KR20120128541A - Rubber composition for tire and pneumatic tire - Google Patents

Abstract

PURPOSE: A rubber composition for pneumatic tire is provided to obtain good control stability, low fuel efficiency, elongation at fracture and control-responsibility with good valance while maintaining good extrusion processability. CONSTITUTION: A rubber composition for pneumatic tire comprises 0.5-20 parts by weight of an alkylphenol resin and 0.04-10 parts by weight of a methylene donor based on 100.0 parts by weight of a rubber component. The alkylphenol resin is a resin obtained from two or more compounds selected from a group consisting of 2-alkyl phenol, 3-alkylphenol and 4-alkylphenol, and formaldehyde. The total content of the 2-alkyl phenol, 3-alkylphenol and 4-alkylphenol of glass comprised in the alkyl phenol resin is 3 weight% or less. The 2-alkyl phenol, 3-alkylphenol and 4-alkylphenol are o-cresol, m-cresol and p-cresol respectively.

Description

Rubber composition and pneumatic tire for tires {RUBBER COMPOSITION FOR TIRE AND PNEUMATIC TIRE}

The present invention relates to a rubber composition for a tire and a pneumatic tire using the same.

The rubber composition used for a tire requires performance, such as high hardness (E *), low tan-delta of 30-70 degreeC, and excellent elongation at break.

In order to satisfy | fill high hardness, there are methods, such as mix | blending sulfur, a vulcanization accelerator, a resorcin resin, polyethylene resin, etc., and increasing the compounding quantity of fillers, such as carbon black and a silica. However, these methods are difficult to satisfy both high hardness (E *) and good elongation at break (EB).

In general, even at high hardness, when the elongation at break is less than 100%, it cannot be used as a rubber composition for tires that requires durability. For example, elongation at break as measured at room temperature (25 ° C.) is at least 100% in the rubber composition used for the bead apex, at least 200% in the rubber composition (the rubber composition for the breaker topping) used in the breaker, and the tread (cap tread). , Base tread) and rubber compositions used for sidewalls are required to be at least 350% or more.

By mix | blending a phenol resin, it is possible to satisfy both high hardness (E *) and elongation at break (EB) 100% or more. However, there is a problem that tan δ increases, and it is difficult to obtain a good balance between high hardness (E *), low tan δ (good low fuel efficiency) and good elongation at break. Therefore, the present situation is that the rubber composition which mix | blended phenol resin is not used very much for tire members other than bead apex and a breaker.

In patent documents 1 and 2, the rubber composition which mix | blended cresol resin as an alkylphenol resin is disclosed. However, cresol resin used in patent documents 1 and 2 is resin obtained by using only m-cresol which is 3-alkylphenol as an alkylphenol component (monomer component), and monomer components other than 3-alkylphenol (2-alkylphenol) , And the content of the monomer components of the glass (remaining) contained in the alkylphenol resin and the use of the resin obtained by using 4-alkylphenol) have not been examined in detail, and have high hardness while maintaining good extrusion processability. (Good steering stability), low tan δ (good low fuel consumption), elongation at break, and good steering response remain balanced.

Patent Document 1: Japanese Patent Laid-Open No. 2008-31427 Patent Document 2: Japanese Patent Laid-Open No. 2010-52724

SUMMARY OF THE INVENTION An object of the present invention is to provide a rubber composition for a tire and a pneumatic tire using the same, which can achieve a good balance of steering stability, low fuel consumption, elongation at break, and steering response while maintaining good extrusion processability by solving the above problems. .

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventor came to consider the following hypothesis.

When the alkylphenol resin contains carbon black and a softener during kneading of the rubber, the alkylphenol resin further interacts with the softener to form a composite sphere. Since there is a variation in the distribution of the composite spheres, when the rubber is deformed, a large energy loss occurs between the filler and the low fuel efficiency is deteriorated.

And in order to solve the said subject, it is thought that it is preferable to disperse | distribute the said composite sphere with high hardness, uniform size, and dispersibility in rubber | gum in a vulcanized composite sphere.

Impurities contained in the alkylphenol resin (remaining), in particular, unreacted (free) alkylphenol component (monomer component), because of its low molecular weight, may substantially function as a plasticizer. Therefore, it is thought that reducing the unreacted monomer component remaining in the resin can increase the hardness of the composite sphere.

Moreover, when the alkylphenol resin obtained by combining the alkylphenol (for example, 2-alkylphenol and 3-alkylphenol) which differ in the positional relationship of a hydroxyl group and an alkyl group as a monomer component is mix | blended with a rubber composition, the said composite sphere will be a more uniform size. The present invention has been completed by discovering that it is possible to disperse well in a furnace and rubber. That is, this invention contains 0.5-20 mass parts of alkylphenol resins and 0.04-10 mass parts of methylene donors with respect to 100 mass parts of rubber components, The said alkylphenol resin is 2-alkylphenol, 3-alkylphenol, 4 It is resin obtained from 2 or more types of compounds chosen from the group which consists of an alkyl phenol, and formaldehyde, and the sum total content of the free 2-alkylphenol, 3-alkylphenol, and 4-alkylphenol contained in the said alkylphenol resin is 3 mass. It relates to a rubber composition for tires which is% or less.

It is preferable that the said 2-alkylphenol, said 3-alkylphenol, and said 4-alkylphenol are o-cresol, m-cresol, and p-cresol, respectively.

It is preferable that the said alkylphenol resin is resin obtained from 2-alkylphenol, 3-alkylphenol, 4-alkylphenol, and formaldehyde.

It is preferable that the sum total content of 2-alkyl phenol, 3-alkyl phenol, and 4-alkyl phenol of glass contained in the said alkyl phenol resin is 1 mass% or less.

It is preferable that the softening point of the said alkylphenol resin is 115-140 degreeC.

It is preferable that the said alkylphenol resin is 96-100 mass% in content of a novolak-type phenol resin.

It is preferable that the said methylene donor is 1 or more types of compounds chosen from the group which consists of hexamethylenetetramine, hexamethoxymethylol melamine, and hexamethylol melamine pentamethyl ether.

The rubber composition for a tire is used as a rubber composition for a breaker topping and / or a rubber composition for a sheet located above and below a breaker edge / breaker topping sheet, and 1 to 5 parts by mass of the alkylphenol resin per 100 parts by mass of a rubber component. It is preferable to contain 1-7 mass parts of hexamethoxy methylol melamine and / or hexamethylol melamine pentamethyl ether as said methylene donor.

The rubber composition for a tire is used as a rubber composition for sidewalls, a rubber composition for base treads, a rubber composition for tie gums, a rubber composition for clinch apex and / or a rubber composition for soft bead apex, and the alkylphenol is used based on 100 parts by mass of the rubber component. It is preferable to contain 0.5-5 mass parts of resin and 0.04-5 mass parts of hexamethylenetetramine as said methylene donor.

The rubber composition for tires is used as a rubber composition for bead apex, a rubber composition for strip apex, a rubber composition for bead wire topping, and 5 to 20 parts by mass of the alkylphenol resin as the methylene donor based on 100 parts by mass of a rubber component. It is preferable to contain 0.4-5 mass parts of hexamethylenetetramine.

The rubber composition for tires is used as a rubber composition for bead apex, rubber composition for strip apex, rubber composition for bead wire topping, and carbon black having a nitrogen adsorption specific surface area of 25 to 50 m ² / g based on 100 parts by mass of the rubber component. It is preferable to contain 40-80 mass parts.

The present invention also relates to a pneumatic tire having a tire member produced using the rubber composition.

The tire member is composed of a sheet positioned above and below the bead apex, cap tread, base tread, sidewall, tie gum, breaker, strip apex, bead wire topping, clinch apex, soft bead apex and breaker edge / breaker topping sheet. It is preferable that it is 1 or more types chosen from.

According to the present invention, a specific amount of alkylphenol resin and methylene donor are included, wherein the alkylphenol resin is at least two compounds selected from the group consisting of 2-alkylphenol, 3-alkylphenol and 4-alkylphenol and formaldehyde. It is resin obtained from the rubber composition for tires whose sum total content of 2-alkylphenol, 3-alkylphenol, and 4-alkylphenol of the glass contained in the said alkylphenol resin (it remains in resin because it is unreacted) is below a specific amount. Therefore, the steering stability, low fuel consumption, elongation at break, and steering response can be obtained with good balance while maintaining good extrusion processability.

The rubber composition for tires of the present invention comprises a specific amount of an alkylphenol resin and a methylene donor, wherein the alkylphenol resin is at least two compounds selected from the group consisting of 2-alkylphenols, 3-alkylphenols and 4-alkylphenols. It is resin obtained from and formaldehyde, and the sum total content (the alkylphenol total amount of glass) of the free 2-alkylphenol, 3-alkylphenol, and 4-alkylphenol contained in the said alkylphenol resin is below a specific amount. Thereby, steering stability, low fuel consumption, and steering response can be improved while maintaining good extrusion processability, and the fall of elongation at break reduced by the compounding of resin can be made small, and steering stability, low fuel efficiency, The pneumatic tire which can obtain the elongation at break and the steering response at a good balance can be manufactured with good productivity.

In the rubber composition of the present invention, the rubber component can be used as a natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), styrene isoprene butadiene rubber (SIBR), isoprene Rubber (IR), ethylene propylene diene rubber (EPDM), chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR) and the like. A rubber component may be used independently and may use 2 or more types together. Among them, NR and IR are preferred because of their excellent workability (extrusion processability), elongation at break, and low fuel efficiency. In addition, BR is preferable because of its excellent crack resistance and abrasion resistance. In addition, SBR is preferable because of excellent grip performance and reversibility.

Moreover, when using as a rubber composition for bead apex, a rubber composition for strip apex, and a rubber composition for bead wire topping, it is preferable to use BR and SBR together with NR.

Moreover, when using as a rubber composition for sidewalls, the rubber composition for base treads, the rubber composition for tie gums, the rubber composition for clinch apex, and the rubber composition for soft bead apex, it is preferable to use BR together with NR.

It does not specifically limit as NR, For example, what is common in the tire industry, such as SIR20, RSS # 3, and TSR20, can be used.

It does not specifically limit as BR, For example, BR of the cis content, such as BR1220 by Nippon Xeon Co., Ltd. product, BR150B by Ubekosan Co., Ltd. product, VCR412 of Ubekosan Co., Ltd., VCR617, etc. The general thing in the tire industry, such as BR (SPB containing BR) containing a -2-syndiotactic polybutadiene crystal (SPB), butadiene rubber (rare earth BR) synthesize | combined using the rare earth element type catalyst, can be used.

BRB contains SPB because it can improve hardness (E *) and wear resistance when used as a rubber composition for bead apex, rubber composition for strip apex, rubber composition for clinch apex, rubber composition for sidewall, or rubber composition for tie gum. BR is preferred.

Moreover, when used as a rubber composition for sidewalls, a rubber composition for base treads, a rubber composition for tie gums, a rubber composition for clinch apex, and a rubber composition for soft bead apex, it is possible to improve elongation at break, abrasion resistance and low fuel efficiency. Rare earth system BR is preferred.

In the SPB-containing BR, the 1,2-syndiotactic polybutadiene crystal (SPB) is preferably not dispersed in the SPB-containing BR, but is dispersed in an unoriented orientation after chemical bonding with the SPB-containing BR. Dispersion and propagation of cracks tend to be suppressed by the dispersion of the crystal after chemical bonding with the rubber component.

180 degreeC or more is preferable and, as for melting | fusing point of SPB, 190 degreeC or more is more preferable. If the melting point of the SPB is less than 180 ° C., the crystals melt during the vulcanization of the tire by the press and the hardness (pilot stability) tends to decrease. Moreover, 220 degrees C or less is preferable, and, as for melting | fusing point of SPB, 210 degrees C or less is more preferable. When the melting point of the SPB exceeds 220 ° C, the molecular weight of the SPB-containing BR increases, so that the dispersibility in the rubber composition tends to deteriorate and the extrusion processability tends to deteriorate.

2.5 mass% or more is preferable, and, as for the content rate of the boiling n-hexane insoluble matter in SPB containing BR, 8 mass% or more is more preferable. If the content of boiling n-hexane insolubles is less than 2.5% by mass, there is a tendency that sufficient hardness (steering stability) of the rubber composition cannot be obtained. Moreover, 22 mass% or less is preferable, as for the content rate of the boiling n-hexane insoluble matter, 20 mass% or less is more preferable, 18 mass% or less is more preferable. When the content of boiling n-hexane insolubles exceeds 22% by mass, the viscosity of the SPB-containing BR itself is high, and the dispersibility of the SPB-containing BR and the filler in the rubber composition tends to deteriorate, and the extrudability tends to deteriorate. Here, a boiling n-hexane insoluble substance shows SPB in SPB containing BR.

A well-known thing can be used as said rare earth element type catalyst, For example, a lanthanum type rare earth element compound, an organoaluminum compound, an aluminoxane, a halogen containing compound, and the catalyst containing a Lewis base as needed. Especially, the Nd type catalyst which used the neodium (Nd) containing compound as a lanthanum rare earth element compound is especially preferable.

Examples of the lanthanum rare earth element compounds include halides, carboxylates, alcoholates, thioalcolates, amides, and the like of the rare earth metals having an atomic number of 57 to 71. Among them, as described above, the use of an Nd-based catalyst is preferable in that BR having a high cis content and a low vinyl content can be obtained.

As the organoaluminum compound, those represented by AlR ^a R ^b R ^c (wherein R ^a , R ^b and R ^c are the same or different and represent hydrogen or a hydrocarbon group having 1 to 8 carbon atoms) can be used. Examples of the aluminoxanes include chain aluminoxanes and cyclic aluminoxanes. As the halogen-containing compound, AlX _k R ^d _{3 -k} (wherein X is halogen, R ^d represents an alkyl, aryl or aralkyl group having 1 to 20 carbon atoms, and k represents 1, 1.5, 2 or 3). Aluminum halide represented by; Me ₃ SrCl, Me ₂ SrCl ₂ , MeSrHCl ₂ , MeSrCl ₃ Strontium halides such as; And metal halides such as silicon tetrachloride, tin tetrachloride, and titanium tetrachloride. The Lewis base is used to complex the lanthanum rare earth element compound, and acetylacetone, ketone, alcohol and the like are suitably used.

The rare earth element catalyst may be used in a state of being dissolved in an organic solvent (n-hexane, cyclohexane, n-heptane, toluene, xylene, benzene, etc.) during the polymerization of butadiene, and suitable for silica, magnesia, magnesium chloride, and the like. It can also be used on a carrier. As polymerization conditions, any of solution polymerization or block polymerization may be sufficient, preferable polymerization temperature is -30-150 degreeC, and a polymerization pressure can also be selected arbitrarily depending on other conditions.

The rare earth metal-based BR has a Mooney viscosity ML _{1 +4} (100 ℃) is preferably 35 or higher, more preferably at least 40. If it is less than 35, the viscosity of the unvulcanized rubber composition is low, and there exists a possibility that extrusion workability may deteriorate. The Mooney viscosity is preferably 55 or less, more preferably 50 or less. If it exceeds 55, there is a fear that the unvulcanized rubber composition becomes excessively hard, making it difficult to extrude to a smooth edge (extrusion workability deteriorates).

In addition, Mooney viscosity is measured according to ISO289 and JIS K6300.

Preferably the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the rare earth-based BR is 1.2 or more, more preferably 1.5 or more. When it is less than 1.2, there exists a tendency for the deterioration of extrusion workability to become remarkable. The Mw / Mn is preferably 5 or less, more preferably 4 or less. When it exceeds 5, there exists a tendency for the improvement effect of abrasion resistance to become small.

Mw of the rare earth system BR is preferably 300,000 or more, more preferably 400,000 or more, and preferably 1.5 million or less, and more preferably 1.2 million or less. Furthermore, Mn of the rare earth-based BR is preferably 100,000 or more, more preferably 150,000 or more, and preferably 1 million or less, and more preferably 800,000 or less. When Mw and Mn are less than a lower limit, there exists a tendency for abrasion resistance to fall or low fuel economy to worsen. When the upper limit is exceeded, deterioration of extrusion processing is feared.

In addition, in this invention, Mw and Mn are the values converted from standard polystyrene using the gel permeation chromatograph (GPC).

The sheath content of the rare earth system BR is preferably 90% by mass or more, more preferably 93% by mass or more, even more preferably 95% by mass or more. If it is less than 90 mass%, wear resistance falls and there exists a possibility that neither abrasion resistance nor low fuel consumption may be satisfied.

The vinyl content of the rare earth-based BR is preferably 1.8 mass% or less, more preferably 1.0 mass% or less, still more preferably 0.5 mass% or less, particularly preferably 0.3 mass% or less. When it exceeds 1.8 mass%, wear resistance falls and there exists a possibility that neither abrasion resistance nor low fuel consumption may be satisfied.

In the present specification, the vinyl content (1,2-bonded butadiene unit amount) and the cis content (cis-1,4-bonded butadiene unit amount) of the rare earth system BR can be measured by infrared absorption spectrum analysis.

It does not specifically limit as SBR, Emulsion polymerization styrene butadiene rubber (E-SBR), solution polymerization styrene butadiene rubber (S-SBR), etc. are mentioned. Among them, E-SBR is preferred because of good workability (extrusion workability), high hardness (E *), and low cost.

When using as a rubber composition (rubber composition for breaker topping) used for a breaker, and a sheet rubber composition located above and below a breaker edge / breaker topping sheet, content of NR in 100 mass% of rubber components becomes like this. Preferably it is 60 mass % Or more, More preferably, it is 80 mass% or more, and 100 mass% may be sufficient. If it is less than 60 mass%, there exists a possibility that a favorable elongation at break may not be obtained.

When using as a rubber composition for bead apex, a rubber composition for strip apex, and a rubber composition for bead wire topping, the content of NR in 100% by mass of the rubber component is preferably 30% by mass or more, and more preferably 40% by mass or more. . If it is less than 30 mass%, there exists a possibility that extrusion workability, such as adhesiveness, an apex upright, and a tip smoothness, may not be obtained. Content of NR becomes like this. Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less, Especially preferably, it is 60 mass% or less. When it exceeds 90 mass%, it tends to be reversible and it is difficult to obtain high hardness (E *).

When used as a rubber composition for bead apex, a rubber composition for strip apex, and a rubber composition for bead wire topping, the content of SBR in 100% by mass of the rubber component is preferably 5% by mass or more, and more preferably 10% by mass or more. . If it is less than 5 mass%, there exists a possibility that hardness (E *) and reversal may deteriorate. Content of SBR becomes like this. Preferably it is 40 mass% or less, More preferably, it is 30 mass% or less. When it exceeds 40 mass%, there exists a possibility that a favorable elongation at break may not be obtained.

When using as a rubber composition for sidewalls, the rubber composition for base treads, the rubber composition for tie gums, the rubber composition for clinch apex, and the rubber composition for soft bead apex, content of NR in 100 mass% of rubber components becomes like this. Preferably it is 40 mass% As mentioned above, More preferably, it is 50 mass% or more. If it is less than 40 mass%, there exists a possibility that favorable workability (extrusion workability) and elongation at break may not be obtained. Content of NR becomes like this. Preferably it is 80 mass% or less, More preferably, it is 70 mass% or less. When it exceeds 80 mass%, there exists a possibility that favorable crack growth resistance and abrasion resistance may not be acquired.

When used as a rubber composition for sidewalls, a rubber composition for base treads, a rubber composition for tie gums, a rubber composition for clinch apex, and a rubber composition for soft bead apex, the content of BR in 100 mass% of the rubber component is preferably 20 mass%. As mentioned above, More preferably, it is 30 mass% or more. If it is less than 20 mass%, there exists a possibility that favorable crack growth resistance and abrasion resistance may not be acquired. Content of BR becomes like this. Preferably it is 60 mass% or less, More preferably, it is 50 mass% or less. When it exceeds 60 mass%, there exists a possibility that favorable workability (extrusion workability) and elongation at break may not be obtained.

In the present invention, a specific alkylphenol resin is used. The alkylphenol resin used in the present invention is a resin obtained from two or more kinds of compounds selected from the group consisting of 2-alkylphenols, 3-alkylphenols and 4-alkylphenols and formaldehyde, and the glass contained in the alkylphenol resins. The total content (that is, the total amount of free alkylphenols) of 2-alkylphenol, 3-alkylphenol and 4-alkylphenol in the formula is 3% by mass or less.

In the alkylphenol resin used in the present invention, since the unreacted alkylphenol component (monomer component) contained in the alkylphenol resin is not more than the specific amount, it is considered that the hardness of the above-mentioned composite sphere can be increased.

In addition, the alkylphenol resin used by this invention is an alkylphenol resin obtained by combining two or more alkylphenols (for example, 2-alkylphenol and 3-alkylphenol) which differ in the positional relationship of a hydroxyl group and an alkyl group as a monomer component. For this reason, it is thought that the above-mentioned composite sphere can be distributed more uniformly and dispersible | distributed in rubber | gum by mix | blending the said alkylphenol resin with a rubber composition. By combining alkylphenols having different positional relations between hydroxyl groups and alkyl groups, the orientation of the alkyl groups is randomized to form a structure that is easy to crosslink. Therefore, the crosslinking density is increased, and the hardness of the composite sphere described above can be made higher. It is thought that a composite sphere can be distributed more uniformly and dispersible in rubber | gum.

By blending the specific alkylphenol resin into the rubber composition, the above-described composite spheres can be dispersed in rubber with high hardness and uniform size and good dispersibility in rubber. It is possible to improve the steering stability, low fuel consumption and steering response while maintaining the stability, and furthermore, it is possible to reduce the width of the elongation at break lowered by the compounding of the resin, so that the steering stability and low fuel efficiency can be maintained while maintaining good extrusion processability. It is estimated that elongation at break and steering response can be obtained in good balance.

The said alkylphenol resin is resin obtained from 2 or more types of compounds chosen from the group which consists of 2-alkylphenol, 3-alkylphenol, and 4-alkylphenol, and formaldehyde. Specifically, the alkylphenol resin is a resin obtained by reacting two or more compounds selected from the group consisting of 2-alkylphenol, 3-alkylphenol and 4-alkylphenol with formaldehyde using an acid catalyst (novolak Type phenolic resin).

The alkylphenol used as the monomer component is two or more compounds selected from the group consisting of 2-alkylphenol, 3-alkylphenol and 4-alkylphenol, and for the reason that the effects of the present invention can be suitably obtained, 2-alkylphenol is used. It is preferable to use three kinds of compounds, 3-alkyl phenol and 4-alkyl phenol.

Although carbon number of the alkyl group which an alkylphenol has is not specifically limited, 1-10 are preferable, 1-5 are more preferable, 1-3 are more preferable, for the reason that the effect of this invention can be acquired suitably, 1 is particularly preferred. As alkylphenol, you may use combining the thing of which the carbon number of an alkyl group differs.

The most preferable monomer component is a case where the 2-alkyl phenol, the 3-alkyl phenol and the 4-alkyl phenol are o-cresol, m-cresol and p-cresol, respectively. That is, it is preferable that the alkylphenol resin is a cresol resin.

It does not specifically limit as an acid catalyst, For example, a boron trifluoride ether complex, a boron trifluoride phenol complex, a boron trifluoride water complex, a boron trifluoride alcohol complex, a boron trifluoride amine complex, a mixture thereof, etc. This is used. Among them, particularly preferred are boron trifluoride, boron trifluoride-phenol complex, boron trifluoride ether complex and the like.

The method for reacting an alkylphenol and formaldehyde in the presence of an acid catalyst is not particularly limited and can be carried out by a known method. For example, an acid catalyst, an alkylphenol, and formaldehyde may be dissolved in a suitable solvent and reacted at 100 to 180 ° C. for 1 to 10 hours.

Although it does not restrict | limit especially as a purification method of the alkylphenol resin obtained by the said reaction, For example, after melt | dissolving in a solvent, refinement | purification operations, such as recrystallization, column chromatography, distillation, are specified, and the total amount of the alkylphenol of the glass contained in the alkylphenol resin is specified. The said alkylphenol resin can be obtained by performing until it becomes below an amount. In addition, as a distillation method, the method of Unexamined-Japanese-Patent No. 2011-74205 can be used suitably.

The total content (the total amount of alkylphenols in the glass) of the 2-alkylphenol, 3-alkylphenol and 4-alkylphenol of the glass contained in the alkylphenol resin is 3% by mass or less, preferably 2% by mass or less, more preferably. Preferably it is 1 mass% or less. When it exceeds 3 mass%, the hardness of the composite sphere after vulcanization falls, and the effect of this invention cannot fully be acquired.

The total amount of alkylphenols in the glass is the value measured by gel filtration chromatography (GPC).

The alkylphenol resin preferably has a content of a novolak-type phenol resin of 96 to 100 mass%, more preferably 98 to 100 mass%, still more preferably 99 to 100 mass%. When content of a novolak-type phenol resin is less than 96 mass%, there exists a possibility that the hardness of the composite sphere after vulcanization may fall and the effect of this invention may not be fully acquired.

Content of a novolak-type phenol resin is a value measured by gel filtration chromatography (GPC).

In order to distribute the above-mentioned composite spheres more uniformly and more dispersible in rubber, it is preferable that the alkylphenol resin itself is sufficiently dispersed during kneading of the rubber, and then the alkylphenol resin is liquefied. If the softening point is too low, there is a fear that the alkylphenol resin is liquefied before the filler is dispersed to some extent during kneading, so that good dispersion of the alkylphenol resin cannot be achieved. On the other hand, if the softening point is too high, the polymer is softened as the temperature rises, so that the torque to break the agglomerates of the alkylphenol resin is insufficient, so that the dispersion of the alkylphenol resin is deteriorated or the liquefaction thereof is insufficient. There is a fear that the formation will be insufficient. By setting the softening point of the alkylphenol resin within the following ranges, the above-described composite spheres can be more uniformly distributed and more dispersible in rubber, and the effects of the present invention can be more suitably obtained.

The softening point of the said alkylphenol resin becomes like this. Preferably it is 115 degreeC or more, More preferably, it is 120 degreeC or more, More preferably, it is 125 degreeC or more. Moreover, the said softening point becomes like this. Preferably it is 140 degrees C or less, More preferably, it is 135 degrees C or less.

In addition, the softening point of an alkylphenol resin measures the softening point prescribed | regulated to JISK6220-1: 2001 with a round ball type | mold softening point measuring device, and is the temperature at which a sphere fell.

The softening point of an alkylphenol resin can be adjusted by adjusting the combination and ratio of the 2-alkylphenol, 3-alkylphenol, and 4-alkylphenol used as a monomer component, and providing suitable anisotropy and crystallinity. For example, since the melting points of o-cresol, m-cresol, and p-cresol are 30 ° C, 12 ° C, and 35.5 ° C, respectively, those skilled in the art adjust the softening point of the alkylphenol resin to a desired temperature by adjusting their ratio based on the melting point information. I can adjust it.

In addition, since the total amount of alkylphenols in the glass contained in the alkylphenol resin also affects the softening point, the softening point of the alkylphenol resin can be adjusted by adjusting this amount.

The weight average molecular weight (Mw) of the said alkylphenol resin becomes like this. Preferably it is 1000 or more, More preferably, it is 1500 or more. Mw is preferably 3000 or less, more preferably 2500 or less, and still more preferably 1900 or less. If Mw is in the said range, the effect of this invention can be acquired more suitably.

In addition, the weight average molecular weight (Mw) was converted from standard polystyrene using the gel permeation chromatograph (GPC).

In addition, in this specification, GPC measured on the following conditions (1)-(8).

(1) Apparatus: HLC-8020 manufactured by Tosoh Corporation

(2) Separation column: GMH-XL (two in series) manufactured by Tosoh Corporation

(3) measuring temperature: 40 ℃

(4) Carrier: Tetrahydrofuran

(5) flow rate: 0.6 mL / min

(6) Injection amount: 5 μL

(7) detector: parallax refraction

(8) Molecular Weight Standard: Standard Polystyrene

Content of the said alkylphenol resin is 0.5-20 mass parts with respect to 100 mass parts of rubber components. If it is less than 0.5 mass part, steering stability, low fuel consumption, and steering response will not be obtained sufficiently. On the other hand, when 20 mass parts is exceeded, elongation at break and low fuel efficiency will deteriorate.

When using as a rubber composition for breaker topping and the sheet | seat rubber composition located above and below a breaker edge / breaker topping sheet, content of the said alkylphenol resin is 1-5 mass parts with respect to 100 mass parts of rubber components, 2 4 mass parts is more preferable. In these rubber compositions, the hardness (E *) required in comparison with the rubber composition for bead apex is low, and if the content of the alkylphenol resin is in the above range, while maintaining the hardness (E *) required for these rubber compositions, good low fuel efficiency, Elongation at break can be obtained, so that steering stability, low fuel consumption, elongation at break, and steering response can be obtained in good balance.

When used as a rubber composition for sidewalls, a rubber composition for base treads, a rubber composition for tie gums, a rubber composition for clinch apex, and a rubber composition for soft bead apex, the content of the alkylphenol resin is 0.5 to 100 parts by mass with respect to 100 parts by mass of the rubber component. 5 mass parts is preferable, and 1-4 mass parts is more preferable.

In these rubber compositions, the hardness (E *) required is lower than that of the bead apex rubber composition, chipping property (elongation at break), and the like are also important. If the content of the alkylphenol resin is in the above range, the hardness required for these rubber compositions It is possible to obtain good low fuel efficiency and elongation at break while securing (E *), so that steering stability, low fuel consumption, elongation at break and steering response can be obtained in a good balance.

When using as a rubber composition for bead apex, a rubber composition for strip apex, and a rubber composition for bead wire topping, the content of the alkylphenol resin is preferably 5 to 20 parts by mass, and 7 to 16 parts by mass relative to 100 parts by mass of the rubber component. More preferred.

Since high hardness (E *) is calculated | required by these rubber compositions, content of the said alkylphenol resin is more compared with the case used for another member.

In the present invention a methylene donor is used. By using a methylene donor together with an alkylphenol resin, it is possible to obtain a good balance of steering stability, low fuel consumption, elongation at break, and steering response while maintaining good extrusion processability.

Examples of the methylene donors include hexamethylenetetramine (HMT), hexamethoxymethylolmelamine (HMMM), hexamethylolmelaminepentamethyl ether (HMMPME), and smcanol 507A. Especially, HMT, HMMM, and HMMPME are preferable.

When using as a rubber composition for breaker topping and the sheet | seat rubber composition located above and below a breaker edge / breaker topping sheet, HMMM and HMMPME are preferable. This is because HMT generates ammonia which adversely affects adhesion to cords in addition to methylene during vulcanization. However, even in the case of using HMT, adhesiveness with the cord can be secured by increasing the organic acid cobalt.

When used as a rubber composition for sidewalls, a rubber composition for base treads, a rubber composition for tie gums, a rubber composition for clinch apex, and a rubber composition for soft bead apex, HMT is preferred.

When used as a rubber composition for bead apex, a rubber composition for strip apex and a rubber composition for bead wire topping, HMT is preferred.

Content of a methylene donor is 0.04-10 mass parts with respect to 100 mass parts of rubber components. If it is less than 0.04 mass part, steering stability, low fuel consumption, and steering response will not be fully acquired. If it exceeds 10 parts by mass, the elongation at break and low fuel efficiency deteriorate.

When used as a rubber composition for a breaker topping and a sheet rubber composition located above and below the breaker edge / breaker topping sheet, the content of the methylene donor (preferably HMMM and / or HMMPME) is the same as that of the content of the alkylphenol resin. For the same reason, 1-7 mass parts is preferable with respect to 100 mass parts of rubber components, and 2-5 mass parts is more preferable.

When used as a rubber composition for sidewalls, rubber composition for base tread, rubber composition for tie gum, rubber composition for clinch apex, and rubber composition for soft bead apex, the content of the methylene donor (preferably HMT) is the content of the alkylphenol resin. 0.04-5 mass parts is preferable with respect to 100 mass parts of rubber components for the same reason as that of the case.

When used as a rubber composition for bead apex, a rubber composition for strip apex, or a rubber composition for bead wire topping, the content of the methylene donor (preferably HMT) is the same as that of the alkylphenol resin. 0.4-5 mass parts is preferable with respect to a part, and 0.5-3 mass parts is more preferable.

In the present invention, softeners such as aroma oils, C5 petroleum resins, C9 petroleum resins, aroma / aliphatic mixed resins, and TDAE oils may be contained.

In the present invention, carbon black may be contained. As a result, good reinforcement can be obtained, and steering stability, low fuel consumption, elongation at break, and steering response can be obtained in a balanced manner. Examples of carbon blacks that can be used include GPF, FEF, HAF, ISAF, and SAF, but are not particularly limited. Carbon black may be used independently and may use 2 or more types together.

When used as a rubber composition for breaker topping and a sheet rubber composition located above and below the breaker edge / breaker topping sheet, the nitrogen adsorption specific surface area (N ₂ SA) of carbon black is preferably 50 to 110 m ² / g, 70-90 m <^2> / g is more preferable.

When used as a rubber composition for sidewall, rubber composition for base tread, rubber composition for tie gum, rubber composition for clinch apex, rubber composition for soft bead apex, N ₂ SA of carbon black is preferably 20 to 70 m ² / g. , 30-50 m ² / g is more preferable.

When used as a rubber composition for bead apex, a rubber composition for strip apex, and a rubber composition for bead wire topping, the carbon black N ₂ SA is preferably 20 to 90 m ² / g, more preferably 25 to 50 m ² / g. desirable.

If N ₂ SA is less than the lower limit, there is a tendency that sufficient reinforcement cannot be obtained. On the other hand, when the N ₂ SA is more than the upper limit Micah viscosity during flow very high, there is a tendency that the extrusion workability deteriorates. In addition, the low fuel consumption tends to deteriorate.

In addition, in this specification, the nitrogen adsorption specific surface area of carbon black is measured based on JISK6217-2: 2001.

When the rubber composition for tires of this invention contains carbon black, content of carbon black becomes like this. Preferably it is 30 mass parts or more, More preferably, it is 40 mass parts or more with respect to 100 mass parts of rubber components. When it is less than 30 mass parts, there exists a possibility that the effect which mix | blended carbon black may not fully be acquired. Moreover, content of carbon black becomes like this. Preferably it is 80 mass parts or less, More preferably, it is 65 mass parts or less. When it exceeds 80 mass parts, extrusion workability and low fuel consumption tend to deteriorate.

When used as a rubber composition for breaker topping and the sheet | seat rubber composition located above and below a breaker edge / breaker topping sheet, it is preferable to contain organic acid cobalt.

Since organic acid cobalt plays a role of bridge | crosslinking a steel cord and rubber | gum, adhesiveness of a steel cord and rubber | gum can be improved by containing organic acid cobalt. Specific examples of the organic acid cobalt include, for example, cobalt stearate, cobalt naphthenic acid, cobalt neodecanoic acid, and cobalt boron 3 neodecanoic acid. Especially, cobalt stearate is preferable.

When used as a rubber composition for a breaker topping and a rubber composition for sheets positioned above and below the breaker edge / breaker topping sheet, the content of the organic acid cobalt is 0.05 parts by mass or more, preferably in terms of cobalt based on 100 parts by mass of the rubber component. It is 0.08 mass part or more. If it is less than 0.05 mass part, adhesiveness will fall and durability will fall.

The content is 0.30 parts by mass or less, preferably 0.20 parts by mass or less, more preferably 0.12 parts by mass or less in terms of cobalt. When it exceeds 0.30 mass part, elongation at break and adhesiveness will fall, and durability will fall.

In addition to the methylene donor, it may contain a crosslinking agent. Examples of the crosslinking agent include sulfur, alkylphenol and sulfur chloride condensates. When using as a rubber composition for bead apex, a rubber composition for strip apex, and a rubber composition for bead wire topping, since a high hardness rubber composition can be obtained, it is preferable to contain an alkylphenol-sulfur chloride condensate.

As a specific example of an alkylphenol-sulfur chloride condensate, TACKIROL V200 by Daoka Chemical Industry Co., Ltd. is mentioned, for example. Moreover, a vulcanization accelerator can also be contained as needed.

When used as a rubber composition for breaker topping, a rubber composition for sheets positioned above and below the breaker edge / breaker topping sheet, a rubber composition for bead apex, a rubber composition for strip apex, a rubber composition for bead wire topping, the content of sulfur is a rubber component Preferably it is 3 mass parts or more, More preferably, it is 5 mass parts or more with respect to 100 mass parts. Moreover, content of sulfur becomes like this. Preferably it is 12 mass parts or less, More preferably, it is 10 mass parts or less with respect to 100 mass parts of rubber components. If content of sulfur is in the said range, the effect of this invention can be acquired more suitably.

In addition, when using the sulfur containing oil, content of sulfur represents content of sulfur content.

When used as a rubber composition for bead apex, a rubber composition for strip apex and a rubber composition for bead wire topping, the content of the alkylphenol-sulfur chloride condensate is preferably 0.5 parts by mass or more, more preferably 100 parts by mass of the rubber component. Is 1 mass part or more. The content of the alkylphenol-sulfur chloride condensate is preferably 8 parts by mass or less, and more preferably 6 parts by mass or less with respect to 100 parts by mass of the rubber component. When content of an alkylphenol-sulfur chloride condensate is in the said range, the effect of this invention can be acquired more suitably.

In addition to the above components, the rubber composition of the present invention may be suitably blended with a compounding agent generally used in the preparation of the rubber composition, such as reinforcing fillers such as silica, silane coupling agents, stearic acid, zinc oxide, various anti-aging agents, waxes, and the like. have.

When used as a rubber composition for breaker topping, a rubber composition for sheets positioned above and below the breaker edge / breaker topping sheet, a rubber composition for bead apex, a rubber composition for strip apex, a rubber composition for bead wire topping, the content of zinc oxide is Preferably it is 5 mass parts or more, More preferably, it is 8 mass parts or more with respect to 100 mass parts of rubber components. Moreover, content of zinc oxide becomes like this. Preferably it is 15 mass parts or less, More preferably, it is 12 mass parts or less with respect to 100 mass parts of rubber components. When content of zinc oxide is in the said range, the effect of this invention can be acquired more suitably.

When used as a rubber composition for sidewalls, a rubber composition for base treads, a rubber composition for tie gums, a rubber composition for clinch apex, and a rubber composition for soft bead apex, the content of zinc oxide is preferably 3 mass per 100 parts by mass of the rubber component. Or more, more preferably 4 parts by mass or more. The content of zinc oxide is preferably 8 parts by mass or less, and more preferably 6 parts by mass or less with respect to 100 parts by mass of the rubber component. When content of zinc oxide is the said range, the effect of this invention can be acquired more suitably.

As a method for producing the rubber composition of the present invention, a known method can be used. For example, each of the above components can be prepared by kneading using a rubber kneading apparatus such as an open roll or a Benbury mixer, followed by vulcanization. Can be.

The rubber composition of the present invention can be used for each tire member. The tire member is not particularly limited, but bead apex, cap tread, base tread, sidewall, tie gum, breaker (member obtained by coating the tire cord with the rubber composition for breaker topping), strip apex, bead wire topping, and clinch It is preferably at least one selected from the group consisting of apex, soft bead apex, and a sheet positioned above and below the breaker edge / breaker topping sheet, and a sheet, bead apex, side positioned above and below the breaker, breaker edge / breaker topping sheet. Wall, base tread and tie gum are more preferable, and breaker, bead apex, and sidewall are more preferable.

The bead apex is a member disposed inside the tire clinch so as to extend radially outward from the bead core, and is specifically, a member shown in FIGS. 1 to 3 and the like of JP 2008-38140 A.

The cap tread is the surface layer portion of the tread having a multilayer structure. The base tread is an inner layer part of a tread having a multilayer structure. In the case of the tread of a two-layer structure, it consists of a surface layer (cap tread) and an inner surface layer (base tread).

The sidewall is a member disposed outside the carcass from the tread portion to the bead core of the bead portion.

A tie gum is a member arranged in the outer side of an inner liner inside a case cord, and is a member specifically, shown in FIG. 1 etc. of Unexamined-Japanese-Patent No. 2010-095705.

A breaker is a member disposed inside the tread and radially outward of the carcass, and specifically, a member shown in FIG. 3 and the like of JP-A-2003-94918.

The seats positioned above and below the breaker edge / breaker topping sheet are members disposed at the end of the breaker or on the inside (between the breaker and ply) or the outside (between the breaker and tread) in the radial direction of the breaker. It is a member shown in FIG. 1 etc. of Unexamined-Japanese-Patent No. 2009-046576.

The strip apex is a reinforcement inner rubber of a side wall part, and is a member specifically, shown in FIG. 1 of Unexamined-Japanese-Patent No. 2010-149677, and FIG. 5 of Unexamined-Japanese-Patent No. 2008-038140.

Bead wire topping is a rubber that coats the bead wire.

A clinch apex is a rubber | gum part arrange | positioned at the inner end of a sidewall, For example, it is a member shown to FIG. 1 of Unexamined-Japanese-Patent No. 2008-75066, FIG. 1 of Unexamined-Japanese-Patent No. 2004-106796, etc., for example.

The soft bead apex is a bead apex that is softer than a normal bead apex. Specifically, the soft bead apex is used for a bead apex that is softer than a normal bead apex used for a run flat tire having a sidewall reinforcement layer (insert) disposed thereon. It is a soft rubber layer of the bead apex of a two-layer structure (a hard rubber layer in the radially inner side of the tire, a soft rubber layer in the radially outer side of the tire).

The pneumatic tire of this invention is manufactured by a conventional method using the said rubber composition. That is, if necessary, the rubber composition containing various additives is molded into the shape of each member in the unvulcanized stage (in the case of the breaker, the tire cord is covered by the tire cord in the unvulcanized stage), and then the other tire member and the like. After bonding together to form an unvulcanized tire, the tire can be manufactured by heating and pressing in a vulcanizer.

Tire cords usable in the present invention include organic fiber cords, steel cords, hybrid cords of organic fibers and steel, and the like. Specifically, a steel steel cord for tires, 2 + 2 / 0.23 (a tire cord braided by joining two cords having a wire diameter of 0.23 mm and two cords), a high tension cord coated with brass, and the like can be given.

The pneumatic tire of the present invention can be used for passenger cars, trucks / buses, light trucks and the like. Since the pneumatic tire of the present invention has high hardness (E *) and good elongation at break, steering stability, low fuel consumption, elongation at break (durability), and steering response can be obtained with good balance. In addition, since it has high hardness (E *) and good elongation at break, good steering stability, steering response, and trauma resistance can be maintained even if it is light in weight. In addition, the flat spot (deformation of the tread of the tire) can be suitably suppressed.

<Examples>

Although this invention is demonstrated concretely based on an Example, this invention is not limited to these.

Hereinafter, the various chemical | medical agents used by the Example and the comparative example are demonstrated collectively.

NR: TSR20

Carbon black (1): Preparation of Cabot Japan _{(Note) N326 (N 2 SA: 81} m 2 / g)

Antioxidant: Antioxidant 6C (SANTOFLEX, 6PPD) manufactured by FLEXSYS Co., Ltd.

Zinc oxide: Zinc oxide (Average particle diameter: 290 nm) manufactured by Mitsui Metal Mining Co., Ltd.

Stearic acid cobalt: cost-F (cobalt content: 9.5 mass%) of Dainippon Ink Chemical Co., Ltd. product

Sulfur: Cristex HSOT20 manufactured by FLEXSYS Co., Ltd. (insoluble sulfur containing 80 mass% of sulfur and 20 mass% of oil)

Vulcanization accelerator DCBS: Nochseller DZ-G (N, N-dicyclohexyl-2- benzothiazolyl sulfenamide) of Shinko Chemical Co., Ltd. make

HMT: Nok cellar H (hexamethylenetetramine) of Shin-Ouchi Chemical Industry Co., Ltd. production

Hmmpme: sumikano 507ap (hexamethylol melamine pentamethyl ether) manufactured by daoka chemical industry Co., Ltd.

C5 petroleum resin: Mitsui Chemical Co., Ltd. high retsu g-100

Cresol resin (PR-X11061): PR-X11061 (the alkylphenol component (monomer component) manufactured by Sumitomo Bakelite Co., Ltd.) is used as o-cresol, m-cresol, p-cresol, and the total amount of free alkylphenols is 0.6 mass. %, Content of novolac-type phenol resin: 99.4% by mass, softening point: 128 ° C, Mw: 1800)

Cresol resin (test preparation A): Resin which changed the purification method in manufacture of PR-X11061, and changed the total amount of alkylphenols of glass (The alkylphenol component is the total amount of alkylphenols of glass: 1.5 mass%, similar to PR-X11061. Content of novolac phenolic resin: 98.5 mass%, softening point: 124 ° C, Mw: 1880)

Cresol resin (test preparation B): Resin which changed the purification method in manufacture of PR-X11061, and changed the total amount of alkylphenols of glass (The alkylphenol component is the total amount of alkylphenols of glass: 5 mass%, similar to PR-X11061. Content of novolac-type phenolic resin: 95% by mass, softening point: 110 ° C, Mw: 2090)

Sumikano 610 lot A: Sumikano 610 manufactured by Sumitomo Chemical Industry Co., Ltd. (m-cresol used only as a metacresol resin (alkylphenol component (monomer component) m- in 100% by mass of alkylphenol component used in the production of resin) Amount of cresol is 100% by mass), total amount of alkylphenols in glass: 8% by mass, content of novolac-type phenolic resin: 92% by mass, softening point: 100 ° C, Mw: 2000)

Sumikano 610 lot B: Sumikano 610 (metacresol resin (the alkylphenol component (monomer component) use only m-cresol (M- in 100 mass% of alkylphenol components used for manufacture of resin) manufactured by Sumitomo Chemical Industries, Ltd.) Amount of cresol is 100% by mass), total amount of alkylphenols in glass: 12% by mass, content of novolak-type phenolic resin: 88% by mass, softening point: 95 ° C, Mw: 2000)

Cashew oil modified phenolic resin: PR12686 (cashew oil modified phenolic resin, phenol amount of glass: 0.2 mass%, content of novolak-type phenolic resin: 99.8 mass%, softening point: 94 degreeC, Mw: by Sumitomo Bakelite Co., Ltd. make) 5330)

SPB containing BR: VCR617 by Ubekosan Co., Ltd. (melting point of SPB: 200 degreeC, content of boiling n-hexane insolubles: 15-18 mass%, content of SPB: 15-18 weight%)

SBR: Nipol 1502 (E-SBR) manufactured by Nihon Xeon Co., Ltd.

Carbon black (2): Preparation of Cabot Japan (Note) N550 (N ₂ SA: 40 m ² / g)

Carbon black (3): N330 (N ₂ SA: 78m ² / g) by Cabot Japan

Non-reactive alkylphenol resin: PR-19900 (softening point: 90 ° C) manufactured by Sumitomo Bakelite Co., Ltd.

Stearic acid: Kiri of Nichiyu Co., Ltd.

Vulcanization accelerator TBBS: Nochseller NS (N-tert-butyl-2- benzothiazolyl sulfenamide) of Ouchi Shinko Chemical Industries, Ltd. product

V200: Taqui roll V200 (alkylphenol-sulfur chloride condensate) by Daoka Chemical Industry Co., Ltd.

PVI: Retarder CTP manufactured by Ouchi Shinko Chemical Industry Co., Ltd.

Nd-based BR: CB24 manufactured by LANXESS (BR synthesized using an Nd-based catalyst, cis content: 96% by mass, vinyl content: 0.7% by mass, ML _{1 +4} (100 ° C): 45, Mw / Mn: 2.69, Mw: 500,000, Mn: 18.6 only)

Silica: Ultrazil VN3 (N ₂ SA: 175 m ² / g) manufactured by Evonik Degussa

Wax: Ozo Ace 0355 by Nippon Seiro Co., Ltd.

TDAE: Vivatec 500 manufactured by H & R Group

Examples 1-21 and Comparative Examples 1-21

According to the compounding prescription shown in Tables 1 to 3 (the amount of sulfur in the table indicates the amount of sulfur component), a mixture of kneaded materials was obtained by kneading the material other than the crosslinking agent in the blending material to 150 ° C. using a 1.7 L Benbury mixer. . Next, the crosslinking agent was added to the obtained kneaded material, it was crushed until it became 105 degreeC using the biaxial open roll, and the unvulcanized rubber composition was obtained.

The vulcanized rubber composition was obtained by pressing and vulcanizing the obtained unvulcanized rubber composition for 12 minutes under conditions of 170 ° C.

Further, in Examples 1 to 7 and Comparative Examples 1 to 7, the steel tires were coated with the obtained unvulcanized rubber composition, processed into a breaker shape, bonded together with other tire members, and vulcanized for 12 minutes under conditions of 170 ° C. (Tire size: 225 / 40R18 92Y XL) was obtained.

In Examples 8 to 14 and Comparative Examples 8 to 14, the obtained unvulcanized rubber composition was assembled with a bead wire to be processed into a bead apex shape, thereby obtaining a test tire (tire size: 225 / 40R18 92Y XL) as described above. .

Moreover, in Examples 15-21 and Comparative Examples 15-21, it processed into the sidewall shape with the obtained unvulcanized rubber composition, and the test tire (tire size: 225 / 40R18 92Y XL) was obtained similarly to the above.

In addition, although Table 1 is mix | blending of the rubber composition for breaker topping, the rubber composition for sheets located on the upper and lower sides of a breaker edge / breaker topping sheet is also the same formulation. In addition, although Table 2 is mix | blending of the rubber composition for bead apex, the rubber composition for strip apex and the rubber composition for bead wire topping are the same formulation.

In addition, although Table 3 is mix | blending of the rubber composition for sidewalls, the rubber composition for base treads, the rubber composition for tie gums, the rubber composition for clinch apex, and the rubber composition for soft bead apex are the same formulation. However, when it is set as the rubber composition for clinch apex, it is preferable to increase the BR amount and the carbon black amount and change the carbon black to N200 or N300.

The following evaluation was performed using the obtained unvulcanized rubber composition, a vulcanized rubber composition, and a test tire. The results are shown in Tables 1-3.

(Complex elastic modulus (hardness) (E *), low fuel consumption (tanδ))

The loss tangent (tanδ) and the complex elastic modulus (E *) of each vulcanized rubber composition were measured using a viscoelastic spectrometer manufactured by Iwamoto Co., Ltd. at 70 ° C., an initial strain of 10%, a dynamic strain of 2%, and a frequency of 10 Hz. Measured.

The smaller tanδ is, the lower the rolling resistance is, indicating that the fuel economy is excellent. Larger E * indicates better steering stability.

(Tension test)

Using a No. 3 dumbbell-type test piece containing a vulcanized rubber composition, a tensile test was conducted at room temperature according to JIS K 6251 "Method for Obtaining Vulcanizing Rubber and Thermoplastic Rubber-Tensile Properties", and the elongation at break at EB (%) was measured. The larger the EB, the better the elongation at break.

(Steer responsiveness)

The test tires were mounted on all wheels of the SUV, and the test course was actually driven, and the steering responsiveness was evaluated by a perfect score of 10 points by the driver's sensory evaluation. The higher the rating, the better the steering response.

(Extrusion Processability)

The unvulcanized rubber composition was introduced into a cold feed extruder to produce a rubber sheet 0.85 mm thick x 0.7 mm wide.

In Examples 1-7 and Comparative Examples 1-7, the produced rubber sheet was crimped from the upper and lower sides of the steel cord, and the flatness, finish, rubber scorching, and edge flatness of the obtained sheet surface were observed. Evaluation was made based on the criteria.

◎: excellent

○: satisfactory level

△: level at which countermeasures are required (level that impairs process productivity)

×: standard production

Further, in Examples 8 to 14 and Comparative Examples 8 to 14, the flatness, uprightness, finish, and rubber scoping of the edges after assembling the produced rubber sheet with the bead wire were observed and evaluated according to the following criteria.

◎: excellent

○: satisfactory level

△: level at which countermeasures are required (level that impairs process productivity)

×: standard production

In addition, in Examples 15 to 21 and Comparative Examples 15 to 21, the flatness, finish, rubber scouring, and edge flatness of the prepared rubber sheet surface were observed and evaluated according to the following criteria.

◎: excellent

○: satisfactory level

△: level at which countermeasures are required (level that impairs process productivity)

×: standard production

From Tables 1 to 3, a specific amount of alkylphenol resin and methylene donor are included, wherein the alkylphenol resin is at least two compounds selected from the group consisting of 2-alkylphenol, 3-alkylphenol and 4-alkylphenol and form The resin obtained from aldehyde, and the amount of the alkylphenol total amount of glass below the specific amount was able to obtain a good balance of steering stability, low fuel consumption, elongation at break, and steering response while maintaining good extrusion processability.

Claims (13)

0.5-20 mass parts of alkylphenol resins with respect to 100 mass parts of rubber components,
Between 0.04 and 10 parts by mass of methylene donor,
The said alkylphenol resin is resin obtained from 2 or more types of compounds chosen from the group which consists of 2-alkylphenol, 3-alkylphenol, and 4-alkylphenol, and formaldehyde, and the free 2 contained in the said alkylphenol resin The rubber composition for tires whose total content of -alkyl phenol, 3-alkyl phenol, and 4-alkyl phenol is 3 mass% or less. The rubber composition for a tire according to claim 1, wherein the 2-alkyl phenol, the 3-alkyl phenol and the 4-alkyl phenol are o-cresol, m-cresol and p-cresol, respectively. The rubber composition for a tire according to claim 1, wherein the alkylphenol resin is a resin obtained from 2-alkylphenol, 3-alkylphenol, 4-alkylphenol, and formaldehyde. The rubber composition for a tire according to claim 1, wherein the total content of 2-alkylphenol, 3-alkylphenol, and 4-alkylphenol of the glass contained in the alkylphenol resin is 1% by mass or less. The rubber composition for a tire according to claim 1, wherein the softening point of the alkylphenol resin is 115 ° C to 140 ° C. The rubber composition for a tire according to claim 1, wherein the alkylphenol resin has a content of a novolak-type phenol resin of 96 to 100 mass%. The rubber composition for a tire according to claim 1, wherein the methylene donor is at least one compound selected from the group consisting of hexamethylenetetramine, hexamethoxymethylolmelamine, and hexamethylolmelaminepentamethyl ether. The method according to claim 1, which is used as a rubber composition for breaker topping, a rubber composition for sheets located above and below the breaker edge / breaker topping sheet, or both.
1-5 mass parts of said alkylphenol resins with respect to 100 mass parts of rubber components,
A rubber composition for a tire comprising 1 to 7 parts by mass of hexamethoxymethylolmelamine, hexamethylolmelaminepentamethyl ether, or both, as the methylene donor. The rubber composition according to claim 1, which is used as at least one selected from rubber compositions for sidewalls, rubber compositions for base treads, rubber compositions for tie gums, rubber compositions for clinch apex, and rubber compositions for soft bead apex.
0.5-5 mass parts of said alkylphenol resins with respect to 100 mass parts of rubber components,
Rubber composition for a tire comprising 0.04 to 5 parts by mass of hexamethylenetetramine as the methylene donor. The method according to claim 1, which is used as at least one selected from a rubber composition for bead apex, a rubber composition for strip apex and a rubber composition for bead wire topping,
5-20 mass parts of said alkylphenol resins with respect to 100 mass parts of rubber components,
Rubber composition for a tire comprising 0.4 to 5 parts by mass of hexamethylenetetramine as the methylene donor. The method according to claim 1, which is used as at least one selected from a rubber composition for bead apex, a rubber composition for strip apex and a rubber composition for bead wire topping,
The rubber composition for tires containing 40-80 mass parts of carbon black whose nitrogen adsorption specific surface area is 25-50 m <^2> / g with respect to 100 mass parts of rubber components. A pneumatic tire having a tire member produced using the rubber composition according to any one of claims 1 to 11. The tire member of claim 12, wherein the tire member is disposed above and below bead apex, cap tread, base tread, sidewall, tie gum, breaker, strip apex, bead wire topping, clinch apex, soft bead apex and breaker edge / breaker topping sheet. Pneumatic tire which is 1 or more types chosen from the group which consists of seats located.