WO2018189878A1 - Vulcanizing agent composition and rubber composition containing same - Google Patents

Vulcanizing agent composition and rubber composition containing same Download PDF

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Publication number
WO2018189878A1
WO2018189878A1 PCT/JP2017/015238 JP2017015238W WO2018189878A1 WO 2018189878 A1 WO2018189878 A1 WO 2018189878A1 JP 2017015238 W JP2017015238 W JP 2017015238W WO 2018189878 A1 WO2018189878 A1 WO 2018189878A1
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Prior art keywords
rubber
vulcanizing agent
agent composition
insoluble sulfur
weight
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PCT/JP2017/015238
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French (fr)
Japanese (ja)
Inventor
貴 天野
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四国化成工業株式会社
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Application filed by 四国化成工業株式会社 filed Critical 四国化成工業株式会社
Priority to PCT/JP2017/015238 priority Critical patent/WO2018189878A1/en
Priority to JP2019512141A priority patent/JP6756039B2/en
Publication of WO2018189878A1 publication Critical patent/WO2018189878A1/en

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Classifications

    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a vulcanizing agent composition and a rubber composition containing the same.
  • Insoluble sulfur is sulfur that is insoluble in carbon disulfide and is used as a rubber vulcanizing agent. Insoluble sulfur, compared with soluble sulfur, can suppress blooming, which is caused by migration of sulfur to the surface of rubber in the process from kneading with rubber to completion of vulcanization. As widely used.
  • Patent Documents 8 to 10 disclose that a reaction product of sulfur and olefin (such as dicyclopentadiene) is used as a rubber vulcanizing agent. These vulcanizing agents contain insoluble sulfur as a component. It is different from the vulcanizing agent.
  • insoluble sulfur has low affinity with rubber, and therefore, dispersibility in rubber is generally poor.
  • insoluble sulfur has low affinity with rubber, and therefore, dispersibility in rubber is generally poor.
  • the tendency is strengthened, resulting in insoluble sulfur agglomerates, resulting in variations in rubber physical properties after vulcanization, and the quality of the rubber product is lowered.
  • Insoluble sulfur is easily charged with static electricity, and is charged by contact and friction between particles of insoluble sulfur or by contact and friction with a metering device and kneading equipment when blended into rubber, and adhesion to the device or equipment may occur. Development such as poor fluidity occurred. Such adhesion to a metering device or the like causes a variation in the amount of sulfur blended, and it is necessary to eliminate this, so workability and productivity may be reduced. In particular, in the automatic metering device, when insoluble sulfur having high adhesion is used, the handling thereof is often difficult.
  • Patent Document 11 0.5 to 10% by weight of an anionic or nonionic surfactant is mixed with oil and added to insoluble sulfur to vulcanize.
  • Patent Document 12 discloses a method of adding a nonionic surfactant such as polyethylene glycol ethers to insoluble sulfur
  • Patent Document 13 describes a method of adding a phosphate ester-based nonionic surfactant to insoluble sulfur.
  • Patent Document 14 discloses a method of adding a fatty acid amide antistatic agent to insoluble sulfur.
  • Patent Document 15 discloses a particulate sulfur dispersion in which insoluble sulfur is dispersed in liquid poly (cis-isoprene).
  • Patent Document 16 discloses a rubber dispersibility improving agent in which an oil in which 0.1 to 30 weight percent of rubber is dissolved in insoluble sulfur is added so that the total amount is 0.5 to 30 weight percent.
  • Document 17 discloses highly dispersible insoluble sulfur in which a rubber coating film is formed on the surface of insoluble sulfur particles and the coating film is crosslinked with sulfur monochloride or the like.
  • Patent Document 18 discloses a method for producing a dicyclopentadiene resin having a controlled molecular weight, molecular weight distribution, and color by thermally polymerizing a dicyclopentadiene monomer together with an olefin-based modifier.
  • this resin can also be used as a green tack accelerator in rubber processing to improve the properties and handling characteristics of rubber materials before vulcanization. It is disclosed.
  • Patent Document 19 discloses a rubber composition for a low-hardness rubber roll obtained by blending dicyclopentadiene resin, sulfur or the like with rubber and vulcanizing.
  • Example 4 of Patent Document 20 discloses a diene rubber composition containing a diene rubber, zinc monomethacrylate, carbon black, insoluble sulfur, and a dicyclopentadiene resin.
  • Patent Documents 18 to 20 do not disclose the use of a mixture containing insoluble sulfur and dicyclopentadiene resin as a vulcanizing agent.
  • dicyclopentadiene resin is used as an additive for rubber and is useful for improving and improving the characteristics of unvulcanized rubber and vulcanized rubber.
  • dicyclopentadiene resin improves the thermal stability of vulcanizing agents, particularly insoluble sulfur, and the dispersibility in rubber.
  • the amount of dicyclopentadiene resin or the like is 5 to 40 parts by weight with respect to 100 parts by weight of rubber (claim 2 etc.).
  • sulfur is used in the ratio of 1.5 weight part with respect to 100 weight part of rubber
  • Patent Document 20 the amount of dicyclopentadiene resin is 0.5 to 8 parts by weight with respect to 100 parts by weight of rubber (claim 1 and the like).
  • the amount of vulcanizing agent (insoluble sulfur) is in a ratio of 4 parts by weight to 100 parts by weight of rubber. in use.
  • the present invention provides a vulcanizing agent composition that contains insoluble sulfur as a vulcanizing agent component, has improved thermal stability of insoluble sulfur, has excellent dispersibility in rubber, and has reduced adhesion to an apparatus or the like.
  • the purpose is to provide. Moreover, it aims at providing the rubber composition containing this vulcanizing agent composition.
  • the present invention provides the following vulcanizing agent composition, a rubber composition containing the same, a vulcanized rubber, and a method for producing them.
  • Item 1 A vulcanizing agent composition comprising insoluble sulfur and dicyclopentadiene resin.
  • Item 2 The vulcanizing agent composition according to Item 1, comprising dicyclopentadiene resin in a proportion of 0.25 to 70 parts by weight with respect to 100 parts by weight of insoluble sulfur.
  • Item 3 The vulcanizing agent composition according to Item 1 or 2, comprising a rubber component at a ratio of 200 parts by weight or less with respect to 100 parts by weight of insoluble sulfur.
  • Item 4 The vulcanizing agent composition according to Item 1, 2 or 3, further comprising process oil.
  • Item 5 A method for producing a vulcanizing agent composition comprising mixing insoluble sulfur and dicyclopentadiene resin.
  • Item 6 The method for producing a vulcanizing agent composition according to Item 5, wherein the solvent is removed after mixing the insoluble sulfur, the dicyclopentadiene resin and the solvent.
  • Item 7 A solution is prepared by dissolving dicyclopentadiene resin in a solvent, a slurry is prepared by mixing the solution and insoluble sulfur, and the solvent is removed from the slurry.
  • a method for producing a vulcanizing agent composition is described in detail below.
  • Item 8 A vulcanizing agent composition produced by the production method according to any one of Items 5 to 7.
  • Item 9 A rubber composition comprising the vulcanizing agent composition according to any one of Items 1 to 4 and 8, and a rubber component.
  • Item 10 A method for producing a rubber composition, comprising mixing the vulcanizing agent composition according to any one of Items 1 to 4 and 8, and a rubber component.
  • Item 11 A vulcanized rubber obtained by vulcanizing the rubber composition according to item 9.
  • Item 12 The vulcanized rubber according to Item 11, wherein the vulcanized rubber is a tire.
  • Item 13 A method for producing a vulcanized rubber, wherein the rubber composition according to Item 9 is vulcanized.
  • the vulcanizing agent composition of the present invention is excellent in thermal stability of insoluble sulfur, is excellent in dispersibility of insoluble sulfur in rubber, and can suppress adhesion of insoluble sulfur to an apparatus or the like when blended with rubber.
  • the rubber composition containing the vulcanizing agent composition and rubber of the present invention has good scorch characteristics in the steps before vulcanization (steps such as kneading with rubber, storage and processing operations) (the scorch time is Long), plasticity is maintained and processability (moldability) is excellent.
  • the vulcanized rubber obtained by vulcanizing the rubber composition containing the vulcanizing agent composition of the present invention has a high strength (tensile strength and tensile elongation) because the rubber vulcanization is uniform due to the above characteristics. )have.
  • Vulcanizing agent composition The vulcanizing agent composition of the present invention is characterized by containing insoluble sulfur and a dicyclopentadiene resin (hereinafter also referred to as "DCPD resin").
  • DCPD resin dicyclopentadiene resin
  • insoluble sulfur is excellent in thermal stability, rearrangement to soluble sulfur is suppressed, dispersibility of insoluble sulfur in rubber is excellent, and fluidity of insoluble sulfur is improved, so that an apparatus, etc. Adhesion to can be suppressed.
  • the vulcanizing agent composition can be used as a vulcanizing agent blended with the rubber component.
  • Insoluble sulfur is generally polymeric sulfur produced when molten sulfur at 159 ° C. or higher is quenched, and means sulfur that is insoluble in carbon disulfide at 20 ° C.
  • the average particle size is usually 0.1 to 300 ⁇ m, preferably 1 to 50 ⁇ m, more preferably 5 to 25 ⁇ m.
  • the average particle diameter can be measured using a particle size distribution measuring apparatus of a laser diffraction method.
  • the DCPD resin is dicyclopentadiene (hereinafter referred to as “DCPD”) which is a dimer of cyclopentadiene (hereinafter also referred to as “CPD”) in a C5 fraction obtained by decomposing naphtha.
  • DCPD dicyclopentadiene
  • C5 fraction obtained by decomposing naphtha.
  • a catalyst When polymerizing DCPD, a catalyst is usually used. Various catalyst systems (polymerization catalysts) are used to impart desired properties to the resulting polymer. The polymerization mechanism varies depending on the type of polymerization catalyst, and gives different polymers.
  • the polymer represented by the formula (IIa) and the polymer represented by the formula (IIb) are derived from the DCPD represented by the formula (II) and are represented by the formula (IIIa).
  • the polymer represented by the formula (IIIb) is derived from the polymer represented by the formula (III).
  • the polymer represented by the formula (IIa) and the polymer represented by the formula (IIIa) are ring-opened polymers, and the polymer represented by the formula (IIb) and the formula (IIIb)
  • the polymer obtained is a vinylene type polymer (see Japanese Patent Publication No. 41-20111).
  • the DCPD resin is a resin (polymer) mainly having a structure derived from DCPD as described above, and specifically, a DCPD polymer or a co-polymer of DCPD and a polymerizable olefin compound. Examples are polymers.
  • the DCPD resin preferably contains 30% by weight or more, more preferably 50% by weight or more, and particularly preferably 70% by weight or more of DCPD in the total weight of the resin.
  • the DCPD resin can be produced from DCPD and, if necessary, other polymerizable olefin compounds using a known polymerization method and polymerization conditions.
  • Examples of olefin compounds polymerizable with DCPD include 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl- Olefinic hydrocarbons such as 2-butene; Diolefinic hydrocarbons such as butadiene and isoprene; and vinyl-substituted aromatic hydrocarbons such as styrene, ⁇ -methylstyrene and vinyltoluene; Vinyl acetate; Acrylic acid esters; Maleic anhydride Phenol and the like. These olefin compounds can be copolymerized with DCPD in the presence of a suitable catalyst.
  • various DCPD resins are produced by allowing the olefin compound or oligomer thereof to coexist during DCPD polymerization, or by adding the olefin compound or oligomer thereof to a DCPD resin obtained by polymerizing DCPD. be able to.
  • the DCPD resin also includes hydrogenated DCPD resin.
  • DCPD resins from liquid DCPD resin to solid DCPD resin having a high softening point can be produced by appropriately selecting and setting a polymerization method and polymerization conditions.
  • a solid (pale yellow) DCPD resin having a softening point of 100 ° C. or higher can be used.
  • DCPD resin has a higher degree of unsaturation than other C5 petroleum resins and C9 petroleum resins, is highly reactive, and easily cures when heated with drying oil, alkyd resins, rosin derivatives, and the like. In addition to this high reactivity, it has a low softening point, but has a low molecular weight and a low melt viscosity. Therefore, it is easy to chemically modify. Can be manufactured.
  • a modified DCPD resin having an ester group or a hydroxyl group in the polymer molecule has improved solubility in solvents such as alcohols, ketones and esters, and compatibility with epoxy resins and polyamide resins.
  • DCPD resin is used as an additive to improve the crack resistance and tackiness of natural rubber and synthetic rubber, improve the drying property of paint, water / alkali resistance, adhesion, etc. by utilizing its high reactivity. in use.
  • rosin-modified products and hydrogenated products exhibit excellent performance as tackifiers for pressure-sensitive adhesives and hot-melt adhesives.
  • those having a polar group introduced into the polymer molecule such as maleated-ester-modified resin, are suitable as components of offset ink.
  • a DCPD resin having an ester group or a hydroxyl group in the polymer molecule is suitable as an additive for improving the adhesion, water resistance, coating film hardness, etc. of the epoxy resin and urethane resin paint ("2016” (See the year edition 16716 Chemical Products, Chemical Industry Daily, published on January 26, 2016, pages 1189-1190)).
  • the DCPD resin has a weight average molecular weight of 100 to 1500, more preferably 250 to 1000, a softening point (JIS K-2207 ring and ball type) of 50 to 200 ° C., further 90 to 170 ° C., and a specific gravity (20 ° C.) of 1. 1.2 g / cm 3 , further 1.05 to 1.15 g / cm 3 , bromine number (ASTM D-1158-57T) is 20 to 180 g / 100 g, further 100 to 180 g / 100 g, acid value (JIS K-2501) includes a DCPD resin having a characteristic of 0.1 mgKOH / g or less.
  • DCPD resins trade names “Quinton 1000 series” (alicyclic hydrocarbon resin) manufactured by ZEON CORPORATION, trade names “Marcaretz M series” manufactured by Maruzen Petrochemical Co., Ltd. ”(Alicyclic hydrocarbon resin), Idemitsu Kosan Co., Ltd. trade name“ Imabe ”(aromatic copolymer hydrogenated petroleum resin), TonenGeneral Sekiyu brand name“ T-REZ H Series ”( Hydrogenated hydrocarbon resin) and the like.
  • the mixing ratio of insoluble sulfur and DCPD resin contained in the vulcanizing agent composition is not particularly limited.
  • the amount of DCPD resin is usually 0.25 to 70 parts by weight, preferably 1 with respect to 100 parts by weight of insoluble sulfur. It is ⁇ 60 parts by weight, more preferably 2.5 to 50 parts by weight, still more preferably 5 to 45 parts by weight, and particularly preferably 10 to 40 parts by weight.
  • the vulcanizing agent composition can further contain process oil in addition to insoluble sulfur and DCPD resin.
  • Process oil is not particularly limited as long as it can be normally used in this technical field.
  • mineral oil system paraffinic process oil / naphthene process oil / aromatic process oil / liquid paraffin / petrotam / gilsonite / petroleum asphalt
  • vegetable oil system castor oil / rapeseed oil / seed oil / cotton seed oil / soybean oil / palm
  • sub factis
  • process oils for rubber such as fatty acids and fatty acid derivatives. 1 type (s) or 2 or more types chosen from these can be used.
  • Process oils such as mineral oils (paraffinic and naphthenic rubber process oils) are preferred.
  • the blending ratio of process oil is not particularly limited. From the viewpoint of scattering of insoluble sulfur and suppression of charging, dispersibility in rubber, prevention of adhesion to a measuring device, etc., the process oil is usually 60 parts by weight or less, preferably 2.5 parts by weight with respect to 100 parts by weight of insoluble sulfur. About 35 parts by weight, more preferably 5 to 35 parts by weight, and particularly preferably 10 to 30 parts by weight.
  • the vulcanizing agent composition may further contain other additives (for example, rubber components, silica, etc.) as necessary.
  • the blending ratio of the rubber component is determined from the viewpoint of dispersibility of the vulcanizing agent composition in rubber, prevention of adhesion to a measuring device, etc.
  • the amount is usually 200 parts by weight or less, preferably about 1 to 100 parts by weight, more preferably 1 to 20 parts by weight, and particularly preferably 1 to 2.5 parts by weight with respect to parts by weight.
  • a rubber component what was enumerated by the rubber component contained in the rubber composition mentioned later is mentioned, for example.
  • the vulcanizing agent composition can be produced by mixing insoluble sulfur and DCPD resin. If necessary, other additives described above can also be mixed. Examples of the production method include a method in which insoluble sulfur and DCPD resin are mixed in a powder state, or a method in which insoluble sulfur, DCPD resin, and a solvent are mixed and then the solvent is removed. Examples of the solvent include organic solvents that can dissolve the DCPD resin, and typically include carbon disulfide, toluene, xylene, cyclohexane, and tetrahydrofuran. Of these, carbon disulfide is preferred.
  • the vulcanizing agent composition is prepared by dissolving a DCPD resin in a solvent (for example, carbon disulfide), preparing a solution, spraying the solution onto insoluble sulfur, and then removing the solvent.
  • a solvent for example, carbon disulfide
  • it can be produced by adding insoluble sulfur to this solution to prepare a slurry and then removing the solvent.
  • the method for removing the solvent include a method for removing the solvent by volatilizing the solvent by means of heating and / or decompression.
  • the vulcanizing agent composition contains process oil
  • it can be produced, for example, by mixing the slurry prepared above and process oil and removing the solvent from the resulting mixture. Or it can manufacture by mixing the vulcanizing agent composition containing the insoluble sulfur and DCPD resin manufactured above, and a process oil. Examples of the mixing method include a method of stirring using a planetary mixer or the like.
  • the above production method is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon from the viewpoint of safety.
  • Rubber composition and vulcanized rubber means a rubber composition before vulcanization treatment containing a rubber component, the above vulcanizing agent composition, and other components as required.
  • the rubber component is not particularly limited.
  • natural rubber NR
  • butadiene rubber BR
  • isoprene rubber IR
  • styrene-butadiene rubber SBR
  • ethylene-propylene rubber EPM, EPDM
  • butyl rubber IIR
  • Halogenated butyl rubber X-IIR
  • chloroprene rubber CR
  • silicone rubber Q
  • fluoro rubber FKM
  • polysulfide rubber T
  • chlorinated polyethylene CPE
  • polyurethane U
  • hypalon Ethylene-vinyl acetate-acrylic ester rubber epichlorohydrin rubber, acrylic rubber and the like.
  • one kind or a mixture of two or more kinds can be used.
  • the compounding amounts of the rubber component and the vulcanizing agent composition in the rubber composition are not particularly limited.
  • the blending ratio of the vulcanizing agent composition is usually 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, more preferably 1 to 6 parts by weight with respect to 100 parts by weight of the rubber component.
  • the rubber composition may contain other components as necessary.
  • other components include other vulcanizing agents (peroxides, etc.), vulcanization accelerators (aldehyde-ammonia system, aldehyde-amine system). , Guanidine, thiourea, thiazole, sulfenamide, thiuram, thidiocarbamate, xanthate, etc.); vulcanization accelerator (zinc oxide, magnesium oxide, red lead, calcium hydroxide) , Stearic acid, zinc stearate, amines, diethylene glycol, etc., especially zinc oxide, stearic acid, etc.), reinforcing agents or fillers (talc, clay, carbon black, white carbon, graphite, calcium carbonate, calcium silicate , Magnesium hydroxide, etc.), anti-aging agents (amine, phenol, sulfur, phosphorus, etc.), softeners or plastics (Mineral oil, vegetable oil, synthetic resin, dioctyl phthalate, dio
  • a sulfenamide type as a vulcanization accelerator, zinc oxide, stearic acid, etc. as a vulcanization acceleration aid, carbon black, etc. as a reinforcing agent or filler
  • an amine or the like as an anti-aging agent and a mineral oil or the like as a softener or plasticizer.
  • the mixing ratio of the other components is not particularly limited.
  • the vulcanization accelerator is usually about 0.1 to 5 parts by weight, and the vulcanization accelerator is usually about 1 to 15 parts by weight.
  • the reinforcing agent or filler is usually about 20 to 100 parts by weight, the anti-aging agent is usually about 0.5 to 4 parts by weight, and the softener or plasticizer is usually about 2 to 20 parts by weight. It is.
  • the rubber composition is produced by kneading a rubber component, a vulcanizing agent composition, and other components as necessary, by a general method using a kneader (kneader, Banbury mixer, etc.), an open roll or the like. be able to. Furthermore, a vulcanized rubber can be obtained by vulcanizing the produced rubber composition at a suitable vulcanization temperature according to the type and blending ratio of each component. Vulcanization can be carried out, for example, at 150 to 170 ° C. for about 1 to 30 minutes.
  • the rubber composition of the present invention contains a vulcanizing agent composition containing insoluble sulfur and DCPD resin in the rubber component, it has excellent dispersibility of insoluble sulfur in the rubber component and also has good scorch characteristics. Suppressing blooming is expected. Moreover, the vulcanized rubber obtained by vulcanizing the rubber composition has good mechanical properties (such as tensile strength and tensile elongation).
  • the vulcanizing agent composition of the present invention is useful as a vulcanizing agent for various rubber components, for example, rubber materials requiring high hardness (particularly, rubber for tires, seismic isolation rubber, vibration damping rubber, It can be suitably used as a vulcanizing agent for producing a conveyor belt or the like.
  • Thermal stability test A test tube containing 20 ml of mineral oil (product name “Daphney Oil CP 15N”, manufactured by Idemitsu Kosan Co., Ltd.) is immersed in an oil bath set at a temperature of 120 ° C., and the mineral oil temperature in the test tube becomes 120 ° C. At that time, the vulcanizing agent composition was added to the test tube so that the amount of insoluble sulfur was 1 g and heated for 15 minutes.
  • mineral oil product name “Daphney Oil CP 15N”, manufactured by Idemitsu Kosan Co., Ltd.
  • test tube is taken out from the oil bath and cooled by immersing it in ice water. Subsequently, the insoluble matter in the test tube is washed with carbon disulfide, and soluble sulfur is dissolved in carbon disulfide, followed by filtration. After drying, powdered insoluble sulfur was weighed, and the residual rate of insoluble sulfur was calculated by the following formula. It was determined that the greater the residual ratio, the better the thermal stability.
  • Residual rate (%) [insoluble sulfur content after heating and washing (g) / vulcanizing agent composition (g)] ⁇ [100 / content of insoluble sulfur in vulcanizing agent composition (% by weight)] ⁇ 100
  • a vulcanizing agent composition having a major axis of 0.5 mm or more in the region of the central part (2 cm ⁇ 10 cm) of the cut surface of the test piece (2 cm ⁇ 15 cm) by stacking five sheet-like test pieces. The number of aggregates was visually measured. It was determined that the smaller the number, the better the dispersibility with respect to rubber.
  • Adhesion rate (%) [weight of vulcanizing agent composition adhering to container (g) / 300 (g)] ⁇ 100
  • Mooney scorch time was measured in accordance with the method defined in “JIS K 6300-1.”
  • the Mooney scorch time is shown in terms of a relative value when the value of Comparative Example 2 described later is set to 100.
  • Mooney scorch time indicates the scorch time of unvulcanized rubber (note: also called initial vulcanization, early vulcanization or burning). The smaller this value, the more the rubber composition (compound rubber) is stored or kneaded. It is determined that vulcanization occurs during processing operations prior to calendering, extrusion, and other vulcanization processes, and as a result, the plasticity decreases, the elasticity increases, and the workability (formability) may decrease. Therefore, the larger the Mooney scorch time value, the better.
  • Example 1 2.5 parts by weight of dicyclopentadiene resin was dissolved in 230 parts by weight of carbon disulfide, and then 100 parts by weight of insoluble sulfur was added and mixed to prepare a slurry (insoluble sulfur concentration: 30% by weight). . Next, this slurry was heated at 65 ° C. for 1 hour to volatilize carbon disulfide, and a vulcanizing agent composition containing a dicyclopentadiene resin was produced. An evaluation test was performed on this vulcanizing agent composition. The test results obtained are shown in Table 1.
  • Example 2 to 6 A vulcanizing agent composition was prepared and evaluated in the same manner as in Example 1 except that the amount of dicyclopentadiene resin used was set to the blending ratio (parts by weight) shown in Table 1. It was. The test results obtained are shown in Table 1.
  • Example 7 Using the vulcanizing agent composition prepared in Example 4, 115 parts by weight of this vulcanizing agent composition and 25 parts by weight of process oil were stirred and mixed in a planetary mixer for 30 minutes to obtain a vulcanizing agent composition. A product (oil-treated product) was produced. An evaluation test was performed on this vulcanizing agent composition. The test results obtained are shown in Table 1.
  • Example 1 An evaluation test was conducted in the same manner as in Example 1 using only insoluble sulfur as a vulcanizing agent. The test results obtained are shown in Table 1.
  • Example 2 100 parts by weight of insoluble sulfur and 25 parts by weight of process oil were stirred and mixed in a planetary mixer for 30 minutes in the same manner as in Example 7 to produce a vulcanizing agent composition (oil-treated product). An evaluation test was performed on this vulcanizing agent composition. The test results obtained are shown in Table 1. The Mooney scorch time, the tensile strength, and the tensile elongation are each shown as 100.
  • Example 3 A vulcanizing agent composition containing dicyclopentadiene was produced in the same manner as in Example 4 except that dicyclopentadiene was used instead of dicyclopentadiene resin. An evaluation test was performed on this vulcanizing agent composition. The test results obtained are shown in Table 1.
  • Comparative Example 4 An evaluation test was conducted in the same manner as in Comparative Example 1 except that only insoluble sulfur was used as a vulcanizing agent and 0.525 part by weight of dicyclopentadiene resin was added to 100 parts by weight of natural rubber. The test results obtained are shown in Table 1.
  • the vulcanizing agent composition of the present invention is characterized by containing insoluble sulfur and dicyclopentadiene resin.
  • insoluble sulfur has excellent thermal stability, rearrangement to soluble sulfur is suppressed, dispersibility of insoluble sulfur in rubber is excellent, and fluidity of insoluble sulfur is improved. Therefore, it is possible to suppress adhesion to the device or the like. Therefore, it can be suitably used as a rubber vulcanizing agent.

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Abstract

The present invention provides a vulcanizing agent composition and a rubber composition containing same. The vulcanizing agent composition exhibits an excellent thermal stability by insoluble sulfur and an excellent dispersibility by insoluble sulfur in rubber, and suppresses the attachment of insoluble sulfur to, e.g., the equipment and so forth, during rubber compounding. The present invention relates to a vulcanizing agent composition containing insoluble sulfur and a dicyclopentadiene resin, a method for producing this vulcanizing agent composition, a rubber composition containing this vulcanizing agent composition and a rubber component, and a method for producing the rubber composition.

Description

加硫剤組成物及びそれを含むゴム組成物Vulcanizing agent composition and rubber composition containing the same
　本発明は、加硫剤組成物及びそれを含むゴム組成物に関する。 The present invention relates to a vulcanizing agent composition and a rubber composition containing the same.
　不溶性硫黄は二硫化炭素に不溶性の硫黄であり、ゴムの加硫剤として使用されている。不溶性硫黄は、可溶性硫黄に比べて、ゴムと混練り後、加硫を終了するまでの工程において、硫黄がゴムの表面に移行して析出するブルーミングを抑制できるため、特にラジアルタイヤの加硫剤として広く使用されている。 Insoluble sulfur is sulfur that is insoluble in carbon disulfide and is used as a rubber vulcanizing agent. Insoluble sulfur, compared with soluble sulfur, can suppress blooming, which is caused by migration of sulfur to the surface of rubber in the process from kneading with rubber to completion of vulcanization. As widely used.
　しかしながら、ゴムの混練り時間を短縮する為に、バンバリーミキサー温度を高くするなどして混練り条件が過酷になると、不溶性硫黄の一部が可溶性硫黄に転移してゴムに溶解するので、ブルーミングが発生する要因となっていた。ブルーミングが発生すると均一にゴムを加硫できず、ゴムの強度不足及び亀裂の原因となる。このことから、加熱時に可溶性硫黄に転移し難い不溶性硫黄、即ち熱安定性の良好な不溶性硫黄の開発が望まれていた。 However, in order to shorten the rubber kneading time, when the kneading conditions become severe, such as by increasing the Banbury mixer temperature, a part of the insoluble sulfur is transferred to soluble sulfur and dissolved in the rubber. It was a factor that occurred. When blooming occurs, the rubber cannot be uniformly vulcanized, resulting in insufficient strength and cracking of the rubber. For this reason, it has been desired to develop insoluble sulfur that is difficult to transfer to soluble sulfur during heating, that is, insoluble sulfur having good thermal stability.
　従来、不溶性硫黄の熱安定性を改善する手段としては、種々の薬剤を不溶性硫黄に配合することが提案されている。当該薬剤として、例えば、特許文献１には、臭素、ヨウ素及び一塩化硫黄（S2Cl2）が、特許文献２には臭素が、特許文献３には一塩化硫黄が、特許文献４にはピネンが、特許文献５にはドデセン、α－メチルスチレン、インデン、ジシクロペンタジエン等のビニル化合物が、特許文献６にはチアゾール系化合物が、特許文献７にはアミンのハロゲン酸塩化合物が開示されている。しかしながら、これらの従来技術では、不溶性硫黄の熱安定性は、まだ十分に満足できる程度ではなかった。 Conventionally, as a means for improving the thermal stability of insoluble sulfur, it has been proposed to add various drugs to insoluble sulfur. Examples of such agents include bromine, iodine and sulfur monochloride (S 2 Cl 2 ) in Patent Document 1, bromine in Patent Document 2, sulfur monochloride in Patent Document 3, and Patent Document 4 Pinene is disclosed in Patent Document 5, vinyl compounds such as dodecene, α-methylstyrene, indene, and dicyclopentadiene, Patent Document 6 discloses thiazole compounds, and Patent Document 7 discloses amine halide salts. ing. However, with these prior arts, the thermal stability of insoluble sulfur has not been fully satisfactory.
　また、特許文献８～１０には、硫黄及びオレフィン（ジシクロペンタジエン等）の反応物をゴムの加硫剤として使用することが開示されているが、これらの加硫剤は、不溶性硫黄を成分とする加硫剤とは異なる。 Patent Documents 8 to 10 disclose that a reaction product of sulfur and olefin (such as dicyclopentadiene) is used as a rubber vulcanizing agent. These vulcanizing agents contain insoluble sulfur as a component. It is different from the vulcanizing agent.
　一方で、不溶性硫黄はゴムとの親和性が低く、それがために一般にゴムへの分散性は悪い。特に不溶性硫黄を多量にゴムに配合するとその傾向は強まり、不溶性硫黄の凝集塊が生じる結果、加硫後のゴム物性にばらつきが生じ、ゴム製品の品質が低下する。 On the other hand, insoluble sulfur has low affinity with rubber, and therefore, dispersibility in rubber is generally poor. In particular, when a large amount of insoluble sulfur is blended with rubber, the tendency is strengthened, resulting in insoluble sulfur agglomerates, resulting in variations in rubber physical properties after vulcanization, and the quality of the rubber product is lowered.
　また、不溶性硫黄は静電気を帯びやすく、不溶性硫黄の粒子同士の接触及び摩擦、或いはゴムへの配合時の計量装置及び混練設備との接触及び摩擦によって帯電し、装置や設備に対する付着が発生したり、流動性が悪くなるなどの現像が発生していた。このような計量装置等への付着は、硫黄配合量の変動を招き、これを解消する必要があることから作業性や生産性が低下することがある。特に自動計量装置においては付着性の大きい不溶性硫黄を使用すると、その取扱いが困難になることが多かった。 Insoluble sulfur is easily charged with static electricity, and is charged by contact and friction between particles of insoluble sulfur or by contact and friction with a metering device and kneading equipment when blended into rubber, and adhesion to the device or equipment may occur. Development such as poor fluidity occurred. Such adhesion to a metering device or the like causes a variation in the amount of sulfur blended, and it is necessary to eliminate this, so workability and productivity may be reduced. In particular, in the automatic metering device, when insoluble sulfur having high adhesion is used, the handling thereof is often difficult.
　このような問題を解決するため、例えば、特許文献１１にはオイルに陰イオン性又は非イオン性の界面活性剤を０．５～１０重量％混合し、これを不溶性硫黄に添加して加硫剤とする方法が、特許文献１２にはポリエチレングリコールエーテル類等の非イオン性界面活性剤を不溶性硫黄に添加する方法が、特許文献１３にはリン酸エステル系非イオン性界面活性剤を不溶性硫黄に添加する方法が、特許文献１４には脂肪酸アミド系帯電防止剤を不溶性硫黄に添加する方法が開示されている。 In order to solve such a problem, for example, in Patent Document 11, 0.5 to 10% by weight of an anionic or nonionic surfactant is mixed with oil and added to insoluble sulfur to vulcanize. Patent Document 12 discloses a method of adding a nonionic surfactant such as polyethylene glycol ethers to insoluble sulfur, and Patent Document 13 describes a method of adding a phosphate ester-based nonionic surfactant to insoluble sulfur. Patent Document 14 discloses a method of adding a fatty acid amide antistatic agent to insoluble sulfur.
　また、ゴム中での不溶性硫黄の分散性を改良することを目的として、特許文献１５には、不溶性硫黄を液体状ポリ（シス－イソプレン）中に分散させた粒子状硫黄分散体が開示され、特許文献１６には、不溶性硫黄に、ゴムを０．１～３０重量パーセント溶解させたオイルを、全量の０．５～３０重量パーセントになるように加えたゴム分散性改良剤が開示され、特許文献１７には、不溶性硫黄の粒子の表面にゴムのコーティング膜を形成し、該コーティング膜を、一塩化硫黄等で架橋させた高分散性不溶性硫黄が開示されている。 For the purpose of improving the dispersibility of insoluble sulfur in rubber, Patent Document 15 discloses a particulate sulfur dispersion in which insoluble sulfur is dispersed in liquid poly (cis-isoprene). Patent Document 16 discloses a rubber dispersibility improving agent in which an oil in which 0.1 to 30 weight percent of rubber is dissolved in insoluble sulfur is added so that the total amount is 0.5 to 30 weight percent. Document 17 discloses highly dispersible insoluble sulfur in which a rubber coating film is formed on the surface of insoluble sulfur particles and the coating film is crosslinked with sulfur monochloride or the like.
　しかしながら、これらの従来技術では、不溶性硫黄の分散性及び付着性の改善はまだ十分に満足できる程度ではなかった。 However, with these conventional techniques, the improvement in dispersibility and adhesion of insoluble sulfur has not been sufficiently satisfactory.
　また、特許文献１８には、ジシクロペンタジエンモノマーをオレフィン系変性剤と共に熱重合させて、分子量、分子量分布、色を制御したジシクロペンタジエン樹脂を製造する方法が開示されている。また、この樹脂が、接着剤、インキ、ワニスに使用される他、加硫前のゴム材料の性質及び取扱い特性を改善する為に、ゴム加工におけるグリーン・タック促進剤としても使用され得る点が開示されている。 Patent Document 18 discloses a method for producing a dicyclopentadiene resin having a controlled molecular weight, molecular weight distribution, and color by thermally polymerizing a dicyclopentadiene monomer together with an olefin-based modifier. In addition to being used in adhesives, inks and varnishes, this resin can also be used as a green tack accelerator in rubber processing to improve the properties and handling characteristics of rubber materials before vulcanization. It is disclosed.
　特許文献１９の表１には、ジシクロペンタジエン樹脂、硫黄等をゴムに配合し、加硫して得られる低硬度ゴムロール用ゴム組成物が開示されている。特許文献２０の実施例４には、ジエン系ゴム、モノメタクリル酸亜鉛、カーボンブラック、不溶性硫黄及びジシクロペンタジエン樹脂を含むジエン系ゴム組成物が開示されている。しかし、特許文献１８～２０には、不溶性硫黄とジシクロペンタジエン樹脂とを含む混合物を加硫剤として使用することについて開示されていない。 Table 1 of Patent Document 19 discloses a rubber composition for a low-hardness rubber roll obtained by blending dicyclopentadiene resin, sulfur or the like with rubber and vulcanizing. Example 4 of Patent Document 20 discloses a diene rubber composition containing a diene rubber, zinc monomethacrylate, carbon black, insoluble sulfur, and a dicyclopentadiene resin. However, Patent Documents 18 to 20 do not disclose the use of a mixture containing insoluble sulfur and dicyclopentadiene resin as a vulcanizing agent.
　ところで、これらの文献によれば、ジシクロペンタジエン樹脂は、ゴムの添加剤として使用され、未加硫ゴムと加硫ゴムの特性改良や改善に有用とされている。しかしながら、ジシクロペンタジエン樹脂が、加硫剤、特に不溶性硫黄の熱安定性やゴム中における分散性を改善する点について開示及び示唆はない。なお、特許文献１９においては、ジシクロペンタジエン樹脂等の配合量が、ゴム１００重量部に対して５～４０重量部とされている（請求項２等）。また、加硫剤（硫黄、ペルオキシド等）の配合量に関する説明はなされていないが、実施例においては、ゴム１００重量部に対して硫黄が１．５重量部の割合で使用されている。 By the way, according to these documents, dicyclopentadiene resin is used as an additive for rubber and is useful for improving and improving the characteristics of unvulcanized rubber and vulcanized rubber. However, there is no disclosure or suggestion that dicyclopentadiene resin improves the thermal stability of vulcanizing agents, particularly insoluble sulfur, and the dispersibility in rubber. In Patent Document 19, the amount of dicyclopentadiene resin or the like is 5 to 40 parts by weight with respect to 100 parts by weight of rubber (claim 2 etc.). Moreover, although the description regarding the compounding quantity of a vulcanizing agent (sulfur, a peroxide, etc.) is not made, in the Example, sulfur is used in the ratio of 1.5 weight part with respect to 100 weight part of rubber | gum.
　一方、特許文献２０においては、ジシクロペンタジエン樹脂の配合量が、ゴム１００重量部に対して０．５～８重量部とされている（請求項１等）。そして、特許文献１９の場合と同様に、加硫剤（不溶性硫黄）の配合量に関する説明はなされていないが、実施例においては、ゴム１００重量部に対して不溶性硫黄が４重量部の割合で使用されている。 On the other hand, in Patent Document 20, the amount of dicyclopentadiene resin is 0.5 to 8 parts by weight with respect to 100 parts by weight of rubber (claim 1 and the like). As in the case of Patent Document 19, there is no explanation about the amount of vulcanizing agent (insoluble sulfur), but in the examples, insoluble sulfur is in a ratio of 4 parts by weight to 100 parts by weight of rubber. in use.
英国特許第６４６９１６号明細書British Patent No. 646916 英国特許第６５２４２１号明細書British Patent No. 652421 米国特許第２４６０３６５号明細書U.S. Pat. No. 2,460,365 米国特許第２４６２１４６号明細書US Pat. No. 2,462,146 英国特許第８０２９６４号明細書British Patent No. 802964 特開平６－１１５９１０号公報JP-A-6-115910 特開平６－１４４８０７号公報JP-A-6-144807 特開平２－７５６４０号公報Japanese Patent Laid-Open No. 2-75640 特開昭６３－０４８３４３号公報JP 63-048343 A 特開昭６２－０８４１３３号公報JP-A-62-084133 特開昭４９－９３２９４号公報JP-A 49-93294 特開昭４７－９０３１号公報JP 47-9031 A 特開平９－１３２６７２号公報JP-A-9-132672 特開２００１－８９５９６号公報JP 2001-89596 A 特開昭６１－２２７９０４号公報Japanese Patent Application Laid-Open No. 61-227904 特開昭６１－１９６４３号公報JP-A 61-19643 特開平７－３０９６０９号公報JP-A-7-309609 特開平８－４８７２３号公報Japanese Patent Laid-Open No. 8-48723 特開平７－６２１５７号公報JP-A-7-62157 特開２００９－２４２５７９号公報JP 2009-242579 A
　本発明は、加硫剤成分として不溶性硫黄を含み、不溶性硫黄の熱安定性が高められ、ゴム中における分散性に優れ、且つ、装置等への付着性が低減された加硫剤組成物を提供することを目的とする。また、この加硫剤組成物を含むゴム組成物を提供することを目的とする。 The present invention provides a vulcanizing agent composition that contains insoluble sulfur as a vulcanizing agent component, has improved thermal stability of insoluble sulfur, has excellent dispersibility in rubber, and has reduced adhesion to an apparatus or the like. The purpose is to provide. Moreover, it aims at providing the rubber composition containing this vulcanizing agent composition.
　本発明者は、上記の課題を解決するために鋭意検討をした結果、不溶性硫黄とジシクロペンタジエン樹脂を含む加硫剤組成物とすることにより、所期の目的を達成し得ることを見出した。更に検討を加えることにより本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventor has found that the intended object can be achieved by using a vulcanizing agent composition containing insoluble sulfur and dicyclopentadiene resin. . Further studies have been made to complete the present invention.
　即ち、本発明は、以下の加硫剤組成物、それを含むゴム組成物、加硫ゴム、及びそれらの製造方法を提供する。 That is, the present invention provides the following vulcanizing agent composition, a rubber composition containing the same, a vulcanized rubber, and a method for producing them.
　項１　不溶性硫黄及びジシクロペンタジエン樹脂を含む加硫剤組成物。 Item 1. A vulcanizing agent composition comprising insoluble sulfur and dicyclopentadiene resin.
　項２　不溶性硫黄１００重量部に対し、ジシクロペンタジエン樹脂を０．２５～７０重量部の割合で含む項１に記載の加硫剤組成物。 Item 2. The vulcanizing agent composition according to Item 1, comprising dicyclopentadiene resin in a proportion of 0.25 to 70 parts by weight with respect to 100 parts by weight of insoluble sulfur.
　項３　不溶性硫黄１００重量部に対し、ゴム成分を２００重量部以下の割合で含む項１又は２に記載の加硫剤組成物。 Item 3. The vulcanizing agent composition according to Item 1 or 2, comprising a rubber component at a ratio of 200 parts by weight or less with respect to 100 parts by weight of insoluble sulfur.
　項４　さらにプロセスオイルを含む項１、２又は３に記載の加硫剤組成物。 Item 4. The vulcanizing agent composition according to Item 1, 2 or 3, further comprising process oil.
　項５　不溶性硫黄及びジシクロペンタジエン樹脂を混合することを特徴とする加硫剤組成物の製造方法。 Item 5. A method for producing a vulcanizing agent composition comprising mixing insoluble sulfur and dicyclopentadiene resin.
　項６　不溶性硫黄、ジシクロペンタジエン樹脂及び溶剤を混合した後、溶剤を除去することを特徴とする項５に記載の加硫剤組成物の製造方法。 Item 6. The method for producing a vulcanizing agent composition according to Item 5, wherein the solvent is removed after mixing the insoluble sulfur, the dicyclopentadiene resin and the solvent.
　項７　ジシクロペンタジエン樹脂を溶剤に溶解して溶液を調製し、この溶液と不溶性硫黄とを混合してスラリーを調製し、このスラリーから溶剤を除去することを特徴とする項５又は６に記載の加硫剤組成物の製造方法。 Item 7: A solution is prepared by dissolving dicyclopentadiene resin in a solvent, a slurry is prepared by mixing the solution and insoluble sulfur, and the solvent is removed from the slurry. A method for producing a vulcanizing agent composition.
　項８　項５～７のいずれか１項に記載の製造方法で製造される加硫剤組成物。 Item 8. A vulcanizing agent composition produced by the production method according to any one of Items 5 to 7.
　項９　項１～４及び８のいずれか１項に記載の加硫剤組成物、及びゴム成分を含むゴム組成物。 Item 9 A rubber composition comprising the vulcanizing agent composition according to any one of Items 1 to 4 and 8, and a rubber component.
　項１０　項１～４及び８のいずれか１項に記載の加硫剤組成物、及びゴム成分を混合することを特徴とするゴム組成物の製造方法。 Item 10. A method for producing a rubber composition, comprising mixing the vulcanizing agent composition according to any one of Items 1 to 4 and 8, and a rubber component.
　項１１　項９に記載のゴム組成物を加硫した加硫ゴム。 Item 11. A vulcanized rubber obtained by vulcanizing the rubber composition according to item 9.
　項１２　前記加硫ゴムがタイヤである項１１に記載の加硫ゴム。 Item 12. The vulcanized rubber according to Item 11, wherein the vulcanized rubber is a tire.
　項１３　項９に記載のゴム組成物を加硫することを特徴とする加硫ゴムの製造方法。 Item 13. A method for producing a vulcanized rubber, wherein the rubber composition according to Item 9 is vulcanized.
　本発明の加硫剤組成物は、不溶性硫黄の熱安定性に優れ、ゴム中での不溶性硫黄の分散性に優れ、ゴムと配合する時に装置等へ不溶性硫黄の付着を抑制することができる。 The vulcanizing agent composition of the present invention is excellent in thermal stability of insoluble sulfur, is excellent in dispersibility of insoluble sulfur in rubber, and can suppress adhesion of insoluble sulfur to an apparatus or the like when blended with rubber.
　また、本発明の加硫剤組成物及びゴムを含むゴム組成物は、加硫前の工程（ゴムとの混練り、貯蔵、加工作業等の工程）におけるスコーチ特性が良好であり（スコーチタイムが長い）、可塑性が維持され加工性（成形性）に優れている。 Moreover, the rubber composition containing the vulcanizing agent composition and rubber of the present invention has good scorch characteristics in the steps before vulcanization (steps such as kneading with rubber, storage and processing operations) (the scorch time is Long), plasticity is maintained and processability (moldability) is excellent.
　さらに、本発明の加硫剤組成物を含むゴム組成物を加硫した加硫ゴムは、上記の特性に起因してゴムの加硫が均一になるため、高い強度（引張り強さ及び引張り伸び）を有している。 Furthermore, the vulcanized rubber obtained by vulcanizing the rubber composition containing the vulcanizing agent composition of the present invention has a high strength (tensile strength and tensile elongation) because the rubber vulcanization is uniform due to the above characteristics. )have.
　以下、本発明を詳細に説明する。
１．加硫剤組成物
　本発明の加硫剤組成物は、不溶性硫黄及びジシクロペンタジエン樹脂（以下、「ＤＣＰＤ樹脂」と表記することもある。）を含むことを特徴とする。この加硫剤組成物では、不溶性硫黄が熱安定性に優れるため可溶性硫黄への転位が抑制されるとともに、不溶性硫黄のゴムへの分散性が優れ、不溶性硫黄の流動性が向上するため装置等への付着を抑制することができる。加硫剤組成物は、ゴム成分に配合する加硫剤として使用することができる。 Hereinafter, the present invention will be described in detail.
1. Vulcanizing agent composition The vulcanizing agent composition of the present invention is characterized by containing insoluble sulfur and a dicyclopentadiene resin (hereinafter also referred to as "DCPD resin"). In this vulcanizing agent composition, since insoluble sulfur is excellent in thermal stability, rearrangement to soluble sulfur is suppressed, dispersibility of insoluble sulfur in rubber is excellent, and fluidity of insoluble sulfur is improved, so that an apparatus, etc. Adhesion to can be suppressed. The vulcanizing agent composition can be used as a vulcanizing agent blended with the rubber component.
　不溶性硫黄とは、一般に１５９℃以上の溶融硫黄を急冷させた時に生ずる高分子状の硫黄であり、２０℃で二硫化炭素に不溶である硫黄を意味する。粉体の場合は、その平均粒子径が、通常、０．１～３００μｍ、好ましくは１～５０μｍ、より好ましくは５～２５μｍである。平均粒子径は、レーザー回折法の粒度分布測定装置を用いて測定できる。 Insoluble sulfur is generally polymeric sulfur produced when molten sulfur at 159 ° C. or higher is quenched, and means sulfur that is insoluble in carbon disulfide at 20 ° C. In the case of powder, the average particle size is usually 0.1 to 300 μm, preferably 1 to 50 μm, more preferably 5 to 25 μm. The average particle diameter can be measured using a particle size distribution measuring apparatus of a laser diffraction method.
　ＤＣＰＤ樹脂とは、ナフサを分解して得られるＣ５留分中の、シクロペンタジエン（以下、「ＣＰＤ」と表記することもある。）のダイマーであるジシクロペンタジエン（以下、「ＤＣＰＤ」と表記することもある。）を、重合させて得られる樹脂状物（重合体）であり、石油系炭化水素樹脂（石油樹脂）に分類される物質である。 The DCPD resin is dicyclopentadiene (hereinafter referred to as “DCPD”) which is a dimer of cyclopentadiene (hereinafter also referred to as “CPD”) in a C5 fraction obtained by decomposing naphtha. Is a resinous substance (polymer) obtained by polymerizing, and is classified as a petroleum hydrocarbon resin (petroleum resin).
　具体的には、ＤＣＰＤ（式（II））を加熱すると、スキーム（１）及び同（２）に示されるディールズ－アルダー（Diels-Alder）反応が競争的に起こる。即ち、ＤＣＰＤは、重合時の加熱された状態においては、ＣＰＤ（式（I））に分解しており（可逆反応）、ＣＰＤとＤＣＰＤとの反応（可逆反応）により得られる重合物（式（III））も生成する（石油学会誌　J. Japan Petrol. Inst., VOL. 27, No. 1, 26-30(1984)を参照）。 Specifically, when DCPD (formula (II)) is heated, the Diels-Alder reaction shown in schemes (1) and (2) occurs competitively. That is, DCPD is decomposed into CPD (formula (I)) (reversible reaction) in a heated state at the time of polymerization, and a polymer (formula (formula (1)) obtained by reaction of CPD and DCPD (reversible reaction). III)) (see J. 石油 Japan Petrol. Inst., VOL. 27, No. 1, 26-30 (1984)).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　ＤＣＰＤを重合させる際には、通常、触媒が使用される。得られる重合物に所望の特性を付与するために、種々の触媒系（重合触媒）が使用されている。なお、重合触媒の種類によって、重合のメカニズムが異なり、異なる重合物を与える。 When polymerizing DCPD, a catalyst is usually used. Various catalyst systems (polymerization catalysts) are used to impart desired properties to the resulting polymer. The polymerization mechanism varies depending on the type of polymerization catalyst, and gives different polymers.
　具体的には、式（IIa）で示される重合物と、式（IIb）で示される重合物は、前記の式（II）で示されるＤＣＰＤに由来し、式（IIIa）で示される重合物と、式（IIIb）で示される重合物は、前記の式（III）で示される重合物に由来する。また、式（IIa）で示される重合物と、式（IIIa）で示される重合物は、開環型の重合物であり、式（IIb）で示される重合物と、式（IIIb）で示される重合物は、ビニレン型の重合物である（特公昭41-20111号公報を参照）。 Specifically, the polymer represented by the formula (IIa) and the polymer represented by the formula (IIb) are derived from the DCPD represented by the formula (II) and are represented by the formula (IIIa). And the polymer represented by the formula (IIIb) is derived from the polymer represented by the formula (III). Further, the polymer represented by the formula (IIa) and the polymer represented by the formula (IIIa) are ring-opened polymers, and the polymer represented by the formula (IIb) and the formula (IIIb) The polymer obtained is a vinylene type polymer (see Japanese Patent Publication No. 41-20111).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　ＤＣＰＤ樹脂とは、上記のようにＤＣＰＤに由来する構造を主体とする樹脂（重合体）であり、具体的には、ＤＣＰＤの重合体、又は、ＤＣＰＤとこれと重合可能なオレフィン化合物との共重合体が例示される。ＤＣＰＤ樹脂は、樹脂の総重量のうち、ＤＣＰＤを通常３０重量％以上、さらには５０重量％以上、特に７０重量％以上含んでいることが好ましい。 The DCPD resin is a resin (polymer) mainly having a structure derived from DCPD as described above, and specifically, a DCPD polymer or a co-polymer of DCPD and a polymerizable olefin compound. Examples are polymers. The DCPD resin preferably contains 30% by weight or more, more preferably 50% by weight or more, and particularly preferably 70% by weight or more of DCPD in the total weight of the resin.
　ＤＣＰＤ樹脂は、ＤＣＰＤ及び必要に応じ他の重合可能なオレフィン化合物から、公知の重合方法及び重合条件を用いて製造することができる。 The DCPD resin can be produced from DCPD and, if necessary, other polymerizable olefin compounds using a known polymerization method and polymerization conditions.
　ＤＣＰＤと重合可能なオレフィン化合物としては、例えば、１－ブテン、２－ブテン、イソブチレン、１－ペンテン、２－ペンテン、２－メチル－１－ブテン、３－メチル－１－ブテン、２－メチル－２－ブテン等のオレフィン系炭化水素；ブタジエン、イソプレン等のジオレフィン系炭化水素；及びスチレン、α－メチルスチレン、ビニルトルエン等のビニル置換芳香族炭化水素；酢酸ビニル；アクリル酸エステル；無水マレイン酸；フェノール等が挙げられる。これらのオレフィン化合物は、適当な触媒の存在下にＤＣＰＤと共重合させることができる。例えば、ＤＣＰＤの重合時に、当該オレフィン化合物又はそのオリゴマーを共存させたり、ＤＣＰＤを重合して得られたＤＣＰＤ樹脂に、当該オレフィン化合物又はそのオリゴマーを添加するなどして、種々のＤＣＰＤ樹脂を製造することができる。 Examples of olefin compounds polymerizable with DCPD include 1-butene, 2-butene, isobutylene, 1-pentene, 2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl- Olefinic hydrocarbons such as 2-butene; Diolefinic hydrocarbons such as butadiene and isoprene; and vinyl-substituted aromatic hydrocarbons such as styrene, α-methylstyrene and vinyltoluene; Vinyl acetate; Acrylic acid esters; Maleic anhydride Phenol and the like. These olefin compounds can be copolymerized with DCPD in the presence of a suitable catalyst. For example, various DCPD resins are produced by allowing the olefin compound or oligomer thereof to coexist during DCPD polymerization, or by adding the olefin compound or oligomer thereof to a DCPD resin obtained by polymerizing DCPD. be able to.
　また、ＤＣＰＤ樹脂の重合体分子中の二重結合を、水素化（水添）により飽和させることにより、透明性、耐熱性、耐候性等に優れたグレードのＤＣＰＤ樹脂（水添ＤＣＰＤ樹脂）を製造することができる。ＤＣＰＤ樹脂には、水添ＤＣＰＤ樹脂も含まれる。 Also, by saturating the double bond in the polymer molecule of the DCPD resin by hydrogenation (hydrogenation), a grade of DCPD resin (hydrogenated DCPD resin) having excellent transparency, heat resistance, weather resistance, etc. Can be manufactured. The DCPD resin also includes hydrogenated DCPD resin.
　ＤＣＰＤを重合させるに当たって、重合方法や重合条件を適宜選択、設定することにより、液状のＤＣＰＤ樹脂から軟化点の高い固体のＤＣＰＤ樹脂まで、幅広いグレードのＤＣＰＤ樹脂を製造することができる。通常は軟化点が１００℃以上の固体（淡黄色）のＤＣＰＤ樹脂が挙げられる。 In polymerizing DCPD, a wide variety of DCPD resins from liquid DCPD resin to solid DCPD resin having a high softening point can be produced by appropriately selecting and setting a polymerization method and polymerization conditions. Usually, a solid (pale yellow) DCPD resin having a softening point of 100 ° C. or higher can be used.
　ＤＣＰＤ樹脂は、他のＣ５系石油樹脂やＣ９系石油樹脂と比べて不飽和度が高く、反応性に富み、乾性油、アルキド樹脂、ロジン誘導体等と共に加熱すると容易に硬化する。また、この高い反応性に加え、高い軟化点を有するにも拘わらず分子量が小さく、溶融粘度が低いところから、化学変性が行い易く、先の共重合と合わせて、更に多様なグレードのＤＣＰＤ樹脂の製造が可能である。 DCPD resin has a higher degree of unsaturation than other C5 petroleum resins and C9 petroleum resins, is highly reactive, and easily cures when heated with drying oil, alkyd resins, rosin derivatives, and the like. In addition to this high reactivity, it has a low softening point, but has a low molecular weight and a low melt viscosity. Therefore, it is easy to chemically modify. Can be manufactured.
　例えば、エステル基や水酸基を重合体分子中に有する変性タイプのＤＣＰＤ樹脂は、アルコール、ケトン、エステル類等の溶剤に対する溶解性や、エポキシ樹脂、ポリアミド樹脂等との相溶性が改善されている。 For example, a modified DCPD resin having an ester group or a hydroxyl group in the polymer molecule has improved solubility in solvents such as alcohols, ketones and esters, and compatibility with epoxy resins and polyamide resins.
　ＤＣＰＤ樹脂は、その高い反応性を利用して、天然ゴムや合成ゴムの耐亀裂性や粘着性等の改善、塗料の乾燥性、耐水・耐アルカリ性、密着性等を改善する為の添加剤として使用されている。 DCPD resin is used as an additive to improve the crack resistance and tackiness of natural rubber and synthetic rubber, improve the drying property of paint, water / alkali resistance, adhesion, etc. by utilizing its high reactivity. in use.
　例えば、ロジン変性品や水添物は、感圧接着剤やホットメルト接着剤用の粘着付与剤として優れた性能を発揮する。一方、マレイン化－エステル変性樹脂等、重合体分子中に極性基を導入したものは、オフセットインキの成分として好適である。また、特にエステル基や水酸基を重合体分子中に有するＤＣＰＤ樹脂は、エポキシ樹脂、ウレタン樹脂塗料の密着性、耐水性、塗膜硬度等の改善を図る為の添加剤として好適である（「2016年版　16716の化学商品、化学工業日報社、2016年1月26日発行、1189-1190頁」参照）。 For example, rosin-modified products and hydrogenated products exhibit excellent performance as tackifiers for pressure-sensitive adhesives and hot-melt adhesives. On the other hand, those having a polar group introduced into the polymer molecule, such as maleated-ester-modified resin, are suitable as components of offset ink. In particular, a DCPD resin having an ester group or a hydroxyl group in the polymer molecule is suitable as an additive for improving the adhesion, water resistance, coating film hardness, etc. of the epoxy resin and urethane resin paint ("2016" (See the year edition 16716 Chemical Products, Chemical Industry Daily, published on January 26, 2016, pages 1189-1190)).
　ＤＣＰＤ樹脂は、重量平均分子量が１００～１５００、さらに２５０～１０００であり、軟化点（ＪＩＳ Ｋ－２２０７ 環球式）が５０～２００℃、さらに９０～１７０℃であり、比重（２０℃）が１～１．２ｇ／ｃｍ３、さらに１．０５～１．１５ｇ／ｃｍ３であり、臭素価（ＡＳＴＭ  Ｄ－１１５８－５７Ｔ）が２０～１８０ｇ／１００ｇ、さらに１００～１８０ｇ／１００ｇであり、酸価（ＪＩＳ Ｋ－２５０１）が０．１ｍｇＫＯＨ／ｇ以下の特性を有するＤＣＰＤ樹脂を包含する。 The DCPD resin has a weight average molecular weight of 100 to 1500, more preferably 250 to 1000, a softening point (JIS K-2207 ring and ball type) of 50 to 200 ° C., further 90 to 170 ° C., and a specific gravity (20 ° C.) of 1. 1.2 g / cm 3 , further 1.05 to 1.15 g / cm 3 , bromine number (ASTM D-1158-57T) is 20 to 180 g / 100 g, further 100 to 180 g / 100 g, acid value (JIS K-2501) includes a DCPD resin having a characteristic of 0.1 mgKOH / g or less.
　より具体的には、市販されているＤＣＰＤ樹脂の例として、日本ゼオン社製の商品名「クイントン１０００シリーズ「（脂環族系炭化水素樹脂）、丸善石油化学社製の商品名「マルカレッツＭシリーズ」（脂環族系炭化水素樹脂）、出光興産社製の商品名「アイマーブ」（芳香族共重合系の水添石油樹脂）、東燃ゼネラル石油社製の商品名「Ｔ－ＲＥＺ　Ｈシリーズ」（水添炭化水素樹脂）等が挙げられる。 More specifically, as examples of commercially available DCPD resins, trade names “Quinton 1000 series” (alicyclic hydrocarbon resin) manufactured by ZEON CORPORATION, trade names “Marcaretz M series” manufactured by Maruzen Petrochemical Co., Ltd. ”(Alicyclic hydrocarbon resin), Idemitsu Kosan Co., Ltd. trade name“ Imabe ”(aromatic copolymer hydrogenated petroleum resin), TonenGeneral Sekiyu brand name“ T-REZ H Series ”( Hydrogenated hydrocarbon resin) and the like.
　加硫剤組成物に含まれる不溶性硫黄及びＤＣＰＤ樹脂の配合割合は特に限定されない。不溶性硫黄の熱安定性、ゴムへの分散性、及び不溶性硫黄の付着防止の観点から、ＤＣＰＤ樹脂の配合量は、不溶性硫黄１００重量部に対し、通常０．２５～７０重量部、好ましくは１～６０重量部、より好ましくは２．５～５０重量部、さらに好ましくは５～４５重量部、特に好ましくは１０～４０重量部である。 The mixing ratio of insoluble sulfur and DCPD resin contained in the vulcanizing agent composition is not particularly limited. From the viewpoint of thermal stability of insoluble sulfur, dispersibility in rubber, and prevention of adhesion of insoluble sulfur, the amount of DCPD resin is usually 0.25 to 70 parts by weight, preferably 1 with respect to 100 parts by weight of insoluble sulfur. It is ˜60 parts by weight, more preferably 2.5 to 50 parts by weight, still more preferably 5 to 45 parts by weight, and particularly preferably 10 to 40 parts by weight.
　加硫剤組成物は、不溶性硫黄及びＤＣＰＤ樹脂に加えて、さらにプロセスオイルを含めることができる。 The vulcanizing agent composition can further contain process oil in addition to insoluble sulfur and DCPD resin.
　プロセスオイルは、本技術分野で通常使用できるものであれば特に限定されない。例えば、鉱物油系(パラフィン系プロセスオイル／ナフテン系プロセスオイル／芳香族系プロセスオイル／流動パラフィン／ペトロタム／ギルソナイト／石油アスファルト)；植物油系(ひまし油／なたね油／あまに油／綿実油／大豆油／パーム油／やし油／ロジンパインオイル／トール油)；サブ(ファクチス)；脂肪酸及び脂肪酸誘導体等のゴム用プロセスオイルが挙げられる。これらから選ばれる１種又は２種以上を使用することができる。好ましくは、鉱物油系（パラフィン系、ナフテン系等のゴム用プロセスオイル等）等のプロセスオイルである。 Process oil is not particularly limited as long as it can be normally used in this technical field. For example, mineral oil system (paraffinic process oil / naphthene process oil / aromatic process oil / liquid paraffin / petrotam / gilsonite / petroleum asphalt); vegetable oil system (castor oil / rapeseed oil / seed oil / cotton seed oil / soybean oil / palm) Oil / coconut oil / rosin pine oil / tall oil); sub (factis); process oils for rubber such as fatty acids and fatty acid derivatives. 1 type (s) or 2 or more types chosen from these can be used. Process oils such as mineral oils (paraffinic and naphthenic rubber process oils) are preferred.
　加硫剤組成物にプロセスオイルを含む場合、プロセスオイルの配合割合は特に限定されない。不溶性硫黄の飛散や帯電の抑制、ゴムへの分散性、計量装置等への付着防止等の観点から、プロセスオイルは、不溶性硫黄１００重量部に対し、通常６０重量部以下、好ましくは２．５～３５重量部程度、より好ましくは５～３５重量部、特に好ましくは１０～３０重量部である。 When process oil is included in the vulcanizing agent composition, the blending ratio of process oil is not particularly limited. From the viewpoint of scattering of insoluble sulfur and suppression of charging, dispersibility in rubber, prevention of adhesion to a measuring device, etc., the process oil is usually 60 parts by weight or less, preferably 2.5 parts by weight with respect to 100 parts by weight of insoluble sulfur. About 35 parts by weight, more preferably 5 to 35 parts by weight, and particularly preferably 10 to 30 parts by weight.
　加硫剤組成物は、さらに必要に応じ、他の添加剤（例えば、ゴム成分、シリカ等）を含めることができる。 The vulcanizing agent composition may further contain other additives (for example, rubber components, silica, etc.) as necessary.
　他の添加剤としてゴム成分を配合する場合、ゴム成分の配合割合は、加硫剤組成物のゴムへの分散性、計量装置等への付着防止等の観点から、ゴム成分は、不溶性硫黄１００重量部に対し、通常２００重量部以下、好ましくは１～１００重量部程度、より好ましくは１～２０重量部、特に好ましくは１～２．５重量部である。ゴム成分としては、例えば、後述するゴム組成物に含まれるゴム成分に列挙されたものが挙げられる。 When the rubber component is blended as another additive, the blending ratio of the rubber component is determined from the viewpoint of dispersibility of the vulcanizing agent composition in rubber, prevention of adhesion to a measuring device, etc. The amount is usually 200 parts by weight or less, preferably about 1 to 100 parts by weight, more preferably 1 to 20 parts by weight, and particularly preferably 1 to 2.5 parts by weight with respect to parts by weight. As a rubber component, what was enumerated by the rubber component contained in the rubber composition mentioned later is mentioned, for example.
　加硫剤組成物は、不溶性硫黄及びＤＣＰＤ樹脂を混合することにより製造することができる。必要に応じ上記の他の添加剤も混合することができる。製造方法として、例えば、不溶性硫黄及びＤＣＰＤ樹脂をそれぞれ粉体の状態で混合する方法、或いは、不溶性硫黄、ＤＣＰＤ樹脂、及び溶剤を混合した後、当該溶剤を除去する方法が挙げられる。溶剤としてはＤＣＰＤ樹脂を溶解し得る有機溶剤が挙げられ、典型的には、二硫化炭素、トルエン、キシレン、シクロヘキサン、テトラヒドロフラン等が挙げられる。このうち、好ましくは二硫化炭素である。 The vulcanizing agent composition can be produced by mixing insoluble sulfur and DCPD resin. If necessary, other additives described above can also be mixed. Examples of the production method include a method in which insoluble sulfur and DCPD resin are mixed in a powder state, or a method in which insoluble sulfur, DCPD resin, and a solvent are mixed and then the solvent is removed. Examples of the solvent include organic solvents that can dissolve the DCPD resin, and typically include carbon disulfide, toluene, xylene, cyclohexane, and tetrahydrofuran. Of these, carbon disulfide is preferred.
　上記製造方法のうち、不溶性硫黄の熱安定性、ゴムへの不溶性硫黄の分散性、計量装置等への不溶性硫黄の付着防止、より均一な混合、不溶性硫黄とＤＣＰＤ樹脂の高い接触効率等の観点から、後者の方法、即ち、不溶性硫黄、ＤＣＰＤ樹脂、及び溶剤を混合した後、当該溶剤を除去する方法を用いて製造することが好ましい。 Among the above production methods, viewpoints such as thermal stability of insoluble sulfur, dispersibility of insoluble sulfur in rubber, prevention of adhesion of insoluble sulfur to a metering device, more uniform mixing, high contact efficiency between insoluble sulfur and DCPD resin, etc. Therefore, it is preferable to produce the latter method, that is, a method in which insoluble sulfur, DCPD resin, and a solvent are mixed and then the solvent is removed.
　より具体的には、加硫剤組成物は、ＤＣＰＤ樹脂を溶剤（例えば、二硫化炭素）に溶解して溶液を調製して、この溶液を不溶性硫黄に噴霧した後に溶剤を除去することにより、又は、この溶液に不溶性硫黄を投入しスラリーを調製した後に溶剤を除去することにより製造することができる。溶剤を除去する方法は、例えば、加熱及び／又は減圧の手段により溶剤を揮発させて除去する方法が挙げられる。 More specifically, the vulcanizing agent composition is prepared by dissolving a DCPD resin in a solvent (for example, carbon disulfide), preparing a solution, spraying the solution onto insoluble sulfur, and then removing the solvent. Alternatively, it can be produced by adding insoluble sulfur to this solution to prepare a slurry and then removing the solvent. Examples of the method for removing the solvent include a method for removing the solvent by volatilizing the solvent by means of heating and / or decompression.
　加硫剤組成物がプロセスオイルを含む場合には、例えば、上記で調製されたスラリーとプロセスオイルとを混合し、得られた混合物から溶剤を除去することにより製造することができる。或いは、上記で製造された不溶性硫黄及びＤＣＰＤ樹脂を含む加硫剤組成物とプロセスオイルとを混合することにより製造することができる。混合の方法は、例えば、プラネタリーミキサー等を用いて撹拌する方法が挙げられる。 When the vulcanizing agent composition contains process oil, it can be produced, for example, by mixing the slurry prepared above and process oil and removing the solvent from the resulting mixture. Or it can manufacture by mixing the vulcanizing agent composition containing the insoluble sulfur and DCPD resin manufactured above, and a process oil. Examples of the mixing method include a method of stirring using a planetary mixer or the like.
　上記の製造方法は、安全性の見地から、窒素、アルゴン等の不活性ガスの雰囲気下で実施することが好ましい。 The above production method is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon from the viewpoint of safety.
２．ゴム組成物及び加硫ゴム
　本発明のゴム組成物は、ゴム成分、上記の加硫剤組成物、及び必要に応じ他の成分を含む加硫処理する前のゴム組成物を意味する。 2. Rubber composition and vulcanized rubber The rubber composition of the present invention means a rubber composition before vulcanization treatment containing a rubber component, the above vulcanizing agent composition, and other components as required.
　ゴム成分としては特に限定されず、例えば、天然ゴム（ＮＲ）、ブタジエンゴム（ＢＲ）、イソプレンゴム（ＩＲ）、スチレン－ブタジエンゴム（ＳＢＲ）、エチレン－プロピレンゴム（ＥＰＭ、ＥＰＤＭ）、ブチルゴム（ＩＩＲ）、ハロゲン化ブチルゴム（Ｘ－ＩＩＲ）、クロロプレンゴム（ＣＲ）、シリコ－ンゴム（Ｑ）、フッ素ゴム（ＦＫＭ）、多硫化ゴム（Ｔ）、塩素化ポリエチレン（ＣＰＥ）、ポリウレタン（Ｕ）、ハイパロン、エチレン－酢酸ビニル－アクリル酸エステルゴム、エピクロルヒドリンゴム、アクリルゴム等が挙げられる。これらのうち１種又は２種以上の混合物を用いることができる。 The rubber component is not particularly limited. For example, natural rubber (NR), butadiene rubber (BR), isoprene rubber (IR), styrene-butadiene rubber (SBR), ethylene-propylene rubber (EPM, EPDM), butyl rubber (IIR) ), Halogenated butyl rubber (X-IIR), chloroprene rubber (CR), silicone rubber (Q), fluoro rubber (FKM), polysulfide rubber (T), chlorinated polyethylene (CPE), polyurethane (U), hypalon Ethylene-vinyl acetate-acrylic ester rubber, epichlorohydrin rubber, acrylic rubber and the like. Among these, one kind or a mixture of two or more kinds can be used.
　ゴム組成物における、ゴム成分及び加硫剤組成物のそれぞれの配合量は特に限定されない。加硫剤組成物の配合割合は、ゴム成分１００重量部に対して、通常０．１～１０重量部、好ましくは０．５～８重量部、より好ましくは１～６重量部である。 The compounding amounts of the rubber component and the vulcanizing agent composition in the rubber composition are not particularly limited. The blending ratio of the vulcanizing agent composition is usually 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, more preferably 1 to 6 parts by weight with respect to 100 parts by weight of the rubber component.
　ゴム組成物は、必要に応じて他の成分を含んでいてもよく、他の成分として、例えば、他の加硫剤（ペルオキシド等）、加硫促進剤（アルデヒド－アンモニア系、アルデヒド－アミン系、グアニジン系、チオウレア系、チアゾール系、スルフェンアミド系、チウラム系、チジオカルバミン酸塩系、キサントゲン酸塩系等）；加硫促進助剤（酸化亜鉛、酸化マグネシウム、鉛丹、水酸化カルシウム、ステアリン酸、ステアリン酸亜鉛、アミン類、ジエチレングリコール等、特に酸化亜鉛、ステアリン酸等）、補強剤又は充填剤（タルク、クレー、カ－ボンブラック、ホワイトカ－ボン、グラファイト、炭酸カルシウム、珪酸カルシウム、水酸化マグネシウム等）、老化防止剤（アミン系、フェノール系、硫黄系、リン系等）、軟化剤又は可塑剤（鉱物油系、植物油系、合成樹脂系、ジオクチルフタレート、ジオクチルセバケート等）等が挙げられる。 The rubber composition may contain other components as necessary. Examples of other components include other vulcanizing agents (peroxides, etc.), vulcanization accelerators (aldehyde-ammonia system, aldehyde-amine system). , Guanidine, thiourea, thiazole, sulfenamide, thiuram, thidiocarbamate, xanthate, etc.); vulcanization accelerator (zinc oxide, magnesium oxide, red lead, calcium hydroxide) , Stearic acid, zinc stearate, amines, diethylene glycol, etc., especially zinc oxide, stearic acid, etc.), reinforcing agents or fillers (talc, clay, carbon black, white carbon, graphite, calcium carbonate, calcium silicate , Magnesium hydroxide, etc.), anti-aging agents (amine, phenol, sulfur, phosphorus, etc.), softeners or plastics (Mineral oil, vegetable oil, synthetic resin, dioctyl phthalate, dioctyl sebacate, etc.) and the like.
　特に、タイヤ用ゴム組成物を製造する場合には、加硫促進剤としてスルフェンアミド系等、加硫促進助剤として酸化亜鉛、ステアリン酸等、補強剤又は充填剤としてカ－ボンブラック等、老化防止剤としてアミン系等、軟化剤又は可塑剤として鉱物油系等を用いることが好ましい。 In particular, when producing a rubber composition for a tire, a sulfenamide type as a vulcanization accelerator, zinc oxide, stearic acid, etc. as a vulcanization acceleration aid, carbon black, etc. as a reinforcing agent or filler, It is preferable to use an amine or the like as an anti-aging agent and a mineral oil or the like as a softener or plasticizer.
　ゴム組成物が他の成分を含む場合、当該他の成分の配合割合は特に限定されない。典型的には、例えば、ゴム成分１００重量部に対して、加硫促進剤は、通常、０．１～５重量部程度、加硫促進助剤については、通常、１～１５重量部程度、補強剤又は充填剤については、通常、２０～１００重量部程度、老化防止剤については、通常、０．５～４重量部程度、軟化剤又は可塑剤については、通常、２～２０重量部程度である。 When the rubber composition contains other components, the mixing ratio of the other components is not particularly limited. Typically, for example, with respect to 100 parts by weight of the rubber component, the vulcanization accelerator is usually about 0.1 to 5 parts by weight, and the vulcanization accelerator is usually about 1 to 15 parts by weight. The reinforcing agent or filler is usually about 20 to 100 parts by weight, the anti-aging agent is usually about 0.5 to 4 parts by weight, and the softener or plasticizer is usually about 2 to 20 parts by weight. It is.
　ゴム組成物は、ゴム成分、加硫剤組成物、及び必要に応じ他の成分を、混練機（ニーダー、バンバリーミキサー等）、オープンロール等を用いる一般的な方法で混練りすることにより製造することができる。さらに、製造されたゴム組成物を、各成分の種類と配合割合に応じた好適な加硫温度で加硫することにより加硫ゴムを得ることができる。加硫は、例えば、１５０～１７０℃で、１分～３０分程度の条件で実施することができる。 The rubber composition is produced by kneading a rubber component, a vulcanizing agent composition, and other components as necessary, by a general method using a kneader (kneader, Banbury mixer, etc.), an open roll or the like. be able to. Furthermore, a vulcanized rubber can be obtained by vulcanizing the produced rubber composition at a suitable vulcanization temperature according to the type and blending ratio of each component. Vulcanization can be carried out, for example, at 150 to 170 ° C. for about 1 to 30 minutes.
　本発明のゴム組成物は、ゴム成分に、不溶性硫黄及びＤＣＰＤ樹脂を含む加硫剤組成物を配合しているため、ゴム成分中において不溶性硫黄の分散性に優れ、さらにスコーチ特性も良好であり、ブルーミングの抑制が期待される。また、ゴム組成物を加硫して得られる加硫ゴムは、良好な機械的特性（引張り強さ及び引張り伸び等）を有している。 Since the rubber composition of the present invention contains a vulcanizing agent composition containing insoluble sulfur and DCPD resin in the rubber component, it has excellent dispersibility of insoluble sulfur in the rubber component and also has good scorch characteristics. Suppressing blooming is expected. Moreover, the vulcanized rubber obtained by vulcanizing the rubber composition has good mechanical properties (such as tensile strength and tensile elongation).
　これより、本発明の加硫剤組成物は、各種ゴム成分の加硫剤として有用であり、例えば、高い硬度が要求されるゴム材料（特に、タイヤ用ゴム、免震ゴム、制振ゴム、コンベヤベルト等）を製造するための加硫剤として好適に用いることができる。 Thus, the vulcanizing agent composition of the present invention is useful as a vulcanizing agent for various rubber components, for example, rubber materials requiring high hardness (particularly, rubber for tires, seismic isolation rubber, vibration damping rubber, It can be suitably used as a vulcanizing agent for producing a conveyor belt or the like.
　以下、本発明を実施例及び比較例によって具体的に説明するが、本発明はこれらに限定されるものではない。実施例の表中に示された数値は、特に断りのない限り、重量部を意味する。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Numerical values shown in the tables of Examples mean parts by weight unless otherwise specified.
　実施例及び比較例において使用した原料は、以下のとおりである。
・不溶性硫黄：四国化成工業社製、品名「ミュークロン」
・ジシクロペンタジエン樹脂：丸善石油化学社製、品名「マルカレッツ　Ｍ－８４５Ａ」
・ジシクロペンタジエン：和光純薬工業社製、試薬
・天然ゴム：野村貿易社製、マレーシア産、品名「ＳＭＲ－ＣＶ６０」
・酸化亜鉛（亜鉛華）：正同化学工業社製、酸化亜鉛（２種）
・ステアリン酸：日油社製
・カーボンブラック：東海カーボン社製、品名「シースト　３」
・プロセスオイル：出光興産社製、品名「ダイアナ　プロセスオイルＮＲ　２６」
・加硫促進剤：三新化学工業社製、品名「サンセラー　ＮＳ－Ｇ」
　また、実施例及び比較例において実施した評価試験は、以下のとおりである。 The raw materials used in the examples and comparative examples are as follows.
Insoluble sulfur: Shikoku Kasei Kogyo Co., Ltd., product name "Muclon"
・ Dicyclopentadiene resin: manufactured by Maruzen Petrochemical Co., Ltd., product name “Marcaretz M-845A”
・ Dicyclopentadiene: Wako Pure Chemical Industries, Reagent ・ Natural rubber: Nomura Trading Co., Malaysia, product name “SMR-CV60”
・ Zinc oxide (Zinc Hana): Zinc Chemical Co., Ltd., zinc oxide (2 types)
・ Stearic acid: NOF Corporation ・ Carbon black: Tokai Carbon Co., Ltd., product name “SEAST 3”
・ Process oil: Idemitsu Kosan Co., Ltd., product name “Diana Process Oil NR 26”
・ Vulcanization accelerator: Sanshin Chemical Industry Co., Ltd., product name "Sunseller NS-G"
Moreover, the evaluation test implemented in the Example and the comparative example is as follows.
［熱安定性試験］
　１２０℃の温度に設定したオイルバス中に、ミネラルオイル（出光興産社製、品名「ダフニー　オイルＣＰ　１５Ｎ」）２０ｍｌを入れた試験管を浸漬し、試験管中のミネラルオイル温度が１２０℃になった時点で、試験管に不溶性硫黄が１ｇとなるように加硫剤組成物を投入して１５分間加熱した。 [Thermal stability test]
A test tube containing 20 ml of mineral oil (product name “Daphney Oil CP 15N”, manufactured by Idemitsu Kosan Co., Ltd.) is immersed in an oil bath set at a temperature of 120 ° C., and the mineral oil temperature in the test tube becomes 120 ° C. At that time, the vulcanizing agent composition was added to the test tube so that the amount of insoluble sulfur was 1 g and heated for 15 minutes.
　次いで、試験管をオイルバスから取り出して氷水中に浸漬して冷却し、続いて、試験管中の不溶物を二硫化炭素で洗浄し、可溶性硫黄を二硫化炭素に溶解させた後、濾過、乾燥して、粉末状の不溶性硫黄を秤量し、次式により不溶性硫黄の残存率を算出した。この残存率が大きい程、熱安定性が優れているものと判定した。 Next, the test tube is taken out from the oil bath and cooled by immersing it in ice water. Subsequently, the insoluble matter in the test tube is washed with carbon disulfide, and soluble sulfur is dissolved in carbon disulfide, followed by filtration. After drying, powdered insoluble sulfur was weighed, and the residual rate of insoluble sulfur was calculated by the following formula. It was determined that the greater the residual ratio, the better the thermal stability.
　残存率（％）＝〔加熱、洗浄後の不溶性硫黄分（ｇ）／加硫剤組成物（ｇ）〕×〔１００／加硫剤組成物中の不溶性硫黄の含有量（重量％）〕×１００ Residual rate (%) = [insoluble sulfur content after heating and washing (g) / vulcanizing agent composition (g)] × [100 / content of insoluble sulfur in vulcanizing agent composition (% by weight)] × 100
［分散性試験］
　天然ゴム１００重量部に、カーボンブラックを５重量部の配合割合で加えて混練りしたもの２１０ｇを、５０±５℃に設定したミキシングロール（２本ロール）のロールに巻きつけ、続いて、不溶性硫黄が６０ｇとなるように加硫剤組成物を添加した。 [Dispersibility test]
210 g of carbon rubber added at a blending ratio of 5 parts by weight with 100 parts by weight of natural rubber was wound around a roll of mixing roll (two rolls) set at 50 ± 5 ° C., followed by insolubility The vulcanizing agent composition was added so that sulfur would be 60 g.
　次いで、３分間混練りして切り返しを２回行い、更に２分間混練りを継続して、厚さ４ｍｍのシート状のゴム組成物を取り出し、５ｃｍ×１５ｃｍのサイズに切り出した試験片を作成した。 Next, kneading for 3 minutes was repeated twice, and further kneading was continued for 2 minutes, and a sheet-like rubber composition having a thickness of 4 mm was taken out to prepare a test piece cut out to a size of 5 cm × 15 cm. .
　このシート状の試験片を５枚重ねて、試験片の切断面（２ｃｍ×１５ｃｍ）の中央部（２ｃｍ×１０ｃｍ）の領域に存在する、長径が０．５ｍｍ以上のサイズの加硫剤組成物の凝集塊の個数を、目視にて測定した。この数が少ない程、ゴムに対する分散性が優れているものと判定した。 A vulcanizing agent composition having a major axis of 0.5 mm or more in the region of the central part (2 cm × 10 cm) of the cut surface of the test piece (2 cm × 15 cm) by stacking five sheet-like test pieces. The number of aggregates was visually measured. It was determined that the smaller the number, the better the dispersibility with respect to rubber.
［付着性試験］
　加硫剤組成物３００ｇをステンレスボウル（直径２６ｃｍ×深さ７．５ｃｍ）に入れ、ステンレスボウルを水平方向に２０回回転させた後、ステンレスボウルをゆっくりと１８０度傾けて（逆さにして）、加硫剤組成物をステンレスボウルから排出した。 [Adhesion test]
Put 300g of the vulcanizing agent composition in a stainless steel bowl (diameter 26cm x depth 7.5cm), rotate the stainless steel bowl 20 times horizontally, and then tilt the stainless steel bowl 180 degrees slowly (invert) The vulcanizing composition was discharged from the stainless steel bowl.
　次いで、ステンレスボウルの内壁に付着した加硫剤組成物の重量を測定し、次式により付着率を算出した（ｎ＝１０）。この付着率が小さい程、付着性が抑制されていると共に、流動性が優れているものと判定した。 Next, the weight of the vulcanizing agent composition adhering to the inner wall of the stainless steel bowl was measured, and the adhesion rate was calculated by the following formula (n = 10). It was determined that the smaller the adhesion rate, the lower the adhesion and the better the fluidity.
　付着率（％）＝〔容器に付着した加硫剤組成物の重量（ｇ）／３００（ｇ）〕×１００ Adhesion rate (%) = [weight of vulcanizing agent composition adhering to container (g) / 300 (g)] × 100
［ムーニースコーチタイムの測定］
　表１記載の成分のうち、加硫剤組成物と加硫促進剤以外の成分を、容量１０リットルの密閉型ミキサにて、１０分間混練りした。続いて、加硫剤組成物と加硫促進剤を加えて８分間混練り後、ミキシングロール（２本ロール）にて、シート状のゴム組成物を製造した。 [Measurement of Mooney scorch time]
Among the components shown in Table 1, components other than the vulcanizing agent composition and the vulcanization accelerator were kneaded for 10 minutes with a closed mixer having a capacity of 10 liters. Subsequently, the vulcanizing agent composition and the vulcanization accelerator were added and kneaded for 8 minutes, and then a sheet-like rubber composition was produced with a mixing roll (two rolls).
　このゴム組成物について、「ＪＩＳ　Ｋ　６３００－１」に規定された方法に準拠して、ムーニースコーチタイムを測定した。このムーニースコーチタイムについては、後述する比較例２の値を１００とした場合の相対値に換算して示した。 For this rubber composition, Mooney scorch time was measured in accordance with the method defined in “JIS K 6300-1.” The Mooney scorch time is shown in terms of a relative value when the value of Comparative Example 2 described later is set to 100.
　ムーニースコーチタイムは、未加硫ゴムのスコーチ（注：初期加硫、早期加硫または焼けとも云う）時間を示し、この数値が小さいほど、ゴム組成物（配合ゴム）が、貯蔵中または混練り、カレンダー、押出し、その他の加硫工程以前の加工作業中に加硫を起こし、その結果、可塑性が減少して弾性が増し、加工性（成形性）が低下するおそれがあると判定される。従って、ムーニースコーチタイムの数値は大きいほど好ましい。 Mooney scorch time indicates the scorch time of unvulcanized rubber (note: also called initial vulcanization, early vulcanization or burning). The smaller this value, the more the rubber composition (compound rubber) is stored or kneaded. It is determined that vulcanization occurs during processing operations prior to calendering, extrusion, and other vulcanization processes, and as a result, the plasticity decreases, the elasticity increases, and the workability (formability) may decrease. Therefore, the larger the Mooney scorch time value, the better.
［加硫ゴムの強度測定］
　ゴム組成物から得られた加硫物（加硫条件：１６０℃×１０分）について、「ＪＩＳ　Ｋ６２５１」に準拠して、引張り強さ（ＭＰａ）と引張り伸び（％）を測定した。得られた測定値については、後述する比較例２の値を１００とした場合の相対値に換算して示した。 [Measurement of vulcanized rubber strength]
Tensile strength (MPa) and tensile elongation (%) of the vulcanizate (vulcanization condition: 160 ° C. × 10 minutes) obtained from the rubber composition were measured according to “JIS K6251”. About the obtained measured value, it converted into the relative value when the value of the comparative example 2 mentioned later is set to 100, and was shown.
　引張り強さについては、数値が大きいほど優れていると判定される。一方、引張り伸びについては、用途により判定が異なるが、加硫剤組成物が加硫剤として使用されるタイヤ用のゴムの引張り伸びについては、数値が大きいほど優れていると判定される。 About tensile strength, it is judged that it is excellent, so that a numerical value is large. On the other hand, the tensile elongation is judged differently depending on the application, but the tensile elongation of tire rubber for which the vulcanizing agent composition is used as a vulcanizing agent is judged to be better as the numerical value is larger.
〔実施例１〕
　ジシクロペンタジエン樹脂２．５重量部を、二硫化炭素２３０重量部に溶解させ、続いて、不溶性硫黄１００重量部を加えて混合して、スラリー（不溶性硫黄の濃度：３０重量％）を調製した。次いで、このスラリーを６５℃にて１時間加熱し、二硫化炭素を揮発させて、ジシクロペンタジエン樹脂を含有する加硫剤組成物を製造した。この加硫剤組成物について評価試験を行った。得られた試験結果を表１に示す。 [Example 1]
2.5 parts by weight of dicyclopentadiene resin was dissolved in 230 parts by weight of carbon disulfide, and then 100 parts by weight of insoluble sulfur was added and mixed to prepare a slurry (insoluble sulfur concentration: 30% by weight). . Next, this slurry was heated at 65 ° C. for 1 hour to volatilize carbon disulfide, and a vulcanizing agent composition containing a dicyclopentadiene resin was produced. An evaluation test was performed on this vulcanizing agent composition. The test results obtained are shown in Table 1.
〔実施例２～６〕
　ジシクロペンタジエン樹脂の使用量を、表１記載の配合割合（重量部）となるように設定した以外は、実施例１の場合と同様にして加硫剤組成物を調製し、評価試験を行った。得られた試験結果を表１に示す。 [Examples 2 to 6]
A vulcanizing agent composition was prepared and evaluated in the same manner as in Example 1 except that the amount of dicyclopentadiene resin used was set to the blending ratio (parts by weight) shown in Table 1. It was. The test results obtained are shown in Table 1.
〔実施例７〕
　実施例４において調製した加硫剤組成物を使用し、この加硫剤組成物１１５重量部と、プロセスオイル２５重量部とを、プラネタリーミキサーにて３０分間攪拌混合して、加硫剤組成物（オイル処理品）を製造した。この加硫剤組成物について評価試験を行った。得られた試験結果を表１に示す。 Example 7
Using the vulcanizing agent composition prepared in Example 4, 115 parts by weight of this vulcanizing agent composition and 25 parts by weight of process oil were stirred and mixed in a planetary mixer for 30 minutes to obtain a vulcanizing agent composition. A product (oil-treated product) was produced. An evaluation test was performed on this vulcanizing agent composition. The test results obtained are shown in Table 1.
〔比較例１〕
　不溶性硫黄のみを加硫剤として用い、実施例１と同様にして評価試験を行った。得られた試験結果を表１に示す。 [Comparative Example 1]
An evaluation test was conducted in the same manner as in Example 1 using only insoluble sulfur as a vulcanizing agent. The test results obtained are shown in Table 1.
〔比較例２〕
　不溶性硫黄１００重量部とプロセスオイル２５重量部とを、実施例７と同様にして、プラネタリーミキサーにて３０分間攪拌混合して、加硫剤組成物（オイル処理品）を製造した。この加硫剤組成物について評価試験を行った。得られた試験結果を表１に示す。なお、ムーニースコーチタイム、引張り強さと、引張り伸びについては、各々１００として示した。 [Comparative Example 2]
100 parts by weight of insoluble sulfur and 25 parts by weight of process oil were stirred and mixed in a planetary mixer for 30 minutes in the same manner as in Example 7 to produce a vulcanizing agent composition (oil-treated product). An evaluation test was performed on this vulcanizing agent composition. The test results obtained are shown in Table 1. The Mooney scorch time, the tensile strength, and the tensile elongation are each shown as 100.
〔比較例３〕
　ジシクロペンタジエン樹脂の代わりにジシクロペンタジエンを使用した以外は、実施例４と同様にして、ジシクロペンタジエンを含有する加硫剤組成物を製造した。この加硫剤組成物について評価試験を行った。得られた試験結果を表１に示す。 [Comparative Example 3]
A vulcanizing agent composition containing dicyclopentadiene was produced in the same manner as in Example 4 except that dicyclopentadiene was used instead of dicyclopentadiene resin. An evaluation test was performed on this vulcanizing agent composition. The test results obtained are shown in Table 1.
〔比較例４〕
　不溶性硫黄のみを加硫剤として用い、天然ゴム１００重量部に対してジシクロペンタジエン樹脂０．５２５重量部を添加すること以外は、比較例１と同様にして評価試験を行った。得られた試験結果を表１に示す。 [Comparative Example 4]
An evaluation test was conducted in the same manner as in Comparative Example 1 except that only insoluble sulfur was used as a vulcanizing agent and 0.525 part by weight of dicyclopentadiene resin was added to 100 parts by weight of natural rubber. The test results obtained are shown in Table 1.
　なお、分散性試験の評価に関しては、天然ゴム１００重量部に、カーボンブラックを５重量部及びジシクロペンタジエン樹脂４．５重量部を添加して混練りを行った。 For evaluation of the dispersibility test, 5 parts by weight of carbon black and 4.5 parts by weight of dicyclopentadiene resin were added to 100 parts by weight of natural rubber and kneaded.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
（１）ジシクロペンタジエン樹脂を配合した加硫剤組成物を用いた場合（実施例１～６）は、ジシクロペンタジエン樹脂を配合していない加硫剤組成物を用いた場合（比較例１及び２）に比べて、不溶性硫黄の熱安定性及び分散性により優れ、付着性も大きく抑制されており、また、ゴム組成物のスコーチ特性も改善し、加硫ゴムの引張り強さ及び引張り伸びも改善している。
（２）実施例１～６の試験結果によれば、加硫剤組成物中のジシクロペンタジエン樹脂の配合割合が増加するに従い、全ての評価試験の結果が向上している。特に、ジシクロペンタジエン樹脂の配合割合が、不溶性硫黄１００重量部に対し１５、２０及び４０重量部の場合（実施例４～６）には、いずれの評価試験においても特に優れた結果が得られている。
（３）加硫剤組成物にプロセスオイルを含む場合（実施例７）は、プロセスオイルを含まない場合（実施例４）に比べて、不溶性硫黄の熱安定性はやや低下するものの、他の特性については良好な結果が得られている。
（４）ジシクロペンタジエン樹脂を配合した加硫剤組成物を用いた場合（実施例４）は、当該樹脂と同配合量のジシクロペンタジエン（モノマー）を配合した加硫剤組成物を用いた場合（比較例３）に比べて、全ての評価試験で顕著に優れた結果が得られている。
（５）不溶性硫黄１００重量部に対してジシクロペンタジエン樹脂が１５重量部の配合割合になるように、ジシクロペンタジエン樹脂を不溶性硫黄に配合した場合（実施例４）と、ジシクロペンタジエン樹脂を天然ゴムに配合した場合（比較例４）とを比べると、前者はゴム組成物のスコーチ特性、加硫ゴムの引張り強さ及び引張り伸びが顕著に優れている。また、不溶性硫黄のゴムへの分散性も飛躍的に向上している。 (1) When using a vulcanizing agent composition containing a dicyclopentadiene resin (Examples 1 to 6), using a vulcanizing agent composition not containing a dicyclopentadiene resin (Comparative Example 1) Compared to 2) and 2), the thermal stability and dispersibility of insoluble sulfur are excellent, the adhesion is greatly suppressed, the scorch characteristics of the rubber composition are improved, and the tensile strength and tensile elongation of the vulcanized rubber are improved. Has also improved.
(2) According to the test results of Examples 1 to 6, the results of all the evaluation tests are improved as the blending ratio of the dicyclopentadiene resin in the vulcanizing agent composition is increased. In particular, when the blending ratio of the dicyclopentadiene resin is 15, 20 and 40 parts by weight with respect to 100 parts by weight of insoluble sulfur (Examples 4 to 6), particularly excellent results are obtained in any of the evaluation tests. ing.
(3) When the process oil is contained in the vulcanizing agent composition (Example 7), the thermal stability of the insoluble sulfur is slightly reduced as compared with the case where the process oil is not contained (Example 4). Good results have been obtained for the properties.
(4) When a vulcanizing agent composition containing a dicyclopentadiene resin was used (Example 4), a vulcanizing agent composition containing the same amount of dicyclopentadiene (monomer) as that of the resin was used. Compared to the case (Comparative Example 3), all the evaluation tests showed significantly superior results.
(5) When dicyclopentadiene resin is blended with insoluble sulfur so that the blending ratio of dicyclopentadiene resin is 15 parts by weight with respect to 100 parts by weight of insoluble sulfur (Example 4), and dicyclopentadiene resin When compared with the case of blending with natural rubber (Comparative Example 4), the former is remarkably superior in the scorch characteristics of the rubber composition, the tensile strength and tensile elongation of the vulcanized rubber. In addition, the dispersibility of insoluble sulfur in rubber has been dramatically improved.
　本発明の加硫剤組成物は、不溶性硫黄及びジシクロペンタジエン樹脂を含むことを特徴とする。この加硫剤組成物は、不溶性硫黄が優れた熱安定性を有し可溶性硫黄への転位が抑制されるとともに、不溶性硫黄のゴム中での分散性が優れ、不溶性硫黄の流動性が向上するため装置等への付着を抑制することができる。そのため、ゴムの加硫剤として好適に用いることができる。 The vulcanizing agent composition of the present invention is characterized by containing insoluble sulfur and dicyclopentadiene resin. In this vulcanizing agent composition, insoluble sulfur has excellent thermal stability, rearrangement to soluble sulfur is suppressed, dispersibility of insoluble sulfur in rubber is excellent, and fluidity of insoluble sulfur is improved. Therefore, it is possible to suppress adhesion to the device or the like. Therefore, it can be suitably used as a rubber vulcanizing agent.

Claims (13)

  1. 不溶性硫黄及びジシクロペンタジエン樹脂を含む加硫剤組成物。 A vulcanizing agent composition comprising insoluble sulfur and dicyclopentadiene resin.
  2. 不溶性硫黄１００重量部に対し、ジシクロペンタジエン樹脂を０．２５～７０重量部の割合で含む請求項１に記載の加硫剤組成物。 The vulcanizing agent composition according to claim 1, comprising dicyclopentadiene resin in a proportion of 0.25 to 70 parts by weight with respect to 100 parts by weight of insoluble sulfur.
  3. 不溶性硫黄１００重量部に対し、ゴム成分を２００重量部以下の割合で含む請求項１又は２に記載の加硫剤組成物。 The vulcanizing agent composition according to claim 1 or 2, comprising a rubber component at a ratio of 200 parts by weight or less with respect to 100 parts by weight of insoluble sulfur.
  4. さらにプロセスオイルを含む請求項１、２又は３に記載の加硫剤組成物。 The vulcanizing agent composition according to claim 1, 2 or 3, further comprising a process oil.
  5. 不溶性硫黄及びジシクロペンタジエン樹脂を混合することを特徴とする加硫剤組成物の製造方法。 A method for producing a vulcanizing agent composition comprising mixing insoluble sulfur and dicyclopentadiene resin.
  6. 不溶性硫黄、ジシクロペンタジエン樹脂及び溶剤を混合した後、溶剤を除去することを特徴とする請求項５に記載の加硫剤組成物の製造方法。 6. The method for producing a vulcanizing agent composition according to claim 5, wherein the solvent is removed after mixing the insoluble sulfur, the dicyclopentadiene resin and the solvent.
  7. ジシクロペンタジエン樹脂を溶剤に溶解して溶液を調製し、この溶液と不溶性硫黄とを混合してスラリーを調製し、このスラリーから溶剤を除去することを特徴とする請求項５又は６に記載の加硫剤組成物の製造方法。 The dicyclopentadiene resin is dissolved in a solvent to prepare a solution, the solution and insoluble sulfur are mixed to prepare a slurry, and the solvent is removed from the slurry. A method for producing a vulcanizing agent composition.
  8. 請求項５～７のいずれか１項に記載の製造方法で製造される加硫剤組成物。 A vulcanizing agent composition produced by the production method according to any one of claims 5 to 7.
  9. 請求項１～４及び８のいずれか１項に記載の加硫剤組成物、及びゴム成分を含むゴム組成物。 A rubber composition comprising the vulcanizing agent composition according to any one of claims 1 to 4 and 8, and a rubber component.
  10. 請求項１～４及び８のいずれか１項に記載の加硫剤組成物、及びゴム成分を混合することを特徴とするゴム組成物の製造方法。 A method for producing a rubber composition, comprising mixing the vulcanizing agent composition according to any one of claims 1 to 4 and 8, and a rubber component.
  11. 請求項９に記載のゴム組成物を加硫した加硫ゴム。 A vulcanized rubber obtained by vulcanizing the rubber composition according to claim 9.
  12. 前記加硫ゴムがタイヤである請求項１１に記載の加硫ゴム。 The vulcanized rubber according to claim 11, wherein the vulcanized rubber is a tire.
  13. 請求項９に記載のゴム組成物を加硫することを特徴とする加硫ゴムの製造方法。 A method for producing a vulcanized rubber, comprising vulcanizing the rubber composition according to claim 9.
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WO2021033747A1 (en) 2019-08-22 2021-02-25 Ｅｎｅｏｓ株式会社 Sulfur-containing unsaturated hydrocarbon polymer, method for manufacturing same, additive for rubber, rubber composition, and tire
WO2024038877A1 (en) * 2022-08-17 2024-02-22 Ｅｎｅｏｓ株式会社 Rubber composition, method for producing same, and tire product
WO2024038876A1 (en) * 2022-08-17 2024-02-22 Ｅｎｅｏｓ株式会社 Rubber composition, production method therefor, and tire product
WO2024038880A1 (en) * 2022-08-17 2024-02-22 Ｅｎｅｏｓ株式会社 Rubber composition, production method therefor, and tire product
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