WO2013018838A1 - ゴム組成物 - Google Patents
ゴム組成物 Download PDFInfo
- Publication number
- WO2013018838A1 WO2013018838A1 PCT/JP2012/069615 JP2012069615W WO2013018838A1 WO 2013018838 A1 WO2013018838 A1 WO 2013018838A1 JP 2012069615 W JP2012069615 W JP 2012069615W WO 2013018838 A1 WO2013018838 A1 WO 2013018838A1
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- WO
- WIPO (PCT)
- Prior art keywords
- rubber
- parts
- mass
- vulcanization
- tire
- Prior art date
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Classifications
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- 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
- C08K5/16—Nitrogen-containing compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/52—Unvulcanised treads, e.g. on used tyres; Retreading
- B29D30/54—Retreading
- B29D30/56—Retreading with prevulcanised tread
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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
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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
- B60C1/0016—Compositions of the tread
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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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
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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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/02—Replaceable treads
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- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
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- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
- C08K5/40—Thiurams, i.e. compounds containing groups
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- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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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
- B60C2001/0075—Compositions of belt cushioning layers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T152/00—Resilient tires and wheels
- Y10T152/10—Tires, resilient
- Y10T152/10495—Pneumatic tire or inner tube
Definitions
- the present invention is particularly useful in the manufacture of retreaded tires that are used in a pneumatic tire such as a truck / bus tire (TBR) or an aircraft tire, and in which the tread rubber is worn and re-used.
- a rubber composition suitable for a cushion rubber of a retread tire adopting a precure tread (PCT) retreading system in which vulcanized precured tread rubber is vulcanized and bonded to a buffed tire through an unvulcanized cushion rubber and
- the present invention relates to a rubber composition suitable for bonding, in which a separately vulcanized rubber member is bonded to each other, and is bonded between a vulcanized rubber member and co-vulcanized.
- a tread surface of a tire that has been worn out and has finished its primary life (hereinafter referred to as a “base tire”) is buffed, and then a precured rehabilitated tire
- COLD cold
- HET hot
- an unvulcanized cushion rubber is first applied to the pedestal tire, and further, the precure tread is applied to the vulcanized can.
- the method of heating at a temperature of 100 to 140 ° C. is generally used.
- the cushion rubber used in this system flows into the buffs of the base tire, smoothes the adhesive surface, and co-vulcanizes with both the base tire and the pre-cured tread to ensure the adhesion between the pre-cured tread and the base tire. It has a function.
- This cushion rubber is required to obtain a high degree of cross-linking by vulcanization in a relatively low temperature region (around 100 ° C.), and it is preferable that the vulcanization rate near 100 ° C. is fast in order to improve vulcanization productivity.
- the cushion rubber may be affixed to the base tire in a state of being rolled into a sheet in advance, or may be directly applied to the base tire by an extruder, but it is 70 to 100 ° C. in both the rolling and extrusion processes. Since the temperature rises to a certain degree, the vulcanization cannot be co-vulcanized when the vulcanization progresses during the rolling and extrusion processes. Longer is preferred.
- the Fmax value which is the maximum vulcanization torque showing a high degree of cross-linking at a temperature near 100 ° C. is high, and the vulcanization speed T0.9 at which the vulcanization is almost completed is fast (time is short). It is necessary to achieve a high degree of trade-off between the vulcanization rate T0.1 at which is started, which is preferably slower (longer time).
- Examples of rubber compositions suitable for cushion rubber and the like that require such characteristics include (1) a compound comprising a specific thiuram compound, a compound such as dibenzothiadisulfides, and a compound such as amines.
- a tire characterized by using the rubber composition as a cushion rubber for example, see Patent Document 1 by the present applicant
- (2) a vulcanization accelerator compound such as benzothiadisulfide, and tetrabenzylthiuram disulfide.
- a rubber composition (for example, see Patent Document 2) obtained by blending a super vulcanization accelerator compound such as the above and a curing amine activator is known.
- At least one compound selected from the group consisting of amines, guanidines, aldehyde amines, and aldehyde ammonia is used as the compound such as amines in the range of 0.1 to 2. Although defined as 0 parts by weight, it does not mention the superiority of aldehyde amines among the amines, and the preferred blending amount range is small, and the blending components are different from the present invention. Is.
- a vulcanization accelerator compound such as benzothiadisulfide is used in combination with an amine activator for curing.
- a supervulcanization accelerator compound such as tetrabenzylthiuram disulfide
- tetrabenzylthiuram disulfide Only a group consisting of tetrabenzylthiuram disulfide and zinc dibenzyldithiocarbamate, and there is no description or suggestion regarding other compounds that do not contain carcinogenic nitrosamine precursors.
- High degree of crosslinking at high temperature and vulcanization rate T0.9 is fast (short time), but vulcanization rate T0.1 at which rubber curing starts is slow (long time).
- the present situation is that a rubber composition excellent in productivity is not obtained. Furthermore, even in tires and the like produced by co-vulcanizing an adhesive rubber composition sandwiched between separately vulcanized rubber members, a sufficient rubber composition has not yet been obtained. .
- JP 2002-356102 A (Claims, Examples, etc.)
- JP-A-8-59898 (Claims, Examples, etc.)
- the present invention is to solve this problem in view of the above-described conventional problems and current situation, and has a high degree of crosslinking at a temperature near 100 ° C., a short vulcanization time, and scorch resistance (processing).
- An object is to provide a rubber composition suitable for adhesion by co-vulcanization and adhesion.
- the present inventor suitably combined specific vulcanization accelerators with respect to 100 parts by mass of the rubber component, and sets each content range to a specific range.
- the inventors have found that the above rubber composition can be obtained, and have completed the present invention.
- the present invention resides in the following (1) to (5).
- (1) With respect to 100 parts by mass of the rubber component, 0.3 to 2.5 parts by mass of aldehyde amines, tetra (2-ethylhexyl) thiuram disulfide, 1,6-bis (N, N′-dibenzylthiocarbamoyl) 0.1 to 1.5 parts by mass of at least one compound selected from dithio) -hexane and 1,6-bis ⁇ N, N′-di (2-ethylhexyl) thiocarbamoyldithio ⁇ -hexane, and thiazole vulcanization
- a rubber composition comprising 0.1 to 2.5 parts by mass of an accelerator.
- a cushion rubber for a retread tire excellent in productivity due to a high degree of crosslinking at a temperature near 100 ° C., a short vulcanization time, and scorch resistance (preventing hardening due to heat generation during processing), and Provided is a rubber composition suitable for bonding a tire produced by bonding rubber members vulcanized separately. Moreover, in the tire of this invention, productivity can be improved without impairing the tire performance of a retreaded tire by using the said rubber composition for the cushion rubber of a rectified tire.
- the rubber composition of the present invention comprises 0.3 to 2.5 parts by mass of an aldehyde amine, tetra (2-ethylhexyl) thiuram disulfide, 1,6-bis (N, N ′) with respect to 100 parts by mass of the rubber component.
- the rubber component used in the present invention natural rubber, diene synthetic rubber and the like can be used.
- the natural rubber and / or the synthetic polyisoprene rubber is preferably contained in 60 to 100 parts by mass in 100 parts by mass of the rubber component, and more preferably in the range of 80 to 100 parts by mass.
- the rubber component other than natural rubber and / or synthetic polyisoprene rubber is not particularly limited, but diene-based synthetic rubber such as SBR and BR is preferable.
- Rubber composition suitably applied to cushion rubber of precure retreaded tire which is an object of the present invention, or rubber for adhesion suitably applied to a tire produced by vulcanizing and bonding separately vulcanized members
- the content of natural rubber and / or synthetic polyisoprene rubber should be 60 parts by mass or more from the viewpoint of not lowering the interfacial adhesion, and obtaining high strength cushion rubber, adhesive rubber and the like. Is preferred.
- aldehyde amines examples include n-butyraldehyde-aniline condensate, butyraldehyde-acetaldehyde-butylidene aniline reactant, butyraldehyde-monobutylamine condensate, butyraldehyde-butylidene aniline reactant, heptaldehyde-aniline.
- a reactant an ⁇ -ethyl- ⁇ -propylacrolein-aniline condensate and the like.
- n-butyraldehyde-aniline condensate is used from the viewpoint of availability.
- tetra (2-ethylhexyl) thiuram disulfide 1,6-bis (N, N′-dibenzylthiocarbamoyldithio) -hexane and 1,6-bis At least one compound selected from ⁇ N, N'-di (2-ethylhexyl) thiocarbamoyldithio ⁇ -hexane is used, and other tetramethylthiuram disulfides (TMTD), tetramethylthiuram mono, which are other than these, are used.
- TMTD tetramethylthiuram disulfides
- TMTD sulfide
- a carcinogenic nitrosamine precursor is included, and the effects of the present invention cannot be exhibited.
- the thiazole vulcanization accelerator include at least one of mercaptobenzothiazole (M) and dibenzothiadisulfide (DM).
- M mercaptobenzothiazole
- DM dibenzothiadisulfide
- the use of dibenzothiadisulfide (DM) is desirable from the viewpoint of exerting further effects of the present invention.
- the content of each of the above three types is 0.3 to 2.5 parts by mass of aldehyde amines with respect to 100 parts by mass of the rubber component, and tetra (2-ethylhexyl) thiuram disulfide, At least one compound selected from 1,6-bis (N, N′-dibenzylthiocarbamoyldithio) -hexane and 1,6-bis ⁇ N, N′-di (2-ethylhexyl) thiocarbamoyldithio ⁇ -hexane
- the content is 0.1 to 1.5 parts by mass
- the content of the thiazole vulcanization accelerator is 0.1 to 2.5 parts by mass.
- the content of at least one compound selected from thiocarbamoyldithio ⁇ -hexane and the thiazole vulcanization accelerator is 0.3, 0.1, and less than 0.1 parts by mass, which are the lower limit values of each. As a result, the degree of cross-linking Fmax or the vulcanization rate T0.9 is lowered.
- the content of at least one compound selected from ethylhexyl) thiocarbamoyldithio ⁇ -hexane and the thiazole vulcanization accelerator exceeds the upper limit of 2.5, 1.5, and 2.5 parts by mass, Not only does the vulcanization rate T0.9 increase (value decreases), but the vulcanization rate T0.1 also becomes too fast (value decreases), resulting in a problem that the scorch resistance deteriorates.
- the content of aldehyde amines should be 0.5 to 2.0 parts by weight, more preferably 0.5 to 1.5 parts by weight.
- the content of at least one compound selected from dithio ⁇ -hexane is preferably 0.1 to 1.0 part by weight, more preferably 0.2 to 1.0 part by weight, and thiazole-based vulcanization acceleration Including agent
- the amount is preferably 0.5 to 2.0 parts by mass, more preferably, desirably 0.5 to 1.5 parts by mass.
- the rubber composition of the present invention in addition to the above vulcanization accelerators and rubber components, in addition to a vulcanizing agent such as sulfur (insoluble sulfur), if necessary, carbon black or silica as a reinforcing filler, Chemicals usually used in the rubber industry such as process oil, anti-aging agent, zinc white, stearic acid, resin (resin) and the like can be appropriately contained.
- the content of the vulcanizing agent such as sulfur (insoluble sulfur) is preferably 0.1 to 10.0 parts by mass, more preferably 1.0 to 5.0 parts by mass with respect to 100 parts by mass of the rubber component. is there.
- the carbon black that can be used as the reinforcing filler is not particularly limited, but preferably contains a highly reinforcing carbon black of HAF (N330) or higher.
- the highly reinforced carbon black of HAF or higher refers to a carbon black having a specific surface area (m 2 / g) evaluated by iodine adsorption amount, DBP adsorption amount or the like that is equal to or larger than that of HAF carbon black. It means a carbon black having an effect of improving the elastic modulus and breaking strength when blended with the composition, which is equal to or higher than that of HAF carbon.
- this carbon black of HAF (N330) or higher a rubber composition capable of further obtaining high fracture strength and high heat resistance can be obtained.
- the content of these carbon blacks is preferably 30 to 60 parts by mass, more preferably 30 to 50 parts by mass with respect to 100 parts by mass of the rubber component. If the carbon black content is less than 30 parts by mass, the mechanical strength is insufficient. On the other hand, if it exceeds 60 parts by mass, the exothermic properties are deteriorated, or the viscosity increases when the resin is not vulcanized. There is a case where the strength is reduced, and problems such as insufficient followability to the buff surface unevenness and poor adhesion when unvulcanized may occur.
- the rubber composition of the present invention when applied to a retread tire, the rubber composition can be suitably used for a cushion rubber disposed between a base tire and a reclaimed tread rubber member.
- the base tire and the recurring precure tread rubber are pasted together via a cushion rubber and then integrally vulcanized.
- the vulcanization temperature is preferably vulcanized at a vulcanization temperature of 120 ° C. or less, more preferably 100 to 120 ° C. Tire over-vulcanization can be suppressed, and commercial production can be carried out with a practical vulcanization time.
- the present invention when applied to a tire produced by bonding separately vulcanized rubber members, adhesion between the vulcanized rubber members and co-vulcanized for adhesion
- the present invention can be suitably applied for use.
- Co-vulcanization is performed between the vulcanized rubber members in this case, but it is necessary to prevent overvulcanization of the vulcanized rubber member.
- the vulcanization temperature in this case is preferably vulcanized at a vulcanization temperature of 120 ° C. or less, more preferably 100 to 120 ° C., and if within this temperature range, a vulcanized rubber member
- the vulcanization speed T0.9 is high (the time is short), and the vulcanization speed T0.1 at which the rubber curing starts is slow (the time is long).
- a rubber composition capable of producing a tire having excellent productivity can be obtained.
- the aldehyde amines used in the present invention but the guanidines shown in the examples of JP-A No. 2002-356102 (Patent Document 1), which is a conventional technique, can be applied as amines.
- the tire of the present invention is characterized in that the rubber composition having the above constitution is used as a cushion rubber for a retread tire, that is, a cushion rubber for joining a retread tread rubber and a retread tire, and other structures. Etc. are not particularly limited.
- productivity can be improved without impairing the tire performance of the retreaded tire.
- the rubber composition is applied to an adhesive rubber that is sandwiched and co-vulcanized between vulcanized rubber members.
- productivity can be improved without impairing tire performance.
- Examples 1 to 14 and Comparative Examples 1 to 10 Rubber compositions having the compounding formulations shown in Tables 1 and 2 below were prepared. About each obtained rubber composition, the vulcanization maximum torque (Fmax) and the vulcanization speed T0.9 and T0.1 were measured by the following method. In addition, a present Example is only an illustration and restricts use of various rubber compounding agents such as commonly used reinforcing fillers such as silica, tackifiers (tackifiers), and softeners (process oils). is not.
- the rubber compositions of Examples 1 to 14 that fall within the scope of the present invention are around 100 ° C. compared to the rubber compositions of Comparative Examples 1 to 10 that fall outside the scope of the present invention.
- the maximum vulcanization torque (Fmax value) showing a high degree of crosslinking at a temperature of 5 is high and the vulcanization speed T0.9 at which the vulcanization is almost completed is fast (short time), but the vulcanization speed T0 at which the rubber curing starts. .1 has been found to be highly compatible with the contradiction that slower (longer) is preferable.
- Comparative Examples 1 to 4 are diphenylguanidine (DPG), thiazole vulcanization accelerator (DM) and tetra (2-ethylhexyl).
- Comparative Example 5 Three combinations of thiuram disulfide (TOT), Comparative Example 5 is a combination of two kinds of thiazole vulcanization accelerator (DM) and tetra (2-ethylhexyl) thiuram disulfide (TOT), Comparative Example 6 is an aldehyde amine (BAA) and tetra (2-ethylhexyl) thiuram disulfide (TOT) in combination of two types, Comparative Example 7 is a combination of two types of aldehyde amines (BAA) and thiazole vulcanization accelerator (DM), Comparative Example 8 Are two combinations of diphenylguanidine (DPG) and thiazole vulcanization accelerator (DM), Comparative Examples 9 and 10 , Aldehyde amines (BAA), a three combinations of thiazole vulcanization accelerator (DM) and tetrabenzylthiuram disulfide (TBZTD), in these cases, it was
- aldehyde amines (BAA) are used for two combinations of thiazole vulcanization accelerator (DM) and tetra (2-ethylhexyl) thiuram disulfide (TOT).
- DM thiazole vulcanization accelerator
- TOT tetra (2-ethylhexyl) thiuram disulfide
- Comparative Examples 9 and 10 are aldehyde amines and thiazole vulcanization accelerators (DM) shown in Examples (Composition 1.5) of JP-A-8-59898 (Patent Document 2) which is a conventional technique.
- Patent Document 2 tetrabenzylthiuram disulfide
- TBZTD tetrabenzylthiuram disulfide
- the rubber composition of the formulation according to the present invention has a high degree of crosslinking at a temperature near 100 ° C. and a short vulcanization time. It has been found that a rubber composition excellent in productivity can be obtained by aging and scorch resistance (preventing curing due to heat generation during processing).
- the vulcanized rubber Productivity could be improved without impairing tire performance by applying it to an adhesive rubber that is sandwiched between members and co-vulcanized for adhesion.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
この方式に用いられるクッションゴムは、台タイヤのバフ目に流れ込み、接着面を平滑化し、台タイヤとプレキュアトレッド双方と共加硫することによって、プレキュアトレッドと台タイヤの接着性を確保する機能を有するものである。
また、上記特許文献2の技術では、ベンゾチアジスルフィド等の加硫促進剤化合物と、硬化用アミン活性化剤とを併用するものであり、テトラベンジルチウラムジスルフィド等の超加硫促進剤化合物に関しては、テトラベンジルチウラムジスルフィドおよび亜鉛ジベンジルジチオカルバメートからなる群しか規定しておらず、発がん性のニトロソアミン先駆体を含まないその他の化合物に関しては全く記載や示唆はないものであり、未だ100℃付近の温度での高い架橋度と、加硫速度T0.9は速い(時間が短い)が、ゴム硬化が始まる加硫速度T0.1は遅い(時間が長い)こととなる2律背反を高度に両立化した生産性に優れるゴム組成物が得られていないのが現状である。
更に、別々に加硫されたゴム部材の間に接着用のゴム組成物を挟み共加硫させて作製されるタイヤ等においても、未だ十分なゴム組成物が得られていないのが現状である。
(1) ゴム成分100質量部に対して、アルデヒドアミン類0.3~2.5質量部と、テトラ(2-エチルヘキシル)チウラムジスルフィド、1,6-ビス(N,N´-ジベンジルチオカルバモイルジチオ)-ヘキサン及び1,6-ビス{N,N´-ジ(2-エチルヘキシル)チオカルバモイルジチオ}-ヘキサンから選ばれる少なくとも1つの化合物0.1~1.5質量部と、チアゾール系加硫促進剤0.1~2.5質量部とを含有してなることを特徴とするゴム組成物。
(2) 120℃以下の加硫温度で加硫されることを特徴とする上記(1)記載のゴム組成物。
(3) ゴム組成物が更生用タイヤのクッションゴムであることを特徴とする上記(1)又は(2)記載のゴム組成物。
(4) 上記(1)~(3)の何れか一つに記載のゴム組成物を更生用タイヤのクッションゴムとしたことを特徴とするタイヤ。
(5) 上記(1)~(3)の何れか一つに記載のゴム組成物を、加硫済のタイヤ用ゴム部材と加硫済のタイヤ用ゴム部材の間に挟み共加硫させることによって接着させて製造されたことを特徴とする空気入りタイヤ。
また、本発明のタイヤでは、上記ゴム組成物を更正タイヤのクッションゴムに用いることにより更生タイヤのタイヤ性能を損なうことなく生産性を向上させることができる。
本発明のゴム組成物は、ゴム成分100質量部に対して、アルデヒドアミン類0.3~2.5質量部と、テトラ(2-エチルヘキシル)チウラムジスルフィド、1,6-ビス(N,N´-ジベンジルチオカルバモイルジチオ)-ヘキサン及び1,6-ビス{N,N´-ジ(2-エチルヘキシル)チオカルバモイルジチオ}-ヘキサンから選ばれる少なくとも1つの化合物0.1~1.5質量部と、チアゾール系加硫促進剤0.1~2.5質量部とを含有してなることを特徴とする。
好ましくは、天然ゴム及び/又は合成ポリイソプレンゴムが、ゴム成分100質量部中に、60~100質量部含まれることが好ましく、より好ましい範囲は、80~100質量部である。天然ゴム及び/又は合成ポリイソプレンゴム以外のゴム成分としては、特に制限ないが、SBR、BR等のジエン系合成ゴムが好ましい。
本発明の対象となるプレキュア方式の更生タイヤのクッションゴムに好適に適用されるゴム組成物、または別々に加硫した部材を加硫接着させて製造するタイヤに好適に適用される接着用のゴム組成物とする場合に、界面接着性を低下させない点、高強度のクッションゴム、接着用ゴムなどを得る点から、天然ゴム及び/又は合成ポリイソプレンゴムの含有量を60質量部以上とすることが好ましいものとなる。
アルデヒドアミン類としては、例えば、n-ブチルアルデヒド-アニリン縮合物、ブチルアルデヒド-アセトアルデヒド-ブチリデンアニリン反応物、ブチルアルデヒド-モノブチルアミン縮合物、ブチルアルデヒド-ブチリデンアニリン反応物、ヘプトアルデヒド-アニリン反応物、α-エチル-β-プロピルアクロレイン-アニリン縮合物等の少なくとも1種が挙げられる。好ましくは、入手しやすさの点から、n-ブチルアルデヒド-アニリン縮合物の使用が望ましい。
また、本発明では、チラウム系加硫促進剤の中で、テトラ(2-エチルヘキシル)チウラムジスルフィド、1,6-ビス(N,N´-ジベンジルチオカルバモイルジチオ)-ヘキサン及び1,6-ビス{N,N´-ジ(2-エチルヘキシル)チオカルバモイルジチオ}-ヘキサンから選ばれる少なくとも1つの化合物を用いるものであり、これ以外のチラウム系であるテトラメチルチウラムジスルフィド(TMTD)、テトラメチルチウラムモノスルフィド(TMTD)等の場合は、発がん性のニトロソアミン先駆体を含むこととなり、本発明の効果を発揮できないこととなる。
チアゾール系加硫促進剤としては、例えば、メルカプトベンゾチアゾール(M)、ジベンゾチアジスルフィド(DM)の少なくとも1種が挙げられる。好ましくは、本発明の更なる効果を発揮せしめる点から、ジベンゾチアジスルフィド(DM)の使用が望ましい。
このアルデヒドアミン類、テトラ(2-エチルヘキシル)チウラムジスルフィド、1,6-ビス(N,N´-ジベンジルチオカルバモイルジチオ)-ヘキサン及び1,6-ビス{N,N´-ジ(2-エチルヘキシル)チオカルバモイルジチオ}-ヘキサンから選ばれる少なくとも1つの化合物、及びチアゾール系加硫促進剤の含有量がそれぞれの下限値である0.3、0.1、及び0.1質量部未満であると、架橋度Fmaxまたは加硫速度T0.9が低下することとなる。一方、アルデヒドアミン類、テトラ(2-エチルヘキシル)チウラムジスルフィド、1,6-ビス(N,N´-ジベンジルチオカルバモイルジチオ)-ヘキサン及び1,6-ビス{N,N´-ジ(2-エチルヘキシル)チオカルバモイルジチオ}-ヘキサンから選ばれる少なくとも1つの化合物、チアゾール系加硫促進剤の含有量がそれぞれの上限値である2.5、1.5、及び2.5質量部を超えると、加硫速度T0.9が上昇(値は低下)するだけでなく、加硫速度T0.1も速く(値は低下)なり過ぎ、耐スコーチ性が悪化する問題が生じることとなる。
硫黄(不溶性硫黄)などの加硫剤の含有量は、ゴム成分100質量部に対して、好ましくは、0.1~10.0質量部、更に好ましくは1.0~5.0質量部である。
本発明において、HAF以上の高補強カーボンブラックとは、ヨウ素吸着量やDBP吸着量等で評価される比表面積(m2/g)がHAFカーボンブラックと同等或いはそれより大きいカーボンブラックを指し、ゴム組成物に配合した時に弾性率や破壊強度を向上させる効果がHAFカーボンと同等或いはそれより高いカーボンブラックのことを意味する。
このN330以上のカーボンブラックの中でも好ましいのは、N330,N335、N339、N343、N347、N351、N356、N358、N375、N220、N234、特に好ましいのは、N330、N335、N339、N343、N347、N220が望ましい。
このHAF(N330)以上のカーボンブラックを使用することにより、更に高破壊強度と高耐熱性を獲得することができるゴム組成物が得られるものとなる。
このカーボンブラックの含有量が30質量部未満であると、機械的強度が不十分であり、一方、60質量部を越えると、発熱特性が悪くなり、または、未加硫時の粘度上昇、粘着力低下が生じ、バフ面凹凸への追従性の不足、未加硫時接着不良等の問題点が生じる場合がある。
これに対して、本発明で用いるアルデヒドアミン類ではなく、従来技術となる特開2002-356102号公報(特許文献1)の実施例で示されるグアニジン類をアミン類として適用しても、加硫速度T0.9を速くする効果がアルデヒドアミン類対比低く、効果を増すために、多量に使用すると、加硫速度T0.1が速くなり過ぎてスコーチ性が悪化してしまうこととなる(この点については更に後述する比較例等において詳述する)。
本発明では、上記3種のアルデヒドアミン類0.3~2.5質量部、及びテトラ(2-エチルヘキシル)チウラムジスルフィド、1,6-ビス(N,N´-ジベンジルチオカルバモイルジチオ)-ヘキサン及び1,6-ビス{N,N´-ジ(2-エチルヘキシル)チオカルバモイルジチオ}-ヘキサンから選ばれる少なくとも1つの化合物を0.1~1.5質量部、加えて、チアゾール系加硫促進剤を0.1~2.5質量部含有させることによって、初めて、100℃付近の温度での高い架橋度と、加硫時間の短時間化と、耐スコーチ性(加工時発熱による硬化防止)により生産性に優れるゴム組成物が得られるものである。
本発明のタイヤでは、更生タイヤのタイヤ性能を損なうことなく生産性を向上させることができることとなる。また、本発明のゴム組成物を別々に加硫されたゴム部材どうしを接着させて作製されるタイヤにおいて、加硫済ゴム部材の間に挟み共加硫させて接着させる接着用ゴムに適用することにより、タイヤ性能を損なうことなく生産性を向上させることができるものとなる。
下記表1及び2に示す配合処方のゴム組成物を調製した。得られた各ゴム組成物について、下記方法により、加硫最大トルク(Fmax)、加硫速度T0.9及びT0.1の測定を行った。
なお、本実施例は、単に例示であり、通常用いられるシリカ等の補強充填剤、粘着付与剤(タッキファイヤ)、および軟化剤(プロセスオイル)等の各種ゴム用配合剤の使用を制限するものではない。
JIS K6300-2に準拠して、温度105℃±1℃で測定した加硫トルクカーブの最大値を測定した。この加硫最大トルク:Fmaxは、105℃における架橋度の指標を示すものである。
JIS K6300-2に準拠して、温度105℃±1℃で測定した加硫トルクカーブの最大値の90%を得るまでに要する時間(分)を測定した。この加硫速度T0.9は、加硫完了までの加硫速度の指標を示すものであり、値が小さいほど加硫速度が速いことを表す。
JIS K6300-2に準拠して、温度105℃±1℃で測定した加硫トルクカーブの最大値の10%を得るまでに要する時間(分)を測定した。この加硫速度T0.1は、耐スコーチ性を示す指標であり、値が小さい程、架橋反応が始まるまでの誘導期間が短くスコーチし易い(耐スコーチ性が悪い)ことを表す。
*1:N-フェニル-N´-(1,3-ジメチルブチル)-p-フェニレンジアミン
*2:N-(1,3-ジメチル-ブチル)-N´-フェニル-p-フェニレンジアミン
(大内新興化学社製 ノクラック 6C)
*3:Polymerized2、2、4-トリメチル-1、2 ジヒドロキノリン:TMDQ(大内新興化学社製 ノクラック 224)
*4:アルキルフェノールホルムアルデヒド樹脂(SI GROUP-RIBECOURT社製 R7521P)
*5:BAA1:n-ブチルアルデヒド-アニリン縮合物(大内新興化学社製 ノクセラー8)
*6:BAA2:n-ブチルアルデヒド-アニリン縮合物(AKROCHEM社製 A40B)
*7:DM:ジベンゾチアジスルフィド(大内新興化学工業社製、ノクセラーDM)
*8:TOT:テトラ(2-エチルヘキシル)チウラムジスルフィドの33%シリカ担持品(シリカ/TOT=1/3、大内新興化学社製、ノクセラーTOT-N)
*9:KA9188:1,6-ビス(N,N´-ジベンジルチオカルバモイルジチオ)-ヘキサン(LANXESS社製、VULCUREN KA9188)
*10:HDC:1,6-ビス{N,N´-ジ(2-エチルヘキシル)チオカルバモイルジチオ}-ヘキサン
*11:DPG:ジフェニルグアニジン(大内新興化学工業社製、ノクセラーD)
*12:TBZTD:テトラベンジルチウラムジスルフィド
これに対して、本発明の範囲外となる比較例を個別的にみると、比較例1~4は、ジフェニルグアニジン(DPG)、チアゾール系加硫促進剤(DM)及びテトラ(2-エチルヘキシル)チウラムジスルフィド(TOT)の3種の組み合わせ、比較例5は、チアゾール系加硫促進剤(DM)及びテトラ(2-エチルヘキシル)チウラムジスルフィド(TOT)の2種の組み合わせ、比較例6はアルデヒドアミン類(BAA)及びテトラ(2-エチルヘキシル)チウラムジスルフィド(TOT)の2種の組み合わせ、比較例7はアルデヒドアミン類(BAA)及びチアゾール系加硫促進剤(DM)の2種の組み合わせ、比較例8は、ジフェニルグアニジン(DPG)及びチアゾール系加硫促進剤(DM)の2種の組み合わせ、比較例9及び10は、アルデヒドアミン類(BAA)、チアゾール系加硫促進剤(DM)及びテトラベンジルチウラムジスルフィド(TBZTD)の3種の組み合わせであり、これらの場合、本発明の効果を発揮できないことが判った。
また、実施例1~6と比較例1~4は、チアゾール系加硫促進剤(DM)及びテトラ(2-エチルヘキシル)チウラムジスルフィド(TOT)の2種の組み合わせに対して、アルデヒドアミン類(BAA)対ジフェニルグアニジン(DPG)との比較であり、加硫速度T0.1が速くなり過ぎてスコーチ性が悪化してしまうこととなる。
更に、比較例9、10は、従来技術となる特開平8-59898号公報(特許文献2)の実施例(組成物1.5)で示されるアルデヒドアミン類、チアゾール系加硫促進剤(DM)及びテトラベンジルチウラムジスルフィド(TBZTD)の組み合わせであるが、この場合も加硫速度T0.1が速くなり過ぎてスコーチ性が悪化してしまうこととなる。
したがって、上記実施例1~14及び比較例1~10の結果から明らかなように、本発明となる処方のゴム組成物では、100℃付近の温度での高い架橋度と、加硫時間の短時間化と、耐スコーチ性(加工時発熱による硬化防止)により生産性に優れるゴム組成物が得られることが判明した。
また、上記実施例1~14のゴム組成物を、更正タイヤのクッションゴムに適用することにより、また、別々に加硫されたゴム部材どうしを接着させて作製されるタイヤにおいて、加硫済ゴム部材の間に挟み共加硫させて接着させる接着用ゴムに適用することにより、タイヤ性能を損なうことなく生産性を向上させることができた。
Claims (5)
- ゴム成分100質量部に対して、アルデヒドアミン類0.3~2.5質量部と、テトラ(2-エチルヘキシル)チウラムジスルフィド、1,6-ビス(N,N´-ジベンジルチオカルバモイルジチオ)-ヘキサン及び1,6-ビス{N,N´-ジ(2-エチルヘキシル)チオカルバモイルジチオ}-ヘキサンから選ばれる少なくとも1つの化合物0.1~1.5質量部と、チアゾール系加硫促進剤0.1~2.5質量部とを含有してなることを特徴とするゴム組成物。
- 120℃以下の加硫温度で加硫されることを特徴とする請求項1記載のゴム組成物。
- ゴム組成物が更生用タイヤのクッションゴムであることを特徴とする請求項1又は2記載のゴム組成物。
- 請求項1~3の何れか一つに記載のゴム組成物を更生用タイヤのクッションゴムとしたことを特徴とするタイヤ。
- 請求項1~3の何れか一つに記載のゴム組成物を、加硫済のタイヤ用ゴム部材と加硫済のタイヤ用ゴム部材の間に挟み共加硫させることによって接着させて製造されたことを特徴とする空気入りタイヤ。
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