JP2013151605A - Method for producing condensate of resorcin and acetone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a condensate of resorcin and acetone, in which the residual amount of unreacted resorcin is reduced.SOLUTION: Provided is a method for producing a condensate of resorcin and acetone, the condensate satisfying the following conditions (1), (2) and (3) described below. The method for producing a condensate of resorcin and acetone comprises a first step where resorcin and acetone are reacted in the presence of at least one chosen from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate, wherein the using amount of the at least one chosen from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate to resorcin is 0.1 to 10 mol%.

Description

  The present invention relates to a method for producing a condensate of resorcin and acetone.

A condensate of resorcin and acetone is useful as a reinforcing agent for various rubber compositions.
In Patent Document 1, after resorcin and acetone are reacted in the presence of an acid and an organic solvent, the acid is neutralized with an aqueous sodium hydroxide solution, and the neutralized mixture is dried under reduced pressure to obtain resorcin and A process for obtaining a condensate with acetone is described.

JP 2004-2431 A

  In the conventional production method, a large amount of unreacted resorcinol may remain.

The present invention includes the following inventions.
[1] including a first step of reacting resorcin and acetone in the presence of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate,
The amount of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate with respect to resorcin is 0.1 to 10 mol%.
A method for producing a condensate of resorcin and acetone satisfying the following (1), (2) and (3).
(1) The ratio of the peak area derived from 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan to the total area of all peaks when gel permeation chromatography (differential refractive index detection) was analyzed (2) When gel permeation chromatography (differential refractive index detection) is analyzed, the area ratio of the first eluting peak to the total area of all peaks is in the range of 10 to 25%. (3) The weight average molecular weight of the first elution peak is in the range of 800 or more.

[2] The first step is a step of reacting resorcin and acetone in the presence of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate and an organic solvent [ 1] The manufacturing method of description.

[3] A first step of reacting resorcin and acetone in the presence of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate;
A second step of mixing the mixture obtained in the first step with a base;
A third step of washing the mixture obtained in the second step with water;
The production method according to [1] or [2].

[4] A condensate obtained by the production method according to any one of [1] to [3].

[5] A rubber composition comprising a condensate obtained by the production method according to any one of [1] to [3], a rubber component, a filler, and a sulfur component.

[6] A tire belt comprising a steel cord coated with the rubber composition according to [5].

[7] A tire carcass including a carcass fiber cord coated with the rubber composition according to [5].

[8] A tire tread or a tire undertread comprising the rubber composition according to [5].

[9] A pneumatic tire produced by processing the rubber composition according to [5].

  According to the production method of the present invention, the residual amount of unreacted resorcin can be reduced.

Hereinafter, the present invention will be described in detail.
<Resorcin and acetone are reacted in the presence of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate (hereinafter sometimes referred to as “first step”). >
Commercially available resorcinol and acetone can be used. The amount of acetone used is preferably in the range of 1 to 6 mol and more preferably in the range of 1.5 to 4 mol with respect to 1 mol of resorcin. If the amount of acetone used is 1 mol or more, it is preferred because the content of resorcin in the resulting condensate tends to be reduced.

  As p-toluenesulfonic acid and p-toluenesulfonic acid hydrate, commercially available products can be used, or they can be used as they are or after being dissolved in an organic solvent or the like and diluted to an appropriate concentration. Although there is no restriction | limiting in particular in the usage-amount of these acids, the range of 0.1-10 mol is preferable with respect to 100 mol of resorcinol, and the range of 0.5-8 mol is more preferable.

  The reaction between resorcin and acetone is preferably performed in the presence of an organic solvent. Examples of the organic solvent include aliphatic hydrocarbons, aromatic hydrocarbons, halogen-substituted aromatic hydrocarbons, and the like. Specific examples of the aliphatic hydrocarbon are hexane, heptane, octane, decane, and the like. Specific examples of the aromatic hydrocarbon are toluene, xylene, ethylbenzene, and the like. Specific examples of the halogen-substituted aromatic hydrocarbon are: Chlorobenzene, dichlorobenzene and the like. Aromatic hydrocarbons are preferred, and toluene or xylene is more preferred. The amount of the organic solvent used is preferably in the range of 0.5 to 3 parts by weight with respect to 1 part by weight of resorcin.

  The reaction temperature of the reaction between resorcin and acetone is preferably in the range of 30 ° C. or higher and 70 ° C. or lower. The progress of the reaction can be confirmed by ordinary analytical means such as gas chromatography (GC), high performance liquid chromatography (HPLC), gel permeation chromatography (GPC), etc., while confirming the progress of the reaction, The end point can be determined.

  The order of mixing resorcin, acetone, and acid is not particularly limited. For example, resorcin and acetone are mixed in the presence of an organic solvent as necessary, and the resulting mixture and acid are mixed under reaction temperature conditions. Can be implemented. The acid charging method is not particularly limited, and may be charged all at once as a solid, or may be charged over time by dropping after dissolving the acid in an organic solvent or the like in order to reduce heat generation during mixing. . Moreover, you may add acetone to a mixture continuously or intermittently with progress of reaction.

７，７’−ジヒドロキシ−４，４，４’，４’−テトラメチル−２，２’−スピロビクロマン（下記の式で示される化合物）、

４，６−ビス（７−ヒドロキシ−２，４，４−トリメチルクロマン−２−イル）−１，３−ベンゼンジオール（式（Ｉ）で表される化合物）及びその異性体、

２，４−ビス（７−ヒドロキシ−２，４，４−トリメチルクロマン−２−イル）−１，３−ベンゼンジオール（式（ＩＩ）で表される化合物）及びその異性体、

式（ＩＩＩ）で表される化合物及びその異性体、

式（ＩＶ）で表される化合物及びその異性体、

［式（ＩＶ）中、ｎは２以上の整数を表す。］
等が挙げられる。 As a compound contained in the condensate of resorcin and acetone, in addition to 2,4,4-trimethyl-2′4′7-trihydroxyflavan (a compound represented by the following formula),

7,7′-dihydroxy-4,4,4 ′, 4′-tetramethyl-2,2′-spirobichroman (compound represented by the following formula),

4,6-bis (7-hydroxy-2,4,4-trimethylchroman-2-yl) -1,3-benzenediol (compound represented by formula (I)) and isomers thereof,

2,4-bis (7-hydroxy-2,4,4-trimethylchroman-2-yl) -1,3-benzenediol (compound represented by formula (II)) and isomers thereof,

Compounds represented by formula (III) and isomers thereof,

Compounds represented by formula (IV) and isomers thereof,

[In the formula (IV), n represents an integer of 2 or more. ]
Etc.

<A step of mixing the mixture obtained in the first step and a base (hereinafter sometimes referred to as “second step”)>
As the base, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrogen carbonates such as sodium hydrogen carbonate, alkali metal carbonates such as sodium carbonate, and the like can be used. Is preferred, and sodium hydroxide is more preferred. The base is preferably used as an aqueous solution having an appropriate concentration.

  The pH of the mixture obtained by mixing with a base is preferably in the range of 5-9, more preferably in the range of 6-8.

<Step of washing the mixture obtained in the second step (hereinafter sometimes referred to as “third step”)>
The mixture obtained in the second step may be directly subjected to a post-treatment step described later, or may be further subjected to a post-treatment step after further subjecting to a third step described later.

  Washing with water is a step of removing unreacted resorcin by mixing the mixture obtained in the second step with water and separating and washing. When the mixture obtained in the second step is a slurry solution in which a condensate of resorcin and acetone is deposited, the precipitate may be dissolved by mixing an organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent that can dissolve precipitates among those that can be used in the first step, but acetone is preferably used from the viewpoint of liquid separation. The amount of the organic solvent used is preferably 2 parts by weight or less with respect to 1 part by weight of resorcin used in the first step. The amount of water used is preferably in the range of 0.5 to 3 parts by weight with respect to 1 part by weight of resorcin used in the first step.

For the purpose of increasing resorcin removal efficiency, the mixture may be washed with water under alkaline conditions by mixing a mixed solution obtained by mixing water and a base in the third step. The pH of the mixed solution obtained by mixing with the base may be in the range of 7 to 11, and more preferably in the range of 8 to 10. As the base, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal hydrogen carbonates such as sodium hydrogen carbonate, alkali metal carbonates such as sodium carbonate, and the like can be used. Is preferred, and sodium hydroxide is more preferred. The base is preferably used as an aqueous solution having an appropriate concentration.

  The temperature when washing and liquid separation is preferably in the range of 45 ° C or higher and 80 ° C or lower. The amount of residual resorcin can be confirmed by ordinary analytical means such as gas chromatography (GC), high performance liquid chromatography (HPLC), gel permeation chromatography (GPC), and while confirming the decrease in resorcin, The required number of water washing can be determined.

<Post-processing process>
If the organic solvent is removed by subjecting the mixture obtained in the second step or the third step to a post-treatment step including a treatment such as a filtration treatment and a concentration treatment, a condensate of resorcin and acetone can be taken out. it can.
The residual ratio of resorcin is preferably 2.0% by weight or less, and more preferably 1.0% by weight or less.

<Condensate obtained>
In the present invention, the “first eluting peak” means a peak having the shortest retention time among all peaks in a chromatogram obtained by analysis by gel permeation chromatography (differential refractive index detection). The “second eluting peak” means a peak having the second shortest retention time among all peaks in a chromatogram obtained by analysis by gel permeation chromatography (differential refractive index detection). “Elution peak” means a peak having the third shortest retention time among all peaks in a chromatogram obtained by analysis by gel permeation chromatography (differential refractive index detection).
In gel permeation chromatography (differential refractive index detection), the compound group consisting of the compound represented by formula (IV) and its isomer is taken as the first elution peak from the compound represented by formula (III) and its isomer. The compound group consisting of the compound represented by formula (I) and its isomer, and the compound group consisting of the compound represented by formula (II) and its isomer as the third elution peak, Detected.

The obtained condensate satisfies (1), (2) and (3).
(1) The ratio of the peak area derived from 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan to the total area of all peaks when gel permeation chromatography (differential refractive index detection) was analyzed (2) When gel permeation chromatography (differential refractive index detection) is analyzed, the area ratio of the first eluting peak to the total area of all peaks is in the range of 10 to 25%. (3) The weight average molecular weight of the first elution peak is in the range of 800 or more.

The weight average molecular weight of the first elution peak when gel permeation chromatography (differential refractive index detection) is analyzed is preferably 800-1200.
The content of 2,4,4-trimethyl-2′4′7-trihydroxyflavan contained in the obtained condensate is preferably in the range of 25 to 55% by weight, more preferably in the range of 30 to 50% by weight. preferable.
4,6-bis (7-hydroxy-2,4,4-trimethylchroman-2-yl) -1,3-benzenediol (compound represented by formula (I)) contained in the obtained condensate And isomers thereof, and 2,4-bis (7-hydroxy-2,4,4-trimethylchroman-2-yl) -1,3-benzenediol (compound represented by formula (II)) and its The total content of isomers is preferably in the range of 25 to 35% by weight.
The total content of the compound represented by formula (III) and its isomer contained in the obtained condensate is preferably in the range of 10 to 20% by weight.
The total content of the compound represented by formula (IV) and the isomers contained in the obtained condensate is preferably in the range of 10 to 25% by weight, and more preferably in the range of 10 to 20% by weight.

The softening point of the resulting condensate of resorcin and acetone is preferably 160 ° C. or lower, and more preferably 140 ° C. or lower.
The resulting condensate of resorcin and acetone can be used as a rubber reinforcing agent. It is particularly useful as a reinforcing agent for rubber for tires.

  Next, a rubber composition containing a condensate of resorcin and acetone, a rubber component, a filler, and a sulfur component will be described.

  Examples of the rubber component include natural rubber, styrene butadiene copolymer rubber, butadiene rubber, isoprene rubber, and the like, and rubber components containing these as main components. The amount of the condensate of resorcin and acetone is preferably in the range of 0.5 to 3 parts by weight and more preferably in the range of 1 to 2 parts by weight with respect to 100 parts by weight of these rubber components.

  Examples of the filler include carbon black, silica, talc, clay and the like that are usually used in the rubber field, and carbon black is more preferably used. As the carbon black, carbon black such as HAF (High Abrasion Furnace), SAF (Super Abrasion Furnace), ISAF (Intermediate SAF) is preferable. It is also preferable to combine several kinds of fillers such as a combination of carbon black and silica. The amount of the filler used is preferably in the range of 10 to 100 parts by weight per 100 parts by weight of the rubber component. More preferably, it is 30-70 weight part.

  Examples of the sulfur component include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Powdered sulfur and insoluble sulfur are preferred. The amount of the sulfur component used is preferably in the range of 1 to 10 parts by weight per 100 parts by weight of the rubber component. More preferably, it is 2 to 6 parts by weight.

  Furthermore, a rubber composition can be produced using a vulcanization accelerator, a methoxylated methylol melamine resin, an organic cobalt compound, zinc oxide and the like.

  Examples of vulcanization accelerators include thiazole-based vulcanization accelerators and sulfur compounds described on pages 412 to 413 of Rubber Industry Handbook <Fourth Edition> (issued by the Japan Rubber Association on January 20, 1994). Examples thereof include phenamide vulcanization accelerators and guanidine vulcanization accelerators. The amount of the vulcanization accelerator used is preferably in the range of 0.5 to 1 part by weight per 100 parts by weight of the rubber component. More preferably, it is 0.6-0.8 weight part.

  Examples of the methoxylated methylol melamine resin include those usually used in the rubber industry such as hexakis (methoxymethyl) melamine, pentakis (methoxymethyl) methylol melamine, and tetrakis (methoxymethyl) dimethylol melamine. Hexakis (methoxymethyl) melamine alone or a mixture based on it is preferred. These methoxylated methylol melamine resins can be used alone or in combination, and the blending amount thereof is preferably in the range of 0.5 to 6.0 parts by weight with respect to 100 parts by weight of the rubber component. A range of ˜3.0 parts by weight is more preferable.

  Examples of the organic cobalt compound include acid cobalt salts such as cobalt naphthenate and cobalt stearate, and fatty acid cobalt / boron complex compounds (for example, trade name “Manobond C (registered trademark)” manufactured by Manchem). . The amount of the organic cobalt compound used is preferably in the range of 0.1 to 0.4 parts by weight, more preferably in the range of 0.1 to 0.3 parts by weight, based on 100 parts by weight of the rubber component.

  In addition, various rubber chemicals commonly used in the rubber industry, for example, antioxidants such as antioxidants and ozone deterioration inhibitors, peptizers, processing aids, waxes, oils, stearic acid, tackifiers One or more of these may be used in combination as necessary. The compounding amount of these chemicals varies depending on the use of the rubber composition, but an amount in a range usually used in the rubber industry can be used.

  The rubber composition can be derived into a rubber product through a process such as molding and vulcanization, for example, in accordance with a method commonly practiced in the rubber industry. In particular, it can be used for various members of tires such as cap treads, under treads, belts, carcass, beads, sidewalls, rubber chafers and the like. Further, it can also be used for anti-vibration rubbers for automobiles such as engine mounts, strut mounts, bushes and exhaust hangers, hoses, rubber belts and the like.

  For example, a tire belt can be manufactured by coating a steel cord with a rubber composition. Steel cords are usually used in an aligned state.

  From the viewpoint of adhesion to rubber, the steel cord is preferably plated with brass, zinc, or an alloy containing nickel or cobalt, and is preferably subjected to brass plating. is there. In particular, a steel cord subjected to a brass plating process in which the Cu content in the brass plating is 75% by weight or less, preferably 55 to 70% by weight is suitable. The twist structure of the steel cord is not limited.

  A plurality of belts may be laminated and used. The belt is mainly used as a carcass reinforcing material.

  In addition, for example, a carcass can be manufactured by extruding a rubber composition in accordance with a carcass shape of a tire and attaching the rubber composition on the upper and lower sides of a carcass fiber cord. The carcass fiber cord is usually used in a state of being aligned in parallel. As the carcass fiber cord, preferred is an inexpensive polyester that has good elastic modulus and fatigue resistance and excellent creep resistance. These are used as a tire reinforcing material by laminating one sheet or a plurality of sheets.

  A pneumatic tire can be manufactured by a normal manufacturing method using a rubber composition. For example, a rubber composition is extruded to obtain a tire member, which is pasted and molded on another tire member by a normal method on a tire molding machine to form a raw tire. The green tire is heated and pressed in a vulcanizer to obtain a tire.

Hereinafter, the present invention will be specifically described with reference to Examples and Test Examples. In the following examples, the contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan, resorcin, and the like were the same as the values determined by the GPC area percentage method.
In GPC analysis, the compound group consisting of the compound represented by formula (IV) and its isomer is the first eluting peak, and the compound group consisting of the compound represented by formula (III) and its isomer is the second eluting peak. As a result, the compound represented by the formula (I) and its isomer, and the compound group consisting of the compound represented by the formula (II) and its isomer were detected as the third elution peak.
The softening point was carried out according to JIS K 6220-1.
<GPC analysis conditions>
Column: TOSOH TSGel Super HZ2000 (4.6mmφx150cm) and two TOSOH TSGel Super HZ1000 (4.6mmφx150cm) connection temperature: 40 ° C
Mobile phase: Tetrahydrofuran Detector: RI

Example 1
A 1000 ml separable flask equipped with a thermometer, a stirrer and a condenser was charged with 88.1 g (0.80 mol) of resorcin, and the inside of the flask was purged with nitrogen. Then, 81.3 g (1.40 mol) of acetone and 264 g of toluene were added. Charged and heated to 40 ° C. Thereto was charged 2.31 g of p-toluenesulfonic acid hydrate, and the resulting mixture was heated to an internal temperature of 65 ° C. and kept for 7 hours.
Then, after cooling to 60 degreeC of internal temperature, it neutralized with 10% sodium hydroxide aqueous solution, and charged the acetone 58.1g (1.00 mol), and dissolved the reaction substance completely. Furthermore, 220 g of hot water was charged at the same temperature, and the pH was adjusted to alkaline (9.0) with a 10% aqueous sodium hydroxide solution, and then unreacted resorcin was removed by liquid separation washing. Separation and washing were repeated until the content of resorcin was 1% or less, followed by drying at 80 ° C. for 12 hours under reduced pressure of 1 KPa or less to obtain 113 g of a resorcin-acetone condensate. The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin in the obtained condensate were as follows. 2,4,4-trimethyl-2'4'7-trihydroxyflavan: 31.1%
Resorcin: 0.5%
First eluting peak: 16.3%
Weight average molecular weight of first elution peak: 1030
Second eluting peak: 19.7%
Third elution peak: 30.2%
Softening point 116 ° C

Example 2
A 1000 ml separable flask equipped with a thermometer, a stirrer and a condenser was charged with 88.1 g (0.80 mol) of resorcin, and the inside of the flask was purged with nitrogen. Then, 81.3 g (1.40 mol) of acetone and 264 g of toluene were added. Charged and heated to 40 ° C. Thereto was charged 2.31 g of p-toluenesulfonic acid hydrate, and the resulting mixture was heated to an internal temperature of 60 ° C. and kept for 7 hours. Thereafter, 55.8 g (0.96 mol) of acetone was charged at the same temperature, and the temperature was further maintained for 6 hours while maintaining the internal temperature at 60 ° C.
Thereafter, the reaction product was completely dissolved by neutralizing with a 10% aqueous sodium hydroxide solution and charging 13.9 g (0.24 mol) of acetone while keeping the internal temperature at 60 ° C. Furthermore, 220 g of hot water was charged at the same temperature, and the pH was adjusted to alkaline (9.0) with a 10% aqueous sodium hydroxide solution, and then unreacted resorcin was removed by liquid separation washing. Separation and washing were repeated until the content of resorcin was 1% or less, followed by drying under reduced pressure of 1 KPa or less at 80 ° C. for 12 hours to obtain 112 g of a condensate of resorcin and acetone. The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin in the obtained condensate were as follows. 2,4,4-trimethyl-2'4'7-trihydroxyflavan: 33.9%
Resorcin: 0.3%
First eluting peak: 19.2%
Weight average molecular weight of first elution peak: 1059
Second eluting peak: 19.5%
Third elution peak: 25.8%
Softening point 119 ℃

Example 3
A 1000 ml separable flask equipped with a thermometer, a stirrer and a condenser was charged with 88.1 g (0.80 mol) of resorcin, and the inside of the flask was purged with nitrogen. Then, 81.3 g (1.40 mol) of acetone and 264 g of toluene were added. Charged and heated to 40 ° C. Thereto was charged 2.31 g of p-toluenesulfonic acid hydrate, and the resulting mixture was heated to an internal temperature of 60 ° C. and kept for 7 hours. Thereafter, 46.5 g (0.80 mol) of acetone was charged at the same temperature, and the mixture was further kept at the internal temperature of 60 ° C. for 2 and a half hours.
Thereafter, the reaction product was completely dissolved by neutralizing with a 10% aqueous sodium hydroxide solution and charging 20.9 g (0.36 mol) of acetone while keeping the internal temperature at 60 ° C. Furthermore, 220 g of hot water was charged at the same temperature, and the pH was adjusted to alkaline (9.0) with a 10% aqueous sodium hydroxide solution, and then unreacted resorcin was removed by liquid separation washing. Separation and washing were repeated until the content of resorcin was 1% or less, followed by drying under reduced pressure of 1 KPa or less at 80 ° C. for 12 hours to obtain 112 g of a condensate of resorcin and acetone. The contents of 2,4,4-trimethyl-2′4′7-trihydroxyflavan and resorcin in the obtained condensate were as follows. 2,4,4-trimethyl-2'4'7-trihydroxyflavan: 39.4%
Resorcin: 0.7%
First eluting peak: 16.0%
Weight average molecular weight of first elution peak: 1051
Second eluting peak: 17.1%
Third elution peak: 24.6%
Softening point 124 ° C

Example 4 (Production of rubber composition)
Using a 0.6 liter lab plast mill, with an initial system temperature of 110 ° C., first, natural rubber (RSS # 1) is added and masticated for 3 minutes, and then carbon Black (N330), hydrous silica, stearic acid, zinc white, anti-aging agent (2,2,4-trimethyl-1,2-dihydroquinoline condensate) and the condensate obtained in Example 1 were added for 5 minutes. Kneaded and discharged. Next, the discharged rubber was transferred to an open roll, the initial product temperature was set to 60 ° C., sulfur, vulcanization accelerator (N, N-dicyclohexyl-2-benzothiazylsulfenamide), methoxylation shown in the following formulation A rubber composition was obtained by adding a methylol melamine resin (Sumikanol 507AP (manufactured by Sumitomo Chemical Co., Ltd.)) and cobalt naphthenate while kneading while controlling the temperature of the rubber to 80 ° C. or less.

<Combination prescription>
・ Natural rubber (RSS # 1) 100 parts ・ N330 carbon black 45 parts ・ Hydrosilicate silica (Nipsil AQ manufactured by Tosoh Silica Co., Ltd.) 10 parts ・ Stearic acid 3 parts ・ Zinc flower 5 parts by weight ・ Anti-aging agent (2, 2,4-trimethyl-1,2-dihydroquinoline condensate) 2 parts, component A (condensate of resorcin and acetone obtained in Example 1) 2 parts, sulfur 5 parts, vulcanization accelerator (N, N- 0.7 part of dicyclohexyl-2-benzothiazylsulfenamide) 4 parts of methoxylated methylol melamine resin (Sumikanol 507AP (Sumitomo Chemical Co., Ltd.)) (2.6 parts of active ingredient)
・ Cobalt naphthenate 2 parts (cobalt content 0.2 parts)

Example 5 (Production of rubber composition)
In Example 4, a rubber composition was obtained in the same manner as in Example 4 except that the condensate obtained in Example 2 was used instead of the condensate obtained in Example 1.

Example 6 (Production of rubber composition)
In Example 4, a rubber composition was obtained in the same manner as in Example 4 except that the condensate obtained in Example 3 was used instead of the condensate obtained in Example 1.

Example 7 (Production of tire belt and tire using the same)
A belt is obtained by covering the steel cord subjected to the brass plating treatment with the rubber composition obtained in Example 4. A tire is obtained by forming a green tire using the obtained belt according to a normal production method and heating and pressing the obtained green tire in a vulcanizer.

Example 8 (Production of tire carcass and tire using the same)
By extruding the rubber composition obtained in Example 4, a rubber composition having a shape corresponding to the carcass shape is prepared, and carcass is obtained by applying the rubber composition on top and bottom of a polyester carcass fiber cord. Using the obtained carcass, a tire is obtained by molding a green tire according to a normal manufacturing method and heating and pressing the obtained green tire in a vulcanizer.

Example 9 (Tire Cap Tread and Manufacturing of Tire Using This)
The rubber composition obtained in Example 4 is extruded to obtain a cap tread. Using the obtained cap tread, a tire is obtained by molding a green tire according to a normal production method and heating and pressing the obtained green tire in a vulcanizer.

Example 10 (Production of tire undertread and tire using the same)
The rubber composition obtained in Example 4 is extruded to obtain an undertread. Using the obtained undertread, a tire is obtained by molding a green tire according to a normal manufacturing method and heating and pressing the obtained green tire in a vulcanizer.

According to the production method of the present invention, the residual amount of unreacted resorcin can be reduced.
The condensate of resorcin and acetone obtained by the production method of the present invention is excellent in performance as a reinforcing agent for various rubber compositions, and can also prevent deterioration of the working environment due to transpiration of residual resorcin during processing of the rubber composition. Therefore, it is industrially advantageous.

Claims (9)

A first step of reacting resorcin and acetone in the presence of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate,
The amount of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate with respect to resorcin is 0.1 to 10 mol%.
A method for producing a condensate of resorcin and acetone satisfying the following (1), (2) and (3).
(1) The ratio of the peak area derived from 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan to the total area of all peaks when gel permeation chromatography (differential refractive index detection) was analyzed (2) When gel permeation chromatography (differential refractive index detection) is analyzed, the area ratio of the first eluting peak to the total area of all peaks is in the range of 10 to 25%. (3) The weight average molecular weight of the first elution peak is in the range of 800 or more. The first step is a step of reacting resorcin and acetone in the presence of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate and an organic solvent. Manufacturing method. A first step of reacting resorcin and acetone in the presence of at least one selected from the group consisting of p-toluenesulfonic acid and p-toluenesulfonic acid hydrate;
A second step of mixing the mixture obtained in the first step with a base;
A third step of washing the mixture obtained in the second step with water;
The manufacturing method of Claim 1 or 2 containing. A condensate obtained by the production method according to claim 1. The rubber composition containing the condensate obtained by the manufacturing method of any one of Claims 1-3, a rubber component, a filler, and a sulfur component. A tire belt comprising a steel cord coated with the rubber composition according to claim 5. A tire carcass comprising a carcass fiber cord coated with the rubber composition according to claim 5. A tire tread or a tire undertread comprising the rubber composition according to claim 5. A pneumatic tire produced by processing the rubber composition according to claim 5.
''