JP2019131653A - Composition and tire - Google Patents

Abstract

To provide a novel rubber composition that exhibits excellent low heat build-up properties and workability when containing an inorganic filler such as silica and a rubber.SOLUTION: A composition has a compound (A) represented by, for example, formula (1), a zinc salt and/or an aluminum salt of a fatty acid (B), a natural rubber and/or a synthetic rubber (C), an inorganic filler (D), a stearic acid (E), a zinc oxide (F), sulfur (G), and a vulcanization accelerator (H), with the total content of zinc and aluminum in the zinc salt and/or the aluminum salt of the fatty acid (B) being 0.15-1.5 pts.mass relative to the compound (A) 1 pts.mass. There is also provided a tire including the composition.SELECTED DRAWING: None

Description

  The present invention relates to a composition and a tire.

  Aminoguanidine is widely known for its usefulness as a synthetic raw material for drugs, dyes, photographic drugs, explosives and the like. Further, aminoguanidine is being studied as a rubber additive in addition to the above uses (see, for example, Patent Document 1). In recent years, physical properties required for use as a rubber additive have been increasingly diversified, and it has been demanded to provide a composition containing aminoguanidine capable of expressing new physical properties.

  On the other hand, the filler used for rubber is a compounding agent used for the purpose of mixing with rubber to reinforce or increase the rubber, or to give a special function to the rubber. Carbon black, which is a typical filler, not only contributes to the improvement (reinforcing effect) of mechanical properties such as the elastic modulus and breaking strength of rubber, but also has a function of imparting conductivity. In addition, a method of using an inorganic filler such as silica is known as a method for obtaining a rubber reinforcing effect as in the case of carbon black and obtaining a composition having low exothermic property, that is, low loss. The method is applied to a method for producing a composition for a low fuel consumption tire in consideration of environmental properties.

  In a rubber composition containing an inorganic filler, when the inorganic filler is compounded, the inorganic filler, particularly hydrophilic silica having a silanol group on the surface has a low affinity with the hydrophobic rubber, and the rubber composition Aggregates inside. Therefore, it is necessary to increase the affinity between silica and rubber in order to enhance the reinforcement by silica and obtain a low heat generation effect. As such a method, for example, a synthetic rubber (for example, see Patent Document 2) in which affinity with an inorganic filler is improved by terminal modification with a polar group is known.

  Recently, as a method for increasing the affinity between the inorganic filler and the rubber, a method for improving the affinity between the rubber and the inorganic filler by modifying the rubber with aminoguanidine has been disclosed (for example, Patent Document 3). reference).

JP 2010-248334 A JP 2010-209253 A International Publication No. 2015/190519

  However, in the conventional method described in Patent Document 3, although the resulting rubber composition is excellent in low heat build-up, there is still room for improvement in processability. Specifically, such a rubber composition has a fluidity, which is an index of processability before curing the rubber composition, and a curing reaction when stored at room temperature before curing the rubber composition. However, there is still room for improvement with respect to the scorch resistance, which is an index of workability that is difficult to proceed.

  The present invention has been made in view of the above-mentioned problems of the prior art, and provides a novel composition that can provide excellent low heat buildup and processability when it contains an inorganic filler such as silica and rubber. The purpose is to do.

  As a result of intensive studies, the present inventors have found a novel composition capable of obtaining excellent low heat buildup and processability, and have completed the present invention.

That is, the present invention is as follows.
[1]
Compound (A) represented by any one or more of formulas (1) to (3), fatty acid zinc salt and / or aluminum salt (B), natural rubber and / or synthetic rubber (C), inorganic filler ( D), stearic acid (E), zinc oxide (F), sulfur (G), vulcanization accelerator (H), zinc contained in the zinc salt and / or aluminum salt (B) of the fatty acid and The composition whose total content of aluminum is 0.15-1.5 mass part with respect to 1 mass part of said compound (A).
Wherein X is an acid that forms a salt with the guanidine moiety, and R ¹ and R ² are each independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, an alkenyl group. A group (all of these groups are selected from the group consisting of a nitrogen atom, one having at least one substituent containing an oxygen atom) and a hydrogen atom.)
[2]
The composition according to [1], wherein X in the formulas (1) to (3) is carbonic acid.
[3]
The composition according to [1] or [2], wherein the compound (A) is aminoguanidine bicarbonate.
[4]
The fatty acid zinc salt and / or aluminum salt (B) fatty acid is a saturated fatty acid having 10 to 24 carbon atoms and / or an unsaturated fatty acid (all of these fatty acids have a substituent containing a nitrogen atom and an oxygen atom. The composition according to any one of [1] to [3].
[5]
The fatty acid zinc salt and / or aluminum salt (B) fatty acid contains one or more selected from the group consisting of stearic acid, oleic acid, myristic acid, palmitic acid, palmitoleic acid, and linoleic acid The composition according to [4].
[6]
The fatty acid zinc salt and / or aluminum salt (B) is one or two selected from the group consisting of a monofatty acid monozinc salt, a monofatty acid dihydroxyaluminum salt, a difatty acid monohydroxyaluminum salt, and a trifatty acid aluminum salt The composition according to any one of [1] to [5], which contains seeds or more.
[7]
The fatty acid zinc salt and / or aluminum salt (B) is zinc stearate, zinc oleate, zinc myristate, zinc palmitate, zinc palmitate, zinc linoleate, dihydroxyaluminum stearate, hydroxyaluminum distearate, and The composition according to [6], containing one or more selected from the group consisting of aluminum tristearate.
[8]
The composition according to any one of [1] to [7], wherein the inorganic filler (D) contains silica.
[9]
A tire comprising the composition according to any one of [1] to [8].

  The composition according to the present invention is useful as a tire or the like.

  Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

<Composition>
The composition of the present embodiment (hereinafter also referred to as “the composition” or “composition”) is a compound (A) represented by any one or more of formulas (1) to (3) (hereinafter, “ "Compound (A)", "Component (A)", also referred to as "(A)"), fatty acid zinc salt and / or aluminum salt (B) (hereinafter "fatty acid zinc salt and / or aluminum salt", "Compound (B)", "Component (B)", also referred to as "(B)"), natural rubber and / or synthetic rubber (C) (hereinafter "natural rubber and / or synthetic rubber", "compound ( C) ”,“ component (C) ”, also referred to as“ (C) ”), inorganic filler (D) (hereinafter referred to as“ inorganic filler ”,“ compound (D) ”,“ component (D) ”, Also referred to as “(D)”), stearic acid (E) (hereinafter referred to as “stearic acid”, “compound (E)”, “component (E)”, “(E)”) ), Zinc oxide (F) (hereinafter also referred to as “zinc oxide”, “compound (F)”, “component (F)”, “(F)”)), sulfur (G) (hereinafter referred to as “sulfur”). , “Compound (G)”, “component (G)”, also referred to as “(G)”), vulcanization accelerator (H) (hereinafter referred to as “vulcanization accelerator”, “compound (H)”, “ Component (H) "and" (H) "). Moreover, the total content of zinc and aluminum contained in the zinc salt and / or aluminum salt (B) of the fatty acid is 0.15 to 1.5 parts by mass with respect to 1 part by mass of the compound (A).
Wherein X is an acid that forms a salt with the guanidine moiety, and R ¹ and R ² are each independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, an alkenyl group. A group (all of these groups are selected from the group consisting of a nitrogen atom, one having at least one substituent containing an oxygen atom) and a hydrogen atom.)

  The compound (A) of the present embodiment is a compound represented by any one or more of the above formulas (1) to (3) (hereinafter referred to as “aminoguanidine salt”, “alkylideneaminoguanidine salt”, “ Also referred to as “diaminoguanidine salt” or “1,3-diaminoguanidine salt”.

  X in the formulas (1) to (3) may be any acid that forms a salt with a guanidine moiety, and the type thereof is not limited. For example, organic acids (acetic acid, oxalic acid, p-toluenesulfonic acid, phenyl And phosphinic acid) and inorganic acids (hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, sulfuric acid, phosphoric acid, carbonic acid, sulfamic acid, perchloric acid, silicic acid, boric acid, etc.). Among these, carbonic acid is preferable.

  The aminoguanidine salt is preferably aminoguanidine bicarbonate.

R ¹ and R ² are each independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, or an alkenyl group (both of these groups are substituents containing a nitrogen atom or an oxygen atom). And a hydrogen atom, and among these, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkenyl group is preferable, and the number of carbon atoms is 1 It is more preferably an alkyl group of ˜5 or a hydrogen atom, and further preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When the upper limit of the carbon number of R ¹ and R ² is preferably 4 or less, more preferably 3 or less, a more excellent effect can be obtained with respect to the modification application described later. Specific examples of such substituents include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, 1-methylbutyl group, 2 -Methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 2-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, vinyl group, 1- A methyl vinyl group, 1-ethyl vinyl group, 1-propyl vinyl group, 2-methyl vinyl group, 2-ethyl vinyl group, 2-propyl vinyl group and the like can be mentioned. Among these, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, vinyl group, 1-methylvinyl group, 1-ethylvinyl group, 2-methylvinyl group, 2-ethylvinyl group and the like are preferable, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, A tert-butyl group, a vinyl group, a 1-methylvinyl group, a 1-ethylvinyl group, a 2-methylvinyl group, and a 2-ethylvinyl group are more preferable.

  Specific examples of the alkylideneaminoguanidine salt include ethylideneaminoguanidine (salt), propylideneaminoguanidine (salt), butylideneaminoguanidine (salt), 3-methylbutylideneaminoguanidine (salt), and 1-methylethylideneaminoguanidine. (Salt), 1-methylpropylideneaminoguanidine (salt), 1-methylbutylideneaminoguanidine (salt), 1-ethylpropylideneaminoguanidine (salt), 1-isopropyl-2-methylpropylideneaminoguanidine (salt) ), Pentylideneaminoguanidine (salt), 1,3-dimethylbutylideneaminoguanidine (salt), 1,2-dimethylpropylideneaminoguanidine (salt), 1-methylbutylideneaminoguanidine (salt), 1-methyl Pentylidene aminoguanidine (salt) 2-methylpropylideneaminoguanidine (salt), 1-methylhexylideneaminoguanidine (salt), arylideneaminoguanidine (salt), 2-methylarylideneaminoguanidine (salt), 2-butenylideneaminoguanidine ( Salt), 2,6-dimethyl-4-heptylideneaminoguanidine (salt), 2-furylmethylideneaminoguanidine (salt), benzylideneaminoguanidine (salt), 4-dimethylaminophenylmethyleneaminoguanidine (salt), 4-methoxyphenylmethyleneaminoguanidine (salt), 4-hydroxyphenylmethyleneaminoguanidine (salt), 1-phenylethylideneaminoguanidine (salt), 1-methyl-3-phenylarylideneaminoguanidine (salt), diphenylmethyleneamino Guanidine (salt), 1- ( , 4-dihydroxyphenyl) benzylidene aminoguanidine (salt) and the like.

  The content of the compound (A) is preferably 0.15 to 1.5 parts by mass, more preferably 0.7 to 1.3 parts by mass with respect to 100 parts by mass of natural rubber and / or synthetic rubber (C). Part, more preferably 0.9 to 1.1 parts by weight.

  Although it does not specifically limit as a fatty acid zinc salt and / or aluminum salt (B), A well-known saturated fatty acid and unsaturated fatty acid are mentioned. Among these, the fatty acid zinc salt and / or the aluminum salt (B) fatty acid is a saturated fatty acid having 10 to 24 carbon atoms and / or an unsaturated fatty acid (all of these fatty acids contain a nitrogen atom and an oxygen atom). Including one having one or more substituents), containing one or more selected from the group consisting of stearic acid, oleic acid, myristic acid, palmitic acid, palmitoleic acid, and linoleic acid Is more preferable.

  The fatty acid zinc salt and / or aluminum salt (B) is one or two selected from the group consisting of a monofatty acid monozinc salt, a monofatty acid dihydroxyaluminum salt, a difatty acid monohydroxyaluminum salt, and a trifatty acid aluminum salt. Preferably, it contains zinc stearate, zinc oleate, zinc myristate, zinc palmitate, zinc palmitate, zinc linoleate, dihydroxyaluminum stearate, hydroxyaluminum distearate, and aluminum tristearate. It is more preferable to contain 1 type or 2 types or more selected more.

  The total content of zinc and aluminum contained in the zinc salt and / or aluminum salt (B) of the fatty acid is 0.15 to 1.5 parts by mass, preferably 1 part by mass of the compound (A). It is 0.7-1.3 mass parts, More preferably, it is 0.9-1.1 mass parts.

  The content of the compound (B) is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and still more preferably with respect to 100 parts by mass of natural rubber and / or synthetic rubber (C). Is 2-7 parts by mass.

  The composition of this embodiment may further contain a modified rubber produced when natural rubber and / or synthetic rubber (C) reacts with compound (A).

  Although it does not specifically limit as natural rubber which concerns on natural rubber and / or synthetic rubber (C), Any shape of the sheet rubber and block rubber obtained by coagulating and drying natural rubber latex can be used as a raw material. The seat rubber is not particularly limited, but is classified according to the rating of “International Quality Packaging Standards for Natural Rubber Grades” (commonly called Green Book), and the ribbed smoked sheet (RSS) dried with smoke while being smoked, Examples include a crepe obtained by thoroughly washing an air dry sheet (ADS) coagulated product obtained by drying a sheet with water and drying with hot air. In addition to this, TC rubber (Technically Classified Rubber), SP rubber (Super Processing Rubber), MG Examples include rubber, PP crepe, softener, peptizer-added rubber, and the like. Examples of the block rubber include, but are not limited to, Malaysian SMR (Standard Malaysian Rubber), Indonesian SIR, Thailand TTR, Sri Lanka SCR, Singapore SSR, and the like. These natural rubber raw materials may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, you may use the rubber | gum solidified after oxidizing natural rubber latex, and oxidation of natural rubber latex can be performed by a well-known method. For example, as described in JP-A-8-81505, natural rubber latex dissolved in an organic solvent at a rate of 1.0 to 30% by mass is oxidized in air in the presence of a metal-based oxidation catalyst to oxidize natural rubber latex. It can be performed. Further, as described in JP-A-9-136903, oxidation can be carried out by adding a carbonyl compound to natural rubber latex. When air oxidation is performed as an oxidation method, as described in JP-A-9-136903, air oxidation may be performed in the presence of a radical generator in order to promote air oxidation. The radical generator is not particularly limited, but a peroxide radical generator, a redox radical generator, and an azo radical generator are preferably used.

  The synthetic rubber according to natural rubber and / or synthetic rubber (C) is not particularly limited, but 1,4-polybutadiene, 1,2-polybutadiene, 1,4-polyisoprene, 3,4-polyisoprene, styrene butadiene. Examples thereof include diene rubbers having a double bond in the molecule, such as rubber, terminal-modified styrene butadiene rubber, chloroprene rubber, nitrile rubber, ethylene propylene rubber, and ethylene propylene diene rubber.

  In the present embodiment, any of the above-described natural rubber and synthetic rubber may be used. These may be used alone or in combination of two or more.

  The composition of the present embodiment comprises the above compound (A), zinc salt and / or aluminum salt (B) of fatty acid, natural rubber and / or synthetic rubber (C), inorganic filler (D), and stearic acid (E). , Zinc oxide (F), sulfur (G), and vulcanization accelerator (H). Moreover, it is preferable that the temperature at the time of the mixing exists in the range of 20-180 degreeC, and it is more preferable that it exists in the range of 50-160 degreeC.

  The inorganic filler (D) of the present embodiment is an inorganic compound containing at least one selected from silicon, oxides or hydroxides of typical metals or transition metals and hydrates thereof, and carbonates of these metals Point to.

  The inorganic filler (D) is not particularly limited as long as it is an inorganic filler used in the industry. The carbon black described later is not included in the inorganic filler (D) here, and does not hit the inorganic filler (D). Inorganic fillers are roughly classified into reinforcing fillers such as silica having active surfaces and surface-treated clay, and non-reinforcing fillers such as calcium carbonate, clay and talc. Specific examples of the inorganic filler (D) include silica, calcium carbonate, magnesium carbonate, aluminum oxide, aluminum hydroxide, aluminum silicate (clay), magnesium silicate (talc), calcium silicate and the like. The inorganic filler (D) is preferably a reinforcing filler, and more preferably silica. The silica is not particularly limited, and wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid) and the like can be used.

When silica is used, the BET specific surface area is preferably 40 to 350 m ² / g. If the BET specific surface area of silica is in this range, the particle diameter of silica is appropriate, the tensile strength is improved, and the hysteresis loss tends to decrease. The BET specific surface area can be measured according to JIS Z8830: 2013.

  In addition to the inorganic filler (D) described above, carbon black can be added as a filler used in the composition of the present embodiment in order to enhance the reinforcing effect. That is, the filler contains carbon black. Carbon black is a different filler from the inorganic filler (D) and is clearly distinguished from the inorganic filler (D). Although it does not specifically limit as carbon black, The thing of various grades, such as GPF, FEF, SRF, HAF, ISAF, SAF, etc. are mentioned.

  The total content of the inorganic filler (D) and carbon black in the composition of the present embodiment is not particularly limited, but the content that does not deteriorate the workability and provides a sufficient low loss effect or reinforcing effect. The amount is preferably in the range of 5.0 to 100 parts by mass and more preferably in the range of 20 to 80 parts by mass with respect to 100 parts by mass of natural rubber and / or synthetic rubber (C).

  Stearic acid (E) and zinc oxide (F) are not particularly limited, and commercially available products can be used. These also function as vulcanization acceleration aids. These stearic acid (E) and zinc oxide (F) may be used singly or in combination of two or more. Their content is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of natural rubber and / or synthetic rubber (C).

  It is preferable that content of sulfur (G) is 0.1-5.0 mass parts with respect to 100 mass parts of natural rubber and / or synthetic rubber (C), More preferably, 0.5-3. 0 parts by mass. When the sulfur (G) content is 0.1 parts by mass or more, sufficient vulcanization tends to be obtained, and the sulfur (G) content is 5.0 parts by mass or less. There is a tendency that the so-called scorch time is shortened and that the rubber is burnt during kneading.

  The type of the vulcanization accelerator (H) is not particularly limited, but examples thereof include thiazoles such as mercaptobenzothiazole and 2,2′-dibenzothiazolyl disulfide, and N-cyclohexyl-2-benzothiazolylsulfenamide. N, N′-dicyclohexyl-2-benzothiazolylsulfenamide, N′-tert-butyl-2-benzothiazolylsulfenamide and other sulfenamides, and diphenylguanidine and other guanidines. These vulcanization accelerators (H) may be used individually by 1 type, and may be used in combination of 2 or more type. The content is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of natural rubber and / or synthetic rubber (C).

  In the composition of this embodiment, the compound (A), zinc salt and / or aluminum salt (B) of fatty acid, natural rubber and / or synthetic rubber (C), inorganic filler (D), stearic acid (E ), Zinc oxide (F), sulfur (G), vulcanization accelerator (H), as well as a compounding agent usually used in the rubber industry, although not particularly limited, silane coupling agent, anti-aging agent, A softener or the like can be appropriately selected and blended within a range that does not impair the purpose of the present embodiment. As these compounding agents, commercially available products can be suitably used.

  The silane coupling agent is not particularly limited, but bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (3-methyldimethoxysilylpropyl) tetrasulfide, bis ( 2-triethoxysilylethyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-trimethoxysilylpropyl) disulfide, bis (3-triethoxysilylpropyl) trisulfide, 3-hexanoylthiopropyl Triethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, 3-lauroylthiopropyltriethoxysilane, 2-hexanoylthioethyltriethoxysilane 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxysilane, 3-hexanoylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3 -Decanoylthiopropyltrimethoxysilane, 3-lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane, 2-octanoylthioethyltrimethoxysilane, 2-decanoylthioethyltrimethoxysilane, 2- Lauroylthioethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3- Examples include trimethoxysilylpropylbenzothiazolyl tetrasulfide and 3-trimethoxysilylpropylmethacryloyl monosulfide. The content is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the inorganic filler (D).

  The type of anti-aging agent is not particularly limited. For example, naphthylamine, p-phenylenediamine, hydroquinone derivatives, bis, tris, polyphenol, diphenylamine, quinoline, monophenol, thiobisphenol, hindered Phenol-based compounds can be used, and p-phenylenediamine-based and diphenylamine-based amine-based antioxidants are preferable from the viewpoint of further anti-aging effects. Although it does not specifically limit as a diphenylamine type | system | group antioxidant, 4,4'-bis ((alpha) -methylbenzyl) diphenylamine, 4,4'-bis ((alpha), alpha-dimethylbenzyl) diphenylamine, p- (p-toluenesulfonyl) Amido) diphenylamine, di (4-octylphenyl) amine and the like. Among these, 4,4′-bis (α-methylbenzyl) diphenylamine is more preferable from the viewpoint of higher anti-aging effect. The p-phenylenediamine anti-aging agent is not particularly limited, but N, N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N, N'-di 2-naphthyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, N-phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methyl) Pentyl) -p-phenylenediamine, N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, and the like. It is, among these, further a high anti-aging effect and cost, N-(1,3-dimethylbutyl)-N'-phenyl -p- phenylenediamine are more preferred. The content of the anti-aging agent in the composition is preferably 0.1 to 5.0% by mass of the natural rubber and / or the synthetic rubber (C) in the composition.

  The kind of the softener is not particularly limited, and examples thereof include mineral oil-based softeners derived from petroleum and coal tar, vegetable oil-based softeners derived from fatty oils and pine trees, and synthetic resin-based softeners.

<Tire>
The tire according to the present embodiment includes the above composition. Moreover, it is preferable that the said composition is used for the tread of a tire member. A tire using the above composition for a tread is excellent in fuel efficiency. The tire of this embodiment is not particularly limited except that the above composition is used for any of the tire members, and can be produced according to a conventional method. Moreover, as gas with which this tire is filled, inert gas, such as nitrogen, argon, helium other than normal or the air which adjusted oxygen partial pressure, can be used.

  When the composition of this embodiment is a composition containing an inorganic filler such as silica and a tire using the composition, excellent low loss and breaking strength can be obtained.

  Hereinafter, the present embodiment will be described in more detail with reference to examples. However, the present embodiment is not limited to the following examples.

[Example 1]
Synthetic rubber (component (C), trade name “Tuffden E581”, manufactured by Asahi Kasei Co., Ltd.) 137.5 parts by mass (oil extension amount: 37.5 parts by mass with respect to 100 parts by mass of rubber), silica (component (D) , Trade name “ULTRASIL7000GR”, manufactured by Evonik Japan Co., Ltd., BET surface area = 170 m ² / g) 80 parts by mass, silane coupling agent (bis (3-triethoxysilylpropyl) tetrasulfide, manufactured by Evonik Japan Co., Ltd.) 6.4 parts by mass, 3 parts by mass of zinc oxide (component (F), Sakai Chemical Industry, two types of zinc oxide), 2 parts by mass of stearic acid (component (E), manufactured by Wako Pure Chemical Industries, Ltd.), amino bicarbonate 1 part by mass of guanidine (component (A), manufactured by Tokyo Chemical Industry Co., Ltd.) and 4 parts by mass of zinc stearate (component (B), manufactured by Wako Pure Chemical Industries, Ltd.) )east (Made by Seiki Seisakusho) and kneaded for about 7 minutes until the kneading temperature reached 150 ° C. Thereafter, the obtained kneaded material was stored at room temperature for 16 hours or more, and 1.5 parts by mass of sulfur (component (G), trade name “HK200-1” manufactured by Hosoi Chemical Co., Ltd.) and vulcanized As an accelerator (component (H)), N-cyclohexyl-2-benzothiazolylsulfenamide (trade name “Accel CZ”, manufactured by Kawaguchi Chemical Co., Ltd.) 2.0 parts by mass and diphenylguanidine (trade name “Accel”) D ”(manufactured by Kawaguchi Chemical Industry Co., Ltd.) 1.0 part by mass was added and kneaded at 90 ° C. for 5 minutes to prepare an unvulcanized rubber composition. Subsequently, a vulcanized rubber composition was obtained by vulcanization at 160 ° C. and 10 MPa for 20 minutes using a press machine (manufactured by Kitagawa Seiki Co., Ltd.).

[Examples 2-14, Comparative Examples 1-6]
Various unvulcanized rubber compositions and vulcanized rubber compositions were obtained in the same manner as in Example 1 except that the types and amounts of the component (A) and fatty acid salt were changed according to the composition of Table 1. It was. It shows about the component used below.
1,3-dimethylbutylideneaminoguanidine carbonate (Synthesis Example 1 below)
Dihydroxyaluminum stearate (Wako Pure Chemical Industries, Ltd.)
Hydroxy aluminum distearate (Wako Pure Chemical Industries, Ltd.)
Aluminum tristearate (manufactured by Kanto Chemical Co., Inc.)
Zinc oleate (Kanto Chemical Co., Ltd.)
"Stractol A50P" (trade name, manufactured by Schill + Seilacher Co., Ltd., zinc soap of unsaturated fatty acid)
“Stractol EF44” (trade name, manufactured by Schill + Seilacher Co., Ltd., fatty acid derivative mixture mainly composed of zinc soap)
Glycerol stearate (Wako Pure Chemical Industries, Ltd.)
Calcium stearate (Wako Pure Chemical Industries, Ltd.)
Potassium stearate (manufactured by Kanto Chemical Co., Ltd.)

(Synthesis Example 1) Synthesis of 1,3-dimethylbutylideneaminoguanidine carbonate (5) In a 50 mL eggplant-shaped flask, 1.329 g (12 mmol) of aminoguanidine hydrochloride,
After adding 6 mL of methanol and 0.25 mL of 12N hydrochloric acid and stirring at room temperature for 10 minutes, 1.568 g (16 mmol) of methyl isobutyl ketone (MIBK) was added, and the mixture was stirred at room temperature using a magnetic stirring bar. After stirring for 2.5 hours, the reaction solution was saturated 20% aqueous sodium hydrogen carbonate solution.
When it was added dropwise to mL, white crystals were precipitated, which were collected by filtration, washed with water, and vacuum-dried at 50 ° C. for 5 hours to obtain 2.357 g (11 mmol) of a white solid. The obtained solid was analyzed by 1H-NMR and confirmed to be 1,3-dimethylbutylideneaminoguanidine carbonate (1H-N
MR (DMSO-d6,500 MHz, δ; ppm) = 0.8 (d; 6H), 1.8 (s
3H), 1.9 (m; 1H), 2.0 (d; 2H), 5.0-5.6 (br)). The molar yield was 92%. Further, when the melting point was measured using a trace melting point measuring device BY-1 (manufactured by Yazawa Kagaku Co., Ltd.), it was 96 to 97 ° C., and a carbon / hydrogen / nitrogen simultaneous determination device CHN coder MT-6 (Yanako Analytical Industries). Elemental analysis using a calculated value C, 44
. 03; H, 8.31; N, 25.67 vs. measured C, 43.93; H, 8.30;
N, 25.57.

  The obtained unvulcanized rubber composition and vulcanized rubber composition were evaluated for low heat build-up, fluidity and scorch resistance by the following methods. The results are shown in Table 1.

(1) Low exothermicity The above vulcanized rubber composition was subjected to a loss tangent at a temperature of 60 ° C., a strain of 0.5%, and a frequency of 10 Hz using a dynamic viscoelasticity measuring device (DMS6100 manufactured by Seiko Instruments Inc.) tan δ) was measured and expressed as an index with the value of Comparative Example 1 in Table 1 being 100. The smaller the index value, the lower the tan δ, indicating that the rubber composition is less exothermic.

(2) Fluidity Using the Mooney Viscometer (manufactured by Toyo Seiki Seisakusho, AM-4) for the above unvulcanized rubber composition, JIS K 6300-1: 2013 “Unvulcanized rubber—physical properties— In accordance with “Part 1: Determination of viscosity and scorch time by Mooney viscometer”, the minimum viscosity of the unvulcanized rubber composition was measured at 125 ° C. using an L-type rotor. The value of the minimum viscosity Vm of the obtained unvulcanized rubber composition was expressed as an index with the value of Comparative Example 1 in Table 1 being 100. It shows that fluidity | liquidity is so favorable that the value of minimum viscosity Vm is low.

(3) Scorch resistance With respect to the above unvulcanized rubber composition, Mooney Viscometer (manufactured by Toyo Seiki Seisakusho, AM-4) was used, and JIS K 6300-1: 2013 “Unvulcanized rubber—physical properties -In accordance with "Part 1: Determination of viscosity and scorch time by Mooney viscometer", the value after starting preheating rises 5 units from the minimum value Vm under the condition of 125 ° C using an L-type rotor. Time (minutes) Mooney scorch time t5 was measured. The value of t5 of the obtained unvulcanized rubber composition was expressed as an index with the value of Comparative Example 1 in Table 1 being 100. The larger the Mooney scorch time value, the better the processing stability (scorch stability).

In the table, each component of the compounding prescription indicates part by mass. In addition, the content of zinc and / or aluminum in component (B) with respect to 1 part by mass of component (A) is a sample obtained by wet ashing with nitric acid using a microwave decomposition apparatus (Multiwave Pro (8NXF100) manufactured by Anton Paar). Was calculated from the measurement results measured with an inductively coupled plasma emission spectrometer (ICP-AES, manufactured by SPECTRO, ICP emission spectrometer SPECTRO ARCOS).

  From Table 1, the rubber compositions of Examples 1 to 14 are Comparative Examples 1 to 1 in which the total content of zinc and aluminum contained in the zinc salt and / or aluminum salt of the fatty acid relative to the compound (A) is not within the predetermined range. Compared with the rubber composition of No. 6, it was at least confirmed to be excellent in low heat generation, fluidity and scorch resistance.

The following table shows the fatty acid composition of “Strectol A50P” (A50P) and “Strectol EF44” (EF44) used above.
In the table, each fatty acid is represented by mass% relative to the total amount (100 mass%) of the fatty acid. The fatty acid composition was calculated from the area fraction of the peak corresponding to each fatty acid obtained by treating the sample with trimethylsilane chloride and measuring the TMS-modified fatty acid with GC-FID. Here, the mass ratio (composition) of each fatty acid was calculated assuming that the area fraction (%) of each fatty acid peak corresponds to the mass ratio (mass%) of each fatty acid as it is at 1: 1.

  The composition according to the present invention can be used as a material for various tire members including treads.

Claims (9)

Compound (A) represented by any one or more of formulas (1) to (3), fatty acid zinc salt and / or aluminum salt (B), natural rubber and / or synthetic rubber (C), inorganic filler ( D), stearic acid (E), zinc oxide (F), sulfur (G), vulcanization accelerator (H), zinc contained in the zinc salt and / or aluminum salt (B) of the fatty acid and The composition whose total content of aluminum is 0.15-1.5 mass part with respect to 1 mass part of said compound (A).
Wherein X is an acid that forms a salt with the guanidine moiety, and R ¹ and R ² are each independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, an alkenyl group. A group (all of these groups are selected from the group consisting of a nitrogen atom, one having at least one substituent containing an oxygen atom) and a hydrogen atom.)   The composition according to claim 1, wherein X in the formulas (1) to (3) is carbonic acid.   The composition according to claim 1 or 2, wherein the compound (A) is aminoguanidine bicarbonate.   The fatty acid zinc salt and / or aluminum salt (B) fatty acid is a saturated fatty acid having 10 to 24 carbon atoms and / or an unsaturated fatty acid (all of these fatty acids have a substituent containing a nitrogen atom and an oxygen atom. The composition as described in any one of Claims 1-3 including what has one or more.   The fatty acid zinc salt and / or aluminum salt (B) fatty acid contains one or more selected from the group consisting of stearic acid, oleic acid, myristic acid, palmitic acid, palmitoleic acid, and linoleic acid The composition according to claim 4.   The fatty acid zinc salt and / or aluminum salt (B) is one or two selected from the group consisting of a monofatty acid monozinc salt, a monofatty acid dihydroxyaluminum salt, a difatty acid monohydroxyaluminum salt, and a trifatty acid aluminum salt The composition as described in any one of Claims 1-5 containing a seed | species or more.   The fatty acid zinc salt and / or aluminum salt (B) is zinc stearate, zinc oleate, zinc myristate, zinc palmitate, zinc palmitate, zinc linoleate, dihydroxyaluminum stearate, hydroxyaluminum distearate, and The composition according to claim 6, comprising one or more selected from the group consisting of aluminum tristearate.   The composition according to any one of claims 1 to 7, wherein the inorganic filler (D) contains silica.   A tire comprising the composition according to claim 1.