Rubber mixing material and closed bale obtained by using rubber mixing material, method for manufacturing rubber mixing material, and method for manufacturing rubber composition

Abstract

Provided are a rubber mixing compound material capable of reliably supplying a prescribed amount of liquid diene rubber (B) and excellent in handling properties, and a closed bale obtained using the rubber mixing compound material. A rubber mixing compound material is produced, which includes a closed bag (A) including an outer layer having a thickness of 30 to 100 μm made of a polymer (a) having a melting point of 60 to 140°C, and liquid diene rubber (B) enclosed inside the aforementioned closed bag (A). Further, a closed bale is produced, which includes a closed container having low water vapor permeability and the aforementioned rubber mixing compound material enclosed inside the aforementioned closed container.

Description

Technical Field

[0001] This invention relates to compounding materials for rubber compounding and sealed bundles obtained using rubber compounding materials. Furthermore, it relates to methods for manufacturing rubber compounding materials and methods for manufacturing rubber compositions. Background Technology

[0002] Plasticizers have been added to rubber compositions that serve as raw materials for crosslinked rubber for purposes such as improving processability during manufacturing. However, oils, which are commonly used as plasticizers, sometimes exhibit leakage problems. To address this issue, liquid diene-based rubbers (see, for example, Patent Document 1) have been studied as components of rubber compositions. These plasticizers possess the same plasticizing effect as oils and are capable of co-crosslinking with the main component of the rubber composition, namely the solid rubber.

[0003] Furthermore, liquid diene rubbers can impart excellent adhesive properties, and therefore are sometimes used in rubber compositions that require adhesive properties. For example, in order to improve the adhesive properties to highly polar materials such as metals, rubber compositions containing maleic anhydride-modified liquid diene rubber have been studied as liquid diene rubbers (see, for example, Patent Document 2).

[0004] Furthermore, in recent years, rubber compositions that improve mechanical strength by blending solid rubber with fillers such as silica and carbon black have been widely used in applications requiring wear resistance and mechanical strength, such as tires. To achieve excellent physical properties in the crosslinked product obtained from this filler-blended rubber composition, and to ensure an ideal dispersion state of the filler in the crosslinked product, a rubber composition containing a liquid diene rubber having silanol groups reactive to silica (see, for example, Patent Document 3).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 57-047337

[0008] Patent Document 2: Japanese Patent Application Publication No. 55-048231

[0009] Patent Document 3: International Publication No. 2018 / 043699 (Single Volume) Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] However, even after liquid diene rubber has been pre-filled and metered into a container, its high viscosity makes it prone to residue in the container, posing operational problems, even if it were to be directly added to the rubber mixing unit. While it has been considered to add the entire container of liquid diene rubber into the mixing unit, the possibility that the material forming the container could adversely affect the properties of the rubber composition is generally foreseeable.

[0012] Furthermore, it is desirable that liquid diene rubbers with functional groups, especially those with highly reactive groups such as silanol groups and alkoxysilyl groups, maintain their functional group properties as little as possible even during long-term storage in industrial use.

[0013] The present invention was made in view of this situation, and its object is to provide a rubber compounding material that can reliably supply a specified amount of liquid diene rubber (B) and has excellent processability, and a sealed bundle obtained using the rubber compounding material.

[0014] Furthermore, the objective is to provide a method for manufacturing a compounding material for rubber compounding that maintains the physical properties of liquid diene rubber (B) to a specified state and can reliably supply a specified amount.

[0015] In addition, the purpose is to provide a method for manufacturing a rubber composition with excellent workability.

[0016] means for solving problems

[0017] The inventors conducted in-depth research and found that the above-mentioned problems were solved by using a rubber compounding material that seals liquid diene rubber inside a specific sealed bag and a sealed bundle that seals the rubber compounding material inside a specific sealed container, thereby completing the present invention. That is, the present invention relates to the following [1] to

[13] .

[0018] [1] Rubber compounding materials, comprising:

[0019] A resealable bag (A) with a thickness of 30–100 μm made from a polymer (a) with a melting point of 60–140 °C; and

[0020] Liquid diene rubber (B) is sealed inside the aforementioned sealed bag (A).

[0021] [2] The rubber compounding material according to [1], wherein the aforementioned polymer (a) is selected from at least one of low-density polyethylene, linear low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer and syndiotactic-1,2-polybutadiene.

[0022] [3] A sealed bundle, comprising:

[0023] A sealed container with low water vapor permeability (C); and

[0024] The rubber compounding material described in [1] or [2] is sealed inside the aforementioned sealed container (C).

[0025] [4] According to the sealed packaging described in [3], the material of the aforementioned sealed container (C) has a moisture permeability of 4.0 g / m³. 2 • Less than 24 hours.

[0026] [5] The sealed package according to [3] or [4], wherein the aforementioned sealed container (C) is a container made of at least one material selected from metal plates and polymer sheets or polymer films with layers of inorganic materials.

[0027] [6] The sealed package according to any one of [3] to [5], wherein the aforementioned liquid diene rubber (B) is a liquid diene rubber (B1) having a group that is highly reactive with water.

[0028] [7] The sealed bundle according to any one of [3] to [6], wherein the shape of the aforementioned sealed container is any one of bag, barrel, or box.

[0029] [8] The sealed package according to any one of [3] to [7], wherein a desiccant is further disposed inside the aforementioned sealed container (C).

[0030] [9] A method for manufacturing compounding materials for rubber compounding, comprising at least the following steps:

[0031] The filling process involves filling a sealed bag (A) with liquid diene rubber (B) through the opening of the sealed bag (A) made of a polymer (a) with a melting point of 60–140°C and a thickness of 30–100 μm; and

[0032] In the sealing process, after the aforementioned filling process, the opening of the aforementioned sealing bag (A) is sealed.

[0033]

[10] The method for manufacturing compound material for rubber compounding according to [9], wherein, in the aforementioned sealing process, the aforementioned opening is sealed by heat sealing.

[0034]

[11] A method for manufacturing a sealed bundle, comprising at least the following steps:

[0035] In the input process, the rubber compounding material described in [1] or [2] is input from the opening of a sealed container (C) with low water vapor permeability; and

[0036] The sealing process involves sealing the opening of the sealing container (C) after the aforementioned input process.

[0037]

[12] According to the method for manufacturing a sealed bundle as described in

[11] , in the aforementioned sealing process, the aforementioned opening is sealed by heat sealing.

[0038]

[13] A method for manufacturing a rubber composition, comprising: a mixing step of mixing the rubber compounding material described in [1] or [2] with solid rubber.

[0039] Invention Effects

[0040] According to the rubber compounding material of the present invention, since the liquid diene rubber (B) is sealed in a sealed bag (A), a specified amount of liquid diene rubber (B) that is difficult to process can be reliably supplied.

[0041] Furthermore, according to the present invention, the sealed package has a double-sealed structure of a sealed bag (A) and a sealed container (C), thus it is possible to maintain the physical properties of the liquid diene rubber (B) to a specified state and reliably supply a specified amount.

[0042] Furthermore, the method for manufacturing compound materials for rubber compounding according to the present invention can reliably seal liquid diene rubber (B) using a simple process, thereby improving the processability of liquid diene rubber (B).

[0043] Furthermore, the method for manufacturing the rubber composition according to the present invention enables the composition to be produced with good workability. Attached Figure Description

[0044] [ Figure 1 ] Figure 1 This is a schematic diagram illustrating the compounding material for rubber compounding according to the present invention.

[0045] [ Figure 2 ] Figure 2 This is a schematic diagram illustrating one embodiment of the sealed packaging material of the present invention.

[0046] [ Figure 3 ] Figure 3 This is a schematic diagram illustrating other embodiments of the sealed packaging of the present invention.

[0047] [ Figure 4 ] Figure 4 This is a schematic diagram illustrating other embodiments of the sealed packaging of the present invention.

[0048] [ Figure 5 ] Figure 5 This is a process diagram illustrating the manufacturing process of the rubber compounding material of the present invention.

[0049] [ Figure 6 ] Figure 6 This is a process diagram illustrating the manufacturing process of the sealed package of the present invention. Detailed Implementation

[0050] Hereinafter, embodiments of the present invention will be described in more detail with reference to the accompanying drawings.

[0051] <10 Compounding Materials for Rubber Mixing>

[0052] Rubber compounding material 10 of the present invention is as follows Figure 1 As shown, it includes a sealing bag (A) and liquid diene rubber (B) sealed inside the sealing bag (A). In particular, the sealing bag (A) is a sealing bag with a thickness of 30 to 100 μm made of a polymer (a) with a melting point of 60 to 140 °C.

[0053] Liquid diene rubber (B) refers to a liquid polymer, in which the monomer units constituting the polymer include conjugated diene units derived from conjugated dienes. Examples of conjugated dienes include, for instance, butadiene, isoprene, α-farnesene, β-farnesene; 2,3-dimethylbutadiene, 2-phenylbutadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octtriene, geraniol, and chloroprene, as well as other conjugated dienes other than butadiene, isoprene, α-farnesene, and β-farnesene (b1). The conjugated diene, which is the conjugated diene unit contained in the liquid diene rubber (B), is preferably isoprene, butadiene, α-farnesene, or β-farnesene, and more preferably isoprene, butadiene, or β-farnesene. One of these conjugated dienes may be used alone, or two or more may be used in combination.

[0054] A preferred embodiment of the liquid diene rubber (B) is that, of all the monomer units constituting the polymer, at least 50% by mass are monomer units derived from at least one monomer selected from isoprene, butadiene, α-farnesene, and β-farnesene. The total content of isoprene, butadiene, α-farnesene, and β-farnesene units relative to all the monomer units of the liquid diene rubber (B) is preferably 60–100% by mass, more preferably 70–100% by mass, further preferably 80–100% by mass, particularly preferably 90–100% by mass, and substantially 100% by mass.

[0055] Other monomer units that may be included in the above-mentioned liquid diene rubber (B), besides isoprene units, butadiene units, α-farnesene units and β-farnesene units, include conjugated diene (b1) units and aromatic vinyl compound (b2) units, in addition to the aforementioned butadiene and isoprene.

[0056] As an aromatic vinyl compound (b2), styrene, α-methylstyrene, and 4-methylstyrene are preferred.

[0057] The content of monomer units other than butadiene, isoprene, α-farnesene, and β-farnesene units in the above-mentioned liquid diene rubber (B) is preferably 50% by mass or less, more preferably 45% by mass or less, further preferably 40% by mass or less, particularly preferably 35% by mass or less, and most preferably 30% by mass or less. For example, if the aromatic vinyl compound (b2) unit is below the above range, there is a tendency for improved processability of the rubber composition.

[0058] The liquid diene rubber (B) can be an unmodified polymer containing conjugated diene units, a modified polymer containing conjugated diene units modified with functional groups, or a hydrogenated polymer or hydrogenated modified polymer in which at least a portion of the carbon-carbon double bonds of the conjugated diene units contained in the unmodified polymer or the modified polymer have been hydrogenated. Furthermore, the modified polymer containing conjugated diene units modified with functional groups can be a liquid diene rubber (B1) having groups with high reactivity with water.

[0059] When liquid diene rubber (B) is a modified polymer containing conjugated diene units modified by utilizing functional groups, examples of such functional groups include, for example, amino, amide, imino, nitrile, imidazole, urea, hydroxyl, ether, carboxyl, carbonyl, alkoxysilyl, epoxy, mercapto, thiol, disulfide, trisulfide, tetrasulfide, isocyanate, and carboxylic anhydride, as well as anhydride groups derived from anhydrides such as dicarboxylic acid monoester and dicarboxylic acid monoamide, borate, vinyl, acryloyl, and methacryloyl groups.

[0060] As a method for manufacturing the aforementioned modified polymer, examples include the following: before adding a polymerization inhibitor, adding a polymerization terminator such as tin tetrachloride, dibutyltin chloride, tetrachlorosilane, dimethyldichlorosilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-diaminomethylcyclohexane and 2,4-toluene diisocyanate, 4,4'-bis(diethylamino)benzophenone and N-vinylpyrrolidone, N-methylpyrrolidone, 4-dimethylaminobenzylaniline, dimethylimidazolium ketone, or other modifiers described in Japanese Patent Application Publication No. 2011-132298. Alternatively, modified polymers can be obtained by using addition-modifying compounds to the separated unmodified liquid diene rubber, such as unsaturated carboxylic acids, unsaturated carboxylic acid derivatives, or silane compounds having groups that react with carbon-carbon unsaturated bonds contained in the conjugated diene units.

[0061] Examples of unsaturated carboxylic acids mentioned above include maleic acid, fumaric acid, itaconic acid, and (meth)acrylic acid.

[0062] Examples of unsaturated carboxylic acid derivatives include, for instance, maleic anhydride, itaconic anhydride, and other unsaturated dicarboxylic acid anhydrides; maleic acid monoester, itaconic acid monoester, fumaric acid monoester, and other unsaturated dicarboxylic acid monoesters; glycidyl acrylate, hydroxyethyl acrylate, and other (meth)acrylates; maleic acid monoamide, itaconic acid monoamide, fumaric acid monoamide, and other unsaturated dicarboxylic acid monoamides; and maleimide, itaconic acid imide, and other unsaturated carboxylic acid imides.

[0063] As a silane compound having a group that reacts with the carbon-carbon unsaturated bond contained in the conjugated diene unit, the silane compound shown in the following formula (1) is an example of a suitable compound.

[0064] [Chemistry 1]

[0065]

[0066] In the above formula (1), R 1 It is a divalent alkylene group having 1 to 6 carbon atoms. Examples of divalent alkylene groups having 1 to 6 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, and hexylene. R 2 R 3 and R 4 Each can independently represent methoxy, ethoxy, phenoxy, methyl, ethyl, or phenyl. Among them, R... 2 R 3 and R 4 At least one of them is methoxy, ethoxy, or phenoxy.

[0067] There are no particular limitations on the method of adding the modified compound to the unmodified liquid diene rubber. For example, a method can be used to add the modified compound to the liquid diene rubber, then add a free radical catalyst as needed, and heat the mixture with or without an organic solvent. Alternatively, an antioxidant can be added during heating.

[0068] The weight-average molecular weight (Mw) of the liquid diene rubber (B) is preferably 1,000 or more and 500,000 or less, more preferably 2,000 or more and 300,000 or less, even more preferably 2,000 or more and 200,000 or less, even more preferably 2,000 or more and 150,000 or less, and particularly preferably 2,000 or more and 100,000 or less. If the Mw of the liquid diene rubber (B) is within the aforementioned range, a rubber composition with excellent properties such as improved processability can be obtained. It should be noted that, in this specification, the Mw of the liquid diene rubber (B) is the weight-average molecular weight converted from standard polystyrene measured using gel permeation chromatography (GPC). In this invention, two or more liquid diene rubbers (B) with different Mws can be used in combination.

[0069] The molecular weight distribution (Mw / Mn) of the liquid diene rubber (B) is preferably 1.0 to 20.0, more preferably 1.0 to 15.0, further preferably 1.0 to 10.0, even more preferably 1.0 to 5.0, particularly preferably 1.0 to 3.0, even more preferably 1.0 to 2.0, and extremely preferably 1.0 to 1.5. If Mw / Mn is within the aforementioned range, the viscosity deviation of the resulting liquid diene rubber (B) is smaller, and therefore preferred. It should be noted that the molecular weight distribution (Mw / Mn) refers to the ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) of standard polystyrene, determined by GPC measurement.

[0070] The polymer area ratio of the liquid diene rubber (B) is preferably 40% or less, more preferably 35% or less, even more preferably 30% or less, and even more preferably 25% or less. If the polymer area ratio is within the aforementioned range, the viscosity deviation of the resulting liquid diene rubber (B) is smaller, and therefore it is more preferred. It should be noted that the polymer area ratio refers to the proportion of polymers in the region where the total area derived from the polymer in the GPC spectrum obtained by GPC determination is set to 100%, and the molecular weight is Mt (peak molecular weight) × 1.45 or higher.

[0071] The melt viscosity of the aforementioned liquid diene rubber (B), measured at 38°C, is preferably 0.1–4,000 Pa·s, more preferably 0.1–3,500 Pa·s, and even more preferably 0.1–3,000 Pa·s. If the melt viscosity of the liquid diene rubber (B) is within the aforementioned range, the resulting rubber composition exhibits improved softness, and therefore, improved processability. It should be noted that, in this invention, the melt viscosity of the liquid diene rubber (B) is a value measured at 38°C using a Brookfield viscometer (Type B viscometer).

[0072] There is no particular limitation on the manufacturing method of liquid diene rubber (B), which can be manufactured by, for example, anionic polymerization.

[0073] By closing the upper opening (not shown) of the sealing bag (A), the liquid diene rubber (B) inside the sealing bag (A) is sealed inside. It should be noted that there is no particular limitation on the means of closing the upper opening of the sealing bag (A), and heat sealing (heat fusion) can be used, for example. Figure 1 In the middle, symbol 16 represents a closed area.

[0074] The sealing bag (A) is made of polymer (a) with a melting point of 60–140°C. By keeping the melting point of polymer (a) within this range, leakage of liquid diene rubber (B) is suppressed when storing or using rubber compounding materials, resulting in excellent workability. Furthermore, during the process of mixing solid rubber with rubber compounding materials, the sealing bag melts and disperses, thereby minimizing any adverse effects on the properties of the rubber composition. From the viewpoint of further balancing leakage suppression, workability, and the properties of the rubber composition, the melting point of polymer (a) is preferably 70–130°C, more preferably 80–120°C. Furthermore, from the viewpoint of suppressing leakage, the melting point of polymer (a) is preferably above 100°C and below 140°C, more preferably 103–140°C, and even more preferably 105–140°C.

[0075] The thickness of the sealing bag (A) is 30–100 μm. By keeping the thickness of the sealing bag within this range, leakage of liquid diene rubber (B) is suppressed when storing or using rubber compounding materials, resulting in excellent workability. Furthermore, during the process of mixing solid rubber with rubber compounding materials, the sealing bag melts and disperses, thereby minimizing any adverse effects on the properties of the rubber composition. From the viewpoint of further balancing leakage suppression, workability, and the properties of the rubber composition, the thickness of the sealing bag (A) is preferably 30–80 μm, more preferably 40–70 μm.

[0076] Furthermore, as described above, the sealing bag (A) is made of a film of polymer (a), and the heat-sealing strength of this film is preferably 1.0 N / 15 mm or more, more preferably 2.5 N / 15 mm or more, and even more preferably 4.0 N / 15 mm or more. Additionally, the heat-sealing strength of this film is generally preferably 40 N / 15 mm or less, and even more preferably 25 N / 15 mm or less. The heat-sealing strength is a value measured by a heat-sealing strength test of the bag according to JIS Z0238 Test Method for Heat-Sealed Flexible Packaging Bags and Semi-rigid Containers.

[0077] Furthermore, the polymer (a) constituting the sealing bag (A) is preferably selected from at least one of low-density polyethylene, linear low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, and syndiotactic-1,2-polybutadiene, more preferably from at least one of low-density polyethylene, ethylene-vinyl acetate copolymer, and syndiotactic-1,2-polybutadiene. Additionally, from the viewpoint of suppressing leakage, polymer (a) is preferably selected from at least one of low-density polyethylene, linear low-density polyethylene, and high-density polyethylene.

[0078] In order to facilitate the use of the rubber compounding material obtained in this invention, it is preferable to measure and seal the liquid diene rubber (B) when sealing it into a sealed bag (A).

[0079] The rubber compounding material 10 of the present invention, constructed in this manner, can improve the processability of liquid diene rubber (B), which has been difficult to process until now, and can reliably supply a specified amount, since the liquid diene rubber (B) is sealed in a sealed bag (A).

[0080] Furthermore, regarding the rubber compounding material 10 of the present invention, when a large amount of liquid diene rubber (B) is added to the inside of the sealed bag (A), or when it is desirable to more reliably prevent leakage of the liquid diene rubber, the sealed bags can be stacked in two or three layers. In this case, multiple sealed bags (A) of the same thickness made of polymer (a) with the same melting point can be used as the sealed bags (A). In this case, for example, the sealed bag can be sealed by introducing liquid diene rubber (B) into the inside of the innermost bag from the upper opening of the multiple layers of sealed bags (A) and then closing the opening. As a means of sealing the upper opening, heat sealing (heat fusion) can be used, for example, in the same way as described above.

[0081] <20 sealed bundles>

[0082] Next, the sealed bundle 20, which further improves the processability of the rubber compound 10, will be described.

[0083] The sealed package 20 of the present invention, as shown Figure 2 As shown, it includes a sealed container 22 (sealed container (C)) with low water vapor permeability, and the aforementioned rubber compounding material 10 sealed inside the sealed container 22.

[0084] Here, the low water vapor permeability of the sealed container 22 refers to the low permeability of water vapor through the sealed container. Regarding the sealed container 22, the water vapor permeability of the container material is preferably 4.0 g / m³. 2 • Less than 24 hours, more preferably 2.0 g / m 2 • Less than 24 hours, preferably 1.0 g / m 2 • Less than 24 hours, preferably 0.5 g / m 2 • Less than 24 hours.

[0085] The aforementioned sealed container is preferably made of at least one material selected from metal plates and polymer sheets or polymer films with laminated inorganic layers.

[0086] Examples of the aforementioned metal plates include stainless steel plates, aluminum plates, tin-plated steel (tin-plated steel sheet), tin-plated iron sheets, etc.

[0087] Examples of polymer sheets or polymer films with inorganic layers include polymer sheets or polymer films with evaporated inorganic layers, polymer sheets or polymer films with inorganic layers bonded by means of an adhesive, and polymer sheets or polymer films with inorganic layers (typically, polymer sheets or polymer films with laminated inorganic layers) bonded by means of a molten thermoplastic polymer film.

[0088] The inorganic substances that make up the inorganic layer are broadly classified into metallic and non-metallic inorganic substances.

[0089] Examples of metals mentioned above include aluminum, copper, and zinc. Examples of non-metallic inorganic materials mentioned above include aluminum oxide and silicon dioxide. From the viewpoint of moisture permeability resistance, metals are preferred among these inorganic materials, and aluminum is more preferred.

[0090] Examples of polymers that constitute polymer sheets or polymer films include polyethylene terephthalate (PET), nylon, low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE).

[0091] From the viewpoint of ease of handling, the aforementioned sealed container is preferably a polymer sheet or polymer film with an inorganic layer laminated on it. From the viewpoint of further improving low moisture permeability, a polymer sheet or polymer film with an aluminum layer laminated on it is more preferred. Furthermore, from the viewpoint of further improving low moisture permeability, a polymer sheet or polymer film laminated with an inorganic layer is preferred, and a polymer sheet or polymer film laminated with an aluminum layer is more preferred.

[0092] Furthermore, the polymer sheet or polymer film can be a polymer sheet or polymer film in which multiple polymers are stacked. For example, from the viewpoint of suppressing cracking and pinholes in the inorganic layer, the outermost layer of the sealed container can be a laminated film containing a polymer with excellent damage resistance, such as PET or nylon, and having an inorganic layer on the inner side of this outer layer. In addition, to improve the heat-welding properties of the polymer sheet or polymer film, the innermost layer of the sealed container can be LLDPE. From these viewpoints, a polymer sheet or polymer film composed of layers sequentially stacked with PET (outermost layer) / LLDPE (innermost layer) and nylon (outermost layer) / LLDPE (innermost layer) is a preferred embodiment. From the viewpoint of further improving low moisture permeability, a polymer sheet or polymer film composed of layers sequentially stacked with PET (outermost layer) / inorganic material (inner layer) / LLDPE (innermost layer) and nylon (outermost layer) / inorganic material (inner layer) / LLDPE (innermost layer) is a more preferred embodiment. It should be noted that, in a preferred embodiment and a more preferred embodiment of the laminated film, layers other than those described above may be included.

[0093] It should be noted that, in the case of liquid diene rubber (B1) which is the compounding material 10 for rubber mixing, this sealed container 22 is particularly effective when it contains groups that are highly reactive with water. Examples of groups that are highly reactive with water include alkoxysilyl groups, isocyanate groups, borate groups, and functional groups derived from acid anhydrides. These groups can be contained individually in the liquid diene rubber (B1), or in combination of two or more.

[0094] In the case of liquid diene rubber (B1) with highly reactive groups that react with water, it is especially necessary to prevent the reaction with water. If such a sealed container 22 is used, the water vapor permeability is low, and a rubber compounding material 10 can be provided to reliably maintain the properties of the aforementioned groups contained in the liquid diene rubber (B1) until rubber compounding is carried out.

[0095] The sealing container 22 is sealed by closing the upper opening (not shown). There are no particular limitations on the means of sealing the upper opening of the sealing container 22; for example, heat sealing (heat fusion welding) can be used. Figure 2 In the middle, symbol 26 represents a closed area.

[0096] It should be noted that, as for the shape of the sealed container 22, it is preferably a bag shape, similar to the sealed bag (A) of the rubber compounding material 10 described above. Alternatively, it can also be... Figure 3A barrel-shaped sealed container 22, as shown, consisting of a reusable main body 28 and a lid 30 secured by a metal strip (not shown) and a convex-concave interlocking mechanism. Figure 4 The box-shaped sealed container 22 is shown. To further improve the airtightness, gaskets or fillers can be installed at the contact portion between the main body 28 and the cover 30. In short, there are no particular limitations on the form as long as it can reliably handle the rubber compounding material 10 in a sealed state.

[0097] Furthermore, a desiccant (not shown) can be placed in the internal space 24 of the sealed container 22. Alternatively, dry nitrogen or air can be filled into the internal space 24, or a combination of dry nitrogen or air and a desiccant (not shown) can be used.

[0098] In this way, the sealed bundle 20 according to the present invention forms a double-sealed structure of a sealed bag (A) and a sealed container 22, thereby enabling the physical properties of the liquid diene rubber (B) to be maintained to a specified state and reliably supplied in a specified amount.

[0099] It should be noted that the above description illustrates an example of sealing one rubber compound 10 within a sealed container 22 to create a sealed bundle 20. However, from a processability perspective, two or more rubber compound 10s can be sealed within a single sealed container 22 to create the sealed bundle of this invention. Of course, the sealed bag (A) for the rubber compound 10 can be used as a single layer or stacked in two or more layers.

[0100] <Method for manufacturing compound 10 for rubber compounding>

[0101] Next, the manufacturing method of the compound material 10 for rubber compounding will be described.

[0102] First, initially as Figure 5 As shown in (a), a sealed bag (A) is prepared with an opening 12 at the top.

[0103] Next, as Figure 5 As shown in (b), liquid diene rubber (B) is filled into the sealed bag (A).

[0104] And, as Figure 5 As shown in (c), the filling of liquid diene rubber (B) is completed after a specified amount of liquid diene rubber (B) is filled into the sealed bag (A).

[0105] Finally, as Figure 5 As shown in (d), the opening 12 of the sealed bag (A) is closed to complete the rubber compounding material 10.

[0106] It should be noted that when it is desired to make two or more sealed bags (A), multiple sealed bags (A) are prepared by overlapping them. Then, liquid diene rubber (B) is filled into the innermost sealed bag (A) through the opening 12 at the top of the overlapping sealed bags (A). Finally, the opening 12 is sealed by heat sealing or the like, thus completing the rubber compounding material 10. Alternatively, when it is desired to make two or more sealed bags (A), considering workability and reduced leakage, the rubber compounding material 10 can be completed as follows: Prepare one bag, fill the bag with liquid diene rubber (B) through the opening 12 at the top of the bag, and seal the opening 12 by heat sealing or the like. Subsequently, a bag is further overlapped on the outside of the bag filled with liquid diene rubber (B) and sealed. The opening of the overlapping bag is sealed by heat sealing or the like. This operation is repeated multiple times as needed to complete the rubber compounding material 10.

[0107] In this way, the method for manufacturing the rubber compound 10 of the present invention can reliably seal liquid diene rubber (B) through a simple process, thereby improving the processability of liquid diene rubber (B).

[0108] <Manufacturing Method of Sealed Bundle 20>

[0109] As an example of manufacturing a sealed package 20, the method will be described using a bag-shaped sealed container 22.

[0110] First, such as Figure 6 As shown in (a), a bag-shaped sealed container 22 with an opening 32 at the top is prepared.

[0111] Next, as Figure 6 As shown in (b), the rubber compounding material 10 is introduced into the interior of the sealed container 22 through the opening 32.

[0112] Furthermore, such as Figure 6 As shown in (c), the opening 32 of the sealed container 22 is closed to complete the sealing of the package 20.

[0113] It should be noted that when sealing the opening 32 of the sealed container 22, for example by heat sealing (heat fusion), dry nitrogen or air can be introduced into the internal space 24 of the sealed container 22. Furthermore, a desiccant (not shown) can be placed in the internal space 24 of the sealed container 22, or dry nitrogen or air can be used in combination with a desiccant (not shown).

[0114] In this way, the method for manufacturing the sealed bundle 20 of the present invention can reliably seal the rubber compounding material 10 through a simple process.

[0115] It should be noted that the rubber compounding material 10 is not limited to being sealed in only one sealed container 22, but two or more rubber compounding materials 10 can also be sealed in one sealed container 22.

[0116] The example described uses a bag-shaped sealed container 22 in the manufacturing method of the aforementioned sealed bundle 20, but the use of... Figure 3 In the case of the barrel-shaped sealed container 22 shown, the lid 30 is removed from the main body 28 beforehand. In this state, the rubber compounding material 10 is added into the main body 28, and then the lid 30 is closed. The lid 30 can be sealed and fixed to the main body 28 using known materials such as metal strips (not shown) or objects based on interlocking joints, and there is no particular limitation.

[0117] Furthermore, in use Figure 4 In the case of the box-shaped sealed container 22 shown, similarly to the barrel-shaped sealed container 22 described above, the lid 30 is pre-removed from the main body 28. In this state, the rubber compounding material 10 is inserted into the main body 28, and then the lid 30 is closed. The lid 30 can be secured to the main body 28 using known structures such as a metal strip (not shown) or an object based on interlocking joints; there are no particular limitations.

[0118] <Method for manufacturing rubber composition>

[0119] The rubber composition used in this invention can be prepared by compounding solid rubber and further adding fillers, vulcanizing agents or crosslinking agents, and other additives as needed, based on a sealed bag (A) containing liquid diene rubber (B). Since the sealed bag (A) containing liquid diene rubber (B) can be directly added to the apparatus during the preparation of the rubber composition, the workability is excellent. Furthermore, because a sealed bag (A) made of a specific material is used as the sealed bag, there are very few cases where the properties of the resulting rubber composition are adversely affected. It should be noted that solid rubber refers to rubber that can be processed in a solid state at 20°C, and the Mooney viscosity (ML) of solid rubber at 100°C is... 1+4Typically, the concentration ranges from 20 to 200, and is usually selected from at least one type of synthetic rubber and natural rubber. Other additives mentioned above include, for example, vulcanization accelerators, vulcanization aids, silane coupling agents, softeners, antioxidants, waxes, lubricants, light stabilizers, anti-scorching agents, processing aids, pigments, colorants, flame retardants, antistatic agents, matting agents, anti-blocking agents, UV absorbers, release agents, foaming agents, antibacterial agents, mildew inhibitors, and fragrances.

[0120] The method for manufacturing the rubber composition of the present invention is not particularly limited as long as the above-mentioned components can be uniformly mixed (kneaded). Examples of apparatus for manufacturing the rubber composition include, for example, tangential or interlocking closed-loop mixers such as Kneader-Ruder, Brabender, Banbury internal mixers, and internal agitators; single-screw extruders; twin-screw extruders; open mill rolls; and rollers. The manufacturing of the above-mentioned rubber composition can generally be carried out in a temperature range of 50–270°C, preferably 130–270°C. By mixing (kneading) at a temperature range of 130°C or higher, melting and dispersion of the sealed bag are promoted, tending to result in rubber compositions with excellent properties.

[0121] A preferred embodiment of the rubber composition of the present invention is that it is used as a crosslinked product (vulcanized rubber) by crosslinking. The vulcanization conditions and methods are not particularly limited, but it is preferred to use a vulcanization mold at a vulcanization temperature of 120–200°C and a vulcanization pressure of 0.5–20 MPa.

[0122] Examples of applications that can utilize the above-described rubber composition and its crosslinked products include tires, seat belts, vibration damping rubber, wire covering rubber, rollers, shoes, sealants, adhesives, greases, printing materials, OCR, OCA, coatings, protective materials, coating agents, gaskets, hoses, brake pads, etc.

[0123] The above-described rubber composition or crosslinker can be suitably used as, for example, part of a tire.

[0124] Examples of tire parts that can use the above-mentioned rubber composition and crosslinked products of the rubber composition include, for example, the tread (top tread, bottom tread), tire sidewall, rubber reinforcement layer (liner, etc.) for runaway tires, rim sealant, bead wrapping, bead wire sealant, tread trim, clinchapex, belt layer, belt layer sealant, buffer layer, buffer layer sealant, bead wrapping, bead wrapping pad, tread trim core, etc.

[0125] Example

[0126] The present invention will be described in more detail below through embodiments, but the present invention is not limited to these embodiments.

[0127] The materials used in the embodiments are shown below.

[0128] [Sealed bag]

[0129] Sealing bag (A-1): Bag made of low-density polyethylene film (melting point 108℃; thickness 49μm) (20cm wide, 30cm long)

[0130] Sealing bag (A-2): Bag made of high-density polyethylene film (melting point 129℃; thickness 52μm) (20cm wide, 30cm long)

[0131] Sealing bag (A-3): Bag made of ethylene-vinyl acetate copolymer film (melting point 86℃; thickness 67μm) (size 20cm wide, 30cm long).

[0132] It should be noted that the melting point of the material of each sealed bag, i.e., the polymer (polymer (a)), is determined under the following measurement conditions. It should be noted that the temperature at the peak of the endothermic peak determined below is taken as the melting point.

[0133] (Conditions for melting point determination)

[0134] DSC measuring device: DSC6200 (manufactured by Hitachi High-Tech Corporation)

[0135] Measurement temperature range: 30℃~200℃

[0136] Heating rate: 10℃ / minute

[0137] [Sealed container]

[0138] Sealed container (C-1): Bag made of aluminum laminate (layer composition: polyethylene terephthalate 12μm / polyethylene 15μm / aluminum 7μm / polyethylene 20μm / linear low-density polyethylene 100μm) (size: 28cm wide, 38cm long; moisture permeability: 0.2g / m³) 2 ·24h)

[0139] Sealed container (C-2): Bag made of high-density polyethylene film (52μm thick) (28cm wide x 38cm long; moisture permeability 4.7g / m³). 2 ·24h)

[0140] Sealed Containers (C-3): 19L removable top-cap drums / tanks with gaskets, based on JIS Z1620 (steel drums), for use with non-hazardous materials (material: Wuxi steel; thickness of this part is approximately 0.4mm; moisture permeability less than 0.1g / m³). 2 ·24h)

[0141] It should be noted that the permeability value was obtained based on the JIS Z0208 cup method under conditions of 40°C and 90% RH. It should also be noted that the results for the sealed container (C-3) were measured for plates of the same thickness and made of the same material.

[0142] [Liquid diene rubber]

[0143] The liquid diene-based rubber (B1-1) produced in Manufacturing Example 1 below

[0144] [Manufacturing Example 1]

[0145] (Preparation of unmodified liquid diene rubber (B'-1))

[0146] A thoroughly dried 5L autoclave was purged with nitrogen. 1280g of cyclohexane and 66g of sec-butyllithium (10.5% by mass cyclohexane solution) were added. After heating to 50°C, butadiene 1350g was added sequentially while maintaining the polymerization temperature at 50°C under stirring. Polymerization was carried out for 1 hour. Subsequently, methanol was added to stop the polymerization reaction, yielding a polymer solution. Water was added to the resulting polymer solution and stirred to wash the polymer solution. After stirring was stopped, and the water was separated after confirming separation of the polymer solution phase from the aqueous phase. The washed polymer solution was then vacuum-dried at 70°C for 24 hours to obtain unmodified liquid diene rubber (B'-1).

[0147] (Modification of unmodified liquid diene rubber (B'-1))

[0148] Next, 700g of the obtained unmodified liquid diene rubber (B'-1) was added to a 1L high-pressure reactor, and nitrogen degassing was carried out while stirring at 60°C for 3 hours. 1.0g of 1,1-bis(tert-butylperoxy)cyclohexane and 50g of (3-mercaptopropyl)triethoxysilane were added, and the mixture was reacted at 110°C for 8 hours to obtain liquid diene rubber (B1-1).

[0149] This series of operations is repeated multiple times to produce the liquid diene rubber (B1-1) used in the following examples, etc.

[0150] [Example 1]

[0151] (Preparation of compounding materials for rubber mixing)

[0152] Two sealed bags (A-1) measuring 20cm in width and 30cm in length are overlapped. 800g of liquid diene rubber (B1-1) prepared in Manufacturing Example 1 is filled into the innermost bag. The opening of the two overlapping sealed bags (A) is then sealed by heat sealing to produce a rubber compounding material (1).

[0153] (Making of sealed packaging materials)

[0154] Rubber compounding material (1) is added into a bag-shaped sealed container (C-1) with a width of 28cm and a length of 38cm, and the opening is sealed by heat sealing to make a sealed bundle (1).

[0155] [Example 2]

[0156] The sealed bag (A-1) was changed to a sealed bag (A-3), but otherwise the same procedure as in Example 1 was followed to prepare the rubber compound (2) and the sealed bundle (2). The stability test of the resulting sealed bundle (2) was carried out under the following conditions. The results are shown in Table 1.

[0157] [Example 3]

[0158] (Making of sealed packaging materials)

[0159] Rubber compound material (1) prepared in the same manner as in Example 1 was introduced into the opening of a barrel (C-3) used as a sealed container. The top cover was fastened to the barrel body with a strap to create a sealed bundle (3). The stability of the resulting sealed bundle (3) was tested under the following conditions. The results are shown in Table 1.

[0160] [Reference Example 1]

[0161] The stability test of the rubber compound (1) prepared in the same manner as in Example 1 was conducted under the following conditions. The results are shown in Table 1.

[0162] [Reference Example 2]

[0163] The sealed bag (A-1) was changed to a sealed bag (A-2), but otherwise the same procedure as in Example 1 was followed to prepare the rubber compound (3). The stability test of the obtained rubber compound (3) was carried out under the following conditions. The results are shown in Table 1.

[0164] [Reference Example 3]

[0165] The stability test of the rubber compound (2) prepared in the same manner as in Example 2 was conducted under the following conditions. The results are shown in Table 1.

[0166] [Reference Example 4]

[0167] (Making of sealed packaging materials)

[0168] The sealed container (C-1) was changed to a sealed container (C-2), but otherwise the same procedure was followed as in Example 1, using rubber compound material (1) to make the sealed bundle (1'). The stability of the resulting sealed bundle (1') was tested under the following conditions. The results are shown in Table 1.

[0169] (Stability test)

[0170] The sealed bundles or rubber compounding materials obtained in the various embodiments and reference examples were placed in a constant temperature and humidity chamber and stored for 4 weeks at a temperature of 60°C and a humidity of 85%Rh.

[0171] Subsequently, the liquid diene rubber (B1-1) filled into a sealed bag was removed from the temperature and humidity control chamber. The rate of change of melt viscosity, the rate of change of functional groups, and the rate of change of polymer area ratio of the liquid diene rubber (B1-1) were calculated as follows to evaluate the stability of the sealed package or the rubber compound.

[0172] (rate of change of melt viscosity)

[0173] The rate of change in melt viscosity can be calculated based on the melt viscosity of the liquid diene rubber (B1-1) at 38°C before and after the stability test, as follows.

[0174] Rate of change of melt viscosity = [{((melt viscosity after stability test) - (melt viscosity before stability test)) / (melt viscosity before stability test)} × 100]

[0175] It should be noted that the melt viscosity of liquid diene rubber (B1-1) at 38°C was measured using a Brookfield viscometer (Type B viscometer) (manufactured by Brookfield Engineering Labs, Inc.).

[0176] (Rate of change of functional groups)

[0177] The rate of change of functional groups contained in liquid diene rubber (B1-1) can be calculated based on the concentration values ​​of functional groups before and after the stability test, as follows.

[0178] The rate of change of functional groups = [{((concentration of functional groups after stability test) - (concentration of functional groups before stability test)) / (concentration of functional groups before stability test)} × 100]

[0179] The concentration of functional groups refers to the number of functional groups bonded to the conjugated diene relative to the monomer mass of the conjugated diene. The concentration of functional groups can be expressed using... 1 H-NMR or 13C-NMR is used to calculate the peak area ratio based on the ratio of peaks originating from functional groups to peaks originating from the polymer backbone. It should be noted that for liquid diene rubber (B1-1), the peaks originating from functional groups refer to peaks originating from alkoxy groups.

[0180] (Rate of change in polymer area ratio)

[0181] The rate of change of polymer area ratio can be calculated based on the value of polymer area ratio before and after the stability test, as follows.

[0182] The rate of change of polymer area ratio = [{((polymer area ratio after stability test) - (polymer area ratio before stability test)) / (polymer area ratio before stability test)} × 100]

[0183] Based on the GPC spectrum obtained by gel permeation chromatography (GPC), the proportion of polymers in the region above Mt (peak molecular weight) × 1.45 is calculated and used as the polymer area ratio.

[0184] (Mt and spectrum determination based on GPC)

[0185] The molecular weight (Mt) and molecular weight spectrum of liquid diene rubber (B1-1) were determined by GPC (gel permeation chromatography) and converted to molecular weight according to standard polystyrene. The apparatus and conditions for determination are shown below.

[0186] • Device: GPC device "GPC8020" manufactured by Tosoh Corporation

[0187] • Separation column: Tosoh Corporation's "TSKgel G4000HXL"

[0188] • Detector: Tosoh Corporation's "RI-8020"

[0189] • Eluent: Tetrahydrofuran

[0190] • Elution flow rate: 1.0 ml / min

[0191] • Sample concentration: 5 mg / 10 ml

[0192] Column temperature: 40℃

[0193] [Table 1]

[0194]

[0195] Explanation of reference numerals in the attached figures

[0196] 10… Rubber compounding materials

[0197] 12…Opening

[0198] 16… Enclosed Area

[0199] 20…closed bundled items

[0200] 22…Sealed containers

[0201] 24… Interior space

[0202] 26… Enclosed Area

[0203] 28…Main Body

[0204] 30… Cover

[0205] 32…Opening

[0206] A…Sealed bag

[0207] B…Liquid diene rubber

Claims

1. Sealed bundled items, including: Sealed containers with low water vapor permeability (C); and The rubber compounding material is sealed inside the sealed container (C). The compounding material for rubber mixing comprises: A resealable bag (A) with a thickness of 30-100 μm made of a polymer (a) with a melting point of 60-140 °C; and Liquid diene rubber (B) is sealed inside the sealed bag (A). The polymer (a) is an ethylene-vinyl acetate copolymer. The liquid diene rubber (B) is a modified polymer containing conjugated diene units that has been modified using functional groups. The functional group is selected from at least one group selected from amino, amide, imino, nitrile, imidazolium, urea, hydroxy, ether, carboxyl, carbonyl, alkoxysilyl, epoxy, mercapto, thiol, disulfide, trisulfide, tetrasulfide, isocyanate, anhydride, dicarboxylic acid monoester, dicarboxylic acid monoamide, borate, vinyl, acryloyl, and methacryloyl. The sealed container (C) is a container made of polymer sheets or polymer films with laminated aluminum layers.

2. The sealed bundle according to claim 1, wherein, The material of the sealed container (C) has a moisture permeability of 4.0 g / m³. 2 • Less than 24 hours.

3. The sealed bundle according to claim 1 or 2, wherein, The liquid diene rubber (B) is a liquid diene rubber (B1) with highly reactive groups that react with water.

4. The sealed bundle according to claim 1 or 2, wherein, The sealed container (C) can be any of the following shapes: bag-shaped, barrel-shaped, or box-shaped.

5. The sealed bundle according to claim 1 or 2, wherein, A desiccant is further disposed inside the sealed container (C).

6. A method for manufacturing sealed bundles, comprising at least the following steps: In the input process, the rubber compounding material of claim 1 is input from the opening of a sealed container (C) with low water vapor permeability; and In the sealing process, after the input process, the opening of the sealing container (C) is sealed.

7. The method for manufacturing a sealed bundle according to claim 6, wherein, In the sealing process, the opening is sealed by heat sealing.

8. A method for manufacturing a rubber composition, comprising: The mixing process of mixing the rubber compounding material as described in claim 1 with solid rubber.

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