aminobenzenesulfonic acid and an aminobenzenesulfonic acid derivative. At least one (hereinafter referred to as “component (b)” in some cases) and (c) at least one selected from the group consisting of formaldehyde and formaldehyde derivatives (hereinafter referred to as “component (c)” in some cases) are reacted. Resin (hereinafter referred to as “bisphenol-based resin”), and the content of alcohol in the resin composition is 0.5% by mass or less. According to this embodiment, a bisphenol-based resin obtained by reacting the component (a), the component (b) and the component (c) is provided, and the bisphenol-based resin according to this embodiment includes the component (a), the component ( It has a structure obtained by reacting component b) and component (c). The resin composition according to the present embodiment is a liquid resin solution at 25 ° C., for example. Hereinafter, the components of the resin composition will be described.

((A) component: bisphenol compound)
A bisphenol-based compound is a compound having two hydroxyphenyl groups. Examples of the bisphenol compound include 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as “bisphenol A”), bis (4-hydroxyphenyl) methane, 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-hydroxy Phenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bis (4-hydroxyphenyl) sulfone (hereinafter “ Bisphenol S "). (A) A component 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 acceptability, and bisphenol S is preferable from the viewpoint of further excellent discharge characteristics.

  As the bisphenol 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% or more based on 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. Is more 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, 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 well-balanced manner. 97 mol% or less is more preferable.

((B) component: aminobenzenesulfonic acid and aminobenzenesulfonic acid derivative)
Examples of the 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).

As the aminobenzenesulfonic acid derivative, a compound in which a part of hydrogen atoms of aminobenzenesulfonic acid is substituted with an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms), a sulfo group of aminobenzenesulfonic acid (—SO _3). And compounds in which the hydrogen atom of H) is substituted with an alkali metal (for example, sodium and potassium). Examples of the compounds in which some of the hydrogen atoms of aminobenzenesulfonic acid are substituted with alkyl groups include 4- (methylamino) benzenesulfonic acid, 3-methyl-4-aminobenzenesulfonic acid, and 3-amino-4-methylbenzene. Examples include sulfonic acid, 4- (ethylamino) benzenesulfonic acid, and 3- (ethylamino) -4-methylbenzenesulfonic acid. Examples of the compound 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-aminobenzenesulfone. Examples include potassium acid, potassium 3-aminobenzenesulfonate, and potassium 4-aminobenzenesulfonate.

  (B) A component can be used individually by 1 type or in combination of 2 or more types. As the component (b), 4-aminobenzenesulfonic acid is preferable from the viewpoint of further improving charge acceptability and cycle characteristics.

  The blending amount of the component (b) for obtaining the bisphenol-based resin is preferably 0.50 mol or more and 0.60 mol or more with respect to 1.00 mol of the component (a) from the viewpoint of further improving the discharge characteristics. Is more preferably 0.80 mol or more, particularly preferably 0.90 mol or more. The blending amount of the component (b) is preferably 1.30 mol or less, more preferably 1.20 mol or less with respect to 1.00 mol of the component (a), from the viewpoint that the discharge characteristics and the cycle characteristics are further improved. The amount is preferably 1.10 mol or less.

((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. In order to prevent polymerization, the formalin generally contains 10 to 15% by mass of methanol. When the alcohol content of the resin composition containing the bisphenol-based resin obtained using such formalin exceeds 0.5% by mass, the cycle characteristics are deteriorated.

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. For example, paraformaldehyde has the following structure.
HO (CH ₂ O) _n1 H (I)
[In Formula (I), n1 shows the integer of 2-100. ]

  From the viewpoint of improving the reactivity of the component (b), the amount of the component (c) for obtaining the bisphenol-based resin is 2.00 mol or more with respect to 1.00 mol of the component (a). The amount is preferably 2.20 mol or more, more preferably 2.40 mol or more. The amount of the component (c) in terms of formaldehyde is preferably 3.50 mol or less with respect to 1.00 mol of the component (a), from the viewpoint of excellent solubility of the resulting bisphenol-based resin in a solvent. 20 mol or less is more preferable, and 3.00 mol or less is still more preferable.

(solvent)
The resin composition according to this embodiment may further contain a solvent. Examples of the solvent include water (for example, ion exchange water), an organic solvent, and the like. The solvent contained in the resin composition may be a reaction solvent used for obtaining a bisphenol-based resin.

  The resin composition according to the present embodiment may further contain a natural resin or a synthetic resin other than the bisphenol-based resin.

The bisphenol-based resin preferably has, for example, at least one of a structural unit represented by the following formula (II-a) and a structural unit represented by the following formula (III-a).
[In Formula (II-a), X ² represents a divalent group, R ²¹ , R ²³ and R ²⁴ each independently represent an alkali metal or a hydrogen atom, and R ²² represents a methylol group (—CH 2 ₂ OH) indicates, n2 represents an integer of 1 to 150, n21 represents an integer of 1 to 3, n22 represents 0 or 1. Moreover, the hydrogen atom directly bonded to the carbon atom constituting the benzene ring may be substituted with an alkyl group having 1 to 5 carbon atoms. ]

[In Formula (III-a), X ³ represents a divalent group, R ³¹ , R ³³ and R ³⁴ each independently represents an alkali metal or a hydrogen atom, and R ³² represents a methylol group (—CH ₂ OH) indicates, n3 represents an integer of 1 to 150, n31 represents an integer of 1 to 3, n32 represents 0 or 1. Moreover, the hydrogen atom directly bonded to the carbon atom constituting the benzene ring may be substituted with an alkyl group having 1 to 5 carbon atoms. ]

  The ratio of the structural unit represented by the formula (II-a) and the structural unit represented by the formula (III-a) is not particularly limited, and may vary depending on synthesis conditions and the like. As the bisphenol-based resin, a resin having only one of the structural unit represented by the formula (II-a) and the structural unit represented by the formula (III-a) may be used.

  The bisphenol-based resin preferably has, for example, at least one of a structural unit represented by the following formula (II-b) and a structural unit represented by the following formula (III-b).

[In Formula (II-b), X ² represents a divalent group, R ²¹ represents an alkali metal or a hydrogen atom, R ²² represents a methylol group (—CH ₂ OH) or a hydrogen atom, R ²³ and R ²⁴ each independently represent an alkali metal or a hydrogen atom, and n2 represents an integer of 1 to 150. Moreover, the hydrogen atom directly bonded to the carbon atom constituting the benzene ring may be substituted with an alkyl group having 1 to 5 carbon atoms. ]

[In formula (III-b), X ³ represents a divalent group, R ³¹ represents an alkali metal or a hydrogen atom, R ³² represents a methylol group (—CH ₂ OH) or a hydrogen atom, R ³³ and ^{R 34} each independently represents an alkali metal or a hydrogen atom, n3 represents an integer of 1 to 150. Moreover, the hydrogen atom directly bonded to the carbon atom constituting the benzene ring may be substituted with an alkyl group having 1 to 5 carbon atoms. ]

  The ratio of the structural unit represented by the formula (II-b) and the structural unit represented by the formula (III-b) is not particularly limited, and may vary depending on synthesis conditions and the like. As the bisphenol-based resin, a resin having only one of the structural unit represented by the formula (II-b) and the structural unit represented by the formula (III-b) may be used.

Formula (II-a), formula (II-b), formula (III-a) and formula (III-b) will be further described. Examples of X ² and X ³ include alkylidene groups (methylidene group, ethylidene group, isopropylidene group, sec-butylidene group, etc.), cycloalkylidene groups (cyclohexylidene group, etc.), phenylalkylidene groups (diphenylmethylidene group, phenyl). An organic group such as an ethylidene group); a sulfonyl group, and the like. From the viewpoint of further excellent charge acceptance, an isopropylidene group (—C (CH ₃ ) ₂ —) group is preferable, and from the viewpoint of further excellent discharge characteristics. A sulfonyl group (—SO ₂ —) is preferred. X ² and X ³ may be substituted with a halogen atom such as a fluorine atom. When X ² and X ³ are cycloalkylidene groups, the hydrocarbon ring may be substituted with an alkyl group or the like. ^Examples of the alkali metal for R ²¹ , R ²³ , R ²⁴ , R ³¹ , R ³³ and R ³⁴ include sodium and potassium. n2 and n3 are preferably 1 to 150, and more preferably 10 to 150, from the viewpoint of further excellent cycle characteristics and solubility in a solvent. n21 and n31 are preferably 1 or 2, and more preferably 1, from the viewpoint of easy improvement in charge acceptance, discharge characteristics, and cycle characteristics. n22 and n32 vary depending on the production conditions, but 0 is preferable from the viewpoint of further excellent cycle characteristics and storage stability.

  The content of the bisphenol-based resin in the resin composition according to the present embodiment is 80% by mass on the basis of the total mass of nonvolatile components in the resin composition from the viewpoint of improving charge acceptability, discharge characteristics, and cycle characteristics in a balanced manner. The above is preferable, 90 mass% or more is more preferable, and 95 mass% or more is still more preferable.

  The weight average molecular weight of the bisphenol-based resin is preferably 30000 or more, more preferably 35000 or more, from the viewpoint that the cycle characteristics are easily improved by suppressing the bisphenol-based resin from eluting from the electrode to the electrolyte in the lead storage battery. 40,000 or more is more preferable, and 50000 or more is particularly preferable. The weight average molecular weight of the bisphenol-based resin is preferably 70000 or less, more preferably 65000 or less from the viewpoint that the cycle characteristics are easily improved by suppressing the adsorptivity to the electrode active material and the dispersibility. 62,000 or less is more preferable.

The weight average molecular weight of the bisphenol-based resin can be measured, for example, by gel permeation chromatography (hereinafter referred to as “GPC”) under the following conditions.
(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 content of alcohol in the resin composition according to this embodiment is 0.5% by mass (5000 ppm) or less based on the total mass of the resin composition. The content of alcohol is more preferably 0.1% by mass (1000 ppm) or less, further preferably 500 ppm or less, and particularly preferably 150 ppm or less from the viewpoint of further improving cycle characteristics. Examples of the alcohol include lower alcohols having 1 to 5 carbon atoms such as methanol, ethanol, propanol, isopropyl alcohol, butanol, ethylene glycol, and glycerin. The alcohol content is obtained, for example, by using a material having a low alcohol content to obtain a resin composition (for example, when a composition obtained by a bisphenol resin production process is used as a resin composition, a bisphenol resin is used). It can be reduced by using a material with a low alcohol content) or by volatilizing the alcohol.

  The content of the unreacted component (b) (residual component (b)) in the resin composition according to this embodiment is 6% by mass based on the total mass of the resin composition from the viewpoint of further improving cycle characteristics. (60000 ppm) or less is preferable, 4 mass% (40000 ppm) or less is more preferable, 2 mass% (20000 ppm) or less is further preferable, and 1.5 mass% (15000 ppm) or less is particularly preferable. The content of the unreacted component (b) is, for example, adjusting the pH of the reaction solution during the reaction of the components (a), (b) and (c) to 10.0 or lower, or (c ) It can be reduced by increasing the amount of component.

  The content of the alcohol and the unreacted component (b) in the resin composition according to the present embodiment can be calculated by, for example, measuring as follows. The alcohol content can be calculated by injecting the resin composition into a gas chromatograph mass spectrometer (GC / MS) and calculating the ratio between the peak area of the alcohol and the peak area of the standard sample (for example, methanol). The unreacted component (b) can be determined from the area ratio of the peak of component (b) to the total peak in the GPC UV-visible spectrophotometer.

  The nonvolatile content in the resin composition according to the present embodiment is preferably 10% by mass or more, more preferably 15% by mass or more, from the viewpoint of further improving the solubility of the bisphenol-based resin and battery characteristics. More preferably, it is more than mass%. From the same viewpoint, the nonvolatile content in the resin composition according to this embodiment is preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less.

The nonvolatile content can be measured, for example, by the following procedure. First, after putting a predetermined amount (for example, 2 g) of a resin composition into a container (for example, a metal petri dish such as a stainless steel petri dish), the resin composition is dried at 150 ° C. for 60 minutes using a hot air dryer. Next, after the temperature of the container returns to room temperature (for example, 25 ° C.), the residual mass is measured. Then, the nonvolatile content is calculated from the following formula.
Nonvolatile content (mass%) = [(residual mass after drying) / (mass of resin composition before drying)] × 100

  The manufacturing method of the resin composition 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. The resin composition according to the present embodiment may be a composition obtained in the resin production process, or may be a composition obtained by mixing a bisphenol-based resin and other components after the resin production process.

  The bisphenol-based resin can be obtained, for example, by reacting the component (a), the component (b), and the component (c) in a reaction solvent. 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 resin production process, from the viewpoint of further improving cycle characteristics, the blending amount of component (b) is 0.50 to 1.30 mol relative to 1.00 mol of component (a), and component (c) The aspect which is 2.00-3.50 mol in conversion of formaldehyde with respect to 1.00 mol of (a) component is preferable. (B) The preferable compounding quantity of a component and (c) component is the range mentioned above about each of the compounding quantity of (b) component and (c) component.

  The bisphenol-based resin is preferably 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 bisphenol-based resin can be easily obtained. In order to adjust to basic conditions, you may use a basic compound. Examples of the basic compound include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate and the like. 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.

  When the reaction solution at the time of the reaction is neutral (pH = 7.0), the formation reaction of the bisphenol-based resin may not proceed easily, and when the reaction solution is acidic (pH <7.0), side reaction May progress. Therefore, the pH of the reaction solution at the time of the reaction is preferably alkaline (more than 7.0) from the viewpoint of suppressing the side reaction from proceeding while the formation reaction of the bisphenol-based resin proceeds, and 7.1 The above is more preferable, and 7.2 or more is more preferable. The pH of the reaction solution is preferably 12.0 or less, more preferably 10.0 or less, and 9.0 or less from the viewpoint of suppressing the hydrolysis of the group derived from the component (b) of the bisphenol resin. Is more preferable. The pH of the reaction solution can be measured, for example, with a twin pH meter AS-212 manufactured by Horiba, Ltd. The pH is defined as the pH at 25 ° C.

  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, relative to 1.00 mol of the component (b), 1.03 mol or more is still more preferable. From the same viewpoint, the compounding amount of the strongly basic compound is preferably 1.10 mol or less, more preferably 1.08 mol or less, and further 1.07 mol or less with respect to 1.00 mol of component (b). preferable. Examples of the strongly basic compound include sodium hydroxide and potassium hydroxide.

  In this embodiment, the reaction product (reaction solution) obtained by the method for producing a bisphenol-based resin may be used as it is for the production of an electrode described later, or the bisphenol-based resin obtained by drying the reaction product is used as a solvent (water Etc.) and may be used for the production of an electrode to be described later.

  The pH of the resin composition is preferably alkaline (greater than 7.0), more preferably 7.1 or more, from the viewpoint of excellent solubility of the bisphenol-based resin in a solvent (such as water). The pH of the resin composition is preferably 10.0 or less, more preferably 9.0 or less, and even more preferably 8.5 or less from the viewpoint of reducing the content of the unreacted component (b). In particular, when the composition 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, for example, with a twin pH meter AS-212 manufactured by Horiba, Ltd. The pH is defined as the pH at 25 ° C.

  The synthesis reaction of the bisphenol-based resin is sufficient if the (a) component, the (b) component, and the (c) component react to obtain a bisphenol-based resin. For example, the (a) component, (b) component, and (c) The components may be reacted at the same time, and the remaining one component may be reacted after reacting two of the components (a), (b) and (c).

  The synthesis reaction of the bisphenol-based resin is preferably performed in two steps as follows. In the first stage reaction, for example, the component (b), the solvent (water, etc.) and the basic compound are charged and stirred, and the hydrogen atom of the sulfo group in the component (b) is replaced with an alkali metal or the like (b ) 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 (b) 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 second-stage reaction, for example, the bisphenol-based resin is obtained by adding the components (a) and (c) to the reaction product obtained in the first stage and causing 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), (b) 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.

<Electrodes and lead acid batteries and methods for producing them>
The electrode according to the present embodiment is manufactured using the resin composition according to the present embodiment. The manufacturing method of the electrode which concerns on this embodiment is equipped with the process of manufacturing an electrode using the resin composition obtained by the manufacturing method of the resin composition which concerns on this embodiment. The electrode includes, for example, an electrode active material, an electrode material containing a raw material for the electrode active material, and a current collector that supports the electrode material. The electrode is, for example, a negative electrode (a negative electrode plate or the like) for a lead storage battery. The constituent component of the electrode material is a solid content obtained by removing the solvent from the electrode paste described later, or a component obtained by chemical conversion of the solid content.

  The lead storage battery according to the present embodiment includes the electrode according to the present embodiment. Examples of the lead storage battery according to this embodiment include a liquid lead storage battery, a control valve type lead storage battery, and the like, and a liquid lead storage battery is preferable. The method for manufacturing a lead storage battery according to the present embodiment includes, for example, an electrode manufacturing process for obtaining an electrode by the electrode manufacturing method according to the present embodiment, and an assembly process for obtaining a lead storage battery by assembling components including the electrode. Yes.

  In the electrode manufacturing process, for example, after filling an electrode paste into a current collector (for example, current collector grid), aging and drying are performed to obtain an unformed electrode. The electrode paste contains, for example, the resin composition according to the present embodiment as a dispersant, and further contains a raw material for the electrode active material, an additive, and the like. When the electrode is a negative electrode, examples of the raw material for the negative electrode active material include lead powder. Examples of the lead powder include lead powder manufactured by a ball mill type lead powder manufacturing machine or a Burton pot type lead powder manufacturing machine (in a ball mill type lead powder manufacturing machine, a mixture of powder of main component PbO and scale-like metal lead) ).

  Examples of the additive 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.

  When the electrode according to this embodiment is a negative electrode, the negative electrode paste can be obtained, for example, by the following method. First, an additive is added to lead powder and kneaded to obtain a mixture. Next, a solvent (water or the like) and the resin composition according to the present embodiment are added to the mixture and mixed. And negative electrode paste is obtained by adding dilute sulfuric acid.

  In the negative electrode paste, the compounding amount of barium sulfate is preferably 0.01 to 1.0% by mass based on the total mass of the lead powder. The blending amount of the carbon material is preferably 0.2 to 1.4% by mass based on the total mass of the lead powder. The compounding amount of the resin composition according to the present embodiment is preferably 0.01 to 2.0% by mass and 0.05 to 1.0% by mass in terms of resin solid content based on the total mass of the lead powder. More preferred is 0.1 to 0.5% by mass.

  Current collector materials include lead-calcium-tin alloys and lead-calcium alloys, and lead-calcium-tin alloys and lead-calcium alloys obtained by adding trace amounts of arsenic, selenium, silver, bismuth, etc. Is mentioned.

  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.

When the electrode which concerns on this embodiment is a negative electrode, the positive electrode (positive electrode plate etc.) for lead acid batteries can be obtained by the following method, for example. First, after adding reinforcing short fibers to lead powder (PbO) which is a raw material of the positive electrode active material, water and dilute sulfuric acid are added. This is kneaded to produce a positive electrode paste. In producing the positive electrode paste, red lead (Pb ₃ O ₄ ) may be added as a raw material for the positive electrode active material. After filling the positive electrode paste into a current collector (current collector grid or the like), aging and drying are performed to obtain an unformed positive electrode. In the positive electrode 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 lead powder. The type of current collector, aging conditions, and drying conditions are almost the same as in the case of the negative electrode.

  In the assembling process, for example, the negative electrode and the positive electrode manufactured as described above are stacked via a separator, and the electrode plate groups are obtained by connecting the ears of the same polarity electrode plates with a strap. This electrode group is arranged in a battery case to produce an unformed battery. Next, dilute sulfuric acid is added to the non-chemical cell to perform chemical conversion treatment. Subsequently, the lead acid battery is obtained by adjusting the specific gravity (converted to 20 ° C.) of the sulfuric acid after conversion to an appropriate electrolyte specific gravity. As for the specific gravity (20 degreeC conversion) of the sulfuric acid used for chemical conversion, 1.20-1.26 are preferable. As for the specific gravity (20 degreeC conversion) of the adjusted sulfuric acid after chemical conversion, 1.25-1.35 are preferable. Moreover, after the said chemical conversion treatment, a lead acid battery can also be obtained by once extracting dilute sulfuric acid and adding sulfuric acid with specific gravity (20 degreeC conversion) 1.25-1.35. The sulfuric acid may contain a sulfate.

  Examples of the material for the separator include polyethylene and glass fiber. The chemical conversion conditions and the specific gravity of sulfuric acid 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 after aging and drying of the electrode manufacturing process (tank chemical conversion).

  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 resin solution>
[Example 1]
The following components were charged into a reaction vessel equipped with a stirrer, a reflux device and a temperature controller to obtain a first mixed solution.
Sodium hydroxide: 1.05 mol [42.0 parts by mass]
Ion exchange water: 44.0 mol [792.6 parts by mass]
4-aminobenzenesulfonic acid: 1.00 mol [173.2 parts by mass]

The first mixture was mixed and stirred at 25 ° C. for 30 minutes. Subsequently, the following components were charged into the first mixed liquid to obtain a second mixed liquid.
Bisphenol A: 0.96 mol [219.2 parts by mass]
Bisphenol S: 0.04 mol [10.4 parts by mass]
Paraformaldehyde (manufactured by Mitsui Chemicals): 3.00 mol [90.9 parts by mass] (formaldehyde conversion)

A resin solution was obtained by reacting the second mixed solution (pH = 8.6) at 90 ° C. for 10 hours. The bisphenol-based resin contained in the resin solution obtained in Example 1 was isolated by low-temperature drying (60 ° C., 6 hours), and a ¹ H-NMR spectrum was measured. The measurement result of ¹ H-NMR spectrum is shown in FIG.

The weight average molecular weight of the bisphenol-based resin was measured by GPC under the following conditions.
(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.)

  A calibration curve calculated from the standard sample is shown in FIG. The horizontal axis is the retention time, and the vertical axis is the logarithm of molecular weight. The weight average molecular weight measured using GPC was 53900.

[Examples 2-7, Comparative Examples 1-2]
Resin solutions of Examples 2 to 7 and Comparative Examples 1 and 2 were obtained in the same manner as in Example 1 except that the constituent components of the resin solution were changed to the components shown in Table 1. Further, the weight average molecular weight of the bisphenol-based resin was measured in the same manner as in Example 1. In Table 1, the blending amount of 37% by mass formalin is a blending amount in terms of formaldehyde.

<Measurement of alcohol content>
The alcohol content in the resin solution was calculated from a peak area calibration curve of a standard sample obtained by gas chromatography under the following conditions. In addition, what diluted the resin solution 100 times with ion-exchange water was used as the measurement sample.
(Gas chromatography conditions)
Gas chromatograph mass spectrometer: GCMSQP-2010 manufactured by Shimadzu Corporation
Column: HP-5MS 5% Phenyl-95% Methylpolysiloxane (0.25 mm ID × 30 m, 0.25 μm) manufactured by Agilent Technologies
Temperature condition: Initial temperature 40 ° C. (5 min)
Temperature increase rate: 20 ° C / min (up to 280 ° C)
Final temperature: 280 ° C
Sample amount: 1 μL inlet condition Injection mode: Split method Standard sample: aqueous solution with methanol concentration adjusted to 20 ppm, 50 ppm, 100 ppm, respectively Carrier gas: Helium (flow rate 1 mL / min)
Detector: FID

<Residual component content>
The contents of aminobenzene sulfonic acid and aminobenzene sulfonic acid derivative in the resin solution were determined from the area ratio of aminobenzene sulfonic acid peak and aminobenzene sulfonic acid derivative to all peaks in the GPC UV-Vis spectrophotometer.

<Measurement of nonvolatile content>
The nonvolatile content was measured by the following procedure. First, 2 g of the resin solution was placed in a 50φ × 15 mm container (stainless steel petri dish) and dried at 150 ° C. for 60 minutes using a hot air dryer. Next, after the temperature of the container returned to room temperature (25 ° C.), the non-volatile content was measured by measuring the residual mass.

<Measurement of pH>
The pH of the resin solution was measured by injecting 500 mL of the resin solution into the sensor part of the following pH measuring device after the reaction was completed.
(Conditions for pH measurement)
pH measuring device: HORIBA, Ltd. Twin pH meter AS-212
Calibration solution: pH calibration solution manufactured by HORIBA, Ltd. (pH 4.01, pH 6.86)

<Preparation of negative electrode plate>
Based on the total mass of the lead powder, the resin solution is 0.2% by mass in terms of solid content, 0.2% by mass of furnace black, and 1.0% by mass of barium sulfate are added to the lead powder and then dry-processed. Mixed. Next, the mixture was kneaded while adding dilute sulfuric acid (specific gravity 1.26 (converted at 20 ° C.)) and water to prepare a negative electrode paste. The negative electrode 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.

<Preparation of positive electrode plate>
Based on the total mass of the lead powder, a cut fiber (reinforcing short fiber) made of 0.01 mass% polyethylene fiber was added to the lead powder and then dry mixed. Next, dilute sulfuric acid (specific gravity 1.26 (converted at 20 ° C.)) and water were added and kneaded to prepare a positive electrode paste. A positive electrode current collector (lead-calcium-tin alloy) made of a cast grid is filled with a positive electrode paste and left to mature for 18 hours in an atmosphere at a temperature of 50 ° C. and a humidity of 95%, and then an atmosphere at a temperature of 50 ° C. It dried below and obtained the unchemically formed positive electrode plate.

<Battery assembly>
After laminating 6 unformed negative plates and 5 unformed positive plates through polyethylene separators so that unformed negative plates and unformed positive plates are alternately laminated, the same polarity electrode plate The electrode plate groups were prepared by connecting the ears of the two pieces with a strap. 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). After dilute sulfuric acid (specific gravity: 1.24 (converted at 20 ° C.)) was poured into this battery, it was formed in a 50 ° C. water bath at an energizing current of 10 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.

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

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

(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. 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 the rated capacity in 1 hour is expressed as “1C”, and a current that can be discharged in 2 hours is expressed as “0.5C”.

(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 improved as compared with the comparative example. In Examples 1 and 2 using bisphenol-based resins synthesized by using bisphenol A and bisphenol S in combination, it can be confirmed that the cycle characteristics are remarkably improved.

  Moreover, in an Example, it can confirm that the outstanding charge acceptance property, discharge characteristic, and cycling characteristics are compatible. In Example 6, although the discharge characteristics are small as compared with the comparative example, characteristics having no practical problems are obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can obtain the cycling characteristics outstanding in the lead acid battery, and its manufacturing method can be provided. Moreover, according to this invention, the electrode and lead acid battery which are manufactured using the said resin composition, and these manufacturing methods can be provided.

Claims (10)

A reaction between (a) a bisphenol compound, (b) at least one selected from the group consisting of aminobenzenesulfonic acid and aminobenzenesulfonic acid derivatives, and (c) at least one selected from the group consisting of formaldehyde and formaldehyde derivatives. Including a resin obtained by
A resin composition having an alcohol content of 0.5% by mass or less.   The resin composition of Claim 1 whose weight average molecular weights of the said resin are 30000-70000.   The resin composition according to claim 1 or 2, wherein the content of the unreacted component (b) is 6% by mass or less.   The resin composition as described in any one of Claims 1-3 whose non volatile matter content is 10-50 mass%.   The electrode manufactured using the resin composition as described in any one of Claims 1-4.   A lead acid battery comprising the electrode according to claim 5. A reaction between (a) a bisphenol compound, (b) at least one selected from the group consisting of aminobenzenesulfonic acid and aminobenzenesulfonic acid derivatives, and (c) at least one selected from the group consisting of formaldehyde and formaldehyde derivatives. A step of obtaining a resin,
The manufacturing method of the resin composition whose content of the alcohol in the resin composition containing the said resin is 0.5 mass% or less.   The blending amount of the component (b) is 0.50 to 1.30 moles with respect to 1.00 mole of the component (a), and the blending amount of the component (c) is 1.00 mole of the component (a). The manufacturing method of the resin composition of Claim 7 which is 2.00-3.50 mol in conversion of formaldehyde with respect to this.   The manufacturing method of an electrode provided with the process of manufacturing an electrode using the resin composition obtained by the manufacturing method of the resin composition of Claim 7 or 8.   The manufacturing method of a lead acid battery provided with the process of obtaining an electrode with the manufacturing method of the electrode of Claim 9.