WO2018051999A1 - Condensate between resorcin and acetone - Google Patents

Abstract

The present invention provides a condensate between resorcin and acetone, wherein, as analyzed by gel permeation chromatography, the proportion of the area of a peak (1) representing a weight-average molecular weight of not less than 160 but less than 480 is 70% or less, the proportion of the area of a peak (2) representing a weight-average molecular weight of not less than 480 but less than 600 is 25-50%, and the sum of the proportion of the area of a peak (3) representing a weight-average molecular weight of not less than 600 but less than 800 and the proportion of the area of a peak (4) representing a weight-average molecular weight of not less than 800 is 26% or less, with respect to the total area of the peaks representing a weight-average molecular weight of 160 or more.

Description

Condensate of resorcin and acetone

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

Resorcin is useful as a reinforcing agent for rubber compositions. However, the rubber composition containing resorcin has a problem that the resorcin is evaporated during processing and the working environment is deteriorated. Therefore, in order to reduce the amount of resorcin in the rubber composition, it has been proposed to use a condensate of resorcin and acetone (for example, Patent Documents 1 and 2).

Patent Document 1 includes a step of reacting resorcin and acetone in the presence of an acid (ie, a condensation step) and a step of removing water produced by the reaction in the presence of an acid (ie, a dehydration step). A method for producing a condensate of resorcin and acetone is described (claim 1 etc.). In such a reaction, the formula (I '):

2,4,4-trimethyl-2 ', 4', 7-trihydroxyflavan (hereinafter sometimes abbreviated as "compound (I ')") is obtained. In such a reaction, the compound (I ′), resorcin and acetone are further condensed to form a further high molecular weight body.

In Patent Document 2, when analyzed by gel permeation chromatography, the ratio of the area of the peak derived from compound (I ′) to the total area of all peaks is 25 to 55%, and the weight average molecular weight is 800. A condensate in which the area ratio of the first elution peak is 10 to 25% is described (claim 4 etc.).

Patent Document 3 describes the formula (I):

(The definition of the group in the formula is as described in Patent Document 3.)
And a method for producing the polyalkyl-2- (2,4-dihydroxyphenyl) -7-hydroxychroman (hereinafter abbreviated as “compound (I)”). ). In Examples 1 and 2 of Patent Document 3, 2,4,4-trimethyl-2- (2,4-dihydroxyphenyl) -7-hydroxychroman (ie, 2,4 which is compound (I ′)) is used. 4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan) has been produced.

JP 2012-184401 A JP 2013-151604 A JP-A-56-5476

In the production method described in Patent Document 1, due to the dehydration step after the condensation step, the amount of the high molecular weight polymer having a high melting point increases, and the softening point of the resulting condensate of resorcin and acetone increases. Further, the melting point of the compound (I ′) produced in Examples 1 and 2 of Patent Document 3 is as high as 225 ° C., and the condensate of resorcin and acetone having a large amount of the compound (I ′) has a softening point. Is expensive. Patent Document 2 specifies the amount of a compound having a high melting point in the condensate of resorcin and acetone (that is, a compound (I ′) and a high molecular weight compound having a weight average molecular weight of 800 or more).

The condensate of resorcin and acetone with a low softening point is expected to improve dispersibility in the rubber component when kneaded with the rubber component, compared to the condensate of resorcin and acetone with a high softening point. Is done. Further, it is expected that kneading of the condensate and the rubber component can be performed at a low temperature by using a condensate of resorcin and acetone having a low softening point.

The present invention has been made in view of the above situation, and an object thereof is to provide a condensate of resorcin and acetone having a low softening point. The present invention capable of achieving this object is as follows.

[1] With respect to the total area of peaks having a weight average molecular weight of 160 or more when analyzed by gel permeation chromatography,
The area ratio of the peak (1) having a weight average molecular weight of 160 or more and less than 480 is 70% or less,
The area ratio of peak (2) having a weight average molecular weight of 480 or more and less than 600 is 25 to 50%, and the area ratio of peak (3) having a weight average molecular weight of 600 or more and less than 800 and the weight average molecular weight of 800 or more The total with the area ratio of the peak (4) is 26% or less.
Condensate of resorcin and acetone.

[2] Resorcin and acetone according to the above [1], wherein the area ratio of the peak (4) having a weight average molecular weight of 800 or more is less than 10% with respect to the total area of the peak having a weight average molecular weight of 160 or more. Condensate with
[3] Resorcin and acetone according to the above [1], wherein the area ratio of the peak (4) having a weight average molecular weight of 800 or more is 9% or less with respect to the total area of the peak having a weight average molecular weight of 160 or more. Condensate with

[4] Any of [1] to [3] above, wherein the area ratio of the peak (4) having a weight average molecular weight of 800 or more is 0% or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.
[5] Any of [1] to [3] above, wherein the area ratio of the peak (4) having a weight average molecular weight of 800 or more is 3% or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.
[6] Any of [1] to [3] above, wherein the area ratio of the peak (4) having a weight average molecular weight of 800 or more is 4% or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.
[7] Any of [1] to [3] above, wherein the area ratio of the peak (4) having a weight average molecular weight of 800 or more is 5% or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.

[8] The above [1] to [7], wherein the area ratio of the peak (1) having a weight average molecular weight of 160 or more and less than 480 is 60% or less with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.
[9] The above [1] to [7], wherein the area ratio of the peak (1) having a weight average molecular weight of 160 or more and less than 480 is 55% or less with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.

[10] The above [1] to [9], wherein the area ratio of the peak (1) having a weight average molecular weight of 160 or more and less than 480 is 0% or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.
[11] The above [1] to [9], wherein the area ratio of the peak (1) having a weight average molecular weight of 160 or more and less than 480 is 10% or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.
[12] The above [1] to [9], wherein the area ratio of the peak (1) having a weight average molecular weight of 160 or more and less than 480 is 20% or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.
[13] The above [1] to [9], wherein the area ratio of the peak (1) having a weight average molecular weight of 160 or more and less than 480 is 30% or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.

[14] The area ratio of the peak (2) having a weight average molecular weight of 480 or more and less than 600 to the total area of the peak having a weight average molecular weight of 160 or more is 27 to 45%. ] The condensate of resorcin and acetone as described in any one of.
[15] The above [1] to [13], wherein the area ratio of the peak (2) having a weight average molecular weight of 480 or more and less than 600 is 30 to 40% with respect to the total area of the peak having a weight average molecular weight of 160 or more. ] The condensate of resorcin and acetone as described in any one of.

[16] The above [1] to [15], wherein the area ratio of the peak (3) having a weight average molecular weight of 600 or more and less than 800 is 25% or less with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.
[17] The above [1] to [15], wherein the area ratio of the peak (3) having a weight average molecular weight of 600 or more and less than 800 is 22% or less with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.
[18] The above [1] to [15], wherein the area ratio of the peak (3) having a weight average molecular weight of 600 or more and less than 800 is 20% or less with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.

[19] The above [1] to [18], wherein the area ratio of the peak (3) having a weight average molecular weight of 600 or more and less than 800 is 0% or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.
[20] The above [1] to [18], wherein the area ratio of the peak (3) having a weight average molecular weight of 600 or more and less than 800 is 8% or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.
[21] The above [1] to [18], wherein the area ratio of the peak (3) having a weight average molecular weight of 600 or more and less than 800 is 10% or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.
[22] The above [1] to [18], wherein the area ratio of the peak (3) having a weight average molecular weight of 600 or more and less than 800 is 12% or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. A condensate of resorcin and acetone according to any one of the above.

[23] The ratio of the area of peak (3) having a weight average molecular weight of 600 or more and less than 800 to the total area of the peak having a weight average molecular weight of 160 or more and the peak (4) having a weight average molecular weight of 800 or more. The condensate of resorcin and acetone according to any one of the above [1] to [22], which has a total area ratio of 25% or less.
[24] The area ratio of the peak (3) having a weight average molecular weight of 600 or more and less than 800 and the peak (4) having a weight average molecular weight of 800 or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. The condensate of resorcin and acetone according to any one of the above [1] to [22], which has a total area ratio of 24% or less.

[25] The area ratio of the peak (3) having a weight average molecular weight of 600 or more and less than 800 and the peak (4) having a weight average molecular weight of 800 or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. The condensate of resorcin and acetone according to any one of [1] to [24], wherein the sum of the area ratios is 0% or more.
[26] The area ratio of the peak (3) having a weight average molecular weight of 600 or more and less than 800 and the peak (4) having a weight average molecular weight of 800 or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. The condensate of resorcin and acetone according to any one of the above [1] to [24], which has a total area ratio of 10% or more.
[27] The ratio of the area of the peak (3) having a weight average molecular weight of 600 or more and less than 800 to the total area of the peak having a weight average molecular weight of 160 or more and the peak (4) having a weight average molecular weight of 800 or more. The condensate of resorcin and acetone according to any one of the above [1] to [24], which has a total area ratio of 12% or more.
[28] The area ratio of the peak (3) having a weight average molecular weight of 600 or more and less than 800 and the peak (4) having a weight average molecular weight of 800 or more with respect to the total area of the peak having a weight average molecular weight of 160 or more. The condensate of resorcin and acetone according to any one of the above [1] to [24], which has a total area ratio of 15% or more.

[29] The condensate of resorcin and acetone according to any one of the above [1] to [28], wherein the residual amount of resorcin in the condensate of resorcin and acetone is 10% by weight or less.
[30] The condensate of resorcin and acetone according to any one of the above [1] to [28], wherein the residual amount of resorcin in the condensate of resorcin and acetone is 8% by weight or less.
[31] The condensate of resorcin and acetone according to any one of the above [1] to [28], wherein the residual amount of resorcin in the condensate of resorcin and acetone is 5% by weight or less.

[32] The condensate of resorcin and acetone according to any one of the above [1] to [31], wherein the residual amount of resorcin in the condensate of resorcin and acetone is 0% by weight or more.
[33] The condensate of resorcin and acetone according to any one of the above [1] to [31], wherein the residual amount of resorcin in the condensate of resorcin and acetone is 0.01% by weight or more.
[34] The condensate of resorcin and acetone according to any one of the above [1] to [31], wherein the residual amount of resorcin in the condensate of resorcin and acetone is 0.05% by weight or more.

[35] The condensate of resorcin and acetone according to any one of the above [1] to [34], wherein the residual amount of acetone in the condensate of resorcin and acetone is 2% by weight or less.
[36] The condensate of resorcin and acetone according to any one of the above [1] to [34], wherein the residual amount of acetone in the condensate of resorcin and acetone is 1% by weight or less.
[37] The condensate of resorcin and acetone according to any one of the above [1] to [34], wherein the residual amount of acetone in the condensate of resorcin and acetone is 0.5% by weight or less.

[38] The condensate of resorcin and acetone according to any one of [1] to [37], wherein the residual amount of acetone in the condensate of resorcin and acetone is 0% by weight or more.
[39] The condensate of resorcin and acetone according to any one of the above [1] to [37], wherein the residual amount of acetone in the condensate of resorcin and acetone is 0.01% by weight or more.
[40] The condensate of resorcin and acetone according to any one of the above [1] to [37], wherein the residual amount of acetone in the condensate of resorcin and acetone is 0.05% by weight or more.
[41] The condensate of resorcin and acetone according to any one of the above [1] to [37], wherein the residual amount of acetone in the condensate of resorcin and acetone is 0.1% by weight or more.

[42] The condensate of resorcin and acetone according to any one of the above [1] to [41], wherein the water content in the condensate of resorcin and acetone is 2% by weight or less.
[43] The condensate of resorcin and acetone according to any one of the above [1] to [41], wherein the water content in the condensate of resorcin and acetone is 1% by weight or less.
[44] The condensate of resorcin and acetone according to any one of the above [1] to [41], wherein the water content in the condensate of resorcin and acetone is 0.5% by weight or less.

[45] The condensate of resorcin and acetone according to any one of the above [1] to [44], wherein the water content in the condensate of resorcin and acetone is 0% by weight or more.
[46] The condensate of resorcin and acetone according to any one of the above [1] to [44], wherein the water content in the condensate of resorcin and acetone is 0.01% by weight or more.
[47] The condensate of resorcin and acetone according to any one of the above [1] to [44], wherein the water content in the condensate of resorcin and acetone is 0.05% by weight or more.
[48] The condensate of resorcin and acetone according to any one of the above [1] to [44], wherein the water content in the condensate of resorcin and acetone is 0.1% by weight or more.

[49] The condensate of resorcin and acetone according to any one of the above [1] to [48], wherein the residual amount of impurities in the condensate of resorcin and acetone is 5% by weight or less.
[50] The condensate of resorcin and acetone according to any one of the above [1] to [48], wherein the residual amount of impurities in the condensate of resorcin and acetone is 3% by weight or less.

[51] The condensate of resorcin and acetone according to any one of the above [1] to [50], wherein the residual amount of impurities in the condensate of resorcin and acetone is 0% by weight or more.
[52] The condensate of resorcin and acetone according to any one of the above [1] to [50], wherein the residual amount of impurities in the condensate of resorcin and acetone is 0.01% by weight or more.
[53] The condensate of resorcin and acetone according to any one of the above [1] to [50], wherein the residual amount of impurities in the condensate of resorcin and acetone is 0.05% by weight or more.
[54] The condensate of resorcin and acetone according to any one of the above [1] to [50], wherein the residual amount of impurities in the condensate of resorcin and acetone is 0.1% by weight or more.

[55] The condensate of resorcin and acetone according to any one of [1] to [54], which has a softening point of 120 ° C. or lower.
[56] The condensate of resorcin and acetone according to any one of [1] to [54], which has a softening point of 118 ° C. or lower.
[57] The condensate of resorcin and acetone according to any one of [1] to [54], which has a softening point of 116 ° C. or lower.

[58] A rubber composition obtained by kneading a condensate of resorcin and acetone according to any one of [1] to [57] and a rubber component.
[59] The rubber composition according to [58], obtained by further kneading a sulfur component.
[60] A vulcanized rubber composition obtained by vulcanizing the rubber composition according to [59].

[61] A method for producing a rubber composition, comprising kneading a condensate of resorcin and acetone according to any one of [1] to [57] and a rubber component.
[62] The method according to [61], further comprising kneading a sulfur component.
[63] A method for producing a vulcanized rubber composition, comprising vulcanizing the rubber composition obtained by the method according to [62].

The condensate of resorcin and acetone of the present invention exhibits a low softening point.

[Condensate of resorcin and acetone]
The condensate of resorcin and acetone of the present invention (hereinafter sometimes abbreviated as “condensate of the present invention”) has a weight average molecular weight of 160 or more when analyzed by gel permeation chromatography (GPC). For the total area of
The area ratio of the peak (1) having a weight average molecular weight of 160 or more and less than 480 (hereinafter sometimes abbreviated as “peak (1)”) is 70% or less,
The area ratio of the peak (2) having a weight average molecular weight of 480 or more and less than 600 (hereinafter sometimes abbreviated as “peak (2)”) is 25 to 50%, and the weight average molecular weight is 600 or more and less than 800 A peak (4) (hereinafter referred to as “peak (4)”) having an area ratio of a certain peak (3) (hereinafter sometimes abbreviated as “peak (3)”) and a weight average molecular weight of 800 or more. ) Area ratio is 26% or less,
It is characterized by that. Here, the area ratio of the peaks (1) to (4) is a value based on the total area of the peaks having a weight average molecular weight of 160 or more.

The above-mentioned GPC can be measured according to the conditions described in Examples described later or conditions equivalent thereto.

Peak (1) corresponds to compound (I ') (molecular weight: 300.14) having a high melting point and a similar condensate thereof. Peaks (3) and (4) correspond to a high molecular weight product obtained by further condensation of compound (I ′), resorcin and acetone. Peak (2) corresponds to an intermediate compound whose molecular weight is between the molecular weight of compound (I ') (peak (1)) and the high molecular weight (peaks (3) and (4)).

As a result of extensive studies by the present inventors, the amount of the above-described high molecular weight (peaks (3) and (4)) is limited, and a certain amount of intermediate compound (peak (2)) is secured. By doing so, it has been found that the softening point of the condensate of resorcin and acetone can be lowered. As a mechanism by which the softening point of the condensate is reduced by such a configuration, the amount of the high molecular weight compound (peaks (3) and (4)) having a high melting point is reduced, and the intermediate compound (peak (2)). Is present in a certain amount, it is presumed that the intermediate compound inhibits crystallization of the compound (I ′) (peak (1)) having a high melting point. However, the present invention is not limited to such estimation.

In claim 4 of Patent Document 2, the area ratio of the peak derived from the compound (I ′) corresponding to the peak (1) in the present invention and the area of the first eluting peak corresponding to the peak (4) in the present invention are described. The percentages are listed. Moreover, in the Example of patent document 2, the area ratio of the 3rd elution peak corresponding to the peak (2) in this invention and the area ratio of the 2nd elution peak corresponding to the peak (3) in this invention are described. ing. However, in Patent Document 2, in order to lower the softening point of the condensate of resorcin and acetone, the area ratio of peak (2) is adjusted to 25 to 50%, and the area ratio of peak (3) It is not described that the total with the area ratio of the peak (4) is adjusted to 26% or less.

Since the peak (1) corresponds to the compound (I ′) having a high melting point, the area ratio of the peak (1) is preferably as small as possible from the viewpoint of lowering the softening point of the condensate of resorcin and acetone. Therefore, the area ratio of the peak (1) is 70% or less, preferably 60% or less, more preferably 55% or less. From the viewpoint of lowering the softening point, the lower limit of the area ratio of peak (1) is not particularly limited, and this area ratio may be zero. However, from the viewpoint of production of the condensate, the area ratio of the peak (1) is preferably 10% or more, more preferably 20% or more, and further preferably 30% or more.

As described above, it is presumed that the intermediate compound corresponding to peak (2) contributes to the lowering of the softening point of the condensate of the present invention. From the viewpoint of reducing the softening point, the area ratio of the peak (2) is 25 to 50%, preferably 27 to 45%, more preferably 30 to 40%.

From the viewpoint of lowering the softening point of the condensate, the sum of the area ratio of peak (3) and the area ratio of peak (4) is 26% or less, preferably 25% or less, more preferably 24% or less. From the viewpoint of lowering the softening point, the lower limit of the total is not particularly limited, and the total may be zero. However, this total is preferably 10% or more, more preferably 12% or more, and still more preferably 15% or more from the viewpoint of the production of the condensate.

In order to lower the softening point of the condensate of the present invention, the area ratio of the peak (3) corresponding to the high molecular weight body is preferably small. From such a viewpoint, the area ratio of the peak (3) is preferably 25% or less, more preferably 22% or less, and further preferably 20% or less. From the viewpoint of lowering the softening point, the lower limit of the area ratio of the peak (3) is not particularly limited, and the area ratio of the peak (3) may be zero. However, from the viewpoint of production of the condensate, the area ratio of the peak (3) is preferably 8% or more, more preferably 10% or more, and further preferably 12% or more.

In order to reduce the softening point of the condensate of the present invention, it is preferable that the area ratio of the peak (4) having the highest weight average molecular weight among the peaks (1) to (4) is small. From such a viewpoint, the area ratio of the peak (4) is preferably less than 10%, more preferably 9% or less. From the viewpoint of lowering the softening point, the lower limit of the area ratio of the peak (4) is not particularly limited, and the area ratio of the peak (4) may be zero. However, from the viewpoint of production of the condensate, the area ratio of the peak (4) is preferably 3% or more, more preferably 4% or more, and further preferably 5% or more.

The softening point of the condensate of the present invention is preferably 120 ° C. or lower, more preferably 118 ° C. or lower, and still more preferably 116 ° C. or lower. This softening point is a value measured according to ASTM D6090. Since this softening point is preferably as low as possible, this lower limit is not particularly limited.

In the condensation reaction between resorcin and acetone and the condensate of resorcin and acetone obtained after devolatilization, unreacted resorcin and acetone may remain. In order to reduce the amount of resorcin transpiration during the processing of the rubber composition, the residual amount of resorcin in the condensate of the present invention is preferably 10% by weight or less, more preferably 8% by weight or less, and further preferably 5% by weight. % Or less. From the viewpoint of reducing the amount of resorcin transpiration, the lower limit of the residual amount is not particularly limited, and the residual amount may be zero. However, from the viewpoint of production of the condensate and the like, the residual amount of resorcin in the condensate of the present invention is preferably 0.01% by weight or more, more preferably 0.05% by weight or more. Here, the residual amount of resorcin means the amount of resorcin remaining unreacted, which is a value based on the whole condensate of the present invention containing impurities such as resorcin.

The residual amount of acetone in the condensate of the present invention is preferably 2% by weight or less, more preferably 1% by weight or less, and further preferably 0.5% by weight or less. There is no particular limitation on the lower limit of the remaining amount, and the remaining amount may be zero. However, from the viewpoint of the production of the condensate, the residual amount of acetone in the condensate of the present invention is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and still more preferably 0.1%. % By weight or more. Here, the residual amount of acetone means the amount of acetone remaining unreacted, and this is a value based on the whole condensate of the present invention containing impurities such as acetone.

In the condensation reaction between resorcin and acetone, water is produced as a by-product. Moreover, as will be described later, a preferred method for producing the condensate of the present invention includes condensing resorcin and acetone in the presence of water. Therefore, water can remain in the condensate of resorcin and acetone obtained after the condensation reaction and devolatilization. The water content in the condensate of the present invention is preferably 2% by weight or less, more preferably 1% by weight or less, and still more preferably 0.5% by weight or less. There is no particular limitation on the lower limit of the moisture content, and the moisture content may be zero. However, from the viewpoint of production of the condensate, the water content in the condensate of the present invention is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and further preferably 0.1% by weight. That's it. This amount of water is a value based on the entire condensate of the present invention containing impurities such as water.

When an organic solvent other than acetone is used in the condensation reaction between resorcin and acetone, the organic solvent can remain as an impurity in the condensate of the present invention. In the condensation reaction between resorcin and acetone, diacetone alcohol and mesityl oxide are generated by dimerization of acetone, and these can remain as impurities in the condensate of the present invention. The residual amount of impurities such as resorcin, acetone, water, organic solvent, diacetone alcohol, mesityl oxide, etc. in the condensate of the present invention is preferably 5% by weight or less, more preferably 3% by weight or less. More preferably, it is 1% by weight or less. There is no particular limitation on the lower limit of the remaining amount, and the remaining amount may be zero. However, from the viewpoint of the production of the condensate, the residual amount of impurities in the condensate of the present invention is preferably 0.01% by weight or more, more preferably 0.05% by weight or more, and still more preferably 0.1%. % By weight or more. Here, the remaining amount of impurities is a value based on the whole condensate of the present invention containing impurities.

[Method for producing condensate of resorcin and acetone]
A condensate of resorcin and acetone can be produced by condensing resorcin and acetone in the presence of an acid catalyst, as generally described in Patent Documents 1 and 2. Commercially available resorcinol and acetone can be used. The amount of acetone used as a raw material is preferably 1 to 6 mol and more preferably 1.5 to 5 mol with respect to 1 mol of resorcin as a raw material.

The condensation reaction between resorcin and acetone is dehydration condensation, and water is produced as a by-product. Therefore, when water is present, the rate of the condensation reaction between resorcin and acetone is reduced. From this point of view, as described in Patent Document 1, it has been conventionally considered that water is preferably removed in the condensation reaction between resorcin and acetone. However, as a result of extensive studies by the present inventors, it has been found that the formation of a high molecular weight product is suppressed by deliberately condensing resorcin and acetone in the presence of water. This is presumably because the presence of water promotes the decomposition (reverse reaction) of the high molecular weight product. However, the present invention is not limited to such estimation.

The condensate of the present invention described above condenses resorcin and acetone in the presence of water using, for example, an H-type acidic cation exchange resin (hereinafter sometimes referred to as “acidic cation exchange resin”). Can be manufactured. The acidic cation exchange resin is preferably a strong acidic cation exchange resin having a sulfo group (—SO ₃ H).

In the above-described production method using an acidic cation exchange resin, the amount of water in the reaction solution at the start of the condensation reaction is preferably 0.1 to 1.0 mol, more preferably 0.1 mol, relative to 1 mol of resorcin as a raw material. 2 to 0.8 mol. In the above production method, the amount of water in the reaction solution at the end of the condensation reaction is preferably 4 to 15% by weight, more preferably 6 to 10% by weight per 100% by weight of the reaction solution.

The concentration of acidic groups in the acidic cation exchange resin (that is, the amount of acidic groups contained in 1 ml of acidic cation exchange resin) is preferably 0.5 to 2.5 meq / ml.

The degree of crosslinking of the acidic cation exchange resin is preferably 1% or more, more preferably 2% or more, more preferably 20% or less, and further preferably 15% or less. Here, the degree of cross-linking refers to the concentration (%) of the cross-linkable monomer in the total raw material monomers used in the production of the acidic cation exchange resin (= 100 × mass of cross-linkable monomer / mass of all raw material monomers). Similar definitions used in the field. If the degree of crosslinking is too small, it is difficult to maintain the strength of the acidic cation exchange resin, and the acidic cation exchange resin is crushed when used as a catalyst.

The amount of the acidic cation exchange resin used is not particularly limited, but is preferably 0.1 to 10 parts by weight, more preferably 0.1 to 3 parts by weight with respect to 1 part by weight of resorcin as a raw material.

The acidic cation exchange resin is preferably granular or powdery in order to increase the contact area with the reaction solution containing resorcin and acetone. The average particle size of the acidic cation exchange resin is preferably 0.1 to 2.0 mm, more preferably 0.2 to 1.5 mm, and still more preferably 0.3 to 1.2 mm. This average particle diameter can be measured by a dry laser diffraction method, a sieve classification method, or the like.

The acidic cation exchange resin is not particularly limited, and a commercially available product can be used. Specific examples include Ambalist series manufactured by Organo Corporation (for example, SC200 and SC300), Diaion Series manufactured by Mitsubishi Chemical Corporation (PK212, PK228), DOWEX Series manufactured by Dow Chemical Co., Ltd. (for example, 50W × 2), Rohm & Haas Co. Duolite series (for example, C26CH), LANXESS Co., Ltd. Lebatit series (for example, S2328, K2629, etc.) and the like.

The condensation reaction between resorcin and acetone is usually performed in a solution. For example, when a large amount of raw material acetone is used, it is not necessary to use another organic solvent because acetone acts as a starting material and an organic solvent. Even if acetone acts as an organic solvent, an organic solvent other than acetone may be used.

When using an organic solvent other than acetone, only one type may be used, or two or more types may be used in combination. Examples of organic solvents other than acetone include aliphatic hydrocarbons, aromatic hydrocarbons, and halogen-substituted aromatic hydrocarbons. Specific examples of the aliphatic hydrocarbon include hexane, heptane, octane, decane and the like. Specific examples of the aromatic hydrocarbon include toluene, xylene, ethylbenzene and the like. Specific examples of the halogen-substituted aromatic hydrocarbon include chlorobenzene and dichlorobenzene. Of these, aromatic hydrocarbons are preferable, and toluene or xylene is more preferable. When an organic solvent other than acetone is used, the amount is preferably 0.5 to 3 parts by weight with respect to 1 part by weight of resorcin as a raw material.

The condensation reaction between resorcin and acetone may be performed in a batch reactor or a continuous reactor.

When a batch reactor is used, the mixing order of resorcin, acetone, acidic cation exchange resin, etc. into the reactor is not particularly limited. For example, the starting material may be added to the reactor charged with the acidic cation exchange resin, and conversely, the acidic cation exchange resin may be added to the reactor containing the starting material. Acetone may be added continuously or intermittently as the condensation reaction proceeds.

When using a batch reactor, it is preferable to perform the condensation reaction in an inert gas (eg, nitrogen) atmosphere.

As an embodiment using a continuous reactor, there can be mentioned, for example, an embodiment in which a reaction solution containing resorcin and acetone is passed through a reaction tube filled with an acidic cation exchange resin to perform a condensation reaction. The reaction solution may be circulated by collecting the reaction solution flowing out from the reaction tube and circulating it again through the reaction tube.

When a continuous reactor is used, the pressure in the reaction tube when the reaction solution is circulated through the reaction tube is preferably 0.001 to 10 MPa (gauge pressure).

The temperature of the condensation reaction is preferably 20 to 120 ° C, more preferably 20 to 100 ° C. The time for the condensation reaction depends on the temperature, but is, for example, 1 to 48 hours, preferably 3 to 24 hours. The progress of the condensation reaction can be confirmed by ordinary analytical means such as gas chromatography (GC), high performance liquid chromatography (HPLC), gel permeation chromatography (GPC) and the like.

A condensate can be obtained by removing volatile components such as unreacted acetone from the reaction solution obtained by the condensation reaction and containing a condensate of resorcin and acetone. Examples of the apparatus for removing acetone and the like include a distillation apparatus such as a batch distillation apparatus, a centrifugal molecular distillation apparatus, and a thin film distillation apparatus, and a devolatilizing extruder. The heat supply section (also called a heat source of the distillation apparatus) of these distillation apparatuses is adjusted to a predetermined temperature (usually the distillation temperature), and the obtained reaction solution is supplied continuously or intermittently there. By doing so, acetone or the like can be removed.

The temperature at which acetone or the like is removed is preferably 0 to 250 ° C., more preferably 60 to 230 ° C. Acetone and the like may be removed under normal pressure or under reduced pressure. When removing acetone or the like under reduced pressure, the pressure is preferably 100 kPa or less, more preferably 70 kPa or less.

The means for taking out the condensate obtained after removing acetone or the like from the apparatus is not particularly limited, and examples thereof include melt granulation, extrusion granulation, crush granulation, and compression granulation. Examples of the apparatus used for melt granulation include Sandvik's Rotoformer, Kaiser's rotary drop former, Mitsubishi Kasei Engineering's drum cooler, Nippon Belding's steel belt cooler, and hybrid former. Can be mentioned.

[Rubber composition, vulcanized rubber composition, and production method thereof]
The present invention provides a rubber composition obtained by kneading the condensate and rubber component of the present invention described above, and a method for producing the same. In addition, the present invention is a rubber composition obtained by kneading the condensate, rubber component, and sulfur component of the present invention described above (hereinafter sometimes referred to as a “rubber composition containing a sulfur component”), And a method for manufacturing the same. The present invention also provides a vulcanized rubber composition obtained by vulcanizing a rubber composition containing a sulfur component, and a method for producing the same.

The condensate of the present invention may react with a rubber component or the like during kneading to form another compound. Further, the condensate of the present invention may be decomposed during kneading, and this decomposed product may react with a rubber component or the like to form another compound. However, with current techniques for analyzing solid rubber compositions, it is not possible, or approximately practical, to directly identify the compounds that may be formed in the rubber composition by their structure or properties. Not right. Therefore, in the present specification and claims, the rubber composition of the present invention is specified as “a rubber composition obtained by kneading the condensate of the present invention and a rubber component”. The same applies to the vulcanized rubber composition.

¡Only one rubber component may be used, or two or more rubber components may be used in combination. Examples of rubber components include natural rubber (NR), epoxidized natural rubber, deproteinized natural rubber, modified natural rubber (HPNR) containing no more than 200 ppm by weight of phosphorus, and other modified natural rubbers; and polyisoprene rubber (IR), styrene / butadiene copolymer rubber (SBR), polybutadiene rubber (BR), acrylonitrile / butadiene copolymer rubber (NBR), isoprene / isobutylene copolymer rubber (IIR), ethylene / propylene / diene copolymer rubber (EPDM) ), Synthetic rubbers such as halogenated butyl rubber (HR), styrene isoprene butadiene rubber (SIBR), and chloroprene rubber (CR).

It is preferable to use a highly unsaturated rubber such as natural rubber, styrene / butadiene copolymer rubber or polybutadiene rubber, and it is more preferable to use natural rubber. It is also effective to combine several rubber components such as a combination of natural rubber and styrene / butadiene copolymer rubber or a combination of natural rubber and polybutadiene rubber depending on the desired application.

Examples of NR include natural rubber of grades such as RSS # 1, RSS # 3, TSR20, SIR20 and the like. As the epoxidized natural rubber, for example, those having a degree of epoxidation of 10 to 60 mol% such as ENR25 and ENR50 manufactured by Kumpulan Guthrie are preferable. As the deproteinized natural rubber, a deproteinized natural rubber having a total nitrogen content of 0.3% by weight or less is preferable. The modified natural rubber includes polar groups obtained by reacting natural rubber with 4-vinylpyridine, N, N, -dialkylaminoethyl acrylate (for example, N, N, -diethylaminoethyl acrylate), 2-hydroxyacrylate, and the like. The modified natural rubber contained is preferred. Isoprene rubbers such as NR and IR are preferable because a vulcanized rubber composition having good elongation at break and durability can be produced therefrom.

Examples of the SBR include emulsion polymerization SBR and solution polymerization SBR described in pages 210 to 211 of the “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. In particular, solution polymerization SBR is preferable as the rubber composition for treads.

Examples of the solution polymerization SBR include a modified solution polymerization SBR obtained by modifying with one or more modifiers and having at least one element of nitrogen, tin and silicon at the molecular end. Examples of the modifier include lactam compounds, amide compounds, urea compounds, N, N-dialkylacrylamide compounds, isocyanate compounds, imide compounds, silane compounds having an alkoxy group, aminosilane compounds, tin compounds and silane compounds having an alkoxy group. And a combined modifier of an alkyl acrylamide compound and a silane compound having an alkoxy group. Examples of the modified solution polymerization SBR include solution polymerization SBR having a molecular end modified with 4,4′-bis (dialkylamino) benzophenone such as “Nipol (registered trademark) NS116” manufactured by Nippon Zeon Co., Ltd. Examples thereof include solution polymerization SBR in which molecular ends are modified using a tin halide compound such as “SL574”, and silane-modified solution polymerization SBR such as “E10” and “E15” manufactured by Asahi Kasei Corporation.

Further, oil-added SBR in which oil such as process oil or aroma oil is added to emulsion polymerization SBR and solution polymerization SBR is also preferable.

The BR may be either a solution polymerization BR having a low vinyl content or a solution polymerization BR having a high vinyl content, but a solution polymerization BR having a high vinyl content is preferred. Particularly preferred is a modified solution polymerization BR obtained by modification with one or more modifiers and having at least one element of nitrogen, tin, or silicon at the molecular end. Examples of the modifier include 4,4′-bis (dialkylamino) benzophenone, tin halide compound, lactam compound, amide compound, urea compound, N, N-dialkylacrylamide compound, isocyanate compound, imide compound, and alkoxy group. Examples thereof include a silane compound having an alkoxy group (for example, a trialkoxysilane compound), an aminosilane compound, a tin compound and a silane compound having an alkoxy group, and a combined modifier having an alkylacrylamide compound and an silane compound having an alkoxy group. Examples of the modified solution polymerization BR include tin-modified BR such as “Nipol (registered trademark) BR1250H” manufactured by Nippon Zeon.

The rubber composition of the present invention containing BR can be preferably used as a rubber composition for a tread or a rubber composition for a sidewall. In the rubber composition of the present invention, for example, BR1220 manufactured by Nippon Zeon Co., Ltd., BR150B manufactured by Ube Industries, Ltd., BR150B, etc., 1 such as VCR412, VCR617, etc. manufactured by Ube Industries, Ltd. , 2- Syndiotactic polybutadiene crystals (SPB) and other BRs such as BR can be used in the tire industry. As BR including SPB, SPB is not simply dispersed in BR, but SPB is chemically bonded to BR and dispersed non-oriented, which tends to suppress the generation and propagation of cracks. Since it has, it is preferable. In addition, tin-modified butadiene rubber (tin-modified BR) modified with a tin compound can also be used. BR is usually used by blending with SBR and / or natural rubber.

The amount of the condensate of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the rubber component.

Only one type of sulfur component may be used, or two or more types may be used in combination. 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 is preferably 1 to 10 parts by weight and more preferably 2 to 6 parts by weight with respect to 100 parts by weight of the rubber component.

The rubber composition may be produced by kneading, for example, a methylene donor, a filler, a vulcanization accelerator, an organic cobalt compound and zinc oxide in addition to the above-described components.

Only one type of methylene donor may be used, or two or more types may be used in combination. Examples of the methylene donor include those usually used in the rubber industry such as hexamethylenetetramine and methoxylated methylolmelamine resin. The methylene donor is preferably a methoxylated methylol melamine resin. Examples of the methoxylated methylol melamine resin include hexakis (methoxymethyl) melamine, pentakis (methoxymethyl) methylol melamine, tetrakis (methoxymethyl) dimethylol melamine, and mixtures thereof. When a methylene donor is used, the amount is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the rubber component.

充填 Only 1 type of filler may be used, or 2 or more types may be used in combination. Examples of the filler include carbon black, silica, talc, and clay that are usually used in the rubber field. The carbon black is preferably carbon black such as FEF (Fast Extruding Furnace), HAF (High Abrasion Furnace), SAF (Super Abrasion Furnace), ISAF (Intermediate A SAF). It is also effective to combine several kinds of fillers such as a combination of carbon black and silica. When the filler is used, the amount thereof is not particularly limited, but is preferably 10 to 100 parts by weight, more preferably 30 to 70 parts by weight with respect to 100 parts by weight of the rubber component.

As the silica, for example, silica having a CTAB specific surface area of 50 to 180 m ² / g and / or silica having a nitrogen adsorption specific surface area of 50 to 300 m ² / g is preferably used. Examples of these include “Nipsil (registered trademark) AQ” and “Nippil (registered trademark) AQ-N” manufactured by Tosoh Silica, Inc., “Ultrasil (registered trademark) VN3” manufactured by Degussa, Trademark) VN3-G "," Ultrasil (registered trademark) 360 "," Ultrasil (registered trademark) 7000 "," Zeosil (registered trademark) 115GR "," Zeosil (registered trademark) 1115MP "," Zeosil "manufactured by Rhodia (Registered trademark) 1205MP "," Zeosil (registered trademark) Z85MP "and other commercial products. Silica having a pH of 6 to 8, silica containing 0.2 to 1.5% by weight of sodium, true spherical silica having a roundness of 1 to 1.3, silicone oil such as dimethyl silicone oil, containing ethoxysilyl group It is also preferable to use an organic silicon compound, silica surface-treated with an alcohol such as ethanol or polyethylene glycol, or a mixture of silica having two or more different nitrogen adsorption specific surface areas.

Only one type of vulcanization accelerator may be used, or two or more types may be used in combination. Examples of vulcanization accelerators include thiazole vulcanization accelerators, sulfenamide vulcanization accelerators, and guanidine vulcanization accelerators described in pages 412 to 413 of Rubber Industry Handbook <Fourth Edition>. Is mentioned. When a vulcanization accelerator is used, the amount thereof is preferably 0.5 to 5.0 parts by weight and more preferably 0.6 to 3.0 parts by weight with respect to 100 parts by weight of the rubber component.

The organic cobalt compound may be used alone or in combination of two or more. Examples of the organic cobalt compound include organic acid cobalt salts such as cobalt naphthenate and cobalt stearate, fatty acid cobalt / boron complex compounds (for example, “Manobond C” manufactured by Manchem, “CoMend A” manufactured by Jhepherd, and "CoMend B"). The amount of the organic cobalt compound used is determined based on the cobalt content. The cobalt content is preferably 0.1 to 0.4 parts by weight, and more preferably 0.1 to 0.3 parts by weight with respect to 100 parts by weight of the rubber component.

When zinc oxide is used, the amount thereof is preferably 1 to 15 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the rubber component.

If necessary, in addition to the above-mentioned components, the rubber composition can be used for various rubber chemicals commonly used in the rubber industry (for example, anti-aging agents such as antioxidants and ozone deterioration inhibitors, peptizers). , One or more of processing aids, waxes, oils, stearic acid, tackifiers and the like) may be kneaded for production. The amount of these chemicals varies depending on the intended use of the rubber composition, but each can be used in an amount normally used in the rubber industry.

The rubber composition can be produced by kneading the condensate of the present invention, a rubber component, and, if necessary, other components (for example, a filler).

In addition to the above components, the rubber composition obtained by further kneading the sulfur component is first a step of kneading the rubber component and a filler or the like (hereinafter sometimes abbreviated as “step 1”), and then a step. It is preferable to produce the rubber composition obtained in 1 through a step of kneading the rubber composition and the sulfur component (hereinafter sometimes abbreviated as “step 2”). Further, a pre-kneading step of kneading the rubber component may be provided before the step 1 (that is, kneading the rubber component with a filler or the like) to facilitate processing of the rubber component.

In the production of a rubber composition containing a sulfur component, the entire amount of the condensate of the present invention may be kneaded with a rubber component or the like in either the preliminary kneading step, step 1 or step 2, and the condensate of the present invention may be mixed. It may be divided and kneaded with a rubber component or the like in at least two steps of the preliminary kneading step to step 2.

When blending zinc oxide, it is preferable to knead with a rubber component or the like in step 1. When a vulcanization accelerator is blended, it is preferably kneaded with a rubber component or the like in step 2. When blending a peptizer, it is preferable to knead with a rubber component or the like in step 1. When providing the preliminary kneading step, it is preferable to knead the entire amount of the peptizer in the preliminary kneading step or to separate the peptizer and knead the rubber component in both the preliminary kneading step and step 1. .

For the kneading in Step 1, for example, an internal mixer including a Banbury mixer, an open kneader, a pressure kneader, an extruder, an injection molding machine, or the like can be used. The discharge temperature of the rubber composition after kneading in step 1 is preferably 200 ° C. or less, more preferably 120 to 180 ° C.

For kneading in step 2, for example, an open roll, a calendar, or the like can be used. The kneading temperature in Step 2 (the temperature of the rubber composition being kneaded) is preferably 60 to 120 ° C.

A vulcanized rubber composition can be produced by vulcanizing a rubber composition containing the above-described sulfur component. You may manufacture a vulcanized rubber composition by processing the rubber composition containing the above-mentioned sulfur component into a specific shape and then vulcanizing it.

The vulcanization temperature is preferably 120 to 180 ° C. A person skilled in the art can appropriately set the vulcanization time according to the composition of the rubber composition. Vulcanization is usually carried out at normal pressure or under pressure.

The rubber composition and the vulcanized rubber composition are useful for producing various products. Examples of products obtained from the rubber composition and the vulcanized rubber composition include various members of tires such as a cap tread, a base tread, an under tread, a belt, a carcass, a bead, a sidewall, and a rubber chafer. Examples of the product include vibration-proof 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 a state of being aligned in parallel.

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. Furthermore, a steel cord subjected to brass plating in which the Cu content in the brass plating is 75 wt% or less, particularly 55 to 70 wt%, is suitable. The twist structure of the steel cord is not limited.

A plurality of belts in which steel cords are coated with a rubber composition may be used. This belt is mainly used as a reinforcing material for carcass.

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

A 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 described more specifically with reference to examples and the like, but the present invention is not limited by the following examples and the like, and appropriate modifications are made within a range that can meet the above and the following purposes. In addition, it is of course possible to carry out them, all of which are included in the technical scope of the present invention.

Example 1 (Production of condensate 1)
(1) A 1000 ml jacketed separable flask equipped with a thermometer, a stirrer, and a condenser was purged with nitrogen, and then a strongly acidic cation exchange resin ("Diaion PK212LH" manufactured by Mitsubishi Chemical Corporation), about 55 wt% About 400 ml of water content, degree of crosslinking: about 6%, average particle size: 0.59 mm (150 g), and acetone (water content: 9% by weight) were charged. Thereafter, while stirring, while discharging the liquid from the bottom of the separable flask, about 2000 ml of acetone (water content: 9% by weight) was continuously supplied from the top of the separable flask. In this way, the ion exchange resin was washed with the liquid discharge rate from the flask and the liquid supply rate to the flask being substantially constant. After washing, acetone in the separable flask was removed.

(2) 300.0 g (2.72 mol) of resorcin was charged into a separable flask containing the strongly acidic cation exchange resin washed in (1) above, and the inside of the flask was purged with nitrogen, and then 364.0 g of acetone ( 6.27 mol) and 24.6 g (1.36 mol) of ion-exchanged water were charged, and the jacket temperature was raised to 83 ° C. The mixture was stirred at this temperature for 23 hours to carry out a condensation reaction (acetone usage relative to 1 mol of resorcin: 2.3 mol, ion exchange water usage relative to 1 mol of resorcin: 0.5 mol, strong acidic cation relative to 1 part by weight of resorcin. The amount of exchange resin used: 0.50 parts by weight). After the 23-hour condensation reaction, the internal temperature was lowered to 60 ° C., then 269.0 g of acetone was added, and the mixture was stirred for 10 minutes. Thereafter, the ion exchange resin and the solution were separated, and only the acetone solution (solution A1) of the condensate of resorcin and acetone was recovered. Next, 158.2 g of acetone was charged into the separable flask, and the mixture of the ion exchange resin and acetone was stirred for 10 minutes to wash the ion exchange resin. Then, the ion exchange resin and the solution were separated, and the acetone solution (solution B1) Was recovered.

(3) The same amount of resorcin, acetone and ion-exchanged water as in (2) above is charged into a separable flask containing the strongly acidic cation exchange resin after the operation in (2) above, and the same as in (2) above Condensation reaction and washing were performed under the same conditions to obtain 887.0 g of solution A2 and 199.5 g of solution B2. The water content in the solution A2 was 7.6% by weight, and the water content in the solution B2 was 5.9% by weight. In addition, only the solution A2 was used for the devolatilization of the next process.

(4) The resulting solution A2 was devolatilized by thin film distillation (evaporator jacket temperature: 220 ° C., pressure: 27 kPa) to obtain a solid condensate 1.

Example 2 (Production of condensate 2)
(1) The same operation as in Example 1 (1) was performed to wash the strongly acidic cation exchange resin.

(2) 300.0 g (2.72 mol) of resorcin was charged into a separable flask containing the strongly acidic cation exchange resin washed in (1) above, and the inside of the flask was purged with nitrogen, followed by 348.1 g of acetone ( 5.99 mol) and 34.4 g (1.91 mol) of ion-exchanged water were charged, and the jacket temperature was raised to 83 ° C. The mixture was stirred at this temperature for 23 hours to carry out a condensation reaction (amount of acetone used for 1 mol of resorcin: 2.2 mol, amount of ion-exchanged water used for 1 mol of resorcin: 0.7 mol, strongly acidic cation for 1 part by weight of resorcin) The amount of exchange resin used: 0.50 parts by weight). After the condensation reaction for 23 hours, the internal temperature was lowered to 60 ° C., 284.8 g of acetone was added, and the mixture was stirred for 10 minutes. Thereafter, the ion exchange resin and the solution were separated, and only an acetone solution (solution C1) of a condensate of resorcin and acetone was recovered. Next, 158.2 g of acetone was charged into the separable flask, and the mixture of the ion exchange resin and acetone was stirred for 10 minutes to wash the ion exchange resin. Then, the ion exchange resin and the solution were separated, and the acetone solution (solution D1) Was recovered.

(3) The same amount of resorcin, acetone and ion-exchanged water as in (2) above is charged into a separable flask containing the strongly acidic cation exchange resin after the operation in (2) above, and the same as in (2) above Condensation reaction and washing were performed under the conditions to obtain 888.3 g of solution C2 and 211.1 g of solution D2. The water content in the solution C2 was 7.7% by weight, and the water content in the solution D2 was 6.9% by weight. In addition, only the solution C2 was used for the devolatilization of the next process.

(4) The resulting solution C2 was devolatilized by thin film distillation (evaporator jacket temperature: 220 ° C., pressure: 27 kPa) to obtain a solid condensate 2.

Example 3 (Production of condensate 3)
1. Production of Solution E2 (1) The same operation as in Example 1 (1) was performed to wash the strongly acidic cation exchange resin.

(2) 100.0 g (0.91 mol) of resorcin was charged in a separable flask containing the strongly acidic cation exchange resin washed in (1) above, and the inside of the flask was purged with nitrogen, and then 263.7 g of acetone ( 4.54 mol) and 5.27 g (2.92 mol) of ion-exchanged water were charged, and the jacket temperature was raised to 70 ° C. The mixture was stirred at this temperature for 22 hours to carry out a condensation reaction (acetone usage relative to 1 mol of resorcin: 5.0 mol, ion exchange water usage relative to 1 mol of resorcin: 0.32 mol, strongly acidic cation relative to 1 part by weight of resorcin) The amount of exchange resin used: 1.50 parts by weight). After the 22-hour condensation reaction, the ion exchange resin and the solution were separated, and only the acetone solution (solution E1) of the condensate of resorcin and acetone was recovered.

(3) A separable flask containing the strongly acidic cation exchange resin after the operation of (2) is charged with the same amounts of resorcin, acetone and ion exchange water as in (2) above, and the stirring time is 8 hours. Except for the change, the condensation reaction was carried out under the same conditions as in (2) above to obtain about 350 g of solution E2. The water content in the solution E2 was 6.0% by weight. In addition, the solution E2 was used for the devolatilization mentioned later, without using the solution E1.

2. Production of Solution F2 (1) 200 g of the strongly acidic cation exchange resin used, 500 ml of acetone (water content: 9% by weight) charged together with the ion exchange resin, and continuously supplied acetone (water content: 9%) %) Was changed to about 2500 ml, and the ion exchange resin was washed in the same manner as in the operation of Example 1 (1).

(2) 100.0 g (0.91 mol) of resorcin was charged in a separable flask containing the strongly acidic cation exchange resin washed in (1) above, and the inside of the flask was purged with nitrogen, and then 263.7 g of acetone ( 4.54 mol) and 5.27 g (2.92 mol) of ion-exchanged water were charged, and the jacket temperature was raised to 70 ° C. The mixture was stirred at this temperature for 22 hours to carry out a condensation reaction (acetone usage relative to 1 mol of resorcin: 5.0 mol, ion exchange water usage relative to 1 mol of resorcin: 0.32 mol, strongly acidic cation relative to 1 part by weight of resorcin) The amount of exchange resin used: 2.00 parts by weight). After the 22-hour condensation reaction, the ion exchange resin and the solution were separated, and only the acetone solution (solution F1) of the condensate of resorcin and acetone was recovered.

(3) A separable flask containing the strongly acidic cation exchange resin after the operation of (2) is charged with the same amounts of resorcin, acetone and ion exchange water as in (2) above, and the stirring time is 8 hours. Except for the change, the condensation reaction was performed under the same conditions as in (2) above to obtain about 350 g of the solution F2. The water content in the solution F2 was 6.5% by weight. In addition, the solution F1 was not used for the devolatilization mentioned later, but the solution F2 was used.

3. Production of Condensate 3 Solution E2 (about 350 g) and solution F2 (about 350 g) were mixed to obtain a mixed solution. The resulting mixed solution was devolatilized by thin film distillation (evaporator jacket temperature: 220 ° C., pressure: 27 kPa) to obtain a solid condensate 3.

Example 4 (Production of condensate 4)
(1) A condensation reaction between resorcin and acetone was performed using a continuous reactor in which the reaction solution was circulated. The reaction tube of the continuous reactor was a jacketed stainless steel (SUS) reaction tube (inner diameter 15.75 mm, length 600 mm), and a strongly acidic cation exchange resin ("Diaion PK212LH" manufactured by Mitsubishi Chemical Corporation). ”, About 55 wt% water content, degree of crosslinking: about 6%, average particle size: 0.59 mm). During the reaction, the reaction solution is circulated from the upper part to the lower part of the reaction tube (down flow type), a back pressure regulator is installed at the outlet of the reaction tube, and the pressure in the reaction tube is 1.9 to 2.1 MPa (gauge pressure) It was adjusted to become. The reaction solution was initially charged in a separable flask, the inside of the separable flask and a plunger pump were connected by a tube, and sent to the upper part of the reaction tube by the plunger pump. By connecting the separable flask from the outlet of the reaction tube with a tube, the reaction solution was returned to the separable flask and circulated between the separable flask and the reaction tube to carry out the reaction.

(2) A separable flask was charged with 40.1 g (0.36 mol) of resorcin, and the inside of the flask was purged with nitrogen, and then 78.3 g (1.35 mol) of acetone and 1.6 g (0.089 mol) of ion-exchanged water were added. First, resorcin was dissolved in acetone and ion-exchanged water. The reaction tube jacket temperature was raised to 75 ° C. The solution was pumped at this temperature for 10 to 12 hours, and the condensation reaction was carried out (acetone use amount relative to 1 mol of resorcin: 3.7 mol, ion exchange water use amount relative to 1 mol of resorcin: 0.24 mol, relative to 1 part by weight of resorcin Use amount of strongly acidic cation exchange resin: 1.92 parts by weight). After the condensation reaction, the pumping is stopped, and nitrogen is introduced from the top of the reaction tube to discharge the reaction solution inside the reaction tube to a separable flask, so that an acetone solution of a condensate of resorcin and acetone ( Solution G) was obtained.

Furthermore, the same circulation operation (condensation reaction) as described above was performed 15 times, and about 120 g of the solution G was obtained per circulation operation. The water content in the solution G was 7.7 to 8.5% by weight.

(3) The solution G obtained by the fifth, sixth, eighth, tenth, eleventh, thirteenth, and fourteen circulation operations (the solution G for seven circulation operations) was mixed to obtain a mixed solution. The resulting mixed solution was devolatilized by thin film distillation (evaporator jacket temperature: 220 ° C., pressure: 27 kPa) to obtain a solid condensate 4.

Comparative Example 1 (Production of condensate 5)
(1) The inside of a 2000 L reaction kettle equipped with a thermometer, a stirrer and a condenser was purged with nitrogen, and then a strongly acidic cation exchange resin (“Diaion PK212LH” manufactured by Mitsubishi Chemical Corporation, containing 50 wt% water, (Degree of crosslinking: about 6%, average particle size: 0.59 mm) 114 kg and 228 kg of acetone were charged and stirred at 48 ° C. for 55 minutes. After leaving to stand after stirring, acetone was removed by filtration to wash the strongly acidic cation exchange resin. A further 114 kg of acetone was poured into the ion exchange resin on the filter, and then allowed to stand for 15 minutes to wash the ion exchange resin. The same washing was repeated 6 times. The amount of water in acetone, which is the cleaning solution after 6 times, was 1.2% by weight.

(2) After replacing the inside of a 2000 L reaction kettle equipped with a thermometer, a stirrer, and a condenser with nitrogen, the strongly acidic cation exchange resin washed in the above (1) was charged into the reaction kettle, and resorcinol 150.5 kg (1367 mol) and 236.7 kg (4075 mol, water content: 0.001 wt%) of acetone was charged, and the temperature was raised to 64 ° C. The mixture was stirred at this temperature for 17 hours to perform a condensation reaction (amount of acetone used for 1 mol of resorcin: 3 mol, amount of strongly acidic cation exchange resin used for 1 part by weight of resorcin: 0.76 parts by weight). After the 17 hour condensation reaction, the condensation reaction was stopped by removing the strongly acidic cation exchange resin by filtration. In this condensation reaction, resorcin and condensate did not precipitate from the reaction solution. The strongly acidic cation exchange resin was removed from the solution after stopping the condensation reaction by filtration. 594 kg of an acetone solution (solution H) of a condensate of resorcin and acetone was obtained.

The resulting solution H was devolatilized by thin-film distillation (evaporator jacket temperature: 270 ° C., pressure: 70 kPa or less) to obtain a solid condensate 5.

Comparative Example 2 (Production of condensate 6)
882.7 kg of an acetone solution of a condensate of resorcin and acetone synthesized in the same manner as in Example 1 was weighed and charged into a 2000 L reaction kettle equipped with a thermometer, a stirrer, and a condenser. After 421.2 kg of solvent was distilled off by simple distillation, 440.3 kg of acetone was charged, and 441.1 kg of solvent was again distilled off by simple distillation. Subsequently, 440.0 kg of acetone was added, and 437.5 kg of the solvent was distilled off by simple distillation. Furthermore, after adding 440.2 kg of acetone, 441.5 kg of the solvent was distilled off by simple distillation. Then, after cooling, 207.7 kg of acetone was added, and the acetone solution (solution I) of the condensate of resealcin and acetone of 649.8 kg was obtained. The water content in the obtained solution I was 0.22% by weight.

262.1 kg of the solution I obtained by the above dehydration operation and 80.5 kg of strongly acidic cation exchange resin (“Diaion PK212LH” manufactured by Mitsubishi Chemical Corporation) washed in the same manner as in Comparative Example 1 were used in a reaction vessel. The mixture was stirred at 20 ° C. for 26 hours under a nitrogen atmosphere to conduct a condensation reaction. After the condensation reaction for 26 hours, the condensation reaction was stopped by filtering to remove the ion exchange resin, and then the ion exchange resin was washed with 127.4 kg of acetone and washed with the acetone solution obtained by the condensation reaction. The acetone solution obtained later was mixed to obtain 370.8 kg of an acetone solution (solution J) of a condensate of resorcin and acetone.

The resulting solution J was devolatilized by thin-film distillation (evaporator jacket temperature: 220 ° C., pressure: 27 kPa) to obtain a solid condensate 6.

Test example 1
Area ratios of peaks (1) to (4) of the condensates obtained in the above examples and comparative examples, residual amounts of impurities (that is, resorcin, acetone, mesityl oxide, diacetone alcohol and water), and condensates The softening point of was measured as follows. These results are shown in Table 1 below.

(1) Area ratio of peaks (1) to (4) of condensate In gel permeation chromatography (GPC), peaks (1) to (4) of condensate with respect to the total area of peaks having a weight average molecular weight of 160 or more ) Area ratio was calculated. Specifically, 0.3 g of the obtained condensate was weighed into a 20 ml volumetric flask, and tetrahydrofuran was added and completely dissolved to obtain 20 ml of a tetrahydrofuran solution of the condensate. The obtained tetrahydrofuran solution was subjected to GPC analysis under the following apparatus and conditions, and the area ratio of peaks (1) to (4) was calculated.
Column: TOSOH TSKgel Super HZ2000 (4.6 mmφ × 150 cm) and two TOSOH TSKgel Super HZ1000 (4.6 mmφ × 150 cm) are connected Temperature: 40 ° C.
Mobile phase: Tetrahydrofuran Detection: Differential refractive index (Refractive Index, RI)
Standard: TSKgel standard polystyrene

(2) Residual amount of resorcin in the condensate The residual amount of resorcin in the condensate was measured by liquid chromatography (LC). Specifically, 1 g of the obtained condensate was weighed into a 20 ml volumetric flask, and acetonitrile was added to completely dissolve it to prepare a 20 ml condensate solution. An acetonitrile solution was obtained. Using the obtained acetonitrile solution, LC analysis was performed with the following apparatus and conditions, and the residual amount of resorcin was calculated.
Equipment: Shimadzu LC-20A
Column: SUMIPEX ODS Z-CLUE (4.6 mmφ × 250 cm, 3 μm)
Temperature: 40 ° C
Flow rate: 1 ml / min
Injection volume: 10 μl
Mobile phase: Liquid A (H ₂ O), Liquid B (acetonitrile)
Detection: UV280nm
Quantification: Absolute calibration curve Condition: gradient
B liquid concentration 0 to 8 min: 15% by volume
8-9 min: 15% by volume → 98% by volume
9 to 25 min: 98% by volume
25 min: 98% by volume → 15% by volume
25 to 35 min: 15% by volume

(3) Remaining amounts of acetone, mesityl oxide and diacetone alcohol in the condensate The residual amounts of acetone, mesityl oxide and diacetone alcohol in the condensate were measured by gas chromatography (GC). Specifically, 1 g of the obtained condensate and 0.1 g of propylene glycol-1-monomethyl ether-2-acetate are weighed into a 20 ml volumetric flask and completely dissolved by adding acetonitrile to obtain 20 ml of an acetonitrile solution of the condensate. It was. Using the obtained acetonitrile solution, GC analysis was performed under the following apparatus and conditions, and the residual amounts of acetone, mesityl oxide and diacetone alcohol were calculated.
Equipment: Agilent 7890B
Column: DB-WAX (250 μm × 30 m, 0.25 μm)
Inlet / detector temperature: 250 ° C
Flow rate: 1 ml / min (constant flow)
Injection volume: 1 μl
Detection: FID
Determination: Internal standard method Oven temperature program 0 to 5 min: 50 ° C
5 to 25 min: 50 ° C → 250 ° C
25 to 50 min: 250 ° C

(4) Residual amount of water in the condensate (water content in the condensate)
The water content in the condensate was measured by the Karl Fischer method. Specifically, it was measured using 30 mg of the condensate under the following apparatus and conditions.
Device: MCU-610 + MKC-610 manufactured by Kyoto Electronics Industry
Measurement method: Coulometric method Anolyte: Fluka HYDRANAL Coulomat AK
Catholyte: Fluka HYDRANAL Coulomat CG-K

(5) Softening point of condensate The softening point of the condensate was measured according to ASTM D6090.

As shown in Table 1, the condensates 1 to 4 satisfying the requirements of the area ratio of the peaks (1) to (4) of the present invention are the ratio of the area of the peak (3) and the area of the peak (4) of the present invention. Compared to condensates 5 and 6, which do not meet the total requirements with proportions, showed a lower softening point.

The condensate of resorcin and acetone of the present invention is useful as a reinforcing agent for rubber compositions.

This application is based on Japanese Patent Application No. 2016-181328 filed in Japan, the contents of which are incorporated in full herein.

Claims (10)

1. When analyzed by gel permeation chromatography, the total area of peaks having a weight average molecular weight of 160 or more,
   The area ratio of the peak (1) having a weight average molecular weight of 160 or more and less than 480 is 70% or less,
   The area ratio of peak (2) having a weight average molecular weight of 480 or more and less than 600 is 25 to 50%, and the area ratio of peak (3) having a weight average molecular weight of 600 or more and less than 800 and the weight average molecular weight of 800 or more The total with the area ratio of the peak (4) is 26% or less.
   Condensate of resorcin and acetone.
2. The condensate of resorcin and acetone according to claim 1, wherein the area ratio of the peak (4) having a weight average molecular weight of 800 or more is less than 10% with respect to the total area of the peak having a weight average molecular weight of 160 or more. .
3. Resorcin and acetone according to claim 1 or 2, wherein the area ratio of the peak (1) having a weight average molecular weight of 160 or more and less than 480 is 60% or less with respect to the total area of the peak having a weight average molecular weight of 160 or more. Condensate with
4. The condensate of resorcin and acetone according to any one of claims 1 to 3, wherein the residual amount of resorcin in the condensate of resorcin and acetone is 10% by weight or less.
5. A rubber composition obtained by kneading the condensate of resorcin and acetone according to any one of claims 1 to 4 and a rubber component.
6. The rubber composition according to claim 5, which is obtained by further kneading a sulfur component.
7. A vulcanized rubber composition obtained by vulcanizing the rubber composition according to claim 6.
8. A method for producing a rubber composition comprising kneading a condensate of resorcin and acetone according to any one of claims 1 to 4 and a rubber component.
9. The method according to claim 8, further comprising kneading a sulfur component.
10. A method for producing a vulcanized rubber composition comprising vulcanizing a rubber composition obtained by the method according to claim 9.