Aqueous dip bath compounds for treating reinforcement inserts and use thereof, as well as methods for producing adhesive reinforcement insert

Abstract

To provide a dip bath compound that makes it possible to produce reinforcement inserts for rubber products having very good adhesion properties, in particular very good adhesion in the peel adhesion test (referred to as H-test), and a good degree of surface coverage following the H-test, without the occurrence of problems resulting from the use of solvents.SOLUTION: An aqueous solid-containing dip bath compound for treating reinforcing inserts of rubber products is provided, the aqueous solid-containing dip bath compound including: (A) at least one fully or partially blocked isocyanate, (B) at least one epoxy, and (C) at least one surfactant for enhancing wetting properties.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an immersion bath compound for treating reinforcing inserts and its use for manufacturing reinforced rubber products. The present invention further relates to a method for manufacturing an adhesive reinforcing insert.

Background Art

[0002] Using an adhesion promoter between a reinforcing insert and rubber to enhance the adhesion strength has proven to be advantageous in the manufacture of reinforced rubber products. Such adhesion promoters are particularly important in the field of belts that function as reinforcing inserts and other high-load composite materials containing reinforcing fibers. Immersion baths containing solvents are utilized, particularly for use in the field of belts that function as rigid applications, in order to achieve the required load on the cord, the corresponding filament bonding, and the resulting belt rigidity.

[0003] Adhesion promoters for manufacturing adhesive reinforcing inserts have been conventionally known. An aqueous immersion bath is used for soft cords, and a solvent-based immersion bath is used for hard cords. Regarding the process, either a one-step method or a two-step method can be adopted.

[0004] In the one-step method, the reinforcing element is impregnated with resorcinol formaldehyde latex (RFL), or preferably a mixture of resorcinol formaldehyde-free (RF-free) and an adhesion promoter.

[0005] In the two-step method, first the reinforcing element is impregnated with an adhesion promoter, and in the second step, RFL (or preferably RF-free) is applied.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

SUMMARY OF THE INVENTION

PROBLEM TO BE SOLVED BY THE INVENTION

[0007] An important problem in the existing prior art regarding immersion bath compounds containing solvents is that a special device including afterburning of the solvent must be operated, and as a result, an appropriate margin for explosion protection must be provided. Methylene diphenyl diisocyanate (MDI) as an active ingredient in a process containing a solvent (e.g., in toluene) is harmful to human health and carcinogenic in the form of free isocyanate.

[0008] An important problem in the existing prior art regarding immersion bath compounds not containing solvents is that the filament bond is not sufficient for use as a rigid cord.

[0009] Therefore, an object of the present invention is to provide a reinforcing insert for rubber products having very good adhesion properties, particularly very good adhesiveness in a peel adhesion test (referred to as the H - test), and good surface coverage after the H - test, and to provide an immersion bath compound that enables the production thereof without causing the above - mentioned problems caused by the use of solvents.

MEANS FOR SOLVING THE PROBLEM

[0010] This object is achieved by the aqueous solid - containing immersion bath compound of the present invention for treating a reinforcing insert according to claim 1, the method for manufacturing an adhesive reinforcing insert according to claim 14, the adhesive reinforcing insert according to claim 16, and its use according to claim 17. Further dependent claims provide advantageous improvements.

[0011] According to the present invention, at least one aqueous solid - containing immersion bath compound for treating a reinforcing insert is provided, which contains or consists of the following components. (A) At least one fully or partially blocked isocyanate, (B) At least one epoxy, (C) At least one surfactant for enhancing wettability, At least one surfactant (C) is selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, silicon-containing surfactants, perfluorinated surfactants, hydrophilically modified polyolefins, and mixtures thereof. Particularly preferred are soaps, alkylbenzene sulfonates, linear alkylbenzene sulfonates, alkane sulfonates, ester sulfonates, methyl ester sulfonates, sulfosuccinic acid derivatives, α-olefin sulfonates, alkyl sulfates, aliphatic alcohol sulfates, aliphatic alcohol ether sulfates, aliphatic alcohol polyglycol ether sulfates, aliphatic alcohol polyglycol ethers, sodium dioctyl sulfosuccinate, alkylphenol polyglycol ethers, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, alkyl polyglucosides, fatty acid glucamides, fatty acid ethoxylates, fatty amine ethoxylates, ethoxylated triacylglycerols, polyethylene glycol ethers alkylated on both sides, alcohol ethoxylates, nonylphenol ethoxylates, polyglycerin fatty acid esters, fatty acid alkanolamides, amine oxides, alkyldimethylamine oxides, alkyl polyglucosides, sucrose esters, sorbitan esters, fatty acid glucamides, fatty acid N-methylglucamides, amphoteric liquids, betaines, sulfobetaines, N-(acylamidalkyl)betaines, N-alkyl-β-aminopropionic acids, N-alkyl-β-iminopropionic acids, long-chain primary amine salts, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, esterquats, polyalkylene glycols, alkoxylated polyalkylene glycols, polysulfones, poly(2-hydroxyalkyl acrylates), poly(2-hydroxyalkyl methacrylates), ethylene oxide-propylene oxide block copolymers, polyethylene glycols, polypropylene glycols, polyethylene oxide resins, polypropylene oxides, oligophosphates, polyphosphates, and mixtures thereof. (D) At least one latex selected from the group consisting of styrene-butadiene-vinylpyridine copolymer, styrene-butadiene-vinylpyridine copolymer modified with carboxylic acid, styrene-butadiene copolymer, styrene-butadiene copolymer modified with carboxylic acid, nitrile-butadiene copolymer, natural latex, chloroprene latex, and mixtures thereof. Similarly, (E) Optionally at least one additive selected from the group consisting of the following: · Antifoaming agent, preferably long-chain alcohol, polymeric glycol, trialkylmethylamine, silicone or mixtures thereof, particularly preferably silicone in the form of a silicone emulsion. · Organic polymer, preferably polylignin, lignin sulfonic acid, kraft lignin. · Filler, preferably silicate. · Dye, preferably carbon black. · Preservative. · Catalyst. · Thickening agent. · Acid. · Caustic alkali solution. · Polyhydric alcohol, and · Mixtures thereof.

Mode for Carrying Out the Invention

[0012] <Definition of Terms> The immersion bath compound according to the present invention is aqueous. That is, water is used as the liquid phase. Hereinafter, water is not described as a component of the immersion bath compound. The immersion bath compound preferably substantially does not contain an organic solvent, i.e., an organic liquid that does not participate in the reaction. Substantially not containing means that there is less than 5% by weight, preferably less than 2% by weight of the organic solvent based on the total weight of the immersion bath compound. The immersion bath compound preferably does not contain any organic solvent at all.

[0013] Furthermore, the immersion bath compound according to the present invention preferably substantially does not contain resorcinol, formaldehyde and their reaction products, i.e., less than 1.0% by weight in total, preferably less than 0.5% by weight, particularly preferably less than 0.16% by weight, is present based on the total weight of the immersion bath compound. Particularly preferably, the immersion bath compound does not contain resorcinol, formaldehyde and their reaction products at all.

[0014] The immersion bath compound according to the present invention can exist in the form of a single bath or multiple baths, particularly two baths.

[0015] The terms "containing" and "comprising" in the present claims and specification are to be understood to mean that further components are not excluded. Within the scope of the present invention, the term "consisting of" is to be understood to mean a preferred embodiment of the term "including" or "comprising". When a group is defined as "containing" or "comprising" at least a certain number of components, this is also to be understood to preferably mean that a group "consisting of" these components is disclosed.

[0016] <Immersion bath compound> Preferred embodiments of the immersion bath compound according to the present invention will be described below.

[0017] According to a preferred embodiment of the present invention, the solid content of the immersion bath compound is 2 to 40% by weight, preferably 3 to 30% by weight, particularly preferably 4 to 22% by weight, more preferably 5 to 16% by weight, based on the total weight of the leaching bath compound containing water.

[0018] According to another preferred embodiment, the aqueous solid-containing leaching bath compound has the following composition, and the parts by weight in each case are based on 200 parts by weight of the total weight of the leaching bath compound containing water. (A) 0.1 to 18.0 parts by weight, preferably 0.2 to 16.0 parts by weight, particularly preferably 1.0 to 14 parts by weight, more preferably 3.0 to 13 parts by weight, (B) 0.4 to 8.0 parts by weight, preferably 0.7 to 6.0 parts by weight, particularly preferably 1.0 to 4.0 parts by weight, more preferably 1.2 to 3.0 parts by weight, (C) 0.01 to 5.0 parts by weight, preferably 0.02 to 2 parts by weight, particularly preferably 0.05 to 0.50 parts by weight, more preferably 0.10 to 0.30 parts by weight, (D) 5 to 40 parts by weight, preferably 8 to 30 parts by weight, particularly preferably 12 to 25 parts by weight, more preferably 15 to 20 parts by weight, and (E) 0 to 20 parts by weight, preferably 0.1 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, each is based on the solid content.

[0019] According to another preferred embodiment, the aqueous solid-containing immersion bath compound is divided into a plurality of baths, particularly two baths. In the case of two baths, the two baths contain the following components. Bath 1: (A) At least one fully or partially blocked isocyanate, (B) At least one epoxy, (C) At least one surfactant for enhancing wetting properties, and optionally (E) At least one additive. Bath 2: (D) At least one latex, and optionally (A) At least one fully or partially blocked isocyanate, and optionally (E) At least one additive.

[0020] According to the present invention, isocyanates blocked particularly with lactams have proven to be advantageous blocking agents with respect to isocyanates. Examples are ε-caprolactam and δ-valerolactam. However, the present invention of course also encompasses other known blocking agents. These are preferably selected from the group consisting of: · Monophenols, particularly phenol, resorcinol, cresol, trimethylphenol and tert-butylphenol, · Lactams, especially ε-caprolactam, δ-valerolactam and laurolactam, · Primary, secondary, and tertiary alcohols, glycol ethers, · Oximes, especially methyl ethyl ketoxime, methyl amyl ketoxime and cyclohexanone oxime, · Enol-forming compounds, especially ethyl acetoacetate, acetylacetone, · Secondary aromatic amines, · Imides, · Mercaptans, · Triazoles, and · Their mixtures.

[0021] The blocking agent is preferably selected from the group consisting of monophenols, especially phenol, cresol, trimethylphenol and tert-butylphenol. Lactams, especially ε-caprolactam, δ-valerolactam and laurolactam, and mixtures thereof. Particularly preferably, the capping agent is selected from the group consisting of phenol, ε-caprolactam and mixtures thereof. It is most preferred that the MDI mixture (A) is capped with ε-caprolactam.

[0022] Furthermore, when the isocyanate used is methylene diphenyl diisocyanate (MDI) and / or toluene diisocyanate (TDI) and / or 1,5-naphthalene diisocyanate (NDI), it has been proven to be advantageous with respect to the adhesion promoter formulation. However, the present invention, of course, also encompasses all other known isocyanates that can be used in such adhesion promoter formulations. In this regard, reference is made, for example, to Patent Document 1 and the diisocyanates described therein.

[0023] According to another preferred embodiment of the present invention, the capped MDI mixture (A) comprises an MDI derivative (i.e., a modified MDI) preferably selected from the group consisting of MDI uretdione, adducts of MDI and / or MDI oligomers with other compounds.

[0024] According to another preferred embodiment of the present invention, the MDI is selected from the group consisting of 4,4'-MDI, 2,4'-MDI, 2,2'-MDI and mixtures thereof, and the contents of 2,4'-MDI and 2,2'-MDI are preferably less than 10% by weight, preferably less than 8% by weight, particularly preferably in the range of 0.1 to 6% by weight, in each case based on the MDI mixture.

[0025] According to a preferred embodiment, the mixture contains one or more MDI oligomers, and n in formula (I) is an integer from 1 to 8, preferably from 1 to 6.

Chemical formula

[0026] According to another preferred embodiment of the present invention, the MDI mixture has the following composition. (i) 25 to 60% by weight, preferably 25 to 49.9% by weight of MDI monomer, (ii) 40 to 75% by weight, preferably 50 to 74.9% by weight of MDI oligomer, and (iii) 0 to 9% by weight, preferably 0.1 to 6% by weight of modified MDI, The sum of the contents of components (i) to (iii) up to 100% by weight.

[0027] The MDI mixture consisting of the MDI oligomer, MDI monomer and optionally MDI derivative of formula (I) is commercially available under the name "polymeric MDI" (PMDI), for example Voronate (DowDuPont), Suprosec (Huntsman), Elastoflex (BASF), Lupronat (BASF), or Autofroth (BASF).

[0028] According to another preferred embodiment of the present invention, at least one epoxy (B) is soluble in the dispersion and / or has a molecular weight of 50 to 2000 g / mol. Particularly preferred are epoxy resins having a molecular weight of 100 to 1000, in particular water-soluble polyglycidyl ethers, epoxy novolac resins, polyfunctional alkylene epoxy resins, diglycidyl ethers and bisphenol A on-type resins. However, the present invention also encompasses all epoxy resins cited in Patent Document 2. Particularly preferably, at least one epoxy (B) is selected from the group consisting of water-soluble polyglycidyl ethers, polyfunctional alkylene epoxy resins, diglycidyl ethers and mixtures thereof.

[0029] According to another embodiment of the present invention, at least one surfactant (C) is selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, silicon-containing surfactants, perfluorinated surfactants, hydrophilically modified polyolefins, and mixtures thereof. The surfactant is selected from the group consisting of soap, alkylbenzene sulfonates, linear alkylbenzene sulfonates, alkane sulfonates, ester sulfonates, methyl ester sulfonates, sulfosuccinic acid derivatives, α-olefin sulfonates, alkyl sulfates, fatty alcohol sulfates, fatty alcohol ether sulfates, fatty alcohol polyglycol ether sulfates, fatty alcohol polyglycol ethers, dioctyl sodium sulfosuccinate, alkylphenol polyglycol ethers, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, alkyl polyglucosides, fatty acid glucamides, fatty acid ethoxylates, fatty amine ethoxylates, ethoxylated triacylglycerols, polyethylene glycol ethers alkylated on both sides, alcohol ethoxylates, nonylphenol ethoxylates, polyglycerol fatty acid esters, fatty acid alkanolamides, amine oxides, alkyldimethylamine oxides, alkyl polyglucosides, sucrose esters, sorbitan esters, fatty acid glucamides, fatty acid N-methylglucamides, amphoteric liquids, betaines, sulfobetaines, N-(acylamidalkyl)betaines, N-alkyl-β-aminopropionate esters, N-alkyl-β-iminopropionate esters, long-chain primary amine salts, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, esterquats, polyalkylene glycols, alkoxylated polyalkylene glycols, polysulfones, poly(2-hydroxyalkyl acrylates), poly(2-hydroxyalkyl methacrylates), ethylene oxide-propylene oxide block copolymers, polyethylene glycols, polypropylene glycols, polyethylene oxide resins, polypropylene oxides, oligophosphates, polyphosphates, and mixtures thereof.At least one surfactant (C) according to the present invention can enhance the wettability of the reinforcing insert to be treated. In particular, this surfactant (C) can wet the inner surface of the fiber bundle used as the reinforcing insert and can improve the rigidity.

[0030] According to another preferred embodiment of the present invention, at least one surfactant (C) is a nonionic surfactant and / or an anionic surfactant.

[0031] According to another preferred embodiment of the present invention, at least one surfactant (C) is selected from the group consisting of sulfosuccinate derivatives, fatty alcohol sulfates, fatty acid ethoxylates, polyethylene glycol ethers alkylated on both sides, and ethylene oxide-propylene oxide block copolymers.

[0032] According to the most preferred embodiment of the present invention, at least one surfactant (C) is a fatty acid ethoxylate and / or dioctyl sodium sulfosuccinate.

[0033] According to another preferred embodiment, at least one surfactant (C) does not contain poly(2-hydroxyalkyl acrylate).

[0034] According to another preferred embodiment of the present invention, at least one latex (D) is selected from the group consisting of styrene-butadiene-vinylpyridine copolymers, styrene-butadiene-vinylpyridine copolymers modified with carboxylic acids, styrene-butadiene copolymers, styrene-butadiene copolymers modified with carboxylic acids, nitrile butadiene copolymers, natural latex, chloroprene latex, and mixtures thereof.

[0035] According to another embodiment of the present invention, at least one additive (E) is selected from the group consisting of the following. · Defoaming agents, preferably long-chain alcohols, high molecular weight glycols, trialkylmethylamines, · It is selected from the group consisting of silicone or a mixture thereof, particularly preferably silicone in the form of a silicone emulsion. · An organic polymer, preferably a polysaccharide, lignin sulfonic acid, kraft lignin, · A filler, preferably a silicate, · A dye, preferably carbon black, · A preservative, · A catalyst, · An acid, · An acid, · A caustic alkali solution, · A polyhydric alcohol, and · Mixtures thereof.

[0036] A further improvement in the reaction rate of the adhesion promoter according to the present invention can be achieved by adding a catalyst in the form of a metal compound as an additive. Suitable catalysts are metal compounds of sodium, potassium, cesium, strontium, silver, cadmium, barium, cerium, uranium, titanium, chromium, tin, antimony, manganese, iron, cobalt, nickel, copper, zinc, lead, calcium and / or zirconium. Among the metal compounds, those of zinc are preferred. Suitable compounds are zinc acetate, zinc sulfate, zinc carbonate, zinc oxide, zinc acetylacetonate and / or zinc chloride. Zinc acetate is particularly preferred. The catalyst is preferably present in the dispersion in a dissolved form, and the catalyst is preferably present at a concentration of 0.0001 to 0.1 mol / 1000 g of the immersion bath compound.

[0037] According to another preferred embodiment of the present invention, the average particle size d of the capped MDI mixture 50 is 0.1 to 2 μm, preferably 0.6 to 1.5 μm.

[0038] According to another preferred embodiment of the present invention, the particle size d of the capped MDI mixture 100 is 0.1 to 6 μm, preferably 0.6 to 5 μm.

[0039] According to another preferred embodiment of the present invention, the number average molecular weight Mn of the capped MDI mixture is 550 to 1200 g / mol, preferably 700 to 1100 g / mol.

[0040] According to another preferred embodiment, the surfactant (C) satisfies a wetting test including the following steps. · Dissolve 2% by weight of the surfactant (C) in 50 ml of water at 20 degrees so that the liquid level of the solution of the surfactant (C) in the beaker is at least 3 cm high. · Provide 0.15 g of an MDI mixture (CL-MDI) capped with ε-caprolactam having a number average molecular weight Mn of 740 g / mol, a particle size d 50 = 1.2 μm, d 100 = 3.6 μm, and a solid content of 100%. · Using a spoon, add 0.15 g of CL-MDI to the stationary, non-stirred surface of the solution of the dissolved surfactant (C) without contacting the spoon with the solution so that the CL-MDI floats on the solution of (C). · The surfactant (C) is considered wettable (less than 20% by weight) when the CL-MDI floating on the solution of (C) can no longer be seen after 10 minutes. · The surfactant (C) is considered non-wettable when more than 50% by weight of the CL-MDI floats on the solution of (C) after 10 minutes.

[0041] Furthermore, it is preferable that the dipping bath compound does not contain tragacanth gum.

[0042] To produce the dipping bath, first, deionized water is held at room temperature in a container, preferably a stirring container, and then components (A), (B), (C), (D) and optionally (E) are stirred.

[0043] <Method for manufacturing an adhesion reinforcing insert> The present invention further relates to a method for manufacturing an adhesion reinforcing insert including at least the following steps. a) Provide at least one reinforcing insert, b) immersing the provided reinforcing insert in at least one of the above immersion bath compounds; c) drying the reinforcing insert from step b) at 80 degrees to 240 degrees; d) baking the coating of the reinforcing insert from step c) at 150 degrees to 250 degrees.

[0044] The following describes a preferred embodiment of the method according to the present invention for manufacturing an adhesive reinforcing insert.

[0045] According to a preferred embodiment of the present invention, step c) is carried out at a temperature of 110 degrees to 210 degrees, preferably 140 degrees to 180 degrees.

[0046] According to another preferred embodiment of the present invention, step d) is carried out at a temperature of 220 degrees to 240 degrees.

[0047] According to another preferred embodiment of the present invention, the reinforcing insert is selected from the group consisting of compounds of polyamide 6, polyamide 66, polyethylene terephthalate, polyethylene naphthalate, rayon, aramid, cotton, basalt fiber, sisal, hemp, linen, coconut fiber, and mixtures thereof.

[0048] According to another preferred embodiment of the present invention, prior to step b), the reinforcing insert is immersed in an aqueous solid-containing immersion bath compound containing at least one blocked isocyanate, preferably containing no other components. The blocked isocyanate (A) contains an MDI oligomer of formula (I) (n is an integer from 1 to 8) and contains an MDI monomer.

Chemical formula

[0049] After the dipping step and before performing step b) of the method of the present invention, it is preferable to dry and bake the layer under the above conditions. Drying is preferably carried out at a temperature of 110°C to 210°C, particularly preferably at a temperature of 140°C to 180°C, and more preferably carried out for a time of 30 seconds to 120 seconds. Furthermore, baking is preferably carried out at a temperature of 220°C to 240°C, and more preferably carried out for a time of 20 seconds to 120 seconds.

[0050] According to another preferred embodiment of the present invention, before performing step b) of the method of the present invention and before introducing at least one latex (D) into the dipping bath compound, the pH value of the dipping bath compound is adjusted to a range of 8 to 12, preferably 9 to 11. That is, before setting the pH value, the dipping bath compound contains only components (A) and (C). It is preferable to use an ammonia solution as a base. Before performing step b), at least one latex (D) is introduced into the dipping bath compound.

[0051] The tire cord or other reinforcing insert can be coated with a conventional coater, where the excess portion of the dipping bath is removed by a mechanical device and / or vacuum extraction at 1 to 5 mbar, and the coating is first dried in a furnace at 100 to 240°C for 20 to 120 seconds, and then fired in a further furnace at 200 to 250°C for 20 to 120 seconds.

[0052] <Method for manufacturing a reinforced rubber product> The present invention further relates to a method for manufacturing a reinforced rubber product including the following steps. (i) Providing at least one layer of an adhesive reinforcing insert manufactured by the method according to the above invention, (ii) Embedding at least one layer of the adhesive reinforcing insert from step (i) into a rubber matrix in a press mold, (iii) Pressing the layer from step (ii), (iv) Vulcanizing the reinforced rubber product from step (iii) at 140 to 210°C and 5 to 110 bar for 5 to 45 minutes, and (v) Removing the reinforced rubber product from the press mold from step (iv).

[0053] According to a preferred embodiment of the present invention, the reinforced rubber product is a tire for passenger cars, motorcycles, commercial vehicles and aircraft, as well as industrial rubber products, in particular conveyor belts, air springs, hoses (e.g., bellows for trains and buses), and drive belts, such as V-belts, ribbed V-belts, circular belts, flat belts, or toothed belts.

[0054] <Adhesive Reinforcement Insert> The present invention further relates to an adhesive reinforcement insert that can be manufactured by the method of the present invention. The adhesive reinforcement insert is preferably a drive belt.

[0055] The reinforcement insert preferably consists of a fiber bundle containing 200 to 500 filaments, the fiber bundle preferably having a fineness of 400 to 1700 dtex, and the reinforcement insert is particularly preferably formed of 3 to 30 of these fiber bundles.

[0056] The fineness of the reinforcement insert is more preferably 4000 to 40000 dtex.

[0057] <Use> The present invention also relates to the use of the adhesive reinforcement insert according to the present invention for manufacturing a reinforced rubber product.

[0058] The present invention further relates to the use of the dipping bath compound according to the present invention for coating a reinforcement insert of a rubber product.

[0059] The reinforced rubber product is preferably a tire for passenger cars, motorcycles, bicycles, commercial vehicles and aircraft, as well as industrial rubber products, in particular conveyor belts, air springs, hoses, and drive belts, such as V-belts, ribbed V-belts, circular belts, flat belts, or toothed belts.

[0060] Without limiting the subject matter of the present invention to the specific embodiments shown herein, a more detailed description will be given based on the following examples.

Example

[0061] <Measurement method> The following measurement methods were used within the scope of this application.

[0062] [Particle size (d 50 or d 100 value)] The particle size was measured by laser diffraction at 23 degrees using a powder or aqueous dispersion conforming to ISO13320. The laser measurement was performed using a Cilas 1064 particle size analyzer manufactured by Quantachrome GmbH.

[0063] [H test] Using a polyester cord (1100x3x3 dtex, S100, z50), the adhesiveness by the H test was measured according to ASTM D4776 at a vulcanization temperature of 160 degrees and a vulcanization time of 15 minutes.

[0064] [Rigidity] Using a polyester cord (1100x3x3 dtex, S100, z50), the rigidity was measured according to ASTM D885.

[0065] [Maximum tensile strength] Using a polyester cord (1100x3x3 dtex, S100, z50), the maximum tensile strength was measured according to ASTM D885.

[0066] [Dip pickup (DPU)] DPU was measured according to ASTM D2970 using a polyester cord (1100x3x3 dtex, S100, z50).

[0067] [Surface coverage rate] The surface coverage rate by the H test was determined by visual inspection by comparing the internal samples with a coverage rate of 0 to 100% and the corresponding tire materials. A coverage rate of 0% means that the adhesion reinforcement insert was completely peeled off from the rubber after the H test, that is, breakage occurred at the boundary layer between the tire cord and the rubber. On the other hand, a coverage rate of 100% means that the adhesion reinforcement insert did not peel off from the rubber, that is, breakage occurred in the rubber.

[0068] [Solid content] The solid content was measured by evaporation in a halogen dryer (Mettler HR73 halogen dryer). For this purpose, about 3 g of the immersion bath compound was evenly dispersed on an aluminum tray (diameter: 95 mm) at the bottom of the tray. The test time was 25 minutes at 80 degrees. The selected display format is dry-dry percentage (100 - 0). The average value of three measurements is shown.

[0069] [Number average molecular weight (Mn)] The measurement of the number average molecular weight (Mn) was carried out by gel permeation chromatography (GPC) using UV detection.

[0070] For the measurement, the sample was dissolved in THF (about 5 mg / 10 ml), filtered through a disposable syringe filter, and then filled into a vial. Apparatus: Waters 2690 Alliance Software: Waters Millennium 32 GPC module Column: PLgel 100 Å, particle size 3 μm Length: 30.0 cm Inner diameter: 7.5 mm Wavelength of UV detector: 254 nm Eluent: THF Flow rate: 1.0 ml / min

[0071] The number average molecular weight (Mn) is confirmed by ordinary calibration. The calibration is performed using polystyrene standards (masses 700, 1100, and 2000) and laurolactam (mass 197). The measurement is carried out three times. The arithmetic mean of the molecular weights is expressed in g / mol. The THF solvent was procured from EGTChemie in Switzerland of HPLC quality. The disposable filter can be obtained from Macheley-Nagel GmbH & Co. KG in Germany under the name Chromafil A-45 / 25 (pore size 0.45 μm, filter diameter 25 mm). The disposable syringe can be obtained from VWR International GmbH in Germany.

[0072] [Evaluation of Wettability] To evaluate the wettability, 2 wt% of surfactant was dissolved in 50 ml of water at 20 degrees so that the liquid level in the beaker was at least 3 cm in height. Furthermore, 0.15 g of an MDI mixture capped with ε-caprolactam having a number average molecular weight Mn of 740 g / mol, particle sizes d 50 = 1.2 μm, d 100 = 3.6 μm, and a solids content of 100% was prepared. 0.15 g of CL-MDI was added to the stationary, non-stirred surfactant solution using a spoon without contacting the solution. If, after 10 minutes (less than 20 wt%), the CL-MDI floating on the solution is no longer visible, the surfactant is considered wettable. If more than half of the added CL-MDI floats on top without wetting, the surfactant is considered non-wettable.

[0073] [Raw Materials] The materials used in the examples and comparative examples are summarized in Table 1. The evaluation results of wettability are illustrated in Table 2. When the evaluation was conducted without using a surfactant, more than half of the CL-capped MDI was floating without wetting even after 10 minutes. Similarly, in the case of lignosulfonate and tragacanth gum, more than half of the CL-capped MDI was floating even after 10 minutes. It has been shown that in the case of lignosulfonate and tragacanth gum, more than 90% by weight of the CL-capped MDI is floating after 10 minutes. Also, in the case of lignosulfonate and tragacanth gum, more than 50% by weight of the CL-capped MDI is floating. The percentage of CL-capped MDI floated to the upper part and did not get wet even after 24 hours. Even if tragacanth gum does not affect wetting, it must be considered that as a result of tragacanth gum, the liquid becomes concentrated and the wettability of the solution decreases. [Table 1] a) The capped MDI mixture (A1) was produced by capping the product "Boronate M600" available from DowDuPont with ε-caprolactam. [Table 2]

[0074] A polyester cord (1100x3x3dtex, S100, z50) was used as the reinforcing insert.

[0075] This polyester cord is made of polyethylene terephthalate with a total adhesive strength of 9900 dtex. Specifically, three fiber bundles containing 200 to 350 filaments (1100 dtex) are twisted together in the S direction at 100 revolutions per meter. Next, these three fiber bundles are twisted together in the Z direction (opposite direction) at 50 revolutions per meter.

[0076] The coating machine used a pilot system from Mehler Engineering & Service GmbH in Fulda, Germany.

[0077] <Examples and Comparative Examples> Table 3 summarizes the results of the examples and comparative examples according to the present invention.

Table 3

[0078] In Examples 3 to 6, this is due to the wetting surfactant (C) used to ensure a high dip pickup even within the fiber bundle.

[0079] Comparing Comparative Example 2 with Examples 4 and 6, it is clear that the wetting surfactant rather than lignosulfonate brings about good rigidity. Lignosulfonate is not a wetting surfactant and does not affect the CL-capped MDI in water in the evaluation of wettability. Comparing Comparative Examples 1 and 2, it is also clear that lignosulfonate does not affect the rigidity.

[0080] When classified by the latex system used, an increase in dip pickup as a result of the wetting surfactant is also easily apparent. The dip pickup is considerably higher in Examples 3 and 5 than in Comparative Example 1, and higher in Examples 4 and 6 than in Comparative Example 2. This improvement in rigidity is important when used as a reinforcing insert (rigid cord). Particularly in the open-side belt, it is important to prevent the fibers of the fiber bundle from fraying during cutting.

[0081] Also, from the comparison of the latex systems in Table 2, it can be seen that there is no significant change in the adhesive strength and maximum tensile strength by the H test.

Claims

1. An aqueous solid-containing immersion bath compound for treating reinforcing inserts for rubber products, comprising: (A) at least one fully or partially blocked isocyanate, (B) at least one epoxy, (C) at least one surfactant for enhancing wettability, At least one surfactant (C) is selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, silicon-containing surfactants, perfluorinated surfactants, hydrophilically modified polyolefins, and mixtures thereof, and particularly preferably, soap, alkylbenzene sulfonates, linear alkylbenzene sulfonates, alkane sulfonates, ester sulfonates, methyl ester sulfonates, sulfosuccinic acid derivatives, α-olefin sulfonates, alkyl sulfates, aliphatic alcohol sulfates, aliphatic alcohol ether sulfates, aliphatic alcohol polyglycol ether sulfates, aliphatic alcohol polyglycol ethers, sodium dioctyl sulfosuccinate, alkylphenol polyglycol ethers, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, alkyl polyglucosides, fatty acid glucamides, fatty acid ethoxylates, fatty amine ethoxylates, ethoxylated triacylglycerols, polyethylene glycol ethers alkylated on both sides, alcohol ethoxylates, nonylphenol ethoxylates, polyglycerol fatty acid esters, fatty acid alkanolamides, amine oxides, alkyldimethylamine oxides, alkyl polyglucosides, sucrose esters, sorbitan esters, fatty acid glucamides, fatty acid N-methylglucamides, amphoteric liquids, betaines, sulfobetaines, N-(acylamidalkyl)betaines, N-alkyl-β-aminopropionic acids, N-alkyl-β-iminopropionic acids, long-chain primary amine salts, quaternary ammonium salts, quaternary phosphonium salts, tertiary sulfonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, esterquats, polyalkylene glycols, alkoxylated polyalkylene glycols, polysulfones, poly(2-hydroxyalkyl acrylates), poly(2-hydroxyalkyl methacrylates), ethylene oxide-propylene oxide block copolymers, polyethylene glycols, polypropylene glycols, polyethylene oxide resins, polypropylene oxides, oligophosphates, polyphosphates, and mixtures thereof, (D) At least one latex selected from the group consisting of styrene-butadiene-vinylpyridine copolymer, styrene-butadiene-vinylpyridine copolymer modified with carboxylic acid, styrene-butadiene copolymer, styrene-butadiene copolymer modified with carboxylic acid, nitrile butadiene copolymer, natural latex, chloroprene latex and mixtures thereof, (E) Optionally at least one additive selected from the group consisting of - Defoaming agents, preferably long-chain alcohols, polymeric glycols, trialkylmethylamines, silicones or mixtures thereof, particularly preferably silicones in the form of silicone emulsions, - Organic polymers, preferably polylignin, lignin sulfonic acid, kraft lignin, - Fillers, preferably silicates, - Dyes, preferably carbon black, - Preservatives, - Catalysts, - Thickening agents, - Acids, - Caustic alkali solutions, - Polyhydric alcohols, and - Mixtures thereof, containing or consisting of components, An aqueous solid-containing dipping bath compound.

2. The solid content of the dipping bath compound is 2 to 40% by weight, preferably 3 to 30% by weight, particularly preferably 5% to 27% by weight, based on the total weight of the dipping bath compound, The aqueous solid-containing dipping bath compound according to claim 1.

3. The dipping bath compound is (A) 0.1 to 18 parts by weight, preferably 0.2 to 16 parts by weight, particularly preferably 1.0 to 14 parts by weight, more preferably 3.0 to 13 parts by weight, (B) 0.4 to 8.0 parts by weight, preferably 0.7 to 6.0 parts by weight, particularly preferably 1.0 to 4.0 parts by weight, more preferably 1.2 to 3.0 parts by weight, (C) 0.01 to 5.0 parts by weight, preferably 0.02 to 2 parts by weight, particularly preferably 0.05 to 0.50 parts by weight, more preferably 0.10 to 0.30 parts by weight, (D) 5 to 40 parts by weight, preferably 8 to 30 parts by weight, particularly preferably 12 to 25 parts by weight, more preferably 15 to 20 parts by weight, and (E) 0 to 20 parts by weight, preferably 0.1 to 10 parts by weight, particularly preferably 0.1 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, having the composition in each case, and the parts by weight are based on the solid content of the dipping bath compound, The aqueous solid-containing dipping bath compound according to claim 1 or 2.

4. The at least one isocyanate (A) is - Monophenols, particularly phenol, resorcinol, cresol, trimethylphenol and tert-butylphenol, - Lactams, especially ε-caprolactam, δ-valerolactam and laurolactam, - Primary, secondary, and tertiary alcohols, glycol ethers, - Oximes, especially methyl ethyl ketoxime, methyl amyl ketoxime and cyclohexanone oxime, - Enol-forming compounds, especially ethyl acetoacetate, acetylacetone, - Secondary aromatic amines, - Imides, - Mercaptans, - Triazoles, and - Mixtures thereof, blocked with a blocking agent selected from the group consisting of, particularly preferably blocked with a lactam as the blocking agent, especially ε-caprolactam, δ-valerolactam, and laurolactam, The aqueous solid-containing immersion bath compound according to claim 1 or 2.

5. The at least one isocyanate (A) is selected from the group consisting of methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), 1,5-naphthalene diisocyanate (NDI), and mixtures thereof, and / or The at least one isocyanate (A) is selected from the group consisting of MDI uretdione, adducts of MDI, other compounds, especially MDI oligomers with polyethylene glycol, and mixtures thereof, containing MDI derivatives, The aqueous solid-containing immersion bath compound according to claim 1 or 2.

6. MDI is selected from the group consisting of 4,4'-MDI, 2,4'-MDI, 2,2'-MDI and mixtures thereof, The content of 2,4'-MDI and 2,2'-MDI is less than 10% by weight, preferably less than 8% by weight, Particularly preferably, the content of 2,4'-MDI and 2,2'-MDI is 0.1 to 6% by weight based on the MDI mixture, Particularly preferably, the mixture contains one or more MDI oligomers, n in formula (I) is an integer from 1 to 8, preferably from 1 to 6, [Chemical 3] Formula (I) The aqueous solid-containing immersion bath compound according to claim 5.

7. The MDI mixture is (i) 25 to 60% by weight, preferably 25 to 49.9% by weight of MDI monomer, (ii) 40 to 75% by weight, preferably 50 to 74.9% by weight of MDI oligomer, and (iii) 0 to 9% by weight, preferably 0.1 to 6% by weight of modified MDI, having a composition such that the contents of components (i) to (iii) are 100% by weight or less, The aqueous solid-containing immersion bath compound according to claim 1 or 2.

8. The at least one epoxy (B) has a molecular weight of 50 to 2000 g / mol, preferably 100 to 1000 g / mol, The at least one epoxy (B) is preferably selected from the group consisting of water-soluble polyglycidyl ethers, epoxy novolac resins, polyfunctional alkylene epoxy resins, diglycidyl ethers, bisphenol A on-type resins, and mixtures thereof, The aqueous solid-containing immersion bath compound according to claim 1 or 2.

9. The average particle diameter d of the capped MDI mixture ５０ is 0.1 to 2 mm, preferably 0.6 to 1.5 mm, and / or The particle size d of the capped MDI mixture １００ is 0.1 to 6 mm, preferably 0.6 to 5 mm, and / or The number average relative molar mass Mn of the capped MDI mixture ranges from 550 to 1200 g / mol, preferably from 700 to 1100 g / mol, The aqueous solid-containing immersion bath compound according to claim 1 or 2.

10. The surfactant (C) is - Dissolve 2% by weight of the surfactant (C) in 50 ml of water at 20 degrees so that the height of the liquid surface of the solution of the surfactant (C) in the beaker is 3 cm or more. ・ The number average molecular weight Mn of the MDI mixture capped with ε-caprolactam is 740 g / mol, and the particle sizes d ５０ = 1.2 μm, d １００ = 3.6 μm. Prepare 0.15 g of an MDI mixture capped with ε-caprolactam (CL-MDI) with a solids content of 100%. - Using a spoon, add 0.15 g of CL-MDI to the stationary, non-stirred surface of the solution of the dissolved surfactant (C) without contacting the spoon with the solution so that the CL-MDI floats on the solution of (C). - The surfactant (C) is considered wettable (less than 20% by weight) when the CL-MDI floating on the solution of (C) can no longer be seen after 10 minutes. - The surfactant (C) satisfies a wetting test including the step of being considered non-wettable when more than 50% by weight of CL-MDI floats on the solution of (C) after 10 minutes. The aqueous solid-containing immersion bath compound according to claim 1 or 2.

11. The immersion bath compound does not contain tragacanth gum. The aqueous solid-containing immersion bath compound according to claim 1 or 2.

12. a) Provide at least one reinforcing insert, b) Immerse the provided reinforcing insert in at least one immersion bath compound according to any one of claims 1 to 9, c) Dry the reinforcing insert of step b) at 80 degrees to 240 degrees, d) Bake the coating of the reinforcing insert of step c) at 150 degrees to 250 degrees, including at least the above steps, A method for manufacturing an adhesive reinforcing insert.

13. The reinforcing insert is selected from the group of compounds consisting of polyamide 6, polyamide 66, polyethylene terephthalate, polyethylene naphthalate, rayon, aramid, cotton, basalt fiber, sisal, hemp, linen, coconut fiber, and mixtures thereof. The method according to claim 12.

14. An adhesive reinforcing insert that can be produced by the method according to any one of claims 12 or 13, Adhesive reinforcing insert.

15. The reinforcing insert preferably consists of a fiber bundle containing 200 to 500 filaments, The fiber bundle preferably has a fineness of 400 to 1700 dtex, The reinforcing insert is formed of 3 to 30 of these fiber bundles, The reinforcing insert particularly preferably has a fineness of 4000 to 40,000 dtex, The adhesive reinforcing insert according to claim 14.

16. For producing a reinforced rubber product, Use of the adhesive reinforcing insert according to claim 14.

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