TW201238958A - Method for producing condensate of resorcin and acetone, and rubber composition including condensate - Google Patents

Abstract

This method for producing a condensate of resorcin and acetone includes: a step for reacting resorcin and acetone in the presence of an acid; and a step for removing, in the presence of an acid, water produced as a byproduct of the reaction.

Description

201238958 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a condensate of isophthalic acid and acetone, a rubber composition containing the condensate, and the like. [Prior Art] A condensate of resorcinol and acetone is used as a reinforcing agent for various rubber compositions. JP-A-2004-243 No. 1 discloses a method for producing a method in which resorcinol and acetone are reacted in the presence of an acid and an organic solvent, and then neutralized with an aqueous solution of cerium oxide, and further The neutralized mixture was dried under reduced pressure to obtain a condensate of resorcinol and acetone. SUMMARY OF THE INVENTION The present invention provides the following: &lt;1;&gt; A method for producing a condensate of resorcinol and acetone, comprising: a step of reacting resorcinol with acetone in the presence of an acid And the step of removing the water by-produced by the above reaction in the presence of I; &lt;2&gt; The manufacturing method of &lt;2&gt; as described above, which comprises: performing the treatment of m-diphenol and acetone in the presence of an acid a step of removing the water by-produced by the above reaction in the presence of hydrazine, and a step of mixing the mixture after removing the water with a base; &lt;3&gt; : a step of reacting resorcinol with acetone in the presence of an acid, 162280.doc 201238958 a step of a by-product water step, and a step of combining; removing the water after removal by the above reaction in the presence of an acid And a mixture of the mixture of the mixture of the acetone and the acetone, and the mixture of the mixture of the above-mentioned reaction, wherein the water produced by the above reaction is removed in the presence of an acid. The steps are based on acid and organic The step of removing the water by-produced by the above reaction in the presence of a solvent; &lt;5&gt; The method of producing the water by the above reaction in the presence of an acid and an organic solvent, as described in the above &lt;4&gt; And a step of removing the water by-produced by the above reaction with an organic solvent in the presence of an acid and an organic solvent, thereby removing; &lt;6&gt;&lt;4&gt; or &lt;5&gt; The organic solvent is an aromatic hydrocarbon. The method of the above <6>, wherein the aromatic hydrocarbon is toluene or diphenylbenzene; &lt;8&gt; is as described above in &lt;&gt;&gt; to &lt;7&gt; A method of producing, wherein the acid is at least one selected from the group consisting of p-toluenesulfonic acid, p-toluenesulfonic acid hydrate, hydrochloric acid, and sulfuric acid; &lt;9&gt; a rubber composition comprising The condensate, the rubber component, the filler, and the sulfur component obtained by the production method according to any one of the above-mentioned items <8>, wherein the belt layer for a tire is contained as described above. &lt;9&gt; The steel cord covered by the rubber composition. &lt;u&gt; - A tire carcass comprising a carcass fiber cord coated with the rubber composition as described in <9> above; 162280.doc 201238958 12&gt; Tyre rubber for tires or base rubber for tires And the rubber composition of the above &lt;9&gt;; ^13 kinds of pneumatic tires which are produced by processing the rubber composition as described above in &lt;9&gt;;&lt;14&gt; a resorcinol a condensate with acetone which satisfies the following (1), (2), and (3): ^(1) at #! by gel permeation chromatography (differential refractive index detection) when the condensate is subjected to cleavage analysis The ratio of the area of the peak generated by the 2,4,4-trimethyl-2,4,7-trihydroxyflavone relative to the total area of all the peaks is in the range of 3 0 to 5 5 ; (2) When the condensate is subjected to a solution by gel permeation chromatography (differential refractive index detection), the ratio of the area of the first elution peak to the total area of all the peaks is in the range of 20 to 50%; (3) The weight average molecular weight of a dissolved peak is in the range of 15 〇〇 to 17 ;; &lt;15&gt; The condensate of the above &lt;14&gt; has a softening point of 16 〇. The condensate of the above &lt;14&gt; or &lt;15&gt; is stored at 12 Torr for 1 hour, and the rate of increase of the benzenediol is 2% or less. [Embodiment] The production method of the present invention is a process for producing a condensate of resorcinol and acetone, which comprises the steps of: reacting resorcin with acetone in the presence of an acid, and removing it in the presence of an acid. The step of water by-produced by the above reaction. &lt;Step of reacting resorcin with acetone in the presence of an acid (hereinafter, J62280.doc 201238958 may be referred to as "first step")&gt; A commercial product may be used for resorcin. The acetone may also be used in the range of 1.5 mol, more preferably 1.5 to 4 mol, based on the amount of the resorcinol i mo丨. When the amount of acetone used is i m 〇丨 or more, there is a tendency to reduce the residual ratio of unreacted benzenediol. The acid acts as a catalyst in the reaction between resorcin and acetone, and may be described as "acid catalyst" hereinafter. Specific examples of the acid include benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid hydrate, oxalic acid, phosphoric acid, polyphosphoric acid, borofluoric acid, hydrochloric acid, and sulfuric acid. Among them, at least one acid selected from the group consisting of p-toluenesulfonic acid, p-toluenesulfonic acid hydrate, hydrochloric acid and sulfuric acid is preferred. These acids can be used either directly or in the form of an aqueous solution of a suitable concentration. The amount of acid used is not limited to the range of 〇·ι~1〇 m〇i, and more preferably 〇5 to 5 m〇i. The reaction of m-phenylene with acetone is preferably carried out in the presence of an organic solvent. The organic solvent may, for example, be an aliphatic hydrocarbon, an aromatic hydrocarbon or a dentate-substituted aromatic hydrocarbon. Specific examples of the aliphatic hydrocarbons include hexane, heptane, octane, and decane; and specific examples of the aromatic hydrocarbons include toluene, xylene, and ethylbenzene; Specific examples of the hydrocarbons include gas and benzene. It is preferably an aromatic hydrocarbon, more preferably toluene or xylene. The amount of the organic solvent to be used is preferably in the range of 0.5 to 3 parts by weight based on 1 part by weight of the resorcin. The reaction temperature of the reaction of m-phenylene and propylene is preferably in the range of 3 Å or more and 65 ° C or less. The reaction can be carried out by gas chromatography (GC, chromatography), high performance liquid chromatography (ΗΡιχ, Η·162280.doc -6 · 201238958 performance liquid chromatography), gel permeation a ◊ chromatography (GPC, gel-permeation chromatography), etc., confirming the normal analysis, and confirming the progress of the reaction, determining the reaction end point, the order of mixing the resorcinol, acetone, and acid is not limited, for example, The mixture is reacted with acetone in the presence of an organic solvent as needed, and the obtained mixture is mixed with an acid at a reaction temperature to react. Further, acetone may be continuously added to the mixture as the reaction progresses. As the reaction proceeds, 2,4,4_trif-based 2,4,7-7-trisole, which is one of the compounds contained in the condensate of the benzene __, precipitates in order to prevent precipitation. 2,4,4·trimethyl-2·,4, stilbene flavonoids are fixed on the wall of the reaction vessel (so-called scale), and 2,4,4_^methyl·2' can also be used. 4',7-trihydroxyflavone as seed crystal. Further, HA·trimethyl _ 2·'4', 7-trihydroxyflavone is a compound represented by the following formula. HO, a η

As a compound contained in the condensate of meta-phenylene and acetophenone, 1 fluorene-trisyl group, 2., 4, 7-trisyl flavonoid (compound represented by the following formula)

162 162280.doc 201238958, exemplified by 7,7-dihydroxy-4,4,4',4'-tetradecyl-2,2·-spirobicyclohexane (compound represented by the following formula), H3c chs h3c ch8 4,6-bis(7-hydroxy-2,4,4-trimethylchroman-2-yl)-1,3-benzenediol (compound represented by formula (I)) and its Structure,

H3c ch3 2,4-bis(7-hydroxy-2,4,4-trimethylchroman-2-yl)-1,3-benzenediol (compound represented by formula (II)) and its isomer Object,

a compound represented by formula (III) and an isomer thereof, and h3c. xh3

162280.doc (IV) (IV) 201238958 A compound represented by the formula (ιν) and an isomer thereof,

[in the formula (IV), 'n represents an integer of 2 or more>. &lt;Step of removing water by-produced by the above reaction in the presence of an acid (hereinafter sometimes referred to as "second step")&gt;; removal of reaction by resorcinol and acetone in the presence of the text The step of raw ice can also be carried out simultaneously with the step of reacting resorcinol with acetone in the presence of an acid 'but effective for water removal, preferably for the purpose of making isophthalic acid and acetone in acid After the reaction is carried out in the presence of water, the water by the above reaction is removed in the presence of an acid. The mixture obtained by removing water in this step contains a condensate of isophthalic acid and acetone and an acid. It can also be carried out by using a substance capable of adsorbing water or a substance which can decompose water, and the addition of steam (4) is carried out, and (4) 11 is obtained by the organic solvent and water m in the presence of an organic solvent, and the water usually contains water. Or co-divisional 'but in the case of separation into an organic layer and an aqueous layer ^ separate into the dewatering layer of the hydrophobic water, and the organic layer is restored to Kunqu, preferably only to the mixture obtained by removing the water It is preferable that the removal of water is preferably carried out until the water content is G-grass to 2 weights and 4 weights.

162280, (j〇Q 201238958 As an organic solvent, an organic solvent used in the reaction of resorcin and acetone is usually used, but an organic solvent similar to this can be used. As an organic solvent, pentane is mentioned. An aliphatic hydrocarbon such as an alkane, hexane or heptane; an alicyclic hydrocarbon such as cyclopentane, cyclohexane or methylcyclohexane; an aromatic hydrocarbon such as stupid, toluene or diphenylbenzene; a chlorinated hydrocarbon such as four gasified carbon, three gas ethylene, four gas ethylene, two gas ethylene, chlorinated benzene, a acetonitrile such as methyl acetate, ethyl acetate, propyl acetate or the like, and a nitrile such as acetonitrile. Among them, aroma is preferred. The family cigarette is more preferably benzene or diphenyl. The mixture obtained by the first step and the second step can be directly delivered to the following post-treatment step, or can be further delivered to the following step 3 as needed. Then, it is delivered to the post-treatment step. <The step of mixing the mixture after removing water with acetone (hereinafter, sometimes referred to as "the third step" is more preferable to remove the resorcinol and acetone in the presence of acid. The mixture after the reaction with the water is mixed with acetone. The third step is a step of reacting with the acetone in the mixture of the condensate of the diphenanthrene and the acetone and the acid, and reacting with the acetone. The amount of acetone used in the third step is the same as that used in the third step. The total amount of acetone used may be in the range of 1 to 6 m〇l relative to the amount of the resorcinol 1 〇1〇1 used in the second step. It may also be in the third step as needed. The acid or organic solvent is used. The reaction temperature in the third step is preferably in the range of 3 〇 C or more and 65 〇 。. Further, the third step can be carried out while removing water. With respect to water removal, the second step can be performed. The third step is to use the usual analysis method such as GC, hplc, GPC, etc. 162280.doc •10-201238958 to make ι2'4,4-mercapto-2''4,7-trihydroxyflavone The content of phenol is one of the best for the winter, the hand and the room, i, c _ until these are the desired range 'can be implemented in this way. &lt;post-processing steps> will be the second Step or step 3, t, ; ^ ^ ^. 侍之混5 delivery to include filtering Ge / Chen Xi·# The treatment step ψ, the soil cockroach 丄 - remove the organic solvent, thereby obtaining the condensate of the meta-diphenol and acetone. &lt;Step of mixing the mixture after removing water&gt; in the second step or the third After the step is neutralized with a base, the solid solution is attached to the obtained solid by washing with water or by filtration. "If necessary, the salt formed by the catalyst or neutralized is carried out. After washing with water, the organic solvent is removed. The gas "" 乍 test" can be enumerated: sodium hydroxide, = potassium, 4 metal hydroxide, sodium bicarbonate, etc., metal carbonate, carbonic acid, sodium carbonate, etc. Depressed, etc., preferably alkali metal hydroxide,

More preferably, it is sodium oxide. The base is preferably used in A. (4) Preferably, the residual ratio of resorcinol is less than or equal to % of the aqueous solution in an appropriate concentration. It is preferably 5.% by weight or less, more preferably! "Heavy &lt; Obtained Condensate&gt; In the present invention, the term "gel permeation chromatography m" means: the layer obtained when the condensate is analyzed by the centrifugation rate detection of coagulation) In the figure, the right oil 1 t 1颂· "/ peak, the peak with the shortest retention time; so-called ^; skin peak" means: using gel permeation chromatography to detect the condensate) In the chromatogram obtained at the time 162280.doc 201238958: Peak:: the second shortest peak of the retention time; the stomach "third gel permeation chromatography (showing the third short peak. Among all the peaks, The retention time is included in the gel permeation chromatography (differential refractive index detection): the compound group of the compound and its isomer is set as the peak, and the compound represented by the formula (III) and the wave are included. The compound group 2 of the structure-dissolution "' contains the compound represented by the formula (1) and its isomer and the compound represented by the formula (II) and the compound group thereof of the isomer thereof are again the first, and the peak is combined The detection is performed separately. The condensate obtained preferably satisfies the following (1), (7) (3) Condensate. When using gel permeation chromatography (differential refractive index detection) for condensate, due to 2,4,4-trimethyl-2,41,7-trihydroxyflavone The ratio of the generated wave area to the total area of all the peaks is 3 (four) $; (7) When the condensate is analyzed by gel permeation chromatography (differential refractive index detection), the area of the first eluted peak is relative to all The ratio of the total area of the peaks is in the range of 20 to 50%; (3) The weight average molecular weight of the first elution peak is in the range of (9) (b) _. The condensate of the obtained condensate preferably has a softening point of i6 〇t or less. The obtained condensate is preferably J 2 〇. The increase rate of the benzene age is 2% or less after storage for 24 hours. 162280.doc 201238958 Methyl-2',4',7-trihydroxy yellow The content of 2,4,4-trione contained in the condensate obtained by more preferably 35 to 50 parts by weight is preferably in the range of 30 to 55 % by weight. 4,6·bis(7,yl-2,4,4•trimethylchroman-2-yl H,3-benzenediindole (a compound represented by the formula (1)) and its isomerization,And the content ratio of 2 buckets (7-carbyl-2,4'4_trimethylchromanyl h,3•benzoic acid (the compound represented by formula (II)) and its isomers It is preferably in the range of 5 to 10% by weight. The total content of the compound represented by the formula _ and the isomer thereof contained in the obtained condensate is preferably in the range of 5 to 15% by weight. The content of the compound represented by the formula (IV) and the total amount of the isomer thereof contained in the product is preferably in the range of 2 Å to 5 Å by weight, more preferably in the range of 25 to 35% by weight. A condensate of resorcinol and acetone can be used as a reinforcing agent for rubber. In particular, it is used 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 a rubber component containing these as a main component. The amount of the condensate of resorcin and acetone is preferably in the range of from 0.5 to 3 parts by weight, more preferably from 1 to 2 parts by weight, per 100 parts by weight of the rubber component. Examples of the filler include carbon black, cerium oxide, talc, and clay which are generally used in the rubber field, and carbon black is more preferably used. As carbon black, it is preferable that I62280.doc .13· 201238958 is HAF (High Abrasion Furnace),

Carbon black such as Abrasion Furnace, super wear-resistant carbon black, SAF, medium wear-resistant carbon black. Further, it is also preferable to use a combination of a plurality of fillers such as carbon black and sulphur trioxide. The amount of the filler to be used is preferably in the range of 1 Torr to 1 Torr, more preferably in the range of 30 to 70 parts by weight per 1 part by weight of the rubber component. Examples of the sulfur component include sulfur powder, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur, and sulfur powder and insoluble sulfur are preferred. The amount of the sulfur component to be used is preferably in the range of 2 to 6 parts by weight based on 100 parts by weight of the rubber component. Further, a rubber composition can be produced using a vulcanization accelerator, a methoxylated methylol melamine resin, an organic cobalt compound, and zinc oxide. As an example of the vulcanization accelerator, there are thiazole-based vulcanization accelerators, which are contained in 412 to 413 pages of 412 to 413 pages of the Rubber Industry Fact Sheets, "The Fourth Edition" (issued by the Japan Rubber Association, January 20, 2008). A sulfoximine vulcanization accelerator and an oxime vulcanization accelerator. The amount of the vulcanization accelerator to be used is preferably in the range of 0.5 to 1 part by weight, more preferably in the range of 0.6 to 0.8 part by weight, per 100 parts by weight of the rubber component. Examples of the methoxylated methylol melamine resin include hexakis(methoxymethyl)melamine, penta(methoxymethyl)hydroxymethylmelamine, and tetrakis(methoxymethyl)dimethylol melamine. The usual user in the rubber industry is preferably 'single hexa(methoxymethyl)melamine alone or a mixture thereof as a main component. These methoxylated methylol melamine resins may be used singly or in combination of two or more kinds, and the amount thereof is preferably in the range of 0.5 to 6.0 parts by weight based on 100 parts by weight of the rubber 162280.doc 201238958 component. More preferably, it is a range of 1·〇~3·〇 by weight. Examples of the organic cobalt compound include acid cobalt salts such as cobalt naphthenate and cobalt stearate, or fatty acid cobalt and boron complex compounds (for example, trade name "Man〇b〇nd C (5 main volume trademark)": The amount of the organic cobalt compound to be used by Manchem is preferably in the range of 0.1 to 0.4 parts by weight, more preferably in the range of 〇1 to 〇3 parts by weight, based on 100 parts by weight of the rubber component. Various rubber chemical buckles commonly used in the rubber industry, such as anti-aging agents such as antioxidants or anti-odor oxidizing agents, peptizers, processing aids, waxes, oils, stearic acid, adhesives, etc., may be used as needed. The amount of the chemicals may vary depending on the use of the rubber composition, but the amount generally used in the rubber industry may be used. The rubber composition is, for example, based on the rubber industry. The method generally carried out can be derivatized into a rubber product β, in particular, various components that can be used for a tire, such as a tread rubber, a base rubber, a belt layer, a carcass, a bead, and a sidewall, through steps of forming, vulcanization, and the like. , rubber blankets, etc. Also, it can be used for anti-vibration rubber, hoses, rubber belts, etc. for engines such as engine feet, shock absorber seats, bushings, exhaust pipe hangers, etc. For example, 'by rubber combination The steel cord is coated with a steel belt to produce a belt layer for a tire. The steel cord is usually used in a state of lacy. In terms of adhesion to rubber, the steel cord is preferably made of yellow steel or zinc. An alloy containing nickel or cobalt is subjected to a plating treatment, and particularly preferably a brass plating treatment is carried out. In particular, a 162280.doc 15 201238958 having a mouthwash in brass plating is used, and the content is 75 wt% or less. Preferably, the brass-plated steel cord is preferably 55 to 70% by weight. The twisted structure of the steel cord is not limited. The belt layer may also be used in a plurality of layers. The belt layer is mainly used as a tire. Further, for example, 'the rubber composition may be extrusion-processed according to the carcass shape of the tire' and attached to the carcass fiber cord above and below, thereby producing a carcass month. Usually used in a state of parallel lagging. As a carcass fiber The cord is preferably a polyester which is excellent in modulus of elasticity and fatigue resistance, excellent in creep resistance, and inexpensive, and is used as a tire reinforcing material by using an i-piece or a plurality of laminated sheets. The pneumatic tire is manufactured by a usual manufacturing method, for example, 'the rubber composition is subjected to extrusion processing to obtain a member for a tire', and then attached to other tire members by a usual method on a tire molding machine to form a yarn. The tire is obtained by heating and pressurizing the green tire in a vulcanizer. EXAMPLES Hereinafter, in the examples and the following examples, 2,4,4-trisole 2 will be specifically described by way of examples and test examples. 4|7, -^ The content of 2,4,7-dihydroxyflavone and m-phenylene phenol is determined by the Gpc method--(9) (four) hundred-knife rate method. The softening point is measured according to JIS Κ6220 -1 implementation. Show "parts by weight". Further, in the examples, the "parts" table contains a compound of the formula (Ιν _, a set-dissolved peak, a compound, an isomer thereof, and an isomer thereof) in a GPC analysis. The group represents the compound, and the compound represented by the formula 162280.doc 201238958 (I), and the isomer thereof, and the compound represented by the formula (II) and the compound group thereof The third elution peak was detected. &lt;GPC analysis conditions&gt; Column: TOSOH TSGel Super HZ2000 (4.6 mm Lu xl5〇cm) was connected to TOSOH TSGel Super HZ1000 (4.6 mm x l50 cm)

Temperature: 40 ° C Mobile phase: Tetrahydrofuran detector: RI Example 1 Adding resorcinol 198.2 g (1.8 mol) to a 1000 ml four-necked flask equipped with a thermometer, a mixer and a condenser After replacing the inside of the flask with nitrogen, 167.3 g (2.88 mol) of acetone and 501 g of toluene were added. After the obtained mixture was heated to 40 ° C, 1.98 g of 98% sulfuric acid was added. The obtained mixture was allowed to warm to an internal temperature of 60 ° C and kept for 4 hours. Thereafter, the inside of the flask was depressurized while the internal temperature was 60 C, and water was removed from the reaction system. At this temperature, 52.3 g of acetone (〇9 mol) was added, and the inside of the flask was depressurized. The water was removed in the reaction system, and the obtained mixture was kept at 6 (rc) for 2 hours. Thereafter, it was neutralized with a 10% aqueous sodium hydroxide solution, and further reduced by KPa or less at 8 G ° C. After drying for 12 hours, 313 g of a condensate of isophthalic acid and propylene was obtained. 2,4,4-trimethyl-2·,4,,7·di-based flavonoids and a mixture were obtained in the obtained condensate. The content of diphenol is as follows: 2,4,4-trimethyl-2i,4,,7-trihydroxyflavone: 44 4% I62280.doc -17- 201238958 Benzene: 0,7〇/. First elution peak: 34.1% Weight average molecular weight of the first elution peak: 1441 Softening point: 144 ° C Example 2 In a 500 ml four-necked flask equipped with a thermometer, a stirrer, and a condenser, 88.1 g of streptophenol was added ( 〇.8 mol), after replacing the inside of the flask with nitrogen, 'add 65.0 g of acetone (1.1 mol) and 132 g of toluene. After warming to 4 ° C, add 98% barium sulfate .88 g ^ and warm the mixture to an internal temperature of 50 ° C for 4 hours. After that, enter &quot;f亍 / dish until the internal temperature is 6 〇c' and the inside of the flask was decompressed and the water was removed from the reaction system. After returning to normal pressure, it was cooled to 45. After 〇, 69.7 g (1.2 mol) of acetone was added, and the obtained mixture was obtained. The mixture was kept at this temperature for 3.5 hours. Thereafter, it was neutralized with a 1% by weight aqueous sodium hydroxide solution, and further dried under a reduced pressure of 1 KPa at 8 (rc) for 12 hours to obtain resorcinol and acetone. The condensate 丨 36 g. The contents of 2,4'4-trimethylidene-2,4,7-trihydroxyflavone and resorcinol in the obtained condensate are as follows. 2, 4, 4-trimethyl-2',4',7-trihydroxyflavone: 50.4% by weight Resorcinol: 0.9% by weight Example 3 Four mils with a thermometer, stirrer and condenser: 88.1 g (〇. 8 mol) of resorcinol was added, and after the inside of the flask was replaced with nitrogen, acetone 65 〇gG 12 m〇1) and 曱 223 were added. §. Eclipse I62280.doc -18. 2 01238958 The mixture obtained was heated to 40 ° C, and then added with 98% barium sulfate 40 g. The obtained mixture was heated to an internal temperature of 5 (rc, heat for 35 hours. At an internal temperature of 60 C) The inside of the flask was decompressed and the water was removed from the reaction system. The pressure was returned to normal pressure, 69 7 g of acetone (i 2 m〇丨) was added, and the obtained mixture was kept at this temperature for 5 hours, after which, 1 was The sodium hydroxide aqueous solution of 〇% was neutralized, and further dried at 80 C under a reduced pressure of 1 KPa or less for 12 hours to obtain 136 g of a condensate of resorcinol and acetone. The contents of 2,4,4-trimethyl-2,4,7-trihydroxyxanone and resorcin in the obtained condensate are as follows. 2,4,4-trimethyl-2',4',7-trihydroxyflavone: 45.8 wt% resorcinol: 〇·97 wt% First dissolution peak: 28.1%

Weight average molecular weight of the first elution peak: 1211 Softening point: 112 ° C Comparative Reference Example 1 In a 500 ml four-necked flask with a thermometer, a stirrer, and a condenser, 44.0 g (〇. 4 mol) of resorcin was added. After the inside of the flask was purged with nitrogen, '25.6 g (0.44 mol) of acetone and 111 g of toluene were added. After the obtained mixture was heated to 40 t, 98% of sulfuric acid was added in an amount of 0.44 g. The obtained mixture was allowed to warm to an internal temperature of 80 t and kept for 3 hours. Then, 23.2 g (0.40 mol) of propylene oxide was added, and the obtained mixture was kept for 4 hours. Then, 23.2 g (0.40 mol) of acetone was added, and the obtained mixed person was kept warm for 3 hours. Thereafter, the mixture was subjected to a sodium hydroxide aqueous solution of 1% by weight and further dried under a reduced pressure of 1 KPa for 8 hours at TC for 2 hours to obtain a condensation of resorcinol with acetone at I62280.doc 19 201238958. 12〇g. The contents of 2,4,4-trimethyl-2,4,7-trihydroxyflavone and resorcinol in the obtained condensate are as follows. 2,4,4- Tridecyl-2',4,,7-trihydroxyflavone: 42.9 wt% resorcinol: 15.8% by weight Example 4 [Manufacturing of rubber composition] The initial system was used using a 0.6 L closed type kneader The internal temperature is set to 150 ° C. Based on the following composition formula, natural rubber (RSS #1) is first introduced for rnastication for 3 minutes, followed by carbon black (N330), hydrated cerium oxide, stearic acid, zinc. White, an anti-aging agent (2,2,4-tridecyl-1,2-dihydroquinoline condensate) and the condensate obtained in Example 1 were kneaded for 5 minutes and discharged. Then, the discharged product was discharged. The rubber was moved to the open drum, and the temperature in the initial vessel was set to 6 (TC, sulfur and vulcanization accelerator (N, N-dicyclohexyl-2-) shown in the following composition was added. And thiazole sulfoximine), methoxylated hydroxy decyl melamine resin (Sumikanol 507AP (manufactured by Sumitomo Chemical Co., Ltd.), and cobalt naphthenate, and the temperature is controlled so that the temperature of the rubber becomes 80 ° C or less, and kneading is performed. Thereby, a rubber composition is obtained. &lt;Composition formula> • Natural rubber (RSS #1) 100 parts • N330 carbon black 45 parts • Hydrated cerium oxide (Tosoh Silica (manufactured by Nipsil AQ) 10 parts • Stearic acid 3 Parts • Zinc White 5 parts by weight 162280.doc -20- 201238958 • Anti-aging agent (2,2,4-tridecyl-1,2-dihydroquinoline condensate) 2 parts • Ingredient A (In Example 1 The obtained condensate of resorcinol and acetone) 2 parts • sulfur 4 parts. vulcanization accelerator (N, N-dicyclohexyl-2-benzothiazole sulfoximine) 0.7 parts • methoxylated hydroxyl Methyl melamine resin (Sumikanol 507AP (manufactured by Sumitomo Chemical Co., Ltd.)) 3 parts (2 parts of active ingredient) • 2 parts of ring-burning acid salt (cobalt content: 0.2 parts) Example 5 [Production of rubber composition] In Example 4 Using the condensate obtained in Example 2 in place of the condensate obtained in Example 1, except The rubber composition was obtained in the same manner as in Example 4. Example 6 [Manufacture of belt for tire and manufacture of tire using the same] Brass plating was carried out by coating the rubber composition obtained in Example 4 The steel cord is treated to obtain a belt layer, and the obtained green belt is formed by using the obtained belt layer according to a usual manufacturing method, and the obtained green tire is heated and pressurized in a vulcanizer, thereby obtaining a tire. Example 7 [Production of Tire for Tire and Tire Using the Same] The rubber composition obtained in Example 4 was subjected to extrusion processing to prepare a rubber composition having a shape corresponding to a shape of a sticker, and was attached to a polyester. The carcass fiber cord is made up and down, thereby obtaining the carcass, and the carcass obtained by using the carcass is formed according to the manufacturing method of the method, and is obtained in the vulcanizer by the 162280.doc -21 - 201238958 The tire is heated and pressurized to obtain a tire. Example 8 [Production of tread rubber for tire and tire using the same] The rubber composition obtained in Example 4 was subjected to extrusion to obtain a tread rubber. The obtained base rubber was molded into a green tire by a usual manufacturing method, and the obtained green tire was heated and pressurized in a vulcanizer to obtain a tire. Example 9 [Production of base rubber for tire and tire using the same] The rubber composition obtained in Example 4 was subjected to extrusion processing to obtain a base rubber. The obtained base rubber was molded into a green tire by a usual manufacturing method, and the obtained green tire was heated and pressurized in a vulcanizer to obtain a tire. Industrial Applicability According to the production method of the present invention, the residual amount of the streptophenol in the unreacted portion can be made small. The condensate of the resorcinol and the propylene obtained by the production method of the present invention is excellent in the performance as a reinforcing agent for various rubber compositions, and also prevents the evapotranspiration of residual resorcinol when processed from the rubber composition. The resulting deterioration of the working environment is industrially advantageous. 162280.doc •22·

Claims (1)

201238958 VII. Patent Application Range 1. A method for producing a condensate of resorcinol and acetone, comprising: a step of reacting m-diphenol with acetone in the presence of an acid, and in the presence of an acid The step of removing water by-produced by the above reaction. 2. The method of claim 1, comprising the steps of: reacting m-diphenol with acetone in the presence of an acid, removing the water by the reaction in the presence of an acid, and removing the water The step of mixing the mixture after water with the base. 3. The method of claim 2 or 2, comprising: the step of reacting m-diphenol with acetone in the presence of an acid, and removing the water by-produced by the reaction in the presence of an acid, The step of mixing the mixture after removing water with acetone, and the step of mixing the mixture with the two mashes. 4. The method according to any one of the items (1) of the present invention, wherein the step (10) of removing the water by the reaction is carried out in the presence of an acid, and removing the water by the reaction . 5. The method of claim 4, wherein the step of removing the water derived from the reaction in the presence of an acid and an organic solvent is carried out by the water of the above reaction in the presence of I and an organic solvent together with the organic solvent. Boiling, the step of removing this. 6. The method of claim 4, wherein the organic solvent is an aromatic hydrocarbon. 7. The method of claim 6, wherein the T^丹T-fragrant hydrocarbon is toluene or xylene. The acid is at least one selected from the group consisting of the production method I62280.doc 201238958 of any one of claims 1 to 7 and the group consisting of methyl sulfonic acid, p-toluenesulfonic acid hydrate, hydrochloric acid and sulfuric acid. A rubber composition comprising the condensate, the rubber component, the filler, and the sulfur component obtained by the production method according to any one of claims 1 to 8. It comprises a steel cord covered with a rubber composition as claimed in claim 9 for a tire belt. A carcass for a tire comprising a carcass fiber cord covered with a rubber composition of the ruthenium, VII, and the ninth article. It comprises a rubber composition as claimed in claim 9 12. A tire tread rubber or a base rubber for a tire. 13. - A pneumatic tire, manufactured by a line of processing. 14· a resorcinol and (3): a condensate of the rubber composition of the item 9 by electro-rejection &gt; a _ f, which further satisfies the following (1), (2) and when performing the analysis, because 2'4,4: trimethyl:, the rate of detection of the two-shot ratio) is the sum of the area of the peak of the contraction with respect to all the peaks: ·: (4) the range of the jaundice; the area of the σ leaf The ratio of 30 (7) in the analysis by gel permeation chromatography, the ratio of the first eluted wave refractive index detection) to the area of the condensate is 20 to 50%; the product is for all the bees. (3) The range of the first elution peak described above. The amount of the knife per thousand is 15 〇〇 17 (9) 162 280. doc 201238958 1 5 The condensate of claim 14 has a softening point of 1 60 ° C or less. 16. The condensate of claim 14 or 15, which is stored at 120 ° C for 24 hours, and the rate of increase of the resorcinol is 2% or less. 162280.doc 201238958 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best indication of the characteristics of the invention. Chemical formula: (none) 162280.doc