WO2017164293A1 - Anti-aging agent composition - Google Patents

Abstract

The present invention provides an anti-aging agent composition containing: a condensation product of at least one of phenol and a phenol derivative and at least one carbonyl compound; and an amine-based anti-aging agent. The total content of the aforementioned ingredients is 80 to 100 wt% in terms of the entire composition.

Description

Anti-aging composition

The present invention relates to an antiaging composition.

As described in Patent Document 1, in order to prevent aging of a vulcanized rubber composition, N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine (also known as N- ( It is known to use amine-based anti-aging agents such as 1,3-dimethylbutyl) -N′-phenyl-p-diaminobenzene (abbreviation: 6PPD).

Further, Patent Document 1 describes that a condensate of resorcin and acetone or the like is used as an adhesive instead of resorcin. In Reference Examples 1 to 6 of Patent Document 1, natural rubber, N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine, the condensate, sulfur and the like are kneaded to obtain a rubber It describes that a vulcanized rubber composition is produced by vulcanizing the composition.

JP 2004-2431 A

Vulcanized rubber compositions are required to maintain good physical properties such as tensile strength and elongation at break even after aging. The present invention has been made paying attention to such circumstances, and an object thereof is to further improve the anti-aging effect of a conventional amine anti-aging agent.

As a result of intensive studies by the present inventors in order to achieve the above object, a condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound and an amine anti-aging agent were obtained in advance. It has been found that if the anti-aging composition is blended with the rubber component, the anti-aging effect can be further improved as compared with the conventional case where these are individually blended with the rubber component. The present invention based on this finding is as follows.

[1] Containing a condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound, and an amine-based antioxidant, and the total content thereof is 80 to 100% by weight based on the whole composition An anti-aging composition.

[2] The antiaging composition according to the above [1], wherein the 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 type antiaging agent is 90 to 100% by weight. object.
[3] The antioxidant composition according to [1], comprising a condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound and an amine-based antioxidant.

[4] Any of the above-mentioned [1] to [3], wherein the amine-based anti-aging agent is at least one selected from the group consisting of an amine-ketone-based anti-aging agent and an aromatic secondary amine-based anti-aging agent. The anti-aging composition as described in one.
[5] The anti-aging composition according to any one of [1] to [3], wherein the amine-based anti-aging agent is an aromatic secondary amine-based anti-aging agent.
[6] The antioxidant composition according to any one of [1] to [3], wherein the amine antioxidant is an N-alkyl-N′-aryl-p-phenylenediamine antioxidant. .
[7] The aging prevention according to any one of the above [1] to [3], wherein the amine-based antioxidant is N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine. Agent composition.

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

[10] The antioxidant composition according to any one of [1] to [9], wherein the carbonyl compound has 1 to 4 carbon atoms.
[11] The antioxidant composition according to any one of [1] to [9], wherein at least one of the carbonyl compounds is acetone, methyl ethyl ketone, formaldehyde, or acetaldehyde.
[12] The antioxidant composition according to any one of [1] to [9], wherein at least one of the carbonyl compounds is formaldehyde or acetone.
[13] The antioxidant composition according to any one of [1] to [9], wherein at least one of the carbonyl compounds is acetone.

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

[16] The content of the condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound is 0.5 to 100 parts by weight with respect to 1 part by weight of the amine-based antioxidant. The antiaging composition according to any one of to [15].
[17] The content of the condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound is 2.5 to 20 parts by weight with respect to 1 part by weight of the amine-based antioxidant. The antiaging composition according to any one of to [15].
[18] The content of [1] to [1] above, wherein the content of the condensate of at least one of phenol and a phenol derivative and at least one of the carbonyl compounds is 4 to 10 parts by weight with respect to 1 part by weight of the amine-based antioxidant. 15] The antiaging composition according to any one of [15].

[19] The aging according to any one of [1] to [18], wherein the condensate of at least one of phenol and a phenol derivative and at least one of the carbonyl compounds has a weight average molecular weight of 150 to 50,000. Inhibitor composition.
[20] The aging according to any one of [1] to [18], wherein the condensate of at least one of phenol and a phenol derivative and at least one of the carbonyl compounds has a weight average molecular weight of 200 to 10,000. Inhibitor composition.

[21] The above [1], comprising adding an amine-based antioxidant to a solution containing a condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound, and then distilling off a volatile component of the solution. A process for producing an antiaging composition according to any one of [20] to [20].
[22] Any one of the above [1] to [20], which comprises mixing a condensate of at least one of phenol and a phenol derivative with at least one of a carbonyl compound and an amine anti-aging agent in the absence of a solvent. The manufacturing method of the anti-aging agent composition as described in any one of.

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

[24] The method according to [23], wherein the amount of the anti-aging composition is 0.5 to 5 parts by weight with respect to 100 parts by weight of the rubber component.
[25] The method according to [23], wherein the amount of the antioxidant composition is 1 to 4 parts by weight with respect to 100 parts by weight of the rubber component.

[26] The method 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 according to [26].

[28] A rubber composition obtained by kneading the antioxidant composition according to any one of [1] to [20] and a rubber component.

[29] The rubber composition according to [28], wherein the amount of the anti-aging composition is 0.5 to 5 parts by weight with respect to 100 parts by weight of the rubber component.
[30] The rubber composition according to [28], wherein the amount of the anti-aging composition is 1 to 4 parts by weight with respect to 100 parts by weight of the rubber component.

[31] The rubber composition according to any one of [28] to [30], obtained by further kneading a sulfur component.
[32] A vulcanized rubber composition obtained by vulcanizing the rubber composition according to [31].

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

[34] The method according to [33], wherein the amount of the anti-aging composition is 0.5 to 5 parts by weight with respect to 100 parts by weight of the rubber component.
[35] The method according to [33], wherein the amount of the antioxidant composition is 1 to 4 parts by weight with respect to 100 parts by weight of the rubber component.

By using the anti-aging composition of the present invention obtained by previously mixing a condensate of at least one of phenol and a phenol derivative with at least one of a carbonyl compound and an amine-based anti-aging agent, the vulcanized rubber composition The anti-aging performance can be further improved.

[Anti-aging agent composition]
The anti-aging composition of the present invention contains a condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound (hereinafter sometimes abbreviated as “condensate”) and an amine-based anti-aging agent. The antioxidant composition of the present invention may contain other additives as long as the effects of the present invention are not impaired. The total content of the condensate and the amine type anti-aging agent is 80 to 100% by weight, preferably 90 to 100% by weight, based on the whole composition. The anti-aging composition of the present invention is more preferably composed of a condensate and an amine-based anti-aging agent.

[Amine-based anti-aging agent]
Only 1 type may be used for an amine type anti-aging agent, and 2 or more types may be used together. As the amine-based anti-aging agent, those known in the art, for example, described in pages 436 to 438 of Rubber Industry Handbook <Fourth Edition> (issued by the Japan Rubber Association on January 20, 1994). You can use what you have.

Examples of the amine anti-aging agent include amine-ketone anti-aging agents and aromatic secondary amine anti-aging agents. Examples of the aromatic secondary amine type anti-aging agent include N, N′-diarylamine type anti-aging agent, N, N′-diaryl-p-phenylenediamine type anti-aging agent, and N-alkyl-N′—. Examples thereof include aryl-p-phenylenediamine-based antioxidants and N, N′-dialkyl-p-phenylenediamine-based antioxidants.

Examples of amine-ketone aging inhibitors include, for example, formula (III):

(In the 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.)
Or a polymer thereof (hereinafter sometimes abbreviated as “compound (III)”).

In the present specification, the alkyl group includes both a linear alkyl group and a branched alkyl group. In the present specification, examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and an isopentyl group. , Neopentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, 1,1,3,3-tetramethylbutyl group (common name: tert-octyl group), nonyl group and decyl group.

In the present specification, the alkoxy group includes both a linear alkoxy group and a branched alkoxy group. In the present specification, examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, Examples include isopentyloxy group, neopentyloxy group, tert-pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group and decyloxy group.

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, “Antioxidant FR” manufactured by Matsubara Sangyo Co., Ltd.).

Examples of the N, N′-diarylamine anti-aging agent include the formula (IV):

(In Formula (IV), R ³ and R ⁴ may each independently have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an α, α-dimethylbenzyl group, or one or more substituents. Represents a good arylsulfonylamino group having 6 to 14 carbon atoms (Ar—SO ₂ —NH— group).
A compound represented by formula (hereinafter sometimes referred to as “compound (IV)”), and formula (V):

(In formula (V), R ⁵ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
(Hereinafter sometimes abbreviated as “compound (V)”).

In the present specification, examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, and a 9-anthryl group. Examples of the substituent that 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-toluenesulfonylamide) diphenylamine, and the like. Examples of compound (V) include phenyl-α-naphthylamine.

N, N'-diaryl-p-phenylenediamine anti-aging agent, N-alkyl-N'-aryl-p-phenylenediamine anti-aging agent, N, N'-dialkyl-p-phenylenediamine anti-aging agent Can be represented by the following formula (VI).

In the N, N′-diaryl-p-phenylenediamine anti-aging agent, R ⁶ and R ⁷ in the formula (VI) each independently have 6 to 6 carbon atoms which may have one or more substituents. 14 aryl groups are represented.
In the N-alkyl-N′-aryl-p-phenylenediamine anti-aging agent, one of R ⁶ and R ^{7 in} the formula (VI) may have one or more substituents having 1 to 1 carbon atoms. 10 represents an alkyl group, and the other represents an aryl group having 6 to 14 carbon atoms which may have one or more substituents.
In the N, N′-dialkyl-p-phenylenediamine anti-aging agent, R ⁶ and R ⁷ in the formula (VI) each independently have 1 or more carbon atoms optionally having one or more substituents. Represents 10 alkyl groups.

In the present specification, examples of the substituent that the alkyl group having 1 to 10 carbon atoms may have include a hydroxy group, an acryloxy group, and a methacryloxy group.

Examples of N, N′-diaryl-p-phenylenediamine antioxidants include N, N′-diphenyl-p-phenylenediamine and N, N′-di-β-naphthyl-p-phenylenediamine. be able to. Examples of the N, N'-dialkyl-p-phenylenediamine anti-aging agent include N, N'-di (1,4-dimethylpentyl) -p-phenylenediamine. Examples of N-alkyl-N′-aryl-p-phenylenediamine antioxidants include N-phenyl-N′-isopropyl-p-phenylenediamine and N-phenyl-N ′-(1,3-dimethylbutyl). ) -P-phenylenediamine (abbreviation: 6PPD), N-phenyl-N '-(3-methacryloxy-2-hydroxypropyl) -p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p -Phenylenediamine etc. can be mentioned.

The amine-based anti-aging agent is preferably an aromatic secondary amine-based anti-aging agent, more preferably an N-alkyl-N′-aryl-p-phenylenediamine-based anti-aging agent, and even more preferably an N— Phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine (abbreviation: 6PPD).

[Condensation product of at least one of phenol and phenol derivatives and at least one of carbonyl compounds]
The present invention is characterized by using a condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound in order to improve the anti-aging effect of the amine-based anti-aging agent. Only 1 type may be used for a condensate and it may use 2 or more types together.

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

Examples of the phenol derivative include resorcin, phenol substituted with an alkyl group having 1 to 10 carbon atoms (eg, 4-methylphenol, 4- (1,1,3,3-tetramethylbutyl) phenol), and the like. It is done. Of these, resorcin is preferred.

At least one of the phenol and the phenol derivative is preferably at least one selected from the group consisting of resorcin, phenol, 4-methylphenol and 4- (1,1,3,3-tetramethylbutyl) phenol, More preferably, it is resorcin.

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

Commercial products can be used as the condensate. Examples of such commercially available products include ス ペ ッ ク Penacolite (registered trademark) Resin B-16-S, Penacolite (registered trademark) Resin B-1A, Penacolite (registered trademark) Resin B-18-S, Penacolite (India Spec 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 .; manufactured by Allnex Examples include Alnovol PN759 and Alnovol PN760; Slazectady International, Inc.'s Elaztobond A-250.

Examples of the condensate are described in, for example, JP-A No. 56-5476, JP-A No. 10-316735, JP-A No. 2004-2431, JP-A No. 2012-184401, JP-A No. 2013-151604, and the like. That are produced by a known method as described above or a method analogous thereto.

The condensate of at least one of phenol and phenol derivative and at least one of carbonyl compounds is particularly preferably at least one selected from the group consisting of a condensate of resorcin and formaldehyde and a condensate of resorcin and acetone, Preferably, it is a condensate of resorcin and acetone.

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

The condensate can be produced by condensing at least one of phenol and a phenol derivative and at least one of a carbonyl compound in the presence of an acid catalyst, as described in the above-mentioned literature. The amount of at least one carbonyl compound used in the condensation reaction is preferably 1 to 6 mol, more preferably 1.5 to 4 mol, based on 1 mol of phenol and phenol derivatives.

The acid catalyst may be used alone or in combination of two or more. Examples of the acid catalyst include benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid hydrate, oxalic acid, phosphoric acid, polyphosphoric acid, boron trifluoride, hydrochloric acid, sulfuric acid and the like. Of these, p-toluenesulfonic acid, p-toluenesulfonic acid hydrate, hydrochloric acid and sulfuric acid are preferred. The amount of these acid catalysts used is preferably from 0.1 to 10 mol, more preferably from 0.5 to 5 mol, based on at least one 100 mol of phenol and phenol derivatives.

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

Among the solid acid catalysts, an acidic cation exchange resin is preferable, and a strong acidic cation exchange resin having a sulfo group (—SO ₃ H) is more preferable.

The acidic cation exchange resin is not particularly limited, and a commercially available product can be used. Specific examples include Ambalist series manufactured by Organo Corporation (for example, SC200 and SC300), Diaion Series manufactured by Mitsubishi Chemical Corporation (PK212, PK228), DOWEX Series manufactured by Dow Chemical Co., Ltd. (for example, 50W × 2), Rohm & Haas Co., Ltd. duolite series (for example, C26CH), LANXESS Co., Ltd. Levacit series (for example, S2328, K2629, etc.), etc., but are not limited thereto.

The condensation reaction between at least one of phenol and a phenol derivative and at least one of a carbonyl compound is usually performed in a solution. For example, when a large amount of acetone is used as at least one of the carbonyl compounds, it is not necessary to use another solvent because acetone acts as a starting material and a solvent. Even when at least one of the carbonyl compounds acts as a solvent, a solvent other than the carbonyl compound may be used.

Only one type of solvent other than the carbonyl compound may be used, or two or more types may be used in combination. As this solvent, an organic solvent is preferable. Examples of organic solvents other than carbonyl compounds include aliphatic hydrocarbons, aromatic hydrocarbons, halogen-substituted aromatic hydrocarbons, and the like. Specific examples of the aliphatic hydrocarbon include hexane, heptane, octane, decane and the like. Specific examples of the aromatic hydrocarbon include toluene, xylene, ethylbenzene and the like. Specific examples of the halogen-substituted aromatic hydrocarbon include chlorobenzene and dichlorobenzene. Of these, aromatic hydrocarbons are preferable, and toluene or xylene is more preferable. When an organic solvent other than the carbonyl compound is used, the amount is preferably 0.5 to 3 parts by weight with respect to at least 1 part by weight of phenol and a phenol derivative.

The temperature of the condensation reaction is generally 30 to 150 ° C., although it varies depending on the starting material and the solvent used if necessary. The progress of the condensation reaction can be confirmed by ordinary analytical means such as gas chromatography (GC), high performance liquid chromatography (HPLC), gel permeation chromatography (GPC), etc. while confirming the progress of the reaction, The reaction end point can be determined.

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

The mixing order of the starting material (at least one of phenol and phenol derivative and at least one of carbonyl compound) to the batch reactor and the acid catalyst is not particularly limited. For example, the starting material may be added to the reactor charged with the acid catalyst, and conversely, the acid catalyst may be added to the reactor containing the starting material. As the condensation reaction proceeds, at least one of the carbonyl compounds may be added continuously or intermittently.

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

As described above, the condensate used in the present invention can be produced. This condensate is often obtained as a mixture of many components. The abundance ratio of each component can be confirmed by, for example, gel permeation chromatography (GPC) under the conditions described in the examples described later. In addition, the weight average molecular weight of each condensate used in the present invention, specifically, the molecular weight by weight average of components contained in one type of condensate (for example, a condensate of resorcin and acetone) is preferably 150 to 50. , 000, more preferably 200 to 10,000. This weight average molecular weight can also be measured by GPC under the conditions described in the Examples.

[Method for producing anti-aging composition]
The manufacturing method of the antioxidant composition of the present invention is not particularly limited. For example, the antioxidant composition of the present invention may be produced by adding an amine-based antioxidant to a solution containing the condensate and then distilling off the volatile components of the solution. As a solution containing a condensate, a reaction solution obtained after stopping the above-mentioned condensation reaction (for example, a solution containing a condensate of resorcin and acetone, unreacted acetone and an organic solvent used as necessary) Is preferred.

As an apparatus used for distilling off volatile components (for example, acetone and an organic solvent used as necessary), for example, a distillation apparatus such as a batch distillation apparatus, a centrifugal molecular distillation apparatus, a thin film distillation apparatus, Examples include a devolatilizing extruder.

The temperature at which the volatile component is distilled off is preferably 0 to 250 ° C, more preferably 120 to 230 ° C. Distillation may be performed under normal pressure or under reduced pressure. When performing distillation under reduced pressure, the pressure at that time is preferably 100 kPa or less, more preferably 50 kPa or less.

Further, the anti-aging composition of the present invention may be produced by mixing the condensate and the amine-based anti-aging agent in the absence of a solvent. For example, the condensate and the amine-based antioxidant may be melt mixed. This melt mixing can be performed by stirring the condensate and the amine anti-aging agent in a reaction kettle while heating. Further, for example, powders or pellets of a condensate and an amine antioxidant may be kneaded. This kneading can be performed using an extruder.

[Rubber composition and vulcanized rubber composition]
Next, the rubber composition obtained by kneading the antioxidant composition of the present invention and the rubber component will be described. Furthermore, the vulcanized rubber composition obtained by vulcanizing the rubber composition obtained by kneading the antioxidant composition, rubber component and sulfur component of the present invention will be described.

One or both of the amine-based anti-aging agent and the condensate contained in the anti-aging composition may react with a rubber component or the like during kneading to form a compound different from these. In addition, one or both of the amine-based anti-aging agent and the condensate contained in the anti-aging composition may be decomposed during kneading, and this decomposition product may react with a rubber component or the like to form another compound. is there. However, it is practically impossible with current techniques for analyzing solid rubber compositions to directly identify the compounds that may be formed in a rubber composition by their structure or properties. Therefore, in the present specification and claims, the rubber composition is specified as “a rubber composition obtained by kneading an anti-aging composition and a rubber component”.

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

Only one type of sulfur component may be used, or two or more types may be used in combination. Examples of the sulfur component include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and highly dispersible sulfur. Powdered sulfur and insoluble sulfur are preferred. The amount of the sulfur component is preferably 1 to 10 parts by weight and more preferably 2 to 6 parts by weight with respect to 100 parts by weight of the rubber component.

The rubber composition contains the anti-aging composition of the present invention, components other than the rubber component and the sulfur component, for example, a filler, a vulcanization accelerator, a methoxylated methylol melamine resin, an organic cobalt compound, zinc oxide, and the like. Also good.

充填 Only 1 type of filler may be used, or 2 or more types may be used in combination. Examples of the filler include carbon black, silica, talc, and clay that are usually 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), ISAF (Intermediate A SAF). It is also effective to combine several kinds of fillers such as a combination of carbon black and silica. When the filler is used, the amount thereof is not particularly limited, but is preferably 10 to 100 parts by weight, more preferably 30 to 70 parts by weight with respect to 100 parts by weight of the rubber component.

Only one type of vulcanization accelerator may be used, or two or more types may be used in combination. Examples of vulcanization accelerators include thiazole vulcanization accelerators, sulfenamide vulcanization accelerators, and guanidine vulcanization accelerators described in pages 412 to 413 of Rubber Industry Handbook <Fourth Edition>. Is mentioned. When a vulcanization accelerator is used, the amount thereof is preferably 0.5 to 1 part by weight and more preferably 0.6 to 0.8 part by weight with respect to 100 parts by weight of the rubber component.

Only one kind of methoxylated methylol melamine resin may be used, or two or more kinds may be used in combination. Examples of the methoxylated methylol melamine resin include those usually used in the rubber industry such as hexakis (methoxymethyl) melamine, pentakis (methoxymethyl) methylol melamine, and tetrakis (methoxymethyl) dimethylol melamine. . When a methoxylated methylol melamine resin is used, the amount thereof is preferably 0.5 to 5 parts by weight and more preferably 1 to 3 parts by weight with respect to 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 Corporation). The amount of the organic cobalt compound used is determined based on the 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 thereof is preferably 1 to 15 parts by weight and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the rubber component.

The rubber composition includes various rubber chemicals commonly used in the rubber industry, for example, anti-aging agents such as antioxidants and ozone degradation inhibitors, peptizers, processing aids, waxes, oils, stearic acid, You may contain 1 type, or 2 or more types, such as a tackifier, as needed. Moreover, you may mix | blend the amine type anti-aging agent mentioned above with the rubber composition separately from the anti-aging agent composition of this invention. The amount of these chemicals varies depending on the intended use of the rubber composition, but each can be used in an amount normally used in the rubber industry.

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

In addition to the above-described components, a rubber composition obtained by further kneading a sulfur component (hereinafter sometimes referred to as “a rubber composition containing a sulfur component”) first comprises a rubber component and a filler. A step of kneading (hereinafter sometimes abbreviated as “step 1”), and then a step of kneading the rubber composition obtained in step 1 and a sulfur component (hereinafter also abbreviated as “step 2”). It is preferable to manufacture via. Further, a pre-kneading step of kneading the rubber component may be provided before the step 1 (that is, kneading the rubber component with a filler or the like) to facilitate processing of the rubber component.

In the production of a rubber composition containing a sulfur component, the entire amount of the anti-aging composition of the present invention may be kneaded with a rubber component or the like in either the preliminary kneading step, step 1 or step 2, The anti-aging composition may be divided and kneaded with a rubber component or the like in at least two steps of the preliminary kneading step to step 2.

When blending zinc oxide, it is preferable to knead with a rubber component or the like in step 1. When a vulcanization accelerator is blended, it is preferably kneaded with a rubber component or the like in step 2. When blending a peptizer, it is preferable to knead with a rubber component or the like in step 1. When providing the preliminary kneading step, it is preferable to knead the entire amount of the peptizer in the preliminary kneading step or to separate the peptizer and knead the rubber component in both the preliminary kneading step and step 1. .

For the kneading in Step 1, for example, an internal mixer including a Banbury mixer, an open kneader, a pressure kneader, an extruder, an injection molding machine, or the like can be used. The discharge temperature of the rubber composition after kneading in step 1 is preferably 200 ° C. or less, more preferably 120 to 180 ° C.

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

A vulcanized rubber composition can be produced by vulcanizing a rubber composition containing the above-described sulfur component. You may manufacture a vulcanized rubber composition by processing the rubber composition containing the above-mentioned sulfur component into a specific shape and then vulcanizing it.

The vulcanization temperature is preferably 120 to 180 ° C. A person skilled in the art can appropriately set the vulcanization time according to the composition of the rubber composition. Vulcanization is usually carried out at normal pressure or under pressure.

The rubber composition and the vulcanized rubber composition are useful for producing various products. Examples of products obtained from the rubber composition and the vulcanized rubber composition include various members of tires such as a cap tread, an under tread, a belt, a carcass, a bead, a sidewall, and a rubber chafer. Examples of the product include vibration-proof rubbers for automobiles such as engine mounts, strut mounts, bushes, and exhaust hangers, hoses, rubber belts, and the like.

For example, a tire belt can be manufactured by coating a steel cord with a rubber composition. Steel cords are usually used in a state of being aligned in parallel.

From the viewpoint of adhesion to rubber, the steel cord is preferably plated with brass, zinc, or an alloy containing nickel or cobalt, and is preferably subjected to brass plating. is there. Furthermore, a steel cord subjected to brass plating in which the Cu content in the brass plating is 75 wt% or less, particularly 55 to 70 wt%, is suitable. The twist structure of the steel cord is not limited.

A plurality of belts in which steel cords are coated with a rubber composition may be used. This belt is mainly used as a reinforcing material for carcass.

Also, for example, the carcass can be manufactured by extruding a rubber composition in accordance with the carcass shape of the tire and attaching the rubber composition on the upper and lower sides of the carcass fiber cord. The carcass fiber cord is usually used in a state of being aligned in parallel. As the carcass fiber cord, preferred is an inexpensive polyester that has good elastic modulus and fatigue resistance and excellent creep resistance. These are used as a tire reinforcing material by laminating one sheet or a plurality of sheets.

A tire can be manufactured by a normal manufacturing method using a rubber composition. For example, a rubber composition is extruded to obtain a tire member, which is pasted and molded on another tire member by a normal method on a tire molding machine to form a raw tire. The green tire is heated and pressed in a vulcanizer to obtain a tire.

The anti-aging performance of the vulcanized rubber composition can be improved by using the anti-aging composition described above. Accordingly, the present invention also provides a method for improving the anti-aging performance of a vulcanized rubber composition comprising kneading the above-mentioned anti-aging composition and a rubber component.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<GPC>
The analysis of the solution after stopping the condensation reaction in the following production examples was performed by GPC under the following conditions.
Column: TOSOH TSKgel Super HZ2000 (4.6 mmφ × 150 cm) and two TOSOH TSKgel Super HZ1000 (4.6 mmφ × 150 cm) are connected Temperature: 40 ° C.
Mobile phase: Tetrahydrofuran Detection: Differential refractive index (Refractive Index, RI)
Standard: TSKgel standard polystyrene

<Production Example 1: Production of acetone solution containing condensate of resorcin and acetone>
A 1,000 ml separable flask equipped with a thermometer, a stirrer and a condenser was charged with 200 g of acidic cation exchange resin ("Diaion PK212LH" manufactured by Mitsubishi Chemical Corporation, containing 50% by weight water), and the atmosphere inside the flask was nitrogen. After the replacement, 400 g of acetone was charged and stirred at 50 ° C. for 15 minutes. After standing after stirring, acetone was removed by filtration to wash the acidic cation exchange resin. Furthermore, the same washing | cleaning operation using 200 g of acetone was repeated 3 times, and the acidic cation exchange resin which reduced the moisture content was obtained.

A 1,000 ml separable flask containing the acidic cation exchange resin washed as described above was charged with 264.0 g (2.39 mol) of resorcin, and the atmosphere inside the flask was purged with nitrogen, followed by 418.7 g of acetone (7. 19 mol) was added, the temperature was raised to 60 ° C., and the mixture was stirred at this temperature for 20 hours to carry out a condensation reaction. Thereafter, the acidic cation exchange resin was removed by filtration to obtain an acetone solution containing a condensate of resorcin and acetone. The obtained solution was measured by GPC under the above conditions. The ratio of the area of the peak (1) having a weight average molecular weight of 160 or more and less than 480 to the total area of the peak having a weight average molecular weight of 160 or more and the weight average molecular weight with respect to the total area of the peak having a weight average molecular weight of 160 or more are The measurement results of the area ratio of peak (2) which is 800 or more and the area ratio of residual resorcin are shown below.
Area ratio of peak (1): 30.8%
Residual area of resorcin: 0.8%
Area ratio of peak (2): 15.3%
Weight average molecular weight of peak (2): 944
Weight average molecular weight of condensate: 536

<Example 1: Production of anti-aging compositions (1) to (3)>
Using a flask equipped with a stirrer and stirring at room temperature, the acetone solution containing the condensate of resorcin and acetone obtained in Production Example 1 was added in various amounts with N-phenyl-N ′-(1,3 After dissolving -dimethylbutyl) -p-phenylenediamine (6PPD), devolatilization by thin film distillation with an evaporator temperature set at 220 ° C. was performed under a reduced pressure of 30 kPa or less to obtain an anti-aging composition (1) to (3) was obtained. Table 1 summarizes the content of 6PPD in the obtained anti-aging compositions (1) to (3).

<Production Example 2: Production of acetone solution containing condensate of resorcin and acetone>
The acetone solution of the condensate obtained in Production Example 1 contained 4.3% by weight of water. Charge 1,000 ml of an acetone solution of the condensate prepared in the same manner as in Production Example 1 to a reaction vessel, distill off 500 ml of acetone by simple distillation, then drop 1,325 ml of acetone at 10 ml / min into the reaction vessel. While dehydrating by distillation. Thereafter, the total amount of newly added acetone was distilled off. After cooling, 500 ml of acetone was added to the concentrate to produce 1,000 ml of a dehydrated acetone solution (water content: 0.58% by weight).

77.5 ml of an acetone solution containing a condensate of resorcin and acetone obtained by the dehydration operation and an acidic cation exchange resin (“Diaion PK212LH” manufactured by Mitsubishi Chemical Corporation) washed in the same manner as in Production Example 1 Was put into the reaction solution and stirred at 20 ° C. for 21 hours under a nitrogen atmosphere to carry out a condensation reaction. After the 21 hour condensation reaction, the condensation reaction was stopped by removing the acidic cation exchange resin by filtration. The obtained solution was measured by GPC under the above conditions. The ratio of the area of the peak (1) having a weight average molecular weight of 160 or more and less than 480 to the total area of the peak having a weight average molecular weight of 160 or more and the weight average molecular weight with respect to the total area of the peak having a weight average molecular weight of 160 or more are The measurement results of the area ratio of peak (2) which is 800 or more and the area ratio of residual resorcin are shown below.
Area ratio of peak (1): 18.2%
Residual area of resorcin: 0.1%
Area ratio of peak (2): 27.2%
Weight average molecular weight of peak (2): 1,084
Weight average molecular weight of condensate: 684

<Example 2: Production of anti-aging composition (4)>
Similarly to Example 1, the acetone solution containing the condensate obtained in Production Example 2 and 6PPD were mixed, and then devolatilization by thin film distillation by thin film distillation with an evaporator temperature set at 220 ° C. was reduced to 30 kPa or less. It went under and obtained anti-aging agent composition (4). The content of 6PPD in the obtained anti-aging composition (4) was 20% by weight. Moreover, as a result of analyzing the obtained anti-aging composition (4) by the high performance liquid chromatography absolute calibration curve method, the amount of residual resorcinol was 0.05 weight%.

<Production Example 3: Production of condensate of resorcin and acetone>
A condensate of resorcin and acetone was obtained in the same manner as in Example 1 except that the devolatilization operation by thin film distillation was performed without using 6PPD.

<Example 3: Production of rubber composition and vulcanized rubber composition>
Using a Banbury mixer (600 ml Labo Plast Mill manufactured by Toyo Seiki Co., Ltd.), 100 parts by weight of natural rubber (RSS # 1), 55 parts by weight of HAF (Asahi Carbon Co., Ltd., trade name “Asahi # 70”), hydrous silica (Tosoh 10 parts by weight of “Nipsil (registered trademark) AQ” manufactured by Silica Co., Ltd., 3 parts by weight of stearic acid, 5 parts by weight of zinc oxide, 1 part by weight of cobalt naphthenate (cobalt content: 0.06 part by weight), Example 1 A rubber composition was obtained by blending 2.5 parts by weight of the anti-aging composition (1) obtained in 1 and 1.5 parts by weight of the anti-aging agent (6PPD), and kneading the mixture at 50 rpm. (Rubber composition discharge temperature: 150 to 160 ° C.) Next, the rubber composition was added to the rubber composition with an open roll (N, N-dicyclohexyl-2-benzothiazolylsulfenamide, D (BS) 0.7 parts by weight, sulfur component (insoluble sulfur) 5 parts by weight, and methoxylated methylol melamine resin (Sumitanol Chemical "Sumikanol 507AP") 3 parts by weight were kneaded (kneading temperature: 60 ° C.). The resulting rubber composition was vulcanized at 145 ° C. to obtain a vulcanized rubber composition.

<Examples 4 to 6: Production of rubber composition and vulcanized rubber composition>
In place of the anti-aging composition (1) obtained in Example 1, the anti-aging composition (2) to (4) obtained in Example 1 or 2 was used. A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 3 except that the product and the antioxidant (6PPD) were blended in the amounts shown in Table 2.

<Comparative Example 1: Production of rubber composition and vulcanized rubber composition>
Instead of 2.5 parts by weight of the anti-aging composition (1) obtained in Example 1 and 1.5 parts by weight of the anti-aging agent (6PPD), 2.0 parts by weight of the condensate obtained in Production Example 3 A rubber composition and a vulcanized rubber composition were obtained in the same manner as in Example 3 except that 2.0 parts by weight of the antioxidant (6PPD) was added.

[Tensile test]
The vulcanized rubber composition obtained in Examples 3 to 6 or Comparative Example 1 was allowed to stand in air at 100 ° C. for 72 hours to promote its aging, and then aging was performed according to JIS K 6301. The subsequent tensile strength and elongation at break were measured. The tensile strength after aging of the vulcanized rubber composition of Comparative Example 1 was 11.9 N / mm ² , and the elongation at break after aging was 130%. Table 2 shows the relative values of the vulcanized rubber compositions of Examples 3 to 6, with these values set to 100, respectively.

As shown in Table 2, although the amount of the condensate of resorcin and acetone and the amount of the anti-aging agent (6PPD) in the rubber composition are the same, the condensate and the anti-aging agent are separated separately. In Examples 3 to 6, in which a pre-manufactured anti-aging composition was added to the rubber component, compared to Comparative Example 1 added to the rubber component, the tensile strength and breaking elongation after aging of the vulcanized rubber composition were improved. did. From this result, compared with the case where the condensate and the anti-aging agent are separately blended with the rubber component, the effect of the anti-aging agent can be improved by blending the anti-aging composition prepared in advance with the rubber component. I understand that.

The anti-aging composition of the present invention is useful for producing a rubber product having excellent anti-aging performance.

This application is based on Japanese Patent Application No. 2016-062135 filed in Japan, the contents of which are incorporated in full herein.

Claims (17)

1. 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, and the total content thereof is 80 to 100% by weight based on the whole composition. Agent composition.
2. 2. The antioxidant composition according to claim 1, wherein the amine antioxidant is an N-alkyl-N′-aryl-p-phenylenediamine antioxidant.
3. 2. The antioxidant composition according to claim 1, wherein the amine antioxidant is N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine.
4. The anti-aging composition according to any one of claims 1 to 3, wherein at least one of phenol and a phenol derivative is resorcin.
5. The anti-aging composition according to any one of claims 1 to 4, wherein the carbonyl compound has 1 to 4 carbon atoms.
6. The antiaging 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.
7. The condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound is at least one selected from the group consisting of a condensate of resorcin and formaldehyde and a condensate of resorcin and acetone. The anti-aging composition as described in any one of these.
8. The content of the condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound is 0.5 to 100 parts by weight with respect to 1 part by weight of the amine-based antioxidant. The anti-aging composition according to claim 1.
9. The method according to any one of claims 1 to 8, comprising adding an amine-based antioxidant to a solution containing a condensate of at least one of phenol and a phenol derivative and at least one of a carbonyl compound, and then distilling off a volatile component of the solution. A method for producing an anti-aging composition according to claim 1.
10. The antiaging agent according to any one of claims 1 to 8, which comprises mixing a condensate of at least one of phenol and a phenol derivative with at least one of a carbonyl compound and an amine type antiaging agent in the absence of a solvent. A method for producing the composition.
11. A method for producing a rubber composition, comprising kneading the anti-aging composition according to any one of claims 1 to 8 and a rubber component.
12. The method according to claim 11, further comprising kneading a sulfur component.
13. A method for producing a vulcanized rubber composition comprising vulcanizing a rubber composition obtained by the method according to claim 12.
14. A rubber composition obtained by kneading the antiaging composition according to any one of claims 1 to 8 and a rubber component.
15. The rubber composition according to claim 14, which is obtained by further kneading a sulfur component.
16. A vulcanized rubber composition obtained by vulcanizing the rubber composition according to claim 15.
17. A method for improving the anti-aging performance of a vulcanized rubber composition comprising kneading the anti-aging agent composition according to any one of claims 1 to 8 and a rubber component.