KR100891297B1 - Reducing cure times rubber composition having storage stability excellent and method for producing of the same - Google Patents

Abstract

A rubber composition for reducing a curing time is provided to secure scorch stability and storage stability by uniformly dispersing a quaternary ammonium modified inorganic layered compound and a titanium organic composite to a rubber base. A rubber composition for reducing a curing time comprises a rubber base and rubber additives. The rubber composition is composed of 3~5wt% of metal oxide, 1~2wt% of stearic acid, 1~2wt% of antioxidant, 3~10wt% of quaternary ammonium modified inorganic layered compound, 30~50wt% of silica, 1~4wt% of titanium organic composite, 1~4wt% of surfactant, 1~2wt% of sulfur, 1~3wt% of vulcanization accelerator, and 0.5~1.5wt% of the other vulcanization accelerator on a 100 part basis of the rubber base.

Description

Reducing cure times rubber composition having storage stability excellent and method for producing of the same}

  The present invention by uniformly dispersing the tetravalent ammonium-modified inorganic layered compound, titanium organic composites and various additives on the rubber substrate, the tetravalent ammonium-modified inorganic layered compound acts as an active catalyst for sulfur crosslinking reaction to promote the crosslinking rate, As the titanium organic composite lowers the reactivity of the rubber composition, the scorch time is secured, excellent storage stability can be maintained, the pattern viscosity of the rubber composition is lowered, and the heat resistance is increased, thereby reducing the heat generation in the screw. The present invention relates to a fast-crosslinking rubber composition capable of plastic injection molding and a method for producing the same.

  In general, rubber compositions have increased the content of sulfur or vulcanization accelerators to promote crosslinking rates. However, the increase in the content of sulfur and vulcanization accelerator is a method of increasing the reactivity itself, there is a limit that the crosslinking properties change due to the gradual reaction at room temperature when storing the rubber composition. This change in crosslinking properties has the disadvantages of increased instability and lowered scorch stability due to appropriate crosslinking time changes.

In addition, since the rubber composition exhibits a tendency that the physical properties of the crosslinking rate and the storage stability are mutually opposite, there is a limit to satisfying the scorch time and improving the storage stability in the fast-crosslinking rubber composition.

  Conventional molding methods of rubber products are carried out by the press molding method, but press molding is labor intensive, and the quality of the product changes according to the skill of the operator, and the working environment is poor. On the contrary, the injection molding has a good working environment, and the product quality is uniform, so that the research for applying the rubber product to the injection molding is continuously made.

  Since most injection molding machines are plastic injection molding machines, conventional rubber has limitations in general use for molding using injection molding machines. In the case of rubber, the flowability is low because of the high viscosity during injection molding, and therefore the structure of the screw and the injection pressure of the injection molding machine should be high. In addition, since the heat generated by the shear force in the internal screw portion is likely to generate scorch, rubber injection is possible only in a rubber injection molding machine having a short screw length (L / D: less than 10).

 On the other hand, as a technique for modifying the inorganic layered compound, penetrating it into a polymer resin, and then peeling and dispersing, a composite manufacturing technology using an organic salt-modified inorganic layered compound is based on a nanoscale sheet-like clay mineral having a silicate layered structure. By peeling it into units and dispersing it in a polymer resin, the concept of raising the limit of low mechanical properties of general-purpose polymers such as polyethylene and polypropylene to the level of engineering plastics is included. In other words, plate silicates, which are the basic units of inorganic layered compounds, are difficult to peel and disperse into polymer resin due to the strong van der wall force, but are modified with low molecular weight organic salts and then modified into polymer resin. It is a technique of peeling and dispersing by making penetration easy.

Such organic salt-modified inorganic layered compounds also affect the sulfur crosslinking reaction. The complex between the organic salt-modified inorganic layer compound and the polymer has a higher crosslinking speed and a higher crosslink density than the unmodified inorganic layer compound. This is due to the reaction of the polymer chain inserted between the layers of the inorganic layered compound and the inorganic layered compound modifier to it, and serves as a catalyst for lowering the activation energy of the overall sulfur crosslinking reaction. (M. Abdul Kader, et al., Polymer , Vol. 45, P. 2237, 2004)

In general, the research applied to the composite using this research has been conducted to improve the mechanical properties by peeling and dispersing the organic salt-modified inorganic layered compound on the substrate. (Herrero B. et al., Polymer, Vol. 44, P2447, 2003) as well as the preparation method for composites using styrene-butadiene rubber (SBR) and organic salt-modified inorganic layered compounds. (Mousa A et al., J. Macromol Mater Eng., Vol 286, P. 260, 2001), a study on the preparation of composites using butadiene rubber and organic salt modified inorganic layered compounds (Ganter M et al. , Rubber Chem Technol.Vol. 74, P. 221, 2001).

In addition, a study on the effect of sulfur crosslinking reaction on the preparation of composites using organic salt-modified inorganic layered compounds for various thermosetting resins (Kong D, et al., Chem. Mater., Vol. 15, P. 419, 2003) Study on the Effect of Sulfur Crosslinking Reaction in the Preparation of Composites Using Natural Rubber and Organic Salt-modified Inorganic Layer Compounds (Arroyo M, et al., J. Appl. Polym. Sci., Vol. 89, P. 1, 2003 Is known.

  In addition, the metal organic complex is a compound having a chelate complex structure centering on a metal element, and in the art of manufacturing a complex using a metal organic complex, US Pat. No. 4,214,058 uses a chelate complex in which a metal and an alkoxy group are bonded to each other. A technique for controlling the reactivity at room temperature by increasing the dispersibility of the compound and lowering the reactivity of the unstable double bond present in the composite is known. US Pat. No. 6,620,871 discloses a structure for alkoxy groups bonded to metals and a chelate-forming structure. There is known a technique relating to a metal organic composite whose effect changes accordingly.

  However, in the case of the fast-crosslinking rubber using the composite manufacturing technology using the organic salt-modified inorganic layered compound and the composite manufacturing technology using the metal organic composite, the crosslinking rate and storage stability of the rubber composition tend to be in conflict with each other. In the cross-linked rubber composition there is a problem that does not satisfy the scorch time and storage stability improvement.

Accordingly, the present inventors have made efforts to solve the above problems, and as a result, by uniformly dispersing the tetravalent ammonium-modified inorganic layer compound and the titanium organic composite in the mixed rubber substrate by using a compounding method, to promote the crosslinking rate, scorch stability It is an object of the present invention to provide a fast-crosslinking rubber composition and a method for producing the same having a high storage stability.

And dispersing the tetravalent ammonium-modified inorganic layered compound and the titanium organic composite in the mixed rubber substrate, thereby reducing the pattern viscosity of the rubber composition and improving the reaction stability against exothermic heat at the screw by increasing the heat resistance, so that both the rubber injection molding machine and the plastic injection molding machine can be used. Another object is to provide a fast-crosslinkable rubber composition which can be molded and a method for producing the same.

According to a feature of the present invention for achieving the above object, the present invention is a fast-crosslinking rubber composition consisting of a rubber substrate and various rubber additives, 3 to 5 parts by weight of metal oxide, stearic acid 1 with respect to 100 parts by weight of the rubber substrate -2 parts by weight, 1 to 2 parts by weight of antioxidant, 3 to 10 parts by weight of tetravalent ammonium-modified inorganic layer compound, 30 to 50 parts by weight of silica, 1 to 4 parts by weight of titanium organic composite, 1 to 4 parts by weight of surfactant, 1 to 2 parts by weight of sulfur, 1 to 3 parts by weight of vulcanization accelerator (1), and 0.5 to 1.5 parts by weight of vulcanization accelerator (2) are added. .

And the present invention in the method for producing a fast-crosslinking rubber composition consisting of a rubber substrate and various additives,

(1) Metal oxide 3 to 100 parts by weight of a rubber substrate while maintaining a speed of 50 to 90 rpm at a temperature of 50 to 110 ℃ using a banbury mixer or kneader capable of temperature control A first mixing step of adding 5 parts by weight, 1 to 2 parts by weight of stearic acid, and 1 to 2 parts by weight of an antioxidant to mix for 3 to 5 minutes;

(2) a second mixing step of adding 3 to 10 parts by weight of a tetravalent ammonium-modified inorganic layered compound to the mixture obtained in the first mixing step and mixing for 3 to 5 minutes;

(3) a third mixing step of adding 30 to 50 parts by weight of silica, 1 to 4 parts by weight of titanium organic composite, and 1 to 4 parts by weight of surfactant to the mixture obtained in the second mixing step and mixing for 3 to 5 minutes;

(4) 1 to 2 parts by weight of sulfur and a vulcanization accelerator in the mixture obtained in the third mixing step while maintaining a speed of 30 to 70 rpm at a temperature of 60 ~ 70 ℃ using an open roll mill (open roll mill) 1) 1 to 3 parts by weight of the vulcanization accelerator (2) by adding 0.5 to 1.5 parts by weight of the fourth mixing step of mixing for 3 to 5 minutes; The manufacturing method is a problem solving means.

As described above, the rapid crosslinking rubber composition capable of plastic injection molding of the present invention is a tetravalent ammonium modified by dispersing a tetravalent ammonium-modified inorganic layer compound and a titanium organic composite uniformly by using a compounding method on a mixed rubber substrate. The inorganic layered compound acts as an active catalyst for the sulfur crosslinking reaction to promote the crosslinking rate. In addition, the titanium organic composite can reduce the reactivity of the rubber composition to ensure scorch time, maintain excellent storage stability, and also reduce the pattern viscosity of the rubber composition, and reduce heat generation from the screw due to increased heat resistance, so that only the rubber injection molding machine can be used. But there is an advantage that can be molded in a plastic injection machine.

According to a feature of the present invention for achieving the above effect, the present invention is a fast crosslinking rubber composition composed of a rubber substrate and various rubber additives, tetravalent ammonium acting as an active catalyst for sulfur crosslinking reaction to promote the crosslinking rate Plastic crosslinking that can be molded in not only rubber injection molding machine but also plastic injection molding machine by adding modified inorganic layer compound and titanium organic composite which lowers reactivity of rubber composition to secure scorch time and maintains excellent storage stability. It relates to a type rubber composition.

In the rubber composition comprising a rubber substrate and various rubber additives, the present invention relates to 3 to 5 parts by weight of a metal oxide, 1 to 2 parts by weight of stearic acid, 1 to 2 parts by weight of antioxidant, and tetravalent ammonium modification based on 100 parts by weight of the rubber substrate. 3 to 10 parts by weight of inorganic layered compound, 30 to 50 parts by weight of silica, 1 to 4 parts by weight of titanium organic composite, 1 to 4 parts by weight of surfactant, 1 to 2 parts by weight of sulfur, 1 to 3 parts by weight of vulcanization accelerator (1) Vulcanization accelerator (2) It is characterized by using 0.5-1.5 weight part.

The present invention is characterized by a tetravalent ammonium-modified inorganic layer compound and a titanium organic composite added to a rubber substrate, and other conventionally added rubber additives are not features of the present invention.

The rubber base material is preferably composed of 60 to 80 parts by weight of butadiene rubber, 10 to 20 parts by weight of styrene rubber, and 20 to 30 parts by weight of natural rubber.

Hereinafter, the components of the fast-crosslinking rubber composition capable of plastic injection molding according to the present invention will be described in detail.

(A) butadiene rubber

Butadiene rubber used in the present invention serves to improve the excellent mechanical strength and wear resistance, the amount is preferably from 60 to 80 parts by weight. When the amount of butadiene rubber is less than 60 parts by weight, open roll mill workability may be improved, but physical properties such as mechanical strength and abrasion resistance may be deteriorated. When the amount of butadiene rubber exceeds 80 parts by weight, the flowability of butadiene rubber is increased. Since this is low, there exists a possibility that open roll mill workability may fall. The butadiene rubber preferably has a pattern viscosity of 40 to 60 and a sheath content of 95 to 99%.

(B) styrene rubber

Styrene rubber used in the present invention exhibits a plasticizer effect in the rubber processing process, maintains the hardness and mechanical strength of the rubber compound, serves to improve the storage properties by adjusting the adhesion of the compound, the amount of use is from 10 to 20 parts by weight is preferred. If the amount of the styrene rubber is less than 10 parts by weight, the physical properties such as hardness and mechanical strength of the rubber composition may be lowered. If the amount of the styrene rubber is more than 20 parts by weight, the hardness of the rubber composition is improved and the moldability is improved. There is a risk of deterioration. In addition, the styrene rubber preferably has a pattern viscosity of 55 to 65 and a sheath content of 60 to 70%.

(C) natural rubber

The natural rubber used in the present invention is excellent in flowability and high in affinity with silica, and serves to improve reinforcement of silica, and its amount is preferably 20 to 30 parts by weight. If the amount of natural rubber used is less than 20 parts by weight, the affinity with silica may decrease, and the reinforcement of silica may be degraded. If the amount of natural rubber used is less than 30 parts by weight, the affinity with silica is high and the reinforcement of silica is improved. Although it can be made, there exists a possibility that a moldability may fall by compression rate fall.

(D) metal oxide

The metal oxide used in the present invention plays a role of controlling the crosslinking rate and improving physical properties, and the amount of the metal oxide used is preferably 3 to 5 parts by weight based on 100 parts by weight of the rubber substrate. If the amount of the metal oxide used is less than 3 parts by weight, the crosslinking rate may drop and the physical properties may be lowered. If the amount of the metal oxide used is more than 5 parts by weight, the crosslinking rate may be too fast, leading to a decrease in physical properties.

The metal oxide used above may be selected from one or more of cadmium oxide, zinc oxide, magnesium oxide, mercury oxide, tin oxide, lead oxide, and calcium oxide.

(E) stearic acid

Stearic acid used in the present invention serves to uniformly disperse the mixture added to the rubber substrate, and the amount of the stearic acid used is preferably 1 to 2 parts by weight based on 100 parts by weight of the rubber substrate. If the amount of stearic acid is less than 1 part by weight, the mixture added to the rubber substrate may not be sufficiently dispersed. If the amount of stearic acid is more than 2 parts by weight, the effect thereof is slight. Stearic acid may be eluted.

(F) anti aging agents

The anti-aging agent used in the present invention serves to prevent the deterioration of the physical properties appearing in the compound preparation, transportation and storage of the rubber, the amount is preferably used 1 to 2 parts by weight based on 100 parts by weight of the rubber substrate. If the amount of the anti-aging agent is less than 1 part by weight, it is difficult to expect anti-aging effect. If the amount of the anti-oxidant is more than 2 parts by weight, the amount of the anti-oxidant is excessive, so that the anti-aging agent is ejected to the surface of the rubber compound or the like. There is a concern.

 The anti-aging agent used above is N, N'-diphenyl-p-phenylenediamine, 4,4'-bis (alpha, alpha-dimethylbenzyl) di-phenyl Amine (4,4'-Bis (alpha, alpha-dimethylbenzyl) di-phenylamine), polymerized 1,2-dihydro-2,2,4-trimethyl quinoline (polymerized 1,2-dihydro-2,2,4- trimethyl quinoline) can be used by selecting one or more.

(G) tetravalent ammonium modified inorganic layered compound

The tetravalent ammonium-modified inorganic layer compound used in the present invention acts as an active catalyst for sulfur crosslinking reaction to promote crosslinking rate and improve dispersibility. The amount of the tetravalent ammonium-modified inorganic layered compound is 3 to 100 parts by weight of the rubber base. Preference is given to using 10 parts by weight. When the amount of the tetravalent ammonium-modified inorganic layered compound is less than 3 parts by weight, the dispersibility may not sufficiently occur due to a decrease in the amount of the tetravalent ammonium-modified inorganic layered compound, and the amount of the tetravalent ammonium-modified inorganic layered compound is 10 parts by weight. When it exceeds, there exists a possibility that a physical property may fall because of the fall of dispersibility.

The tetravalent ammonium-modified inorganic layer compound used in the above can be used by selecting one type from Cloisite, Montmorillonite, Saponite and Hectorite.

(H) silica

Silica used in the present invention is used to improve the mechanical properties of the rubber, the amount of the silica is preferably used 30 to 50 parts by weight based on 100 parts by weight of the rubber substrate. When the amount of silica used is less than 30 parts by weight, there is a fear that the reinforcing effect does not occur, and when the amount of silica exceeds 50 parts by weight, the hardness may be improved and flowability may be lowered due to the increase in viscosity. In addition, the silica used in the present invention has a BET surface area of 140 to ²⁰⁰ m ² / g, and preferably has a pH of 6.5 to 7.5.

(I) titanium organic composite

Titanium organic composites used in the present invention is an organic composite that forms a ligand structure centered on titanium metal ions to lower the reactivity of the rubber composition to ensure scorch time, and has a role of having excellent storage stability. It is preferable to use 1-4 weight part with respect to 100 weight part of rubber base materials. When the amount of the titanium organic composite is less than 1 part by weight, it is difficult to lower the reactivity of the rubber composition. Therefore, the scorch time may be short and the storage stability may decrease. When the amount of the organic composite is more than 4 parts by weight, the reactivity of the rubber composition may be decreased. It can save scorch time and improve storage stability, but its effect is weak compared to the usage amount.

 The titanium organic composite used above is neopentyl (diallyl) oxy trineodecanoyl titanate, neopentyl (diallyl) oxy tri (dodecyl) benzenesulfonyl titanate, neopentyl (diallyl) oxy tri ( Select one or more of dioctyl) phosphate titanate, neopentyl (diallyl) oxy tri (N-ethylenediamino) ethyl titanate, neopentyl (diallyl) oxy tri (m-amino) phenyl titanate Can be used.

(J) surfactant

 Surfactant used in the present invention serves to improve the mechanical properties such as tensile strength to improve wear resistance, etc., the amount of the surfactant is preferably used 1 to 4 parts by weight based on 100 parts by weight of the rubber substrate. If the amount of the surfactant is less than 1 part by weight, it is difficult to expect the effect of improving the mechanical properties. If the amount of the surfactant is more than 4 parts by weight, it is effective to improve the mechanical properties but to improve the wear resistance. This is weak.

The surfactant used above is a nonionic surfactant, and one or more of polyethylene glycol, polyoxyethylene sorbitan monoparmitate, polyoxyethylene sorbitan monostearate, glycerol monostearate, and glycerol monooleate Can be selected and used.

(K) sulfur

Sulfur used in the present invention is a vulcanizing agent, the amount of which is preferably used 1 to 2 parts by weight based on 100 parts by weight of the rubber substrate. If the amount of sulfur is less than 1 part by weight, the rubber composition may not be vulcanized properly and rubber molding may be difficult. If the amount of sulfur is more than 2 parts by weight, premature vulcanization may occur and the hardness of the molded rubber may be rapidly increased. .

(L) Vulcanization accelerator (1)

The vulcanization accelerator used in the present invention is used to shorten the molding time of the rubber composition and to obtain an appropriate crosslinked structure, and the amount of the vulcanization accelerator used is preferably 1 to 3 parts by weight based on 100 parts by weight of the rubber substrate. If the amount of the vulcanization accelerator is less than 1 part by weight, the rubber composition may not be vulcanized properly and the physical properties of the rubber molding may not appear properly. If the amount of the vulcanization accelerator is more than 3 parts by weight, the crosslinking density may be increased due to excessive vulcanization. There is a fear that the physical properties of the rubber is significantly reduced.

The vulcanization accelerator (1) used above may be selected from one or more of bis (2-benzothiazole) disulfide, 2-mercaptobenzothiazole, and 2-mercaptoimidazole.

(M) Vulcanization accelerator (2)

The vulcanization accelerator used in the present invention serves to accelerate the vulcanization reaction of the rubber substrate to shorten the vulcanization time. The amount of the vulcanization accelerator is preferably 0.5 to 1.5 parts by weight to 100 parts by weight of the rubber substrate. If the amount of the vulcanization accelerator is less than 0.5 parts by weight, the activation and effect of the vulcanization accelerator is difficult to obtain. If the amount of the vulcanization accelerator is more than 1.5 parts by weight, the preliminary vulcanization may occur due to excessive accelerated activation and the hardness of the molded rubber may increase rapidly. There is.

The vulcanization accelerator (2) used above may be selected from one or more of tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide and tetraethyl thiuram disulfide.

In addition, the fast-crosslinking rubber composition having excellent storage stability according to the present invention can be added to the conventional additives, such as silane coupling agent, if necessary, it is common in the art that can be mixed in the appropriate amount of the known additives. .

On the other hand, when explaining the manufacturing method of a fast-crosslinking rubber composition capable of plastic injection molding according to the present invention.

delete

The present invention provides a method for producing a fast-crosslinking rubber composition composed of a rubber substrate and various additives,

(1) Metal oxide 3 to 100 parts by weight of a rubber substrate while maintaining a speed of 50 to 90 rpm at a temperature of 50 to 110 ℃ using a banbury mixer or kneader capable of temperature control A first mixing step of adding 5 parts by weight, 1 to 2 parts by weight of stearic acid, and 1 to 2 parts by weight of an antioxidant to mix for 3 to 5 minutes;

(2) a second mixing step of adding 3 to 10 parts by weight of a tetravalent ammonium-modified inorganic layered compound to the mixture obtained in the first mixing step and mixing for 3 to 5 minutes;

(3) a third mixing step of adding 30 to 50 parts by weight of silica, 1 to 4 parts by weight of titanium organic composite, and 1 to 4 parts by weight of surfactant to the mixture obtained in the second mixing step and mixing for 3 to 5 minutes;

(4) 1 to 2 parts by weight of sulfur and a vulcanization accelerator in the mixture obtained in the third mixing step while maintaining a speed of 30 to 70 rpm at a temperature of 60 ~ 70 ℃ using an open roll mill (open roll mill) 1) 1 to 3 parts by weight, the vulcanization accelerator (2) by adding 0.5 to 1.5 parts by weight of the fourth mixing step of mixing for 3 to 5 minutes; to produce a fast-crosslinking rubber capable of plastic injection molding.

In the step (1), the rubber base is preferably made of 60 to 80 parts by weight of butadiene rubber, 10 to 20 parts by weight of styrene rubber, and 20 to 30 parts by weight of natural rubber.

In the case of the fast-crosslinked rubber composition having excellent storage stability prepared as described above, it promotes the crosslinking speed compared to the existing rubber composition, secures the scorch time, maintains the excellent storage stability, and the pattern viscosity is low, and the heat resistance Since the heat generation decreases due to the increase, it can be molded in a rubber injection machine and a plastic injection machine.

And since the specific features related to the rubber substrate and various additives used in the present invention have already been described above, they are omitted here.

In addition, in the present invention, when the stirring conditions and mixing time is less than the above range, various additives may not be properly mixed in the rubber raw material, and thus mechanical properties may be deteriorated, and when the above range is exceeded, various additives may be well mixed in the rubber raw material. However, the mechanical properties may be lowered due to the stirring conditions and the mixing time exceeded.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.

1. Preparation of crosslinked rubber

According to the compounding ratio of the following [Table 1] to manufacture a fast-cross-linking rubber composition capable of plastic injection molding, and then to produce a rubber molded product in a rubber injection machine and a plastic injection machine according to the method of manufacturing a fast-crosslinked rubber capable of plastic injection molding.

                                       (Unit: parts by weight) division Example Comparative example One 2 3 4 One 2 3 Butadiene rubber 50 50 50 50 50 50 50 Styrene rubber 15 15 15 15 15 15 15 caoutchouc 35 35 35 35 35 35 35 Metal Oxide ^{1 )} 5 5 5 5 5 5 5 Stearic acid One One One One One One One Antioxidant ^{2 )} One One One One One One One Tetravalent ammonium-modified inorganic layered compound ^{3 )} 15A 5 - 5 - - - - 20A - 5 - 5 - - - Tetravalent ammonium salt ^{4 )} SB-25 - - - - - - 0.1 Silica 35 35 35 35 40 40 40 Silane Coupling Agents ^{5 )} 3.5 3.5 - - 3.5 3.5 3.5 Titanium Organic Composite ^{6 )} LICA 01 - - 2 - - - - LICA 44 - - - 2 - - - Surfactant ^{7 )} 3 3 3 3 3 3 3 sulfur 1.0 1.0 1.0 1.0 1.0 1.2 1.0 Vulcanization accelerator (1) ^{8 )} 0.5 0.5 0.5 0.5 0.5 1.0 0.5 Vulcanization accelerator (2) ^{9 )} 1.5 1.5 1.5 1.5 1.5 2.5 1.5 1) Metal oxide: Zinc oxide 2) Antioxidant: N, N'-diphenyl-p-phenylenediamine 3) 15A, 20A: Tetravalent ammonium-modified montmorillonite of Southern Clay Products Company 4) SB-25: Stearyl dimethyl benzyl ammonium chloride of the U.S. company 5) Silane coupling agent: Bistriethoxysilylpropyl tetrasulfane 6) LICA 01: Neopentyl (diallyl) oxy trineodecanoyl titanate LICA 44: Neopentyl (Diallyl) oxy tri (N-ethylenediamino) ethyl titanate 7) Surfactant: Polyethylene glycol (molecular weight 4000) 8) Vulcanization accelerator (1): Bis (2-benzothiazole) disulfide 9) Vulcanization accelerator (2): tetramethylthiuram monosulfide

2. Test method

end. Specific gravity: The specific gravity of the outsole was measured five times using an automatic specific gravity measurement apparatus after removing the surface, and the average value was taken.

I. Hardness: Hardness was measured in accordance with ASTM D-2240 with an Asker A type hardness meter on the surface of the outsole.

All. Tensile strength: After making the outsole to a thickness of about 3mm and made a test piece with a cutter (type 2) according to KS M6518, tensile strength and elongation were measured in accordance with KS M6518. At this time, three test pieces were used for the same test.

la. Tear strength: The tear test was performed according to KS M6518, and the measurement speed was measured five times at 100 m / min.

hemp. Abrasion resistance test: To measure the abrasion resistance characteristics of the manufactured outsole, five times of standardized specimens were tested by using an NBS abrasion tester.

bar. Slip resistance: The slip resistance of the manufactured outsole was measured and averaged three times in the dry and wet conditions, respectively, using a slip resistance meter, and the average value was taken as the test value.

four. Crosslinking characteristics: The prepared compound was measured by ODR (Oscillated disk rheometer) to determine the scorch time, proper crosslinking time, minimum and maximum torque.

Ah. Storage stability: The prepared compound was heat-treated at 80 ° C. 2 hs for ODR measurement, and the change rate was calculated by comparing the measurement result with the measurement result before heat treatment.

character. Compound Flowability: The flowability of the prepared compounds was compared by measuring torque over time using a torque rheometer, and the state of the compound discharged from a general plastic injection molding machine was compared.

car. Exothermic characteristics: The temperature of the prepared compound was measured with a torque rheometer to compare the exothermic characteristics.

3. Test result

The properties of the fast crosslinked rubber compositions prepared according to Examples 1 to 4 and Comparative Examples 1 to 3 were measured according to the above test method, and the results are shown in the following [Table 2].

Characteristic measurement unit Example Comparative example One 2 3 4 One 2 3 importance 66/67 65/66 63/68 63/68 65/66 65/66 65/66 Hardness Asker A 1.120 1.120 1.120. 1.120 1.120 1.120 1.120 The tensile strength kgf / cm ² 147/153 135/140 135/145 130/140 132/135 123/130 111/120 Elongation % 590/620 600/620 530/550 500/530 580/600 610/620 590/610 300% modulus kgf / cm ² 45/49 42/45 60/65 55/60 45/48 42/46 44/46 Tear strength kgf / cm 40/42 38/40 50/52 45/50 40/45 35/36 32/35 Wear test % 320/350 320/330 260/280 200/220 310/320 280/300 250/270 Dynamic Sleep (Dry) - 0.89 0.84 0.94 0.90 0.69 0.72 0.75 Dynamic Sleep (Wet) - 0.68 0.66 0.76 0.70 0.43 0.48 0.51 t ₉₀ at 155 sec 3.20 3.50 3.00 2.50 7.42 3.41 3.61 t ₁₀ at 155 sec 2.30 2.20 2.00 1.80 4.12 2.11 2.56 Storage stability 23% 32% 5% 15% + 36% × ⁾ × ⁾

1) Not measurable

Torque rheometer was used to change the torque and temperature with time to compare and evaluate the molding stability of the rubber compound of the rubber compound according to Examples 1 to 4 and Comparative Examples 1 to 3. Examples 1 to 4 1A to 1D and Comparative Examples 1 to 3 (FIGS. 1E to 1G) were used to evaluate rubber injection processability using a general rubber injection machine and a plastic injection machine, and the results are shown in FIGS. 2 to 5 below. Shown in

As a result of combining the Examples and Comparative Examples as shown in FIGS. 2 to 5, Examples 1 to 4 show the tetravalent ammonium-modified inorganic layered compound and titanium as shown in [Table 1] and [Table 2]. As the organic composite is added, as shown in FIGS. 2A to 2D, 3A to 3D, 4A to 4D, and 5A to 5D, the rubber composition exhibits high crosslinking speed and storage stability. This is because the tetravalent ammonium-modified inorganic layered compound, which is peeled and dispersed on a nano scale, acts as an active catalyst for the sulfur crosslinking reaction, so that the crosslinking rate is accelerated. It has been shown to have good storage stability.

In addition, when the tetravalent ammonium-modified inorganic layer compound and the titanium organic composite are dispersed in the mixed rubber substrate, the rubber composition and the plastic injection machine can be molded since the pattern viscosity of the rubber composition is lowered and the heat generation from the screw is reduced due to the increased heat resistance. appear.

In addition, Example 3, including both the tetravalent ammonium modified inorganic layered compound and the metal organic composite, was found to have excellent high speed crosslinking and storage stability. The most stable and low torque in the torque rheometer showed excellent compound flow characteristics, and due to the low heat generation, the process stability of the compound was also excellent. The injection stability and the processability in the plastic injection molding machine were found to be excellent.

In contrast, the rubber composition using silica alone as in Comparative Example 1 was found to have a problem in securing the crosslinking time as shown in FIGS. 2E, 3E, and 4E. In addition, the flowability of the rubber compound is poor, it is difficult to mold in the plastic injection machine due to the heat generated during the injection molding.

When the crosslinking time was shortened by controlling the content of sulfur and the vulcanization accelerator as in Comparative Example 2, as shown in FIGS. 2F, 3F, and 4F, the crosslinking rate was promoted, but the scorch stability and storage stability were lowered. It was also found that molding is difficult in plastic injection molding machines due to heat generation.

In Comparative Example 3, which secures the crosslinking rate using tetravalent ammonium, as shown in FIGS. 2G, 3G, and 4G, the crosslinking rate promoting effect and the storage stability are significantly decreased, and mechanical properties are decreased due to the increase of unreacted material. Appeared to be. It was also found that molding is difficult in plastic injection molding machines due to heat generation.

Therefore, to secure high-speed crosslinking and storage stability with respect to the rubber composition, and molding using a plastic injection machine, it can be seen that it is important for the crosslinking promotion system using the tetravalent ammonium-modified inorganic layered compound and titanium organic composite developed in the present invention. there was.

As described above, the present invention has proved its superiority through the above embodiments, but the present invention is not necessarily limited only by the above configuration, and various substitutions may be made without departing from the technical spirit of the present invention. , Modifications and variations are possible.

1a to 1g is a fast-crosslinking rubber compound according to the present invention, relates to a graph showing a torque and temperature change over time.

2A to 2G relate to an image photograph shown after a HAAKE experiment of a fast-crosslinking rubber compound according to the present invention.

3A to 3G relate to an image photograph showing a rubber compound discharge product in which a fast-crosslinking rubber compound is discharged from a general plastic injection machine.

4A to 4G relate to an image photograph showing a rubber compound outsole injection molded product manufactured in a general rubber injection molding machine using a fast-crosslinking rubber compound according to the present invention.

Figures 5a to 5d relates to an image photograph showing a rubber compound outsole injection molding produced in a general plastic injection molding machine using a fast-crosslinking rubber compound according to the present invention.

Claims (5)

In a fast-crosslinking rubber composition composed of a rubber base material and various rubber additives, The rubber composition is based on 100 parts by weight of a rubber substrate consisting of 60 to 80 parts by weight of butadiene rubber, 10 to 20 parts by weight of styrene rubber and 20 to 30 parts by weight of natural rubber. 3 to 5 parts by weight of metal oxide, 1 to 2 parts by weight of stearic acid, 1 to 2 parts by weight of anti-aging agent, 3 to 10 parts by weight of tetravalent ammonium-modified inorganic layered compound, 30 to 50 parts by weight of silica, 1 to 4 parts by weight of titanium organic composite Parts, 1 to 4 parts by weight of surfactant, 1 to 2 parts by weight of sulfur, 1 to 3 parts by weight of vulcanization accelerator (1), 0.5 to 1.5 parts by weight of vulcanization accelerator (2), The metal oxide is selected from one or more selected from cadmium oxide, zinc oxide, magnesium oxide, mercury oxide, tin oxide, lead oxide and calcium oxide, The anti-aging agent may be N, N'-diphenyl-p-phenylenediamine (N, N'-diphenyl-p-phenylenediamine), 4,4'-bis (alpha, alpha-dimethylbenzyl) di-phenylamine (4 , 4'-Bis (alpha, alpha-dimethylbenzyl) di-phenylamine), polymerized 1,2-dihydro-2,2,4-trimethyl quinoline Select one or more of them and use it. The tetravalent ammonium-modified inorganic layered compound is selected from montmorillonite, hectorite and saponite, and used. The titanium organic complex is neopentyl (diallyl) oxy trineodecanoyl titanate, neopentyl (diallyl) oxy tri (dodecyl) benzenesulfonyl titanate, neopentyl (diallyl) oxy tri (dioctyl) One or more selected from phosphate titanate, neopentyl (diallyl) oxy tri (N-ethylenediamino) ethyl titanate, neopentyl (diallyl) oxy tri (m-amino) phenyl titanate , The surfactant is a nonionic surfactant, one or more selected from polyethylene glycol, polyoxyethylene sorbitan monopartate, polyoxyethylene sorbitan monostearate, glycerol monostearate, and glycerol monooleate Use, The vulcanization accelerator (1) is used by selecting one or more from bis (2-benzothiazole) disulfide, 2-mercaptobenzothiazole, and 2-mercaptoimidazole, The vulcanization accelerator (2) is a fast-crosslinking rubber composition capable of plastic injection molding, characterized in that one or more selected from tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide and tetraethyl thiuram disulfide is used. . In the method for producing a fast-crosslinking composition composed of various additives to the rubber substrate, (1) 60 to 80 parts by weight of butadiene rubber, styrene rubber 10 while maintaining a speed of 50 to 90 rpm at a temperature of 50 to 110 ℃ using a banbury mixer or kneader capable of temperature control 3 to 5 parts by weight of a metal oxide, 1 to 2 parts by weight of stearic acid, and 1 to 2 parts by weight of an antioxidant are added to 100 parts by weight of a rubber base composed of 20 parts by weight to 20 parts by weight and natural rubber, and mixed for 3 to 5 minutes. In the first mixing step, The metal oxide is selected from one or more selected from cadmium oxide, zinc oxide, magnesium oxide, mercury oxide, tin oxide, lead oxide and calcium oxide, The anti-aging agent may be N, N'-diphenyl-p-phenylenediamine (N, N'-diphenyl-p-phenylenediamine), 4,4'-bis (alpha, alpha-dimethylbenzyl) di-phenylamine (4 , 4'-Bis (alpha, alpha-dimethylbenzyl) di-phenylamine), polymerized 1,2-dihydro-2,2,4-trimethyl quinoline Select one or more of them and use it. (2) In the second mixing step of adding 3 to 10 parts by weight of the tetravalent ammonium-modified inorganic layered compound to the mixture obtained in the first mixing step and mixing for 3 to 5 minutes, The tetravalent ammonium-modified inorganic layered compound is selected from montmorillonite, hectorite and saponite, and used. (3) In the third mixing step of adding 30-50 parts by weight of silica, 1-4 parts by weight of titanium organic composite, 1-4 parts by weight of surfactant, and mixing for 3-5 minutes to the mixture obtained in the second mixing step, The titanium organic complex is neopentyl (diallyl) oxy trineodecanoyl titanate, neopentyl (diallyl) oxy tri (dodecyl) benzenesulfonyl titanate, neopentyl (diallyl) oxy tri (dioctyl) One or more selected from phosphate titanate, neopentyl (diallyl) oxy tri (N-ethylenediamino) ethyl titanate, neopentyl (diallyl) oxy tri (m-amino) phenyl titanate , The surfactant is a nonionic surfactant, one or more selected from polyethylene glycol, polyoxyethylene sorbitan monopartate, polyoxyethylene sorbitan monostearate, glycerol monostearate, and glycerol monooleate Use, (4) 1 to 2 parts by weight of sulfur and a vulcanization accelerator in the mixture obtained in the third mixing step while maintaining a speed of 30 to 70 rpm at a temperature of 60 ~ 70 ℃ using an open roll mill (open roll mill) 1) in a fourth mixing step of adding 1 to 3 parts by weight, 0.5 to 1.5 parts by weight of the vulcanization accelerator (2) and mixing for 3 to 5 minutes, The vulcanization accelerator (1) is used by selecting one or more from bis (2-benzothiazole) disulfide, 2-mercaptobenzothiazole, and 2-mercaptoimidazole, The vulcanization accelerator (2) may be selected from one or more of tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide and tetraethyl thiuram disulfide; Method for producing a fast-crosslinking rubber composition capable of plastic injection molding, characterized in that is produced through. delete delete delete

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