A steel wire rubber coating composition, a steel wire rubber coating, a method for preparing the rubber coating, and a tire using the rubber coating.

Abstract

This invention relates to the field of composite material technology, specifically to a steel wire coating composition, a steel wire coating, a method for preparing the coating, and a tire using the coating. The steel wire coating composition provided by this invention, by weight, comprises: 80-100 parts of bio-based itaconic acid ester rubber; 0-20 parts of natural rubber; and 69.5-107 parts of auxiliary fillers. Compared with ordinary steel wire coating formulations, the steel wire coating composition provided by this invention can achieve high viscosity, low rolling resistance, and high aging resistance without the addition of adhesives, solving the problems of increased rolling resistance and aging during long-term use caused by the addition of adhesives in traditional steel wire coatings. Experiments show that the steel wire coating samples prepared using the composition provided by this invention have mechanical properties comparable to those of traditional steel wire coatings, with a significant decrease in rolling resistance. The maximum pull-out force before aging increases to 598 N, and the pull-out force does not decrease significantly after aging.

Description

Technical Field

[0001] This invention relates to the field of composite material technology, specifically to a steel wire adhesive composition, a steel wire adhesive, a method for preparing the adhesive, and a tire using the adhesive. Background Technology

[0002] Currently, tire steel wire coating formulations typically use 1-10 parts of adhesive. This is because the raw rubber system in the formulation has relatively low adhesion to the steel wire. However, adding fillers to the formulation further reduces the adhesion to the steel wire. Therefore, adding adhesive to the steel wire coating is crucial. While adhesives can improve the adhesion between the coating and the steel wire, they also increase the tire's rolling resistance. Furthermore, during long-term tire use, the generated heat accelerates the aging of the adhesive itself, leading to delamination between the coating and the steel wire. In severe cases, this can even cause safety accidents. Therefore, to completely solve this problem, the most important thing is for the coating formulation to maintain good adhesion while possessing long-term anti-aging capabilities. Summary of the Invention

[0003] In view of this, the technical problem to be solved by the present invention is to provide a steel wire coating composition, a steel wire coating, a method for preparing the coating, and a tire using the coating. The steel wire coating composition provided by the present invention can be used to prepare a steel wire coating with high viscosity, low rolling resistance, and high aging resistance.

[0004] This invention provides a steel wire adhesive composition, comprising, by weight:

[0005] Bio-based itaconic acid ester rubber: 80-100 parts;

[0006] Natural rubber: 0-20 parts;

[0007] And auxiliary fillers: 69.5 to 107 parts.

[0008] The inventors of this application have creatively discovered that by replacing or completely replacing traditional natural rubber with bio-based itaconic acid ester rubber in the preparation of steel wire coatings, steel wire coatings with high viscosity, low rolling resistance, and high aging resistance can be obtained without the addition of adhesives. This solves the problems of aging of traditional steel wire coatings during long-term use due to the addition of adhesives and the increase in tire rolling resistance after the addition of adhesives.

[0009] The steel wire coating composition of this invention comprises 80-100 parts of bio-based itaconic acid ester rubber. In some embodiments of this invention, the steel wire coating composition comprises 80-90 parts of bio-based itaconic acid ester rubber. The bio-based itaconic acid ester rubber of this invention is a bio-based itaconic acid ester rubber with abundant polar side groups. The presence of a large number of side groups not only gives the prepared coating excellent anti-aging ability, but also greatly improves the dispersion ability of auxiliary fillers in the rubber.

[0010] The bio-based itaconic acid ester rubber of this invention is a binary copolymer containing itaconic acid ester and a conjugated diene. In some embodiments of this invention, the bio-based itaconic acid ester rubber is obtained by copolymerization of raw materials including itaconic acid ester and conjugated diene; the itaconic acid ester is selected from one or two of dimethyl itaconic acid, diethyl itaconic acid, di-n-propyl itaconic acid, di-n-butyl itaconic acid, diisopropyl itaconic acid, diisobutyl itaconic acid, di-n-pentyl itaconic acid, and diisopentyl itaconic acid; the conjugated diene is selected from isoprene or butadiene.

[0011] The bio-based itaconic acid ester rubber of the present invention can also be a terpolymer or quaternary copolymer containing itaconic acid ester, conjugated diene, and one or two third components. In other embodiments of the present invention, the itaconic acid ester rubber is obtained by copolymerization of raw materials including itaconic acid ester, conjugated diene, and a third component; the third component is selected from one or two of glycidyl methacrylate, styrene, vinyl chloride acetate, acrylamide, cyclopentadiene, ethylenediene norbornene, methyl acrylate, ethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, hydroxyethyl methacrylate, and 2-hydroxyethyl acrylate.

[0012] The steel wire coating composition of the present invention comprises 0 to 20 parts of natural rubber. In some embodiments of the present invention, the steel wire coating composition comprises 10 to 20 parts of natural rubber. In some embodiments of the present invention, the natural rubber is selected from either No. 1 smoked sheet rubber or standard rubber 20.

[0013] The steel wire coating composition of this invention includes 69.5 to 107 parts of auxiliary filler. The auxiliary filler includes one or more of the following: antioxidant, carbon black, zinc oxide, plasticizer, sulfur, and accelerator. The antioxidant is selected from one or two of TMQ and 6PPD; the carbon black is one or two of N326 and N330; the plasticizer is selected from one of aromatic oil plasticizers or alkane oil plasticizers; the sulfur is selected from one or two of soluble sulfur and insoluble sulfur; and the accelerator is selected from one or more of CBS, DCBS, and HMMM.

[0014] Specifically, the steel wire coating composition of the present invention comprises, by weight, the following: 80-100 parts of bio-based itaconic acid ester rubber; 0-20 parts of natural rubber; 2-4 parts of antioxidant; 60-80 parts of carbon black; 2-5 parts of zinc oxide; 2-10 parts of plasticizer; 3-6 parts of sulfur; and 0.5-2 parts of accelerator.

[0015] In some embodiments of the present invention, the steel wire coating composition of the present invention comprises, by weight: 80-90 parts of bio-based itaconic acid ester rubber; 10-20 parts of natural rubber; 2-4 parts of antioxidant; 60-80 parts of carbon black; 2-5 parts of zinc oxide; 2-10 parts of plasticizer; 3-6 parts of sulfur; and 0.5-2 parts of accelerator.

[0016] In one embodiment, the steel wire coating composition of the present invention comprises, by weight, 100 parts of bio-based itaconic acid ester rubber; 2 parts of antioxidant TMQ; 2 parts of antioxidant 6PPD; 60 parts of carbon black N330; 3 parts of zinc oxide; 2 parts of aromatic oil plasticizer; 4 parts of insoluble sulfur; and 1 part of accelerator DCBS.

[0017] In one embodiment, the steel wire coating composition of the present invention comprises, by weight,: 90 parts of bio-based itaconic acid ester rubber; 10 parts of standard rubber 20; 2 parts of antioxidant TMQ; 2 parts of antioxidant 6PPD; 60 parts of carbon black N330; 3 parts of zinc oxide; 2 parts of aromatic oil plasticizer; 4 parts of insoluble sulfur; and 1 part of accelerator DCBS.

[0018] In one embodiment, the steel wire coating composition of the present invention comprises, by weight, 80 parts of bio-based itaconic acid ester rubber; 20 parts of standard rubber 20; 2 parts of antioxidant TMQ; 2 parts of antioxidant 6PPD; 60 parts of carbon black N330; 3 parts of zinc oxide; 2 parts of aromatic oil plasticizer; 4 parts of insoluble sulfur; and 1 part of accelerator DCBS.

[0019] In one embodiment, the steel wire coating composition of the present invention comprises, by weight, 100 parts of bio-based itaconic acid ester rubber; 2 parts of antioxidant TMQ; 2 parts of antioxidant 6PPD; 60 parts of carbon black N326; 3 parts of zinc oxide; 2 parts of aromatic oil plasticizer; 4 parts of insoluble sulfur; and 1 part of accelerator DCBS.

[0020] In one embodiment, the steel wire coating composition of the present invention comprises, by weight, 100 parts of bio-based itaconic acid ester rubber; 2 parts of antioxidant TMQ; 2 parts of antioxidant 6PPD; 60 parts of carbon black N330; 3 parts of zinc oxide; 2 parts of aromatic oil plasticizer; 4 parts of soluble sulfur; and 1 part of accelerator DCBS.

[0021] In one embodiment, the steel wire coating composition of the present invention comprises, by weight, 100 parts of bio-based itaconic acid ester rubber; 2 parts of antioxidant TMQ; 2 parts of antioxidant 6PPD; 60 parts of carbon black N330; 3 parts of zinc oxide; 2 parts of aromatic oil plasticizer; 4 parts of insoluble sulfur; and 1 part of accelerator CBS.

[0022] In one embodiment, the steel wire coating composition of the present invention comprises, by weight, 100 parts of bio-based itaconic acid ester rubber; 2 parts of antioxidant TMQ; 2 parts of antioxidant 6PPD; 60 parts of carbon black N330; 3 parts of zinc oxide; 2 parts of aromatic oil plasticizer; 4 parts of insoluble sulfur; and 1 part of accelerator HMMA.

[0023] The present invention provides a steel wire coating, which is prepared from the above-mentioned composition.

[0024] This invention also provides a method for preparing steel wire adhesive, comprising: mixing and vulcanizing the above-mentioned steel wire adhesive composition to obtain steel wire adhesive. In some embodiments of this invention, the above-mentioned steel wire adhesive comprises bio-based itaconic acid ester rubber, natural rubber, antioxidant, carbon black, zinc oxide, plasticizer, sulfur, and accelerator. The bio-based itaconic acid ester rubber, natural rubber, auxiliary fillers, antioxidant, carbon black, zinc oxide, and plasticizer are firstly mixed to obtain a first compound; sulfur, accelerator, and the first compound are secondly mixed to obtain a compound; the compound is then left to stand and vulcanized to obtain steel wire adhesive. Before the second mixing, this invention further includes cooling the first compound to below 70°C. The first mixing temperature of the present invention is 150-165°C, and the first mixing time is 2-5 min; the second mixing temperature is 95-105°C, and the second mixing time is 1-3 min; the mixing rubber is left to stand for 16-24 h; the vulcanization temperature is 150-180°C, and the vulcanization time is 5-10 min.

[0025] The present invention also provides a tire with steel wire coated with rubber, which is prepared by applying the above-described steel wire coating or by the above-described preparation method.

[0026] This invention provides a steel wire coating composition, a steel wire coating, a method for preparing the coating, and a tire using the coating. The steel wire coating composition provided by this invention, by weight, comprises: 80-100 parts of bio-based itaconic acid ester rubber; 0-20 parts of natural rubber; and 69.5-107 parts of auxiliary fillers. Compared with ordinary steel wire coating formulations, the steel wire coating composition provided by this invention does not require the use of adhesives, and the large number of side groups in its bio-based itaconic acid ester rubber component blocks oxygen from attacking the rubber backbone, improving aging performance and maintaining good tack during long-term tire use. Simultaneously, due to the excellent dispersion of the fillers, it reduces the overall rolling resistance of the tire. Experiments show that steel wire coating samples prepared using the composition provided by this invention have mechanical properties comparable to traditional steel wire coatings, with a significant decrease in rolling resistance. The maximum pull-out force before aging increases to 598 N, and the pull-out force does not decrease significantly after aging. Detailed Implementation

[0027] This invention discloses a steel wire adhesive composition, a steel wire adhesive, a method for preparing the adhesive, and a tire using the adhesive. Those skilled in the art can refer to the content of this document and appropriately modify the process parameters to achieve the desired result. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in this invention. The methods and applications of this invention have been described through preferred embodiments, and those skilled in the art can clearly modify or appropriately change and combine the methods and applications described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.

[0028] The present invention will be further described below with reference to the embodiments:

[0029] Example 1

[0030] A method for preparing steel wire coating without using adhesives, the formula of which is as follows:

[0031] 100 parts of bio-based itaconic acid ester rubber; 2 parts of TMQ; 2 parts of 6PPD; 60 parts of carbon black N330; 3 parts of zinc oxide; 2 parts of aromatic oil; 4 parts of insoluble sulfur; 1 part of DCBS;

[0032] Its preparation process is as follows:

[0033] (1) Except for sulfur and accelerator, other materials are placed in an internal mixer for mixing for 4 minutes at a temperature of 160°C.

[0034] (2) Cool the material after mixing in step (1), and the temperature of the cooled material is less than 70°C;

[0035] (3) The cooled material, sulfur and accelerator from step (2) are mixed for 2 minutes at 100°C to obtain the compound.

[0036] (4) After the compound is left to stand for 16-24 hours, the compound obtained in step (3) is vulcanized at a vulcanization temperature of 160℃ for 7 minutes using a vulcanizer to obtain a vulcanized rubber sample.

[0037] Example 2

[0038] Compared to Example 1, 10 parts of natural rubber standard rubber 20 were used instead of 10 parts of itaconic acid ester rubber, that is, 100 parts of bio-based itaconic acid ester rubber were changed to 90 parts of bio-based itaconic acid ester rubber and 10 parts of standard rubber 20, while other aspects remained unchanged.

[0039] Example 3

[0040] Compared to Example 1, 20 parts of natural rubber standard rubber 20 were used instead of 20 parts of itaconic acid ester rubber, that is, 100 parts of bio-based itaconic acid ester rubber were changed to 80 parts of bio-based itaconic acid ester rubber and 20 parts of standard rubber 20, while other aspects remained unchanged.

[0041] Example 4

[0042] Compared to Example 1, carbon black N330 was replaced with N326, while everything else remained the same.

[0043] Example 5

[0044] Compared to Example 1, insoluble sulfur was replaced with soluble sulfur, while everything else remained the same.

[0045] Example 6

[0046] Compared to Example 1, the accelerator was replaced with CBS, while everything else remained the same.

[0047] Example 7

[0048] Compared to Example 1, the accelerator was replaced with HMMA, while everything else remained the same.

[0049] Comparative Example 1:

[0050] Compared to Example 1, the itaconic acid ester rubber in the raw rubber system was replaced with natural rubber standard 20, that is, 100 parts of bio-based itaconic acid ester rubber was replaced with 100 parts of standard 20, and 5 parts of adhesive resin RS were added, while the rest remained unchanged.

[0051] The performance of the vulcanizates prepared in the embodiments and comparative examples of the present invention was tested, and the results are shown in Table 1:

[0052] Table 1

[0053]

[0054] Hardness was tested according to GB / T 2411-2008, tensile strength and elongation at break were tested according to GB / T528-2009, and pull-out force was tested according to GB / T 16586-2014. The aging conditions were 100℃*48h, and the DMA test conditions were temperature scan at a frequency of 10Hz; static strain: 7%; dynamic strain: 0.25%; heating rate: 2℃ / min.

[0055] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. The application of a steel wire coating composition in the preparation of steel wire coating, characterized in that, The steel wire adhesive composition comprises, by weight, the following components: Bio-based itaconic acid ester rubber: 80-100 parts; Natural rubber: 0-20 parts; And auxiliary fillers: 69.5~107 parts; The auxiliary filler includes 2-4 parts antioxidant, 60-80 parts carbon black, 2-5 parts zinc oxide, 2-10 parts plasticizer, 3-6 parts sulfur and 0.5-2 parts accelerator.

2. The application according to claim 1, characterized in that, The steel wire adhesive composition comprises, by weight, the following components: Bio-based itaconic acid ester rubber: 80-90 parts; Natural rubber: 10-20 parts; And auxiliary fillers: 69.5~107 parts.

3. The application according to claim 1, characterized in that, The bio-based itaconic acid ester rubber is obtained by copolymerization of raw materials including itaconic acid ester and conjugated diene; The itaconic acid ester is selected from one or two of dimethyl itaconic acid, diethyl itaconic acid, dipropyl itaconic acid, dibutyl itaconic acid, diisopropyl itaconic acid, diisobutyl itaconic acid, dipentyl itaconic acid, and diisopentyl itaconic acid. The conjugated diene is selected from either isoprene or butadiene.

4. The application according to claim 3, characterized in that, The itaconic acid ester rubber is obtained by copolymerization of raw materials including itaconic acid ester, conjugated diene and a third component; The third component is selected from one or two of glycidyl methacrylate, styrene, vinyl chloroacetate, acrylamide, cyclopentadiene, ethylenediene norbornene, methyl acrylate, ethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, hydroxyethyl methacrylate, and 2-hydroxyethyl acrylate.

5. The application according to claim 1, characterized in that, The natural rubber is selected from either No. 1 smoked sheet rubber or standard rubber 20; The antioxidant is selected from one or both of TMQ and 6PPD; The carbon black is one or both of N326 and N330; The plasticizer is selected from either aromatic oil plasticizers or alkane oil plasticizers; The sulfur is selected from one or both of soluble sulfur and insoluble sulfur; The accelerator is selected from one or more of CBS, DCBS and HMMM.

6. The application according to claim 5, characterized in that, The steel wire adhesive composition includes: Bio-based itaconic acid ester rubber: 100 parts; antioxidant TMQ: 2 parts; antioxidant 6PPD: 2 parts; carbon black N330: 60 parts; zinc oxide: 3 parts; aromatic oil plasticizer: 2 parts; insoluble sulfur: 4 parts; accelerator DCBS: 1 part; Alternatively, the steel wire adhesive composition may include: Bio-based itaconic acid ester rubber: 90 parts; Standard rubber 20: 10 parts; Antioxidant TMQ: 2 parts; Antioxidant 6PPD: 2 parts; Carbon black N330: 60 parts; Zinc oxide: 3 parts; Aromatic oil plasticizer: 2 parts; Insoluble sulfur: 4 parts; Accelerator DCBS: 1 part; Alternatively, the steel wire adhesive composition may include: Bio-based itaconic acid ester rubber: 80 parts; Standard rubber 20: 20 parts; Antioxidant TMQ: 2 parts; Antioxidant 6PPD: 2 parts; Carbon black N330: 60 parts; Zinc oxide: 3 parts; Aromatic oil plasticizer: 2 parts; Insoluble sulfur: 4 parts; Accelerator DCBS: 1 part; Alternatively, the steel wire adhesive composition may include: Bio-based itaconic acid ester rubber: 100 parts; antioxidant TMQ: 2 parts; antioxidant 6PPD: 2 parts; carbon black N326: 60 parts; zinc oxide: 3 parts; aromatic oil plasticizer: 2 parts; insoluble sulfur: 4 parts; accelerator DCBS: 1 part; Alternatively, the steel wire adhesive composition may include: Bio-based itaconic acid ester rubber: 100 parts; antioxidant TMQ: 2 parts; antioxidant 6PPD: 2 parts; carbon black N330: 60 parts; zinc oxide: 3 parts; aromatic oil plasticizer: 2 parts; soluble sulfur: 4 parts; accelerator DCBS: 1 part; Alternatively, the steel wire adhesive composition may include: Bio-based itaconic acid ester rubber: 100 parts; antioxidant TMQ: 2 parts; antioxidant 6PPD: 2 parts; carbon black N330: 60 parts; zinc oxide: 3 parts; aromatic oil plasticizer: 2 parts; insoluble sulfur: 4 parts; accelerator CBS: 1 part; Alternatively, the steel wire adhesive composition may include: Bio-based itaconic acid ester rubber: 100 parts; antioxidant TMQ: 2 parts; antioxidant 6PPD: 2 parts; carbon black N330: 60 parts; zinc oxide: 3 parts; aromatic oil plasticizer: 2 parts; insoluble sulfur: 4 parts; accelerator HMMA: 1 part.

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