WO2016039375A1 - ゴムと金属との接着促進剤、ゴム組成物及びタイヤ - Google Patents
ゴムと金属との接着促進剤、ゴム組成物及びタイヤ Download PDFInfo
- Publication number
- WO2016039375A1 WO2016039375A1 PCT/JP2015/075592 JP2015075592W WO2016039375A1 WO 2016039375 A1 WO2016039375 A1 WO 2016039375A1 JP 2015075592 W JP2015075592 W JP 2015075592W WO 2016039375 A1 WO2016039375 A1 WO 2016039375A1
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- WIPO (PCT)
- Prior art keywords
- rubber
- acid
- metal
- adhesion promoter
- carboxylic acid
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/124—Acids containing four carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/126—Acids containing more than four carbon atoms
- C07C53/128—Acids containing more than four carbon atoms the carboxylic group being bound to a carbon atom bound to at least two other carbon atoms, e.g. neo-acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C9/00—Reinforcements or ply arrangement of pneumatic tyres
- B60C9/0007—Reinforcements made of metallic elements, e.g. cords, yarns, filaments or fibres made from metal
- B60C2009/0021—Coating rubbers for steel cords
Definitions
- the present invention relates to an adhesion promoter between rubber and metal, and a rubber composition and a tire using the same.
- an adhesion promoter capable of exerting a high adhesive force between a rubber and a metal, equivalent to or more than an adhesion promoter containing cobalt, without containing cobalt, which is concerned about toxicity.
- a rubber composition and a tire using the same are particularly preferred.
- cobalt compounds such as the organic acid cobalt metal soap are listed in Group 2B, which is “suspected to be carcinogenic to humans” in the list of carcinogenic risks of the International Agency for Research on Cancer.
- metallic cobalt which is a raw material for various cobalt compounds, is a rare metal, its supply is unstable.
- cobalt compounds organic acid cobalt metal soap
- an adhesion promoter containing boron or phosphorus is known.
- a structure containing three atoms of nickel or bismuth bonded to boron or phosphorus through an oxygen atom and having both an aromatic carboxylic acid residue and an aliphatic carboxylic acid residue is known (for example, refer patent document 1).
- the adhesion promoter disclosed in Patent Document 1 has a problem that the adhesion force when adhering rubber and metal is not sufficient.
- the problem to be solved by the present invention is to promote adhesion that can exhibit a higher adhesion force between rubber and metal than an adhesion promoter containing cobalt, even without containing cobalt, which is concerned about toxicity.
- the present invention provides an agent, and a rubber composition and a tire using the agent.
- a metal salt of an aliphatic carboxylic acid having 2 to 25 carbon atoms wherein the metal is bismuth, copper, antimony, silver or niobium.
- those having a specific structure containing any of bismuth, copper, antimony, silver or niobium bonded to boron or phosphorus through an atom and having a residue of an aliphatic carboxylic acid are also disclosed in Patent Document 1 above.
- Patent Document 1 thus, it has been found that it becomes an adhesion promoter capable of exerting a higher adhesive force between rubber and metal than those positively having an aromatic carboxylic acid residue, and has led to the completion of the present invention.
- M is bismuth, copper, antimony, silver or niobium.
- (RCOO) is a residue of an aliphatic carboxylic acid having 2 to 25 carbon atoms.
- x is an integer of (valence of M ⁇ 1).
- gum and metal characterized by containing the compound (2) represented by these.
- the rubber-metal adhesion promoter according to [1] above, which contains the metal salt (1) of the carboxylic acid, and the metal in the metal salt (1) of the carboxylic acid is bismuth or copper.
- a rubber composition comprising the rubber and metal adhesion promoter according to any one of [1] to [10], and a rubber component.
- a tire comprising a steel cord / rubber composite comprising the rubber composition according to [11] or [12] and a steel cord.
- the rubber-metal adhesion promoter of the present invention is non-cobalt, but has a higher adhesion force between the rubber and the metal than a cobalt-containing adhesion promoter, particularly even under wet heat conditions. Can be played.
- the adhesion promoter of this invention the rubber composition which can manufacture suitably the tire for motor vehicles, the belt conveyor, etc. with strong adhesion
- the adhesion promoter for rubber and metal of the present invention is characterized by containing a metal salt (1) or a compound (2) as described above.
- the metal salt (1) will be described in detail.
- the metal salt of carboxylic acid (1) in the present invention is a metal salt of an aliphatic carboxylic acid having 2 to 25 carbon atoms.
- the metal species is bismuth, copper, antimony, silver or niobium.
- bismuth, copper, antimony or silver is preferred, and bismuth or copper is more preferred because adhesion between the steel cord and rubber is good even under wet heat conditions.
- Preferred examples of the aliphatic carboxylic acid having 2 to 25 carbon atoms include aliphatic monocarboxylic acids and aliphatic dicarboxylic acids.
- the number of carbon atoms of the aliphatic carboxylic acid refers to a number including the number of carbon atoms of the carboxyl group.
- Examples of the aliphatic carboxylic acid having 2 to 25 carbon atoms include saturated aliphatic monocarboxylic acids and unsaturated aliphatic monocarboxylic acids.
- Examples of the saturated aliphatic monocarboxylic acid include ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, isononanoic acid, decanoic acid, and neodecane.
- Examples include acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, and naphthenic acid.
- Examples of the unsaturated aliphatic monocarboxylic acid include 9-hexadecenoic acid, cis-9-octadecenoic acid, 11-octadecenoic acid, cis, cis-9,12-octadecadienoic acid, 9,12,15- Octadecatrienoic acid, 6,9,12-octadecatrienoic acid, 9,11,13-octadecatrienoic acid, eicosanoic acid, 8,11-eicosadienoic acid, 5,8,11-eicosatrienoic acid, 5, 8,11,14-eicosatetraenoic acid, tung oil acid, linseed oil acid, soybean oil acid, resin acid, tall oil fatty acid, rosin acid, abietic acid, neoabietic acid, parastrinic acid, pimaric acid, dehydroabietic acid, etc. Is mentioned.
- Examples of the aliphatic dicarboxylic acid having 2 to 25 carbon atoms include saturated aliphatic dicarboxylic acids and unsaturated aliphatic dicarboxylic acids.
- Examples of the saturated aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and the like.
- Examples of the unsaturated aliphatic dicarboxylic acid include fumaric acid and maleic acid.
- saturated aliphatic monocarboxylic acids are obtained because rubber cured products that hardly affect the sulfur cross-linking of rubber and as a result have little adverse effect on the physical properties of rubber used in automobile tires, belt conveyors, etc. Is preferred.
- saturated fatty acids a saturated aliphatic monocarboxylic acid having 2 to 20 carbon atoms is preferable, and 2-ethylhexanoic acid, neodecanoic acid, hexadecanoic acid or octadecanoic acid is more preferable.
- the metal salt (1) of carboxylic acid in the present invention can be obtained, for example, by the method shown below.
- Production method 1 Aliphatic carboxylic acid (a) having 2 to 25 carbon atoms, metal (bismuth, copper, antimony, silver, niobium) oxide (b-1), metal (bismuth, copper, antimony, silver, A method of producing by directly reacting a hydroxide (b-2) of niobium and one or more carbonates (b-3) of metals (bismuth, copper, antimony, silver, niobium) (direct method) ).
- Production method 2 After reacting an aliphatic carboxylic acid (a) having 2 to 25 carbon atoms with sodium hydroxide in the presence of water to obtain a sodium salt of the aliphatic carboxylic acid, sodium of the aliphatic carboxylic acid Sulfates (c-1) of salts and metals (metal salts of bismuth, copper, antimony, silver, niobium), chlorides (c-2) of metals (bismuth, copper, antimony, silver, niobium) and metals (bismuth) , Copper, antimony, silver, niobium nitrate (c-3) and a method of producing it by reacting with one or more (metathesis method).
- a sodium salt of the aliphatic carboxylic acid sodium of the aliphatic carboxylic acid Sulfates (c-1) of salts and metals (metal salts of bismuth, copper, antimony, silver, niobium), chlorides (c-2) of metals (bismut
- Examples of the metal (bismuth, copper, antimony, silver, niobium) oxide (b-1) used in the production method 1 include bismuth (III) oxide, copper (I) oxide, copper (II) oxide, and antimony oxide. (III), antimony oxide (V), silver oxide (I), silver oxide (II), silver oxide (III), niobium oxide (IV), niobium oxide (V) and the like.
- Examples of the metal (bismuth, copper, antimony, silver, niobium) hydroxide (b-2) include copper (II) hydroxide.
- Examples of the carbonate (b-3) of the metal (bismuth, copper, antimony, silver, niobium) include bismuth (III) carbonate, bismuth carbonate (III), and copper (II) carbonate.
- Examples of the sulfate (c-1) of the metal (bismuth, copper, antimony, silver, niobium) used in the production method 2 include copper (II) sulfate.
- Examples of the chloride (c-2) of the metal (bismuth, copper, antimony, silver, niobium) include bismuth chloride (III) chloride, copper (I) chloride, copper (II) chloride, and antimony (III) chloride. , Antimony chloride (V), silver chloride (I), niobium chloride (V) and the like.
- Examples of the nitrate (c-3) of the metal (bismuth, copper, antimony, silver, niobium) include bismuth nitrate (III), bismuth nitrate (III), and silver (I) nitrate.
- the reaction temperature when reacting the aliphatic carboxylic acid (a) having 2 to 25 carbon atoms with the compounds (b-1) to (b-3) is usually 50 to 150 ° C. .
- the reaction time is usually 1 to 20 hours.
- the reaction temperature when the aliphatic carboxylic acid (a) having 2 to 25 carbon atoms and sodium hydroxide are reacted in the presence of an organic solvent is usually 20 to 100 ° C.
- the reaction time is usually 1 to 5 hours.
- the reaction temperature when the sodium salt of aliphatic carboxylic acid and compounds (c-1) to (c-3) are reacted is usually 20 to 100 ° C.
- the reaction time is usually 1 to 5 hours.
- the sodium salt of the aliphatic carboxylic acid is reacted with the compounds (c-1) to (c-3), and then the aqueous layer in the reaction system is separated. Thereafter, the solvent present in the oil layer is removed by distillation under reduced pressure, whereby the rubber-metal adhesion promoter (fatty acid metal salt) of the present invention can be obtained.
- (RCOO) of the compound (2) is an aliphatic carboxylic acid residue having 2 to 25 carbon atoms. Residues of aliphatic carboxylic acids having less than 2 carbon atoms are less likely to be adhesion promoters with excellent compatibility with rubber, and as a result, adhesion promoters with high adhesion between rubber and metal are less likely to be obtained. That is not preferable. Moreover, in the case of a carboxylic acid residue having more than 25 carbon atoms, it is difficult to synthesize the compound (2), and also difficult to disperse in rubber or adsorb on the surface of the steel cord.
- the number of carbon atoms in (RCOO) refers to the number including the number of carbon atoms in the carboxyl group.
- an aliphatic monocarboxylic acid residue can be preferably exemplified.
- residues for example, the above-mentioned residues derived from aliphatic monocarboxylic acids can be preferably exemplified.
- saturated fats can be developed because they do not crosslink with rubber, can be dispersed near the steel cord or adsorbed on the surface of the steel cord, and can exhibit more performance as an adhesion promoter.
- Residues of group monocarboxylic acids are preferred.
- the saturated aliphatic monocarboxylic acid residues having 2 to 20 carbon atoms are preferred, such as 2-ethylhexanoic acid residue, neodecanoic acid residue, hexadecanoic acid residue. Or a residue of octadecanoic acid is more preferred.
- M in the compound represented by the general formula (A) is a metal species, specifically, bismuth, copper, antimony, silver or niobium.
- metal species bismuth, copper, antimony or silver is preferred, and bismuth or copper is more preferred because adhesion between the steel cord and rubber is good even under wet heat conditions.
- x is an integer of (M valence-1).
- Z in the compound (2) represented by the general formula (A) has a structure selected from the following formulas (z-1) to (z-4).
- a structure represented by the above formula (z-1) is preferable because an adhesion promoter exhibiting high adhesion between rubber and metal can be easily obtained.
- the compound (2) represented by the general formula (A) includes, for example, an aliphatic carboxylic acid (a) having 2 to 25 carbon atoms and a boric acid ester (d-1) of a lower alcohol having 1 to 5 carbon atoms. ), Metaboric acid esters of lower alcohols having 1 to 5 carbon atoms (d-2), phosphoric acid esters of lower alcohols having 1 to 5 carbon atoms (d-3) and lower alcohols having 1 to 5 carbon atoms.
- a volatile ester of phosphite (d-4) and a lower alcohol residue having 1 to 5 carbon atoms present in the ester (d-1) to (d-4) can be generated.
- the acid (e) and the metal compound M (f) which is a metal source can be mixed and heated to produce the volatile ester obtained.
- Examples of the monocarboxylic acid (a) include aliphatic monocarboxylic acids having 2 to 25 carbon atoms.
- boric acid ester (d-1) of the lower alcohol examples include trimethyl borate, triethyl borate, tripropyl borate, tributyl borate and the like.
- metaborate ester (d-2) of the lower alcohol examples include trimethyl metaborate, triethyl metaborate, tripropyl metaborate, and tributyl metaborate.
- the lower alcohol phosphate ester (d-3) examples include methyl phosphate, ethyl phosphate, propyl phosphate, and butyl phosphate.
- the lower alcohol phosphite (d-4) examples include methyl phosphite, ethyl phosphite, propyl phosphite, butyl phosphite and the like.
- the metal compound M (f) as the metal source for example, the oxide (b-1), hydroxide (b-2), carbonate (b-3), etc. can be used.
- Examples of the acid (e) include ethanoic acid, propanoic acid, butanoic acid, and the like.
- the ratio of the metal compound M (f) used as the metal source is, for example, 20 to 100 parts by mass per 100 parts by mass of the aliphatic carboxylic acid (a) having 2 to 25 carbon atoms.
- the use ratio of (d) is, for example, 10 to 50 parts by mass per 100 parts by mass of the aliphatic carboxylic acid (a) having 2 to 25 carbon atoms.
- the ratio of the acid (e) used is, for example, 10 to 50 parts by mass per 100 parts by mass of the aliphatic carboxylic acid (a) having 2 to 25 carbon atoms.
- a volatile ester of an aliphatic carboxylic acid (a) having 2 to 25 carbon atoms and a lower alcohol residue having 1 to 5 carbon atoms present in the ester (d) is produced.
- water is removed from the reaction system containing the reaction product.
- a second step of adding the esters (d-1) to (d-4) to the reaction system from which water has been removed and reacting the reactants with the esters (d-1) to (d-4) is included.
- the production method can prevent hydrolysis of the esters (d-1) to (d-4) by water produced in the first step, and as a result, the compound (2) in the present invention can be produced efficiently. To preferred.
- the temperature for the reaction is, for example, 100 to 250 ° C., preferably 150 to 220 ° C.
- the reaction time is, for example, 1 to 20 hours, preferably 1 to 5 hours.
- the rubber composition of the present invention contains the adhesion promoter of the present invention and a rubber component.
- a diene rubber can be used.
- the diene rubber include natural rubber (NR) and diene synthetic rubber.
- the diene-based synthetic rubber include isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), styrene isoprene butadiene rubber (SIBR), ethylene propylene diene rubber (EPDM), chloroprene rubber (CR), Examples include acrylonitrile butadiene rubber (NBR).
- NR which is easy to stretch and crystallize and has excellent fracture characteristics is preferable.
- the rubber composition according to the present invention may contain a filler such as carbon black or silica as a reinforcing agent.
- the carbon black is not particularly limited, and for example, SAF, ISAF, HAF, FEF grade carbon black can be used, and two or more of them may be used in a blend.
- the compounding amount of the carbon black is not particularly limited, but is preferably 20 to 100 parts by mass, more preferably 40 to 80 parts by mass with respect to 100 parts by mass of the diene rubber.
- silica examples include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), and surface-treated silica.
- the blending amount is not particularly limited, but it is preferably 0 parts by mass or more and 40 parts by mass or less, more preferably 0.1 parts by mass or more, 20 parts per 100 parts by mass of the diene rubber. It is below mass parts.
- sulfur as a vulcanizing agent is usually blended.
- the amount of sulfur is preferably 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, based on 100 parts by weight of the diene rubber.
- sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, and oil-treated sulfur, and are not particularly limited.
- the rubber composition of the present invention can contain a vulcanization accelerator.
- the vulcanization accelerator include sulfenamide vulcanization accelerators.
- the sulfenamide vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide (CZ, JIS abbreviation: CBS), N-tert-butyl-2-benzothiazole sulfenamide ( NS, JIS abbreviation: BBS), N-oxydiethylene-2-benzothiazole sulfenamide (OBS), N, N-diisopropyl-2-benzothiazole sulfenamide (DPBS), N, N-dicyclohexyl-2-benzo And thiazole sulfenamide (DZ, JIS abbreviation: DCBS).
- the content of the vulcanization accelerator is preferably 1 to 12 parts by mass, more preferably 2 to 10 parts by mass, and more preferably 3 to 9 parts by mass with respect to 100 parts by mass of the rubber component.
- various compounding agents can be arbitrarily blended in addition to the above components.
- a compounding agent include stearic acid, wax, oil, anti-aging agent, processing aid and the like.
- the rubber composition of the present invention can be prepared by kneading using a commonly used mixer such as a Banbury mixer or a kneader.
- the rubber composition of the present invention can be particularly suitably used as a rubber composition for coating various steel cords.
- it is preferably used as a rubber composition for coating (topping) of steel cords used as a reinforcing material for belt layers, carcass layers, chacher layers, etc. of pneumatic tires.
- a tire having a steel cord / rubber composite can be manufactured by manufacturing a cord topping fabric and using this as a tire reinforcing member and molding and vulcanizing according to a conventional method.
- the content of the rubber-metal adhesion promoter according to the present invention is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the rubber component. Part is more preferred.
- Synthesis Example 2 (Adhesion promoter (1-2): Synthesis of metal salt (1-2)) A metal salt (1-2) used in the present invention was obtained in the same manner as in Synthesis Example 1 except that 483 g of neodecanoic acid was used instead of 400 g of 2-ethylhexanoic acid.
- the metal salt (1-2) can also be said to be the adhesion promoter (1-2) of the present invention containing the metal salt (1-2).
- Synthesis Example 3 (Adhesion promoter (1-3): Synthesis of metal salt (1-3)) A flask was charged with 483 g of neodecanoic acid and 43 g of niobium (II) oxide, and heated and stirred at 120 ° C. for 2 hours. Thereafter, it was dried under reduced pressure at 120 ° C. for 1 hour to obtain a metal salt (1-3) used in the present invention.
- the metal salt (1-3) can also be said to be the adhesion promoter (1-3) of the present invention containing the metal salt (1-3).
- Synthesis Example 7 (Adhesion promoter (2-4): Synthesis of compound (2-4)) Compound (2-4) used in the present invention was obtained in the same manner as in Synthesis Example 4 except that 124 g of silver (II) oxide was used instead of 233 g of bismuth (III) oxide.
- the compound (2-4) can also be said to be the adhesion promoter (2-4) of the present invention containing the compound (2-4).
- the comparative compound (2′-1) has the following formula B (OCoOCOB ′) (OCoOCOA ′) 2 [Wherein OCOA ′ is a neodecanoic acid ester and OCOB ′ is a benzoic acid ester].
- the comparative compound (2′-1) can also be said to be a comparative adhesion promoter (2′-1) containing the comparative compound (2′-1).
- Example 1 (Preparation of rubber composition of the present invention) 100 parts of natural rubber (grade: RSS1), 4 parts of adhesion promoter (1-1), 50 parts of carbon black (Seast GS manufactured by Tokai Carbon Co., Ltd.), 5 parts of oil (Dutrex R manufactured by Shell Chemicals Japan Co., Ltd.) 8 parts of zinc oxide, 1 part of anti-aging agent (Nocrack 810NA manufactured by Ouchi Shinsei Chemical Co., Ltd.), 5 parts of insoluble sulfur, 2 parts of stearic acid, and vulcanization accelerator (Noxeller CZ manufactured by Ouchi Shinsei Chemical Co., Ltd.) 0.5 part was kneaded at 40 ° C. to obtain a rubber composition (1) of the present invention.
- natural rubber grade: RSS1
- 50 parts of carbon black Seast GS manufactured by Tokai Carbon Co., Ltd.
- 5 parts of oil Dutrex R manufactured by Shell Chemicals Japan Co., Ltd.
- 8 parts of zinc oxide
- a cured product (test piece) of the rubber composition in which the steel cord was sandwiched was prepared, and the adhesion between the steel cord and the rubber was evaluated.
- the preparation method of a test piece and the evaluation method of adhesiveness are shown below.
- the evaluation results are shown in Table 1.
- the rubber composition (1) was heat-kneaded with two test rolls to produce a rubber sheet having a width of 100 mm, a thickness of 6 mm, and a length of 100 mm. Two rubber pieces having a width of 10 mm, a thickness of 6 mm, and a length of 60 mm were cut out from the rubber sheet. A 1 ⁇ 4 ⁇ 0.25 mm steel cord plated with brass (Cu 65%, Zn 35%) is sandwiched between the two pieces of rubber, vulcanized at 160 ° C. for 10 minutes, and a rubber composition to which the steel cord is bonded. A test piece was prepared.
- ⁇ Adhesive evaluation method> A pull-out test was performed using the test piece by a method according to ASTM D2229, and the adhesion between rubber and steel cord was measured. The adhesive strength was measured by the following three types of measurements. Initial adhesive strength: Vulcanized under the above vulcanization conditions to prepare a test piece and measured 24 hours later. Adhesive strength after wet heat aging test: A test piece vulcanized under the above vulcanization conditions was immersed in hot water at 90 ° C. for 72 hours, and then the adhesive strength was measured. Adhesive strength after heat aging test: A test piece vulcanized under the above vulcanization conditions was allowed to stand at 110 ° C. for 72 hours to measure the adhesive strength. The measured values of the above three adhesive strengths are relative adhesive strengths when the adhesive strength of the comparative metal salt (1′-2) described later is defined as 100.
- Example 1 was repeated except that the metal salts (1-1) to (1-10) or compounds (2-1) to (2-5) [the adhesion promoter of the present invention] shown in Table 1 were used. Thus, rubber compositions (1) to (15) were obtained. An adhesive evaluation test was conducted in the same manner as in Example 1, and the results are shown in Table 1. In Examples 2 to 15, the amount of each of the metal salts (1-1) to (1-10) or the compounds (2-1) to (2-5) used is the metal molar concentration in the rubber composition. Were added so as to be the same.
- Comparative Examples 1 to 12 (Preparation of rubber composition for comparison) Except for using metal salts (1'-2) to (1'-11) or compound (2'-1) [adhesion promoter for comparison] and compound (2'-2) shown in Table 2 Comparative rubber compositions (1 ′) to (12 ′) were obtained in the same manner as in Example 1. An adhesive evaluation test was conducted in the same manner as in Example 1, and the results are shown in Table 2. In Comparative Examples 1 to 12, the amount of each of the metal salts (1′-2) to (1′-11) or the compounds (2′-1) to (2′-2) used in the rubber composition Were added so that their metal molar concentrations were the same.
- the present invention is used, for example, in automobile tires, belt conveyors, etc., to promote adhesion between rubber and metal and enhance performance.
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Abstract
Description
[1] 炭素原子数2~25の脂肪族カルボン酸の金属塩であって、該金属がビスマス、銅、アンチモン、銀またはニオブであるカルボン酸の金属塩(1)、または、下記一般式(A)
から選ばれる構造である。Mはビスマス、銅、アンチモン、銀またはニオブである。(RCOO)は炭素原子数2~25の脂肪族カルボン酸の残基である。xは、(Mの価数-1)の整数である。〕
で表される化合物(2)を含有することを特徴とするゴムと金属との接着促進剤。
[2] 前記カルボン酸の金属塩(1)を含有し、該カルボン酸の金属塩(1)中の金属がビスマスまたは銅である前記[1]記載のゴムと金属との接着促進剤。
[3] 前記カルボン酸の金属塩(1)を含有し、該カルボン酸の金属塩(1)における脂肪族カルボン酸が、脂肪族モノカルボン酸または脂肪族ジカルボン酸である前記[1]または[2]に記載のゴムと金属との接着促進剤。
[4] 前記カルボン酸の金属塩(1)における脂肪族カルボン酸が、炭素原子数2~20の飽和の脂肪族モノカルボン酸である前記[3]記載のゴムと金属との接着促進剤。
[5] 前記カルボン酸の金属塩(1)におけるカルボン酸が、2-エチルヘキサン酸、ネオデカン酸、ヘキサデカン酸またはオクタデカン酸である前記[4]記載のゴムと金属との接着促進剤。
[6] 前記化合物(2)を含有し、該化合物(2)中のMがビスマスまたは銅である前記[1]記載のゴムと金属との接着促進剤。
[7] 前記化合物(2)を含有し、該化合物(2)中のZが前記式(z-1)で表される構造である前記[1]または[6]に記載のゴムと金属との接着促進剤。
[8] 前記化合物(2)を含有し、該化合物(2)における(RCOO)が、炭素原子数2~20の飽和の脂肪族モノカルボン酸の残基である前記[1]、[6]または[7]に記載のゴムと金属との接着促進剤。
[9] 前記化合物(2)における(RCOO)が、2-エチルヘキサン酸の残基、ネオデカン酸の残基、ヘキサデカン酸の残基またはオクタデカン酸の残基である前記[8]記載のゴムと金属との接着促進剤。
[10] ゴムとスチールコードとを接着させる用途に用いる前記[1]~[9]のいずれか1項に記載のゴムと金属との接着促進剤。
[12] 前記ゴムと金属との接着促進剤を、前記ゴム成分100質量部に対して0.01~10質量部含有する前記[11]記載のゴム組成物。
不飽和の脂肪族ジカルボン酸としては、例えば、フマル酸、マレイン酸等が挙げられる。
製法1:炭素原子数2~25の脂肪族カルボン酸(a)と、金属(ビスマス、銅、アンチモン、銀、ニオブ)の酸化物(b-1)、金属(ビスマス、銅、アンチモン、銀、ニオブ)の水酸化物(b-2)及び金属(ビスマス、銅、アンチモン、銀、ニオブ)の炭酸塩(b-3)から選ばれる一種以上とを、直接反応させて製造する方法(直接法)。
2-エチルヘキサン酸400g及び酸化アンチモン(III)134gをフラスコに仕込み、120℃で2時間加熱撹拌した。その後、120℃で1時間、減圧乾燥し、本発明で用いる金属塩(1-1)を得た。尚、金属塩(1-1)は、該金属塩(1-1)を含む本発明の接着促進剤(1-1)ともいえる。
2-エチルヘキサン酸400gの代わりにネオデカン酸483gを用いた以外は合成例1と同様にして本発明で用いる金属塩(1-2)を得た。尚、金属塩(1-2)は、該金属塩(1-2)を含む本発明の接着促進剤(1-2)ともいえる。
ネオデカン酸483g及び酸化ニオブ(II)43gをフラスコに仕込み、120℃で2時間加熱撹拌した。その後、120℃で1時間、減圧乾燥し、本発明で用いる金属塩(1-3)を得た。尚、金属塩(1-3)は、該金属塩(1-3)を含む本発明の接着促進剤(1-3)ともいえる。
酢酸63g及びネオデカン酸342gの混合酸に、酸化ビスマス(III)233gを添加した後、120℃で2時間加熱撹拌した。その後、120℃で1時間減圧乾燥した後、生成したビスマス金属塩にホウ酸トリブチル80gを反応させ、副生する酢酸ブチルを留去して、本発明で用いる化合物(2-1)を得た。尚、化合物(2-1)は、該化合物(2-1)を含む本発明の接着促進剤(2-1)ともいえる。
酸化ビスマス(III)233gの代わりに酸化銅(II)80gを用いた以外は合成例4と同様にして本発明で用いる化合物(2-2)を得た。尚、化合物(2-2)は、該化合物(2-2)を含む本発明の接着促進剤(2-2)ともいえる。
酸化ビスマス(III)233gの代わりに酸化アンチモン(III)146gを用いた以外は合成例4と同様にして本発明で用いる化合物(2-3)を得た。尚、化合物(2-3)は、該化合物(2-3)を含む本発明の接着促進剤(2-3)ともいえる。
酸化ビスマス(III)233gの代わりに酸化銀(II)124gを用いた以外は合成例4と同様にして本発明で用いる化合物(2-4)を得た。尚、化合物(2-4)は、該化合物(2-4)を含む本発明の接着促進剤(2-4)ともいえる。
酸化ビスマス(III)233gの代わりに酸化ニオブ(IV)125gを用いた以外は実験例4と同様にして本発明で用いる化合物(2-5)を得た。尚、化合物(2-5)は、該化合物(2-5)を含む本発明の接着促進剤(2-5)ともいえる。
ネオデカン酸210g、プロピオン酸147gおよびキシレン300gを反応フラスコに充填し、そして機械的に撹拌しながら50℃に加熱した。水酸化コバルト(II)171gを加え、そして機械的に撹拌しながら温度を90℃に上昇させて可動性の青色液体を生成した。さらに熱を適用して反応水をディーン・アンド・スターク・トラップを用いてキシレン担持により除去した。温度が140℃に達した後に、キシレン150g中に溶解されている安息香酸73gを徐々に反応混合物に加えながら、生成した水を連続的に除去した。
B(OCoOCOB’)(OCoOCOA’)2
[式中、OCOA’はネオデカン酸エステルであり、OCOB’は安息香酸エステルである]の硬い青色固体であった。尚、比較対照用化合物(2´-1)は、該比較対照用化合物(2´-1)を含む比較対照用の接着促進剤(2´-1)ともいえる。
天然ゴム(グレード:RSS1)100部、接着促進剤(1-1)4部、カーボンブラック(東海カーボン株式会社製シーストG-S)50部、オイル(シェルケミカルズジャパン株式会社製Dutrex R)5部、亜鉛華8部、老化防止剤(大内新興化学工業株式会社製ノクラック810NA)1部、不溶性硫黄5部、ステアリン酸2部及び加硫促進剤(大内新興化学工業株式会社製ノクセラーCZ)0.5部を40℃で混練し、本発明のゴム組成物(1)を得た。得られたゴム組成物(1)を用いてスチールコードがはさまれたゴム組成物の硬化物(試験片)を作成し、スチールコードとゴムの接着性の評価を行った。試験片の作成方法及び、接着性の評価方法を下記に示す。また、評価結果を第1表に示す。
ゴム組成物(1)を試験用2本ロールにより熱練し、幅100mm、厚さ6mm、長さ100mmのゴムシートを作製した。このゴムシートから幅10mm、厚さ6mm、長さ60mmのゴム片を2枚切り出した。真鍮(Cu65%、Zn35%)をメッキした1×4×0.25mmのスチールコードを前記2枚のゴム片で挟み、160℃で10分間加硫し、スチールコードが接着されたゴム組成物の試験片を作製した。
前記試験片を用いてASTM D2229に準ずる方法で引き抜き試験を行い、ゴムとスチールコードとの接着力を測定した。接着力の測定は、下記の3種類の測定を行った。
初期接着力:上記加硫条件で加硫し試験片を作成し24時間後に測定した。
湿熱老化試験後の接着力:上記加硫条件で加硫した試験片を90℃の温水に72時間浸水劣化させた後、接着力を測定した。
加熱老化試験後の接着力:上記加硫条件で加硫した試験片を110℃で72時間放置し接着力を測定した。
尚、上記3つの接着力の測定値は、後述する比較対照用金属塩(1´-2)の接着力を100としたときの相対的な接着力である。
第1表に示す金属塩(1-1)~(1-10)または化合物(2-1)~(2-5)〔本発明の接着促進剤〕を用いた以外は実施例1と同様にしてゴム組成物(1)~(15)を得た。実施例1と同様にして接着性の評価試験を行い、その結果を第1表に示す。尚、実施例2~15において、各々の金属塩(1-1)~(1-10)または化合物(2-1)~(2-5)の使用量は、ゴム組成物中の金属モル濃度が同一となるように添加した。
第2表に示す金属塩(1´-2)~(1´-11)または化合物(2´-1)〔比較対照用接着促進剤〕、化合物(2´-2)を用いた以外は実施例1と同様にして比較対照用ゴム組成物(1´)~(12´)を得た。実施例1と同様にして接着性の評価試験を行い、その結果を第2表に示す。尚、比較例1~12において、各々の金属塩(1´-2)~(1´-11)または化合物(2´-1)~(2´-2)の使用量は、ゴム組成物中の金属モル濃度が同一となるように添加した。
Claims (13)
- 前記カルボン酸の金属塩(1)を含有し、該カルボン酸の金属塩(1)中の金属がビスマスまたは銅である請求項1記載のゴムと金属との接着促進剤。
- 前記カルボン酸の金属塩(1)を含有し、該カルボン酸の金属塩(1)における脂肪族カルボン酸が、脂肪族モノカルボン酸または脂肪族ジカルボン酸である請求項1に記載のゴムと金属との接着促進剤。
- 前記カルボン酸の金属塩(1)における脂肪族カルボン酸が、炭素原子数2~20の飽和の脂肪族モノカルボン酸である請求項3記載のゴムと金属との接着促進剤。
- 前記カルボン酸の金属塩(1)におけるカルボン酸が、2-エチルヘキサン酸、ネオデカン酸、ヘキサデカン酸またはオクタデカン酸である請求項4記載のゴムと金属との接着促進剤。
- 前記化合物(2)を含有し、該化合物(2)中のMがビスマスまたは銅である請求項1記載のゴムと金属との接着促進剤。
- 前記化合物(2)を含有し、該化合物(2)中のZが前記式(z-1)で表される構造である請求項1に記載のゴムと金属との接着促進剤。
- 前記化合物(2)を含有し、該化合物(2)における(RCOO)が、炭素原子数2~20の飽和の脂肪族モノカルボン酸の残基である請求項1に記載のゴムと金属との接着促進剤。
- 前記化合物(2)における(RCOO)が、2-エチルヘキサン酸の残基、ネオデカン酸の残基、ヘキサデカン酸の残基またはオクタデカン酸の残基である請求項8記載のゴムと金属との接着促進剤。
- ゴムとスチールコードとを接着させる用途に用いる請求項1に記載のゴムと金属との接着促進剤。
- 請求項1~10のいずれか1項に記載のゴムと金属との接着促進剤と、ゴム成分とを含有することを特徴とするゴム組成物。
- 前記ゴムと金属との接着促進剤を、前記ゴム成分100質量部に対して0.01~10質量部含有する請求項11記載のゴム組成物。
- 請求項11に記載のゴム組成物とスチールコードとからなるスチールコード/ゴム複合体を有することを特徴とするタイヤ。
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CN201580048181.8A CN106687518B (zh) | 2014-09-12 | 2015-09-09 | 橡胶与金属的粘接促进剂、橡胶组合物及轮胎 |
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JP2021054985A (ja) * | 2019-09-30 | 2021-04-08 | 株式会社ブリヂストン | ゴム組成物、複合体、ホース、コンベヤベルト、クローラおよびタイヤ |
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- 2015-09-09 EP EP15839903.0A patent/EP3196243B1/en active Active
- 2015-09-09 CN CN201580048181.8A patent/CN106687518B/zh active Active
- 2015-09-09 BR BR112017004594A patent/BR112017004594A2/pt not_active Application Discontinuation
- 2015-09-09 US US15/507,848 patent/US20170253722A1/en not_active Abandoned
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JPWO2016039376A1 (ja) * | 2014-09-12 | 2017-06-22 | Dic株式会社 | ゴムと金属との接着促進剤、ゴム組成物及びタイヤ |
WO2021065244A1 (ja) | 2019-09-30 | 2021-04-08 | 株式会社ブリヂストン | 金属-ゴム複合体、コンベヤベルト、ホース、ゴムクローラ及びタイヤ |
WO2021065931A1 (ja) * | 2019-09-30 | 2021-04-08 | 株式会社ブリヂストン | ゴム組成物、ゴム-金属複合体、タイヤ、コンベヤベルト、ホース及びクローラ |
JP2021054976A (ja) * | 2019-09-30 | 2021-04-08 | 株式会社ブリヂストン | ゴム組成物、複合体、ホース、コンベヤベルト、クローラおよびタイヤ |
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Also Published As
Publication number | Publication date |
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BR112017004594A2 (pt) | 2017-12-05 |
EP3196243A4 (en) | 2018-05-02 |
EP3196243A1 (en) | 2017-07-26 |
TW201615645A (zh) | 2016-05-01 |
KR20170056528A (ko) | 2017-05-23 |
CN106687518B (zh) | 2019-04-02 |
US20170253722A1 (en) | 2017-09-07 |
JPWO2016039375A1 (ja) | 2017-06-22 |
KR102326285B1 (ko) | 2021-11-15 |
US20190375911A1 (en) | 2019-12-12 |
CN106687518A (zh) | 2017-05-17 |
TWI686396B (zh) | 2020-03-01 |
EP3196243B1 (en) | 2020-07-15 |
JP6817812B2 (ja) | 2021-01-20 |
US11427698B2 (en) | 2022-08-30 |
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