JP2016014110A - Co-condensate and method for producing the same, and rubber composition containing co-condensate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel co-condensate for an adhesive used in a filed of rubber products reinforced with reinforcement materials, which does not contain p-tert-octylphenol and p-nonylphenol, the use of which is possible to be limited by legislation, has the same level of softening point as those of the heretofore known co-condensates and therefore disperses efficiently in rubber when kneading, and further contains p-tert-butylphenol which can be available inexpensively, and to provide a resin composition and a method for producing these.SOLUTION: It was found that, by further adding o-phenylphenol as a constituent unit to a co-condensate containing p-tert-butylphenol and resorcin, a softening point of the co-condensate drops significantly, that a coumarone resin can be used specifically as a softener for the co-condensate, and that, by optimizing reaction conditions, a reaction solvent having a boiling point of 190°C or less in the co-condensate and the resin composition can be reduced to 1 wt% or less.

Description

The present invention relates to an improvement in a method for producing a cocondensate obtained from alkylphenol or the like, a cocondensate obtained by the production method, and a resin composition containing the cocondensate.

In rubber products such as tires, belts, hoses, and the like that need to be reinforced with reinforcing materials such as steel cords and organic fibers, strong adhesion between the rubber and the reinforcing material is required. In order to bond with rubber, a method of treating a reinforcing material with various adhesives and a method of blending an adhesive together with other various compounding agents in a rubber processing step are known. Among these, a method of blending an adhesive in the rubber processing step is widely adopted because it can be firmly vulcanized and bonded regardless of whether or not the reinforcing material is treated with an adhesive. As an adhesive used in such a rubber processing step, a resol-type condensate is obtained by reacting alkylphenols such as p-tert-octylphenol and p-nonylphenol with formalins in the presence of an aromatic hydrocarbon such as toluene. A co-condensate obtained by further reacting resorcin with the resole-type condensate is known. (For example, patent document 1).

However, p-tert-octylphenol and p-nonylphenol are now candidates for SVHC defined in the REACH regulations, which are regulations within the EU region, and there is a high possibility that their use will be restricted in the EU region in the future. Also, organic solvents such as aromatic hydrocarbons such as toluene are called volatile organic compounds (VOC), and it is desired that they are not released into the environment as much as possible. It is preferred that low organic solvents are not present in the product as much as possible.

Therefore, simultaneously with the development of an alternative resin that does not use p-tert-octylphenol or p-nonylphenol, there is a need for the development of a resin that contains as little organic solvent as possible with a boiling point lower than the use temperature of the product. For example, a method of removing an organic solvent having a boiling point lower than the use temperature of the product from the resin by using a solvent at the time of the reaction and removing the reaction solvent by concentration to produce a product can be considered, but the reaction solvent is completely concentrated by concentration. If it is attempted to be removed, the polymerization of the cocondensate proceeds during polymerization, resulting in a high softening point of the resulting cocondensate, making it unsuitable as an adhesive used in rubber processing steps. There was a problem.

JP-A-6-234824

The present invention is a co-condensate for adhesives used in the field of rubber products reinforced with a reinforcing material, such as p-tert-octylphenol and p-nonylphenol, which may be restricted by legal regulations. Since it does not contain specific phenols and has a softening point similar to that of a conventionally known cocondensate, it is efficiently dispersed in rubber during kneading, and a new co-polymer containing p-tert-butylphenol, which is available at low cost. In order to reduce the amount of the organic solvent contained in the condensate and the cocondensate, it is an object of the present invention to provide a novel production method that does not use an organic solvent such as an aromatic hydrocarbon during the production of the cocondensate.

As a result of intensive studies aimed at solving the problems by the present inventors, the softening point is greatly increased by using a cocondensate containing o-phenylphenol as a constituent unit of the cocondensate containing p-tert-butylphenol and resorcin. To a novel cocondensate containing p-tert-butylphenol which can be suitably used as an adhesive used in the field of rubber products reinforced with a reinforcing material. It was simultaneously found that by optimizing the production conditions, the above-mentioned cocondensate can be provided without using an organic solvent. Specifically, the following inventions [1] to [8] are included.

[1]
The following formula (1) including the steps <a> and <b>

で表されるｐ−ｔｅｒｔ−ブチルフェノール、以下式（２）

P-tert-butylphenol represented by the following formula (2)

で表されるｏ−フェニルフェノール及び以下式（３）

O-phenylphenol represented by the following formula (3)

で表されるレゾルシン由来の構成単位を含む共縮合物の製造方法。
＜ａ＞ｐ−ｔｅｒｔ−ブチルフェノールとｏ−フェニルフェノールの混合物を、ｐ−ｔｅｒｔ−ブチルフェノールとｏ−フェニルフェノールの総量（物質量基準）に対し０．２倍モル以上のアルカリ存在下、７０℃以下で反応させ、レゾール型共縮合物得る工程
＜ｂ＞前記レゾール型共縮合物にレゾルシンを反応させる工程

The manufacturing method of the cocondensate containing the structural unit derived from resorcin represented by these.
<a> A mixture of p-tert-butylphenol and o-phenylphenol is 70 ° C. or less in the presence of 0.2 moles or more of alkali with respect to the total amount (substance basis) of p-tert-butylphenol and o-phenylphenol. <B> Resorcin is reacted with the resol-type cocondensate

[2]
[1] The method for producing a cocondensate according to [1], wherein the amount of resorcin used is 1.0 to 2.0 times mol based on the total amount (substance basis) of p-tert-butylphenol and o-phenylphenol.

[3]
It is a cocondensate comprising p-tert-butylphenol represented by the above formula (1), o-phenylphenol represented by the above formula (2), and a resorcin-derived structural unit represented by the above formula (3). The total content of aliphatic hydrocarbons having a boiling point of 190 ° C. or less, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, and optionally branched ketones having 1 to 5 carbon atoms Cocondensate in an amount of 1% by weight or less.

[4]
The co-condensate according to [3], wherein the content of free resorcin is 10% by weight or less and the softening point is 150 ° C. or less.

[5]
A resin composition comprising the cocondensate according to [3] or [4] and a coumarone resin.

[6]
[5] The resin composition according to [5], wherein the content of free resorcin is 5% by weight or less and the softening point is 120 ° C. or less.

[7]
A rubber composition comprising the cocondensate according to [3] or [4].

[8]
A rubber composition comprising the resin composition according to [5] or [6].

According to the present invention, p-tert-butylphenol which is inexpensive and generally available can be used as a raw material, and is efficiently dispersed in rubber at the time of kneading, and adhesion between the rubber obtained by vulcanizing it and a reinforcing material In addition, it is possible to produce a cocondensate and a resin composition containing the cocondensate that are unlikely to be restricted in the future by law and regulation without using an organic solvent. It becomes possible to do.

Hereinafter, the present invention will be described in detail.

<Co-condensate>
A cocondensate containing structural units derived from p-tert-butylphenol, o-phenylphenol and resorcin obtained by the production method of the present invention (hereinafter also referred to as the cocondensate of the present invention) will be described.

The cocondensate of the present invention has the following formula (1) in the main chain.

で示されるｐ−ｔｅｒｔ−ブチルフェノール由来の構成単位と、以下式（２）

A structural unit derived from p-tert-butylphenol represented by formula (2):

で示されるｏ−フェニルフェノール由来の構成単位、及び以下式（３）

A structural unit derived from o-phenylphenol represented by formula (3):

で示されるレゾルシン由来の構成単位を必ず含んでいることを特徴とする。なお、これら構成単位は通常共縮合物の主鎖中に含まれるが、側鎖中に含まれる場合もある。

The structural unit derived from resorcin represented by is necessarily included. These structural units are usually contained in the main chain of the cocondensate, but may be contained in the side chain.

Among these structural units, when a structural unit derived from o-phenylphenol is not included, the softening point becomes high, resulting in problems of poor dispersibility when blended with rubber during kneading. As a result, blended with rubber during kneading. It becomes unsuitable as an adhesive between rubber and reinforcing material used. In addition, when a constituent unit derived from resorcin is not contained, the ability as an adhesive between a rubber and a reinforcing material used by mixing with rubber during kneading is not sufficiently exhibited. Furthermore, when the structural unit derived from p-tert-butylphenol is not included, the cost as a cocondensate becomes very high, and the cocondensate of the present invention cannot be obtained industrially advantageously.

These structural units are preferably 0.5 to 15 moles of the structural unit (2) derived from o-phenylphenol relative to 1 mole of the structural unit (1) derived from p-tert-butylphenol. It is more preferable to set it as 5-10 times mole, and it is especially preferable to set it as 1.5-6 times mole. When the amount is less than 0.5 times mole, the softening point may be too high and the above-mentioned problems may occur. When the amount is more than 15 times mole, the rubber and the reinforcing material used by blending with rubber at the time of kneading are used. Although it does not affect the performance as an adhesive, the raw material cost of the cocondensate increases, and the cocondensate described in the present application may not be produced industrially advantageously.

The structural unit (3) derived from resorcin is usually 0.5 to 2.0 moles per mole of the total amount of the structural unit (1) derived from p-tert-butylphenol and the structural unit (2) derived from o-phenylphenol. included. When the amount is less than 0.5 times mol, the ability as an adhesive between the rubber and the reinforcing material to be used by mixing with rubber during kneading may not be sufficiently exhibited. It may be difficult to manufacture.

These structural units are usually connected by a linking group such as an alkyl group and / or an alkyl ether group derived from an aldehyde used in the reaction. Among them, the linking group is preferably a methylene group and / or a dimethylene ether group derived from formaldehyde. The linking group is usually contained in an amount of 1 to 2 moles per mole of the total amount of the structural unit (1) derived from p-tert-butylphenol and the structural unit (2) derived from o-phenylphenol.

The ratio of these structural units can be determined, for example, by analyzing the cocondensate using ¹ H-NMR. Specifically, a method is exemplified in which the cocondensate is analyzed by ¹ H-NMR, and the ratio is determined from the proton integral value derived from each constituent unit in the obtained analysis results.

In the cocondensate of the present invention, components other than structural units derived from p-tert-butylphenol, o-phenylphenol and resorcin can be included as necessary. Examples of such structural units include structural units derived from various alkylphenols used as raw materials for cocondensates generally used as adhesives used in rubber processing steps.

The softening point of the co-condensate of the present invention is 150 ° C. or lower when used as an adhesive between a rubber and a reinforcing material used by mixing with rubber at the time of kneading as it is without mixing with a coumarone resin, which will be described later. It needs to be. In addition, it is preferable that the softening point of the cocondensate of the present invention is 80 to 150 ° C., even when the resin composition is mixed with coumarone resin or used as an adhesive as it is. More preferably, it is -140 degreeC, and it is especially preferable that it is 90-130 degreeC. When the softening point is higher than 150 ° C., when the co-condensate of the present invention is used as an adhesive as it is, dispersion becomes poor when kneaded with a rubber component, and it becomes unsuitable as an adhesive between rubber and a reinforcing material. In addition, since the co-condensate is polymerized and mixed with a coumarone resin to obtain a resin composition, the softening point is not sufficiently lowered because it cannot be mixed with a sufficient amount of coumarone resin. Problems may occur. If the softening point is lower than 80 ° C., blocking may occur during storage.

An organic solvent which can be generally used in the production of the cocondensate contained in the cocondensate of the present invention, and is intended for use of the cocondensate, that is, an upper limit temperature at which the rubber is kneaded, 190 The total content of aliphatic hydrocarbons having a boiling point lower than ° C., aromatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, and optionally branched ketones having 1 to 5 carbon atoms is It is 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.1% by weight or less. Regarding the total content of aliphatic hydrocarbons having a boiling point of 190 ° C. or less, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, and optionally branched ketones having 1 to 5 carbon atoms Can be analyzed using an analyzer such as gas chromatography. Even if the total content is 1% by weight or more, it can be used as an adhesive between rubber and reinforcing material used by mixing with rubber at the time of kneading. As a compound (VOC), it may become a cause of suspended particulate matter and photochemical oxidant, and problems in working environment such as odor may occur. In the production of the co-condensate of the present invention, an organic solvent that is not generally used due to a side reaction or a high softening point, such as alcohols, esters, ethers, etc., has a boiling point of 190 ° C. The total content of the following organic solvents is also preferably 1% by weight or less for the same reason as described above.

The content of free resorcin contained in the co-condensate is preferably 5% by weight or less when the co-condensate is used as it is as an adhesive between a rubber and a reinforcing material that is used by mixing it with rubber during kneading. . By setting it to 5% by weight or less, it is possible to suppress transpiration of resorcin at the time of rubber kneading, which is preferable in terms of the working environment. When the cocondensate is mixed with coumarone resin and used as a resin composition, it is preferably 10% by weight or less although it depends on the mixing ratio of the cocondensate and coumarone resin.

The total amount of p-tert-butylphenol and o-phenylphenol, which are unreacted monomers other than free resorcin in the cocondensate, is the adhesive between the rubber and the reinforcing material used by mixing the cocondensate with the rubber during kneading. When used as, preferably 5% by weight or less, more preferably 3% by weight or less. By setting the content to 5% by weight or less, the odor derived from the unreacted monomer can be reduced. When the cocondensate is mixed with coumarone resin and used as a resin composition, it is preferably 10% by weight or less although it depends on the mixing ratio of the cocondensate and coumarone resin.

The cocondensate of the present invention may contain water. When water is contained, the content is usually preferably 2% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.5% by weight or less. By setting the content to 2% by weight or less, the possibility that the cocondensate of the present invention causes blocking during storage is reduced.

The ash content (nonvolatile inorganic substance) in the cocondensate of the present invention is usually 5% by weight or less, preferably 2% by weight or less. When the ash content is more than 5% by weight, the ash content is separated and deposited when the resin composition containing the co-condensate of the present invention and coumarone resin described later is used, or the active ingredient decreases by the ash content, so kneading. Occasionally, the ability as an adhesive between a rubber and a reinforcing material used by blending with rubber may be reduced.

<Resin composition>
Subsequently, a resin composition containing the above-described cocondensate of the present invention and coumarone resin will be described. (Hereinafter, the resin composition containing the cocondensate of the present invention and coumarone resin may be simply referred to as a resin composition.)

When the softening point of the cocondensate of the present invention described above is high, the softening point is lowered by mixing the cocondensate of the present invention with a coumarone resin to obtain a resin composition containing the cocondensate of the present invention and coumarone resin. It is possible to make it. In addition, when process oil usually used for rubber processing is used instead of coumarone resin, the resin layer and the oil layer are separated when mixed because the compatibility with the cocondensate of the present invention is poor, and the softening agent As a result, it is not possible to sufficiently obtain the effect as described above, and it is impossible to produce a uniform product.

The coumarone resin in the present invention refers to a copolymer having an average degree of polymerization of 4 to 8 containing a coumarone residue in its skeleton structure, and has an indene and styrene residue in addition to the coumarone residue. Generally available. As the coumarone resin used in the present invention, those having a softening point of 120 ° C. or lower are used, preferably those having a softening point of 100 ° C. or lower. When a temperature higher than 120 ° C. is used, the softening point of the resin composition cannot be effectively reduced. Specific examples of coumarone resins having a softening point of 120 ° C. or less include Novales C series (Novares C10, C30, C70, C80, C90, C100, C120), Novales CA series (Novares CA80, CA100, CA120) manufactured by Rutgers, Japan Examples thereof include Knit Resin Coumarone (G-90, L-5, L-20) manufactured by Coating Chemical Co., Ltd. and Process Resin manufactured by Kobe Oil Chemical Co., Ltd. These coumarone resins may be used alone or in combination of two or more as required.

The content of coumarone resin in the resin composition is usually 5 to 70% by weight, preferably 10 to 60% by weight, based on the total amount of the resin composition. When the content exceeds 70% by weight, the resin composition may be blocked or the performance as a rubber adhesive may be deteriorated. If the amount is less than 5% by weight, the softening point may not be sufficiently lowered, and the significance of mixing coumarone resin may not be found. Moreover, when using the oily coumarone resin whose softening point is 40 degrees C or less, it is preferable that the usage-amount is 40 weight% or less. If it exceeds 40% by weight, blocking tends to occur. Therefore, in order to increase the content of coumarone resin while largely avoiding blocking and to greatly reduce the softening point, an oily coumarone resin having a softening point of 40 ° C. or lower is used in a range not exceeding 40% by weight, and further, the softening point is further increased. It is preferable to use a solid coumarone resin at 70 ° C. or higher in combination.

The softening point of the resin composition is preferably 150 ° C. or lower, more preferably 80 ° C. to 140 ° C., and particularly preferably 90 ° C. to 120 ° C. When the resin composition of the present invention is kneaded into rubber at a normal kneading temperature of about 170 ° C., a softening point of 150 ° C. or less is sufficient, but 100 to 100 for the purpose of suppressing resorcinol transpiration during kneading. When kneading at a low temperature of 130 ° C., the problem of poor dispersibility may occur unless the softening point is 120 ° C. or lower, which is lower than the kneading temperature, and the performance as an adhesive between the rubber and the reinforcing material is sufficiently developed. May not be. On the other hand, if it is lower than 80 ° C., it may block during storage.

Aliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons having a boiling point of 190 ° C. or less in the resin composition, and optionally branched ketones having 1 to 5 carbon atoms The total content of is preferably 1% by weight or less, more preferably 0.5% by weight or less, and particularly preferably 0.1% by weight, in the same manner as the cocondensate of the present invention that is the raw material of the resin composition. The following. For this purpose, it is necessary to mix the coumarone resin having the smallest total content as much as possible with the cocondensate of the present invention. Even if the total content of these in the resin composition is 1% by weight or more, it can be used as an adhesive between the rubber and the reinforcing material used by mixing with the rubber at the time of kneading. By doing so, it may become a cause of suspended particulate matter and photochemical oxidant as a volatile organic compound (VOC), and problems in working environment such as odor may occur. In addition, the total content of other organic solvents such as alcohols, esters, ethers, and the like having a boiling point of 190 ° C. or lower is preferably 1% by weight or less for the same reason as described above.

The content of free resorcin contained in the resin composition is preferably 5% by weight or less. By setting it to 5% by weight or less, it is possible to suppress transpiration of resorcin at the time of rubber kneading, which is preferable in terms of the working environment.

The total amount of p-tert-butylphenol and o-phenylphenol which are unreacted monomers other than free resorcin in the resin composition is not particularly limited, but is preferably 5% by weight or less, and preferably 3% by weight or less. Further preferred. By setting the content to 5% by weight or less, the odor derived from the unreacted monomer can be reduced.

<Method for producing co-condensate>
Then, the manufacturing method of the cocondensate of this invention is explained in full detail. The method for producing the cocondensate of the present invention comprises:
<a> A mixture of p-tert-butylphenol and o-phenylphenol is 70 ° C. or less in the presence of 0.2 moles or more of alkali with respect to the total amount (substance basis) of p-tert-butylphenol and o-phenylphenol. <B> The step of reacting resorcin with the resole-type cocondensate is performed in this order.

The ratio of o-phenylphenol in the mixture of p-tert-butylphenol and o-phenylphenol (hereinafter sometimes referred to as a phenol derivative) used in step <a> is the ratio of p-tert-butylphenol and o-phenylphenol. It is preferably 35% to 94% by mole, more preferably 40% to 91% by mole, and particularly preferably 60% to 85% by mole based on the total amount. When the amount is less than 35 mol%, the softening point of the resulting cocondensate is increased, which may result in poor dispersion when kneaded with the rubber component. If it exceeds 94 mol%, it does not affect the performance as an adhesive between the rubber and the reinforcing material used by mixing with rubber during kneading, but a large amount of expensive o-phenylphenol is required, which is industrially advantageous. In some cases, the cocondensate described in the present application cannot be produced. In addition, the mixture of p-tert-butylphenol and o-phenylphenol in the present invention is a mixture mixed in advance before being charged into the reactor, and separately charged into the reactor, resulting in a mixture in the reactor. Also included are.

As the formaldehyde used in the step <a>, in addition to formaldehyde itself, a formalin that is an aqueous solution, and a compound that easily generates formaldehyde, such as paraformaldehyde and trioxane, can be used. The charged molar ratio of formaldehyde is usually 1 to 3 times, preferably 1.5 to 2.5 times, the total amount of phenol derivative (based on the amount of substance). When the amount is less than 1 mole, unreacted monomers may increase and odor may increase. Further, when the amount is more than 3 times mole, a large amount of formaldehyde remains unreacted, so that the resin may have a three-dimensional structure and the softening point may be increased.

As the alkali used in the step <a>, those used for producing ordinary resol-type condensates such as hydroxides or carbonates of alkali metals or alkaline earth metals, ammonia, and amines are used. be able to. Specific examples of the alkali metal or alkaline earth metal hydroxide or carbonate include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, and potassium carbonate. Among these, sodium hydroxide and potassium hydroxide are preferable. These alkalis can be used in the form of a solid or an aqueous solution, but it is preferable to use an aqueous solution in terms of reactivity and handling. When an aqueous solution is used, the concentration is usually 10% to 50% by weight.

The amount of alkali used in the step <a> needs to be 0.2 times mol or more, preferably 0.3 to 0.8 times mol based on the total amount of phenol derivative (based on the amount of substance). When the amount of alkali used is less than 0.2 times mol, when the phenol derivative and formaldehyde are reacted under the conditions described later, the reaction does not proceed sufficiently, and p-tert-butylphenol and o- in the cocondensate are not reacted. Formaldehyde and resorcin that remain unreacted when the residual amount of phenylphenol becomes high and the odor at the time of rubber kneading becomes a problem or when reacting resorcin in step <b> after step <a> Reaction occurs, the resin has a three-dimensional structure and has a high softening point, and cannot be used as an adhesive between the rubber and the reinforcing material blended with the rubber during kneading.

The reaction of the step <a> is an organic solvent that can be generally used in the present reaction, that is, an aliphatic hydrocarbon, aromatic hydrocarbon, halogenated aliphatic hydrocarbon, halogenated aromatic having a boiling point of 190 ° C. or less. Although it may be carried out using hydrocarbons and C1-C5 ketones which may have branches, when these organic solvents are used, the final product is the cocondensate or resin composition of the present invention. In the present invention, it is preferable not to use these organic solvents, and it is preferable to carry out the reaction in the presence of water instead. The amount of water used is usually 0.3 to 2.0 times by weight, preferably 0.5 to 1.0 times by weight based on the total amount of the phenol derivative. When water is used, it may be added to an individual reaction vessel, or aqueous formaldehyde or alkali may be used.

The reaction in the step <a> is performed by, for example, adding p-tert-butylphenol, o-phenylphenol, and formalin (formaldehyde aqueous solution) to the reactor, and then raising the temperature to about 40 to 50 ° C. Further, it is carried out by reacting at 70 ° C. or lower for 1 to 48 hours. In addition, it is necessary to implement reaction of process <a> at 70 degrees C or less, Preferably it is 50-70 degreeC. When the reaction is carried out at a temperature higher than 70 ° C., the polymerization becomes too advanced, the reaction product is emulsified at the end of the step <a>, and the neutralization washing step described later cannot be performed unless an organic solvent is used. Therefore, the resole-type condensate cannot be separated from the alkali, and as a result, the reaction with resorcin does not occur sufficiently in the step <b>, so the content of free resorcin in the co-condensate becomes high, and rubber kneading The transpiration of resorcin produced therein becomes a problem, the ash content in the resulting cocondensate becomes high, and the quality deteriorates.

After the step <a> is completed, the step <b> may be carried out subsequently. However, the reaction product containing the resol-type condensate obtained in the step <a> may be added with water, acid, and sodium sulfate as necessary. It is preferable to carry out a step of separating the resol-type condensate from the aqueous layer (hereinafter also referred to as neutralized water washing step) after adding a water-soluble salt such as salt or salt as a specific gravity adjusting agent and stirring. . When the neutralization water washing step is not performed, when the polymerization is excessively advanced by the reaction with resorcin described below, or the alkali used in the step <a> remains in the cocondensate or resin composition of the present invention and becomes ash. As a result, when the resin composition containing the co-condensate of the present invention and coumarone resin is used, the ash is separated and deposited, or the active ingredient is reduced by the amount of the ash, so the rubber used by blending with the rubber during kneading In some cases, the capacity of the adhesive and the reinforcing material decreases.

In the case of carrying out the neutralized water washing step, the resol-type condensate is usually dissolved in an organic solvent and carried out in the presence of the organic solvent. However, if the step <a> is carried out under the conditions described above, Since it is possible to carry out the neutralization washing step without dissolving the resol-type condensate, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated aliphatics having a boiling point of 190 ° C. or less contained in the cocondensate The total content of hydrocarbons, halogenated aromatic hydrocarbons, and optionally branched ketones having 1 to 5 carbon atoms can be 1% by weight or less.

The amount of water used in the neutralized water washing step is usually 0.2 to 1 times the weight of the total amount of p-tert-butylphenol and o-phenylphenol. In addition, when water is used at the process <a>, the water may be used as it is as the water for the neutralization washing process, or water may be newly added.

In the neutralized water washing step, it is preferable to use an acid together in order to more efficiently remove the alkali used in step <a> from the resol-type condensate. Examples of acids that can be used in the neutralized water washing step include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, and p-toluenesulfonic acid. These acids may be used alone or in combination of two or more. In addition, the total amount of acid used is usually an acid equal to or greater than the alkali used in step <a> (substance amount basis). These acids can be used in the form of an aqueous solution. In this case, the concentration may be adjusted appropriately so that the total amount of water used in the neutralized water washing step falls within the above-mentioned range.

The temperature at the time of carrying out the neutralized water washing step (temperature at the time of stirring and standing) is usually 40 to 100 ° C., preferably 50 to 80 ° C.

When carrying out the neutralized water washing step, the resol-type condensate and the alkali used in step <a>, or the water containing the salt produced by neutralization (water layer) when the alkali is neutralized with an acid, are efficiently used. In order to make separation well, it is preferable to add a salt as a specific gravity adjusting agent. A salt that can be used as a specific gravity adjusting agent does not react with the resol-type condensate and has only high solubility in water. Examples thereof include sodium sulfate, ammonium sulfate, and their hydrates and sodium chloride. These salts may be used alone or in combination of two or more. The amount of salt used may be usually less than or equal to the amount completely dissolved in the aqueous layer. For example, when sodium sulfate is used, the amount of salt is 0.10 to 0 with respect to the total amount of p-tert-butylphenol and o-phenylphenol. Use 16 times the weight.

After completion of the neutralization water washing step, the resol-type condensate may be further washed with water if necessary, or a conventional purification treatment such as activated carbon treatment may be performed.

Next, step <b> will be described in detail. The amount of resorcin used in step <b> is usually 0.5 to 4.0 times, preferably 1 to 2 times, particularly 1.0 to 1.6 times, the total amount of phenol derivative. Is preferred. When the amount is more than 4.0 times, a large amount of unreacted resorcin remains, and volatilization of resorcin from the cocondensate may be a problem. When it is lower than 0.5 times mol, the reaction may not be completed and the performance as an adhesive between the rubber and the reinforcing material used by mixing with rubber during kneading may not be obtained. In addition, when performing reaction without using an organic solvent in process <b>, it is necessary to use the usage-amount of resorcinol 1-2 times with respect to the total amount of a phenol derivative.

In the step <b>, the reaction may be carried out in the presence of an inert organic solvent such as an aliphatic hydrocarbon having a boiling point of 190 ° C. or less, an aromatic hydrocarbon, a halogenated aliphatic hydrocarbon, or a halogenated aromatic hydrocarbon. However, in order for the total content of the obtained cocondensate to be 1% by weight or less, it is preferable to carry out the reaction without using an inert organic solvent. When the reaction is carried out using an inert organic solvent, it is necessary to remove the inert organic solvent from the cocondensate by concentration after completion of the step <b>, but the softening point of the resulting cocondensate becomes very high, When kneaded, it may be unsuitable as an adhesive between rubber and reinforcing material used in rubber, or may be colored or decomposed by being placed under high temperature during a concentration operation.

Step <b> is usually performed at an internal temperature of 40 to 150 ° C. for 1 to 8 hours. In the reaction between the resole-type condensate and resorcin, the reaction rate tends to be slow if water is present in the system. Therefore, after the step <a> is completed, the excess water layer is removed in the neutralization washing step. For this purpose, the resol-type condensate should be produced under the conditions defined in the step <a> in order to make it possible to separate the resol-type condensate and the aqueous layer without using an organic solvent. Is important. Further, when performing the step <b>, the reaction rate may be lowered by the water generated by the reaction of the resole-type condensate and resorcin. Therefore, the reaction is preferably performed while dehydrating for the purpose of promoting the reaction. .

After completion of step <b>, the co-condensate of the present invention is obtained. If necessary, after the step <b>, the solvent used in the reaction, unreacted phenol derivative, resorcin, etc. can be concentrated and removed. It is. (Hereinafter, it may also be called a concentration removal process.) A concentration removal process can be implemented by the method generally performed according to the boiling point of the substance to remove, and in this case, the inside of a reactor is pressure-reduced and concentrated. By doing so, it is possible to increase the removal efficiency of the substance to be removed. However, the concentration removal process tends to increase the softening point of the co-condensate, and coloring and decomposition of the resin may progress when placed under high temperatures. Preferably not.

<Method for producing resin composition>
The method for producing a resin composition containing the cocondensate of the present invention and coumarone resin will be described in detail. In the case where coumarone resin is added to the cocondensate of the present application to form a resin composition, coumarone resin is an optional component during the step of obtaining the resin composition of the present invention before reacting alkylphenol and formaldehyde in the presence of an alkali catalyst. However, after completion of the step <b>, a coumarone resin is added to the reactor, and if necessary, the concentration removal step is performed to obtain a resin composition. A method is preferably used in which the cocondensate is once produced and then the obtained cocondensate and coumarone resin are added to the reactor at an arbitrary ratio, and then the mixture is stirred and mixed to obtain a uniform resin composition.

The co-condensate and resin composition of the present invention obtained as described above can be used as an adhesive between rubber and various reinforcing materials by kneading into the rubber composition. This is particularly effective in vulcanization adhesion with a reinforcing material. Examples of the reinforcing material include organic fibers such as nylon, rayon, polyester, and aramid, and steel cords such as a brass-plated steel cord and a galvanized steel cord. In particular, it is particularly effective in vulcanization adhesion with a steel cord plated with brass. In addition, the cocondensate and resin composition of this invention can be used for the use mentioned above individually or in mixture as needed.

<Rubber composition>
Subsequently, the rubber composition containing the cocondensate and / or resin composition of the present invention will be described in detail.

  The rubber composition of the present invention is obtained by kneading the above-mentioned cocondensate and / or resin composition, rubber component, filler and sulfur. It is preferable to knead a vulcanization accelerator, zinc oxide, a methylene donor compound and an organic cobalt compound together with these.

The amount of the above-mentioned cocondensate and / or resin composition used is usually in the range of 0.5 to 10 parts by weight per 100 parts by weight of the rubber component. Among these, the range of 1 to 5 parts by weight is preferable. When the amount is less than 0.5 parts by weight, it does not function usefully as an adhesive between the reinforcing material and the rubber. Absent.

Rubber components include natural rubber, epoxidized natural rubber, deproteinized natural rubber and other modified natural rubber, as well as polyisoprene rubber (IR), styrene / butadiene copolymer rubber (SBR), polybutadiene rubber (BR), and acrylonitrile. -Various synthetic rubbers such as butadiene copolymer rubber (NBR), isoprene / isobutylene copolymer rubber (IIR), ethylene / propylene-diene copolymer rubber (EPDM), halogenated butyl rubber (HR), etc. are exemplified. Highly unsaturated rubbers such as rubber, styrene / butadiene copolymer rubber and polybutadiene rubber are preferably used. Particularly preferred is natural rubber. It is also effective to combine several rubber components such as a combination of natural rubber and styrene / butadiene copolymer rubber, a combination of natural rubber and polybutadiene rubber.

Examples of natural rubber include natural rubber of grades such as RSS # 1, RSS # 3, TSR20, SIR20 and the like. As the epoxidized natural rubber, those having a degree of epoxidation of 10 to 60 mol% are preferable, and examples thereof include ENR25 and ENR50 manufactured by Kumpoulan Guthrie. 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 contains a polar group obtained by reacting natural rubber with 4-vinylpyridine, N, N, -dialkylaminoethyl acrylate (for example, N, N, -diethylaminoethyl acrylate), 2-hydroxyacrylate, or the like in advance. Natural rubber is preferably used.

Examples of the SBR include emulsion polymerization SBR and solution polymerization SBR described in pages 210 to 211 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. In particular, solution polymerization SBR is preferably used, and further, solution polymerization SBR, JSR in which molecular ends are modified with 4,4′-bis- (dialkylamino) benzophenone such as “Nippol (registered trademark) NS116” manufactured by Nippon Zeon Co., Ltd. Solution polymerized SBR having a molecular end modified with a tin halide compound such as “SL574” manufactured by the company, commercially available silane-modified solution polymerized SBR such as “E10” and “E15” manufactured by Asahi Kasei Corporation, lactam compounds, amide compounds, A urea compound, an N, N-dialkylacrylamide compound, an isocyanate compound, an imide compound, a silane compound having an alkoxy group (trialkoxysilane compound, etc.), an aminosilane compound alone, or a tin compound and an alkoxy group Silane compounds with alkyl and alkyl acrylamide compounds And silane compound having an alkoxy group or the like, and using two or more different compounds described above and modifying the molecular terminals, respectively, nitrogen, tin, silicon, or a plurality of these elements A solution-polymerized SBR having the following is particularly preferably used.

Examples of BR include solution polymerization BR such as high cis BR having 90% or more of cis 1,4 bond and low cis BR having cis bond of around 35%, and low cis BR having a high vinyl content is preferably used. . Furthermore, tin-modified BR such as “Nipol (registered trademark) BR 1250H” manufactured by Nippon Zeon, 4,4′-bis- (dialkylamino) benzophenone, tin halide compound, lactam compound, amide compound, urea compound, N, An N-dialkylacrylamide compound, an isocyanate compound, an imide compound, a silane compound having an alkoxy group (trialkoxysilane compound, etc.), an aminosilane compound alone, or a silane compound having a tin compound and an alkoxy group, Using two or more different compounds as described above, such as an alkylacrylamide compound and a silane compound having an alkoxy group, each of the molecular ends obtained by modifying the molecular ends is either nitrogen, tin, or silicon, or those Solution polymerization B with multiple elements But particularly preferably used. These BRs are usually used in blends with natural rubber.

Natural rubber is preferred as the rubber component, and the proportion of natural rubber in the rubber component is preferably 70% by weight or more.

Examples of the filler include carbon black, silica, talc, clay, aluminum hydroxide, titanium oxide and the like that are usually used in the rubber field. Carbon black and silica are preferably used, and carbon black is particularly preferable. Preferably used. Examples of the carbon black include those described in page 494 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. HAF (High Ablation Furnace), SAF (Super Ablation Furnace), ISAF (Intermediate). Carbon black such as SAF), FEF (Fast Extension Furnace), MAF, GPF (General Purpose Furnace), SRF (Semi-Reinforcing Furnace) is preferable. Carbon black having a CTAB surface area of 40 to 250 m <2> / g, a nitrogen adsorption specific surface area of 20 to 200 m <2> / g, and a particle diameter of 10 to 50 nm is preferably used for the tire tread rubber composition, and the carbon black having a CTAB surface area of 70 to 180 m <2> / g. More preferable examples include N110, N220, N234, N299, N326, N330, N330T, N339, N343, and N351 in the ASTM standard. A surface-treated carbon black in which 0.1 to 50% by weight of silica is attached to the surface of the carbon black is also preferable. Furthermore, it is also effective to combine several kinds of fillers such as a combination of carbon black and silica.

Examples of the silica include silica having a CTAB specific surface area of 50 to 180 m <2> / g and a nitrogen adsorption specific surface area of 50 to 300 m <2> / g. "AQ", "AQ-N" manufactured by Tosoh Silica Corporation, manufactured by Degussa "Ultrasil (registered trademark) VN3", "Ultrasil (registered trademark) 360", "Ultrasil (registered trademark) 7000", "Zeosil (registered trademark) 115GR", "Zeosil (registered trademark) 1115MP" manufactured by Rhodia Commercially available products such as “Zeosil (registered trademark) 1205MP”, “Zeosil (registered trademark) Z85MP”, and “Nip Seal (registered trademark) AQ” manufactured by Nippon Silica Co., Ltd. are preferably used. When silica is usually used as a filler, bis (3-triethoxysilylpropyl) tetrasulfide ("Si-69" manufactured by Degussa) or bis (3-triethoxysilylpropyl) disulfide ("Si-" manufactured by Degussa) 75 "), bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-diethoxymethylsilylpropyl) disulfide, octanethioic acid S- [3- (triethoxysilyl) propyl] ester (General Electronic Silicones) It is preferable to add a compound having an element such as silicon that can be bonded to silica or a functional group such as alkoxysilane, such as one or more silane coupling agents selected from the group consisting of “NXT silane” manufactured by the same manufacturer.

The aluminum hydroxide is exemplified by aluminum hydroxide having a nitrogen adsorption specific surface area of 5 to 250 m <2> / g and a DOP oil supply amount of 50 to 100 ml / 100 g.

The amount of the filler used is not particularly limited, but is preferably in the range of 10 to 120 parts by weight per 100 parts by weight of the rubber component. Particularly preferred is 30 to 70 parts by weight.

The filler is preferably carbon black, and the proportion of carbon black in the filler is preferably 70% by weight or more.

Examples of the sulfur component include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Usually, powdered sulfur is preferred, and insoluble sulfur is preferred when used for tire members having a large amount of sulfur such as tire belt members. Although the usage-amount of a sulfur component is not specifically limited, The range of 1-10 weight part per 100 weight part of rubber components is preferable. The range of 5 to 10 parts by weight is preferable for tire belt members and the like.

Examples of vulcanization accelerators include thiazole-based vulcanization accelerators and sulfur compounds described on pages 412 to 413 of Rubber Industry Handbook <Fourth Edition> (issued by the Japan Rubber Association on January 20, 1994). Examples thereof include phenamide vulcanization accelerators and guanidine vulcanization accelerators.

Specifically, for example, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N, N-dicyclohexyl-2 -Benzothiazolylsulfenamide (DCBS), 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), diphenylguanidine (DPG). Among them, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N, N-dicyclohexyl-2-benzothiazolylsulfur It is preferable to use phenamide (DCBS) or dibenzothiazyl disulfide (MBTS) and diphenylguanidine (DPG) in combination.

Although the usage-amount of a vulcanization accelerator is not specifically limited, The range of 0.5-3 weight part per 100 weight part of rubber components is preferable. In particular, the range of 0.5 to 1.2 parts by weight is particularly preferable.

Although the usage-amount of zinc oxide is not specifically limited, The range of 3-15 weight part per 100 weight part of rubber components is preferable. Among these, the range of 5 to 10 parts by weight is particularly preferable.

Examples of the formaldehyde generator include those usually used in the rubber industry such as hexamethylenetetramine, hexakis (methoxymethyl) melamine, pentakis (methoxymethyl) methylolmelamine, and tetrakis (methoxymethyl) dimethylolmelamine. Among them, hexakis (methoxymethyl) melamine alone or a mixture containing it as a main component is preferable. These formaldehyde generators can be used alone or in combination, and the blending amount thereof is preferably in the range of about 0.5 to 4 parts by weight with respect to 100 parts by weight of the rubber component, and 1 to 3 parts by weight. A range of the degree is more preferable.

Examples of the organic cobalt compound include acid cobalt salts such as cobalt naphthenate and cobalt stearate, and fatty acid cobalt / boron complex compounds (for example, trade name “Manobond C (registered trademark)” manufactured by Rhodia). . The amount of the organic cobalt compound used is preferably in the range of 0.05 to 0.4 parts by weight in terms of cobalt content with respect to 100 parts by weight of the rubber component.

The rubber composition of the present invention can be compounded with various compounding agents conventionally used in the rubber field and kneaded. Examples of such compounding agents include anti-aging agents, oils, retarders, peptizers, and stearic acid.

Examples of the anti-aging agent include those described in pages 436 to 443 of “Rubber Industry Handbook <Fourth Edition>” edited by the Japan Rubber Association. Among them, N-phenyl-N′-1,3-dimethylbutyl-p-phenylenediamine (6PPD), reaction product of aniline and acetone (TMDQ), poly (2,2,4-trimethyl-1,2-) dihydro Quinoline) (“Antioxidant FR” manufactured by Matsubara Sangyo Co., Ltd.), synthetic wax (paraffin wax, etc.) and vegetable wax are preferably used.

Examples of the oil include process oil and vegetable oil. Examples of the process oil include paraffinic process oil, naphthenic process oil, and aromatic process oil.

Examples of the retarder include phthalic anhydride, benzoic acid, salicylic acid, N-nitrosodiphenylamine, N- (cyclohexylthio) -phthalimide (CTP), sulfonamide derivatives, diphenylurea, bis (tridecyl) pentaerythritol-diphosphite, etc. N- (cyclohexylthio) -phthalimide (CTP) is preferably used.

  The rubber composition containing the cocondensate and / or resin composition of the present invention can be obtained, for example, by the following method.

(A) Process of kneading filler and rubber component The filler and rubber component can be kneaded using a closed kneading apparatus such as a Banbury mixer. Such kneading usually involves heat generation, and the temperature at the end of kneading is preferably in the range of 140 ° C. to 180 ° C., more preferably in the range of 150 ° C. to 170 ° C. The kneading time is about 5 to 10 minutes.

(B) The kneaded product obtained in step A, the sulfur component and the vulcanization accelerator are kneaded. The kneaded product obtained in step A, the sulfur component and the vulcanization accelerator are kneaded, for example, in a sealed manner such as a Banbury mixer. It can be performed using a kneading apparatus or an open roll. The temperature of the kneaded product at the end of kneading is preferably 30 ° C to 100 ° C, and more preferably 60 ° C to 90 ° C. The kneading time is usually about 5 to 10 minutes.

Since the cocondensate and / or resin composition of the present invention has a low softening point, it can be added in the step (A) or (B), but is preferably added in the step (A).

When using zinc oxide, an antioxidant, oil, fatty acids, and peptizer, these are preferably added in the step (A).

When using a retarder, it is preferable to add at the process of (B).

The rubber composition containing the cocondensate and / or resin composition of the present invention thus obtained is particularly effective in vulcanization adhesion with a reinforcing material. Examples of the reinforcing material include organic fibers such as nylon, rayon, polyester, and aramid, and steel cords such as a brass-plated steel cord and a galvanized steel cord. In particular, it is particularly effective in vulcanization adhesion with a steel cord plated with brass.

A rubber composition containing the cocondensate and / or resin composition of the present invention is molded together with a reinforcing material, and a rubber product in which the rubber and the reinforcing material are firmly bonded can be obtained through a vulcanization process. The vulcanization step is preferably performed at 120 ° C to 180 ° C. The vulcanization step is performed at normal pressure or under pressure.

Hereinafter, the present invention will be described more specifically by showing examples and comparative examples. The present invention is not limited by these examples. In addition, unless otherwise specified, the content of each component, the amount of residual solvent, and the amount of free monomer described in the following Examples and Comparative Examples are the same for the total amount of the resin composition containing the obtained cocondensate or coumarone resin. % By weight of the substance.

Analysis and performance evaluation of the cocondensate and resin composition were performed as follows.
[1] Measurement of average molecular weight of resin The average molecular weight of the cocondensate and the resin composition was calculated as a polystyrene-converted weight average molecular weight by gel permeation chromatography (GPC).
Equipment used: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: TSK guard column SUPER HZ-L (manufactured by Tosoh)
+ TSK-GEL SUPER HZ1000 (4.6 mmφ × 150 mm)
+ TSK-GEL SUPER HZ2500 (4.6mmφ × 150mm)
+ TSK-GEL SUPER HZ4000 (4.6 mmφ × 150 mm)
Column temperature: 40 ° C
Injection volume: 10 μL
Carrier and flow rate: Tetrahydrofuran 0.35 mL / min
Sample preparation: About 0.02 g of the present compound or resin composition is dissolved in 20 mL of tetrahydrofuran.

[2] Measurement of free monomer and residual solvent The free monomer and the residual solvent were quantified by gas chromatography based on the following conditions.
Equipment used: Gas chromatograph GC-14B manufactured by Shimadzu Corporation
Column: Glass column outer diameter 5 mm x inner diameter 3.2 mm x length 3.1 m
Filler: Filler Silicone OV-17 10% Chromosorb WHP 80/100 mesh, max. temp. 340 ° C
Column temperature: 80 ° C → 280 ° C
Vaporization chamber temperature: 250 ° C
Detector temperature: 280 ° C
Detector: FID
Carrier: N2 (40 ml / min)
Combustion gas: Hydrogen (60 kPa), Air (60 kPa)
Injection volume: 2 μL
1 g of the cocondensate or resin composition was dissolved in 10 mL of acetone and analyzed under the above conditions. By the absolute calibration curve method (GC-ES method), the type and content (%) of the residual solvent in the resin and the content (%) of the residual monomer were measured.

[3] Measurement of softening point Measured by a method based on JIS-K2207.

[4] ¹ H-NMR analysis was performed by a method based on the following conditions of the mixing ratio of each structural unit in the cocondensate.
Equipment: “JMN-ECS” (400 MHz) manufactured by JEOL Ltd.
Solvent: Deuterium-substituted dimethyl sulfoxide Sample: Dissolved at about 2 mg / 1 mL Chemical shift of each component: Tetramethylsilane was used as a standard (0 ppm), and the peaks shown below were taken as the peak of each component.
Proton of p-tert-butyl group derived from p-tert-butylphenol: 1.0 to 1.2 ppm
Proton of methylene group derived from formaldehyde: 3.4 to 3.9 ppm
Proton of o-phenyl group derived from o-phenylphenol: 7.1 to 7.5 ppm
Since it was difficult to separate and assign the protons of the phenolic hydroxyl group derived from resorcin, all the protons derived from the phenolic hydroxyl group: from the integral value of 7.80 to 9.30 ppm, one derived from p-tert-butylphenol The integral value of two phenolic hydroxyl groups derived from resorcin was calculated by subtracting the integral value of protons derived from phenolic hydroxyl group and the integral value of protons derived from one phenolic hydroxyl group derived from o-phenylphenol.
In addition, about the component ratio in an Example below, it is a ratio based on the following references | standards.
o-Phenylphenol: Ratio (molar times) when p-tert-butylphenol 1 is used
Methylene group derived from formaldehyde: ratio (mole times) to the total amount of o-phenylphenol and p-tert-butylphenol
Resorcin: Ratio (molar times) when p-tert-butylphenol 1 is used. Figures in parentheses are percentages of the total amount of o-phenylphenol and p-tert-butylphenol. (Mole times)

[5] Moisture analysis method Measured by a method based on JIS-K0068.

[6] Ash content analysis The ash content was measured by a method based on JIS-K6201.

1. Production of cocondensate and resin composition and evaluation of physical properties <Example 1>
A four-necked separable flask equipped with a reflux condenser and a thermometer was charged with 180.0 g (2.22 mol) of formalin having a purity of 37%, 30.0 g (0.20 mol) of p-tert-butylphenol, 170 of o-phenylphenol. 0.0 g (1.00 mol) was added in order. Thereafter, the internal temperature was raised to 40 ° C., 80.0 g (0.48 mol) of a 24% aqueous sodium hydroxide solution was added, and the mixture was stirred until the exotherm subsided. After confirming that the exotherm had subsided, the temperature was raised to an internal temperature of 65 ° C., and the reaction was performed at the same temperature for 2 hours.
After completion of the reaction, 70.5 g (0.216 mol) of 30% sulfuric acid and 3.02 (0.024 mol) of oxalic acid dihydrate were added and stirred for 0.2 hours. After removing and removing the aqueous layer, it was returned to the flask.
184.8 g (1.68 mol) of resorcin was added, the temperature was raised to an internal temperature of 110 ° C., and dehydration was performed for 3 hours under slightly reduced pressure (92 kPa). During this time, the internal temperature rose from 115 ° C to 118 ° C. Subsequently, the internal temperature was raised to 140 ° C. and dehydration (92 kPa) was performed for 2 hours. Then, it heated up to 145-150 degreeC of internal temperature, and water was distilled off by heat-retaining for 1 hour. Thereafter, the pressure was reduced to 16 kPa while maintaining the internal temperature at 140 to 150 ° C., and water was further distilled off. By the above operation, 414 g of a yellow cocondensate was obtained.
Average molecular weight of co-condensate: 1576, softening point: 127 ° C., free p-tert-butylphenol content: 0.0%, free o-phenylphenol content: 0.8%, free resorcin content: 7.9%, boiling point Is 190 ° C. or lower organic solvent: 0.0%, moisture content 0.2%, ash content 0.0%. Ratio of each structural unit of co-condensate: o-phenylphenol: 5.31, methylene group: 1.69, resorcin: 8.73 (1.38)
Subsequently, in a four-neck separable flask equipped with a reflux condenser and a thermometer, 200.0 g of the obtained cocondensate, Novales C10 manufactured by Rutgers as a coumarone resin (oil-free at room temperature, 100.0 g), Rutgers Novares C90 (softening point: 85-95 ° C., 100.0 g) was added in order. Thereafter, the temperature was raised to an internal temperature of 150 ° C., and the mixture was stirred for 2 hours while keeping the internal temperature at 140 to 150 ° C., thereby mixing the cocondensate and the coumarone resin uniformly. By the above operation, 398.2 g of a resin composition containing coumarone resin was obtained.
Average molecular weight of resin composition containing coumarone resin: 1207, softening point: 108 ° C., free p-tert-butylphenol: 0.0%, free o-phenylphenol: 0.4%, free resorcin: 3.7%, Organic solvent having a boiling point of 190 ° C. or lower: 0.0%, moisture content 0.1%, ash content 0.0%. Coumarone resin content: 50%.

<Example 2>
A four-necked separable flask equipped with a reflux condenser and a thermometer was charged with 180.0 g (2.22 mol) of formalin having a purity of 37%, 30.0 g (0.20 mol) of p-tert-butylphenol, 170 of o-phenylphenol. 0.0 g (1.00 mol) was added in order. Thereafter, the internal temperature was raised to 40 ° C., 80.0 g (0.48 mol) of a 24% aqueous sodium hydroxide solution was added, and the mixture was stirred until the exotherm subsided. After confirming that the exotherm had subsided, the temperature was raised to an internal temperature of 65 ° C., and the reaction was performed at the same temperature for 2 hours.
After completion of the reaction, 70.5 g (0.216 mol) of 30% sulfuric acid, 3.02 (0.024 mol) of oxalic acid dihydrate, and 26.0 g (0.0183 mol) of sodium sulfate were added and the mixture was stirred for 0.2 hours. And the aqueous layer was removed.
171.6 g (1.56 mol) of resorcin was added, the temperature was raised to an internal temperature of 110 ° C., and dehydration was performed under a slightly reduced pressure (92 kPa) for 1.5 hours. During this time, the internal temperature rose from 115 ° C to 125 ° C. Subsequently, the internal temperature was raised to 145 ° C., and dehydration (92 kPa) was performed for 1 hour. Then, it heated up to 145-150 degreeC of internal temperature, and water was distilled off by heat-retaining for 1 hour. Thereafter, the pressure was reduced to 16 kPa while maintaining the internal temperature at 140 to 150 ° C., and water was further distilled off. By the above operation, 389 g of a yellow cocondensate was obtained.
Average molecular weight of co-condensate: 1728, softening point: 135 ° C., free p-tert-butylphenol content: 0.0%, free o-phenylphenol content: 0.7%, free resorcin content: 5.9%, boiling point Is 190% or lower organic solvent: 0.0%, moisture content 0.2%, ash content 0.1%. Ratio of each structural unit of co-condensate: o-phenylphenol: 5.23, methylene group: 1.62, resorcin: 7.97 (1.28)
Subsequently, in a four-neck separable flask equipped with a reflux condenser and a thermometer, 200.0 g of the obtained cocondensate, Novales C10 manufactured by Rutgers as a coumarone resin (oil at room temperature, 120.0 g), Rutgers Novares C90 (softening point: 85-95 ° C., 80.0 g) was added in order. Thereafter, the temperature was raised to an internal temperature of 150 ° C., and the mixture was stirred for 2 hours while keeping the internal temperature at 140 to 150 ° C., thereby mixing the cocondensate and the coumarone resin uniformly. By the above operation, 398.5 g of a resin composition containing coumarone resin was obtained.
Average molecular weight of resin composition containing coumarone resin: 1242, softening point: 109 ° C., free p-tert-butylphenol: 0.0%, free o-phenylphenol: 0.5%, free resorcin: 2.9%, Organic solvent having a boiling point of 190 ° C. or lower: 0.0%, moisture content 0.1%, ash content 0.1%. Coumarone resin content: 50%.

<Example 3>
A four-necked separable flask equipped with a reflux condenser and a thermometer was charged with 180.0 g (2.22 mol) of formalin having a purity of 37%, 30.0 g (0.20 mol) of p-tert-butylphenol, 170 of o-phenylphenol. 0.0 g (1.00 mol) was added in order. Thereafter, the internal temperature was raised to 40 ° C., 60.0 g (0.36 mol) of a 24% aqueous sodium hydroxide solution was added, and the mixture was stirred until the exotherm subsided. After confirming that the exotherm had subsided, the temperature was raised to an internal temperature of 65 ° C., and the reaction was carried out at the same temperature for 2 hours.
After completion of the reaction, 52.9 g (0.162 mol) of 30% sulfuric acid, 2.26 (0.018 mol) of oxalic acid dihydrate and 26.0 g (0.0183 mol) of sodium sulfate were added, and the mixture was stirred for 0.2 hours. And the aqueous layer was removed.
184.8 g (1.68 mol) of resorcin was added, the temperature was raised to an internal temperature of 110 ° C., and dehydration was performed over 2.0 hours under slightly reduced pressure (92 kPa). During this time, the internal temperature rose from 118 ° C to 120 ° C. Subsequently, the internal temperature was raised to 147 ° C., and dehydration (92 kPa) was performed for 1 hour. Then, the temperature was raised to an internal temperature of 145 to 151 ° C., and water was distilled off by keeping the temperature for 1 hour. Thereafter, the pressure was reduced to 16 kPa while maintaining the internal temperature at 145 to 150 ° C., and water was further distilled off. By the above operation, 403 g of a yellow cocondensate was obtained.
Average molecular weight of the cocondensate: 1889, softening point: 129 ° C, free p-tert-butylphenol: 0.0%, free o-phenylphenol: 0.7%, free resorcin: 7.1%, boiling point 190 ° C The following organic solvents: 0.0%, moisture content 0.2%, ash content 0.2%. Ratio of each structural unit of co-condensate: o-phenylphenol: 5.25, methylene group: 1.66, resorcin: 8.70 (1.41)
Subsequently, in a four-neck separable flask equipped with a reflux condenser and a thermometer, 200.0 g of the obtained cocondensate, Novales C10 manufactured by Rutgers as a coumarone resin (oil at room temperature, 120.0 g), Rutgers Novares C90 (softening point: 85-95 ° C., 80.0 g) was added in order. Thereafter, the temperature was raised to an internal temperature of 150 ° C., and the mixture was stirred for 2 hours while keeping the internal temperature at 140 to 150 ° C., thereby mixing the cocondensate and the coumarone resin uniformly. By the above operation, 397.5 g of a resin composition containing coumarone resin was obtained.
Average molecular weight of resin composition containing coumarone resin: 1339, softening point: 105 ° C., free p-tert-butylphenol: 0.0%, free o-phenylphenol: 0.3%, free resorcin: 3.5%, Organic solvent having a boiling point of 190 ° C. or lower: 0.0%, moisture content 0.1%, ash content 0.1%. Coumarone resin content: 50%.

<Example 4>
The same operation as in Example 3 except that 80.0 g of Ruggers Novares C10 (oily at room temperature) and 120.0 g of Ruggers Novares C90 (softening point: 85 to 95 ° C.) are used as the coumarone resin in Example 3. To obtain 399.5 g of a resin composition containing coumarone resin.
Average molecular weight of resin composition containing coumarone resin: 1368, softening point: 110 ° C., free p-tert-butylphenol: 0.0%, free o-phenylphenol: 0.4%, free resorcin: 3.7%, Organic solvent having a boiling point of 190 ° C. or lower: 0.0%, moisture content 0.1%, ash content 0.1%. Coumarone resin content: 50%.

<Example 5>
In a four-necked separable flask equipped with a reflux condenser and a thermometer, 360.0 g (4.44 mol) of formalin having a purity of 37%, 60.0 g (0.40 mol) of p-tert-butylphenol, o-phenylphenol 340 0.0 g (2.00 mol) was added in order. Thereafter, the temperature was raised to 40 ° C., 120.0 g (0.72 mol) of a 24% aqueous sodium hydroxide solution was added, and the mixture was stirred until the exotherm subsided. After confirming that the exotherm had subsided, the temperature was raised to an internal temperature of 65 ° C., and the reaction was carried out at the same temperature for 2 hours.
After completion of the reaction, 105.1 g (0.324 mol) of 30% sulfuric acid, 4.53 (0.036 mol) of oxalic acid dihydrate, and 50.0 g (0.0352 mol) of sodium sulfate were added, and the mixture was stirred for 0.2 hours. And the aqueous layer was removed.
369.6 g (3.36 mol) of resorcin was added, the temperature was raised to an internal temperature of 125 ° C., and dehydration was performed for 3 hours under slightly reduced pressure (92 kPa). During this time, the internal temperature rose from 115 ° C to 125 ° C. Subsequently, the internal temperature was raised to 140 ° C. and dehydration (92 kPa) was performed for 2 hours. Then, it heated up to 145-150 degreeC of internal temperature, and water was distilled off by heat-retaining for 1 hour. Thereafter, the pressure was reduced to 16 kPa while maintaining the internal temperature at 140 to 150 ° C., and water was further distilled off. By the above operation, 808 g of a yellow cocondensate was obtained.
Average molecular weight of cocondensate: 1857, softening point: 132.3 ° C., free p-tert-butylphenol: 0.0%, free o-phenylphenol: 1.5%, free resorcinol: 7.8%, boiling point Organic solvent at 190 ° C. or lower: 0.0%, water content 0.5%, ash content 0.0%. Ratio of each structural unit of co-condensate: o-phenylphenol: 5.30, methylene group: 1.69, resorcin: 8.76 (1.39)
Subsequently, in a four-necked separable flask equipped with a reflux condenser and a thermometer, the obtained cocondensate 200.0 g, Novales C10 manufactured by Rutgers as a coumarone resin (oil at room temperature, 80.0 g), Rutgers Novares C90 (softening point: 85-95 ° C., 120.0 g) was added in order. Thereafter, the temperature was raised to an internal temperature of 150 ° C., and the mixture was stirred for 2 hours while keeping the internal temperature at 140 to 150 ° C., thereby mixing the cocondensate and the coumarone resin uniformly. By the above operation, 397.5 g of a resin composition containing coumarone resin was obtained.
Average molecular weight of resin composition containing coumarone resin: 1189, softening point: 109 ° C., free p-tert-butylphenol: 0.0%, free o-phenylphenol: 0.8%, free resorcin: 3.8%, Organic solvent having a boiling point of 190 ° C. or lower: 0.0%, moisture content 0.4%, ash content 0.0%. Coumarone resin content: 50%.

<Example 6>
The same operation as in Example 3 except that 80.0 g of Ruggers Novales C30 (oily at normal temperature) and 120.0 g of Rutgers Novales C90 (softening point: 85 to 95 ° C.) are used as the coumarone resin in Example 5. To obtain 399.0 g of a resin composition containing coumarone resin.
Average molecular weight of resin composition containing coumarone resin: 1398, softening point: 111 ° C., free p-tert-butylphenol: 0.0%, free o-phenylphenol: 0.7%, free resorcin: 3.7%, Organic solvent having a boiling point of 190 ° C. or lower: 0.0%, water content 0.5%, ash content 0.0%. Coumarone resin content: 50%.

<Example 7>
In a four-necked separable flask equipped with a reflux condenser and a thermometer, 360.0 g (4.44 mol) of formalin having a purity of 37%, 60.0 g (0.40 mol) of p-tert-butylphenol, o-phenylphenol 340 0.0 g (2.00 mol) was added in order. Thereafter, the internal temperature was raised to 40 ° C., 160.0 g (0.96 mol) of a 24% aqueous sodium hydroxide solution was added, and the mixture was stirred until the exotherm subsided. After confirming that the exotherm had subsided, the temperature was raised to an internal temperature of 68 ° C., and the reaction was carried out at the same temperature for 2 hours.
After completion of the reaction, 140.1 g (0.432 mol) of 30% sulfuric acid, 6.04 (0.048 mol) of oxalic acid dihydrate and 45.0 g (0.0316 mol) of sodium sulfate were added, and the mixture was stirred for 0.2 hours. And the aqueous layer was removed.
343.2 g (3.24 mol) of resorcin was added, the temperature was raised to an internal temperature of 125 ° C., and dehydration was performed under a slightly reduced pressure (92 kPa) over 2.5 hours. During this time, the internal temperature rose from 118 ° C to 125 ° C. Subsequently, the internal temperature was raised to 140 ° C. and dehydration (92 kPa) was performed for 2 hours. Then, it heated up to 145-150 degreeC of internal temperature, and water was distilled off by heat-retaining for 1 hour. Thereafter, the pressure was reduced to 16 kPa while maintaining the internal temperature at 140 to 150 ° C., and water was further distilled off. By the above operation, 772 g of a yellow cocondensate was obtained.
Average molecular weight of co-condensate: 2003, softening point: 134 ° C., free p-tert-butylphenol: 0.0%, free o-phenylphenol: 0.7%, free resorcin: 7.5%, boiling point of 190 ° C. The following organic solvents: 0.0%, moisture content 0.4%, ash content 0.0%. Ratio of each structural unit of co-condensate: o-phenylphenol: 5.32, methylene group: 1.69, resorcin: 8.46 (1.34)
Subsequently, in a four-necked separable flask equipped with a reflux condenser and a thermometer, 200.0 g of the obtained cocondensate, Novales 10 manufactured by Rutgers as a coumarone resin (oil at room temperature, 120.0 g), Rutgers Novares C90 (softening point: 85-95 ° C., 80.0 g) was added in order. Thereafter, the temperature was raised to an internal temperature of 150 ° C., and the mixture was stirred for 2 hours while keeping the internal temperature at 140 to 150 ° C., thereby mixing the cocondensate and the coumarone resin uniformly. By the above operation, 398.1 g of a resin composition containing coumarone resin was obtained.
Average molecular weight of resin composition containing coumarone resin: 1401, softening point: 107 ° C., free p-tert-butylphenol: 0.0%, free o-phenylphenol: 0.3%, free resorcin: 3.5%, Organic solvent having a boiling point of 190 ° C. or lower: 0.0%, moisture content 0.4%, ash content 0.0%. Coumarone resin content: 50%.

<Example 8>
A four-necked separable flask equipped with a reflux condenser and a thermometer was charged with 180.0 g (2.22 mol) of formalin having a purity of 37%, 30.0 g (0.20 mol) of p-tert-butylphenol, 170 of o-phenylphenol. 0.0 g (1.00 mol) was added in order. Thereafter, the internal temperature was raised to 40 ° C., 160.0 g (0.96 mol) of a 24% aqueous sodium hydroxide solution was added, and the mixture was stirred until the exotherm subsided. After confirming that the exotherm had subsided, the temperature was raised to an internal temperature of 54 ° C., and the reaction was carried out at the same temperature for 2 hours.
After completion of the reaction, 141 g (0.432 mol) of 30% sulfuric acid, 6.04 (0.048 mol) of oxalic acid dihydrate, and 26.0 g (0.0183 mol) of sodium sulfate were added and stirred for 0.2 hours and left to stand. The aqueous layer was removed.
Resorcin 198.0g (1.80mol) was added, it heated up to the internal temperature of 110 degreeC, and it spin-dry | dehydrated over 3 hours under slight reduced pressure (92 kPa). During this time, the internal temperature rose from 110 ° C to 125 ° C. Subsequently, the internal temperature was raised to 145 ° C., and dehydration (92 kPa) was performed for 1 hour. Then, it heated up to 145-150 degreeC of internal temperature, and water was distilled off by heat-retaining for 1 hour. Thereafter, the pressure was reduced to 16 kPa while maintaining the internal temperature at 140 to 150 ° C., and water was further distilled off. By the above operation, 416 g of a yellow cocondensate was obtained.
Average molecular weight of co-condensate: 1568, softening point: 122 ° C, free p-tert-butylphenol: 0.3%, free o-phenylphenol: 1.2%, free resorcin: 8.0%, boiling point 190 ° C The following organic solvents: 0.0%, moisture content 0.2%, ash content 0.1%. Ratio of each structural unit of co-condensate: o-phenylphenol: 5.28, methylene group: 1.72, resorcin: 9.23 (1.47)
Subsequently, in a four-neck separable flask equipped with a reflux condenser and a thermometer, the obtained cocondensate 200.0 g, Novales C10 manufactured by Rutgers as a coumarone resin (oil at room temperature, 120.0 g), Rutgers Novares C90 (softening point: 85-95 ° C., 80.0 g) was added in order. Thereafter, the temperature was raised to an internal temperature of 150 ° C., and the mixture was stirred for 2 hours while keeping the internal temperature at 140 to 150 ° C., thereby mixing the cocondensate and the coumarone resin uniformly. By the above operation, 396.5 g of a resin composition containing coumarone resin was obtained.
Average molecular weight of resin composition containing coumarone resin: 1087, softening point: 104 ° C., free p-tert-butylphenol: 0.0%, free o-phenylphenol: 0.5%, free resorcin: 4.0%, Organic solvent having a boiling point of 190 ° C. or lower: 0.0%, moisture content 0.1%, ash content 0.0%. Coumarone resin content: 50%.
<Example 9>
A four-necked separable flask equipped with a reflux condenser and a thermometer was charged with 180.0 g (2.22 mol) of formalin having a purity of 37%, 30.0 g (0.20 mol) of p-tert-butylphenol, 170 of o-phenylphenol. 0.0 g (1.00 mol) was added in order. Thereafter, the temperature was raised to an internal temperature of 40 ° C., 40.0 g (0.24 mol) of a 24% aqueous sodium hydroxide solution was added, and the mixture was stirred until the exotherm subsided. After confirming that the exotherm had subsided, the temperature was raised to an internal temperature of 65 ° C. and reacted at the same temperature for 4 hours.
After completion of the reaction, 35.3 g (0.108 mol) of 30% sulfuric acid, 1.51 (0.012 mol) of oxalic acid dihydrate, and 26.0 g (0.0183 mol) of sodium sulfate were added and the mixture was stirred for 0.2 hours. And the aqueous layer was removed.
184.8 g (1.68 mol) of resorcin was added, the temperature was raised to an internal temperature of 110 ° C., and dehydration was performed for 2 hours under slightly reduced pressure (92 kPa). During this time, the internal temperature rose from 110 ° C to 125 ° C. Subsequently, the internal temperature was raised to 145 ° C., and dehydration (92 kPa) was performed for 1 hour. Thereafter, the temperature was raised to an internal temperature of 145 to 150 ° C., and water was distilled off by keeping the temperature for 2 hours. Thereafter, the pressure was reduced to 16 kPa while maintaining the internal temperature at 140 to 150 ° C., and water was further distilled off. By the above operation, 414 g of a yellow cocondensate was obtained.
Average molecular weight of co-condensate: 1865, softening point: 133 ° C., free p-tert-butylphenol: 0.0%, free o-phenylphenol: 1.5%, free resorcin: 7.1%, boiling point 190 ° C. The following organic solvents: 0.0%, moisture content 0.2%, ash content 0.0%. Ratio of each structural unit of co-condensate: o-phenylphenol: 5.25, methylene group: 1.64, resorcin: 8.75 (1.40)

<Reference Example 1>
A four-necked separable flask equipped with a reflux condenser and a thermometer was charged with 180.0 g (2.22 mol) of formalin having a purity of 37%, 30.0 g (0.20 mol) of p-tert-butylphenol, 170 of o-phenylphenol. 0.0 g (1.00 mol) was added in order. Thereafter, the internal temperature was raised to 45 ° C., 60.0 g (0.36 mol) of a 24% aqueous sodium hydroxide solution was added, and the mixture was stirred until the exotherm subsided. After confirming that the exotherm had subsided, the temperature was raised to an internal temperature of 65 ° C., and the reaction was carried out at the same temperature for 2 hours.
After completion of the reaction, 52.9 g (0.162 mol) of 30% sulfuric acid, 2.26 (0.018 mol) of oxalic acid dihydrate, and 154.0 of methyl isobutyl ketone were added and stirred for 0.2 hours, and left to stand. The layer was removed.
171.6 g (1.56 mol) of resorcin was added, the temperature was raised to an internal temperature of 118 ° C., and azeotropic dehydration was performed under reduced pressure (45 kPa) for 6 hours. During this time, the internal temperature rose to 122-124 ° C. Subsequently, the internal temperature was raised to 140 ° C., and azeotropic dehydration (decompression degree 66 kPa) was performed for 2 hours. Thereafter, the temperature was raised to an internal temperature of 145 to 150 ° C., and the solvent methyl isobutyl ketone was distilled off by keeping the temperature for 2 hours while gradually increasing the degree of vacuum. Thereafter, the pressure was reduced to 16 kPa while maintaining the internal temperature at 140 to 150 ° C., and the solvent methyl isobutyl ketone was further distilled off. By the above operation, 416 g of orange cocondensate was obtained.
Average molecular weight of cocondensate: 1931, softening point: 121 ° C., residual methyl isobutyl ketone content: 1.7%, organic solvent having a boiling point other than methyl isobutyl ketone of 190 ° C. or less: 0.0%, free p-tert- Butylphenol content: 0.0%, free o-phenylphenol content: 1.2%, free resorcin content: 7.2%, moisture content 0.1%, ash content 0.0%. Ratio of each structural unit of co-condensate: o-phenylphenol: 5.19, methylene group: 1.58, resorcin: 8.48 (1.37)
Subsequently, in a four-neck separable flask equipped with a reflux condenser and a thermometer, 60.0 g of the obtained cocondensate, Novales C10 manufactured by Rutgers as a coumarone resin (oil at room temperature, 36.0 g), manufactured by Rutgers Novales C90 (softening point: 85-95 ° C., 24.0 g) was added in order. Thereafter, the temperature was raised to an internal temperature of 150 ° C., and the mixture was stirred for 2 hours while keeping the internal temperature at 140 to 150 ° C., thereby mixing the cocondensate and the coumarone resin uniformly. By the above operation, 119 g of a resin composition containing coumarone resin was obtained.
Average molecular weight of resin composition containing coumarone resin: 1330, softening point: 102 ° C., residual methyl isobutyl ketone: 0.6%, organic solvent having a boiling point other than methyl isobutyl ketone of 190 ° C. or lower: 0.0%, free p -Tert-butylphenol: 0.0%, free o-phenylphenol: 0.7%, free resorcin: 3.3%, moisture content 0.1%, ash content 0.0%, coumarone resin content: 50%.

<Comparative Example 1>
In a four-necked separable flask equipped with a reflux condenser and a thermometer, 270 g (3.33 mol) of formalin having a purity of 37%, 45.0 g (0.30 mol) of p-tert-butylphenol, and 255 g of o-phenylphenol (1 .50 mol) was added in order. Thereafter, the internal temperature was raised to 45 ° C., 53.9 g (0.32 mol) of a 24% sodium hydroxide aqueous solution was added, and the mixture was stirred until the exotherm was stopped. After confirming that the exotherm had subsided, the temperature was raised to an internal temperature of 65 ° C. and kept at that temperature for 1.5 hours. Thereafter, the temperature was raised again until the internal temperature reached 75 ° C., and the reaction was further continued at the same temperature for 3 hours.
After completion of the reaction, the mixture was cooled to an internal temperature of 65 ° C. or lower, and 47.6 g (0.14 mol) of 30% sulfuric acid and 2.04 g (0.018 mol) of oxalic acid dihydrate were added and stirred for 0.2 hours. Since it was viscous and emulsified and not separated into layers, the liquid separation and the aqueous layer were not removed.
Next, 197.5 g (1.79 mol) of resorcin was added, the temperature was raised to an internal temperature of 80 ° C., and concentration was carried out over 8 hours at a gradually reduced pressure (92 kPa → 45 kPa). During this time, the internal temperature rose to 120 ° C. Then, it heated up to 140 degreeC of internal temperature, and concentrated for 6 hours. During this time, the degree of vacuum was changed from 45 kPa to 15 kPa. Thereafter, the pressure was reduced to 11 kPa while maintaining the internal temperature at 140 to 150 ° C., and the water was further distilled off by keeping the temperature for 2 hours. By the above operation, 506 g of a brown cocondensate was obtained. Average molecular weight of cocondensate: 6604, softening point: 158 ° C., free p-tert-butylphenol: 0.0%, free o-phenylphenol: 0.1%, free resorcin: 4.1%, boiling point 190 ° C. The following organic solvents: 0.0%, moisture content 0.2%, ash content 5.2%. Ratio of each structural unit of co-condensate: o-phenylphenol: 5.13, methylene group: 1.36, resorcin: 6.02 (0.98)
Subsequently, in a four-neck separable flask equipped with a reflux condenser and a thermometer, 60.0 g of the obtained cocondensate, Novales C10 manufactured by Rutgers as a coumarone resin (oil at room temperature, 36.0 g), manufactured by Rutgers Novales C90 (softening point: 85-95 ° C., 24.0 g) was added in order. Thereafter, the temperature was raised to an internal temperature of 150 ° C., and the mixture was stirred for 2 hours while keeping the internal temperature at 140 to 160 ° C. However, the compatibility was low, and as a mixture in which the cocondensate and the coumarone resin were partially compatible, 119 g of a resin composition containing was obtained.
Average molecular weight of resin composition containing coumarone resin: 3816, softening point: 144 ° C., free p-tert-butylphenol: 0.0%, free o-phenylphenol: 0.1%, free resorcin: 2.1%, Organic solvent having a boiling point of 190 ° C. or lower: 0.0%, moisture content 0.1%, ash content 2.5%, coumarone resin content: 50%.
<Comparative Example 2>
A four-necked separable flask equipped with a reflux condenser and a thermometer was charged with 180.0 g (2.22 mol) of formalin having a purity of 37%, 30.0 g (0.20 mol) of p-tert-butylphenol, 170 of o-phenylphenol. 0.0 g (1.00 mol) was added in order. Thereafter, the temperature was raised to an internal temperature of 40 ° C., 40.0 g (0.24 mol) of a 24% aqueous sodium hydroxide solution was added, and the mixture was stirred until the exotherm subsided. After confirming that the exotherm had subsided, the temperature was raised to an internal temperature of 65 ° C. and kept at that temperature for 1.5 hours. Thereafter, the temperature was raised again until the internal temperature reached 75 ° C., and the reaction was further continued at the same temperature for 3 hours.
After completion of the reaction, 35.2 g (0.108 mol) of 30% sulfuric acid, 1.56 (0.012 mol) of oxalic acid dihydrate and 26.0 g (0.0183 mol) of sodium sulfate were added and stirred for 0.2 hours. Although it was allowed to stand, it was viscous and emulsified, and was not separated. Therefore, 154.0 g of methyl isobutyl ketone was added, and the mixture was stirred for 0.2 hours and allowed to stand for separation to remove the aqueous layer.
Next, 184.8 g (1.68 mol) of resorcin was added, the temperature was raised to an internal temperature of 118 ° C., and azeotropic dehydration was performed under reduced pressure (45 kPa) over 6 hours. During this time, the internal temperature rose to 122-124 ° C. Subsequently, the internal temperature was raised to 140 ° C., and azeotropic dehydration (decompression degree 66 kPa) was performed for 2 hours. Thereafter, the temperature was raised to an internal temperature of 145 to 150 ° C., and methyl isobutyl ketone was distilled off by keeping the temperature for 2 hours while gradually increasing the degree of vacuum. Thereafter, the pressure was reduced to 16 kPa while maintaining the internal temperature at 140 to 150 ° C., and methyl isobutyl ketone was further distilled off. By the above operation, 419 g of orange cocondensate was obtained.
Average molecular weight of co-condensate: 2735, softening point: 129 ° C., residual methyl isobutyl ketone: 1.5%, organic solvent having a boiling point other than methyl isobutyl ketone of 190 ° C. or less: 0.0%, free p-tert-butylphenol Minute: 0.0%, Free o-phenylphenol content: 0.2%, Free resorcin content: 12.6%, Water content 0.2%, Ash content 0.0%. Ratio of each structural unit of co-condensate: o-phenylphenol: 5.18, methylene group: 1.39, resorcin: 8.53 (1.38)

<Comparative Example 3>
To a four-necked separable flask equipped with a reflux condenser and a thermometer, 180.0 g (2.22 mol) of formalin having a purity of 37% and 180.0 g (1.20 mol) of p-tert-butylphenol were sequentially added. Thereafter, the internal temperature was raised to 40 ° C., 80.0 g (0.48 mol) of a 24% aqueous sodium hydroxide solution was added, and the mixture was stirred until the exotherm subsided. After confirming that the exotherm had subsided, the temperature was raised to an internal temperature of 65 ° C., and the reaction was carried out at the same temperature for 2 hours.
After completion of the reaction, 70.5 g (0.216 mol) of 30% sulfuric acid, 3.01 (0.024 mol) of oxalic acid dihydrate and 6.46 g (0.0045 mol) of sodium sulfate were added and the mixture was stirred for 0.2 hours. And the aqueous layer was removed.
184.8 g (1.68 mol) of resorcin was added, the temperature was raised to an internal temperature of 117 ° C., and dehydration was performed under a slightly reduced pressure (92 kPa) over 2.0 hours. During this time, the internal temperature rose from 109 ° C to 127 ° C. Next, the viscosity increased during stirring at 129 ° C., and stirring became impossible. Therefore, the contents were once taken out with a spatula, and dehydrated again after pulverization. At that time, the internal temperature was raised from 137 ° C. to 145 ° C., and dehydration (92 kPa) was performed for 1 hour. Thereafter, the pressure was reduced to 16 kPa while maintaining the internal temperature at 145 to 152 ° C., and water was further distilled off. By the above operation, 391 g of a yellow cocondensate was obtained. The obtained cocondensate was not like a thermoplastic resin but was a hard and brittle solid.
Average molecular weight of cocondensate: 1658, softening point: not measurable (> 200 ° C.), free p-tert-butylphenol content: 0.0%, free o-phenylphenol content: 1.0%, free resorcin content: 7 Organic solvent with a boiling point of 190 ° C. or less: 0.0%, moisture content 0.2%, ash content 0.1%. Ratio of each structural unit of co-condensate; o-phenylphenol: 0.45, methylene group: 1.67, resorcin: 1.97 (1.36)
Subsequently, in a four-neck separable flask equipped with a reflux condenser and a thermometer, 200.0 g of the obtained cocondensate, Novales C10 manufactured by Rutgers as a coumarone resin (oil at room temperature, 120.0 g), Rutgers Novares C90 (softening point: 85-95 ° C., 80.0 g) was added in order. Thereafter, the temperature was raised to an internal temperature of 150 ° C. and stirred for 2 hours while maintaining the internal temperature at 140 to 150 ° C., but it was found that the cocondensate did not melt and the cocondensate and coumarone resin were not uniform.

<Comparative Example 4>
The cocondensation obtained was carried out in the same manner as in Example 5 except that Diana Process Oil PW-380 (oily at room temperature, 20.0 g) manufactured by Idemitsu Kosan Co., Ltd. was used as the process oil instead of the coumarone resin in Example 5. 99.2 g of resin composition containing process oil (solid content: 93.0 g) was obtained by mixing with product 80.0 g. From the resin composition containing an orange opaque process oil, 6.2 g of an oily substance bleeded, indicating that the compatibility was poor.
Average molecular weight of resin composition containing process oil: 1425, softening point: 129 ° C., free p-tert-butylphenol: 0.0%, free o-phenylphenol: 1.3%, free resorcin: 6.8%, Organic solvent having a boiling point of 190 ° C. or lower: 0.0%, moisture content 0.1%, ash content 0.0%. Process oil content: 14%.

The physical properties and the like of the cocondensates of Examples 1 to 3, 5, and 7 to 9, and the cocondensates of Reference Example 1 and Comparative Examples 1 to 3 are shown in Tables 1 and 2 below. In addition, all the contents in a table | surface were described on the basis of weight (weight%). The meanings of the abbreviations in the table are as follows.
RES: Resorcin PTBP: p-tert-butylphenol OPP: o-phenylphenol

As shown in Table 1 above, the resol type cocondensate is reacted at 70 ° C. or lower in the presence of 0.2 times mole or more of alkali with respect to the total amount of p-tert-butylphenol and o-phenylphenol (based on the amount of substance). When produced, the resol-type cocondensate does not emulsify and can be separated without using an organic solvent. By reacting the resol-type cocondensate with resorcin, an organic solvent having a boiling point of 190 ° C. or lower In addition, a cocondensate having a physical property equivalent to that of Reference Example 1 was obtained.

On the other hand, as shown in Table 2 above, the reaction is carried out in the presence of less than 0.2-fold mole of alkali and / or at a temperature higher than 70 ° C. with respect to the total amount of p-tert-butylphenol and o-phenylphenol (substance basis). When the resol-type cocondensate was produced, the resol-type cocondensate was emulsified and could not be separated as it was. (Comparative Examples 1 and 2)
Therefore, in Comparative Example 1, when it was reacted with resorcinol without liquid separation, as shown in Table 2, it was found that the ash content was high and the softening point was 150 ° C. or higher.
In Comparative Example 2, the resole-type cocondensate was dissolved using methyl isobutyl ketone and the aqueous layer was separated and then reacted with resorcin. It was found that a large amount remained in the co-condensate in which the reaction point with the unreacted resorcin was reduced.
In addition, as shown in Comparative Example 3, it was found that the cocondensate produced using p-tert-butylphenol and resorcin without using o-phenylphenol had a very high softening point of 200 ° C. or higher.

Tables 3 and 4 below show the physical properties and the like of the resin compositions containing the cocondensates and coumarone resins prepared in Examples 1 to 8, Reference Example 1 and Comparative Examples 1 and 4. In addition, all the contents in a table | surface were described on the basis of weight (weight%). The meanings of the abbreviations in the table are as follows.
RES: Resorcin PTBP: p-tert-butylphenol OPP: o-phenylphenol

As shown in Table 3 above, when a coumarine resin synthesized under the conditions shown in each example was mixed with a coumarone resin to obtain a resin composition, the softening point was significantly lowered, and the softening point reducing effect of the coumarone resin was exhibited. did. On the other hand, as shown in Comparative Example 1 in Table 4, when the softening point of the cocondensate before addition of coumarone resin is higher than 150 ° C., the compatibility with coumarone resin is lowered due to the high molecular weight of the cocondensate, and softening It was found that the point reduction effect was not sufficient. Further, as shown in Comparative Example 4, it was found that when process oil was used instead of coumarone resin, the compatibility with the cocondensate of the present invention was low, the process oil bleeded, and the softening point reducing effect was hardly exhibited. .

2. Production examples and physical property evaluation of rubber compositions using the resin compositions obtained in the above Examples and Comparative Examples

<Manufacture of an unvulcanized rubber composition containing the resin composition obtained in the above example>
As a resin adhesive, in order to compare the physical properties of the resin composition produced in Example 1 and the resin composition, a conventional product, SUMIKANOL620 (manufactured by Taoka Chemical Industry Co., Ltd.), a solvent, is used. An unvulcanized rubber composition was produced without using a resin adhesive as a resin composition obtained in Reference Example 1 and a blank. The physical properties of each resin composition are shown in Table 5 below. (Hereinafter,% in Table 1 represents% by weight.)

＊：レゾルシン以外の樹脂を製造する際に用いるモノマーの残量。

*: Remaining amount of monomer used when producing a resin other than resorcin.

  In accordance with the composition shown in Table 6 below, first, components other than insoluble sulfur, vulcanization accelerator and methylene donor and a resin adhesive shown in Table 1 were added and mixed in a pressure kneader made by Toshin, and discharged when the temperature reached 160 ° C. did. Subsequently, insoluble sulfur, a vulcanization accelerator, and a methylene donor were added to and mixed with the obtained mixture using a 6-inch open roll made of Kansai Roll that was kept at 60 ° C. to prepare a rubber composition for coating a steel cord. The details of each component in Table 6 are as follows. (The numerical values in Table 6 below represent parts by mass.)

・ Natural rubber: SMR-CV60
Carbon black: “Seast 300” (HAF-LS grade) manufactured by Tokai Carbon Co., Ltd.
・ Zinc flower: Zohua Chemical Industry Co., Ltd.
Anti-aging agent: “Antioxidant FR” manufactured by Matsubara
・ Cobalt salt: Cobalt stearate (reagent)
Insoluble sulfur: “Cristex HS OT-20” manufactured by Flexis
・ Vulcanization accelerator: N, N-dicyclohexyl-2-benzothiazolylsulfenamide (reagent)
・ Methylene donor: “Sumikanol 507AP” manufactured by Bara Chemical Co., Ltd.

<Rubber physical property test of unvulcanized rubber composition containing resin composition obtained in the above Examples, Reference Examples and Comparative Examples>
Using the unvulcanized rubber composition obtained as described above, Mooney viscosity test (based on JIS K 6300-1: 2001, measured at 130 ° C.) and rheometer test (based on JIS K 6300-2: 2001, 160 ° C.) Measured). Further, after preparing an unvulcanized sample, it was allowed to stand at room temperature for 24 hours, and then vulcanized under pressure at 160 ° C. and 6 MPa under conditions of t90 + 5 minutes to prepare a vulcanized rubber sheet having a thickness of 2 mm. Next, using a rubber test piece prepared from the vulcanized rubber sheet, a tensile test (based on JIS K 6251: 2010, measured at 25 ° C.) and a hardness measurement (based on JIS K 6253: 2006, measured at 25 ° C.) were performed. did.

With respect to the rubber physical property test results, a rubber composition to which no resin was added was designated as Comparative Example 5 (100), and a relative evaluation was performed. The results are shown in Table 7.

As shown in Table 7 above, the rubber composition containing the resin composition obtained in Example 1 is the result of the unvulcanized rubber physical property test and the vulcanized rubber physical property test. As a result, a known resin adhesive “SUMIKANOL620” or a solvent is used. It was confirmed that each physical property was improved as compared with a rubber composition to which no resin composition was added.

<Evaluation methods and evaluation results of initial adhesiveness and wet heat adhesiveness of vulcanized rubber compositions containing the resin compositions obtained in the above Examples, Reference Examples and Comparative Examples>

A rubber-steel cord composite sample was prepared using each of the unvulcanized rubber compositions obtained as described above. Specifically, a brass-plated steel cord (diameter of about 0.8 mm, 3 × 0.20 + 6 × 0.35 mm structure, brass plating of copper / zinc = 64/36 (mass ratio)) at intervals of 1/10 mm For the peel adhesion test, both sides of the array of five were coated with about 2 mm thick unvulcanized rubber sheets made of each of the above unvulcanized rubber compositions, and the cords were laminated in parallel. An unvulcanized sample was prepared. Using the obtained unvulcanized sample, initial adhesiveness and wet heat adhesiveness were evaluated by the following methods.

<Initial adhesiveness>
After preparing the above unvulcanized sample, it was allowed to stand at room temperature for 24 hours, then vulcanized under pressure at 160 ° C. and 6 MPa under conditions of t90 + 5 minutes, and a 1 cm × 1 cm × 6 cm rectangular parallelepiped with 1 cm of 5 steel cords sandwiched A piece of rubber was obtained. This rubber piece is subjected to a steel cord pull-out test for each piece using an autograph “AGC-X” manufactured by Shimadzu Corporation, and the stress when pulling out vertically at 100 mm / min is the rubber pulling stress (kgf ). Moreover, the rubber coverage of the steel cord after drawing was visually observed and evaluated at 0 to 100%. Measurement and evaluation were carried out at N = 10 (pieces), and an average value was obtained. The results are shown in Table 8 below.

<Wet heat adhesion (adhesion after wet heat aging)>
The above-mentioned unvulcanized sample was prepared and allowed to stand at room temperature for 24 hours, and then vulcanized under conditions of t90 + 5 minutes under a pressure of 160 ° C. and 6 MPa. After leaving for 5 days, 10 days, 20 days, and 40 days, a pull-out test similar to the above initial adhesion was performed, and the rubber coverage of the steel cord after pulling was visually observed and evaluated at 0 to 100%. . Measurement and evaluation were performed at N = 5 (main), and an average value was obtained. The results are shown in Table 9 below. The pulling strength change rate in the following table is the change rate when the initial tensile strength is 100 (tensile strength after wet heat aging / tensile strength before wet heat aging × 100).

As shown in Tables 8 and 9 above, the rubber composition containing the resin composition obtained in Example 1 has a greatly improved rubber-steel cord adhesion compared to the rubber composition to which no resin adhesive is added. In addition, it has been found that the performance is equal to or better than that of a known resin adhesive “SUMIKANOL620” or a cocondensate produced using a solvent.

Claims (8)

The following formula (1) including the steps <a> and <b>

P-tert-butylphenol represented by the following formula (2)

O-phenylphenol represented by the following formula (3)

The manufacturing method of the cocondensate containing the structural unit derived from resorcin represented by these.
<a> A mixture of p-tert-butylphenol and o-phenylphenol is 70 ° C. or less in the presence of 0.2 moles or more of alkali with respect to the total amount (substance basis) of p-tert-butylphenol and o-phenylphenol. <B> Resorcin is reacted with the resol-type cocondensate The method for producing a cocondensate according to claim 1, wherein the amount of resorcin used is 1.0 to 2.0 times mol of the total amount (substance basis) of p-tert-butylphenol and o-phenylphenol. It is a cocondensate comprising p-tert-butylphenol represented by the above formula (1), o-phenylphenol represented by the above formula (2), and a resorcin-derived structural unit represented by the above formula (3). The total content of aliphatic hydrocarbons having a boiling point of 190 ° C. or less, aromatic hydrocarbons, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, and optionally branched ketones having 1 to 5 carbon atoms Cocondensate in an amount of 1% by weight or less. The cocondensate according to claim 3, wherein the content of free resorcin is 10% by weight or less and the softening point is 150 ° C or less. A resin composition comprising the cocondensate according to claim 3 or 4 and a coumarone resin. 6. The resin composition according to claim 5, wherein the content of free resorcin is 5% by weight or less and the softening point is 120 ° C. or less. A rubber composition comprising the cocondensate according to claim 3 or 4. A rubber composition comprising the resin composition according to claim 5.