JP2019183060A - Novolak type co-condensate for rubber blending, and manufacturing method of rubber composition containing the co-condensate - Google Patents

Abstract

To provide a co-condensate containing no constitutional unit derived from resorcin, and providing a rubber composition exhibiting viscoelasticity equal to or more than a rubber composition containing co-condensates widely used.SOLUTION: The above described problem can be solved by a co-condensate containing p-tert-butyl phenol, m-cresol, and formaldehyde derived constitutional unit, in which polydispersity of a molecular weight of the co-condensate (Mw/Mn) is reduced, and content of a component having a specific molecular weight is set in a specific range.SELECTED DRAWING: None

Description

  The present invention relates to a novolak-type alkylphenol-formaldehyde cocondensate containing structural units derived from p-tert-butylphenol, m-cresol, and formaldehyde, a method for producing the novolak-type cocondensate, and the novolac-type cocondensate or the resin. The present invention relates to a rubber composition containing the composition.

  In rubber products that need to be reinforced with reinforcing materials such as tire cords, belts and hoses, 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 methods, 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 a rubber processing step, for example, a cocondensate containing structural units derived from alkylphenols such as p-tert-octylphenol or p-nonylphenol, formaldehyde and resorcin (for example, Patent Document 1) has been widely used. However, since p-tert-octylphenol or p-nonylphenol has recently been a candidate substance of SVHC (highly concerned substance) as defined in the REACH regulation, which is a regulation within the EU region, alkylphenols are considered to be p-tert-butylphenol and A cocondensate substituted with o-phenylphenol has also been proposed (for example, Patent Document 2).

  On the other hand, the above-mentioned cocondensate contains a structural unit derived from resorcin. However, since resorcin exhibits sublimation properties, it is necessary to take measures against clogging of the pipe such as heating the pipe at the time of production. In addition, since unreacted resorcin is contained in the cocondensate during its use, there is a risk of contamination of the equipment used, contamination, and safety and health problems for workers. In some cases, a condensate was required.

Japanese Patent Laid-Open No. 06-234824 JP-A-2015-52097

  Furthermore, when the present inventors manufactured a rubber composition using the cocondensate described in Patent Document 2, alkylphenols such as p-tert-octylphenol or p-nonylphenol, formaldehyde, and the like that have been widely used so far. It has been found that the viscoelastic properties are deteriorated as compared with a cocondensate containing a structural unit derived from resorcin. Specifically, when the value of E ′ representing the elastic modulus is reduced, or when the rubber composition is used as a tire, tan δ under high temperature (for example, 70 ° C.), which is one index of low fuel consumption. It represents the magnitude of hysteresis loss. A smaller value is considered to have better fuel efficiency. In such a case, the durability, hardness and fuel efficiency of the rubber composition containing the cocondensate will be deteriorated.

  An object of the present invention is a cocondensate that does not contain a resorcin-derived constituent unit, and exhibits a viscoelastic property equivalent to or higher than that of a rubber composition containing a cocondensate that has been widely used so far. It is to provide a cocondensate that gives a product and a method for producing the same.

  As a result of intensive studies aimed at solving the problems by the present inventors, it is a cocondensate containing structural units derived from p-tert-butylphenol, m-cresol, and formaldehyde, and the polydispersity of the molecular weight of the cocondensate It has been found that the above problem can be solved by reducing (Mw / Mn) and setting the content of a component having a specific molecular weight within a specific range. Specifically, the following invention is included.

[1]
a novolak-type alkylphenol-formaldehyde cocondensate comprising structural units derived from p-tert-butylphenol, m-cresol, and formaldehyde,
The polydispersity (Mw / Mn) of molecular weight in terms of polystyrene obtained when the cocondensate is analyzed using a gel permeation chromatograph (GPC) method is 5 or less,
Among the area values of the mass chromatogram obtained when the cocondensate is analyzed using a liquid chromatograph mass spectrometer (LCMS), the mass numbers m / z = 347.165, 431.2259, 467.222, and The ratio of the area value caused by the mass number m / z = 431.259 is 90% or more with respect to the total amount of area values caused by 1199.734, and the area value caused by the mass number m / z = 1199.734 The ratio is 10% or less,
Cocondensate.

[2]
The method for producing a cocondensate according to claim 1, comprising the following steps (1), (2) and (3) in this order.
(1) With respect to 1 mol of p-tert-butylphenol, in the presence of 0.05 mol or more of base, p-tert-butylphenol and 1.5 to 2.5 mol of formaldehyde are reacted at 50 to 70 ° C. A step of obtaining a resol-type condensate having a number average molecular weight (Mn) of 300 or less in a permeation chromatograph (GPC) method.
(2) A step of neutralizing the base used in step (1) with an acid equivalent to or more than the base, and separating and removing the aqueous layer from the resol-type condensate.
(3) A step of reacting a resol-type condensate with 0.5 to 1.5 mol of m-cresol with respect to 1 mol of p-tert-butylphenol.

[3]
[1] A rubber composition comprising the cocondensate according to [1], a methylene donor compound and rubber.

[4]
The rubber composition according to [3], wherein the methylene donor compound is at least one selected from the group consisting of hexakis (methoxymethyl) melamine, pentakis (methoxymethyl) methylolmelamine, and tetrakis (methoxymethyl) dimethylolmelamine.

  According to the present invention, it is a cocondensate that does not contain a resorcin-derived constituent unit, and has a viscoelastic property that is comparable to or higher than that of a rubber composition that includes a cocondensate that has been widely used so far. Cocondensates that give products can be provided. Therefore, the co-condensate of the present invention can be suitably used as an additive for rubber for the purpose of reinforcing the rubber composition and improving heat resistance, in addition to the adhesive used in the rubber processing step. .

<Novolac type cocondensate of the present invention>
The novolak-type cocondensate of the present invention is a novolak-type alkylphenol-formaldehyde cocondensate containing structural units derived from p-tert-butylphenol, m-cresol, and formaldehyde, and includes the following (a) and (b) Has characteristics.
(A) Polydispersity (Mw / Mn) of molecular weight in gel permeation chromatograph (GPC) method is 5 or less.
(B) Mass number m / z in the area value of the mass chromatogram obtained when analyzed using a liquid chromatograph mass spectrometer (LCMS) = 347.165, 431.2259, 467.222, and 1199.734 The ratio of the area value caused by the mass number m / z = 431.259 is 90% or more with respect to the total amount of the four area values caused by the area value, and the area value caused by the mass number m / z = 1199.734 The ratio is 10% or less.

  The novolak-type cocondensate of the present invention has a molecular weight polydispersity (Mw / Mw) calculated from the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the standard polystyrene equivalent molecular weight in the gel permeation chromatograph (GPC) method. Mn) is 5 or less, preferably 3.5 or less. When the polydispersity of molecular weight (Mw / Mn) is higher than 5, when the cocondensate is blended with rubber, poor dispersion in rubber may occur. Further, the weight average molecular weight (Mw) is preferably 10,000 or less, more preferably 6000 or less, and particularly preferably 3000 or less. In addition, the number average molecular weight (Mn), the weight average molecular weight (Mw), and the polydispersity (Mw / Mn) of the molecular weight of the novolak-type cocondensate are determined by the method described in Examples described later.

The novolak-type cocondensate of the present invention has mass numbers m / z = 347.165, 431.259, and 467 in the area value of the mass chromatogram obtained when analyzed using a liquid chromatograph mass spectrometer (LCMS). The ratio of the area value caused by the mass number m / z = 431.259 is 90% or more with respect to the total amount of the four area values caused by .222 and 1199.734, and the mass number m / z = 1199. .734, the area value ratio is 10% or less. By setting the ratio of the area value due to the mass number m / z = 431.259 to 90% or more, the viscoelastic properties of the rubber composition containing the cocondensate are improved (tan δ is lowered or / and E ′ can be increased). Moreover, since the ratio of the area value resulting from mass number m / z = 1199.734 is set to 10% or less, a decrease in the crosslinking density of the rubber composition containing the cocondensate can be suppressed. It is possible to improve performance as a product (hardness, modulus, and viscoelastic properties of a rubber composition containing a cocondensate).

  In addition, the mass numbers m / z = 347.165 and 467.4 with respect to the total amount of the four area values resulting from the mass numbers m / z = 347.165, 431.259, 467.222, and 1199.734. The ratio of the sum of area values due to 222 is preferably 30% or less, more preferably 20% or less, and particularly preferably 10% or less. By setting the ratio of the sum of area values to 30% or less, the compatibility of the cocondensate with rubber can be further improved, and bloom / bleed from the rubber composition can be prevented.

  The mass chromatogram is a chromatogram in which a mass spectrum is measured and stored at regular time intervals, a specific mass number is taken out, time is plotted on the horizontal axis, and ion intensity is plotted on the vertical axis. Among compounds having the same chemical behavior, it is known that the ionic strength (area value) of the mass spectrum is proportional to the concentration of ions. Therefore, the LCMS analysis of the novolak-type cocondensate is performed under certain conditions, and the concentration of specific components contained in the novolak-type cocondensate is compared by comparing the ionic strength (area value) of the obtained mass spectrum. The ratio can be compared. The mass chromatogram of the novolak-type cocondensate is obtained by the method described in the examples described later.

Moreover, it is estimated that the substance corresponding to mass number m / z = 347.165, 431.2259, 467.222, and 1199.734 is a substance which has the following structures, respectively.
Mass number m / z = 347.165: derived from a compound represented by a composition formula of C ₂₃ H ₂₄ O ₃ , _three m-cresol-derived structural units and a methylene group that is a structural unit derived from formaldehyde Presumed to have two structures.
Mass number m / z = 431.259: derived from a compound represented by a composition formula of C ₂₉ H ₃₆ O ₃ , two structural units derived from p-tert-butylphenol, and a structural unit derived from m-cresol It is presumed to be a structure having one and two methylene groups, which are structural units derived from formaldehyde.
Mass number m / z = 467.222: derived from a compound represented by a composition formula of C ₃₁ H ₃₂ O ₄ , _four m-cresol-derived constitutional units and a methylene group that is a formaldehyde-derived constitutional unit It is estimated that the structure has three.
Mass number m / z = 1199.734: derived from a compound represented by the composition formula of C ₈₁ H ₁₀₀ O ₈ , six structural units derived from p-tert-butylphenol, and structural units derived from m-cresol It is presumed that the structure has two and seven methylene groups, which are formaldehyde-derived structural units.

  Moreover, it is essential that the novolak-type cocondensate of the present invention contains a structural unit derived from p-tert-butylphenol. A rubber composition comprising the co-condensate by improving the compatibility of the co-condensate with rubber by including a structural unit derived from p-tert-butylphenol and preventing bloom / bleed from the rubber composition. It becomes possible to improve the stability of things. Moreover, it is preferable that 0.8-1.5 mol is included with respect to 1 mol of structural units derived from p-tert-butylphenol, and it is more preferable that 0.8-1.3 mol is included for the structural unit derived from m-cresol. . By setting the structural unit derived from m-cresol to 1.5 mol or less, compatibility with the rubber can be improved when the co-condensate is blended with the rubber. Moreover, since it is possible to avoid the high molecular weight of this cocondensate and to reduce an insoluble and infusible component by setting it as 0.8 mol or more, the shaping | molding process to flakes and a pellet becomes easy. . Moreover, the structural unit derived from formaldehyde (methylene group and / or dimethylene ether group) is usually contained in an amount of 1 to 2 moles, preferably 1.2 to 1.9 moles per mole of the structural unit derived from p-tert-butylphenol. More preferably, it contains 1.4 to 1.8 mol. By making the structural unit derived from formaldehyde 2 mol or less, the high molecular weight of the cocondensate can be avoided, so that the compatibility with rubber when blending the cocondensate into rubber is improved. It becomes possible. Moreover, by setting it as 1 mol or more, a cocondensate becomes solid and it becomes possible to improve the handling at the time of mix | blending with rubber | gum.

The ratio of the above-mentioned structural units can be confirmed by analyzing the novolak-type cocondensate using ¹ H-NMR. Specifically, about 5 mg of a novolak-type cocondensate was dissolved in 0.75 mL of a solvent (deuterated chloroform 0.03% (v / v) TMS), analyzed by ¹ H-NMR, and the obtained analysis Among the results, a method of determining the ratio from the proton integral value derived from each constituent unit is exemplified.

  The novolak type cocondensate of the present invention usually has a softening point of 80 ° C or higher, preferably 90 ° C or higher, and 150 ° C or lower, preferably 140 ° C or lower. By setting the softening point to 150 ° C. or less, it is possible to improve dispersibility in rubber when the cocondensate is blended into rubber. Moreover, it becomes possible to reduce the blocking at the time of a preservation | save by making a softening point 80 degreeC or more. In addition, even if it mix | blends with a rubber | gum after mixing with a softening agent by the method mentioned later, it is preferable that the softening point of the novolak-type cocondensate of this invention is the said range.

  The content of unreacted m-cresol contained in the novolak-type cocondensate of the present invention is preferably 8% by weight or less, and more preferably 5% by weight or less. Further, the content of p-tert-butylphenol contained in the novolak-type cocondensate of the present invention is preferably 5% by weight or less. Furthermore, the content of a volatile organic compound (such as a solvent used in the production if necessary) contained in the novolak-type cocondensate of the present invention is preferably 3% by weight or less. More preferably, it is particularly preferably not contained. In addition, the unreacted m-cresol and unreacted p-tert-butylphenol mentioned above are not contained in the volatile organic compound in this invention.

<Method for producing novolak-type cocondensate>
The production method of the novolak type cocondensate of the present invention will be described in detail. By carrying out the production method described below, it is possible to suppress the formation of a resin comprising p-tert-butylphenol and formaldehyde, or a resin comprising m-cresol and formaldehyde, and p-tert-butylphenol, m-cresol, and formaldehyde Since the production of a resin containing a derived structural unit and having a relatively high molecular weight can be suppressed, the novolak-type cocondensate of the present invention having the above-described characteristics can be produced.

The method for producing a novolak type cocondensate according to the present invention includes the following steps (1), (2) and (3) in this order.
(1) With respect to 1 mol of p-tert-butylphenol, in the presence of 0.05 mol or more of base, p-tert-butylphenol and 1.5 to 2.5 mol of formaldehyde are reacted at 50 to 70 ° C. A step of obtaining a resol-type condensate having a number average molecular weight (Mn) of 300 or less in a permeation chromatograph (GPC) method.
(2) A step of neutralizing the base used in step (1) with an acid equivalent to or more than the base, and separating and removing the aqueous layer from the resol-type condensate.
(3) A step of reacting a resol-type condensate with 0.5 to 1.5 mol of m-cresol with respect to 1 mol of p-tert-butylphenol.

  As the formaldehyde used in the step (1), not only gaseous formaldehyde but also formalin which is an aqueous solution of formaldehyde, and compounds that easily generate formaldehyde such as paraformaldehyde and trioxane can be used. The usage-amount of formaldehyde is 1.5-2.5 mol normally with respect to 1 mol of p-tert- butylphenol, Preferably it is 1.5-1.9 mol. By using 1.5 mol or more, it becomes possible to reduce unreacted monomers, and by using less than 2.5 mol, it is possible to easily obtain a cocondensate having a low softening point. It becomes.

  As the base used in the step (1), a base used for producing a usual resol-type condensate such as alkali metal or alkaline earth metal hydroxide or carbonate, ammonia, amine or the like can be used. . Specific examples of these bases include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate and the like. Among these bases, sodium hydroxide and potassium hydroxide are preferable. These bases may be used alone or in combination of two or more if necessary. These bases can be solid or liquid (aqueous solution or organic solution), but an aqueous solution is preferred because of its reactivity and easy handling. When an aqueous solution is used, the base contained in the aqueous solution is usually 10% to 50% by weight. The usage-amount of a base needs to use 0.05 mol or more with respect to 1 mol of p-tert- butylphenol, Preferably it is 0.2-0.5 mol. If the amount of base used is less than 0.05 mol, unreacted monomers and odor may increase.

  When carrying out step (1), it is possible to use an organic solvent, but it is preferable to use water instead of the organic solvent. As usable organic solvents, for example, aromatic hydrocarbons such as toluene, xylene and ethylbenzene, and ketones having 3 to 7 carbon atoms such as methyl isobutyl ketone are preferably used. These organic solvents may be used alone or in combination of two or more if necessary. In the case of using an organic solvent, the amount used is usually 0.4 to 4.0 times by weight based on 1 time by weight of p-tert-butylphenol.

  As a method for carrying out step (1), for example, p-tert-butylphenol and formaldehyde and, if necessary, an organic solvent are charged into the reactor, then a base is further charged into the reactor, and the base is dissolved or suspended to react. carry out. The reaction is carried out at 50 to 70 ° C., the reaction solution is appropriately analyzed using a gel permeation chromatograph (GPC), and the number average molecular weight (Mn) of the resol-type condensate in the reaction solution is 300 as a standard polystyrene equivalent molecular weight. It is necessary to carry out the reaction so that: Moreover, the number average molecular weight (Mn) of the resol type condensate in the reaction solution is usually 180 to 260. When the number average molecular weight (Mn) of the resol-type condensate is higher than 300 in step (1), the cocondensate of the present invention cannot be obtained, and the aqueous layer is formed from the resol-type condensate by neutralizing with an acid, which will be described later. In the step of separating and removing (step (2)), an intermediate layer is formed between the reaction solution and the aqueous layer, so that a separation failure occurs or the step of reacting the resol-type condensate with m-cresol (step (3)). A large amount of unreacted m-cresol may remain. When a co-condensate containing a large amount of unreacted m-cresol is blended with rubber, the rubber composition may be softened and odor may be generated. In addition, the number average molecular weight of a resol type condensate is determined by the method described in the Example mentioned later.

  The resol-type condensate obtained in the step (1) described above needs to be neutralized before the step (3) is performed. When neutralization is not carried out, the physical properties of the rubber composition may be deteriorated when the resulting novolac-type cocondensate is blended with rubber. Furthermore, when unreacted p-tert-butylphenol, m-cresol, etc. are removed in step (3), the remaining base may cause coloration or decomposition of the resulting novolak-type cocondensate, resulting in a reduction in quality. is there. Further, by carrying out neutralization, separation and removal of the aqueous layer in the step (2) can be easily carried out, and it becomes possible to reduce the hygroscopicity of the obtained cocondensate.

  The neutralization in the present invention refers to an operation of mixing the reaction solution containing the resol-type condensate obtained in the step (1) with the base used in the step (1) and an acid of an equivalent amount or more. Examples of the acid used for neutralization include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as formic acid, acetic acid, oxalic acid, and p-toluenesulfonic acid. These acids may be used alone or in combination of two or more, or an aqueous solution of these acids may be used. The usage-amount of an acid should just be an equivalent or more with respect to the base content of the base used at process (1), Preferably it is 1-2 mol with respect to 1 mol of base contents. In the neutralization, the reaction solution containing the resol-type condensate obtained in the step (1) and the acid are mixed in multiple times, and the total amount of the acid used is equal to or more than the base used in the step (1). You may carry out in the form.

  In step (2), after neutralization, in order to remove unreacted formaldehyde and inorganic salts generated by neutralization, it is generated by organic phase containing resol-type condensate and unreacted formaldehyde or neutralization. The aqueous layer containing the inorganic salt is separated, and the aqueous layer is removed from the system. When the aqueous layer is not separated and removed after neutralization, in the subsequent step (3), a large amount of low molecular weight resin comprising m-cresol and formaldehyde is produced. As a result, when the resulting cocondensate is blended with rubber, Compatibility may be low, resulting in poor dispersion. In addition, you may implement this liquid separation process, after extracting a resol type condensate to an organic phase using the organic solvent and water which are not miscible with water as needed. Further, an additional water washing step may be performed.

  The amount of m-cresol used in step (3) needs to be 0.5 to 1.5 moles per mole of p-tert-butylphenol used in step (1), preferably 0.8 to 1.2 mol. When the amount used is more than 1.5 mol, a large amount of unreacted m-cresol remains in the cocondensate, which causes a problem of odor, or contains a large amount of low molecular weight resin composed of m-cresol and formaldehyde. Since a cocondensate is obtained, when the cocondensate is blended with rubber, the compatibility with the rubber is low, and dispersion failure may occur. When the amount used is less than 0.5 mol, the cocondensate of the present invention having the above-described characteristics may not be obtained.

  The reaction in step (3) is usually carried out at 40 to 150 ° C, preferably 100 to 150 ° C. In addition, during the reaction between the resol-type condensate and m-cresol, the reaction rate may be slowed if water is present in the system, so the reaction is carried out while removing the water produced as a by-product from the reaction. It is preferable to do.

  Step (3) can be carried out regardless of whether or not a solvent is used, and m-cresol may be used in place of the solvent. When using a solvent separately, it is preferable to use 0.2 to 2.0 times by weight with respect to 1 time by weight of p-tert-butylphenol used in the step (1). By using a solvent of 0.2 weight times or more, it becomes possible to efficiently remove water produced as a by-product during the formation of the novolak-type cocondensate out of the system by azeotropic distillation, thereby shortening the reaction time. It becomes possible. In addition, when the amount of the solvent used is 2.0 weight times or less, when it is desired to remove the solvent used in the reaction from the cocondensate, the solvent can be efficiently removed from the cocondensate.

  Examples of solvents that can be used in the step (3) include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, ketones having 3 to 7 carbon atoms such as methyl isobutyl ketone, and ethyl acetate, n-propyl acetate, isopropyl acetate, Examples include ester organic solvents such as n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, ethyl butanoate, methyl pentanoate, and toluene. , Xylene and n-butyl acetate are preferred. These solvents may be used alone or in combination of two or more if necessary.

  After the completion of the step (3), the novolak-type cocondensate of the present invention having the characteristics described later is obtained. The solvent used in the reaction, unreacted p-tert-butylphenol and m contained in the novolak-type cocondensate are obtained. -When it is necessary to remove cresol or the like, it can be concentrated and removed by a conventional method (hereinafter, this step may be referred to as a concentration and removal step). When carrying out the concentration removal step, if the internal temperature exceeds 165 ° C., the cocondensate may be colored or decomposed during the concentration.

  The novolak type cocondensate of the present invention may be mixed with a softening agent to form a resin composition. The softener that can be used may be any substance that is compatible with the novolak-type cocondensate of the present invention. As such a substance, for example, coumarone generally used as a softener for a novolak-type cocondensate Examples thereof include a solid having a low softening point such as resin, and a liquid such as cashew nut shell liquid (CNSL). Furthermore, the novolak-type cocondensate obtained by the production method of the present invention is compatible with fatty acids having 8 to 32 carbon atoms such as stearic acid which is widely used as a vulcanization aid in the rubber processing step. Therefore, fatty acids having 8 to 32 carbon atoms can be used as a softening agent. In addition, the novolak-type cocondensate containing a large amount of low molecular weight resin composed of m-cresol and formaldehyde, which is manufactured regardless of the manufacturing method of the present invention, is not compatible with fatty acids having 8 to 32 carbon atoms, Separation of the resin layer and the oil layer may occur.

  These softeners may be used alone or in combination of two or more as required. In particular, a resin composition using a fatty acid having 8 to 32 carbon atoms, particularly stearic acid, as a softening agent can reduce its softening point without newly adding a material not normally used in the rubber processing step as a softening agent. For this reason, it can be suitably used for applications in which a substance added separately as a softener becomes a problem (for example, when the softener reacts with other components contained in rubber).

  Cashew nut shell liquid is a natural plant liquid obtained from cashew nut shells. Cashew nut shell liquid is a mixture composed of phenol derivatives having saturated or unsaturated hydrocarbon side chains. In particular, anacardic acid, cardanol, cardol (also referred to as curdle), and methyl cardol (also referred to as methyl curdle) are mainly included as its components. As a method for preparing the cashew nut shell liquid, there are a heating method and a solvent extraction method. Usually, an industrial cashew nut shell liquid is heated. Anacardic acid is decarboxylated by this heat treatment and converted to cardanol, so cardanol, cardol, and methyl cardol are the main components. Therefore, the composition ratio (wt% ) Are cardanol (75-85%), cardol (15-20%), methyl cardol (1-5%). In addition, the cashew nut shell liquid in the present invention is obtained by appropriately purifying each component contained in the liquid by separating and purifying the cashew nut shell liquid, or adding another component to the cashew nut shell liquid and polymerizing a part thereof. Also included is a cashew nut shell polymer.

  As commercially available cashew nut shell liquid, for example, cashew liquid products (CNSL, LB-7000, LB-7250, CD-5L) manufactured by Tohoku Kako Co., Ltd., TAN HOA HOP PHAT Co. , Ltd. CNSL and the like. These cashew nut shell liquids may be used alone or in combination of two or more as required.

  Examples of the fatty acids having 8 to 32 carbon atoms include saturated or unsaturated fatty acids having 8 to 32 carbon atoms, or metal salts thereof. Specifically, examples of the saturated fatty acid include caprylic acid (octanoic acid), pelargonic acid, capric acid, undecyl acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Examples include oleic acid and undecenoic acid. These fatty acids may be used alone or in combination of two or more as required. Of these fatty acids, stearic acid, palmitic acid, myristic acid, lauric acid, and behenic acid are preferable from the viewpoints of price and availability. Further, stearic acid is particularly preferable because it is a common organic acid as an additive to rubber.

Specific examples of stearic acid used in the present invention include, for example, beads stearic acid Tsubaki (C18: 63%, C16: 32%), beads stearic acid Sakura (C18: 66%, C16: 31%), etc., manufactured by NOF Corporation. Is mentioned.

  The content of the softening agent contained in the resin composition is 2% by weight or more, preferably 4% by weight or more, and 20% by weight or less, preferably 15% by weight or less based on the total amount of the resin composition. By making the content 20% by weight or less, it becomes possible to reduce the deterioration of the performance as a novolak-type cocondensate used together with the methylene donor compound in the process of rubber blocking and resin processing. By making the amount 2% by weight or more, the effect of reducing the softening point is sufficiently exhibited.

  The softening point of the resin composition of the present invention is usually 150 ° C. or lower, preferably 120 ° C. or lower. By setting the softening point to 150 ° C. or less, it is possible to improve dispersibility in rubber when the resin composition is blended into rubber. Moreover, by setting it as 120 degrees C or less, when mix | blending this resin composition with rubber | gum and knead | mixing, it becomes possible to knead | mix at the low temperature of 100-130 degreeC in order to suppress the odor during kneading | mixing. In addition, blocking during storage can be avoided by setting the softening point to 80 ° C. or higher.

  The resin composition is obtained by mixing the novolak-type cocondensate of the present invention obtained by the method of steps (1), (2) and (3) described above and a softening agent. After mixing the softener or before mixing the softener, if necessary, a concentration removal step for removing the solvent used in the reaction, unreacted p-tert-butylphenol, m-cresol, etc. is performed. Also good.

  When the softening agent contained in the resin composition is a fatty acid having 8 to 32 carbon atoms, when the resol-type condensate is reacted with m-cresol (step (3)), the reaction is performed with 8 to 32 carbon atoms. You may manufacture the resin composition of this invention by implementing in the presence of a saturated or unsaturated fatty acid. By carrying out step (3) in the presence of a saturated or unsaturated fatty acid having 8 to 32 carbon atoms, a resin composition with a small amount of residual raw material monomer and a relatively low softening point of 80 to 120 ° C. can be easily obtained. Obtainable. The amount used in the step (3) when a saturated or unsaturated fatty acid having 8 to 32 carbon atoms is used is usually 1.5 to 20 parts by weight with respect to 100 parts by weight of the total amount of the resol-type condensate and m-cresol. , Preferably 2 to 10 parts by weight, more preferably 4 to 8 parts by weight.

<Rubber composition>
Next, the rubber composition containing the novolak type cocondensate of the present invention will be described in detail.

  The rubber composition of the present invention contains the above-described novolak-type cocondensate and a rubber component, and is typically a novolak-type cocondensate, rubber component, filler, sulfur and formaldehyde generator, and / or methylene. It can be obtained by kneading a donor compound. A vulcanization accelerator, zinc oxide, and an organic cobalt compound can also be kneaded with these.

  The novolak-type cocondensate of the present invention is used in the range of 0.5 to 10 parts by weight per 100 parts by weight of the rubber component, for example. Among these, the range of 1 to 5 parts by weight is preferable. When the amount is less than 0.5 parts by weight, the viscoelastic property is not significantly improved. When the amount is more than 10 parts by weight, there is no problem in the above-described effect, but the effect corresponding to the addition amount is not exhibited, which is economically undesirable.

  As rubber components, natural rubber, epoxidized natural rubber, deproteinized natural rubber and other modified natural rubber, polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), 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% by mole are preferable, and examples thereof include ENR25 and ENR50 manufactured by Kungpu Langley Company. As the deproteinized natural rubber, a deproteinized natural rubber having a total nitrogen content of 0.3% by weight or less is preferable. As the modified natural rubber, modified rubber containing a polar group obtained by reacting natural rubber with 4-vinylpyridine, N, N-dialkylaminoethyl acrylate (for example, N, N-diethylaminoethyl acrylate), 2-hydroxyethyl acrylate 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 solution polymerization SBR, JSR in which molecular ends are modified with 4,4′-bis- (dialkylamino) benzophenone such as “Nipol (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 A silane compound having N, N-dialkylacrylate Using two or more different compounds as described above, such as an amide compound and a silane compound having an alkoxy group, each of the molecular ends obtained by modifying the molecular ends is nitrogen, tin, silicon, or a plurality thereof The solution polymerization SBR having these elements 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 about 35%, and low cis BR having high vinyl content is preferably used. It is done. 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 BR having a plurality of elements , Particularly preferably used. These BRs are usually used in blends with natural rubber.

  The rubber component preferably contains natural rubber, 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 which are usually used in the rubber field, but 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 Extraction Furnace), MAF (Medium Abrasion Furnace), GPF (General Purpose Furnace), SRF (Semi-Reinforcing Furnace) and the like are preferable. The rubber composition for a tire tread CTAB surface 40~250m ² / g, nitrogen adsorption specific surface area 20 to 200 m ² / g, carbon black having a particle diameter 10~50nm is preferably used, with CTAB surface 70~180m ² / g A certain carbon black is more preferable, and examples thereof include N110, N220, N234, N299, N326, N330, N330T, N339, N343, N351 and the like 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 CTAB specific surface area of 50 to 180 m ² / g and nitrogen adsorption specific surface area of 50 to 300 m ² / g, and “AQ”, “AQ-N”, Degussa manufactured by Tosoh Silica Co., Ltd. "Ultrasil (registered trademark) VN3", "Ultrasil (registered trademark) 360", "Ultrasil (registered trademark) 7000", Rhodia "Zeosil (registered trademark) 115GR", "Zeosil (registered trademark)" Commercially available products such as “1115MP”, “Zeosil (registered trademark) 1205MP”, “Zeosil (registered trademark) Z85MP”, “Nippal (registered trademark) AQ” manufactured by Nippon Silica Co., Ltd. are preferably used. Usually, when silica is used as a filler, bis (3-triethoxysilylpropyl) tetrasulfide (“Si-69” manufactured by Degussa) or bis (3-triethoxysilylpropyl) disulfide (“Degussa” Si-75 "), bis (3-diethoxymethylsilylpropyl) tetrasulfide, bis (3-diethoxymethylsilylpropyl) disulfide, octanethioic acid S- [3- (triethoxysilyl) propyl] ester (general electronic silicon) A compound having an element such as silicon or a functional group such as alkoxysilane that can be bonded to silica, such as one or more silane coupling agents selected from the group consisting of preferable.

Examples of the aluminum hydroxide include 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 preferably contains 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 vulcanization accelerators 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 sulfenamide 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 methylene donor compound include those usually used in the rubber industry such as hexamethylenetetramine, hexakis (methoxymethyl) melamine, pentakis (methoxymethyl) methylolmelamine, tetrakis (methoxymethyl) dimethylolmelamine. Among them, hexakis (methoxymethyl) melamine alone or a mixture containing it as a main component is preferable. These methylene donor compounds can be used alone or in combination of two or more, 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. The range of about 3 parts by weight is more preferable.

  Examples of the organic cobalt compound include fatty 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 novolak-type cocondensate of the present invention can be obtained, for example, by the following method.

(A) Step of kneading filler and rubber component Kneading of the filler and rubber component can be performed 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 step of kneading the kneaded product obtained in step A, the sulfur component and the vulcanization accelerator 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.

  The novolak-type cocondensate of the present invention 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 novolak type cocondensate 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 novolac-type cocondensate 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 in more detail by showing examples, comparative examples, and reference examples (hereinafter also referred to as examples and the like). 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 unreacted monomer described in the examples and the like are the substances with respect to the total amount of the resin composition containing the obtained cocondensate or softener. % By weight. Moreover, the various measured values in each Example etc. were acquired as follows.

[1] Gel permeation chromatograph (GPC) analysis condition equipment: HLC-8220 GPC (manufactured by Tosoh Corporation)
Detector: RI (differential refraction) detector column: TSK guard column SUPER HZ-L (manufactured by Tosoh Corporation)
+ 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
Standard substance for obtaining the converted molecular weight (preparation of GPC calibration curve): 1,1-bis (4-hydroxyphenyl) cyclohexane (FW268) and phenol (FW94) are added to the TSK-GEL standard polystyrene kit (PS-oligomer kit) A calibration curve was created.
Sample preparation: About 0.02 g of the cocondensate, resin composition or reaction mixture of the present application was dissolved in 10 mL of tetrahydrofuran.

  Based on the results obtained by the GPC analysis, the average molecular weight of the resol-type condensate, the average molecular weight of the novolac-type cocondensate and the resin composition, and the polydispersity (Mw) of the molecular weight of the novolac-type cocondensate and the resin composition / Mn) was calculated as follows.

(A) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the resol type condensate
The multimodal peak obtained by the measurement of the resol type condensate was handled as a lump, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated. In calculating the average molecular weight of the resol-type condensate, when an organic solvent was used during production, peaks corresponding to the organic solvent were excluded.

(B) Average molecular weight of novolak-type cocondensate The multimodal peaks obtained by measurement of the novolak-type cocondensate were handled as a group, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated. When calculating the average molecular weight of the novolak-type cocondensate, the peak derived from the unreacted monomer (p-tert-butylphenol, m-cresol), and the peak corresponding to the organic solvent when an organic solvent was used during the production, Excluded.

(C) Average molecular weight of resin composition The multimodal peaks obtained by measuring the resin composition were handled as a group, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated. In calculating the average molecular weight of the resin composition, peaks derived from unreacted monomers (p-tert-butylphenol, m-cresol) and peaks corresponding to the organic solvent were excluded when an organic solvent was used during production.

(D) Polydispersity of molecular weight (Mw / Mn)
The polydispersity (Mw / Mn) of the molecular weight was calculated using the average molecular weight (Mw) and the number average molecular weight (Mn) obtained by the method described in (b) or (c) above.

[2] Liquid Chromatograph Mass Spectrometry (LCMS) Analysis Conditions LCMS analysis was performed under the following analysis conditions, and among the area values of the obtained mass chromatogram, mass number m / z = 347.165, 431259, A ratio of area values was calculated from four area values resulting from 467.222 and 1199.734.
<UPLC conditions>
Equipment used: Waters ACQUITY UPLC
Column: Waters ACQUITY UPLC CSH C18
(2.1mmφ × 100mm, 1.7μm)
Column temperature: 40 ° C
Flow rate: 0.40 mL / min
Wavelength: 200-500nm
Injection volume: 1 μL
Mobile phase: A liquid 10 mM ammonium acetate aqueous solution B liquid acetonitrile C liquid THF
Mobile phase conditions: Initial A / B / C = 50/45/5
6 min A / B / C = 25/70/5
35 min A / B / C = 7/88/5
40 min A / B / C = 0/95/5
<MS conditions>
Equipment used: Waters Xevo G2 Q-Tof
Ionization method: ESI (-)
Capillary voltage: 1.5 kV
Ion source temperature: 120 ° C
Desolvation gas temperature: 500 ° C
Cone gas flow rate: 50 L / Hr
Desolvation gas flow rate: 1000 L / Hr
Cone voltage: 10V
Mass range: 100-1400
<Waveform processing conditions>
Smooth Chromatogram: ± 3scan
Number of smooths: 2
Smoothing method: Mean
Peak to Peak baseline Noise: 5
Peak Width at 5% Height: 0.15 mins
Baseline Start Threshold: 0.15%
Baseline End Threshold: 0.15%
Absolute height: 50
Absolute area: 5
Sample preparation: About 10 mg of the cocondensate or resin composition of the present application was weighed into a 10 mL volumetric flask, dissolved in 1 mL of tetrahydrofuran, and then diluted with acetonitrile. In addition, the co-condensate of Comparative Example 3 and Comparative Example 4 in which a dissolved component was generated during dissolution was obtained by filtering the insoluble component with a 0.2 μm membrane filter. In addition, Leucine-Enkephalin was used as a reference for MS.

[3] Measurement of unreacted monomer and volatile organic compound content The unreacted monomer and volatile organic compound content were determined by gas chromatography based on the following conditions.
Equipment used: Gas chromatograph GC-2014 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: N ₂ (40 ml / min)
Combustion gas: Hydrogen (60 kPa), Air (60 kPa)
Injection volume: 2 μL
Sample preparation conditions: 1 g of a novolak-type cocondensate or resin composition was dissolved in 10 mL of a standard solution (an acetone solution of anisole (about 1 g / 200 mL)) and analyzed under the above conditions.
Quantitative method: Internal standard method (GC-IS method).

[4] Measurement of softening point It measured by the method based on JIS-K2207. As the bath solution, silicone oil (Shin-Etsu Silicone KF-96-100CS) was used.

[5] Ratio of each structural unit of cocondensate or resin composition ¹ H-NMR analysis was performed by a method based on the following conditions.
Equipment: “JMN-ECS” (400 MHz) manufactured by JEOL Ltd.
Solvent: deuterated chloroform 0.03% (v / v) TMS
Sample: About 5 mg of the solvent was subjected to dissolution analysis with 0.75 mL of sample. Sample: The novolak-type cocondensate or resin composition was pulverized and subjected to ¹ H-NMR analysis. As the cocondensate of Comparative Example 3 and Comparative Example 4 in which an insoluble matter was generated in the solvent, the insoluble matter was filtered through a 0.2 μm membrane filter.

Regarding the attribution of ¹ H-NMR analysis results and the like, the chemical shift of each component: Tetramethylsilane was used as a reference (0 ppm), and the peak indicated by the following values was used as the peak of each component.
Proton of p-tert-butyl group derived from p-tert-butylphenol: 0.9 to 1.3 ppm
Proton of methyl group derived from m-cresol: 1.9 to 2.4 ppm
Proton of methylene group derived from formaldehyde: 3.5 to 4.1 ppm

In addition, about the component ratio described in the following Examples etc., it is a ratio based on the following references | standards.
m-cresol: A ratio (mole times) when the structural unit derived from p-tert-butylphenol is 1.
Formaldehyde: Proportion (mole times) when the structural unit derived from p-tert-butylphenol is 1.

1. Production and physical properties of cocondensates and resin compositions

<Example 1>
To a four-necked separable flask equipped with a reflux condenser and a thermometer, 180.0 g (1.20 mol) of p-tert-butylphenol and 150.8 g (1.86 mol) of formalin with a purity of 37% 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 reacted at the same temperature for 3 hours.
When the reaction mixture was analyzed by GPC, the molecular weight of the resol-type condensate was weight average molecular weight (Mw) = 239, number average molecular weight (Mn) = 206 (hereinafter, the weight average molecular weight was abbreviated as Mw, and the number average molecular weight was abbreviated as Mn). It was). Next, 78.4 g (0.24 mol) of 30% sulfuric acid was added and stirred for 0.2 hours, whereby the resol-type condensate layer and the aqueous layer were separated. After standing for 0.1 hour, the lower aqueous layer was removed. The resol-type condensate in the four-neck separable flask was 262 g.
Subsequently, 129.6 g (1.20 mol) of m-cresol was added, the temperature was raised to an internal temperature of 90 ° C., and the reaction was performed while concentrating and dehydrating at an internal temperature of 90 to 105 ° C. over 4 hours. Subsequently, the temperature was raised to an internal temperature of 110 to 120, and the reaction was carried out while concentrating and dehydrating for 1.5 hours. After the reaction, the temperature was raised while distilling water to an internal temperature of 142 to 145 ° C. under normal pressure, and the pressure was reduced to 45 kPa while maintaining the internal temperature of 140 to 150 ° C. 326 g of type cocondensate was obtained. The physical properties of the obtained novolak type cocondensate are as follows.
Weight average molecular weight (Mw): 1757
Number average molecular weight (Mn): 963
Polydispersity (Mw / Mn): 1.8
Softening point: 115 ° C
P-tert-butylphenol: 4.4%
M-cresol: 5.2%
-Ratio of each structural unit of cocondensate Formaldehyde: 1.49, m-cresol: 1.00.

<Example 2>
To a four-necked separable flask equipped with a reflux condenser and a thermometer, 180.0 g (1.20 mol) of p-tert-butylphenol and 180.0 g (2.22 mol) of formalin with a purity of 37% were sequentially added. Thereafter, the temperature was raised to an internal temperature of 40 ° C., 46.0 g (0.28 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 3 hours.
When the reaction mixture was analyzed by GPC, the molecular weight of the resol-type condensate was Mw = 239 and Mn = 224. Then, 45.1 g (0.14 mol) of 30% sulfuric acid was added and stirred for 0.2 hours, whereby the resol-type condensate layer and the aqueous layer were separated. After standing for 0.1 hour, the lower aqueous layer was removed. The resol-type condensate in the four-neck separable flask was 266 g.
Subsequently, 155.5 g (1.44 mol) of m-cresol was added, the temperature was raised to an internal temperature of 90 ° C., and the reaction was performed while concentrating and dehydrating at an internal temperature of 90 to 105 ° C. over 2.5 hours. Subsequently, the temperature was raised to an internal temperature of 110 to 120, and the reaction was carried out while concentrating and dehydrating for 1.5 hours. After the reaction, the temperature was raised while distilling water to an internal temperature of 142 to 145 ° C. under normal pressure, and the pressure was reduced to 45 kPa while maintaining the internal temperature of 140 to 150 ° C. 332 g of a type cocondensate was obtained. The physical properties of the obtained novolak type cocondensate are as follows.
Weight average molecular weight (Mw): 1758
Number average molecular weight (Mn): 997
Polydispersity (Mw / Mn): 1.8
Softening point: 122 ° C
P-tert-butylphenol: 1.5%
M-cresol: 2.8%
-Ratio of each structural unit of cocondensate Formaldehyde: 1.62, m-cresol: 1.14.

<Example 3>
The same procedure as in Example 2 was repeated except that 14.1 g of stearic acid (bead stearate Tsubaki (solid at room temperature) manufactured by NOF CORPORATION) was added at the time of charging 155.5 g (1.44 mol) of m-cresol. 351 g of a resin composition containing a novolak-type cocondensate was obtained. The physical properties and the like of the resin composition containing the obtained novolak type cocondensate are as follows.
Weight average molecular weight (Mw): 1775
Number average molecular weight (Mn): 1000
Polydispersity (Mw / Mn): 1.8
Softening point: 113 ° C
P-tert-butylphenol: 1.8%
-M-cresol: 4.7%
・ Stearic acid: 4.0%
-Ratio of each structural unit of cocondensate Formaldehyde: 1.62, m-cresol: 1.14.

<Comparative Example 1>
In a four-necked separable flask equipped with a reflux condenser and a thermometer, 60.7 g (1.86 mol) of paraform having a purity of 92%, 180.0 g (1.20 mol) of p-tert-butylphenol, and 146.0 g of toluene were added. Added in order. Thereafter, the temperature was raised to an internal temperature of 40 ° C., 46.0 g (0.28 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 1 hour. Next, the temperature was raised to 88 ° C. and the reaction was carried out at the same temperature for 5.5 hours. The molecular weight of the resol-type condensate after the reaction was Mw = 1512 and Mn = 827.
After completion of the reaction, 45.1 g (0.14 mol) of 30% sulfuric acid was added and stirred for 0.2 hours, whereby the resol-type condensate layer and the aqueous layer were separated. After standing for 0.1 hour, the lower aqueous layer was removed. The resol-type condensate in the four-neck separable flask was 390 g (pure content 63%).
Subsequently, 77.8 g (0.72 mol) of m-cresol was added, the temperature was raised to an internal temperature of 110 ° C., and the reaction was carried out under reflux and dehydration at an internal temperature of 110 to 124 ° C. for 2.5 hours. After the reaction, toluene was distilled off under atmospheric pressure at an internal temperature of 142 to 146 ° C., and then the pressure was reduced to 29 kPa while maintaining the internal temperature of 140 to 150 ° C., thereby further distilling off the toluene and producing a pale yellow novolak type. 279 g of cocondensate was obtained. The physical properties of the obtained novolak type cocondensate are as follows.
Weight average molecular weight (Mw): 2966
Number average molecular weight (Mn): 1472
Polydispersity (Mw / Mn): 2.0
Softening point: 143 ° C
P-tert-butylphenol: 0.0%
M-cresol: 7.5%
・ Toluene: 1.9%
-Ratio of each structural unit of cocondensate Formaldehyde: 1.14, m-cresol: 0.60.

<Comparative example 2>
Instead of 77.8 g (0.72 mol) of m-cresol, 90.7 g (0.84 mol) of m-cresol and 32.7 g of stearic acid (bead stearic acid Tsubaki (solid at room temperature) manufactured by NOF CORPORATION) were added. In the same manner as in Comparative Example 1 except that the reaction was performed, 330 g of a resin composition containing a pale yellow novolac cocondensate was obtained. The physical properties and the like of the resin composition containing the obtained novolak type cocondensate are as follows.
Weight average molecular weight (Mw): 2210
Number average molecular weight (Mn): 1195
Polydispersity (Mw / Mn): 1.8
Softening point: 106 ° C
P-tert-butylphenol: 0.0%
-M-cresol: 6.1%
・ Stearic acid: 9.9%
・ Toluene: 1.6%
-Ratio of each structural unit of cocondensate Formaldehyde: 1.04, m-cresol: 0.65.

Hereafter, the manufacture example of the novolak-type cocondensation resin containing the structural unit derived from well-known p-tert- butylphenol, m-cresol, and formaldehyde and the physical-property value of this cocondensation resin are shown.
<Comparative Example 3 Japanese Patent Laid-Open No. 4-39663 Example 10 Additional Test>
In a four-necked separable flask equipped with a reflux condenser and a thermometer, m-cresol 243.8 (2.26 mol), p-tert-butylphenol 84.4 g (0.56 mol), and 37% pure formalin 433. 3 g (5.34 mol) and 0.45 g (0.005 mol) of oxalic acid were sequentially added. Then, the temperature was raised to an internal temperature of 100 ° C. and reacted at the same temperature for 1 hour. Subsequently, m-cresol 243.8 (2.26 mol) and p-tert-butylphenol 84.4 g (0.56 mol) were continuously added with the progress of the reaction, and the mixture was reacted at an internal temperature of 100 ° C. for 2 hours. Thereafter, the oil bath temperature was raised to 180 ° C., and water, unreacted formaldehyde, m-cresol, p-tert-butylphenol and oxalic acid were removed under a reduced pressure of 0.4 kPa, and a pale yellow novolac cocondensate was obtained. 711 g was obtained. The physical properties of the obtained novolak type cocondensate are as follows.
Weight average molecular weight (Mw): 1398324
Number average molecular weight (Mn): 1766
Polydispersity (Mw / Mn): 792
Softening point: 166 ° C
P-tert-butylphenol: 11.3%
M-cresol: 1.9%
-Ratio of each structural unit of cocondensate Formaldehyde: 0.42, m-cresol: 0.80.

<Comparative Example 4 Japanese Patent Application Laid-Open No. 11-143067 Production Example 6 Additional Test>
To a four-necked separable flask equipped with a reflux condenser and a thermometer, m-cresol 21.6 (0.20 mol), p-tert-butylphenol 30.0 g (0.20 mol), and 37% pure formalin 77. 0 g (0.95 mol) and 0.01 g (0.0001 mol) of oxalic acid were sequentially added. Then, the temperature was raised to an internal temperature of 100 ° C. and reacted at the same temperature for 1 hour. Subsequently, m-cresol 21.6 (0.20 mol) and p-tert-butylphenol 30.0 g (0.20 mol) were continuously added along with the progress of the reaction, and the mixture was reacted at an internal temperature of 100 ° C. for 2 hours. Thereafter, the oil bath temperature was raised to 180 ° C., and water, unreacted formaldehyde, m-cresol, p-tert-butylphenol and oxalic acid were removed under a reduced pressure of 0.4 kPa, and a pale yellow novolac cocondensate was obtained. 104 g was obtained. The physical properties of the obtained novolak type cocondensate are as follows.
-Weight average molecular weight (Mw): 1006509
Number average molecular weight (Mn): 1698
Polydispersity (Mw / Mn): 593
Softening point: 101 ° C
P-tert-butylphenol: 25.6%
-M-cresol: 1.3%
-Ratio of each structural unit of a cocondensate formaldehyde: 0.63, m-cresol: 0.52.

The physical properties of the cocondensates and resin compositions of Examples 1 to 3 and Comparative Examples 1 to 4 are shown in Table 1 below. In the following table, the content of each component is represented by weight basis (% by weight), and the m / z ratio is the mass number m / z = 347.165, 431 among the area values of the mass chromatogram obtained by the measurement method. Represents the ratio of the area value due to each mass number in the table to the total amount of the four area values due to .259, 467.222, and 1199.734, p-tert-butylphenol, m-cresol and formaldehyde Each derived structural unit represents the ratio (molar ratio) of each structural unit to the structural unit derived from p-tert-butylphenol. The meanings of the abbreviations in the following tables are as follows.
PTBP: p-tert-butylphenol m-CL: m-cresol HCHO: formaldehyde

2. Production examples and physical property evaluation of rubber compositions

(1) Production of unvulcanized rubber composition Unvulcanized rubber comprising the cocondensate produced in Examples 1, 2 and Comparative Example 1, and the resin composition produced in Example 3 and Comparative Example 2 The composition was produced by the method described below. In addition, in order to compare the performance of the cocondensate and resin composition of the present invention, SUMIKANOL620 (manufactured by Taoka Chemical Industry Co., Ltd., hereinafter also referred to as SKL620), which is a commercially available novolac-type cocondensate, and novolak An unvulcanized rubber composition containing no mold cocondensate was produced by the following method.

<Method for producing unvulcanized rubber composition>
In accordance with the composition shown in Table 2 below, first, components other than insoluble sulfur, vulcanization accelerator and methylene donor, and co-condensate or resin composition are added and mixed in a pressure kneader made by Toshin, and discharged when the temperature reaches 160 ° C. did. Next, by adding and mixing insoluble sulfur, a vulcanization accelerator and a methylene donor to the obtained mixture with a 6-inch open roll manufactured by Kansai Roll Co., Ltd., which was kept at 60 ° C., Examples 4 to 6, Reference Example 1, Unvulcanized rubber compositions of Comparative Examples 5 to 7 were produced.
The numerical values in Table 2 below represent parts by weight. Details of each component in Table 2 are as follows.

・ Natural rubber: SVR-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 Sangyo Co., Ltd.
Cobalt salt: Cobalt stearate (reagent, manufactured by Alfa Aesar)
Insoluble sulfur: “Cristex HS OT-20” manufactured by Flexis
・ Vulcanization accelerator: N, N-dicyclohexyl-2-benzothiazolylsulfenamide (reagent, manufactured by Wako Pure Chemical Industries, Ltd.)
・ Methylene donor: “Sumikanol 507AP” manufactured by Bara Chemical Co., Ltd.

(2) Unvulcanized rubber composition physical property test and vulcanized rubber composition physical property test Using the unvulcanized rubber compositions of Examples 4 to 6, Reference Example 1 and Comparative Examples 5 to 7 obtained as described above. The Mooney viscosity test (JIS K 6300-1: 2001 compliant, measured at 130 ° C.) and the rheometer test (JIS K 6300-2: 2001 compliant, measured at 160 ° C.) were carried out.

  Further, unvulcanized samples were prepared using the unvulcanized rubber compositions of Examples 4 to 6, Reference Example 1 and Comparative Examples 5 to 7, and allowed to stand at room temperature for 24 hours, and then heated at 160 ° C. and 6 MPa. Vulcanization was performed under conditions of t90 + 5 minutes under pressure 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 (measured at 25 ° C.), a hardness measurement (measured at 25 ° C.), and a viscoelasticity measurement were performed.

<Testing method and evaluation of unvulcanized rubber composition and vulcanized rubber>
-Mooney viscosity It tested by the method based on JISK6300-1: 2001.
Specifically, the unvulcanized rubber composition was measured at 130 ° C. with a rotorless Mooney viscometer, and ML (1 + 4) of the unvulcanized rubber composition was measured and compared with the reference example and the comparative example. Under these conditions, the viscosity of the rubber composition at a certain point in the vulcanization process is related to ease of molding. A smaller value is better.

-Vulcanization characteristic The test was done by the method based on JIS K6300-2: 2001.
Specifically, an unvulcanized rubber composition was measured with a rotorless rheometer at 160 ° C. at a peak setting, MH (dN · m) of the unvulcanized rubber composition: maximum torque, a cross-linking curve was measured, and a reference example The relative comparison was made with the comparative example. This condition relates to the crosslink density at some point during the vulcanization process. A larger value is better.

-Hardness The test was conducted by a method according to JIS K6253: 2006. (Type of testing machine Type A durometer)
Specifically, a test piece was prepared from vulcanized rubber, and the measured value Hs was compared with a reference example and a comparative example. This is the hardness of the crosslinked rubber, and a larger value is better.

-Tensile test It tested by the method based on JISK6251: 2010. (Specimen shape Dumbbell shape)
Specifically, the modulus M10 (MPa), M100 (MPa), the breaking strength Tb (MPa), and the breaking elongation Eb (%) were measured using a rubber test piece prepared from a vulcanized rubber sheet. Compared. M10 is the tensile stress when the elongation percentage of the specimen is 10%, and M100 is the tensile stress when the specimen is 100%, which is related to the crosslinking density of the vulcanized rubber. A larger value is better.
Tb is a tensile stress at the time of rupture of the test piece, and is a value related to the strength (crosslinking density) of the rubber. The value tends to decrease if the dispersibility of the resin or the molding of the rubber sheet is poor. A larger value is better.
Eb is the elongation at break of the test piece, and is related to the strength (crosslinking density) of the rubber. When Tb increases, Eb tends to decrease due to a trade-off. Moreover, there is a problem when the dispersibility of the resin and the influence of molding of the rubber sheet are likely to appear, and these are both bad. Bigger is better.

-Viscoelasticity measurement It measured on condition of the following using the rubber test piece created from the vulcanized rubber sheet.
Viscoelastic device: SII Nano Technology Co., Ltd. DMS6100
Conditions: Temperature 40 ° C. to 80 ° C. (Temperature increase rate: 2 ° C./min) Dynamic strain 0.2%,
10Hz frequency
Test piece: long side 50 mm × short side 5 mm × thickness 2 mm
E ′ represents the elastic modulus of the rubber. If E ′ is large, the rubber is hard and has high elasticity. Therefore, for rubber applications that require durability and high hardness, a larger value is better. Tan δ (loss tangent) represents the magnitude of hysteresis loss of rubber, and when the value at 70 ° C. is small as an index of low fuel consumption performance, low fuel consumption performance tends to be improved. A smaller value is better.

Regarding the rubber physical property test results described above, relative evaluation results when using each cocondensate or resin composition when Comparative Example 5 (100) is a rubber composition not containing a novolak-type cocondensate Table 2 shows.

上記表２に示す通り、本発明の共縮合物及び樹脂組成物を配合したゴム組成物は、ノボラック型共縮合物を含まないゴム組成物（比較例５）よりも各物性が向上し、公知のノボラック型共縮合物「ＳＵＭＩＫＡＮＯＬ６２０」を配合したゴム組成物に比べ、ゴム組成物の加工性や粘弾性が優れた性能を示すことが判明した。

As shown in Table 2 above, the rubber composition containing the cocondensate and the resin composition of the present invention has improved physical properties and is well known in comparison with the rubber composition not containing the novolac type cocondensate (Comparative Example 5). It was found that the rubber composition exhibited superior processability and viscoelasticity as compared with the rubber composition containing the novolac-type cocondensate “SUMIKANOL620”.

Claims (4)

a novolak-type alkylphenol-formaldehyde cocondensate comprising structural units derived from p-tert-butylphenol, m-cresol, and formaldehyde,
The polydispersity (Mw / Mn) of molecular weight in terms of polystyrene obtained when the cocondensate is analyzed using a gel permeation chromatograph (GPC) method is 5 or less,
Among the area values of the mass chromatogram obtained when the cocondensate is analyzed using a liquid chromatograph mass spectrometer (LCMS), the mass numbers m / z = 347.165, 431.2259, 467.222, and The ratio of the area value caused by the mass number m / z = 431.259 is 90% or more with respect to the total amount of area values caused by 1199.734, and the area value caused by the mass number m / z = 1199.734 The ratio is 10% or less,
Cocondensate. The method for producing a cocondensate according to claim 1, comprising the following steps (1), (2) and (3) in this order.
(1) With respect to 1 mol of p-tert-butylphenol, in the presence of 0.05 mol or more of base, p-tert-butylphenol and 1.5 to 2.5 mol of formaldehyde are reacted at 50 to 70 ° C. A step of obtaining a resol-type condensate having a number average molecular weight (Mn) of 300 or less in a permeation chromatograph (GPC) method.
(2) A step of neutralizing the base used in step (1) with an acid equivalent to or more than the base, and separating and removing the aqueous layer from the resol-type condensate.
(3) A step of reacting a resol-type condensate with 0.5 to 1.5 mol of m-cresol with respect to 1 mol of p-tert-butylphenol. A rubber composition comprising the cocondensate according to claim 1, a methylene donor compound, and rubber. The rubber composition according to claim 3, wherein the methylene donor compound is at least one selected from the group consisting of hexakis (methoxymethyl) melamine, pentakis (methoxymethyl) methylolmelamine and tetrakis (methoxymethyl) dimethylolmelamine.