TWI381014B - A rubber composition, a rubber roller obtained by using the composition, and a method for producing the same - Google Patents

Description

Rubber composition, rubber roller prepared by using the same, and preparation method thereof

The present invention relates to a rubber composition, and more particularly to a rubber composition for preparing a rubber roller, and a rubber roller manufactured using the same and a method for preparing the same.

In the past, in the process of preparing the rubber composition, it is required to meet the mechanical properties, wear resistance or acid resistance requirements of the final product, for example, to prepare the steel plate production and processing plant pickling tank. The rubber composition must have acid resistance, etc., and most of it will be added with heavy metals or dioctyl esters to adjust its properties.

The inner tube rubber layer and the outer tube rubber layer of the automobile power steering tube disclosed in the case of the mainland publication No. CN1701949A contain dioctyl ester, wherein the inner tube rubber layer is obtained by kneading from the following components: Chlorosulfonated polyethylene, nitrile rubber, magnesium oxide, zinc oxide, accelerator, lead dan, sulfur, stearic acid, spray carbon black, coumarone and dioctyl ester. However, in recent years, with the rise of environmental awareness, the European Union has regarded heavy metals and dioctyl esters as listed substances, so in order to comply with environmental standards, the components that make up the rubber composition must be adjusted.

In addition, CN100348656 discloses a super-resistant strong acid rubber material containing the following raw materials by weight: 70-80 parts of chlorosulfonated polyethylene, 20-30 parts of chlorinated polyethylene, 10-15 parts Fluororubber, 2~4 parts of PTFE, 5~10 parts of zinc methacrylate, 3~6 parts of magnesium methacrylate, 15~60 parts of carbon black, 5~30 parts of filler, 5~ 20 parts of oligoester, 2~3 parts of vulcanizing agent and 0.5~2 parts of accelerator. Although the case does not use dioctyl ester, the fluororubber used therein is expensive, so that the rubber material thus obtained has the disadvantage of being too costly and not in conformity with the production economic efficiency, and it can be known from the formulation of the embodiment of the specification. It is also generally necessary to add lead monoxide as a vulcanization activator, and lead monoxide is classified as a heavy metal.

Therefore, there is still a need to develop a rubber composition that has good properties, low cost, and does not contain EU-listed substances.

In view of environmental protection requirements, dioctyl ester could not be used. Therefore, the inventor finally found a unique benzene ring-free diisononyl dicarboxylate with a variety of tests and tests. The amount of the rubber composition which has good properties, low cost and does not contain EU tubular substances and is suitable for the preparation of rubber rollers.

Accordingly, a first object of the present invention is to provide a rubber composition which is free of EU tubular materials and which is suitable for use in the preparation of rubber rollers.

Therefore, the rubber composition of the present invention for preparing a rubber roller is a chlorosulfonated polyethylene rubber, a nitrile rubber, a stearic acid, a benzene ring-free diisononyl dicarboxylate, a reaction product of a mixture of a filler and a vulcanizing agent, and the chlorosulfonated polyethylene gum is used in an amount of between 10% by weight and 90% by weight based on the total weight of the chlorosulfonated polyethylene gum and the nitrile rubber; The benzene ring-free diisononyl dicarboxylate is used in an amount of from 1% by weight to 15% by weight; the filler is used in an amount of from 25% by weight to 75% by weight; the amount of the sulfide is in the range of 0.5% by weight Between 3wt%.

A second object of the present invention is to provide a rubber roller which has good properties, is low in preparation cost and does not contain EU tubular substances.

The rubber roller of the present invention comprises a cylindrical shaft and at least one rubber layer covering the outer circumference of the shaft, and the rubber layer is composed of the rubber composition as described above.

A third object of the present invention is to provide a method of producing the above rubber roller.

The preparation method of the rubber roller of the present invention comprises the following steps: (a) a chlorosulfonated polyethylene gum, a nitrile rubber, a stearic acid, and a benzene ring-free diisononyl dicarboxylate. And a mixture of a filler and a vulcanizing agent is subjected to a calendering treatment to obtain a rubber sheet, and the amount of the chlorosulfonated polyethylene rubber is based on the total weight of the chlorosulfonated polyethylene rubber and the nitrile rubber. Between 10 wt% and 90 wt%; the amount of the benzene ring-free diisononyl dicarboxylate is between 1 wt% and 15 wt%; the filler is used in an amount of between 25 wt% and 75 wt%; The amount of the sulfide is between 0.5% and 3% by weight; (b) applying a surface blasting treatment and a primer treatment to a cylindrical shaft to obtain a surface treated shaft; Applying a layer of an adhesive to the surface treated rod of the step (b), thereby adhering the rubber sheet of the step (a) to the shaft to obtain a rubber sheet coated a shaft; and (d) placing the rubber sheet-coated shaft of the step (c) in a heating device at a temperature between 100 ° C and 180 ° C to cause the rubber sheet to be sulfur To form a rubber layer on the outer periphery of the shaft, in order to obtain the rubber roller.

The effect of the invention is that, in the preparation of the rubber composition, the dioctyl dicarboxylate containing no benzene ring is used to replace the dioctyl phthalate (hereinafter referred to as DOP) which is commonly used in the industry, and is matched with The specific formulation amount obtained by a plurality of experiments, and then a low-cost preparation of a rubber composition having good properties, containing no EU train material and suitable for preparing a rubber roller, can indeed achieve the effects of the present invention.

In view of the fact that the existing rubber composition cannot meet the requirements of the EU-free tube material at the same time, and has good properties suitable for the preparation of rubber rollers, the inventors tested various additives and different component amounts, and finally found a suitable one for preparation. The rubber composition of the rubber roller.

The rubber composition for preparing the rubber roller of the present invention is a chlorosulfonated polyethylene rubber, a nitrile rubber, a stearic acid, a benzene ring-free diisononyl dicarboxylate, and a filling. The reaction product of the mixture of the agent and the vulcanizing agent, and the amount of the chlorosulfonated polyethylene gum is between 10% by weight and 90% by weight based on the total weight of the chlorosulfonated polyethylene rubber and the nitrile rubber; The benzene ring-containing diisononyl dicarboxylate is used in an amount of from 1% by weight to 15% by weight; the filler is used in an amount of from 25% by weight to 75% by weight; and the amount of the sulfide is from 0.5% by weight to 3wt% %between.

Preferably, the filler is selected from the group consisting of carbon black, white smoke, (bis-(3-(triethoxy-silyl)-propyl) tetrasulfide), or a combination thereof. More preferably, the filler is carbon black.

Preferably, the vulcanizing agent is selected from the group consisting of sulfur, ethylenethiourea (hereinafter referred to as ETU), tetramethylthiuramdisulfide (hereinafter referred to as TMTD), and benzothiazolyl. Disulfide; hereinafter referred to as DM) and dipentamethylene thiuram tetrasulfide (hereinafter referred to as TRA), or a combination thereof.

Preferably, the mixture further comprises an accelerator selected from the group consisting of active magnesium oxide, zinc oxide, or a combination thereof.

Preferably, the mixture further comprises a delaying agent which is a sulfonamide derivative. More preferably, the retarder is selected from the group consisting of N-oxydiethylene-2-benzothiazyl sulfenamode, N-cyclohexylthiophthalimide (N -(cyclohexylthio)phthalimide), or a combination of these.

Preferably, the mixture further comprises an anti-aging agent which is a 1,2-dihydro-2,2,4-trimethylquinoline polymer (TMQ polymerized 1,2-dihydro-2,2,4 -trimethylquinoline).

Preferably, the rubber composition is in the form of a sheet.

The rubber roller of the present invention comprises a cylindrical shaft and at least one rubber layer covering the outer circumference of the shaft, and the rubber layer is composed of the rubber composition as described above.

Preferably, the cylindrical shaft is made of iron.

The preparation method of the rubber roller of the present invention comprises the following steps: (a) a chlorosulfonated polyethylene gum, a nitrile rubber, a stearic acid, and a benzene ring-free diisononyl dicarboxylate. And a mixture of a filler and a vulcanizing agent is subjected to a calendering treatment to obtain a rubber sheet, and the amount of the chlorosulfonated polyethylene rubber is based on the total weight of the chlorosulfonated polyethylene rubber and the nitrile rubber. Between 10 wt% and 90 wt%; the amount of the benzene ring-free diisononyl dicarboxylate is between 1 wt% and 15 wt%; the filler is used in an amount of between 25 wt% and 75 wt%; The amount of the sulfide is between 0.5% and 3% by weight; (b) applying a surface blasting treatment and a primer treatment to a cylindrical shaft to obtain a surface treated shaft; Applying a layer of an adhesive to the surface treated rod of the step (b), thereby adhering the rubber sheet of the step (a) to the shaft to obtain a rubber sheet layer And (d) placing the shaft of the step (c) coated with the rubber sheet layer in a heating device at a temperature between 100 ° C and 180 ° C to allow the rubber sheet to enter The outer periphery of the sulfurization reaction in the shaft form a rubber layer, to obtain the rubber roller.

Preferably, the temperature of step (d) is between 140 ° C and 160 ° C.

Example

The invention is further described in the following examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting.

<Chemicals>

1. 100% pure chlorosulfonated polyethylene (hereinafter referred to as CSM): purchased from DuPont; model 40S.

2. Stearic acid: purchased from: Chengde oil; model is specialic acid.

3. White smoke: purchased from: Taimao; model number is 233-T.

4. Active Magnesium Oxide: purchased from Shendao Chemical, Japan; model number STARMAG-150.

5. Ethylthiourea, tetramethylthiocarbamamine disulfide, dithiobenzoazole and bis-pentamethylene thiocarbamate tetrasulfide were purchased from Fuyuan Chemical.

6. Nitrile rubber (hereinafter referred to as NBR): purchased from Nandi Chemical; model: NANCAR 1052.

7. Dioctyl phthalate: purchased from Liancheng Chemical; model DEHP (DOP).

8. Diphenyl isophthalate dicarboxylate without benzene ring: purchased from the agent's first; model NB-7.

9. Carbon black: purchased from the agent Extreme East Trade; model number N-330.

10. Clay: purchased from: Shouli; model PF-216.

11. N-oxydiethylene-2-phenylthiazole sulfonamide: manufactured by Monsanto (USA); model number is Santoc MOR; Table 2 below is represented by retarder a.

12. N-Cyclohexylthiophthalimide: manufactured by Monsanto (USA); model is Santoguard PVI; Table 2 below is represented by retarder b.

13. 1,2-Dihydro-2,2,4-trimethylquinoline polymer: purchased from Kawaguchi Chemical; model is Antage RD; Table 2 below shows it as an anti-aging agent.

Vulcanization test

Generally, before preparing the vulcanized rubber roller, the vulcanization reaction is first tested with a relatively simple mixture of components, and the degree of vulcanization is judged by a single vulcanizer (Monsanto 2000), thereby finding a better set of vulcanization conditions, usually from MH, ML, t90 and ts2 in the vulcanization curve, where MH is the highest point on the vulcanization curve, representing the highest torque, which can be seen from the shear modulus or stiffness of the sample after sufficient vulcanization; ML is the vulcanization curve The lowest point above represents the lowest torque, which can be seen as the viscosity of the sample before unvulcanization; t90 is the time required to reach 90% of MH, which can reflect the positive vulcanization time of the sample; ts2 is the time to reach ML+2 The time required can reflect the scorch time of the sample.

In the present case, the inventors used the values of MH, ML, t90 and ts2 on the vulcanization curves of different formulations to find out the types and amounts of the components of a mixture having a better vulcanization effect, as in Test Example 1 of Table 1 below. As shown, Table 1 also lists the comparative comparisons of test cases containing lead oxide (PbO) (purchased from Fuyuan Chemical) and lead trioxide (Pb ₃ O ₄ ) (purchased from Fuyuan Chemical). In particular, since the color of the carbon black is deep, in order to facilitate the observation of the degree of vulcanization, the inventors of the present invention first used white smoke for the vulcanization test.

Preparation of vulcanized rubber <Examples 1 to 3 and Comparative Example 1> [Preparation]

In Examples 1 to 3 and Comparative Example 1, a desktop kneading machine (label: Fuzhi Instrument; model Kneader-PBV) and a double roller mixer (label: SCHWABENTHAN; model: diameter 6" × length 14") The formulation shown in Table 2 below is uniformly mixed, that is, kneaded for about 8 to 10 minutes to prepare a rubber composition, and then the rubber composition is placed at a temperature. The vulcanization reaction was carried out on a hot plate at 160 ° C for 1 hour to obtain a vulcanized rubber.

[assessment of nature]

The inventors of the present invention evaluated the properties of the vulcanized rubbers of Examples 1 to 3 and Comparative Example 1 with reference to the operation procedures described in the different standard test methods, wherein tensile strength (kg/cm ² ) and elongation (%) were respectively evaluated. Refer to CNS3553; wear resistance (cc) is based on ASTM D4060; permanent deformation rate (%) is based on CNS3560; ASTM#1 oil weight change (%), strong acid weight change (%) and strong alkali weight change (%) are Refer to CNS3562; hardness (shore A) refers to CNS3555; ASTM#1 oil hardness change (A), strong acid hardness change (A) and strong alkali hardness change (A) refer to CNS3555; density refers to CNS5341, another special It is stated that the above mentioned strong acid weight and hardness test is to immerse the test piece in 30% concentrated hydrochloric acid at a temperature of 80 ° C for 24 hours, while the strong base is to soak the test piece at a temperature of 80 ° C. The change in weight and hardness before and after immersion was carried out in 30 wt% of potassium hydroxide for 24 hours, and the results are shown in Table 2 below.

Preparation of vulcanized rubber roller <Application Example 1>

The preparation step of the application example 1 is that an unvulcanized rubber composition of about 2.1 kg is disposed with reference to the formulation ratio of the rubber composition of the first embodiment, and then it is subjected to a small rubber roller molding trial production by an oversealing manufacturer to perform rubber coating. Previously, the manufacturer would first prepare a test iron core (52 mm in diameter; 150 mm in length), and perform the sandblasting and primer application on the surface of the iron core one day before the rubber coating.

Furthermore, in this case, the rubber coating process is first carried out, and the rubber compound is mixed and discharged by the 14" roller operation, and the glueing operation is performed by the 2.5M glue applicator in the extrusion group, wherein the bottom package The thickness of the glue is 6mm, and the thickness of the outer layer is 8mm. After the glue is completed, the test iron core is placed in a vulcanization tank, and the vulcanization reaction is carried out at 150 ° C for 4 hours, and then, after standing for 24 hours, The final tread roughing and surface grinding treatment were carried out to obtain a small rubber roller having a surface roughness of 0.54 μm.

In summary, in the preparation of the rubber composition, the conventionally used dioctyl ester, such as dioctyl phthalate, as a softener, is replaced by a diphenyl phthalate-free diisononyl dicarboxylate. The component is limited to a specific ratio, and it is possible to obtain a rubber composition having a standard property which can be produced at a low cost without using the EU-listed substance, and therefore, the object of the present invention can be achieved.

The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.

Claims (10)

A rubber composition for preparing a rubber roller, comprising a chlorosulfonated polyethylene rubber, a nitrile rubber, a stearic acid, a benzene ring-free diisodecyl dicarboxylate, and a filling The reaction product of the mixture of the agent and the vulcanizing agent, and the amount of the chlorosulfonated polyethylene gum is between 10 wt% and 90 wt%, based on the total weight of the chlorosulfonated polyethylene gum and the nitrile rubber; The amount of the benzene ring-free diisononyl dicarboxylate is between 1 wt% and 15 wt%; the amount of the filler is between 25 wt% and 75 wt%; Between 0.5 wt% and 3 wr%. The rubber composition according to claim 1, wherein the filler is selected from the group consisting of carbon black, white smoke, and (bis-(3-(triethoxy-decyl)-propyl) tetrasulfide. ()), or a combination of these. The rubber composition according to claim 2, wherein the filler is carbon black. The rubber composition according to claim 1, wherein the vulcanizing agent is selected from the group consisting of sulfur, ethylthiourea, tetramethylthiocarbamamine disulfide, dithiobenzazole, and bis-pentamethyl Thioammonium hexasulfide, or a combination of these. The rubber composition according to claim 1, wherein the mixture further comprises an accelerator selected from the group consisting of active magnesium oxide, zinc oxide, or a combination thereof. The rubber composition according to claim 1, wherein the mixture further comprises a retarder, and the retarder is a sulfonamide derivative. According to the rubber composition of claim 1, wherein The mixture also contains an anti-aging agent which is a 1,2-dihydro-2,2,4-trimethylquinoline polymer. The rubber composition according to the first aspect of the patent application is in the form of a sheet. A rubber roller comprising a cylindrical shaft and at least one rubber layer covering the outer circumference of the shaft, and the rubber layer is composed of the rubber composition as described in claim 1. The rubber roller according to claim 9, wherein the cylindrical shaft is made of iron or stainless steel.