Adhesive composition, rubber reinforcing material and article

Abstract

SUMMARY OF THE DISCLOSURE This application relates to adhesive compositions comprising at least a naturally occurring acid, a nitrogen compound, and a latex; and rubber reinforcements and articles comprising the same.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0070911 filed on June 10, 2022 and Korean Patent Application No. 10-2023-0064194 filed on May 18, 2023, and all contents disclosed in the documents of said Korean patent applications are incorporated herein by reference.

[0002] Technical Field This application relates to adhesive compositions, rubber reinforcing materials (eg, cords) and articles (eg, tires). [Background technology]

[0003] Fiber reinforcing materials are used to reinforce the strength of rubber structures. For example, polyester fiber, polyamide fiber, aromatic polyamide fiber, polyvinyl alcohol fiber, etc. can be used as reinforcing materials for rubber tires. Some fibers do not adhere well to rubber, so adhesives are coated on the fiber surface to supplement the adhesion between the rubber and the fiber. For example, adhesives are applied to polyester fibers to improve the adhesion between polyester fiber for tire cords (raw cord) and tire rubber.

[0004] In the prior art, resorcinol-formaldehyde (RF condensate) or its derived components have generally been used in adhesives for the above-mentioned applications. However, RF, which contains resorcinol, a phenol, and formaldehyde, a known carcinogen, is harmful to the human body, and additional costs are incurred for the post-processing and post-treatment of waste adhesives containing RF. The use of such RF adhesives is gradually decreasing.

[0005] Therefore, there is a need for a technology that is less harmful to humans and more environmentally friendly, yet provides the same or better physical properties as prior art products (adhesives, cords and / or tires). Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present application is to provide an adhesive that is less harmful to the human body and is environmentally friendly.

[0007] Another object of the present application is to provide an adhesive that can provide physical properties (e.g., adhesive strength) that are equal to or better than those of prior art adhesives in that application.

[0008] It is yet another object of the present application to provide an adhesive that is simpler and easier to manufacture.

[0009] It is still another object of the present application to provide a reinforcing material (eg, a cord) manufactured using the adhesive, and an article (eg, a tire) including the same.

[0010] The above and other objects of the present application can all be met by the present application as described below. [Means for solving the problem]

[0011] According to the present application, a tire cord adhesive is provided that contains a polyphenol-based naturally derived extract that can replace RF condensates that are harmful to humans and the environment.

[0012] In the prior art, tire adhesive compositions generally contain RF condensate components. However, the inventors of the present application have invented an adhesive composition containing a naturally derived acid to solve the problem of environmental or human toxicity caused by the use of RF condensates. The adhesive composition of the present application containing a naturally derived acid component is not only non-toxic and environmentally friendly compared to the prior art in which RF was used, but also simplifies the adhesive manufacturing process. In addition, the adhesive of the present application provides adhesive strength at the same level or higher than that of the prior art adhesive in which RF condensates were used.

[0013] Hereinafter, a more detailed description will be given of an adhesive composition comprising a predetermined amount of a natural or naturally derived acid, a nitrogen compound, a basic substance, and latex, provided according to specific embodiments of the present invention; an adhesive composition comprising a condensate of a natural acid and a nitrogen compound, a basic substance, and latex; a rubber reinforcing material comprising a coating layer formed from the adhesive composition and a fiber cord; and an article comprising the rubber reinforcing material.

[0014] First aspect: adhesive composition In one embodiment of the present application, the present application relates to an adhesive composition comprising: (a) a naturally occurring acid, (b) a nitrogen compound, (c) a basic material, and (d) a latex.

[0015] In the present application, the term "naturally derived acid" is used to distinguish it from artificially synthesized acid components, and may refer to an acid derived from a plant and / or a microorganism, or an acid containing a substance derived from a plant and / or a microorganism. For example, the naturally derived acid may be a component extracted from the bark, oak galls, or leaves of a plant. More specifically, plants such as Mimosa wattle (Acacia mollissima), Quebracho (Schnopsis sp.), and Radiata pine (Pinus radiate), which contain a significant amount of tannins, can be used to extract naturally derived acids. Such naturally derived acids may be, for example, aromatic compounds having a hydroxyl group, i.e., phenols or polyphenolic compounds.

[0016] In one example, the naturally occurring acid may be or may include naturally occurring tannic acid. Tannic acid is an aromatic compound having a phenolic hydroxyl group, and is known as a substance that may have a gallol unit and / or a catechol unit. Such tannic acid may be a mixture of various naturally occurring substances including plants.

[0017] Such naturally occurring acids have aromatic structures with hydroxy groups and thus can provide suitable cohesion to the composition through hydrogen and / or hydrophobic bonds.

[0018] In one example, the naturally occurring acid may have infrared absorption peak characteristics as shown in FIG. 1, which will be described later. Specifically, the naturally occurring acid may have an infrared absorption peak characteristic as shown in FIG. 1, which will be described later. -1 It may also exhibit an absorption peak at or below 0.15.

[0019] As shown in Figure 1, unlike naturally occurring tannic acid, synthetic tannic acid has a wavenumber of approximately 1707 cm-1 The synthetic tannic acid shows an absorption peak at 1000 nm, which corresponds to the C=O bond. This is thought to be because more units containing C=O are produced during the synthesis of tannic acid than in naturally occurring tannic acid. The higher the C=O bond, the higher the affinity for water, so an adhesive containing synthetic tannic acid may be more diluted than an adhesive containing the same amount of naturally occurring tannic acid. This may reduce the adhesive's adhesive strength.

[0020] In a specific example of the present application, the composition may contain 1.0 wt % or more of the naturally occurring acid based on the total content of the composition being 100 wt %, where the content may refer to the solid content of the naturally occurring acid in the composition.

[0021] Unless otherwise specified, the content of each component in the compositions described herein, excluding the solvent, may be the solid content. The "solid content" may refer to the content of the active ingredient (which may be in solid form) remaining after evaporating water or liquid components (e.g., solvent) for the composition or each component contained in the composition. The conditions for evaporating water or liquid components (e.g., solvent) are not particularly limited, but for example, heating conditions in the range of 70 to 100°C for about 0.5 to 3 hours are applicable.

[0022] Specifically, the lower limit of the content of the naturally occurring acid may be, for example, 1.5 wt% or more, 2.0 wt% or more, 2.5 wt% or more, 3.0 wt% or more, 3.5 wt% or more, 4.0 wt% or more, or 4.5 wt% or more. And the upper limit may be, for example, 5.0 wt% or less, 4.5 wt% or less, 4.0 wt% or less, 3.5 wt% or less, 3.0 wt% or less, 2.5 wt% or less, 2.0 wt% or less, 1.5 wt% or less, 1.0 wt% or less, or 0.5 wt% or less. When the content is satisfied, it is advantageous for the adhesive to provide an appropriate level of adhesive strength.

[0023] In one example, the naturally occurring acid may be dispersed in a solvent (e.g., water or an organic solvent) and mixed with other components of the composition. In this case, the content and type of the solvent that disperses the naturally occurring acid component can be determined so as to satisfy the content of the naturally occurring acid in the overall composition described above and not to reduce physical properties such as adhesive strength.

[0024] RF condensates (e.g., resorcinol-formalin) used in the prior art require a separate manufacturing process before application to an adhesive composition. Specifically, since resorcinol has a small molecular weight, a manufacturing process was required to make a condensate with a large molecular weight by condensing resorcinol with formalin in order to compensate for this shortcoming. However, in the present application, the above-mentioned naturally derived substance (naturally derived acid) and the nitrogen compound described below react under the condition of a basic substance to form a condensate, so that a separate condensate manufacturing process is not required. For this reason, the adhesive composition of the present application contains a nitrogen compound and a basic substance. Here, such a condensate-forming reaction may be carried out at room temperature (e.g., in a range of 15 to 35°C, 15 to 25°C, in particular, without heating or lowering).

[0025] The nitrogen compound may be a substance that contains nitrogen and can form a condensation reaction product with tannic acid. As the nitrogen compound, a substance different from the basic substance described below may be selected.

[0026] In one example, the nitrogen compound may include, but is not limited to, one or more selected from the group consisting of piperazine, piperidine, pyridine, pyrimidine, pyrrolidine, pyrrole, imidazole, indole, aniline, histidine, tryptophan, and hexamine.

[0027] In one example, the composition may contain 0.01 wt% or more of the nitrogen compound based on the total content of the composition being 100 wt%. The content may refer to the solid content of the nitrogen compound in the composition. Specifically, the lower limit of the content of the nitrogen compound may be, for example, 0.05 wt% or more, 0.10 wt% or more, 0.20 wt% or more, 0.30 wt% or more, 0.40 wt% or more, 0.50 wt% or more, 0.60 wt% or more, 0.70 wt% or more, 0.80 wt% or more, 0.90 wt% or more, 1.0 wt% or more, 1.10 wt% or more, 1.20 wt% or more, 1.30 wt% or more, 1.40 wt% or more, 1.50 wt% or more, 1.60 wt% or more, 1.70 wt% or more, 1.80 wt% or more, 1. It may be 90% by weight or more, 2.00% by weight or more, 2.10% by weight or more, 2.20% by weight or more, 2.30% by weight or more, 2.40% by weight or more, 2.50% by weight or more, 2.60% by weight or more, 2.70% by weight or more, 2.80% by weight or more, 2.90% by weight or more, 3.00% by weight or more, 3.10% by weight or more, 3.20% by weight or more, 3.30% by weight or more, 3.40% by weight or more, 3.50% by weight or more, 3.60% by weight or more, 3.70% by weight or more, 3.80% by weight or more, or 3.90% by weight or more. And the upper limit may be, for example, 4.00% by weight or less, 3.50% by weight or less, 3.00% by weight or less, 2.50% by weight or less, 2.00% by weight or less, 1.50% by weight or less, 1.00% by weight or less, or 0.50% by weight or less. When the above content is satisfied, a condensation product of a naturally occurring acid and a nitrogen compound can be obtained stably, which is advantageous in ensuring stable adhesive performance of the adhesive.

[0028] In one example, the nitrogen compound may be dispersed in a solvent (e.g., water or an organic solvent) and mixed with other components of the composition. In this case, the content and type of the solvent for dispersing the nitrogen compound can be determined so as to satisfy the nitrogen compound content in the overall composition described above and not to deteriorate physical properties such as adhesive strength.

[0029] In a specific example of the present application, the basic substance may include two or more different basic substances. For example, ammonia (NH 3 ), Sodium Carbonate (Na 2 CO 3 ), potassium hydroxide (KOH), magnesium hydroxide (Mg(OH) 2 At least two or more substances selected from the group consisting of ammonium nitrate (Aminonitrile) and sodium hydroxide (NaOH) can be used as the basic substance. However, in the present application, the types of basic substances that can be used are not limited to the above-mentioned basic substances, so long as the conditions for the condensation reaction of the naturally occurring acid and the nitrogen compound are formed and the pH of the composition described below is satisfied. In this way, when two or more different basic substances are contained, it is possible to ensure physical properties (e.g., adhesive strength, fatigue resistance, etc.) that are equal to or higher than those of conventional tire cords in their application, as in the examples described below.

[0030] In one example, the composition may contain 0.01 wt% or more of the basic substance based on the total content of the composition being 100 wt%. The content may refer to the solid content of the basic substance in the composition. Specifically, the lower limit of the content of the basic substance may be, for example, 0.05 wt% or more, 0.10 wt% or more, 0.20 wt% or more, 0.30 wt% or more, 0.40 wt% or more, 0.50 wt% or more, 0.60 wt% or more, 0.70 wt% or more, 0.80 wt% or more, 0.90 wt% or more, 1.00 wt% or more, 1.10 wt% or more, 1.20 wt% or more, 1.30 wt% or more, 1.40 wt% or more, 1.50 wt% or more, 1.60 wt% or more, 1.70 wt% or more, 1.80 wt% or more, 1.9 ... It may be 0.70% by weight or more, 1.80% by weight or more, 1.90% by weight or more, 2.00% by weight or more, 2.10% by weight or more, 2.20% by weight or more, 2.30% by weight or more, 2.40% by weight or more, 2.50% by weight or more, 2.60% by weight or more, 2.70% by weight or more, 2.80% by weight or more, 2.90% by weight or more, 3.00% by weight or more, 3.10% by weight or more, 3.20% by weight or more, 3.30% by weight or more, 3.40% by weight or more, or 3.50% by weight or more. And the upper limit may be, for example, 4.00% by weight or less, 3.50% by weight or less, 3.00% by weight or less, 2.50% by weight or less, 2.00% by weight or less, 1.50% by weight or less, 1.00% by weight or less, or 0.50% by weight or less. When the above content is satisfied, conditions in which condensation between the naturally occurring acid and the nitrogen compound can occur can be stably created, which is advantageous in ensuring stable adhesive performance of the adhesive.

[0031] In one example, the basic substance may include a first basic substance, sodium hydroxide (NaOH), and a second basic substance different from the first basic substance. If the pH of the adhesive composition is not adjusted, uniform mixing may not be achieved during the adhesive manufacturing process, which may result in a decrease in adhesive strength. However, sodium hydroxide is more suitable for adjusting the pH of naturally occurring acids. In addition, sodium hydroxide has good compatibility with the first coating layer forming composition (e.g., containing an epoxy compound and an isocyanate compound) described below, and therefore can provide excellent adhesive strength in cord applications. The second basic substance may be, for example, sodium carbonate (Na 2 CO 3 ), potassium hydroxide (KOH), magnesium hydroxide (Mg(OH) 2 ) and ammonia (NH 3 At least one selected from the group consisting of

[0032] The contents of the first basic substance and the second basic substance can be adjusted to a level that ensures sufficient adhesive strength and fatigue resistance, as will be described in the experiments below.

[0033] In one example, the adhesive composition may contain, as a basic substance, 0.01 to 1.5 wt % of a first basic substance, sodium hydroxide (NaOH), and 0.01 to 2.5 wt % of a second basic substance different from the first basic substance.

[0034] In a specific example of the present application, the first basic substance, sodium hydroxide, may be included in an amount of 0.05% by weight or more, 0.1% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.4% by weight or more, 0.5% by weight or more, 0.6% by weight or more, 0.7% by weight or more, 0.8% by weight or more, 0.9% by weight or more, 1.0% by weight or more, 1.1% by weight or more, 1.2% by weight or more, 1.3% by weight or more, or 1.4% by weight or more. The upper limit of the content may be, for example, 1.4% by weight or less, 1.3% by weight or less, 1.2% by weight or less, 1.1% by weight or less, 1.0% by weight or less, 0.9% by weight or less, 0.8% by weight or less, 0.7% by weight or less, 0.6% by weight or less, 0.5% by weight or less, 0.4% by weight or less, 0.3% by weight or less, 0.2% by weight or less, or 0.1% by weight or less.

[0035] In specific examples of the present application, the second basic substance may be included in an amount of 0.05 wt% or more, 0.1 wt% or more, 0.2 wt% or more, 0.3 wt% or more, 0.4 wt% or more, 0.5 wt% or more, 0.6 wt% or more, 0.7 wt% or more, 0.8 wt% or more, 0.9 wt% or more, 1.0 wt% or more, 1.1 wt% or more, 1.2 wt% or more, 1.3 wt% or more, 1.4 wt% or more, 1.5 wt% or more, 1.6 wt% or more, 1.7 wt% or more, 1.8 wt% or more, 1.9 wt% or more, 2.0 wt% or more, 2.1 wt% or more, 2.2 wt% or more, 2.3 wt% or more, or 2.4 wt% or more. The upper limit of the content may be, for example, 2.4 wt% or less, 2.3 wt% or less, 2.2 wt% or less, 2.1 wt% or less, 2.0 wt% or less, 1.9 wt% or less, 1.8 wt% or less, 1.7 wt% or less, 1.6 wt% or less, 1.5 wt% or less, 1.4 wt% or less, 1.3 wt% or less, 1.2 wt% or less, 1.1 wt% or less, 1.0 wt% or less, 0.9 wt% or less, 0.8 wt% or less, 0.7 wt% or less, 0.6 wt% or less, 0.5 wt% or less, 0.4 wt% or less, 0.3 wt% or less, 0.2 wt% or less, or 0.1 wt% or less.

[0036] In one example, the basic substance may be mixed with other components of the composition in a state where it is dispersed in a solvent (e.g., water or an organic solvent). In this case, the content and type of the solvent for dispersing the basic substance can be determined so as to satisfy the content of the basic substance in the entire composition described above and not to deteriorate physical properties such as adhesive strength.

[0037] In a non-limiting embodiment of the present application, the adhesive may be any of the following (in addition to latex): tannic acid, hexamine, sodium hydroxide (NaOH), and ammonia (NH 3 As a result, a condensation reaction can occur between tannic acid, a naturally occurring acid, and hexamine, a nitrogen compound, under basic conditions, and the adhesive composition can include a condensate having a unit of the following chemical formula 1:

[0038] <Chemical formula 1> JPEG2025514318000002.jpg6598

[0039] The latex component is a component used in consideration of the application of the composition. Specifically, the adhesive composition can be used for reinforcing the adherend, such as a rubber composite or a rubber reinforcing material, and the latex can be advantageous in ensuring affinity, miscibility, or adhesive strength with the adherend. In some cases, the latex component contained in the adhesive composition can be selected from the same rubber component that forms the adherend.

[0040] There is no particular limitation on the type of latex that can be used in the composition, so long as it does not contradict the achievement of the technical object of the present application.

[0041] In one example, the latex may be natural rubber latex, vinyl-pyridine latex such as vinyl-pyridine-styrene-butadiene copolymer latex (hereinafter referred to as "VP latex"), styrene-butadiene copolymer latex, acrylic acid ester copolymer latex, butyl rubber latex, chloroprene rubber latex, or modified latexes thereof. In relation to the modified latex, the method of modifying the latex and the specific type of latex are not limited. For example, modified latex obtained by modifying a vinyl-pyridine-styrene-butadiene copolymer with a carboxyl group or the like may be used.

[0042] As long as it does not interfere with the achievement of the technical object of the present application, commercially available latexes can be used. For example, commercially available VP latexes include LM-60 from Denaka, VP-150 from APCOTEX, VB-1099 from Nippon A&L, 5218 from Closlen, and 0653 from Closlen.

[0043] In one example, a latex component including one or more of the latices described above can be used in the adhesive composition.

[0044] In one example, the latex may be dispersed in a solvent (e.g., water or an organic solvent) and mixed with other composition components, in which case the content and type of solvent used in the latex component can be determined at a level that does not impair the adhesive strength of the adhesive composition.

[0045] In one example, the adhesive composition may contain 5.0 wt% or more of the latex based on the total content of the composition. Here, the content may refer to the content of the latex solid content in the composition. Specifically, the lower limit of the content of the latex may be, for example, 6.0 wt% or more, 7.0 wt% or more, 8.0 wt% or more, 9.0 wt% or more, 10.0 wt% or more, 11.0 wt% or more, 12.0 wt% or more, 13.0 wt% or more, 14.0 wt% or more, 15.0 wt% or more, 16.0 wt% or more, 17.0 wt% or more, 18 wt% or more, 19 wt% or more, 20 wt% or more, 21 wt% or more, 22 wt% or more, 23 wt% or more, 24 wt% or more, or 25 wt% or more. The upper limit may be, for example, 50% by weight or less, 45% by weight or less, 40% by weight or less, or 35% by weight or less, and specifically may be 30% by weight or less, 29% by weight or less, 28% by weight or less, 27% by weight or less, 26% by weight or less, 25% by weight or less, 24% by weight or less, 23% by weight or less, 22% by weight or less, 21% by weight or less, 20% by weight or less, 19% by weight or less, 18% by weight or less, 17% by weight or less, 16% by weight or less, or 15% by weight or less. When the above range is satisfied, it may be advantageous to ensure affinity, compatibility, and / or adhesive strength to the rubber-containing adherend to which the adhesive is used.

[0046] In one example, the adhesive composition can contain 3.0 to 50.0 parts by weight of the naturally occurring acid component based on 100 parts by weight of the latex. For example, the lower limit of the content of the naturally occurring acid component (based on 100 parts by weight of the latex) can be 4 parts by weight or more, 5 parts by weight or more, 6 parts by weight or more, 7 parts by weight or more, 8 parts by weight or more, 9 parts by weight or more, 10 parts by weight or more, 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, 14 parts by weight or more, 15 parts by weight or more, 16 parts by weight or more, 17 parts by weight or more, 18 parts by weight or more, 19 parts by weight or more, 20 parts by weight or more, 21 parts by weight or more, 22 parts by weight or more, 23 parts by weight or more, and the like. parts or more, 24 parts or more, 25 parts or more, 26 parts or more, 27 parts or more, 28 parts or more, 29 parts or more, 30 parts or more, 31 parts or more, 32 parts or more, 33 parts or more, 34 parts or more, 35 parts or more, 36 parts or more, 37 parts or more, 38 parts or more, 39 parts or more, 40 parts or more, 41 parts or more, 42 parts or more, 43 parts or more, 44 parts or more, or 45 parts or more by weight. The upper limit of the content of the naturally occurring acid component is, for example, (based on 100 parts by weight of latex) 50 parts by weight or less, 49 parts by weight or less, 48 ​​parts by weight or less, 47 parts by weight or less, 46 parts by weight or less, 45 parts by weight or less, 44 parts by weight or less, 43 parts by weight or less, 42 parts by weight or less, 41 parts by weight or less, 40 parts by weight or less, 39 parts by weight or less, 38 parts by weight or less, 37 parts by weight or less, 36 parts by weight or less, 35 parts by weight or less, 34 parts by weight or less, 33 parts by weight or less, 32 parts by weight or less, parts by weight or less, 31 parts by weight or less, 30 parts by weight or less, 29 parts by weight or less, 28 parts by weight or less, 27 parts by weight or less, 26 parts by weight or less, 25 parts by weight or less, 24 parts by weight or less, 23 parts by weight or less, 22 parts by weight or less, 21 parts by weight or less, 20 parts by weight or less, 19 parts by weight or less, 18 parts by weight or less, 17 parts by weight or less, 16 parts by weight or less, 15 parts by weight or less, 14 parts by weight or less, 13 parts by weight or less, 12 parts by weight or less, 11 parts by weight or less, or 10 parts by weight or less. When the above range is satisfied, stable adhesive performance can be ensured, and the adhesive can have properties suitable for a tire cord adhesive in achieving the technical problem of the present application.

[0047] In one example, the adhesive composition may contain 0.3 to 25.0 parts by weight of the nitrogen compound based on 100 parts by weight of the latex. For example, the lower limit of the content of the nitrogen compound (based on 100 parts by weight of the latex) may be, for example, 0.5 parts by weight or more, 1.0 parts by weight or more, 1.5 parts by weight or more, 2.0 parts by weight or more, 2.5 parts by weight or more, 3.0 parts by weight or more, 3.5 parts by weight or more, 4.0 parts by weight or more, 4.5 parts by weight or more, 5.0 parts by weight or more, 5.5 parts by weight or more, 6.0 parts by weight or more, 6.5 parts by weight or more, 7.0 parts by weight or more, 7.5 parts by weight or more, 8.0 parts by weight or more, 8.5 parts by weight or more, 9.0 parts by weight or more, 9.5 parts by weight or more, 10. or more than 17.0 parts by weight, 17.5 parts by weight, 18.0 parts by weight, 18.5 parts by weight, 19.0 parts by weight, 20.5 parts by weight, 21.0 parts by weight, 22.0 parts by weight, 23.0 parts by weight, 24.0 parts by weight, 25.0 parts by weight, 26.0 parts by weight, 27.0 parts by weight, 28.0 parts by weight, 29.0 parts by weight, 30.0 parts by weight, 31.0 parts by weight, 32.0 parts by weight, 33.0 parts by weight, 34.0 parts by weight, 35.0 parts by weight, 36.0 parts by weight, 37.0 parts by weight, 38.0 parts by weight, 39.0 parts by weight, 40.0 parts by weight, 41.0 parts by weight, 42.0 parts by weight, 43.0 parts by weight, 44.0 parts by weight, 45.0 parts by weight, 46.0 parts by weight, 47.0 parts by weight, 48.0 parts by weight, 49.0 parts by weight, 50.0 parts by weight, 51.0 parts by weight, 52.0 parts by weight, 53.0 parts by weight, 54.0 parts by weight, 55.0 parts by weight, 56.0 parts by weight, 57.0 parts by weight, 58.0 parts by weight, 59 ...9.0 parts by weight, 54.0 parts by weight, 55.0 parts by weight, 55.0 parts by weight, 55.0 parts by weight, 55.The upper limit of the content of the nitrogen compound (based on 100 parts by weight of latex) is, for example, 24.5 parts by weight or less, 24.0 parts by weight or less, 23.5 parts by weight or less, 23.0 parts by weight or less, 22.5 parts by weight or less, 22.0 parts by weight or less, 21.5 parts by weight or less, 21.0 parts by weight or less, 20.5 parts by weight or less, 20.0 parts by weight or less, 19.5 parts by weight or less, 19.0 parts by weight or less, 18.5 parts by weight or less, 18.0 parts by weight or less, 17.5 parts by weight or less, 17.0 parts by weight or less, 16.5 parts by weight or less, 16.0 parts by weight or less, 15.5 parts by weight or less, 15.0 parts by weight or less, 14.5 parts by weight or less, 14.0 parts by weight or less, parts by weight or less, 13.5 parts by weight or less, 13.0 parts by weight or less, 12.5 parts by weight or less, 12.0 parts by weight or less, 11.5 parts by weight or less, 11.0 parts by weight or less, 10.5 parts by weight or less, 10.0 parts by weight or less, 9.5 parts by weight or less, 9.0 parts by weight or less, 8.5 parts by weight or less, 8.0 parts by weight or less, 7.5 parts by weight or less, 7.0 parts by weight or less, 6.5 parts by weight or less, 6.0 parts by weight or less, 5.5 parts by weight or less, 5.0 parts by weight or less, 4.5 parts by weight or less, 4.0 parts by weight or less, 3.5 parts by weight or less, 3.0 parts by weight or less, 2.5 parts by weight or less, 2.0 parts by weight or less, 1.5 parts by weight or less, or 1.0 parts by weight or less. When the content range is satisfied, stable adhesive performance and fatigue resistance can be ensured.

[0048] In one example, the adhesive composition may contain 0.1 to 20 parts by weight of the basic substance based on 100 parts by weight of the latex. For example, the lower limit of the content of the basic substance may be, for example, 0.5 parts by weight or more, 1.0 parts by weight or more, 1.5 parts by weight or more, 2.0 parts by weight or more, 2.5 parts by weight or more, 3.0 parts by weight or more, 3.5 parts by weight or more, 4.0 parts by weight or more, 4.5 parts by weight or more, 5.0 parts by weight or more, 5.5 parts by weight or more, 6.0 parts by weight or more, 6.5 parts by weight or more, 7.0 parts by weight or more, 7.5 parts by weight or more, 8.0 parts by weight or more, 8.5 parts by weight or more, 9.0 parts by weight or more, 9.5 parts by weight or more, 10. or more than 17.0 parts by weight, 17.5 parts by weight, 18.0 parts by weight, 18.5 parts by weight, 19.0 parts by weight, 20.5 parts by weight, 21.0 parts by weight, 22.0 parts by weight, 23.0 parts by weight, 24.0 parts by weight, 25.0 parts by weight, 26.0 parts by weight, 27.0 parts by weight, 28.0 parts by weight, 29.0 parts by weight, 30.0 parts by weight, 31.0 parts by weight, 32.0 parts by weight, 33.0 parts by weight, 34.0 parts by weight, 35.0 parts by weight, 36.0 parts by weight, 37.0 parts by weight, 38.0 parts by weight, 39.0 parts by weight, 40.0 parts by weight, 41.0 parts by weight, 42.0 parts by weight, 43.0 parts by weight, 44.0 parts by weight, 45.0 parts by weight, 46.0 parts by weight, 47.0 parts by weight, 48.0 parts by weight, 49.0 parts by weight, 50.0 parts by weight, 51.0 parts by weight, 52.0 parts by weight, 53.0 parts by weight, 54.0 parts by weight, 55.0 parts by weight, 56.0 parts by weight, 57.0 parts by weight, 58.0 parts by weight, 59.0 parts by weight, 54.0 parts by weight, 55.0 parts by weight, 55.0 parts by weight, 56.0 parts by weight, 57.0 parts by weight, 58.0 parts by weight, 59.0 parts by weight, 59.0 parts by weight, 54.0 parts by weight, 55.0 parts by weight, 55.0 parts by weight, 55.

[0049] The upper limit of the content of the nitrogen compound is, for example, 19.5 parts by weight or less, 19.0 parts by weight or less, 18.5 parts by weight or less, 18.0 parts by weight or less, 17.5 parts by weight or less, 17.0 parts by weight or less, 16.5 parts by weight or less, 16.0 parts by weight or less, 15.5 parts by weight or less, 15.0 parts by weight or less, 14.5 parts by weight or less, 14.0 parts by weight or less, 13.5 parts by weight or less, 13.0 parts by weight or less, 12.5 parts by weight or less, 12.0 parts by weight or less, 1 It may be 1.5 parts by weight or less, 11.0 parts by weight or less, 10.5 parts by weight or less, 10.0 parts by weight or less, 9.5 parts by weight or less, 9.0 parts by weight or less, 8.5 parts by weight or less, 8.0 parts by weight or less, 7.5 parts by weight or less, 7.0 parts by weight or less, 6.5 parts by weight or less, 6.0 parts by weight or less, 5.5 parts by weight or less, 5.0 parts by weight or less, 4.5 parts by weight or less, 4.0 parts by weight or less, 3.5 parts by weight or less, 3.0 parts by weight or less, 2.5 parts by weight or less, 2.0 parts by weight or less, or 1.5 parts by weight or less. When the content range is satisfied, stable adhesive performance and fatigue resistance can be ensured.

[0050] In one example, the coating layer may include, as a basic substance, 0.1 to 9.0 parts by weight of a first basic substance, sodium hydroxide (NaOH), and 0.1 to 14.0 parts by weight of a second basic substance different from the first basic substance, where the contents of the first basic substance and the second basic substance are based on 100 parts by weight of the latex component.

[0051] For example, the content of the first basic substance, sodium hydroxide (NaOH), (based on 100 parts by weight of the latex component) may be, for example, 0.5 parts by weight or more, 1.0 parts by weight or more, 1.5 parts by weight or more, 2.0 parts by weight or more, 2.5 parts by weight or more, 3.0 parts by weight or more, 3.5 parts by weight or more, 4.0 parts by weight or more, 4.5 parts by weight or more, 5.0 parts by weight or more, 5.5 parts by weight or more, 6.0 parts by weight or more, 6.5 parts by weight or more, 7.0 parts by weight or more, 7.5 parts by weight or more or 8.0 parts by weight or more, and the upper limit may be, for example, 8.5 parts by weight or less, 8.0 parts by weight or less, 7.5 parts by weight or less, 7.0 parts by weight or less, 6.5 parts by weight or less, 6.0 parts by weight or less, 5.5 parts by weight or less, 5.0 parts by weight or less, 4.5 parts by weight or less, 4.0 parts by weight or less, 3.5 parts by weight or less, 3.0 parts by weight or less, 2.5 parts by weight or less, 2.0 parts by weight or less, 1.5 parts by weight or less, 1.0 parts by weight or less, or 0.5 parts by weight or less.

[0052] In other examples, the content of the second basic substance (based on 100 parts by weight of the latex component) is, for example, 0.5 parts by weight or more, 1.0 parts by weight or more, 1.5 parts by weight or more, 2.0 parts by weight or more, 2.5 parts by weight or more, 3.0 parts by weight or more, 3.5 parts by weight or more, 4.0 parts by weight or more, 4.5 parts by weight or more, 5.0 parts by weight or more, 5.5 parts by weight or more, 6.0 parts by weight or more, 6.5 parts by weight or more, 7.0 parts by weight or more, 7.5 parts by weight or more, 8.0 parts by weight or more, 8.5 parts by weight or more, 9.0 parts by weight or more, 9.5 parts by weight or more, 10.0 parts by weight or more, 10.5 parts by weight or more, 11.0 parts by weight or more, 11.5 parts by weight or more, 12.0 parts by weight or more, 12.5 parts by weight or more, 13.0 parts by weight or more, 13.5 parts by weight or more, or 14.0 parts by weight or more. parts by weight or more, and the upper limit may be, for example, 14.5 parts by weight or less, 14.0 parts by weight or less, 13.5 parts by weight or less, 13.0 parts by weight or less, 12.5 parts by weight or less, 12.0 parts by weight or less, 11.5 parts by weight or less, 11.0 parts by weight or less, 10.5 parts by weight or less, 10.0 parts by weight or less, 9.5 parts by weight or less, 9.0 parts by weight or less, 8.5 parts by weight or less, 8.0 parts by weight or less, 7.5 parts by weight or less, 7.0 parts by weight or less, 6.5 parts by weight or less, 6.0 parts by weight or less, 5.5 parts by weight or less, 5.0 parts by weight or less, 4.5 parts by weight or less, 4.0 parts by weight or less, 3.5 parts by weight or less, 3.0 parts by weight or less, 2.5 parts by weight or less, 2.0 parts by weight or less, 1.5 parts by weight or less, 1.0 parts by weight or less, or 0.5 parts by weight or less.

[0053] In one example, the adhesive composition may further include a solvent. The solvent component contained in the adhesive may refer to a component excluding the other components described above whose content can be measured in solid content. For example, the solvent component may be referred to as a non-solid component.

[0054] The solvent may include, for example, one or more selected from the group consisting of known organic solvents and water. The known organic solvent is not particularly limited, and examples thereof include toluene and ethanol.

[0055] In one example, in the adhesive composition, the solvent component may include or be water.

[0056] In addition, in the specific example of the present application, in consideration of the harmfulness to the human body and flammability, the adhesive composition may contain water as a solvent component without using an organic solvent (e.g., toluene, ethanol, etc.) Alternatively, the solvent of the adhesive composition may be a small amount of organic solvent and an excess of water.

[0057] In one example, the content of the solvent in the adhesive composition may be 30% by weight or more, 35% by weight or more, 40% by weight or more, 45% by weight or more, 50% by weight or more, 55% by weight or more, 60% by weight or more, 65% by weight or more, 70% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, or 90% by weight or more, based on the total weight of the adhesive composition. The upper limit of the content of the solvent may be, for example, 95% by weight or less, 90% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less, or 65% by weight or less. The content of the above-mentioned solvent may be appropriately adjusted in consideration of the dispersibility and degree of miscibility of each component forming the composition, the coating workability of the adhesive, the processability, and the cost.

[0058] In one example, the solvent included in the above content range may be or may include water.

[0059] In another example, the excess or majority of the solvent content may be water. For example, the excess of the solvent component content in the composition (e.g., about 30 wt% or more, 35 wt% or more, 40 wt% or more, 45 wt% or more, 50 wt% or more, or 55 wt% or more based on the total weight of the adhesive composition) may be water, and the remaining content excluding water in the solvent (e.g., 15 wt% or less, 10 wt% or less, or 5 wt% or less based on the total weight of the adhesive composition) may be an organic solvent or the like.

[0060] In one example, the adhesive composition may be a water-based or aqueous composition. Specifically, the solvent may include an excess of water and a small amount of an organic solvent. Alternatively, the solvent may be water.

[0061] Although there is no particular limitation, the water used as a solvent in the adhesive composition may be demineralized water (or pure water).

[0062] In one example, the water content may be 30% by weight or more, 35% by weight or more, 40% by weight or more, 45% by weight or more, 50% by weight or more, 55% by weight or more, 60% by weight or more, 65% by weight or more, 70% by weight or more, 75% by weight or more, 80% by weight or more, 85% by weight or more, or 90% by weight or more, based on the total weight of the composition. And the upper limit of the water content may be, for example, 95% by weight or less, 90% by weight or less, 85% by weight or less, 80% by weight or less, 75% by weight or less, 70% by weight or less, 65% by weight or less, 60% by weight or less, 55% by weight or less, or 50% by weight or less.

[0063] The water content can be appropriately adjusted in consideration of the degree of dispersibility and miscibility of each component forming the composition, the workability, processability, and cost of coating the adhesive, etc.

[0064] In one example, the content of the solvent in the total composition may refer to the content of water mixed as a solvent.

[0065] In another example, the content of the solvent in the overall composition may mean not only the content of water mixed as a solvent, but also the content of a solvent (e.g., organic solvent and / or water) for dispersing each component, for example, when latex dispersed in a solvent is mixed with other components to form a composition.

[0066] In one example, the adhesive composition may further contain a small amount of a known adhesive component known in the technical field related to tires and tire cords. Here, a small amount may mean that the latex component, acid component, basic substance, and nitrogen compound are contained in the composition in a content less than the component that is most commonly used. Alternatively, the small amount may mean that the latex component, acid component, basic substance, and nitrogen compound are contained in the composition in a content less than the component that is least commonly used.

[0067] Examples of known adhesive components that can be used include isocyanates, epoxies, urethanes, various additives, etc. The specific types of compounds such as isocyanates, epoxies, and urethanes can be selected at a level that does not interfere with the achievement of the technical object of the present application, and their content can be used in small amounts at a level that does not interfere with the achievement of the technical object of the present application.

[0068] In one example, the adhesive composition may be formed by mixing a solvent with other components other than the solvent. Specifically, in a specific example of the present application, the adhesive composition may be a mixture of a naturally occurring acid, a nitrogen compound, a basic substance, a latex, and a solvent. Alternatively, the adhesive composition may be a mixture of a naturally occurring acid, a nitrogen compound, a basic substance, a latex, a solvent, and a known adhesive component. For example, the composition may contain a solvent (non-solid component) in an amount of 25 wt% or more, 30 wt% or more, 35 wt% or more, 40 wt% or more, 45 wt% or more, 50 wt% or more, 55 wt% or more, 60 wt% or more, 65 wt% or more, 70 wt% or more, or 75 wt% or more, and 95 wt% or less, 90 wt% or less, 85 wt% or less, or 80 wt% or less, and may contain only the remaining residual solid content. The content of other components in the composition other than the solvent, i.e., the solid components, is, for example, 75% by weight or less, 70% by weight or less, 65% by weight or less, 60% by weight or less, 55% by weight or less, 50% by weight or less, 45% by weight or less, 40% by weight or less, 35% by weight or less, 30% by weight or less, or 25% by weight or less, and may be 5% by weight or more, 10% by weight or more, 15% by weight or more, or 20% by weight or more. Alternatively, the solid components in the above content and the remaining amount of the solvent (non-solid components) can form the composition.

[0069] In a specific example related to the present application, the adhesive composition does not contain resorcinol-formaldehyde (RF) or a component derived therefrom. In other words, the composition of the present application may be a so-called RF-free composition. As a result, an adhesive composition that is less harmful to the human body and more environmentally friendly than conventional techniques that use RF components can be provided. In addition, the use of such an adhesive composition provides the advantage of reducing post-treatment and post-processing costs.

[0070] Second aspect: adhesive composition In another embodiment of the present application, the present application relates to an adhesive composition comprising the above-mentioned components, specifically, the components contained in the above-mentioned composition are mixed together.

[0071] Specifically, the adhesive composition includes the latex and a condensate of a naturally occurring acid and a nitrogen compound, and has a pH in the range of 9.0 to 11.0. As described above, the naturally occurring acid and the nitrogen compound are condensed in the presence of a basic substance that forms the above-mentioned pH condition, so that the adhesive composition can have such a configuration.

[0072] For example, the pH of the adhesive composition may be 9.1 or more, 9.2 or more, 9.3 or more, 9.4 or more, 9.5 or more, 9.6 or more, 9.7 or more, 9.8 or more, 9.9 or more, 10.0 or more, 10.1 or more, 10.2 or more, 10.3 or more, 10.4 or more, 10.5 or more, 10.6 or more, 10.7 or more, 10.8 or more, or 10.9 or more. The upper limit of the pH may be, for example, 10.9 or less, 10.8 or less, 10.7 or less, 10.6 or less, 10.5 or less, 10.4 or less, 10.3 or less, 10.2 or less, 10.1 or less, 10.0 or less, 9.9 or less, 9.8 or less, 9.7 or less, 9.6 or less, 9.5 or less, 9.4 or less, 9.3 or less, 9.2 or less, or 9.1 or less.

[0073] In one example, the adhesive composition may contain 5 to 50% by weight of latex. The specific content of the latex is the same as that described above, so it is omitted here.

[0074] In one example, the adhesive composition may contain a condensate of a naturally occurring acid and a nitrogen compound. Specifically, the adhesive composition may contain, for example, a condensate of 1.0 to 5.0% by weight of a naturally occurring acid and 0.01 to 4.0% by weight of a nitrogen compound. The specific contents of the naturally occurring acid and the nitrogen compound are the same as those described above, and therefore will not be described here.

[0075] In one example, the adhesive composition may contain 0.01 to 4.0% by weight of a basic substance. The specific content of the basic substance is the same as that described above, and therefore will not be described here.

[0076] In one example, the adhesive composition may contain the condensate (condensate of a naturally occurring acid-nitrogen compound) in the range of 1.0 to 15.0 wt %. The content of the condensate may also mean the solid content as described above. Specifically, the lower limit of the content of the condensate may be, for example, 1.5% by weight or more, 2.0% by weight or more, 2.5% by weight or more, 3.0% by weight or more, 3.5% by weight or more, 4.0% by weight or more, 4.5% by weight or more, 5.0% by weight or more, 5.5% by weight or more, 6.0% by weight or more, 6.5% by weight or more, 7.0% by weight or more, 7.5% by weight or more, 8.0% by weight or more, 8.5% by weight or more, 9.0% by weight or more, 10.0% by weight or more, 10.5% by weight or more, 11.0% by weight or more, 11.5% by weight or more, 12.0% by weight or more, 12.5% ​​by weight or more, 13.0% by weight or more, 13.5% by weight or more, 14.0% by weight or more, or 14.5% by weight or more. The upper limit may be, for example, 14.5 wt % or less, 14.0 wt % or less, 13.5 wt % or less, 13.0 wt % or less, 12.5 wt % or less, 12.0 wt % or less, 11.5 wt % or less, 11.0 wt % or less, 10.5 wt % or less, 10.0 wt % or less, 9.5 wt % or less, 9.0 wt % or less, 8.5 wt % or less, 8.0 wt % or less, 7.5 wt % or less, 7.0 wt % or less, 6.5 wt % or less, 6.0 wt % or less, 5.5 wt % or less, 5.0 wt % or less, 4.5 wt % or less, 4.0 wt % or less, 3.5 wt % or less, 3.0 wt % or less, 2.5 wt % or less, 2.0 wt % or less, or 1.5 wt % or less.

[0077] In a specific example of the present application, the adhesive composition may further contain other components in addition to the latex and the condensate.

[0078] For example, the adhesive composition may further include a naturally occurring acid. The description of the component (type, content, etc.) is the same as that described above, so it will be omitted.

[0079] For example, the adhesive composition may further include a nitrogen compound. As described above, the nitrogen compound may be a substance that contains nitrogen and can form a condensation reaction product with tannic acid. As the nitrogen compound, a substance different from the basic substance described below can be selected. The explanation of the component (type, content, etc.) is the same as that described above, and therefore will be omitted.

[0080] For example, the adhesive composition may further include one or more basic substances. In this case, the basic substance may include two or more different basic substances, as described above. The explanation of the components (type, content, etc.) is the same as that described above, so it will be omitted.

[0081] For example, the adhesive may further include a solvent. The description of the components (type, content, etc.) is the same as that described above, so it will be omitted.

[0082] Third aspect: Rubber reinforcement In yet another embodiment of the present application, the present application relates to a rubber reinforcing material. The rubber reinforcing material may be, for example, a tire cord having a base substrate coated with the above-mentioned adhesive. The base substrate may be a raw cord including a fiber component.

[0083] Specifically, the rubber reinforcing material (e.g., tire cord) may include a raw cord and a coating layer formed on the raw cord. The coating layer may be a coating layer formed from the adhesive composition described above or may include the coating layer, and may be coated in a shape surrounding the surface of the raw cord.

[0084] The low cord may be or may include a fiber fabric formed by twisting filament fibers. In a specific example of the present application, the low cord may be formed by twisting one or more fibers (e.g., multifilament) (e.g., ply and / or ply). For example, the low cord may be a 2-ply or 3-ply cord.

[0085] The fibers contained in the low cord are not particularly limited, but may include, for example, one or more selected from the group consisting of polyester fibers (e.g., PET fibers), nylon fibers, aramid fibers, carbon fibers, polyketone fibers, cellulose fibers (e.g., lyocell fibers, rayon fibers), and glass fibers.

[0086] In one example, the low cord may be a hybrid cord, for example, the low cord may be a hybrid cord formed by top twisting ply yarns having different types of fibers, such as aramid ply yarns and nylon ply yarns.

[0087] In the case of a hybrid cord formed by plying different types of ply yarns, the difference in physical properties (e.g., modulus, etc.) between the ply yarns may result in poor fatigue resistance, which may lead to poor tire stability. However, the adhesive composition described above not only forms an appropriate coating layer on the hybrid low cord as an adherend, but also imparts excellent adhesive strength between the hybrid low cord as an adherend and the adjacent tire structure, and is therefore expected to alleviate to some extent the problem of reduced fatigue resistance of tires caused by the use of hybrid cords.

[0088] In one example, the number of twists of the fiber yarn used to form the low cord may be 150 or more and 900 or less in the upper twist and / or lower twist. For example, the number of twists may be 200 TPM or more, 250 TPM or more, 300 TPM or more, 350 TPM or more, 400 TPM or more, 450 TPM or more, 500 TPM or more, or 550 TPM or more. The upper limit of the number of twists may be, for example, 850 TPM or less, 800 TPM or less, 750 TPM or less, 700 TPM or less, 650 TPM or less, 600 TPM or less, 550 TPM or less, 500 TPM or less, 450 TPM or less, or 400 TPM or less.

[0089] Although not particularly limited, the total fineness of the low cord may be in the range of 400 to 9000 dtex. Specifically, when considering securing mechanical properties, the total fineness of the low cord may be 1300 dtex or more, 1350 dtex or more, 1400 dtex or more, 1450 dtex or more, 1500 dtex or more, 1550 dtex or more, 1600 dtex or more, 1650 dtex or more, 1750 dtex or more, or 1800 dtex or more, and the upper limit thereof may be, for example, 2000 dtex or less, 1950 dtex or less, 1900 dtex or less, 1850 dtex or less, 1800 dtex or less, 1750 dtex or less, 1700 dtex or less, 1650 dtex or less, or 1600 dtex or less.

[0090] In one example, the coating layer may be or may include a coating layer formed from the adhesive composition described above. Specifically, the tire cord may be formed by coating the adhesive composition on a row cord. The method of coating the adhesive composition is not particularly limited. For example, coating may be performed by a known dipping or spraying method.

[0091] According to a specific example of the present application, a rubber reinforcing material (e.g., tire cord) having a raw cord surface coated with the above-mentioned adhesive composition can provide excellent adhesive strength as described below.

[0092] In one example, the coating layer of the tire cord may include a first coating layer and a second coating layer formed on the first coating layer. Specifically, the tire cord may include a row cord, a first coating layer, and a second coating layer in this order (see FIG. 2).

[0093] Although not particularly limited, the first coating layer and the second coating layer may have a visible boundary.

[0094] In one example, the first coating layer can include the same components as the second coating layer.

[0095] In another example, the first coating layer can include a different component than the second coating layer.

[0096] Specifically, when the first coating layer and the second coating layer contain different components, the first coating layer may be formed by dipping the raw cord into a first coating layer forming composition (first coating liquid) containing a reactive group imparting component. That is, the first coating layer is formed so as to surround the raw cord or its surface. The type of reactive group imparting component used in the first coating layer is not particularly limited, but for example, the first coating liquid may contain one or more compounds selected from epoxy and isocyanate. The solvent component contained in the first coating layer forming composition (first coating liquid) is not particularly limited, but when considering miscibility with the second coating layer, the same solvent (e.g. water) as that contained in the second coating layer forming composition may be contained in the first coating layer forming composition. The second coating layer is formed by dipping a tire cord (or a tire cord precursor) on the surface of which the first coating layer is formed, into a second coating layer forming composition (second coating liquid), and the second coating layer forming composition (second coating liquid) may be the same as the adhesive composition of the present application described above.

[0097] In one example, the first coating liquid can include an isocyanate compound and an epoxy compound, in which the epoxy compound and the isocyanate compound can be used in a weight ratio of 4:1 to 1:4, 3:1 to 1:3, or 2:1 to 1:2 to ensure sufficient crosslinking and an appropriate level of curing.

[0098] In another example, the weight of the isocyanate compound in the entire composition may be greater than the weight of the epoxy compound, provided that the above content range is satisfied.

[0099] 4th aspect: Rubber reinforcement In yet another embodiment of the present application, the present application relates to a rubber reinforcing material. The rubber reinforcing material may be, for example, a tire cord having a base substrate coated with the above-mentioned adhesive. The base substrate may be a raw cord containing a fiber component. The description of the base substrate is the same as that described above, and therefore will be omitted.

[0100] In one example, the coating layer may contain 100 parts by weight of latex, 3.0 to 25.0 parts by weight of natural acid, 0.3 to 25.0 parts by weight of nitrogen compound, and 0.1 to 15.0 parts by weight of basic substance. The specific types and contents of each component are the same as those described above, so they will not be described here.

[0101] In one example, the coating layer may contain, as basic substances, 0.1 to 9.0 parts by weight of a first basic substance, sodium hydroxide (NaOH), and 0.1 to 14.0 parts by weight of a second basic substance different from the first basic substance. Here, the contents of the first basic substance and the second basic substance are based on 100 parts by weight of the latex component. The specific types and contents of each component are the same as those described above, so they will not be described here.

[0102] In one example, the coating layer may further include a condensate of the naturally occurring acid and the nitrogen compound. The specific types and contents of each component are the same as those described above, so they will not be described here.

[0103] In one example, the coating layer may contain 2.0 to 300 parts by weight of the condensate (condensate of naturally occurring acid and nitrogen compound) based on 100 parts by weight of latex. Specifically, the coating layer may contain 5 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight or more, 30 parts by weight or more, 35 parts by weight or more, 40 parts by weight or more, 45 parts by weight or more, or 50 parts by weight or more of the condensate (based on 100 parts by weight of latex), and may contain 250 parts by weight or less, 200 parts by weight or less, 150 parts by weight or less, 100 parts by weight or less, or 50 parts by weight or less of the condensate.

[0104] In one example, the basic substance may include a first basic substance, sodium hydroxide (NaOH), and a second basic substance different from the first basic substance. The specific type of the second basic substance and the content of each basic substance are as described above.

[0105] Fifth aspect: Method for manufacturing rubber reinforcement material In yet another embodiment of the present application, the present application relates to a method for manufacturing a rubber reinforcing material, the method for manufacturing the rubber reinforcing material includes applying a coating liquid onto a base substrate for the rubber reinforcing material to form a coating layer.

[0106] The method of applying the coating liquid onto the base substrate is not particularly limited, and may be, for example, spraying or dipping, and preferably, dipping.

[0107] In one example, the rubber reinforcing material may be a tire cord.

[0108] In one example, the base material may be a fiber material, specifically, a raw cord. The materials forming the raw cord are as described above.

[0109] In one example, the coating liquid may be the adhesive composition described above.

[0110] In one example, the method can include applying a first coating liquid onto a base substrate for a rubber reinforcing material to form a first coating layer on the base substrate; and applying a second coating liquid onto the first coating layer to form a second coating layer on the first coating layer.

[0111] The method of applying the first coating liquid onto the base substrate or applying the second coating liquid onto the first coating layer is not particularly limited, and may be, for example, spraying or immersion, and preferably immersion.

[0112] After application of the coating liquid for forming the first and / or second coating layer, the coating liquid may be dried and / or cured, if necessary.

[0113] In one example, the components of the first and second coating liquids may be the same or different.

[0114] For example, the first coating liquid may contain an epoxy compound and an isocyanate compound to provide reactive groups to a fiber substrate, etc. Here, the epoxy compound and the isocyanate compound may be used in a weight ratio of 4:1 to 1:4, 3:1 to 1:3, or 2:1 to 1:2 to achieve sufficient crosslinking and an appropriate level of curing.

[0115] In one example, the first coating liquid may include a solvent, that is, the first coating liquid may include an epoxy compound, an isocyanate compound, and a solvent.

[0116] If the solvent is insufficient, the primary coating by immersion is not performed smoothly, and if the solvent content is excessively high, reactive groups are not sufficiently imparted to the base material for rubber reinforcement. Considering this point, the solvent has a content of 94 to 99 wt% and the mixture of the epoxy compound and the isocyanate compound has a content of 1 to 6 wt% based on the total weight of the first coating liquid. In other words, the first coating liquid contains 1 to 6 wt% of the mixture of the epoxy compound and the isocyanate compound and 94 to 99 wt% of the solvent based on the total weight. Although not particularly limited, the solvent contained in or usable in the first coating liquid may contain the same components as the solvent of the second coating liquid.

[0117] In one example, the base substrate for rubber reinforcement can be immersed in the first coating liquid and then dried. Specifically, the first coating liquid is applied onto the base substrate for rubber reinforcement by immersion. Thereafter, the first coating liquid is dried and cured to form a first coating layer.

[0118] In a specific example of the present application, the first coating liquid applied onto the base substrate may be dried at a temperature of 100 to 160°C for 30 to 150 seconds. In addition, in a specific example of the present application, after the drying, a step of curing the first coating liquid dried at a temperature of 200 to 260°C for 30 to 150 seconds may be performed. By the drying and curing, a first coating layer is formed on the base substrate for rubber reinforcement. By drying and curing under the above conditions, the first coating layer can be stably formed on the base substrate for rubber reinforcement.

[0119] Although not particularly limited, tension in the range of 0.05 to 3.00 g / d may be applied to the drawstring during the immersion, drying, and / or curing process. However, other embodiments of the present invention are not limited thereto, and tension may not be applied to the drawstring.

[0120] In one example, the second coating liquid, which is different from the first coating liquid containing the epoxy compound and the isocyanate compound, may be the adhesive composition of the present application described above. In a specific example of the present application, the second coating liquid may contain at least a naturally occurring acid, a nitrogen compound, a basic substance, and a latex.

[0121] In an embodiment according to the present application, the method may further include forming a second coating layer on the base substrate for rubber reinforcing material to which reactive groups are added, i.e., on the first coating layer. The process (e.g., method and conditions) of forming the second coating layer may be the same as or similar to that of forming the first coating layer.

[0122] For example, the second coating layer may be formed by applying the second coating liquid onto the base substrate and the first coating layer. Alternatively, the second coating liquid may be applied onto the base substrate and the first coating layer, and then the second coating liquid may be dried and cured. The application of the second coating liquid may be performed by immersion, spraying, or the like.

[0123] In a specific example of the present application, the second coating liquid may be dried at a temperature of 100 to 160°C for 30 to 150 seconds. In addition, in a specific example of the present application, after the drying, the second coating liquid may be cured at a temperature of 200 to 260°C for 30 to 150 seconds. By drying and curing under the above conditions, the second coating layer can be stably formed on the first coating layer. As a result, a rubber reinforcing material having a coating layer is provided.

[0124] Although not particularly limited, tension in the range of 0.05 to 3.00 g / d may be applied to the drawstring during the immersion, drying, and / or curing process. However, other embodiments of the present invention are not limited thereto, and tension may not be applied to the drawstring.

[0125] A method for producing a rubber reinforcing material according to an embodiment of the present application will be described below with reference to FIGS.

[0126] The raw cord 10 may be manufactured and / or distributed in a state where it is wound on a first winder 100. The raw cord 10 may then be immersed in a first coating liquid 21' contained in a first coating tank 200, and the first coating liquid 21' may be applied onto the raw cord 10. During the immersion process, tension, immersion time, and temperature may be appropriately adjusted, which may be appropriately adjusted by those skilled in the art.

[0127] Next, the first coating liquid 21' applied to the raw cord 10 may be dried and cured. The drying may be performed by the drying device 300. The conditions for drying and curing, such as temperature and time, are as described above.

[0128] Next, a step of forming a second coating layer 22 on the first coating layer 21 is performed. The step of forming the second coating layer is a step of applying a rubber-based adhesive composition to the raw cord 10 to which active groups have been imparted by the first coating layer 21. To form the second coating layer, a second coating liquid having a different composition from the first coating liquid can be used, and a dipping process can be applied in the same manner as in the formation of the first coating layer.

[0129] To form the second coating layer 22, the raw cord 10 coated with the first coating layer 21 is immersed in a second coating liquid 22'. The second coating liquid 22' is placed in a second coating bath 400. The immersion causes the second coating liquid 22' to be applied onto the first coating layer 21. During the immersion process, tension, immersion time, and temperature can be appropriately adjusted, which can be appropriately adjusted by those skilled in the art.

[0130] Next, the second coating liquid 22' is dried and cured in the drying device 500. The conditions for drying and curing, such as temperature and time, are as described above.

[0131] Through this fixing, the second coating layer 22 is formed on the first coating layer 21. The tire cord 30 thus produced is wound on the second winder 600.

[0132] As described above, the tire cord 30 having a coating layer formed by dipping can be referred to as a dipped cord.

[0133] Sixth aspect: Article In yet another embodiment of the present application, the present application relates to an article (or rubber composite) comprising the rubber reinforcement. The rubber composite may be, for example, a tire. The tire comprises the tire cord described above.

[0134] The tire may have a tire cord and other commonly known configurations (eg, the tire may have a tread, body plies, belts, sidewalls, beads, inner liner, cap plies, or apex, etc.) (see FIG. 4). Effect of the Invention

[0135] According to one embodiment of the present application, an adhesive can be provided that is less harmful to the human body and environmentally friendly, as well as facilitating the cord manufacturing process and reducing costs. In addition, the present application has an effect of providing an adhesive that can provide physical properties (e.g., adhesive strength) that are equal to or higher than those of the prior art. In addition, according to another embodiment of the present application, a rubber reinforcing material (e.g., tire cord) and an article (e.g., tire) manufactured using the adhesive can be provided. [Brief description of the drawings]

[0136] [Figure 1]This is a graph showing the results of wavelength analysis of naturally occurring tannic acid (TA1), synthetic tannic acid (synthetic tannic acid produced by Sigma-Aldrich) (TA2), and RF condensate (dihydric phenol, HiRENOL KOSABOND-R50 by Kolon Industry) (RF) by infrared spectroscopy. The peak observed in the vicinity of wave numbers of about 1600 to 1620 cm-1, which is commonly confirmed, is a peak corresponding to an aromatic ring. RF condensate and tannic acid both have a benzene ring, but RF is known to be a harmful substance. In contrast, tannic acid is not a harmful substance, except for direct inhalation of dust. On the other hand, it is confirmed that naturally occurring tannic acid and synthetic tannic acid can be distinguished by the presence or absence of a peak in the vicinity of wave numbers of about 1700 cm-1. The peak at around 1700 cm-1 is a peak that appears in the C=O bond, but this peak is thought to be due to the C=O bond generated in the process of artificially synthesizing tannic acid. In other words, synthetic tannic acid can be distinguished from naturally occurring tannic acid in that naturally occurring tannic acid has fewer units containing C=O. [Diagram 2] 1 is a schematic representation of a cross section of a tire cord that can be produced using an adhesive composition according to one example of the present application. [Diagram 3] 1 is a schematic diagram showing a tire cord manufacturing process. [Figure 4] 1 is a schematic representation of a cross-section of a tire that can be manufactured using an adhesive composition according to one example of the present application. [Diagram 5] 5A and 5B are diagrams for explaining the directions of the forces applied to the test pieces in Experiment 1 and Experiment 2 for evaluating the adhesive strength of the adhesive composition of the present application. Fig. 5A shows the directions of the forces applied in the H-test in Experiment 1, and Fig. 5B shows the directions of the forces applied in the Peel-test in Experiment 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0137] The functions and effects of the present invention will be described in more detail below through specific examples of the present invention, which are presented as examples of the present invention and are not intended to limit the scope of the invention in any way.

[0138] Preparation of compositions of examples and comparative examples The compositions of the examples and comparative examples were prepared by mixing and stirring under the same conditions, except for the content ratios (wt%) shown in Table 1 below. Specifically, each component was mixed and stirred at room temperature (about 20°C) for 24 hours. As a result, condensation polymerization of tannic acid and hexamine occurred in the presence of a basic substance.

[0139] Table 1 relates to examples, and Table 2 relates to comparative examples. For reference, each component (solvent, NaOH, tannic acid, ammonia, hexamine, and latex) shown in the table below was prepared in a state of being dispersed in water and then mixed, and the pH of the composition after mixing was in the range of 9.0 to 11.0.

[0140] Adhesive compositions of the examples JPEG2025514318000003.jpg221170

[0141] Comparative adhesive compositions JPEG2025514318000004.jpg164170

[0142] Manufacturing Example Two ply yarns (Z-direction) with a twist of 360 TPM were prepared using polyester raw yarn, and then the two ply yarns were plyed together (S-direction) with a twist of 360 TPM to produce a ply yarn (1650 dtex / 2 ply). The ply yarn thus produced was used as a raw cord.

[0143] A polyester raw cord was immersed in the first coating liquid, and then treated at a drying temperature of 150°C and a curing temperature of 240°C for about 1 minute each to form a first coating layer, thereby providing reactive groups to the raw cord. Here, the first coating liquid was prepared by mixing an epoxy compound and an isocyanate compound in a weight ratio of about 1:2 together with 97% by weight of demineralized water.

[0144] Next, the raw cord on which the first coating layer was formed was immersed in a second coating liquid (the adhesive composition prepared in each of the Examples and Comparative Examples) and dried and cured to form a second coating layer. In this case, the raw cord was dried and cured at a drying temperature of 150°C and a curing temperature of 235°C for about 1 minute each. The immersion process in the first coating liquid and the immersion process in the second coating liquid were performed continuously, and the tension condition was 1.0 g / d. Through this process, a tire cord was manufactured in the form of a dipped cord.

[0145] The prepared code was used in Experiments 1 and 2 below.

[0146] Experiment 1: H-test (Pull-OUT test) The tire cord thus produced was subjected to a pull-out adhesion test according to ASTM D4776, and the results are shown in Table 3.

[0147] Specifically, a 6 mm thick rubber sheet, a cord (manufactured in the manufacturing example) and a 6 mm thick rubber sheet were laminated in this order, and subjected to a load of 50 kg / cm 2The tire was vulcanized at 170°C for 15 minutes under a pressure of 1000g to prepare a test specimen. A peel test was performed on the prepared test specimen at 25°C and a speed of 125mm / min using a universal material testing machine (Instron) to measure the adhesive strength of the tire cord to the carcass layer, and the relative value of the measured adhesive strength was recorded. Here, the adhesive strength is the average value of three loads generated during peeling, and is normalized based on the value of the adhesive layer formed by the adhesive composition of Example 1 for relative comparison.

[0148] The difference between this type of H-Test is that after lamination and vulcanization of the rubber sheets, the peel test is conducted in a vertical direction, whereas in the case of the peel test (PEEL Test) described later, after lamination and vulcanization of the rubber sheets, the peel test is conducted in a horizontal direction. Through such an experiment, it is possible to compare and confirm the adhesive strength and durability of the cord according to the direction of the force applied to the tire cord.

[0149] Experiment 2: PEEL Test The tire cord produced as above was subjected to adhesion evaluation according to ASTM D4393 in order to evaluate adhesion per unit area, and the results are shown in Table 3.

[0150] Specifically, a 0.6 mm thick rubber sheet, cord fabric (a cord fabric containing the cord produced in the manufacturing example is used, and after removing the weft according to ASTM D4393, evaluation is carried out with a warp thread count of 25.4 EPI (end per inch)), a 0.6 mm thick rubber sheet, cord fabric (a cord fabric containing the cord produced in the manufacturing example is used, and after removing the weft according to ASTM D4393, evaluation is carried out with a warp thread count of 25.4 EPI (end per inch)), and a 0.6 mm thick rubber sheet are laminated in this order, and a test piece is subjected to a load of 60 kg / cm 2 The sample was prepared by vulcanizing the mixture at 170° C. for 15 minutes under a pressure of 1000 MPa, and then cut into test pieces having a width of 1 inch.

[0151] The prepared test specimens were subjected to a peel test at 25°C and a speed of 125mm / min using a universal testing machine (Instron) to measure the adhesive strength of the tire cord to the carcass layer, and the relative value of the measured adhesive strength was recorded. In this case, the average value of the load generated during peeling three times was calculated as the adhesive strength, and the measured value was normalized based on the value of the adhesive layer formed by the adhesive composition of Example 1 for relative comparison.

[0152] Experiment 3: Dynamic Adhesion Test (Bending Fatigue Test) In connection with the fatigue evaluation of the adhesive composition, the fatigue evaluation of the tire cord produced was carried out according to ASTM D430, and the results are recorded in Table 3.

[0153] Specifically, a 3.2 mm thick rubber sheet, a cord fabric (manufactured in the manufacturing example), a 0.5 mm thick rubber sheet, a cord fabric (manufactured in the manufacturing example), and a 3.2 mm thick rubber sheet were laminated in this order, and the resulting laminate was subjected to a load of 60 kg / cm 2 The sample was prepared by vulcanizing the mixture at 170° C. for 15 minutes under a pressure of 1000 MPa, and then cut into test pieces having a width of 1 inch.

[0154] The adhesive strength of the tire cord after fatigue was measured while a fatigue test was performed on the prepared test piece using a bending fatigue tester at 100°C and a speed of 180 rpm. The adhesive strength after fatigue was calculated using the following formula:

[0155] <Calculation formula> Adhesion after fatigue (%) = (Adhesive strength of fatigued part / Adhesive strength of non-fatigued part) x 100

[0156] Here, fatigued and non-fatigued areas may be distinguished by markings that allow each area to be distinguished prior to proceeding with such fatigue evaluation, or, alternatively, fatigued and non-fatigued areas may be distinguished by the naked eye without such markings.

[0157] The adhesive strength after fatigue was an average value of three measurements, and was normalized based on the value measured for the adhesive composition of Example 1 for relative comparison.

[0158] Experiment 4: Tire imitation evaluation A 1.6mm thick rubber sheet, a cord fabric (manufactured in the manufacturing example), and a 0.5mm thick rubber sheet are layered in this order, and a 60kg / cm 2 The adhesive composition was vulcanized at 160°C for 20 minutes under a pressure of 1.0 mm. The sample was then cut to prepare a test piece having a width of 1 inch by 10 cm. The test piece was pulled at a speed of 125 mm / min at 25°C using a universal material testing machine (Instron) to measure the tensile strength when the test piece was cut. Here, the tensile strength is the average value of the load generated at the time of cutting three times, and is normalized to the value measured for the adhesive composition of Example 1 for relative comparison.

[0159] In the above-mentioned Experiment 1-3, peeling evaluation (adhesion evaluation) after vulcanization was carried out, but in the case of Experiment 4, peeling evaluation was not carried out, but the tensile strength of the rubber test piece itself containing the tire cord was tested. In other words, unlike the adhesion evaluation in Experiment 1-3, Experiment 4 can be considered as a replica experiment that can estimate the durability performance of the tire containing the cord.

[0160] Evaluation results JPEG2025514318000005.jpg208170 [Explanation of symbols]

[0161] 10: Low cord, 11: Under twisted yarn 12: Ply yarn, 20: Coating layer 21: first coating layer, 21': first coating liquid 22: second coating layer, 22': second coating liquid 30: Tire cord, 100: First winder 200: first coating tank, 300: first drying device 400: second coating tank, 500: second drying device 600: 2nd winder, 1000: tread 2000: Shoulder, 3000: Sidewall 4000: Cap ply, 5000: Belt 6000: Body ply or carcass, 7000: Inner liner 8000: Apex, 9000: Bead

Claims

1. (a) 1.0 to 5.0 wt. % of naturally occurring acids; (b) 0.01 to 4.0% by weight of a nitrogen compound; (c) 0.01 to 4.0% by weight of a basic substance; and (d) Latex: 5.0 to 50% by weight An adhesive composition comprising: The adhesive composition contains, as basic substances, 0.01 to 1.5 wt % of sodium hydroxide (NaOH) as a first basic substance, and 0.01 to 2.5 wt % of a second basic substance different from the first basic substance (wherein the weight % of the contents of the components (a) to (d) refers to the solid content of each component in the composition, and the nitrogen compound and the basic substance are different from each other).

2. The adhesive composition of claim 1 , wherein the naturally occurring acid comprises a naturally occurring phenol.

3. The adhesive composition of claim 1 , wherein the naturally occurring acid comprises naturally occurring tannic acid.

4. 2. The adhesive composition according to claim 1, comprising 3.0 to 50.0 parts by weight of the naturally occurring acid based on 100 parts by weight of the latex.

5. 2. The adhesive composition according to claim 1, comprising 0.3 to 25.0 parts by weight of the nitrogen compound based on 100 parts by weight of the latex.

6. 2. The adhesive composition according to claim 1, comprising 0.1 to 20.0 parts by weight of the basic substance based on 100 parts by weight of the latex.

7. The adhesive composition of claim 1 further comprising a solvent.

8. The adhesive composition according to claim 7 , wherein the solvent is contained in an amount of 30% by weight or more based on 100% by weight of the total content of the composition.

9. The adhesive composition according to claim 7 or 8, wherein the solvent comprises water.

10. 2. The adhesive composition according to claim 1, wherein the nitrogen compound comprises one or more selected from the group consisting of piperazine, piperidine, pyridine, pyrimidine, pyrrolidine, pyrrole, imidazole, indole, aniline, histidine, tryptophan, and hexamine.

11. The second basic substance is sodium carbonate (Na 2 CO 3 ), potassium hydroxide (KOH), magnesium hydroxide (Mg(OH) 2 ) and ammonia (NH 3 2. The adhesive composition according to claim 1, comprising at least one selected from the group consisting of:

12. The adhesive composition of claim 1 further comprising a condensate of said naturally occurring acid and said nitrogen compound.

13. 5.0-50% by weight of latex; Condensates of 1.0 to 5.0% by weight of naturally occurring acids and 0.01 to 4.0% by weight of nitrogen compounds; and An adhesive composition comprising 0.01 to 4.0% by weight of a basic substance, The adhesive composition contains, as basic substances, 0.01 to 1.5 wt % of sodium hydroxide (NaOH) as a first basic substance, and 0.01 to 2.5 wt % of a second basic substance different from the first basic substance; An adhesive composition having a pH in the range of 9.0 to 11.0, wherein the nitrogen compound and the basic substance are different from each other.

14. The adhesive composition of claim 13 , wherein the naturally occurring acid comprises a naturally occurring phenol.

15. 14. The adhesive composition of claim 13, wherein the naturally occurring acid comprises naturally occurring tannic acid.

16. 14. The adhesive composition according to claim 13, wherein the nitrogen compound comprises one or more selected from the group consisting of piperazine, piperidine, pyridine, pyrimidine, pyrrolidine, pyrrole, imidazole, indole, aniline, histidine, tryptophan, and hexamine.

17. The second basic substance is sodium carbonate (Na 2 CO 3 ), potassium hydroxide (KOH), magnesium hydroxide (Mg(OH) 2 ) and ammonia (NH 3 The adhesive composition according to claim 13, comprising at least one selected from the group consisting of:

18. A rubber reinforcement material comprising: a raw cord comprising fibers; and a coating layer formed on the raw cord; 14. A rubber reinforcement, wherein the coating layer comprises the adhesive composition of claim 1 or 13.

19. A rubber reinforcement material comprising: a raw cord comprising fibers; and a coating layer formed on the raw cord, The coating layer includes a coating layer including 100 parts by weight of latex, 3.0 to 25.0 parts by weight of a naturally occurring acid, 0.3 to 25.0 parts by weight of a nitrogen compound, and 0.1 to 15.0 parts by weight of a basic substance; The coating layer is a rubber reinforcing material comprising, based on 100 parts by weight of a latex component, 0.1 to 9.0 parts by weight of a first basic substance, sodium hydroxide (NaOH), and 0.1 to 14.0 parts by weight of a second basic substance different from the first basic substance.

20. A tire comprising a rubber reinforcement according to any one of claims 18 and 19.

Images