TW201829512A - Novolak type co-condensate for rubber compounding and method for manufacturing the co-condensate - Google Patents

Abstract

An object of the present invention is to provide a novolak type co-condensate mainly composed of p-tert-butylphenol and a method for manufacturing the same, wherein the novolak type co-condensate has a softening point comparable to that of a conventionally known novolac type co-condensate and does not block during storage, and has sufficient performance as adhesive used in rubber processing step. The above problem can be solved by the following: when a phenol having a p-tert-butylphenol as a main component is reacted with formaldehyde to form a resol type condensate, the reaction is carried out till a resol type condensate having a number average molecular weight (Mn) of 600 or more is obtained, and after the reaction, the base used in the reaction is neutralized, and then it is reacted with 0.5 to 0.8 mol of resorcin per l mol of the phenol.

Description

 Novolak type cocondensate for rubber preparation and method for producing the same  

The present invention relates to a novolak type which can be used as an adhesive in a rubber processing step and which is obtained from an alkyl phenol or a phenyl phenol (hereinafter, also referred to as a phenol). A modified condensate, a novolak-type cocondensate obtained by the process, a resin composition containing the novolak-type cocondensate, and a rubber composition containing the novolak-type cocondensate or the resin composition Things.

In rubber products such as tires, belts, hoses, etc., which are reinforced with reinforcing materials such as steel cords and organic fibers, it is required that the rubber can be firmly adhered to the reinforcing material. In order to be followed by the rubber, a method of treating the reinforcing material with various adhesives and a method of simultaneously adjusting the other various formulating agents in the rubber processing step are known. In such a method, the method of formulating the adhesive in the processing step of the rubber can be strongly vulcanized and then widely used, regardless of whether or not the reinforcing material is subjected to an adhesive treatment.

On the other hand, the use of an adhesive in the rubber processing step requires softening in the rubber processing step. The temperature at which the rubber processing step is carried out is known, for example, in the range of rubbers for tires suitable for the use of the adhesive, and is usually about 170 ° C (for example, Japanese Rubber Association Vol. 73 (2000), No. 9, p 488-493 (Non-Patent Document 1)]. Therefore, the adhesive used in the rubber processing step needs to have a softening point which is sufficiently lower than the maximum temperature at the time of rubber processing, that is, 150 ° C or lower. Further, from the viewpoint of improving the dispersibility of the adhesive at the time of use, the softening point of the adhesive is as low as possible, to the extent that it is not blocked during the storage of the adhesive. Therefore, in the adhesive used in the rubber processing step, a condensate obtained by reacting a phenol such as p-t-octylphenol or p-nonylphenol with a formaldehyde solution is widely used, and the condensate is further used. A cocondensate which reacts with meta- benzenediol (for example, Patent Document 1).

However, p-tert-octylphenol and p-nonylphenol are currently regulated in the EU region and may be restricted in the REACH Regulation as SVHC (Highly Attention Substances), and their use in the EU region will be restricted in the future. The possibility will be higher.

Therefore, the adhesive used in the rubber processing step is currently developed to use phenols other than p-t-octyl phenol and p-nonyl phenol, and contains constituent units derived from phenol and resorcin. Co-condensate development. For example, Patent Document 2 describes a cocondensate in which only a copolycondensate of p-tert-butylphenol of phenol type is used, and a softening point is a cocondensate of 80 ° C or more and 190 ° C or less, and a method for producing the same. However, when the inventors of the present invention continued to test the method described in the literature, it was found that the obtained cocondensate had high hygroscopicity and was easy to agglomerate. Further, it has been found that when the obtained cocondensate is used as an adhesive in the rubber processing step, problems such as foaming of the rubber occur, and thus it is not suitable as an adhesive.

Further, Japanese Laid-Open Patent Publication No. 2015-052097 (Patent Document 3) also discloses the use of p-t-butylphenol and o-phenylphenol as co-condensates of phenols.

 [Previous Technical Literature]    [Patent Literature]  

[Patent Document 1] Japanese Laid-Open Patent Publication No. 06-234824

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2014-152220

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2015-52097

[Non-Patent Document 1] Japan Rubber Association Vol. 73 (2000), No. 9, 488-493

In Patent Document 3, it is known that when only a third butyl phenol is used as the phenol, the softening point is very high (200 ° C or higher), and it is not suitable as an adhesive used in the processing step of the rubber, and o-benzene. When the phenol is used in combination, the softening point of the cocondensate can be greatly reduced, and therefore it is suitable for use as an adhesive in the rubber processing step. However, o-phenylphenol is expensive, so it is desirable to not use o-phenylphenol in combination or to minimize its use.

Then, the inventors of the present application reviewed whether the amount of o-phenylphenol used can be reduced in the method described in Patent Document 3, and the use ratio of p-tert-butylphenol is relative to o-phenylphenol and p- When the total amount of the tributyl phenol is more than 65 mol%, when a resole type condensate obtained by reacting a phenol with formaldehyde water is reacted with meta- benzenediol, the reaction liquid swells and foams. When the fluidity is lowered and the reaction liquid is not uniform, the workability is remarkably deteriorated, and it is difficult to industrially manufacture, and the softening point of the cocondensate exceeds 150 °C.

Therefore, an object of the present invention is to provide a novolac type cocondensate whose main component is p-tert-butylphenol, which has the same softening point as the previously known novolak-type cocondensate and does not agglomerate when stored. A co-condensate having a property as an adhesive used in a rubber processing step and a method for producing the same.

As a result of deliberate review of the above problems, the present inventors have found that under the specific conditions described below, the production of phenols, formaldehyde and meta- stilbene containing: p-tert-butyl phenol as a main component is produced. The constituent units of the novolac type co-condensate can solve the aforementioned problems. Specifically, the following inventions are included.

[1] A method for producing a novolak-type co-condensate, wherein the novolak-type cocondensate contains one or more kinds of phenols, formaldehyde, and m-benzene derived from the following formula (i). The constituent unit of phenol, R represents an alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a branched chain, and the constituent unit derived from the above phenols contains 65 mol% or more of a constituent unit derived from p-tert-butylphenol, and the above-mentioned production The method comprises the following steps (1), (2) and (3) in sequence;

(1) reacting the phenol with formaldehyde at 75 ° C or higher in the presence of a base of 0.05 mol or more relative to the phenolic 1 molar to obtain a number average molecular weight (Mn) of a colloidal filtration chromatography (GPC) method. The step of a novolac type condensate of 600 or more.

(2) A step of mixing a reaction liquid containing the novolac type condensate obtained in the above step (1) with an acid having an equivalent or more with respect to the base used in the above step (1).

(3) a step of reacting the above-mentioned novolac type condensate with m-benzenediol of 0.5 to 1.2 mol with respect to the aforementioned phenolic 1 molar.

[2] The method for producing a novolak-type cocondensate according to [1], wherein the amount of the resorcin to be used is 0.5 to 0.8 mol per mol of the phenol.

[3] The method for producing a novolak-type cocondensate according to [1] or [2], wherein the amount of the base used in the step (1) is 1 mol relative to the phenol. It is 0.05 to 0.25 m.

[4] A novolac type cocondensate which satisfies all of the following (a) to (e).

(a) a constituent unit containing one or two or more kinds of phenols, formaldehyde, and resorcinol represented by the following formula (i). R represents an alkyl group or a phenyl group which may have a branched carbon number of 1 to 12.

(b) The constituent unit derived from the above phenols contains 65 mol% or more of a constituent unit derived from p-tert-butylphenol.

(c) The number average molecular weight (Mn) of the colloidal filtration chromatography (GPC) method is 750 or more.

(d) The softening point is 80 to 150 °C.

(e) The constituent unit derived from the resorcin is 0.80 mol or less based on 1 mol of the constituent unit derived from the phenol.

[5] The novolac type cocondensate according to [4], which further satisfies the following (f), (f) in the colloidal filtration chromatography (GPC) method, containing 1 to 10% by area percentage The component having a peak molecular weight of 700 to 520 (oligomer-1) contains 0.01 to 2% of a component having a peak molecular weight of 430 to 320 (oligomer-2) in terms of area percentage.

[6] The novolac type cocondensate according to [4] or [5], wherein a solution obtained by dissolving 2.0 g of a novolak-type cocondensate in 20 mL of tetrahydrofuran is penetrating at a wavelength of 610 nm. The rate is over 80%.

[7] A resin composition comprising the novolac type cocondensate according to any one of [4] to [6], and a softening agent.

[8] The resin composition according to [7], wherein the softener is a fatty acid having 8 to 32 carbon atoms.

[9] The resin composition according to [7], wherein the softening agent is cashew nut shell liquid (CNSL).

[10] The resin composition according to any one of [7], wherein the content of the softener in the resin composition is 5 to 40% by weight.

[11] The resin composition according to any one of [7], wherein a solution of 2.0 g of the resin composition in 20 mL of tetrahydrofuran has a light transmittance at a wavelength of 610 nm. More than 80%.

[12] A rubber composition comprising the novolac type cocondensate according to any one of [4] to [6], or the item [7] to [11] The resin composition and the rubber component described.

According to the present invention, a novolak-type cocondensate having a main component of p-t-butylphenol can be produced, which has a softening point which is the same as that of a conventionally known novolak-type cocondensate and does not agglomerate when stored. It is sufficient to have a co-condensate which is used as a binder in the processing step of rubber, and it is difficult to industrially work such as reduction in fluidity and unevenness of reaction liquid, such as swelling of the reaction liquid and foaming at the time of production. The problem.

Further, in the production method of the present invention, even if a method generally known in the prior art is used which is not suitable for use as a binder in the rubber processing step due to a high softening point, only a novolac type which uses p-tert-butylphenol as a phenol type is used. The cocondensate may also reduce the softening point of the cocondensate to such an extent that it can be used as an adhesive in the processing step of the rubber without degrading the performance as an adhesive. Further, in an embodiment of the production method of the present invention, it is also possible to provide a cocondensate which improves the odor as needed while maintaining the performance as an adhesive.

In summary, it is understood that the novolak-type cocondensate obtained by the production method of the present invention is mutually miscible with a fatty acid having a carbon number of 8 to 32, which is represented by stearic acid, in addition to the cashew nut shell liquid (CNSL). The above-mentioned fatty acid is widely used as a vulcanization aid in the rubber processing step, and therefore, when it is desired to further reduce the softening point of the cocondensate of the present invention, it is not necessary to use a substance which is not usually used in the processing step of the rubber as a softening agent. When a substance added as a softening agent becomes a problem (for example, a rubber in which a softener reacts with other components contained in the rubber) is also suitable for the purpose.

<Method for Producing Novolak-type Cocondensate>

Hereinafter, the method for producing the novolak-type cocondensate of the present invention will be described in detail. The method for producing a novolak-type cocondensate of the present invention is characterized by comprising the following steps (1), (2) and (3).

(1) In the presence of a base of 0.05 mol or more with respect to one or two or more kinds of phenolic moles represented by the above formula (i), one type represented by the above formula (i) or Two or more kinds of phenols are reacted with formaldehyde at 75 ° C or higher to obtain a step of a colloidal phenol condensate having a number average molecular weight (Mn) of 600 or more by a colloidal filtration chromatography (GPC) method.

(2) a step of mixing a reaction liquid containing the novolac type condensate obtained in the step (1) with an acid equivalent to or more than the equivalent of the base used in the step (1).

(3) A step of reacting a resol-type condensate with m-benzenediol having 0.5 or 1.2 mols of one or more phenols 1 molar represented by the above formula (i).

In the production method of the present invention, the ratio of use of p-tert-butylphenol as one or two or more kinds of phenols (hereinafter sometimes referred to as phenols) represented by the above formula (i) When the amount is higher, the novolak-type cocondensate of the present invention can be produced at a lower cost, but a phenol other than p-t-butylphenol can also be used in combination. Examples of the phenols other than the p-tert-butylphenol which may be used together include o-tert-butylphenol, o-phenylphenol, p-phenylphenol, p-cresol, and p-third. The octylphenol, p-nonylphenol or the like may also contain a phenol which may have a branched chain and an alkyl group having 1 to 12 carbon atoms or a phenyl group as a substituent. Among these phenols, it is preferred from the viewpoint of the above-mentioned regulations to include phenols which may have a branched alkyl group having 1 to 6 carbon atoms or a phenyl group, particularly o-tertiary butyl phenol. More preferably, o-phenylphenol, p-phenylphenol, and p-cresol. When other phenols are used in combination, the amount of other phenols other than p-tert-butylphenol in all phenols is usually 35 mol% or less, and the price of other phenols and the resulting novolac type The viewpoint of the solubility of the cocondensate to the fatty acid having 8 to 32 carbon atoms is preferably 20 mol% or less, more preferably 10 mol% or less, and particularly preferably 5 mol% or less.

The formaldehyde used in the step (1) may be a compound of formaldehyde which can be easily produced by using formaldehyde water which is an aqueous solution of formaldehyde, and paraformaldehyde and trioxane, in addition to gaseous formaldehyde. The amount of formaldehyde used is preferably from 1 to 3 moles, more preferably from 1.5 to 2.5 moles, based on the phenolic 1 molar. When 1 mol or more is used, the generation of volatile organic compounds can be suppressed, and when the amount is 3 mol or less, the softening point of the obtained novolak-type cocondensate may be further reduced.

As the base to be used in the step (1), a hydroxide or a carbonate of an alkali metal or an alkaline earth metal, ammonia, an amine or the like can be used, and a base which is usually used in the production of a novolac type condensate can be used. Specific examples of such a base include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, and potassium carbonate. Among such bases, sodium hydroxide or potassium hydroxide is preferred. These bases may be used alone or in combination of two or more kinds as needed. Further, such a base may be a solid or a liquid (aqueous solution or organic solution), but an aqueous solution is preferred because of its reactivity and ease of handling. When an aqueous solution is used, the base contained in the aqueous solution may be usually 10% by weight to 50% by weight. The amount of the base to be used is 0.05 mol or more with respect to the phenolic 1 molar, and preferably 0.05 to 0.8 mol, more preferably 0.2 to 0.5 mol. When the amount of the base used is less than 0.05 mol, there is a case where the unreacted monomer increases to increase the odor and the volatile organic compound, and it is difficult to obtain the number average molecular weight of the colloidal filtration chromatography (GPC) method (Mn). The case of a novolac type condensate of 600 or more. Further, in the case where it is desired to reduce the odor of the novolak-type cocondensate, the amount of the base to be used is preferably 0.05 mol or more and 0.25 mol or less with respect to the phenolic 1 mol. The reason why the amount of the base used is less than 0.25 m to reduce the odor is not known, and it is presumed that the so-called Cannizzaro reaction and the formose reaction are caused by the inhibition of the side reaction product of formaldehyde and alkali. .

When the step (1) is carried out, an organic solvent can also be used. As an example of the organic solvent which can be used, an aromatic hydrocarbon such as toluene, xylene or ethylbenzene or a ketone having 3 to 7 carbon atoms such as methyl isobutyl ketone is preferably used. These organic solvents may be used singly or in combination of two or more kinds as needed. The amount of the organic solvent to be used is usually 0.4 to 4.0 times by weight with respect to 1 part by weight of the phenol. When the reaction is carried out without using an organic solvent, water may be used instead of the organic solvent.

The method of carrying out the step (1) is, for example, adding a phenol and formaldehyde, if necessary, an organic solvent to the reactor, and then adding a base to the reactor to dissolve or suspend the alkali to carry out the reaction. When the reaction is carried out, the reaction liquid needs to be analyzed by a suitable colloidal filtration chromatography (GPC), and the number average molecular weight (Mn) of the molecular weight of the standard polystyrene converted to the novolak type condensate in the reaction liquid is converted. It is 600 or more. Further, usually, the number average molecular weight (Mn) of the novolac type condensate in the reaction liquid is 1,500 or less. In the step (1), if the number average molecular weight (Mn) of the novolac type condensate is lower than 600, the reaction liquid swelling may occur in the step of reacting with the resorcinol (step (3)) described later. Further, since the fluidity is lowered and the reaction liquid is not uniform, which is difficult in industrial operation, in order to solve the problem, there is a tendency to require high-temperature conditions or high stirring strength conditions which are difficult in industrial operation. Further, when the reaction is carried out under the conditions of high temperature or high stirring strength, when the obtained novolak-type cocondensate is reduced in moisture, unreacted phenols, solvent or the like, the softening point of the cocondensate is more than 150. °C, in this case, it is not suitable for the use of an adhesive for rubber and a reinforcing material in rubber when mixing. Further, the number average molecular weight of the resol type condensate can be determined by the method described in the following examples.

In order to carry out the step (1) to obtain a novolac type condensate having a number average molecular weight (Mn) of 600 or more, the reaction temperature is usually 75 ° C or more, and preferably 75 to 120 ° C. When the reaction is carried out at less than 75 ° C, it is difficult to obtain a resol type condensate having a number average molecular weight (Mn) of 600 or more. Further, when the reaction is carried out in the step (1), it is not necessary to always be 75 ° C or higher, and it is sufficient that the reaction is carried out at any time in the reaction at 75 ° C or higher.

The step (2) can be carried out by mixing the reaction liquid containing the novolac type condensate obtained in the step (1) with an acid equivalent to or more than the base used in the step (1). Examples of the acid used in the step (2) 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 singly or in combination of two or more kinds, and an aqueous solution of such an acid may also be used. The amount of the acid to be used may be more than or equal to the equivalent of the base portion of the base used in the step (1), and is preferably 1 to 2 moles per mole of the base portion. In the step (2), the reaction liquid containing the novolac type condensate obtained in the step (1) may be mixed with the acid in multiple portions, and the total amount of the acid to be used is the base used in the step (1). The form of the equivalent or more is carried out.

When the step (2) is not carried out, when the obtained novolak-type cocondensate is added to the rubber, the physical properties of the vulcanized rubber are deteriorated, and the performance as an adhesive in the rubber processing step cannot be sufficiently exhibited. The situation. Further, in the step (3), when the reaction with the resorcin is not sufficiently carried out, there is a case where a large amount of unreacted phenol remains, and when unreacted phenols, stilbene, etc. are removed, The coloring of the remaining alkali and the resulting novolak-type cocondensate are decomposed, and the quality of the adhesive is deteriorated. Further, by carrying out the step (2), it is also possible to reduce the hygroscopicity of the obtained cocondensate.

After the step (2) is carried out, in order to remove unreacted formaldehyde and by-product inorganic salts, etc., depending on the need, an organic solvent and water which are not mixed with water may be used to extract the resol-type condensation in the organic phase. And separating the unreacted formaldehyde in the aqueous phase and the inorganic salts as a by-product, and performing a water washing step.

The amount of hydroquinone used in the step (3) is from 0.5 to 1.2 mol, and from 0.5 to 1.0 mol, relative to the amount of the phenol used in the step (1). Preferably, 0.5 to 0.8 moles is better. When the amount of the use of the resorcin is more than 1.2 moles, a large amount of unreacted hydroquinone remains, so that there is a problem that volatility becomes a problem. Further, there is a tendency that it is difficult to obtain a novolak-type cocondensate which is well miscible with stearic acid. When the amount of use of the resorcinol is less than 0.5 mol, there is a case where the performance of the adhesive used in the rubber processing step is not easily exhibited, and the molecular weight of the obtained novolak-type cocondensate is increased and softened. The point cannot be below 150 °C.

Step (3) may also be carried out without using a solvent, but it is preferably carried out in the presence of a solvent of 0.2 times or more by weight relative to 1 part by weight of the phenol used in the step (1), and is 0.4 to 2.0 times by weight. It is more preferably carried out in the presence of a solvent. When the solvent is used in an amount of 0.2 times by weight or more, the amount of unreacted hydroquinone in the obtained novolak-type cocondensate can be reduced by avoiding macromolecularization of the obtained novolak-type cocondensate. Further, when the solvent is used in an amount of 2.0 times by weight or less, when the solvent used in the reaction is removed by the cocondensate, the solvent can be efficiently removed from the cocondensate. Examples of the solvent which can be used in the step (3) include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene, and ketones having 3 to 7 carbon atoms such as methyl isobutyl ketone, and ethyl acetate. N-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, acetic acid-second butyl ester, n-amyl acetate, acetic acid-second amyl ester, methyl amyl acetate, acetic acid-2-B An ester-based organic solvent such as butyl butyrate, ethyl butyrate or methyl valerate is preferred, and toluene, xylene and n-butyl acetate are preferred. The solvent used in the step (3) may be directly used as it is in the solvent used in the water washing step after the step (1) and/or the step (2), or a new solvent may be appropriately added.

The reaction of the step (3) is usually carried out at 40 to 150 ° C, preferably at 100 to 150 ° C. Further, when the resol-type condensate is reacted with meta- benzenediol, the reaction rate is slowed down due to the presence of water in the system. Therefore, the reaction is carried out while removing the by-product water. good.

After the completion of the step (3), the novolak-type cocondensate of the present invention having the following characteristics can be obtained, except that the solvent used in the reaction contained in the novolak-type co-condensate, unreacted phenols, and the like are removed. When resorcinol or the like is used, it can be removed by a general method (hereinafter, this step is sometimes referred to as a concentration removal step). In addition, when the internal temperature is more than 165 ° C, the softening point of the obtained novolak-type cocondensate tends to be 150 ° C or more, and it is difficult to use the adhesive as a binder in the rubber processing step. And the case where the novolac type cocondensate is colored, decomposed, and the like.

<Novolak type cocondensate of the present invention>

The novolac type cocondensate of the present invention has the following characteristics (a) and (b).

(a) A constituent unit containing one or two or more kinds of phenols, formaldehyde, and resorcinol represented by the above formula (i).

(b) The constituent unit derived from the above phenols contains 65 mol% or more of constituent units derived from p-tert-butylphenol. The constituent unit derived from the above phenols preferably contains 80 mol% or more of the constituent unit derived from p-tert-butylphenol, more preferably 90 mol% or more.

Further, the novolak-type co-condensate of the present invention usually contains 1 to 2 moles of a constituent unit derived from formaldehyde (methylene group and/or) in a total amount of 1 mole from a constituent unit derived from a phenol. Dimethylene ether based). The ratio of these constituent units can be determined, for example, by analyzing the novolak-type cocondensate using ¹ H-NMR. Specifically, the produced novolak-type cocondensate is washed with a solvent such as water to remove unreacted monomers such as unreacted hydroquinone contained in the novolak-type cocondensate, and then subjected to ¹ H. - NMR analysis, in which the ratio of the proton integral value from each constituent unit is determined within the obtained analysis result.

Meanwhile, the novolac type cocondensate of the present invention also has the following features (c), (d) and (e).

(c) The number average molecular weight (Mn) of the colloidal filtration chromatography (GPC) method is 750 or more.

(d) The softening point is 80 to 150 °C.

(e) The constituent unit derived from the resorcin is 0.80 mol or less with respect to the constituent unit of one or two or more kinds of phenols represented by the above formula (i).

The novolac type co-condensate of the present invention is a colloidal filtration chromatography (GPC) method in which the number average molecular weight (Mn) is converted to a standard polystyrene molecular weight of 750 or more, and more preferably 1,000 or more. When the number average molecular weight is less than 750, agglomeration may occur during storage. The number average molecular weight of the novolak-type cocondensate can be determined by the method described in the following examples. Further, the number average molecular weight is preferably 3,000 or less, more preferably 2,000 or less. When the number average molecular weight is 3,000 or less, the softening point of the novolak-type cocondensate can be further reduced.

The novolak-type cocondensate of the present invention has a softening point of 80 ° C or more, more preferably 90 ° C or more, and 150 ° C or less, more preferably 140 ° C or less. When the softening point is higher than 150 ° C, when it is used as an adhesive in the rubber processing step, it may not be completely dispersed in the rubber, and the subsequent performance may not be sufficiently exhibited. Further, when the softening point is lower than 80 ° C, agglomeration tends to occur during storage. Further, even if it is a resin composition by mixing with a softening agent by the following method, the softening point of the novolak-type cocondensate of the present invention is preferably in the above range when it is used as an adhesive in the rubber processing step.

The novolak-type co-condensate of the present invention contains 1 mol of the constituent unit derived from the phenol, and the constituent unit derived from the resorcin is 0.80 mol or less, and 0.30 to 0.80 mol. Preferably, 0.30 to 0.70 moles are better. When the constituent unit derived from the resorcinol is more than 0.80 mol, the hygroscopicity is increased, so that the problem of agglomeration tends to occur when the co-condensate is preserved, and the cocondensate is used in the rubber processing step. When it is used as an adhesive, problems such as foaming of rubber tend to occur. Further, when the constituent unit derived from the resorcin is more than 0.80 mol, when the cocondensate is melted, a high-viscosity liquid is formed due to rheology, so that the fluidity is deteriorated, and granulation and tableting are caused. The case where the forming process is difficult and the case where it is not miscible with the fatty acid having 8 to 32 carbon atoms. Further, when it is less than 0.30 mol, there is a case where performance as an adhesive cannot be expressed. The ratio of the constituent units derived from the resorcin can be determined by the method described in the following examples.

Further, when the novolak-type cocondensate of the present invention has the following feature (f), the mutual solubility with a fatty acid having 8 to 32 carbon atoms can be improved.

(f) In the colloidal filtration chromatography (GPC) method, 1 to 10% of the component having a peak molecular weight of 700 to 520 (oligomer 1) in an area percentage, and 0.01 to 2% by area percentage The peak top molecular weight is 430 to 320 (oligomer 2).

Whether the above characteristics are present or not can be determined by colloidal filtration chromatography (GPC) under the following conditions.

Further, when the novolak-type cocondensate of the present invention is not colored brown, it tends to be a co-condensate having a reduced odor. Specifically, when a solution of 2.0 g of the cocondensate of the present invention dissolved in 20 mL of tetrahydrofuran has a light transmittance of 80% or more at a wavelength of 610 nm, it tends to be a co-condensate having a reduced odor. The spectral transmittance at a wavelength of 610 nm can be determined by the method described in the following examples. The relationship between coloring and odor is still unclear. It is speculated that there is a correlation between coloring and odor due to the influence of some color components on odor.

The content of the unreacted m-catechol contained in the novolac type co-condensate of the present invention is preferably 8% by weight or less. When it is set to 8% by weight or less, when the novolak-type cocondensate is directly used as an adhesive in the rubber processing step, it may suppress the evapotranspiration of the hydroquinone during rubber mixing, so that it is in the working environment. good. When the novolak-type cocondensate is mixed with a softener as a resin composition, the mixing ratio of the novolak-type cocondensate and the softener is not more than 10% by weight of the unreacted hydroquinone. It is better. Further, the content of the unreacted phenol (one or two or more kinds of phenols represented by the above formula (i) used as a raw material) in the novolak-type co-condensate of the present invention is 3% by weight or less. Preferably, 1% by weight or less is more preferable. By making the content of unreacted phenols 3% by weight or less, the harmful effects on humans/ecological systems can be reduced. In addition, the content of the volatile organic compound (solvent or the like used in the production), which is contained in the novolak-type co-condensate of the present invention, is preferably 5% by weight or less, and 3% by weight or less based on the environment. Better. Further, the volatile organic compound does not include the aforementioned unreacted meta- benzenediol and unreacted phenol.

<Resin composition>

Next, a resin composition containing the novolak-type cocondensate and softener of the present invention will be described. (Hereinafter, the resin composition containing the novolak-type cocondensate and softener of the present invention may be simply referred to as a resin composition.)

The softening agent used in the present invention may be one which is compatible with the novolak-type cocondensate of the present invention and which can reduce the softening point of the resin composition. As an example of such a substance, a softener such as a novolac type cocondensate, a solid having a low softening point such as a xanthanone resin, or a liquid such as a cashew nut shell liquid (CNSL) can be used. Further, the novolac type co-condensate obtained by the production method of the present invention has mutual carbonic acid having a carbon number of 8 to 32 which is represented by stearic acid as a vulcanization aid which is widely used as a vulcanization aid in a rubber processing step. Solubility, so fatty acids having 8 to 32 carbon atoms can be used as softeners. Further, the novolac type cocondensate obtained by the conventionally known production method according to the production method of the present invention is not miscible with the fatty acid having 8 to 32 carbon atoms, and the resin layer and the oil layer are separated.

These softeners may be used singly or in combination of two or more kinds as needed. In particular, a fatty acid having a carbon number of 8 to 32 is used as a softening agent, in particular, a resin composition using stearic acid, and the softening thereof can be reduced even if a substance which is not used in a rubber processing step is not newly added as a softening agent. Therefore, when a substance added as a softener may become a problem (for example, a rubber in which a softener reacts with other components contained in the rubber) is also suitable for the purpose.

Cashew nut shell liquid, a natural plant liquid obtained from the shell of cashew nuts. Cashew nut shell liquid refers to a mixture of phenol derivatives having a branched chain of a saturated or unsaturated hydrocarbon. In particular, its composition mainly contains anacardic acid, cardanol, cardol, and methylcardol. The preparation method of the cashew nut shell liquid has a heating method and a solvent extraction method, and is usually prepared by heating the cashew nut shell liquid for industrial use. Since the main component is converted into cardanol, cardanol, and cardanol by the decarburization of a succinic acid by the heat treatment, the composition ratio of the industrial cashew nut shell liquid is generally available ( The weight %) is cardanol (75 to 85%), cardanol (15 to 20%), and methyl cardanol (1 to 5%). Moreover, the cashew nut shell liquid referred to in the present invention also includes a method in which the cashew nut shell liquid is separated and refined to appropriately adjust the components contained in the liquid, and the other components are not added to the cashew nut shell liquid, and the partial aggregation is carried out. And get the cashew nut shell polymer.

Examples of industrially available cashew nut shell liquids include: Cashew liquid products (CNSL, LB-7000, LB-7250, CD-5L) manufactured by Tohoku Chemical Co., Ltd., TAN HOA HOP PHAT Co., Ltd. Manufacturing CNSL and so on. The cashew nut shell liquid can be used alone or in combination of two or more kinds as needed.

Examples of the fatty acid having 8 to 32 carbon atoms include a saturated or unsaturated fatty acid having 8 to 32 carbon atoms, or a metal salt thereof. Specifically, examples of the saturated fatty acid include octanoic acid (octanoic acid), citric acid, n-decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and twenty-two. Examples of the unsaturated fatty acid such as a carbaic acid include oleic acid or undecylenic acid. These fatty acids may be used alone or in combination of two or more kinds as needed. Among these fatty acids, stearic acid, palmitic acid, myristic acid, lauric acid, and behenic acid are preferred from the viewpoints of price and ease of availability. Further, it is more preferable that stearic acid is a general organic acid in terms of a rubber additive.

Specific examples of the stearic acid used in the present invention include, for example, a beryllium stearate grade (C18: 63%, C16: 32%) produced by Nippon Oil Co., Ltd., and beaded stearin. Sour cherry grade (C18: 66%, C16: 31%) and the like.

The content of the softening agent contained in the resin composition is 5% by weight or more based on the total amount of the resin composition, preferably 10% by weight or more, more preferably 40% by weight or less, and still more preferably 30% by weight or less. When the content is 40% by weight or less, the agglomeration of the resin composition and the performance as an adhesive for rubber may be deteriorated, and the content may be 5% by weight or more, and the effect of reducing the softening point can be sufficiently exhibited.

When the resin composition of the present invention is mixed in a rubber at a usual mixing temperature of about 170 ° C, the softening point of the resin composition is sufficient as long as it is 150 ° C or less, but the mixing of the intermediate hydroquinone is suppressed. When the mixing is carried out at a low temperature of 100 to 130 ° C for the purpose of evapotranspiration, if the softening point is not lower than the mixing temperature by 120 ° C or less, the problem of poor dispersibility may occur. Reinforced materials may not be able to fully perform. Further, when the softening point of the resin composition is lower than 80 ° C, the case of agglomeration during storage is therefore poor.

Similarly to the novolak-type cocondensate of the present invention, the resin composition of the present invention tends to be a resin composition having a reduced odor when it is not colored brown. Specifically, a solution obtained by dissolving 2.0 g of the resin composition of the present invention in 20 mL of tetrahydrofuran is a resin composition having a reduced odor when the light transmittance at a wavelength of 610 nm is 80% or more. The spectral transmittance at a wavelength of 610 nm can be determined by the method described in the following examples.

The content of the unreacted m-catechol contained in the resin composition is preferably 8% by weight or less. When it is 8% by weight or less, it is possible to suppress the evapotranspiration of the resorcinol when the rubber is mixed, which is preferable in the working environment. Further, the content of the unreacted phenol contained in the resin composition is preferably 3% by weight or less, more preferably 1% by weight or less. The content of unreacted phenols is 3% by weight or less, that is, the harmful effects on humans/ecosystems may be reduced. In addition, the content of the volatile organic compound (solvent or the like used in the production), which is contained in the resin composition, is preferably 5% by weight or less, more preferably 3% by weight or less. Further, the above volatile organic compound does not include the aforementioned unreacted m-catechol and unreacted phenol.

The resin composition is obtained by mixing the novolak-type cocondensate of the present invention obtained by the methods of the above steps (1), (2) and (3) with a softener. After the softening agent is mixed, or before the softening agent is mixed, a solvent used in the removal reaction and a concentrated removal step of unreacted p-tert-butylphenol, resorcin, or the like may be carried out as needed.

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 resorcin (step (3)), the reaction may also be in the number of carbon atoms. The resin composition of the present invention is produced by carrying out the presence of a saturated or unsaturated fatty acid of 8 to 32. Step (3) is carried out in the presence of a saturated or unsaturated fatty acid having 8 to 32 carbon atoms, and a resin having a reduced amount of hydroquinone and a softening point of 80 to 120 ° C can be easily obtained. Composition. When a saturated or unsaturated fatty acid having 8 to 32 carbon atoms is used in the step (3), the amount thereof is usually 15 to 40 with respect to 100 parts by weight of the total of the novolac type condensate and the resorcin. The parts by weight are preferably 15 to 35 parts by weight, more preferably 18 to 32 parts by weight.

<Rubber composition>

Next, the rubber composition containing the novolac type co-condensate and/or the resin composition of the present invention will be described in detail.

The rubber composition of the present invention contains the novolak-type cocondensate and/or the resin composition and the rubber component, and typically a novolak-type cocondensate and/or a resin composition, a rubber component, a filler, and Sulfur and methylene supply agent compounds are obtained by mixing. The above components may be mixed together with a vulcanization accelerator, zinc oxide, or an organic cobalt compound.

The novolak-type cocondensate and/or resin composition of the present invention can be used, for example, in an amount of from 0.5 to 10 parts by weight per 100 parts by weight of the rubber component. Among them, it is preferably in the range of 1 to 5 parts by weight. When it is less than 0.5% by weight, it cannot be used as an adhesive acting as a reinforcing material and a rubber. When it is more than 10 parts by weight, although it is not problematic in terms of the aforementioned effects, it is not economically unsatisfactory to exhibit the effect of meeting the above-mentioned addition amount. .

The rubber component can be exemplified by natural rubber, epoxidized natural rubber, deproteinized natural rubber and other modified natural rubber, and polyisoprene rubber (IR), styrene/butadiene copolymer rubber (SBR), polybutylene. Diene rubber (BR), acrylonitrile/butadiene copolymer rubber (NBR), isoprene/isobutylene copolymer rubber (IIR), ethylene/propylene-diene copolymer rubber (EPDM), halogenated butane rubber (HR) Various synthetic rubbers are used, and high-unsaturated rubbers such as natural rubber, styrene/butadiene copolymer rubber, and polybutadiene rubber are preferably used. Especially natural rubber is better. Further, it is also effective to combine various rubber components by using a combination of natural rubber and a styrene/butadiene copolymer rubber, and a combination of natural rubber and polybutadiene rubber.

Examples of natural rubber include natural rubbers such as RSS #1, RSS #3, TSR 20, and SIR 20. The epoxidized natural rubber is preferably an epoxidized degree of 10 to 60 mol%, and may be exemplified by ENR 25 and ENR 50 manufactured by Kumpulan Guthrie. The deproteinized natural rubber is preferably a deproteinized natural rubber having a total nitrogen content of 0.3% by weight or less. Modification of natural rubber to use natural rubber in advance with 4-vinylpyridine, N,N-dialkylaminoethyl acrylate (such as N,N-diethylaminoethyl acrylate), 2-hydroxy acrylate, etc. It is preferred to obtain a modified natural rubber containing a polar group.

Examples of the SBR include an emulsion polymerization SBR and a solution polymerization SBR described on pages 210 to 211 of the Rubber Industry Handbook <Fourth Edition> edited by the Japan Rubber Association. In particular, it is preferable to use solution-polymerized SBR, and it is more preferable to use a molecular terminal of 4,4'-bis(dialkylamino)diphenyl ketone such as "Nipol (registered trademark) NS 116" manufactured by Zeon Corporation of Japan. Modified solution polymerization SBR; "SL 574" manufactured by JSR Corporation, etc., solution polymerization of SBR with terminal modification of tin halide compound molecules; "E 10" and "E 15" manufactured by Asahi Kasei Co., Ltd., polymerization of decane modified solution SBR products; use of indoleamine compounds, guanamine compounds, urea compounds, N,N-dialkyl acrylamide compounds, isocyanate compounds, quinone imine compounds, alkoxy-containing decane compounds (trial alkoxides) a solution polymerization SBR having any element of nitrogen, tin or bismuth at the molecular terminal of any one of the amino decane compound and the amino decane compound; and is selected from the group consisting of an indoleamine compound and a guanamine compound. , a urea compound, an N,N-dialkyl acrylamide compound, an isocyanate compound, a quinone compound, a decyl compound having an alkoxy group (a trialkoxy decane compound, etc.), and an amino decane compound are The compound (a tin compound and a decane compound having an alkoxy group, an alkyl acrylamide compound and an alkoxy group-containing decane compound, etc.) is subjected to molecular terminal modification, and the molecular terminal has two kinds selected from tin and bismuth. The solution polymerization SBR of the above elements is more preferable.

Examples of the BR include a solution polymerization BR in which a cis-1,4-bond is 90% or more high cis-BR, and a cis-bond is about 35% low cis-BR, and is used. High cis-BR with a high ethylene content is preferred. For better use: tin-modified BR such as "Nipol (registered trademark) BR 1250H" manufactured by Zeon Corporation of Japan; 4,4'-bis(dialkylamino)diphenyl ketone, tin halide compound, and internal use a guanamine compound, a guanamine compound, a urea compound, an N,N-dialkylpropenylamine compound, an isocyanate compound, a quinone compound, a decane compound having an alkoxy group (a trialkoxy decane compound, etc.), Any one of the aminodecane compounds which is subjected to molecular terminal modification to obtain a solution polymerization BR having any element of nitrogen, tin or antimony at the molecular end; and is selected from the group consisting of: 4,4'-di(dialkylamino) Phenyl ketone, tin halide compound, indoleamine compound, guanamine compound, urea compound, N,N-dialkyl acrylamide compound, isocyanate compound, ruthenium compound, decane compound having alkoxy group (three Two or more compounds of an alkoxydecane compound and the like and an aminodecane compound (a tin compound and a decane compound having an alkoxy group, an alkyl acrylamide compound, a decane compound having an alkoxy group, etc.) are subjected to molecular terminal modification. Quality Having a molecular terminal two or more kinds of elements selected from nitrogen, silicon, tin, and the solution polymerization BR. Such BRs are usually used in combination with natural rubber.

The rubber component preferably contains natural rubber, and the proportion of the natural rubber in the rubber component is preferably 70% by weight or more.

As the filler, carbon black, cerium oxide, talc, clay, aluminum hydroxide, titanium oxide or the like which is usually used in the rubber category can be used, and carbon black and cerium oxide are preferably used, and carbon black is particularly preferable. For carbon black, use the Japan Rubber Association's "Rubber Industry Fact Sheet <Fourth Edition>" on page 494: HAF (High Abrasion Furnace), SAF (Super Abrasion Furnace), ISAF (Intermediate SAF), FEF (Fast Carbon black such as Extrusion Furnace), MAF (Medium Abrasion Furnace), GPF (General Purpose Furnace), and SRF (Semi-Reinforcing Furnace) are preferred. A tire tread rubber composition using a CTAB surface area of 40 to 250m ² / g, nitrogen adsorption / g, a particle size of carbon black is preferably 10 to 50nm specific surface area of 20 to 200m ^2, to CTAB surface area of 70 to 180m ² / g of Carbon black is more preferable, and examples thereof are N 110, N 220, N 234, N 299, N 326, N 330, N 330T, N 339, N 343, N 351 and the like in the ASTM specification. Further, it is preferred that the surface of the carbon black is surface-treated with carbon black to be 0.1 to 50% by weight of cerium oxide. Further, a combination of carbon black and cerium oxide is also effective in combination of various fillers.

The cerium oxide can be exemplified by a cerium oxide 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, preferably using "AQ" and "AQ-N" manufactured by Tosoh / Oxide Corporation. "Ultrasil (registered trademark) VN3", "Ultrasil (registered trademark) 360", "Ultrasil (registered trademark) 7000" manufactured by Degussa Corporation; "Zeosil (registered trademark) 115GR" and "Zeosil" (registered by Rhodia) Trademarks) 1115MP", "Zeosil (registered trademark) 1205MP", "Zeosil (registered trademark) Z85MP", and "Nipsil (registered trademark) AQ" manufactured by Nippon Oxide Corporation. Further, in general, when cerium oxide is used as a filler, a compound selected from the group consisting of bis(3-triethoxydecylpropyl)tetrasulfide ("Si-69" manufactured by Degussa Co., Ltd.) and bis(3-triethyl) is added. Oxylylpropyl)disulfide ("Si-75" manufactured by Degussa Corporation), bis(3-diethoxymethylmercaptopropyl)tetrasulfide, bis(3-diethoxymethyloxime) One or more groups consisting of propyl)disulfide and octanesulfuric acid-S-[3-(triethoxymethyl)propyl] ester ("NXT decane" manufactured by General Electronic Silicons Co., Ltd.) The decane coupling agent or the like is preferably a compound having a functional group such as an anthracene bonded to cerium oxide or a functional group such as an alkoxysilane.

The aluminum hydroxide can be 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 to be used is not particularly limited, and is preferably in the range of 10 to 120 parts by weight based on 100 parts by weight of the rubber component. It is particularly preferably 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. In general, powdered sulfur is preferred, and in the case of a tire member having a large sulfur content such as a belt member for a tire, insoluble sulfur is preferred. The amount of the sulfur component used is not particularly limited, and is preferably in the range of 1 to 10 parts by weight based on 100 parts by weight of the rubber component. The member for the belt of the tire is preferably in the range of 5 to 10 parts by weight.

Examples of the vulcanization accelerators are described in the Rubber Industry Handbook <Fourth Edition> (issued by the Japan Rubber Association, Japan, January 20, 2006), pages 412 to 413: Thiazole-based vulcanization accelerators, Sulfonamide is a vulcanization accelerator and an oxime vulcanization accelerator.

Specifically, it may, for example, be N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N , N-dicyclohexyl-2-benzothiazolylsulfenamide (DCBS), 2-hydrothiobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), diphenyl sulfonium (DPG) . Among them, N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), N-tert-butyl-2-benzothiazolylsulfenamide (BBS), N,N-dicyclohexyl Preferably, -2-benzothiazolylsulfenamide (DCBS) or dibenzothiazyl disulfide (MBTS) is used in combination with diphenylphosphonium (DPG).

The amount of the vulcanization accelerator to be used is not particularly limited, and is preferably in the range of 0.5 to 3 parts by weight per 100 parts by weight of the rubber component. It is more preferably in the range of 0.5 to 1.2 parts by weight.

The amount of zinc oxide used is not particularly limited, and is preferably in the range of 3 to 15 parts by weight per 100 parts by weight of the rubber component. Among them, it is more preferably in the range of 5 to 10 parts by weight.

Examples of the methylene donor compound include hexamethylenetetramine, hexakis(methoxymethyl)melamine, penta(methoxymethyl)hydroxymethylmelamine, and tetrakis(methoxymethyl). A common user in the rubber industry such as methyl melamine. Among them, hexa(methoxymethyl)melamine alone or a mixture thereof as a main component is preferred. These methylene supply agent compounds may be used singly or in combination of two or more kinds, and the compounding amount thereof is preferably in the range of about 0.5 to 4 parts by weight, based on 100 parts by weight of the rubber component. A range of about 3 parts by weight is more preferable.

Examples of the organic cobalt compound include an acid cobalt salt such as cobalt naphthenate or cobalt stearate, and a fatty acid cobalt/boron compound (for example, "Manobond C (registered trademark)": manufactured by Rhodia Co., Ltd.). . The amount of the organic cobalt compound used is preferably in the range of 0.05 to 0.4 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition of the present invention can also be blended with various blending agents which have been used in the rubber category and mixed. Examples of the formulation include anti-aging agents, oils, retardants, debonding agents, stearic acid, and the like.

Examples of the anti-aging agent include those described in the "Rubber Industry Handbook <Fourth Edition>" edited by the Japan Rubber Association, pages 436 to 443. Among them, N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (6PPD), reaction product of aniline with acetone (TMDQ), poly(2,2,4- Trimethyl-1,2-)dihydroquinoline ("Antioxidant FR" manufactured by Matsubara Industries Co., Ltd.), synthetic wax (paraffin, etc.), and vegetable wax are preferred.

Examples of oils include softening oils, vegetable oils, and the like. Examples of the softening oil include paraffin-based softening oil, naphthenic-based softening oil, and aromatic-based softening oil.

Examples of the retarding agent include phthalic anhydride, benzoic acid, salicylic acid, N-nitrosodiphenylamine, N-(cyclohexylthio)-phthalimide (CTP), a sulfonamide derivative, diphenylurea, di(tridecylalkyl)pentaerythritol diphosphite, etc., using N-(cyclohexylthio)-phthalimide (CTP) It is better.

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

(A) Step of mixing the filler with the rubber component

The mixture of the filler and the rubber component can be carried out by a closed mixing device such as a Banbury mixer. The mixing is usually accompanied by heat generation, so the temperature at the end of the mixing is preferably in the range of 140 ° C to 180 ° C, and more preferably in the range of 150 ° C to 170 ° C. Mixing time is about 5 minutes to 10 minutes.

(B) a step of mixing the mixture obtained in the step (A) with a sulfur component and a vulcanization accelerator

The mixture obtained in the step (A) may be mixed with a sulfur component and a vulcanization accelerator, and may be carried out in a closed mixing device such as a Banbury mixer or an open roller. The temperature of the mixture at the end of the mixing is preferably from 30 ° C to 100 ° C, more preferably from 60 ° C to 90 ° C. The mixing time is usually from 5 minutes to 10 minutes.

The novolac type cocondensate and/or resin composition of the present invention may be added in the step (A) or (B) because of its low softening point, and it is preferably added in the step (A).

In the case of using zinc oxide, an anti-aging agent, an oil, a fatty acid, or a debonding agent, it is preferred to add them in the step (A).

In the case of using a retarding agent, it is preferred to add it in the step (B).

In this manner, the obtained rubber composition containing the novolak-type cocondensate and/or resin composition of the present invention is particularly effective in vulcanization with a reinforcing material. Examples of the reinforcing material include organic fibers such as nylon, enamel, polyester, and polyarsenamide, and steel curtains such as copper-plated steel curtains and galvanized steel curtains. Among them, the rubber composition of the present invention is particularly effective when it is followed by vulcanization with a copper-plated steel wire curtain.

The rubber composition containing the novolac type co-condensate and/or the resin composition of the present invention is formed together with the reinforcing material, and then subjected to a vulcanization step to obtain a rubber product in which the rubber and the reinforcing material are firmly adhered. The vulcanization step is preferably carried out at 120 ° C to 180 ° C. The vulcanization step can be carried out under normal pressure or under pressure.

 [Examples]  

Hereinafter, the present invention will be further specifically described by way of examples, comparative examples, and reference examples (hereinafter, sometimes referred to as examples). However, the invention is not limited by these examples. Further, the content of each component described in the examples and the like, the amount of the remaining solvent, and the amount of the unreacted monomer are, unless otherwise limited, the total amount of the obtained co-condensate or the resin composition containing the softener, the weight of the substance. %, the content of the oligomer component is the area percentage. Further, various measurement systems in the respective examples and the like were carried out as follows.

[1] Analytical conditions for colloidal filtration chromatography (GPC)

Machine used: HLC-8220 GPC (manufactured by Tosoh Corporation)

Detector: RI (differential refraction) detector

Pipe string: TSK Guard Column SUPER HZ-L (made by Tosoh Corporation) + TSK-GEL SUPER HZ 1000 (4.6mm ×150mm)+TSK-GEL SUPER HZ 2500(4.6mm ×150mm)+TSK-GEL SUPER HZ 4000(4.6mm ×150mm)

Column temperature: 40 ° C

Injection volume: 10μL

Evaporation solution and flow rate: tetrahydrofuran 0.35mL/min

Standard for converting molecular weight (manufactured by GPC standard curve): Adding 1,1-bis(4-hydroxyphenyl)cyclohexane to TSK-GEL standard polystyrene kit (PS-oligomer kit) Alkane (FW 268) and phenol (FW 94) were prepared to prepare a standard curve. Modulation of the sample: the cocondensate or the resin composition is dissolved in a solution of about 0.02 g in 10 mL of tetrahydrofuran.

Based on the results of the above GPC analysis, the average molecular weight of the novolac type condensate, the average molecular weight of the novolac type cocondensate and the resin composition, and the respective contents contained in the novolac type cocondensate and the resin composition were calculated as follows. The content of the oligomer component (area percentage).

(a) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the resol type condensate

The multi-wavelength peaks obtained by measurement of the novolac type condensate were grouped, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated. Further, when the average molecular weight of the novolac type condensate is calculated, when an organic solvent is used in the production, the peak corresponding to the organic solvent is excluded.

(b) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the novolac type cocondensate

The multi-wavelength peaks obtained by the measurement of the novolac type co-condensate were grouped, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated. Further, when the average molecular weight of the novolak-type cocondensate is calculated, the peaks corresponding to the organic solvent are also excluded when the unreacted monomer (the peak of the phenol or the resorcin) and the organic solvent used in the production are used.

(c) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin composition

The multi-wavelength peaks obtained by the measurement of the resin composition were grouped, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated. Further, when the average molecular weight of the resin composition is calculated, when an organic solvent is used in the production, the peak corresponding to the organic solvent is excluded.

(d) content of oligomer components

From the GPC curve obtained by measuring the average molecular weight of the novolak-type cocondensate, each peak of the multimodality is separated from the peak bottom, and the peak molecular weight (hereinafter, sometimes referred to as the peak top in the examples and the like) is calculated. The percentage (%) of the area of the peak. Further, when the content (area percentage) of the oligomer component is calculated, when an organic solvent is used in the production, the peak corresponding to the organic solvent is excluded.

[2] Determination of unreacted monomers and volatile organic compounds

The content of unreacted monomers and volatile organic compounds was quantified by gas chromatography according to the following conditions.

Machine used: manufactured by Shimadzu Corporation Gas chromatography GC-2014

Column: Glass column Outer diameter 5mm × inner diameter 3.2mm × length 3.1m

Filler: Filler Silicone OV-17 10% Chromosorb WHP 80/100mesh, max.temp.340°C

Column temperature: 80 ° C → 280 ° C

Gasification tank temperature: 250 ° C

Detector temperature: 280 ° C

Detector: FID

Extraction gas: N ₂ (40mL/min)

Combustion gas: hydrogen (60kPa), air (60kPa)

Injection volume: 2μL

Conditions for preparation of the sample: 2.0 g of a resol type condensate, a novolak type cocondensate, or a resin composition is dissolved in a standard solution (acetone solution of anisole (about 1 g/200 mL)) in 10 mL.

Further, the novolak-type cocondensate or the resin composition having an unreacted monomer and a volatile organic compound content of 0.1% or less is a sample of 2.0 g of an acetone solution in anisole (about 1 g/200 mL). The analysis was carried out under the above conditions in 10 mL.

Quantitative method: internal standard method (GC-IS method).

In addition, the pure material (% by weight, expressed as % below) of the novolac type condensate described in each of the examples and the like is used to quantify the amount of the organic solvent contained in the solution containing the novolac type condensate by the above method. It is assumed that all components other than the quantified organic solvent are calculated as a novolac type condensate.

[3] Determination of softening point

It was measured in accordance with the method of JIS-K 2207.

[4] Proportion of each constituent unit of the cocondensate or the resin composition

¹ H-NMR analysis was carried out in accordance with the following conditions.

Device: "JMN-ECS" (400MHz) manufactured by JEOL

Solvent: dimethyl hydrazine substituted with heavy hydrogen in 0.03% (v/v) TMS tubule

Sample: about 3 mg dissolved in solvent 0.75 mL

For the preparation of the analysis sample, in order to remove the unreacted monomer such as unreacted m-benzenediol contained in the novolak-type cocondensate or the resin composition, the co-condensate is washed with water in advance by the following method. For ¹ H-NMR analysis.

The cocondensate or the resin composition obtained in each of the examples and the like was poured into a 200 mL three-necked separable flask in a mortar and pulverized into 30 g of a square of 5 mm or less and 60 g of water. Next, oxalic acid was added to the aqueous layer to have a pH of 5 to 7, and then heated to an internal temperature of about 100 ° C, and then mixed under reflux at the same temperature for 30 minutes while stirring under a mechanical stirrer. Then, the stirring was stopped and the aqueous layer was quickly removed at the same internal temperature (water washing 1). Then, 60 g of water was again added, and the temperature was raised to an internal temperature of about 100 ° C, and then mixed under reflux at the same temperature for 30 minutes while stirring under a mechanical stirrer. After mixing for 30 minutes under reflux, the aqueous layer was similarly removed (water washing 2). Then, the water was distilled off under reduced pressure at an internal temperature of 140 to 150 ° C, and the pressure was further reduced to 16 kPa while maintaining the same temperature to dry the cocondensate or the resin composition.

Classification of ¹ H-NMR analysis results, etc.

Chemical shift of each component: based on tetramethyl decane (0 ppm), the peak represented by the following values is the peak of each component.

Proton of p-tert-butyl group from p-tert-butylphenol: 1.00 to 1.15 ppm

Protons from methylene of formaldehyde: 3.4 to 4.0 ppm

Proton-t-butyl proton from o-butyl phenol: 1.25 to 1.35 ppm

Protons from o-phenyl groups of o-phenylphenol: 7.2 to 7.5 ppm

Proton of p-phenyl group from p-phenylphenol: 7.2 to 7.5 ppm

Further, since the protons derived from the phenolic hydroxyl group of the resorcinol are difficult to be classified separately, all of the protons derived from the phenolic hydroxyl group are integrated values of 7.80 to 9.80 ppm, and subtracted from the resorcinol. The integral value of one phenolic hydroxyl group derived from a phenolic hydroxyl group is calculated, and the integral value of two phenolic hydroxyl groups derived from the resorcinol is calculated.

Specifically, in the case of the novolak-type cocondensate containing p-tert-butylphenol and o-phenylphenol, the protons from all phenolic hydroxyl groups are integrated values of 7.80 to 9.80 ppm. Substituting the integral value of one proton derived from p-tert-butylphenol from a phenolic hydroxyl group and the integral value of a proton derived from a phenolic hydroxyl group from o-phenylphenol, and calculating from meta-benzene The integral value of the two phenolic hydroxyl groups of the phenol.

Moreover, the structural ratio described in the following examples and the like is based on the ratio of the following criteria.

Resorcinol: A ratio (mole times) when the constituent unit derived from p-tert-butylphenol is 1.

o-Phenol: a ratio when the constituent unit derived from p-tert-butylphenol is 1 (mole)

O-tertiary butyl phenol: ratio in which the constituent unit derived from p-tert-butylphenol is 1 (mole)

P-Phenol: ratio in which the constituent unit derived from p-tert-butylphenol is 1 (mole)

Further, in the examples in which p-tert-butylphenol is used in combination with other phenols, when the constituent unit of the resorcin is described, the parentheses together indicate that the constituent unit derived from all the phenols is 1 proportion.

[5] Determination of penetration rate

The transmittance of a solution obtained by dissolving a cocondensate or a resin composition in 20 Ml of tetrahydrofuran at a wavelength of 610 nm was measured under the following conditions.

Device: Color difference meter ("SE 6000" manufactured by Nippon Denshoku Industries Co., Ltd.)

Measuring temperature: 25 ° C

Measurement method: A solution obtained by dissolving 2.0 g of a cocondensate or a resin composition in 20 mL of tetrahydrofuran was prepared, and a spectroscopic transmittance of the solution at a wavelength of 380 to 780 nm was measured using a square quartz tube (light path: 10 mm). Further, the spectral transmittance of tetrahydrofuran used for dissolution was 100% at a wavelength of 610 nm.

1. Manufacturing and physical properties of co-condensates and resin compositions

<Example 1>

In a four-necked flask equipped with a reflux condenser and a thermometer, 180.0 g (2.22 mol) of formaldehyde water having a purity of 37% and 180.0 g (1.20 mol) of p-tert-butylphenol were sequentially added. Then, the temperature was raised to an internal temperature of 40 ° C, and 80.0 g (0.48 mol) of a 24% aqueous sodium hydroxide solution was added thereto, and the mixture was stirred until the heat generation was terminated. After the termination of the heat generation was confirmed, the temperature was raised to an internal temperature of 65 ° C and reacted at the same temperature for 1 hour. After the reaction, the reaction mixture was subjected to GPC analysis, and the molecular weight of the resol type condensate was a weight average molecular weight (Mw) = 370, and a number average molecular weight (Mn) = 317 (hereinafter, the weight average molecular weight is Mw for short, and the number average molecular weight is Mn). ).

Thereafter, the temperature was raised again to an internal temperature of 82 ° C and reacted at the same temperature for 9 hours. The molecular weight of the resol type condensate after the reaction was Mw = 1514 and Mn = 943.

After the completion of the reaction, 135.0 g of methyl isobutyl ketone (hereinafter also referred to as MIBK), 72.0 g (0.220 mol) of 30% sulfuric acid, and 3.02 g (0.024 mol) of oxalic acid dihydrate were added thereto, and the mixture was stirred for 0.1 hour, and then allowed to stand. The lower layer of water is removed. The novolac type condensate in the four-part separable flask was 374 g (60% pure).

Thereafter, 79.2 g (0.72 mol) of meta- benzenediol was added, and the temperature was raised to an internal temperature of 90 ° C, and after a slight pressure reduction (internal pressure of 92 kPa), the mixture was refluxed at an internal temperature of 90 to 119 ° C for 2 hours while the reaction was carried out. Next, the pressure was recovered with nitrogen, and the reaction was carried out while refluxing at 125 to 135 ° C for 2 hours under normal pressure.

After the reaction, after MIBK was distilled off at a normal pressure and an internal temperature of 142 to 145 ° C, the internal temperature was maintained at 140 to 150 ° C and the pressure was reduced to 16 kPa, and MIBK was distilled off to obtain 268 g of a yellow novolak-type cocondensate. The physical properties and the like of the obtained novolak-type cocondensate are shown in Table 3 below.

<Example 2>

In a four-necked flask equipped with a reflux condenser and a thermometer, 144.9 g (4.44 mol) of polyoxymethylene having a purity of 92%, 360.0 g (2.40 mol) of p-tert-butylphenol, and 252.0 g of toluene were sequentially added. Then, the temperature was raised to an internal temperature of 40 ° C, and 160.0 g (0.96 mol) of a 24% aqueous sodium hydroxide solution was added thereto, and the mixture was stirred until the heat generation was terminated. After the termination of the heat generation was confirmed, the temperature was raised to an internal temperature of 66 ° C and reacted at the same temperature for 1 hour. After the reaction, the reaction mixture was subjected to GPC analysis, and the molecular weight of the resol type condensate was Mw = 273 and Mn = 258. Next, the temperature was raised to an internal temperature of 88 ° C and reacted at the same temperature for 4 hours. The molecular weight of the resol type condensate after the reaction was Mw = 1587 and Mn = 998.

After the completion of the reaction, 142.0 g (0.435 mol) of 30% sulfuric acid and 6.04 g (0.048 mol) of oxalic acid dihydrate were further added and stirred for 0.2 hours, and then allowed to stand, and the lower aqueous layer was removed. The novolac type condensate in the four-part separable flask was 661 g (pure 61%).

Thereafter, 171.5 g (1.56 mol) of m-catechol was added, and the temperature was raised to an internal temperature of 95 ° C, and after a slight decompression (internal pressure of 92 kPa), the mixture was refluxed at an internal temperature of 95 to 122 ° C for 2 hours while the reaction was carried out. Next, the pressure was recovered with nitrogen, and the reaction was carried out while refluxing at 125 to 135 ° C for 2.5 hours under normal pressure.

After the reaction, the toluene was distilled off at a normal pressure and an internal temperature of 141 to 142 ° C, and then kept at an internal temperature of 140 to 150 ° C and reduced to 16 kPa, and toluene was distilled off to obtain 590 g of a yellow novolak-type cocondensate. The physical properties and the like of the obtained novolak-type cocondensate are shown in Table 3 below.

<Example 3>

In a four-necked flask equipped with a reflux condenser and a thermometer, 120.0 g of the cocondensate obtained in Example 2, stearic acid as a softening agent (manufactured by Nippon Oil Co., Ltd.) was prepared. (solid at normal temperature)) After 30.0 g, the mixture was stirred at an internal temperature of 140 to 150 ° C for 1 hour to uniformly mix the cocondensate with stearic acid. Then, the mixture was taken out and placed in a bath to be cooled, whereby 149.1 g of a resin composition containing a cocondensate and stearic acid was obtained. The physical properties and the like of the obtained resin composition are shown in Table 5 below.

Except that the manufacturing conditions are changed as shown in Tables 1 and 2, Examples 4 to 6, 8, 11 and 12 are the same as in Embodiment 1, and Embodiments 7 and 10 are operated in the same manner as in Embodiment 3, that is, A novolac type cocondensate can be obtained. The physical properties and the like of the obtained novolak-type cocondensate are shown in Table 3.

<Example 9>

120.0 g of the cocondensate obtained in Example 8 and 30.0 g of stearic acid were mixed in the same manner as in Example 3 to obtain 148.8 g of a resin composition containing a cocondensate and stearic acid. The physical properties and the like of the obtained resin composition are shown in Table 5.

<Example 13>

120.0 g of the cocondensate obtained in Example 12 and 30.0 g of stearic acid were mixed in the same manner as in Example 3 to obtain 147.0 g of a resin composition containing a cocondensate and stearic acid. The physical properties and the like of the obtained resin composition are shown in Table 5 below.

<Example 14>

120.0 g of the cocondensate obtained in Example 4 and 30.0 g of industrial cashew nut shell liquid (CNSL manufactured by TAN HOA HOP PHAT Co., Itd.) (oil at normal temperature) were mixed in the same manner as in Example 3. A resin composition containing a cocondensate and CNSL was obtained in an amount of 149.5 g. The physical properties and the like of the obtained resin composition are shown in Table 5.

<Example 15>

120.0 g of the cocondensate obtained in Example 8 and 30.0 g of CNSL were mixed in the same manner as in Example 3 to obtain 146.6 g of a resin composition containing a cocondensate and CNSL. The physical properties and the like of the obtained resin composition are shown in Table 5.

<Example 16>

In a four-necked flask equipped with a reflux condenser and a thermometer, 117.4 g (3.60 mol) of polyoxymethylene 92%, 352.5 g (2.35 mol) of p-tert-butylphenol, p-phenylphenol were sequentially added. 8.5 g (0.05 mol) and toluene 350.0 g. Then, the temperature was raised to an internal temperature of 40 ° C, and 46.0 g (0.55 mol) of a 48% aqueous sodium hydroxide solution was added thereto, followed by stirring until the heat generation was terminated. After the termination of the heat generation was confirmed, the temperature was raised to an internal temperature of 64 ° C and reacted at the same temperature for 1 hour. After the reaction, the reaction mixture was subjected to GPC analysis, and the molecular weight of the resol type condensate was Mw = 226 and Mn = 203. Next, the temperature was raised to an internal temperature of 88 ° C and reacted at the same temperature for 6 hours. The molecular weight of the resol type condensate after the reaction was Mw=1144 and Mn=739.

After the completion of the reaction, 81.2 g (0.248 mol) of 30% sulfuric acid and 3.47 g (0.028 mol) of oxalic acid dihydrate were added and stirred for 0.2 hours, and then allowed to stand, and the lower aqueous layer was removed. The novolac type condensate in the four-part separable flask was 778 g (purity 55%).

Then, 211.2 g (1.92 mol) of m-catechol was further added, and the temperature was raised to an internal temperature of 101 ° C, and the reaction was carried out while refluxing at normal pressure and internal temperature of 101 to 120 ° C for 1.5 hours. Next, the pressure was recovered with nitrogen, and the reaction was carried out while refluxing at normal pressure at 121 to 128 ° C for 1 hour.

After the reaction, the toluene was distilled off at a normal pressure and an internal temperature of 142 to 144 ° C, and the pressure was reduced to 16 kPa while maintaining the internal temperature at 140 to 150 ° C, and then toluene was distilled off to obtain a yellow novolak-type cocondensate 611 g. . The physical properties and the like of the obtained novolak-type cocondensate are shown in Table 3.

<Example 17>

According to the same procedure as in Example 3, 400.0 g of the cocondensate obtained in Example 16 and 101.0 g of stearic acid were mixed, whereby 500.2 g of a resin composition containing a cocondensed product and stearic acid was obtained. The physical properties and the like of the obtained resin composition are shown in Table 5.

<Example 18>

The same operation as in Example 16 was carried out except that the conditions shown in Table 2 and the addition of the resorcin were simultaneously added with 148.8 g of stearic acid (manufactured by Nippon Oil Co., Ltd.). A uniform resin composition of 713 g containing a novolac type cocondensate was obtained. The physical properties and the like of the obtained resin composition are shown in Table 5.

<Example 19>

The same operation as in Example 16 was carried out except that the production conditions shown in Table 2 and the addition of the resorcin were simultaneously added with 158.7 g of stearic acid (manufactured by Nippon Oil Co., Ltd.). A uniform resin composition of 789 g containing a novolac type cocondensate was obtained. The physical properties and the like of the obtained resin composition are shown in Table 5.

<Example 20>

The production conditions were as shown in Table 2, and when the resol-type condensate was synthesized, the temperature was raised to an internal temperature of 86 ° C, and dehydrated by Dinstach's tube, and water (46.6 g) was distilled off from the reaction system, and Examples The same operation can be carried out to obtain a novolac type cocondensate. The physical properties and the like of the obtained novolak-type cocondensate are shown in Table 3.

<Reference Example 1: Japanese Laid-Open Patent Publication No. 2015-52097. Example 4 Additional Test>

In a four-necked flask equipped with a reflux condenser and a thermometer, 90.0 g (1.11 mol) of formaldehyde water having a purity of 37%, 15.0 g (0.10 mol) of p-tert-butylphenol, and o-phenylphenol were sequentially added. 85.0 g (0.50 mol). Then, the temperature was raised to an internal temperature of 45 ° C, and 20.0 g (0.12 mol) of a 24% aqueous sodium hydroxide solution was added thereto, and the mixture was stirred until the heat generation was terminated. After the termination of the heat was determined, the temperature was raised to an internal temperature of 65 ° C and incubated at the same temperature for 1.5 hours. Thereafter, the temperature was raised again to an internal temperature of 75 ° C, and the temperature was maintained for 3 hours to terminate the reaction. The molecular weight of the resol type condensate after the reaction was Mw = 570 and Mn = 400.

After the end of the reaction, it was cooled to an internal temperature of 65 ° C or lower, and diluted with 77.0 g of MIBK. Thereafter, the reaction solution was neutralized, stirred for 10 minutes, and then allowed to stand to remove the aqueous layer. The novolac type condensate in the four-part separable flask was 217 g (64% pure).

Then, 69.3 g (0.63 mol) of m-catechol was further added, and the temperature was raised to an internal temperature of 100 ° C, and the pressure was reduced (internal pressure: 65 kPa), and then the mixture was refluxed at an internal temperature of 100 to 120 ° C for 4 hours while the reaction was carried out. Thereafter, the pressure was again restored with nitrogen, and the reaction was carried out while refluxing at normal pressure at 125 ° C for 8 hours.

After the reaction, after concentration under reduced pressure (internal pressure: 10 kPa) and internal temperature of 140 to 150 ° C for 2 hours, 183 g of an orange novolak-type cocondensate was obtained. The physical properties and the like of the obtained novolak-type cocondensate are shown in Table 4 below.

<Reference Example 2: JP-A-2014-152220 Example 2 Additional test>

In a four-necked flask equipped with a reflux condenser and a thermometer, 43.5 g (1.33 mol) of polyoxymethylene having a purity of 92%, 150.0 g (1.00 mol) of p-tert-butylphenol, and 75.0 g of toluene were sequentially added. Then, the temperature was raised to an internal temperature of 45 ° C, and 4.16 g (0.05 mol) of a 48% aqueous sodium hydroxide solution was added, and the mixture was stirred until the heat was terminated. After the termination of the heat generation was confirmed, the temperature was raised to an internal temperature of 65 ° C and kept at the same temperature for 2 hours. Thereafter, the temperature was raised again to an internal temperature of 80 ° C and held for 1.5 hours. After the foregoing reaction, the reaction mixture was subjected to GPC analysis, and the molecular weight of the resol type condensate was Mw = 297 and Mn = 241.

After the completion of the reaction, the mixture was cooled to an internal temperature of 75 ° C or lower, and 110.0 g (1.00 mol) of resorcin was added without neutralizing. The azeotropic dehydration was carried out by raising the temperature to an internal temperature of 108 to 112 ° C over 3 hours. Next, the temperature was raised to an internal temperature of 140 to 150 ° C under normal pressure, and toluene was distilled off for 2 hours. Then, the pressure was reduced to 21 kPa under the internal temperature of 140 to 150 ° C, and the toluene was distilled off by keeping the temperature for 2 hours. Through the above operation, 280 g of a non-uniform orange novolac type cocondensate was obtained.

The physical properties of the obtained novolak-type cocondensate (sampled as uniformly as possible) are shown in Table 4 below.

<Reference Example 3: JP-A-2007-9047 Comparative Example 3 Additional Test>

In a four-necked flask equipped with a reflux condenser and a thermometer, 52.2 g (1.60 mol) of polyoxymethylene having a purity of 92%, 150.0 g (1.00 mol) of p-tert-butylphenol, and 200.0 g of toluene were sequentially added. Then, the temperature was raised to an internal temperature of 45 ° C, and 6.66 g (0.05 mol) of a 30% aqueous sodium hydroxide solution was added, followed by stirring until the end of heat generation. After the termination of the heat generation was confirmed, the temperature was raised to an internal temperature of 70 ° C, and the temperature was kept at the same temperature for 1 hour. After the foregoing reaction, the reaction mixture was subjected to GPC analysis, and the molecular weight of the resol type condensate was Mw = 215 and Mn = 192.

After the completion of the reaction, the mixture was cooled to an internal temperature of 40 ° C, and 9.40 g (0.037 mol) of oxalic acid dihydrate and 132.2 g (1.20 mol) of m-benzenediol were added. Thereafter, the temperature was raised to an internal temperature of 108 to 112 ° C to carry out azeotropic dehydration. Further, the refluxing dehydration was continued at an internal temperature of 110 to 118 ° C, and the viscosity of the reactants began to rise. After 0.5 hours, the reactants swelled and separated into a colorless and transparent solution portion and a yellow swelled resin portion. After reacting for 2 hours in this manner, the temperature was further raised to an internal temperature of 140 ° C under the distillation of toluene, but the form of the separated reactant remained unchanged. Further, since the reactants are separated, only the stirring shaft is rotatable, so that it is not uniformly stirred.

Thereafter, toluene was distilled off by heating for 2 hours while the reactants were not uniformly stirred. Then, while maintaining the internal temperature at 140 to 150 ° C under reduced pressure to 12 kPa, the reactants are foamed and partially cured.

Through the above operation, 314 g of a non-uniform orange novolac type cocondensate was obtained. The physical properties of the obtained novolak-type cocondensate (sampled as uniformly as possible) are shown in Table 4 below.

<Comparative Example 1>

In a four-necked flask equipped with a reflux condenser and a thermometer, 180.0 g (2.22 mol) of formaldehyde water having a purity of 37% and 180.0 g (1.20 mol) of p-tert-butylphenol were sequentially added. Then, the temperature was raised to an internal temperature of 40 ° C, and 30.0 g (0.18 mol) of a 24% aqueous sodium hydroxide solution was added, and the mixture was stirred until the heat was terminated. After the termination of the heat generation was confirmed, the temperature was raised to an internal temperature of 65 ° C, and reacted at the same temperature for 1 hour, and further reacted at an internal temperature of 82 ° C for 3 hours. After the reaction, the reaction mixture was subjected to GPC analysis, and the molecular weight of the resol type condensate was Mw = 708 and Mn = 450.

After the completion of the reaction, 135.0 g of MIBK, 30% sulfuric acid 27.0 g (0.083 mol), and oxalic acid dihydrate 1.13 g (0.009 mol) were further added and stirred for 0.1 hour, and then allowed to stand, and the lower aqueous layer was removed. The novolac type condensate in the four-part separable flask was 380 g (67% pure).

Next, 158.4 g (1.44 mol) of m-catechol was further added, and the temperature was raised to an internal temperature of 96 ° C, and after a slight pressure reduction (92 kPa), the mixture was refluxed at 110 ° C to 115 ° C for 2 hours while the reaction was carried out. Thereafter, the mixture was refluxed and dehydrated at an internal temperature of 115 ° C, and the viscosity of the reactant began to rise. After 0.5 hours, the reactant was swollen, and the colorless and transparent solution portion and the yellow swollen resin portion were separated. Thereafter, 135.0 g of MIBK was added to try to dissolve the resin portion, but it was not dissolved.

Secondly, the pressure was again restored by nitrogen, and the temperature was sequentially raised to an internal temperature of 137 ° C, but the form of the separated reactant remained unchanged. At the same time, since the reactants are separated, only the stirring shaft is rotatable, so that it is not uniformly stirred.

Thereafter, after the reactants are not uniformly stirred, MIBK is distilled off under normal pressure and internal temperature of 140 to 142 ° C, and then MIBK is further distilled off by maintaining the internal pressure at 140 to 150 ° C under reduced pressure to 16 kPa. 366 g of a heterogeneous yellow novolac type cocondensate was obtained. The physical properties of the obtained novolak-type cocondensate (sampled as uniformly as possible) are shown in Table 4 below.

<Comparative Example 2>

In a four-necked flask equipped with a reflux condenser and a thermometer, 120.0 g of the cocondensate obtained in Comparative Example 1 and stearic acid as a softening agent (manufactured by Nippon Oil Co., Ltd.) were sequentially added. (solid at room temperature)) 30.0 g. Thereafter, the temperature was raised to an internal temperature of 145 ° C, and the mixture was stirred at an internal temperature of 140 to 150 ° C for 1 hour, but was still partially separated. Under the partially separated state, the contents were taken out and placed in a tank to be cooled, whereby 147.9 g of a solid (resin composition) in which the cocondensate and the stearic acid were not uniformly mixed were obtained. The physical properties and the like of the obtained resin composition which are not uniform are shown in Table 5 below.

<Comparative Example 3>

In a four-necked flask equipped with a reflux condenser and a thermometer, 180.0 g (2.22 mol) of formaldehyde water having a purity of 37% and 180.0 g (1.20 mol) of p-tert-butylphenol were sequentially added. Then, the temperature was raised to an internal temperature of 40 ° C, and 160.0 g (0.96 mol) of a 24% aqueous sodium hydroxide solution was added thereto, followed by stirring until the heat generation was terminated. After the termination of the heat generation, the temperature was raised to an internal temperature of 55 ° C, and the reaction was carried out by holding at the same temperature for 1 hour. The reaction mixture was analyzed by GPC, and the molecular weight of the resol type condensate was Mw = 254 and Mn = 237. Next, the temperature was raised to an internal temperature of 65 ° C and reacted at the same temperature for 1.5 hours. The molecular weight of the resol type condensate after the reaction was Mw = 284 and Mn = 273.

After the completion of the reaction, 135.0 g of toluene, 142.0 g (0.435 mol) of 30% sulfuric acid, and 6.05 g (0.048 mol) of oxalic acid dihydrate were added thereto, and the mixture was stirred for 0.1 hour, and then allowed to stand, and the lower aqueous layer was removed. The novolac type condensate in the four-part separable flask was 421 g (26% pure).

Thereafter, 224.4 g (2.04 mol) of resorcin was added, and the temperature was raised to an internal temperature of 100 ° C, and after a slight decompression (92 kPa), the reaction was carried out by refluxing at an internal temperature of 100 ° C to 117 ° C for 1 hour. Thereafter, the refluxing of the reactants was continued at an internal temperature of 115 ° C, and the viscosity of the reactants began to rise. After 0.5 hours, the reactants were swollen, and the colorless and transparent solution portion and the yellow swollen resin portion were separated. Then, 135.0 g of toluene was further added to try to dissolve the resin portion, but it was not dissolved.

Secondly, the pressure was again restored with nitrogen, and the temperature was raised to an internal temperature of 137 ° C, but the morphology of the separated reactants remained unchanged. Further, since the reactants are separated, only the periphery of the stirring shaft can be rotated, so that it is not possible to uniformly stir.

Thereafter, after the reactants are not uniformly stirred, the toluene is distilled off under normal pressure and internal temperature of 140 to 142 ° C, and then toluene is further distilled off by maintaining the internal temperature at 140 to 150 ° C under reduced pressure to 16 kPa. Thus, a heterogeneous yellow novolac type cocondensate of 448 g was obtained. The physical properties of the obtained novolak-type cocondensate (sampled as uniformly as possible) are shown in Table 4 below.

<Comparative Example 4>

In a four-necked flask equipped with a reflux condenser and a thermometer, 180.0 g (2.22 mol) of formaldehyde water having a purity of 37%, 144.0 g (0.96 mol) of p-tert-butylphenol, and o-tributyl were sequentially added. 36.0 g (0.24 mol) of phenol. Then, the temperature was raised to an internal temperature of 40 ° C, and 80.0 g (0.48 mol) of a 24% aqueous sodium hydroxide solution was added, followed by stirring until the heat generation was terminated. After the termination of the heat generation was determined, the temperature was raised to an internal temperature of 55 ° C and reacted at the same temperature for 6 hours. The reaction mixture was analyzed by GPC, and the molecular weight of the resol type condensate was Mw = 310 and Mn = 286.

After the completion of the reaction, 135.0 g of MIBK, 30% sulfuric acid 72.0 g (0.220 mol), and oxalic acid dihydrate 3.02 g (0.024 mol) were further added and stirred for 0.1 hour, and then allowed to stand, and the lower aqueous layer was removed. The novolac type condensate in the four-part separable flask was 383 g (pure 65%).

Next, 198.0 g (1.80 mol) of resorcin was added, and the temperature was raised to an internal temperature of 100 ° C, and after a slight decompression (92 kPa), the reaction was carried out by refluxing at 100 ° C to 115 ° C for 1.5 hours. Thereafter, the mixture was refluxed and dehydrated at an internal temperature of 115 to 120 ° C, and the viscosity of the reactant began to rise. After 0.5 hours, the reactant was swollen, and the colorless and transparent solution portion and the yellow swollen resin portion were separated.

Secondly, the pressure was gradually restored by nitrogen gas, and the temperature was sequentially raised to an internal temperature of 141 ° C, but the morphology of the separated reactant did not change. At the same time, since the reactants are separated, only the stirring shaft is rotatable, so that it is not uniformly stirred.

Thereafter, after the reactants are not uniformly stirred, MIBK is distilled off under normal pressure and internal temperature of 142 to 144 ° C, and then MIBK is further distilled off by maintaining the internal pressure at 140 to 150 ° C under reduced pressure to 16 kPa. A heterogeneous yellow novolac type cocondensate 406g was obtained. The physical properties of the obtained novolak-type cocondensate (sampled as uniformly as possible) are shown in Table 4 below.

<Comparative Example 5>

In a four-necked flask equipped with a reflux condenser and a thermometer, 180.0 g (2.22 mol) of formaldehyde water having a purity of 37%, 121.5 g (0.81 mol) of p-tert-butylphenol, and o-phenylphenol were sequentially added. 66.3 g (0.39 mol). Then, the temperature was raised to an internal temperature of 40 ° C, and 60.0 g (0.36 mol) of a 24% aqueous sodium hydroxide solution was added, followed by stirring until the heat generation was terminated. After the termination of the heat generation was determined, the temperature was raised to an internal temperature of 65 ° C and reacted at the same temperature for 3 hours. The molecular weight of the reaction mixture was Mw = 445 and Mn = 371. After the completion of the reaction, 135.0 g of toluene, 53.0 g (0.16 mol) of 30% sulfuric acid, and 2.40 g (0.019 mol) of oxalic acid dihydrate were added thereto, and the mixture was stirred for 0.1 hour, and then allowed to stand, and the lower aqueous layer was removed. The novolac type condensate in the four-part separable flask was 383 g (26% pure).

Next, 171.6 g (1.56 mol) of m-catechol was added, and the temperature was raised to an internal temperature of 106 ° C, and after a slight pressure reduction (92 kPa), the mixture was refluxed at 106 ° C to 119 ° C for 2 hours while the reaction was carried out. Thereafter, when the internal temperature was 115 °C to 120 °C, the viscosity of the reactants began to rise. After 0.5 hours, the reactants were swollen, and the colorless and transparent solution portion and the yellow swollen resin portion were separated.

Secondly, the pressure was again restored by nitrogen, and the temperature was raised to an internal temperature of 132 ° C in the same order, but the form of the separated reactant remained unchanged. At the same time, since the reactants are separated, only the stirring shaft is rotatable, so that it is not uniformly stirred.

Thereafter, after the reactants are not uniformly stirred, the toluene is distilled off under normal pressure and an internal temperature of 132 to 144 ° C, and then the toluene is further distilled off by maintaining the internal pressure at 140 to 150 ° C under reduced pressure to 16 kPa. A non-uniform yellow novolac type cocondensate 330 g was obtained. The physical properties of the obtained novolak-type cocondensate (sampled as uniformly as possible) are shown in Table 4 below.

<Comparative Example 6>

In a four-necked flask equipped with a reflux condenser and a thermometer, 180.0 g (2.22 mol) of formaldehyde water having a purity of 37% and 176.4 g (1.18 mol) of p-tert-butylphenol were sequentially added. O-phenylphenol 4.3 g (0.03 mol). Then, the temperature was raised to an internal temperature of 40 ° C, and 80.0 g (0.48 mol) of a 24% aqueous sodium hydroxide solution was added, followed by stirring until the heat generation was terminated. After the termination of the heat generation was confirmed, the temperature was raised to an internal temperature of 65 ° C and stirred at the same temperature for 1 hour. The reaction mixture was analyzed by GPC, and the molecular weight of the resol type condensate was Mw = 251 and Mn = 233. Next, the temperature was raised to an internal temperature of 82 ° C and reacted at the same temperature for 2 hours. The molecular weight of the resol type condensate after the reaction was Mw = 409 and Mn = 355.

After the completion of the reaction, 135.0 g of toluene and 30% sulfuric acid (72.0 g (0.220 mol)) were added. Oxalic acid dihydrate 3.02 g (0.024 mol) was stirred for 0.1 hour, and then allowed to stand, and the lower aqueous layer was removed. The soluble phenol aldehyde condensate in the four-part separable flask was 399 g (26% pure). Next, the reaction mixture after the above mixing operation was again heated and kept at an internal temperature of 82 ° C for 4 hours. The molecular weight of the resol type condensate after the heat retention was Mw=1085 and Mn=649.

Next, 92.4 g (0.84 mol) of resorcin was added, and the temperature was raised to an internal temperature of 106 ° C, and after a slight pressure reduction (92 kPa), the mixture was refluxed at 106 to 113 ° C for 2 hours while the reaction was carried out. Thereafter, the reflux of the reactants was continued at 115 ° C, and the viscosity of the reactants began to rise. After 0.5 hours, the reactants were swollen, and the colorless and transparent solution portion and the yellow swollen resin portion were separated.

Next, the pressure was restored by nitrogen gas, and the temperature was sequentially raised to an internal temperature of 132 °C. However, the morphology of the separated reactants remains unchanged. At the same time, since the reactants are separated, only the stirring shaft is rotatable, so that it is not uniformly stirred.

Thereafter, after the reactants are not uniformly stirred, the toluene is distilled off under normal pressure and an internal temperature of 140 to 142 ° C, and then the toluene is further distilled off by maintaining the internal pressure at 140 to 150 ° C under reduced pressure to 16 kPa. A heterogeneous yellow novolac type cocondensate 343 g was obtained. The physical properties of the obtained novolak-type cocondensate (sampled as uniformly as possible) are shown in Table 4 below.

<Comparative Example 7>

In a four-necked flask equipped with a reflux condenser and a thermometer, 120.0 g of the cocondensate obtained in Reference Example 1 and stearic acid as a softening agent (manufactured by Nippon Oil Co., Ltd. in the form of beryllium stearate) were sequentially added. (solid at room temperature)) 30.0 g. Then, the temperature was raised to an internal temperature of 145 ° C, and the mixture was stirred at an internal temperature of 140 to 150 ° C for 1 hour, and a part thereof was separated. The contents were taken out in a partially separated state and cooled in a tank to obtain 149.3 g of a solid (resin composition) in which the cocondensate and the stearic acid were not uniformly mixed. The physical properties and the like of the obtained heterogeneous resin composition are shown in Table 5 below.

Tables 1 and 2 below show the detailed conditions of the above respective examples, Tables 3 and 4 show the physical properties of the cocondensate obtained in each of the examples and the like, and Table 5 shows the physical properties of the resin composition obtained in the examples and the like.

In addition, the content of each component in each of the following tables is a value based on weight (% by weight) excluding each oligomer component, and the oligomer component is an area percentage value. The constituent unit derived from PTBP is a constituent unit (mol%) derived from p-tert-butylphenol with respect to a constituent unit of total phenols (other than resorcin), and a constituent unit derived from resorcin is relatively A constituent unit (mol%) derived from resorcin in a constituent unit of total phenols (other than meta- benzenediol).

Further, the abbreviations in the following tables are as follows.

RES: m-catechol

PTBP: p-tert-butyl phenol

OPP: o-phenylphenol

OTBP: o-tertiary butyl phenol

PPP: p-phenylphenol

MIBK: methyl isobutyl ketone

Oligomer 1: content of a component having a peak top molecular weight of 700 to 520 in a colloidal filtration chromatography (GPC) method

Oligomer 2: content of a component having a peak molecular weight of 430 to 320 in a colloidal filtration chromatography (GPC) method

Peak: The peak value (molecular weight) of the peak of the oligomer component contained in each co-condensate was measured.

The evaluation criteria of the physical properties of the reactants in Tables 1 and 2 below are as follows.

 Physical form of the reactant  

‧The reactants in step (3) can be stirred without swelling, separation, etc.: good

‧The reaction in the step (3) is swollen, separated, etc., stirring is difficult / not: bad

The evaluation criteria of the mutual solubility of the cocondensate and the softener in the following Table 5 ("resin mutual solubility" in Table 5) are as follows. The mutual solubility of the cocondensate and the softener is good, and a uniform resin composition which is solid at room temperature (25 ° C) can be obtained. The resin composition was free from turbidity and white mist: the mutual solubility of the good cocondensate and the softener was poor, and a uniform resin composition which was solid at room temperature (25 ° C) could not be obtained. The resin composition is opaque, turbid and white mist are scattered: bad

2. Evaluation of hygroscopicity/blocking property and odor of co-condensate and resin composition

(1) Assessment of hygroscopicity/causedness

The condensate produced in Example 16, the reference example 1 and the reference example 2, and the resin composition manufactured in the Example 3 and the Example 19, and the SUMIKANOL 620 which is a commercial resin adhesive agent (Takaoka Chemical Industry Co., Ltd.) The company manufactures, hereinafter sometimes referred to as SKL 620), which is placed on a PE cover (disc), and is placed in a constant temperature and humidity chamber at 40 ° C and 90% RH in a state where the covers are arranged on an aluminum pan. After the time shown in the following Table 6, the weight increase rate and the appearance of each sample were evaluated based on the following criteria. The results are shown in Table 6 below.

○: The co-condensate or the resin composition particles are not adhered to each other, and the initial appearance can be maintained.

△: The co-condensate or the resin composition particles adhere to each other, partially occur, and partially exist as agglomerates.

X: The co-condensate or the resin composition particles all adhere to each other and become a whole.

××: The co-condensate or the resin composition particles all adhere to each other, and melt and the boundary disappears.

As shown in the above Table 6, it is understood that the commercially available SKL 620 and the co-condensate obtained in Reference Example 1 and Reference Example 2 which are produced by a generally known method are hygroscopic and have low blocking resistance. The cocondensate and the resin composition produced by the method of the present invention are not only low in hygroscopicity but also excellent in blocking resistance.

(2) Estimation of odor

The co-condensate produced in Examples 6 and 16 and the resin composition produced in Examples 3 and 19 and SKL 620 were pulverized and placed in a 15 g polystyrene bottle as a test sample. The obtained test sample was subjected to odor detection by six assessors to cover the internal state, and the odor was evaluated. Further, the odor was measured on the basis of the following criteria. The results of the assessment are shown in Table 7 below. Further, the presence or absence of brown coloration of the cocondensate or the resin composition and the spectral transmittance at a wavelength of 610 nm are also shown in Table 7 below.

Odor intensity: 0 (no odor) to 5 (strong odor)

Hedonic sacle: +4 (fast) to -4 (unpleasant)

Improvement: The improvement rate of the average based on SKL 620

As shown in the above Table 7, it is understood that the cocondensate and the resin composition of the present invention can improve the odor as compared with the commercially available SKL 620. In particular, it has been found that the odor of the co-condensate and the resin composition having a spectral transmittance (wavelength: 610 nm) of 80% or more can be greatly improved.

3. Production example and physical property evaluation of the rubber composition using the cocondensate and the resin composition obtained in the above examples

(1) Manufacture of an unvulcanized rubber composition containing the cocondensate and resin composition obtained in the above examples

The co-condensate produced in Example 6 and Example 11 as a resin adhesive, and the resin compositions produced in Example 3, Example 9, Example 14, Example 15, and Example 19 were not The vulcanized rubber composition was produced by the following method. Further, an unvulcanized rubber composition containing SKL 620 and the cocondensate obtained in Reference Example 1 and an unvulcanized rubber composition containing no resin adhesive were produced by the following method.

<Method for Producing Unvulcanized Rubber Composition>

According to the formulation shown in the following Table 8, first, insoluble sulfur, a vulcanization accelerator, a component other than the methylene supply agent, and a resin adhesive are added to a pressurizing kneader manufactured by Toshin Co., Ltd., and mixed. Discharge at 160 °C. Next, the obtained mixture was mixed with an insoluble sulfur, a vulcanization accelerator, and a methylene supply agent in a 6-inch Open Roll manufactured by Kansai Roll Co., Ltd., which was kept at 60 ° C, to produce an unvulcanized rubber composition.

Further, the numerical values in the following Table 8 represent parts by weight. Further, each component in the following Table 8 is as follows in detail.

‧ Natural rubber: SMR-CV60

‧Carbon Black: "SEAST 300" manufactured by Tokai Carbon Co., Ltd. (HAF-LS grade)

‧ Zinc Oxide: Zhengtong Chemical Industry Co., Ltd.

‧Anti-aging agent: "Antioxidant FR" manufactured by Matsubara Industrial Co., Ltd.

‧Cobalt salt: Cobalt stearate (pharmaceutical)

‧Insoluble sulfur: "Crystex HS OT-20" manufactured by Flexsys

‧Vulcanization accelerator: N,N-dicyclohexyl-2-benzothiazolylsulfenamide (agent)

‧ Methylene supply agent: "Sumikanol 507AP" manufactured by Bara Chemical Co., Ltd.

(2) Test of physical properties of unvulcanized rubber composition and test of physical properties of vulcanized rubber composition

Using the unvulcanized rubber composition obtained as described above, the Mooney viscosity test (measured in accordance with JIS K 6300-1:2001, measured at 130 ° C) and the rheometer test (measured at 160 ° C according to JIS K 6300-2:2001) .

Further, the unvulcanized sample was allowed to stand at room temperature for 24 hours after the production, and then vulcanized under the conditions of 160 ° C, 6 MPa pressure, and t90 + 5 minutes to prepare a vulcanized rubber sheet having a thickness of 2 mm. Then, a rubber test piece made of the vulcanized rubber sheet was used, and a tensile test (measured in accordance with JIS K 6251:2010, measured at 25 ° C), hardness measurement (measured in accordance with JIS K 6253:2006, measured at 25 ° C), and adhesion were carried out. Determination of elasticity. The viscoelasticity was measured under the following conditions.

Viscoelastic device: SII Nano Technology Co., Ltd. manufactures DMS 6100

Conditions: Temperature 40 ° C to 80 ° C (heating rate: 2 ° C / min) dynamic strain 0.2%, frequency 10Hz

Test piece: long side 50mm × short side 5mm × thickness 2mm

As a result of the rubber property test, the physical property values (relative values) of the respective rubber properties of the rubber composition to which the resin adhesive was not added (Comparative Example 8) were as shown in Table 9.

As shown in the above Table 9, it was confirmed that the rubber composition prepared by the cocondensate and the resin composition of the present invention is improved in physical properties as compared with the rubber composition (Comparative Example 8) to which no resin adhesive is added. It is understood that the performance is equal to or higher than that of the generally known resin binder "SUMIKANOL 620" and the rubber composition of the cocondensate obtained in Reference Example 1.

(3) Initial adhesion and wet heat adhesion of vulcanized rubber composition

A sample of the rubber-steel curtain composite was produced using each of the unvulcanized rubber compositions obtained as described above. Specifically, in the case of a copper-plated steel wire curtain (a diameter of about 0.8 mm, a structure of 3 × 0.20 + 6 × 0.35 mm, copper plating with copper / zinc = 64 / 36 (weight ratio)) at intervals of 1 / 10 mm Both sides of the five aligners were coated with an unvulcanized rubber sheet of about 2 mm thick composed of the above-described unvulcanized rubber compositions, and the unpeeled samples for the test were laminated in parallel with the curtain. Thereafter, the obtained unvulcanized sample was used, and the initial adhesion and the wet heat adhesion were evaluated in accordance with the following methods.

<Initial adhesion>

The above unvulcanized sample was prepared and allowed to stand at room temperature for 24 hours, then vulcanized at 160 ° C, 6 MPa pressure, and t90 + 5 minutes to obtain 1 cm × 1 cm × 6 cm of 5 1 cm steel curtains. Cuboid rubber sheet. Then, using the Autograph "AGC-X" manufactured by Shimadzu Corporation, the rubber sheet was subjected to the pull-off test of each steel curtain, that is, the stress at the time of pulling out in the vertical direction at 100 mm/min was the rubber resistance stress (kgf). ) Perform the measurement. Moreover, the rubber coverage of the steel curtain after the pull-off was visually observed and evaluated from 0 to 100%. The measurement and evaluation were carried out with N = 10 (branch), and the average value was obtained. The results are shown in Table 10 below.

<Wet heat adhesion (adhesion after damp heat aging)>

The above-mentioned unvulcanized sample was prepared, and a vulcanized rubber sheet was prepared as a test piece in the same order as in the initial adhesion evaluation. The test piece was allowed to stand in a vapor of 80 ° C × 95% RH for 7 days, 14 days, and 21 days later. Further, the pull-off test was carried out in the same manner as the above initial adhesion, and the rubber coating ratio of the steel curtain after the pull-off was visually observed and evaluated from 0 to 100%. The measurement and evaluation were carried out with N = 10 (branch), and the average value was obtained. The results are shown in Table 10 below. Further, the rate of change in the pull-out strength in the following Table 10 refers to the rate of change at the initial value (0 day, before wet heat aging) when the pull-off strength is 100 (the pull-off strength after wet heat aging/pre-wet heat aging) Pull strength × 100).

As shown in the above Table 10, it was found that the rubber composition prepared by the cocondensate and the resin composition of the present invention can greatly improve the rubber composition without the resin adhesive (Comparative Example 8) and the comparative rubber-steel cord. The adhesion of the rubber composition of the commonly known resin binder "SUMIKANOL 620" and the co-condensate obtained in Reference Example 1 was exhibited.

Claims (12)

A method for producing a novolak-type co-condensate, wherein the novolak-type co-condensate contains one or more kinds of phenols, formaldehyde, and meta-benzenediol represented by the following formula (i) unit, R represents a branched alkyl group having 1 to 12 carbon atoms or a phenyl group, and the constituent unit derived from the above phenols contains 65 mol% or more of constituent units derived from p-tert-butylphenol, and the above production method The following steps (1), (2), and (3) are sequentially included: (1) the phenol and formaldehyde are at 75 ° C or higher in the presence of a base of 0.05 mol or more relative to the phenolic 1 molar. a reaction to obtain a resol type condensate having a number average molecular weight of 600 or more by colloidal filtration chromatography; (2) a reaction liquid containing the resol type condensate obtained in the above step (1) and relative to The base used in the above step (1) is a step in which an acid of an equivalent or more is mixed; (3) the above-mentioned novolak-type condensate is made between 0.5 and 1.2 mols relative to the phenolic 1 molar. The step of the phenol reaction.  The method for producing a novolak-type cocondensate according to the first aspect of the invention, wherein the amount of the resorcin is from 0.5 to 0.8 mol per mol of the phenolic mole.    The method for producing a novolak-type cocondensate according to the first or second aspect of the invention, wherein the amount of the base used in the step (1) is 0.05 with respect to the phenol 1 molar. To 0.25 m.   A novolac type co-condensate which satisfies all of the following (a) to (e): (a) contains one or more kinds of phenols, formaldehyde and inter-forms represented by the following formula (i) a constituent unit of hydroquinone, R represents an alkyl group or a phenyl group which may have a branched carbon number of 1 to 12; (b) a constituent unit derived from the above phenols contains 65 mol% or more of a constituent unit derived from p-tert-butylphenol; c) the number average molecular weight of the colloidal filtration chromatography is 750 or more; (d) the softening point is 80 to 150 ° C; (e) the composition of the resorcinol relative to the constituent unit of the above phenols: 1 mole The unit is below 0.80 mol.  The novolac type cocondensate according to claim 4 of the patent application further satisfies the following (f), (f) in the colloidal filtration chromatography, the peak top molecular weight of 1 to 10% by area percentage is A composition of 700 to 520, and contains 0.01 to 2% of a component having a peak molecular weight of 430 to 320 in an area percentage.    The novolak-type cocondensate according to the fourth or fifth aspect of the invention, wherein a solution of a solution of a novolak-type cocondensate of 2.0 g in 20 mL of tetrahydrofuran at a wavelength of 610 nm is obtained. More than 80%.    A resin composition comprising a novolac type cocondensate according to any one of claims 4 to 6, and a softening agent.    The resin composition according to claim 7, wherein the softener is a fatty acid having 8 to 32 carbon atoms.    The resin composition according to claim 7, wherein the softening agent is a cashew nut shell liquid.    The resin composition according to any one of claims 7 to 9, wherein the content of the softener in the resin composition is 5 to 40% by weight.    The resin composition according to any one of claims 7 to 10, wherein a solution of 2.0 g of the resin composition in 20 mL of tetrahydrofuran has a light transmittance of 80% at a wavelength of 610 nm. the above.    A rubber composition comprising a novolac type cocondensate according to any one of claims 4 to 6, or as described in any one of claims 7 to 11. The resin composition, as well as the rubber component.