TW201805319A - Anti-aging composition - Google Patents

Abstract

The present invention provides an anti-aging composition comprising a condensation product of at least one of phenol and phenol derivative with at least one carbonyl compound, and an amine anti-aging agent, wherein the total content thereof is 80 to 100% by weight, based on the total weight of the composition.

Description

Anti-aging agent composition

The present invention relates to a composition for preventing aging.

As described in Patent Document 1, in order to prevent aging of the vulcanized rubber composition, it is known to use N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine (alias: N- (1 , 3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, abbreviation: 6PPD) and other amine-based anti-aging agents.

Further, it is described in Patent Document 1 that, as an adhesive, instead of resorcinol, a condensate of resorcinol and acetone can be used. In Reference Examples 1 to 6 of Patent Document 1, natural rubber, N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine, the aforementioned condensate, sulfur, and the like are described. Kneading is performed to vulcanize the obtained rubber composition to produce a vulcanized rubber composition.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-2431

Vulcanized rubber composition, which is sought after aging Physical properties such as tensile strength and elongation at break are well maintained. The present invention is directed to such a subject, and its object is to further improve the aging prevention effect of the conventional amine-based aging prevention agent.

As a result of repeated and careful review by the present inventors in order to achieve the above-mentioned object, it was found that if at least one of a phenol and a phenol derivative and a condensate of at least one of a carbonyl compound and an amine-based aging preventive agent are mixed in advance, The compounding of the agent composition to the rubber component can further improve the effect of preventing aging, as compared with the case where these components are individually formulated to the rubber component. The invention based on this finding is as follows.

[1] An anti-aging agent composition containing a condensate of at least one of a phenol and a phenol derivative and at least one of a carbonyl compound, and an amine-based anti-aging agent, based on the entire composition, the total of these The content is 80 to 100% by weight.

[2] The anti-aging agent composition according to the above [1], wherein a total content of a condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound and an amine-based anti-aging agent is 90 to 100% by weight.

[3] The anti-aging agent composition according to the above [1], which is composed of a condensate of at least one of a phenol and a phenol derivative and at least one of a carbonyl compound, and an amine-based anti-aging agent.

[4] The anti-aging agent composition according to any one of the above [1] to [3], wherein the amine-based anti-aging agent is selected from amine-ketone-based anti-aging agents and aromatic secondary amine-based aging At least one of the groups of preventive agents By.

[5] The anti-aging agent composition according to any one of the above [1] to [3], wherein the amine-based anti-aging agent is an aromatic secondary amine-based anti-aging agent.

[6] The anti-aging agent composition according to any one of the above [1] to [3], wherein the amine-based anti-aging agent is N-alkyl-N'-aryl-p-phenylenediamine-based aging Preventive.

[7] The anti-aging agent composition according to any one of the above [1] to [3], wherein the amine-based anti-aging agent is N-phenyl-N '-(1,3-dimethylbutane ) -P-phenylenediamine.

[8] The anti-aging agent composition according to any one of the above [1] to [7], wherein at least one of phenol and a phenol derivative is selected from resorcinol, phenol, At least one of 4-methylphenol and 4- (1,1,3,3-tetramethylbutyl) phenol.

[9] The anti-aging agent composition according to any one of the above [1] to [7], wherein at least one of the phenol and the phenol derivative is resorcinol.

[10] The aging preventive composition according to any one of the aforementioned [1] to [9], wherein the carbon number of the carbonyl compound is 1 to 4.

[11] The anti-aging agent composition according to any one of the aforementioned [1] to [9], wherein at least one of the carbonyl compounds is acetone, methyl ethyl ketone, formaldehyde, or acetaldehyde.

[12] The aging preventive composition according to any one of the above [1] to [9], wherein at least one of the carbonyl compounds is formaldehyde or acetone.

[13] The anti-aging agent composition according to any one of the above [1] to [9], wherein at least one of the carbonyl compounds is acetone.

[14] The anti-aging agent composition according to any one of the above [1] to [7], wherein the condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound is selected from the group consisting of At least one of the group consisting of a condensate of resorcinol and formaldehyde and a condensate of resorcinol and acetone.

[15] The anti-aging agent composition according to any one of the above [1] to [7], wherein the condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound is m-benzene Condensate of diphenol and acetone.

[16] The anti-aging agent composition according to any one of the above [1] to [15], wherein at least one of a phenol and a phenol derivative and a carbonyl compound are present with respect to 1 part by weight of an amine-based anti-aging agent. The content of at least one of the condensates is 0.5 to 100 parts by weight.

[17] The anti-aging agent composition according to any one of the above [1] to [15], wherein at least one of a phenol and a phenol derivative and a carbonyl compound are present with respect to 1 part by weight of an amine-based anti-aging agent. The content of the condensate of at least one of them is 2.5 to 20 parts by weight.

[18] The anti-aging agent composition according to any one of the above [1] to [15], wherein at least one of a phenol and a phenol derivative and a carbonyl compound are present with respect to 1 part by weight of an amine-based anti-aging agent. The content of the condensate of at least one of them is 4 to 10 parts by weight.

[19] The aging preventive composition according to any one of the aforementioned [1] to [18], wherein a weight average molecular weight of a condensate of at least one of a phenol and a phenol derivative and at least one of a carbonyl compound , From 150 to 50,000.

[20] The aging preventive agent composition according to any one of the above [1] to [18] The weight average molecular weight of the phenol and the condensation product of at least one of the phenol derivative and the carbonyl compound is 200 to 10,000.

[21] A method for producing an aging preventive composition according to any one of the above [1] to [20], comprising: containing at least one of a phenol and a phenol derivative and at least one of a carbonyl compound An amine-based aging preventive agent is added to the solution of the condensate, and then the volatile components of the solution are distilled off.

[22] A method for producing an aging preventive composition according to any one of the above [1] to [20], which comprises: at least one of a phenol and a phenol derivative and a carbonyl compound without a solvent At least one of the condensates is mixed with an amine-based aging preventive agent.

[23] A method for producing a rubber composition, comprising kneading the aging preventive composition according to any one of the above [1] to [20] and a rubber component.

[24] The method for producing a rubber composition according to the above [23], wherein the amount of the anti-aging agent composition is 0.5 to 5 parts by weight based on 100 parts by weight of the rubber component.

[25] The method for producing a rubber composition according to the aforementioned [23], wherein the amount of the anti-aging agent composition is 1 to 4 parts by weight relative to 100 parts by weight of the rubber component.

[26] The method for producing a rubber composition according to any one of [23] to [25], further comprising kneading a sulfur component.

[27] A method for producing a vulcanized rubber composition, comprising vulcanizing a rubber composition obtained by the method for producing a rubber composition described in the above [26].

[28] A rubber composition obtained by kneading the anti-aging agent composition described in any one of the above [1] to [20] and a rubber component.

[29] The rubber composition according to the aforementioned [28], wherein the amount of the anti-aging agent composition is 0.5 to 5 parts by weight relative to 100 parts by weight of the rubber component.

[30] The rubber composition according to the aforementioned [28], wherein the amount of the anti-aging agent composition is 1 to 4 parts by weight relative to 100 parts by weight of the rubber component.

[31] The aging preventive agent composition according to any one of the above [28] to [30], which is obtained by further kneading a sulfur component.

[32] A rubber composition obtained by vulcanizing the rubber composition described in the above [31].

[33] A method for improving aging prevention performance of a vulcanized rubber composition, comprising kneading the aging prevention agent composition according to any one of the above [1] to [20] and a rubber component.

[34] The method for improving the aging prevention performance of the vulcanized rubber composition according to the aforementioned [33], wherein the amount of the aging preventing agent composition is 0.5 to 5 parts by weight relative to 100 parts by weight of the rubber component.

[35] The method for improving the aging prevention performance of the vulcanized rubber composition according to the aforementioned [33], wherein the amount of the aging preventing agent composition is 1 to 4 parts by weight relative to 100 parts by weight of the rubber component.

If using at least one of phenol and phenol derivatives with carbonyl The condensate of at least one of the base compounds and the amine-based aging preventive agent obtained by the aging preventive agent composition of the present invention can further improve the aging preventive performance of the vulcanized rubber composition.

[Aging inhibitor composition]

The anti-aging agent composition of the present invention contains a condensate of at least one of a phenol and a phenol derivative and at least one of a carbonyl compound (hereinafter referred to as a "condensate" for short) and an amine-based anti-aging agent. The anti-aging agent composition of the present invention may contain other additives as long as it does not inhibit the effects of the present invention. The total content of the condensate and the amine-based aging preventive agent is 80 to 100% by weight, and preferably 90 to 100% by weight based on the entire composition. The anti-aging agent composition of the present invention is preferably composed of a condensate and an amine-based anti-aging agent.

[Amine-based anti-aging agent]

The amine-based anti-aging agent may be used alone or in combination of two or more. As the amine-based aging preventive agent, those known in this field can be used, for example, those described in pages 436 to 438 of the Rubber Industry Handbook <Fourth Edition> (published on January 20, 2006 by the Japan Rubber Association).

Examples of the amine-based anti-aging agent include amine-ketone-based anti-aging agents, aromatic secondary amine-based anti-aging agents, and the like. Aromatic secondary amine Examples of the anti-aging agent include N, N'-diarylamine-based anti-aging agents, N, N'-diaryl-p-phenylenediamine-based anti-aging agents, and N-alkyl-N'-aromatics. Base-p-phenylenediamine-based aging preventive, N, N'-dialkyl-p-phenylenediamine-based aging preventive, and the like.

The amine-ketone-based aging preventive agent is, for example, a compound represented by the following formula (III) (hereinafter referred to as "compound (III)") or a polymer thereof.

(式(III)中，R¹表示氫原子或碳數1至10的烷基。R²表示氫原子或碳數1至10的烷氧基。)

(In formula (III), R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ² represents a hydrogen atom or an alkoxy group having 1 to 10 carbon atoms.)

In this specification, an alkyl group includes both a linear alkyl group and a branched alkyl group. Examples of the alkyl group having 1 to 10 carbon atoms in this specification include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, and iso. Amyl, neopentyl, third pentyl, hexyl, heptyl, octyl, 1,1,3,3-tetramethylbutyl (common name: third octyl), nonyl, decyl.

In this specification, an alkoxy group includes both a linear alkoxy group and a branched alkoxy group. In this specification, an alkoxy group having 1 to 10 carbon atoms is, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a second butoxy group, or a third group. Butoxy, pentyloxy, isopentyloxy, Neopentyloxy, tertiary pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy.

Examples of the compound (III) or a polymer thereof include 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (ETMDQ), 2,2,4-trimethyl -1,2-dihydroquinoline, poly (2,2,4-trimethyl-1,2-dihydroquinoline) (for example, "AntioxidantFR" manufactured by Matsubara Industry Co., Ltd.), and the like.

The N, N'-diarylamine-based aging preventive agent includes, for example, a compound represented by the following formula (IV) (hereinafter referred to as "compound (IV)"), and a compound represented by the following formula (V) (Hereinafter referred to as "compound (V)").

(式(IV)中，R³以及R⁴各自獨立表示氫原子、碳數1至10的烷基、α,α-二甲基苯甲基、或可具有一者以上取代基之碳數6至14的芳基磺醯基胺基(Ar-SO₂-NH-基))。

(In formula (IV), R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, α, α-dimethylbenzyl, or a carbon number 6 which may have one or more substituents. To 14 arylsulfonamidoamine (Ar-SO ₂ -NH- group)).

(式(V)中，R⁵表示氫原子或碳數1至10的烷基)。

(In the formula (V), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).

Examples of the aryl group having 6 to 14 carbon atoms in the present specification include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, and 9-anthryl. Examples of the substituent which the aryl group may have include an alkyl group having 1 to 10 carbon atoms.

Examples of the compound (IV) include alkylated diphenylamine, octylated diphenylamine, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine, (p- Tosyl sulfonamide) diphenylamine and the like. Examples of the compound (V) include phenyl-α-naphthylamine.

N, N'-diaryl-p-phenylenediamine-based aging preventive agent, N-alkyl-N'-aryl-p-phenylenediamine-based aging preventive agent, N, N'-dialkyl-p-phenylenediamine The amine-based anti-aging agent can be represented by the following formula (VI).

In the N, N'-diaryl-p-phenylenediamine-based aging preventive agent, R ⁶ and R ⁷ in formula (VI) each independently represent a carbon number of 6 to 14 which may have one or more substituents. Aryl.

In the N-alkyl-N'-aryl-p-phenylenediamine-based aging preventive agent, one of R ⁶ and R ⁷ in formula (VI) represents a carbon number of 1 which may have one or more substituents. Alkyl to 10, the other represents an aryl group having 6 to 14 carbons which may have one or more substituents.

In the N, N'-dialkyl-p-phenylenediamine-based aging preventive agent, R ⁶ and R ⁷ in formula (VI) each independently represent a carbon number of 1 to 10 which may have one or more substituents. alkyl.

In the present specification, the substituent which the alkyl group having 1 to 10 carbon atoms may have, for example, a hydroxy group, a propylene fluorenyloxy group, and a methacryl fluorenyloxy group.

N, N’-diaryl-p-phenylenediamine-based anti-aging agent Examples include N, N'-diphenyl-p-phenylenediamine, N, N'-di-β-naphthyl-p-phenylenediamine, and the like. Examples of the N, N'-dialkyl-p-phenylenediamine-based aging preventive include N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine. Examples of the N-alkyl-N'-aryl-p-phenylenediamine-based aging preventive include N-phenyl-N'-isopropyl-p-phenylenediamine and N-phenyl-N '-( 1,3-dimethylbutyl) -p-phenylenediamine (abbreviation: 6PPD), N-phenyl-N '-(3-methylpropenyloxy-2-hydroxypropyl) -p-phenylenediamine , N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine and the like.

Amine-based anti-aging agent, preferably aromatic secondary amine-based anti-aging agent, more preferably N-alkyl-N'-aryl-p-phenylenediamine-based anti-aging agent, and more preferably N-phenyl -N '-(1,3-dimethylbutyl) -p-phenylenediamine (abbreviation: 6PPD).

[Condensate of at least one of phenol and phenol derivative and at least one of carbonyl compound]

In order to improve the aging prevention effect of an amine-based aging preventive agent, the present invention uses a condensate of at least one of a phenol and a phenol derivative and at least one of a carbonyl compound. The condensate system may be used alone or in combination of two or more.

The condensate may be obtained by using one of phenol and a phenol derivative, or may be obtained by using two or more of these. Similarly, the condensate may be obtained by using one of the carbonyl compounds, or may be obtained by using two or more of the carbonyl compounds.

Phenol derivatives, for example, resorcinol, carbon 1 to 10 alkyl-substituted phenols (for example, 4-methylphenol, 4- (1,1,3,3-tetramethylbutyl) phenol) and the like. Among these, resorcinol is preferred.

At least one of phenol and phenol derivative is preferably selected from the group consisting of resorcinol, phenol, 4-methylphenol, and 4- (1,1,3,3-tetramethylbutyl) phenol At least one of them is more preferably resorcinol.

At least one of the carbonyl compounds, preferably at least one of the carbonyl compounds having 1 to 4 carbon atoms, more preferably acetone, methyl ethyl ketone, formaldehyde or acetaldehyde, and still more preferably formaldehyde or acetone, particularly preferably For acetone.

As a condensate, a commercially available product can be used. The commercially available products include, for example, Penacolite (registered trademark) Resin B-16-S, Penacolite (registered trademark) Resin B-1A, Penacolite (registered trademark) Resin B-18-S, Penacolite (registered trademark) manufactured by INDSPEC Chemical Corporation. (Registered trademark) Resin B-19-S and Penacolite (registered trademark) Resin B-20-S; SUMIKANOL (registered trademark) 620 and SUMIKANOL (registered trademark) 610 manufactured by Taoka Chemical Industry Co., Ltd .; Alnovol PN759 and Alnovol by Allnex Corporation PN760; Elaztobond A-250 manufactured by Schenectady International, Inc., etc.

The condensate can be used, for example, in Japanese Patent Laid-Open No. 56-5476, Japanese Patent Laid-Open No. 10-316735, Japanese Patent Laid-Open No. 2004-2431, Japanese Patent Laid-Open No. 2012-184401, and Japanese Patent Laid-Open No. 2013 -151604 Manufactured by a known method or a method similar thereto.

A condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound, particularly preferably a condensation selected from resorcinol and formaldehyde Preferably, at least one of the group consisting of a condensate of resorcinol and acetone is a condensate of resorcinol and acetone.

The content of the condensate in the aging-preventing agent composition is preferably 0.5 to 100 parts by weight, more preferably 2.5 to 20 parts by weight, and still more preferably 4 to 10 parts by weight based on 1 part by weight of the amine-based anti-aging agent. .

The condensate can be produced by condensing at least one of a phenol and a phenol derivative and at least one of a carbonyl compound in the presence of an acid catalyst, as described in the aforementioned document. The use amount of at least one of the carbonyl compound in the condensation reaction is preferably 1 to 6 mol, more preferably 1.5 to 4 mol, with respect to 1 mol of at least one of the phenol and the phenol derivative.

The acid catalyst may be used singly or in combination of two or more kinds. Examples of acid catalysts include benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid hydrate, oxalic acid, phosphoric acid, metaphosphoric acid, boric trifluoride acid, hydrochloric acid, and sulfuric acid. Among these, p-toluenesulfonic acid, p-toluenesulfonic acid hydrate, hydrochloric acid, and sulfuric acid are preferred. The amount of these acid catalysts used is preferably 0.1 to 10 mol, more preferably 0.5 to 5 mol, relative to 100 mol of at least one of the phenol and the phenol derivative.

As the acid catalyst, a solid acid catalyst can be used. Examples of solid acid catalysts include acid catalysts obtained by modifying carbon, polystyrene, alumina, and the like with sulfuric acid, phosphoric acid, and carboxylic acid, zeolites, and acidic cation exchange resins. When the above-mentioned hydrochloric acid or the like is used as an acid catalyst, neutralization and water washing are necessary after the condensation reaction is stopped. However, when a solid acid catalyst is used, it can be removed by a simple method such as filtration. The filtration temperature of the acid catalyst for removing solids is preferably 15 to 60 ° C.

Among solid acid catalysts, an acidic cation exchange resin is preferred, and a strongly acidic cation exchange resin having a sulfonic acid group (-SO ₃ H) is more preferred.

The acidic cation exchange resin is not particularly limited, and a commercially available product can be used. Specific examples are Amberlyst series (e.g. SC200, SC300, etc.) manufactured by ORGANO Co., Ltd., DIAION series (PK212, PK228) manufactured by Mitsubishi Chemical Co., Ltd., and DOWEX series (e.g. 50W × manufactured by Dow Chemical Co., Ltd.) 2 etc.), Duolite series (for example, C26CH) manufactured by ROHM AND HAAS Co., Ltd., Lewatit series (for example, S2328, K2629, etc.) manufactured by LANXESS, etc., but are not limited to these.

The condensation reaction of at least one of a phenol and a phenol derivative and at least one of a carbonyl compound is usually performed in a solution. When at least one of the carbonyl compounds is used, for example, when a large amount of acetone is used, since acetone acts as a starting material and a solvent, there is no need to use another solvent. In addition, even when at least one of the carbonyl compounds functions as a solvent, a solvent other than a carbonyl compound can be used.

The solvents other than the carbonyl compound may be used alone or in combination of two or more. This solvent is preferably an organic solvent. Examples of the organic solvent other than the carbonyl compound include aliphatic hydrocarbons, aromatic hydrocarbons, and halogen-substituted aromatic hydrocarbons. Specific examples of the aliphatic hydrocarbon include hexane, heptane, octane, and decane. Specific examples of the aromatic hydrocarbon include toluene, xylene, and ethylbenzene. Specific examples of the halogen-substituted aromatic hydrocarbons include chlorobenzene and dichlorobenzene. Among these, an aromatic hydrocarbon is preferable, and toluene or xylene is more preferable. When using organic solvents other than carbonyl compounds At least one of the substances is 1 part by weight, and the amount thereof is preferably 0.5 to 3 parts by weight.

Although the temperature of the condensation reaction varies depending on the starting materials and the solvent used, etc., it is generally 30 to 150 ° C. The progress of the condensation reaction can be confirmed by common analytical methods such as gas chromatography (GC), high performance liquid chromatography (HPLC), and gel permeation chromatography (GPC). While proceeding, determine the end point of the reaction.

The condensation reaction of at least one of phenol and a phenol derivative and at least one of a carbonyl compound can be performed using a batch reactor.

The mixing order of the starting materials (at least one of a phenol and a phenol derivative and at least one of a carbonyl compound) used in a batch reaction with an acid catalyst is not particularly limited. For example, the starting material can be added to the reactor fed with the acid catalyst, or the acid catalyst can be added to the reactor containing the starting material. Further, as the condensation reaction proceeds, at least one of the carbonyl compounds may be added continuously or intermittently.

From the reaction solution after the condensation reaction is stopped, a solid condensate can be obtained by removing volatile starting materials such as acetone and the solvent used as required. The amount of at least one of the remaining phenol and the phenol derivative in the condensate is preferably 5% by weight or less, and more preferably 3% by weight or less.

As described above, the condensate used in the present invention can be produced. This condensate is usually a mixture of a plurality of components. The existence ratio of each component can be confirmed by, for example, gel permeation chromatography (GPC) under conditions described in Examples described later. In addition, the weight average molecular weight of each condensate used in the present invention is, in detail, a molecule having a weight-averaged component contained in one kind of condensate (for example, a condensate of resorcinol and acetone). The amount is preferably 150 to 50,000, and more preferably 200 to 10,000. This weight average molecular weight can also be measured by GPC under the conditions described in the examples.

[Manufacturing method of anti-aging agent composition]

The manufacturing method of the aging preventive composition of this invention is not specifically limited. For example, by adding an amine-based anti-aging agent to a solution containing a condensate, and then distilling off the volatile components of the solution, the anti-aging agent composition of the present invention can be produced. The solution containing the condensate is preferably a reaction solution obtained by stopping the above-mentioned condensation reaction (for example, a solution containing a condensate of resorcinol and acetone, unreacted acetone, and an organic solvent used as required).

Devices used in order to distill off volatile components (for example, acetone and organic solvents as required) include, for example, distillation devices such as batch distillation devices, centrifugal molecular distillation devices, and thin-film distillation devices, Extruder and so on.

The temperature at which the volatile components are distilled off is preferably 0 to 250 ° C, and more preferably 120 to 230 ° C. Distillation can be performed under normal pressure or under reduced pressure. When vacuum distillation is performed, the pressure at this time is preferably 100 kPa or less, and more preferably 50 kPa or less.

In addition, the condensate and the amine-based aging preventive agent can be mixed without a solvent to produce the aging preventive agent composition of the present invention. For example, a condensate and an amine-based aging preventive agent can be melt-mixed. This melt mixing can be performed by stirring the condensate and the amine-based aging preventive agent in a reaction kettle under heating. Moreover, for example, Powders and pellets of chemicals and amine-based anti-aging agents. This kneading can be performed using an extruder.

[Rubber composition and vulcanized rubber composition]

Next, a rubber composition obtained by kneading the aging preventive composition of the present invention and a rubber component will be described. Furthermore, a vulcanized rubber composition obtained by vulcanizing a rubber composition obtained by kneading the aging preventive composition, rubber component, and sulfur component of the present invention will be described.

One or both of the amine-based aging preventive agent and the condensate contained in the aging preventive agent composition may react with rubber components and the like during kneading, and may form other compounds different from these. In addition, one or both of the amine-based aging preventive agent and the condensate contained in the aging preventive agent composition are decomposed during the kneading, and the decomposed product reacts with the rubber component and the like to form a substance different from those. Possibility of other compounds. However, it is practically impossible to directly specify the aforementioned compounds that may be formed in the rubber composition by the structure or characteristics of the current technology for analyzing the solid rubber composition. Accordingly, the scope of this specification and the patent application is to specify the rubber composition as "a rubber composition obtained by kneading an anti-aging agent composition and a rubber component."

The rubber component may be used alone or in combination of two or more. Examples of the rubber component include natural rubber, styrene butadiene copolymer rubber, butadiene rubber, and isoprene rubber. The amount of the anti-aging agent composition of the present invention is preferably 0.5 to 5 parts by weight, and more preferably 1 to 4 parts by weight with respect to 100 parts by weight of the rubber component.

The sulfur component may be used alone or in combination of two or more. Sulfur components include, for example, powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Powder sulfur and insoluble sulfur are preferred. The amount of the sulfur component relative to 100 parts by weight of the rubber component is preferably 1 to 10 parts by weight, and more preferably 2 to 6 parts by weight.

The rubber composition may contain a component other than the aging preventive composition of the present invention, a rubber component, and a sulfur component, for example, a filler, a vulcanization accelerator, a methoxylated methylol melamine resin, an organic cobalt compound, and zinc oxide. Wait.

The filler may be used alone or in combination of two or more. Examples of the filler include carbon black, silicon oxide, talc, clay and the like commonly used in the rubber field. The carbon black is preferably carbon black such as FEF (Fast Extruding Furnace), HAF (High Abrasion Furnace), SAF (Super Abrasion Furnace), and ISAF (Intermediate SAF). Furthermore, a combination of carbon black and silicon oxide is also effective, and a combination of several fillers is also effective. When a filler is used, its amount is not particularly limited, but it is preferably from 10 to 100 parts by weight, and more preferably from 30 to 70 parts by weight based on 100 parts by weight of the rubber component.

The vulcanization accelerator may be used alone or in combination of two or more. Examples of the vulcanization accelerator include a thiazole-based vulcanization accelerator, a sulfenamidine-based vulcanization accelerator, and a guanidine-based vulcanization accelerator described in pages 412 to 413 of the Rubber Industry Handbook <Fourth Edition>. When a vulcanization accelerator is used, the amount is preferably 0.5 to 1 part by weight, and more preferably 0.6 to 0.8 part by weight based on 100 parts by weight of the rubber component.

Methoxylated methylol melamine resin can be used only Use 1 type, or you can use 2 or more types together. Examples of the methoxylated methylolmelamine resin include ter (methoxymethyl) melamine, wood (methoxymethyl) methylolmelamine, and methyl (methoxymethyl) dimethylol. Melamine and the like are commonly used in the rubber industry. When a methoxylated methylolmelamine resin is used, its amount is preferably 0.5 to 5 parts by weight, and more preferably 1 to 3 parts by weight, based on 100 parts by weight of the rubber component.

The organic cobalt compound may be used alone or in combination of two or more. Examples of the organic cobalt compound include organic acid cobalt salts such as cobalt naphthenate and cobalt stearate, and fatty acid cobalt / boron complex compounds (for example, trade name "Manobond C": manufactured by Manchem). The amount of the organic cobalt compound used is determined based on its cobalt content. The cobalt content is preferably 0.1 to 0.4 parts by weight, and more preferably 0.1 to 0.3 parts by weight with respect to 100 parts by weight of the rubber component.

When zinc oxide is used, the amount is preferably 1 to 15 parts by weight, and more preferably 1 to 10 parts by weight based on 100 parts by weight of the rubber component.

Rubber composition is a variety of rubber chemicals commonly used in the rubber industry, for example, it can contain anti-aging agents such as antioxidants, anti-ozone degradants, plasticizers, processing aids, paraffin, oil, stearic acid as required Or one or more types of adhesion-imparting agents. Moreover, the said amine-type aging preventive agent may be mix | blended with the rubber composition, and the aging preventive agent composition of this invention may be mix | blended separately. The amount of these medicines varies depending on the intended use of the rubber composition, but an amount in the range generally used in the rubber industry can be used.

The rubber composition is produced by kneading the anti-aging agent composition of the present invention, a rubber component, and other components (for example, a filler) as required.

In addition to the aforementioned components, a rubber composition obtained by further kneading sulfur components (hereinafter referred to as a "rubber composition containing sulfur components") is preferably prepared by first kneading the rubber components with a filler and the like. (Hereinafter referred to as "step 1"), and then the step of kneading the rubber composition obtained in step 1 and the sulfur component (hereinafter referred to as "step 2") is performed. Further, before step 1 (that is, kneading of the rubber component with a filler, etc.), in order to facilitate processing of the rubber component, a preliminary kneading step of kneading the rubber component may be provided.

The sulfur-containing rubber composition can be produced by kneading the entire amount of the anti-aging agent composition of the present invention with the rubber component of any one of the preliminary kneading step, step 1 or step 2, and the present invention can also be kneaded. The anti-aging agent composition is divided into batches and kneaded with rubber components and the like in at least two steps from the preliminary kneading step to step 2.

In the preparation of zinc oxide, it is preferable to knead with rubber components and the like in step 1. When blending a vulcanization accelerator, it is preferred to knead with a rubber component or the like in step 2. When preparing a peptizing agent, it is preferable to knead with a rubber component and the like in step 1. When the preliminary kneading step is set, it is preferable to knead the entire amount of the peptizing agent with the rubber component in the preliminary kneading step, or to batch the peptizing agent with the rubber component in both the preliminary kneading step and step 1. Perform the mixing.

In step 1 of the mix, you can use, for example, Closed mixers, open kneaders, pressurized kneaders, extruders, injection molding machines, etc. of the Burbury mixer. The discharge temperature of the rubber composition after the kneading in step 1 is preferably 200 ° C or lower, and more preferably 120 to 180 ° C.

For the kneading in step 2, for example, an open roll, a calender, or the like can be used. The kneading temperature (temperature of the rubber composition during kneading) in step 2 is preferably 60 to 120 ° C.

The vulcanized rubber composition can be produced by vulcanizing the rubber composition containing the sulfur component. The vulcanized rubber composition can also be produced by processing the rubber composition containing the sulfur component into a specific shape and vulcanizing the rubber composition.

The vulcanization temperature is preferably 120 to 180 ° C. Those with ordinary knowledge in the technical field can appropriately set the vulcanization time according to the composition of the rubber composition. Vulcanization is usually carried out under normal pressure or pressure.

The rubber composition and the vulcanized rubber composition are useful in the manufacture of various products. The products obtained from the rubber composition and the vulcanized rubber composition include, for example, various parts of tires such as a tread running surface, a base tread, a belt, a carcass, a bead, a sidewall, and a rubber bead covering. In addition, the series of products mentioned above include, for example, automotive shock-absorbing rubbers, hoses, rubber bands, and the like, such as engine brackets, pillar brackets, bushings, and exhaust hangers.

For example, a belt for a tire can be manufactured by coating a strand with a rubber composition. Tasseled ropes are usually used in parallel.

From the viewpoint of adhesion to rubber, a steel wire rope is preferred In order to perform plating treatment with brass, zinc, or an alloy containing nickel or cobalt therein, it is particularly suitable to perform a brass plating treatment. Further particularly suitable is a steel wire rope having a brass plating treatment in which the Cu content in the brass plating is 75% by weight, especially 55 to 70% by weight. There are no restrictions on the twisting structure of the steel rope.

The steel wire rope is covered by a rubber composition, and a plurality of layers can be used. This belt is mainly used as a reinforcing material for the carcass.

Furthermore, the carcass can be manufactured, for example, by extruding the rubber composition so as to conform to the shape of the carcass of the tire, and then attaching it to the carcass fiber rope. The carcass fiber rope is generally used in a state of being arranged in parallel. The carcass fiber rope is preferably a low-cost polyester that has good elastic modulus and fatigue resistance, excellent creep resistance, and good resistance to creep. These can be laminated as one or a plurality of pieces and used as a tire reinforcing material.

A tire can be manufactured using a rubber composition according to a general manufacturing method. For example, a rubber composition is extruded to obtain a tire material, and the tire tire is formed by pasting and molding other tire materials by a conventional method on a tire building machine. This raw tire was heated and pressurized in a vulcanizer to obtain a tire.

By using the aforementioned anti-aging agent composition, the anti-aging performance of the vulcanized rubber composition can be improved. Therefore, the present invention also provides a method comprising kneading the aforementioned anti-aging agent composition and a rubber component to improve the anti-aging performance of the vulcanized rubber composition.

[Example]

Hereinafter, the present invention is exemplified by examples and comparative examples. Specific description will be made, but the present invention is not limited by these.

<GPC>

The solution analysis after the condensation reaction was stopped in the following production examples was performed using GPC under the following conditions.

×150cm)與TOSOH TSKgel Super HZ1000(4.6mm

×150cm)2根接續 Column: TOSOH TSKgel Super HZ2000 (4.6mm

× 150cm) and TOSOH TSKgel Super HZ1000 (4.6mm

× 150cm) 2 pieces

Temperature: 40 ° C

Mobile phase: tetrahydrofuran

Detection: Refractive Index (RI)

Standard: TSKgel Standard Polystyrene

<Production Example 1: Production of an acetone solution containing a condensate of resorcinol and acetone>

A 1,000-ml separable flask equipped with a thermometer, a stirrer, and a condenser was charged with 200 g of an acidic cation exchange resin ("DIAION PK212LH" manufactured by Mitsubishi Chemical Corporation, 50% by weight of water), and the environment inside the flask was replaced with nitrogen. Then, 400 g of acetone was fed and stirred at 50 ° C for 15 minutes. After being stirred and left to stand, acetone was removed by filtration, and the acidic cation exchange resin was washed. Furthermore, the same washing operation using 200 g of acetone was repeated three times to obtain an acidic cation exchange resin having a reduced water content.

Into a 1,000-ml separable flask containing the washed acidic cation exchange resin as described above, 264.0 g (2.39 mol) of resorcinol was fed, and the environment inside the flask was replaced with nitrogen, and then fed into propylene. 418.7 g (7.19 mol) of the ketone was heated to 60 ° C. and stirred at this temperature for 20 hours to perform a condensation reaction. Thereafter, the acidic cation exchange resin was removed by filtration to obtain an acetone solution containing a condensate of resorcinol and acetone. The obtained solution was measured by GPC under the above conditions. Based on the total area of the peaks having a weight average molecular weight of 160 or more, the weight ratio of the area ratio of the peaks (1) having a weight average molecular weight of 160 or more to 480, and the total area of the peaks having a weight average molecular weight of 160 or more was determined. The measurement results of the area ratio of the peak (2) having an average molecular weight of 800 or more and the area ratio of the residual resorcinol are shown below.

Area ratio of the peak (1): 30.8%

Area ratio of resorcinol: 0.8%

Peak (2) area ratio: 15.3%

Weight average molecular weight of the peak (2): 944

Weight average molecular weight of condensate: 536

<Example 1: Production of anti-aging agent composition (1) to (3)>

Using a flask equipped with a stirrer, various amounts of N-phenyl-N '-(1) were dissolved in the acetone solution containing the condensate of resorcinol and acetone obtained in Production Example 1 while stirring at room temperature. , 3-Dimethylbutyl) -p-phenylenediamine (6PPD), the volatiles were removed by thin film distillation at a temperature set to 220 ° C under a reduced pressure of 30 kPa to obtain an anti-aging agent composition (1) Go to (3). The content of 6PPD in the obtained anti-aging agent compositions (1) to (3) is summarized in Table 1.

<Production Example 2: Production of an acetone solution containing a condensate of resorcinol and acetone>

The acetone solution of the condensate obtained in Production Example 1 contained 4.3% by weight of water. 1,000 ml of an acetone solution of the condensate prepared in the same manner as in Production Example 1 was fed into a reaction vessel, and 500 ml of acetone was distilled off by a single distillation, while 1,325 ml of acetone was dropped to the reaction vessel at 10 ml / min Dehydration was performed by distillation. Thereafter, the entire amount of the newly dropped acetone was distilled off. After cooling, 500 ml of acetone was added to the concentrate to produce 1,000 ml of dehydrated acetone solution (water content: 0.58% by weight).

77.5 ml of an acetone solution containing a condensate of resorcinol and acetone obtained in the above dehydration operation was placed in the reaction solution, and an acidic cation exchange resin (manufactured by Mitsubishi Chemical Corporation) was washed in the same manner as in Production Example 1. 15 g of DIAION PK212LH ") was stirred under a nitrogen atmosphere at 20 ° C for 21 hours to perform a condensation reaction. After the condensation reaction for 21 hours, the acidic cation exchange resin was removed by filtration to stop the condensation reaction. The obtained solution was measured by GPC under the above conditions. The area ratio of the peak (1) with a weight average molecular weight of 160 or more and 480 to the total area of the peak with a weight average molecular weight of 160 or more, and The measurement results of the total area of the peaks having a weight average molecular weight of 160 or more, the area ratio of the peaks (2) having a weight average molecular weight of 800 or more, and the area ratio of residual resorcinol are shown below.

Peak (1) area ratio: 18.2%

Area ratio of resorcinol: 0.1%

Peak (2) area ratio: 27.2%

Weight average molecular weight of the peak (2): 1,084

Weight average molecular weight of condensate: 684

<Example 2: Production of anti-aging agent composition (4)>

In the same manner as in Example 1, the acetone solution containing the condensate obtained in Production Example 2 was mixed with 6PPD, and the volatiles were distilled off through a thin film with an evaporation tank temperature of 220 ° C under a reduced pressure of 30 kPa or less to obtain an aging preventive agent. Composition (4). The content of 6PPD in the obtained anti-aging agent composition (4) was 20% by weight. In addition, as a result of analyzing the obtained anti-aging agent composition (4) by the high performance liquid chromatography absolute detection method, the amount of residual resorcinol was 0.05% by weight.

<Production Example 3: Production of Condensate of Resorcinol and Acetone>

A condensate of resorcinol and acetone was obtained in the same manner as in Example 1 except that the volatiles were removed by thin film distillation without using 6PPD.

<Example 3: Production of rubber composition and vulcanized rubber composition>

By using a Banbury mixer (600ml Labo Plastomill from Toyo Seiki), 100 parts by weight of natural rubber (RSS # 1), 55 parts by weight of HAF (made by Asahi Carbon, trade name "Asahi # 70"), and water 10 parts by weight of "Nipsil (registered trademark) AQ" manufactured by Tosoh Silica Co., Ltd., 3 parts by weight of stearic acid, 5 parts by weight of zinc oxide, and 1 part by weight of cobalt naphthenate (cobalt content: 0.06 parts by weight) 2. 2.5 parts by weight of the anti-aging agent composition (1) and 1.5 parts by weight of the anti-aging agent (6PPD) obtained in Example 1 were kneaded at a revolution of a kneader of 50 rpm to obtain a rubber composition (the discharge temperature of the rubber composition). : 150 to 160 ° C). Next, 0.7 parts by weight of a vulcanization accelerator (N, N-dicyclohexyl-2-benzothiazylsulfenamidine, DCBS) and a sulfur component were kneaded in the rubber composition with an open roll. (Insoluble sulfur) 5 parts by weight and methoxylated methylol melamine resin ("SUMIKANOL 507AP" manufactured by Sumitomo Chemical Co., Ltd.) 3 parts by weight (kneading temperature: 60 ° C). The rubber composition obtained by kneading was performed at 145 ° C. Vulcanization treatment to obtain a vulcanized rubber composition.

<Examples 4 to 6: Production of rubber composition and vulcanized rubber composition>

Instead of using the aging preventive agent composition (2) to (4) obtained in Example 1 or 2 in place of the aging preventive agent composition (1) obtained in Example 1, the aging preventive agent composition and aging preventive A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 3 except that the agent (6PPD) was prepared in the amounts described in Table 2.

<Comparative Example 1: Production of rubber composition and vulcanized rubber composition>

In addition to replacing the aging preventive composition (1) obtained in Example 1, 2.5 weight A rubber composition was prepared in the same manner as in Example 3 except that the amount of the compound and 1.5 parts by weight of the antiaging agent (6PPD) were 2.0 parts by weight and 2.0 parts by weight of the condensate obtained in Production Example 3 and the antiaging agent (6PPD). And vulcanized rubber composition.

[Stretching test]

After the vulcanized rubber compositions obtained in Examples 3 to 6 or Comparative Example 1 were left to stand in an air environment at 100 ° C. for 72 hours to promote aging, the tensile strength and elongation at break were measured in accordance with JIS K 6301. The vulcanized rubber composition of Comparative Example 1 had a tensile strength after aging of 11.9 N / mm ² and a breaking elongation after aging of 130%. The respective values are set to 100, and the relative values of the vulcanized rubber compositions of Examples 3 to 6 are shown in Table 2.

As shown in Table 2, although the amount of the resorcinol and acetone condensate in the rubber composition and the amount of the anti-aging agent (6PPD) are the same, the aforementioned condensate and the anti-aging agent are blended into the rubber component separately. In Comparative Example 1, Examples 3 to 6 in which a pre-manufactured aging preventive agent composition was blended with a rubber component were used to increase the tensile strength and elongation at break of the vulcanized rubber composition after aging. From this result, it can be seen that the effect of the anti-aging agent can be improved by blending the pre-made anti-aging agent composition to the rubber component, as compared with the case where the aforementioned condensate and anti-aging agent are separately formulated to the rubber component.

[Industrial availability]

The anti-aging agent composition of the present invention is used for producing rubber products having excellent anti-aging properties.

This case is based on Japanese Patent Application No. 2016-062135, the entire contents of which are included in the description of this case.

Claims (17)

An anti-aging agent composition containing a condensate of at least one of a phenol and a phenol derivative and at least one of a carbonyl compound, and an amine-based anti-aging agent, based on the entire composition, the total content of which is 80 Up to 100% by weight. The anti-aging agent composition according to item 1 of the scope of application for a patent, wherein the amine-based anti-aging agent is an N-alkyl-N'-aryl-p-phenylenediamine-based anti-aging agent. The aging-preventing agent composition according to item 1 of the scope of application, wherein the amine-based aging-preventing agent is N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine. The anti-aging agent composition according to any one of claims 1 to 3, wherein at least one of the phenol and the phenol derivative is resorcinol. The aging preventive agent composition according to any one of claims 1 to 4, wherein the carbon number of the carbonyl compound is 1 to 4. The aging preventive agent composition according to any one of claims 1 to 4, wherein at least one of the carbonyl compounds is acetone, methyl ethyl ketone, formaldehyde, or acetaldehyde. The aging preventive composition according to any one of claims 1 to 3, wherein the condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound is selected from m-phenylene At least one of the group consisting of a condensate of phenol and formaldehyde and a condensate of resorcinol and acetone. Anti-aging agent as described in any one of claims 1 to 7 The composition contains 0.5 to 100 parts by weight of a condensate of at least one of a phenol and a phenol derivative and at least one of a carbonyl compound with respect to 1 part by weight of an amine-based aging preventive agent. A method for producing an aging preventive agent composition, which is the method for producing an aging preventive agent composition according to any one of claims 1 to 8, including: containing at least one of a phenol and a phenol derivative and a carbonyl group; An amine-based aging preventive agent is added to a solution of a condensate of at least one of the compounds, and then the volatile component of the solution is distilled off. A method for producing an anti-aging agent composition, which is the method for producing an anti-aging agent composition according to any one of claims 1 to 8 in the scope of patent application, comprising: in the absence of a solvent, at least phenol and a phenol derivative A condensate of one of them and at least one of a carbonyl compound is mixed with an amine-based aging preventive agent. A method for manufacturing a rubber composition, comprising: kneading the anti-aging agent composition described in any one of claims 1 to 8 and a rubber component. The method for manufacturing a rubber composition according to item 11 of the scope of patent application, further comprising: kneading the sulfur component. A method for manufacturing a vulcanized rubber composition, comprising: vulcanizing a rubber composition obtained by the method for manufacturing a rubber composition described in item 12 of the scope of patent application. A rubber composition obtained by kneading the aging preventive composition and the rubber component described in any one of claims 1 to 8 of the scope of patent application. The rubber composition according to item 14 of the scope of patent application, which is obtained by further kneading the sulfur component. A rubber composition obtained by vulcanizing the rubber composition described in item 15 of the scope of patent application. A method for improving the aging prevention performance of a vulcanized rubber composition, comprising: kneading the aging prevention agent composition described in any one of claims 1 to 8 and a rubber component.