CN116218464A - Adhesive for improving adhesive property of rubber and copper-plated steel wire and preparation method thereof - Google Patents
Adhesive for improving adhesive property of rubber and copper-plated steel wire and preparation method thereof Download PDFInfo
- Publication number
- CN116218464A CN116218464A CN202211099795.7A CN202211099795A CN116218464A CN 116218464 A CN116218464 A CN 116218464A CN 202211099795 A CN202211099795 A CN 202211099795A CN 116218464 A CN116218464 A CN 116218464A
- Authority
- CN
- China
- Prior art keywords
- parts
- adhesive
- rubber
- copper
- improving
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Tires In General (AREA)
Abstract
The invention discloses an adhesive for improving the adhesive property of rubber and copper-plated steel wires and a preparation method thereof, wherein the adhesive comprises the following components in parts by weight: 1 to 4 parts of pepter, 2 to 5 parts of ZnO, 30 to 45 parts of N326 carbon black, 5 to 15 parts of low polycyclic aromatic hydrocarbon oil, 1 to 5 parts of phenolic resin, 1 to 4 parts of precipitated silica, and 0.1 to 0.5 part of 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ];0.5 to 3 parts of TMQ and 1 to 5 parts of DCBS. The tyre produced by the adhesive can obviously enhance the adhesive force between the tyre rubber and the steel wire, improve the safety of the tyre in the use process, and simultaneously, after the adhesive is used, the quality of a rubber finished product can be improved, the durability of the tyre rubber is obviously improved, and the tyre produced by the adhesive is beneficial to keeping certain adhesive force between the aged rubber and the steel wire, and further improves the use safety of the tyre finished product.
Description
Technical Field
The invention relates to the technical field of rubber preparation, in particular to an adhesive for improving the adhesive property of rubber and copper-plated steel wires and a preparation method thereof.
Background
Tires are one of the most durable composite materials that work under dynamic conditions, where adhesion between the rubber compound and the steel wire is the most important parameter to ensure durability, the tire undergoes millions of cycles of deformation over its service life, separation between the rubber compound and the steel wire may occur due to differences in modulus, and in order to avoid this, sufficient adhesion between the Natural Rubber (NR) -based degreasing compound and the brass-coated steel wire is required, in which the adhesion between the rubber and the steel wire not only ensures normal use of the tire, but more importantly ensures safety of the vehicle.
In general, brass alloy is coated on steel wires in order to establish strong adhesion between rubber compound and brass coated steel wires, adhesion in composite materials follows a unique mechanism which has been studied for the past 30 years or more, and as an active research field, adhesion of metal rubber has been studied intensively, and Cu is formed between rubber compound and steel wires in the initial stage of the rubber vulcanization process X S layer, in the process, znS also reacts with Cu X Together, since zinc is another constituent element of brass alloys, cu forms Cu of different stoichiometric ratios by interstitial lattice defects of ZnS X S layer, dendritic Cu X The S layer and the vulcanized rubber form a firm physical interlocking key;
although some researchers have investigated the characteristics of the interfacial layer between rubber and brass plating lines, cu at the rubber-metal interface X The relationship between the depth of the S layer and its effect on adhesion remains a subject to be studied.
Disclosure of Invention
The invention aims to provide an adhesive for improving the adhesive property of rubber and copper-plated steel wires and a preparation method thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
an adhesive for improving the adhesive property of rubber and copper-plated steel wires, which comprises the following components in parts by weight: 1 to 4 parts of peptiser (peptide), 2 to 5 parts of ZnO, 30 to 45 parts of N326 carbon black, 5 to 15 parts of low polycyclic aromatic hydrocarbon oil, 1 to 5 parts of phenolic resin, 1 to 4 parts of precipitated silica, 0.1 to 0.5 part of 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ], 0.1 to 0.2 part of silane coupling agent, 0.1 to 0.3 part of fatty acid, 0.05 to 0.2 part of paraffin wax, 0.5 to 3 parts of TMQ (rubber antioxidant) and 1 to 5 parts of DCBS (rubber vulcanization accelerator).
Preferably, the TMQ comprises the following components in parts by weight: 0.1 to 0.8 part of (2, 4-trimethyl-1, 2-dihydroquinoline), 0.2 to 1 part of cobalt stearate, 0.1 to 0.5 part of resorcinol and 0.1 to 0.7 part of hexamethoxy methyl melamine.
Preferably, the DCBS includes, in parts by weight: 0.6 to 3 parts of dicyclohexyl-2-benzothiazole sulfonamide and 0.4 to 2 parts of cyclohexylthiophene carboxamide.
Preferably, the low polycyclic aromatic hydrocarbon oil is any one or a combination of any two or more of benzene, toluene, xylene and ethylbenzene.
Preferably, the preparation method of the adhesive for improving the adhesive property of the rubber and the copper-plated steel wire comprises the following steps:
s1, weighing peptiser, znO, N carbon black, phenolic resin and precipitated silica, firstly heating the phenolic resin to 80-120 ℃ in a container, adding N326 carbon black, znO and the precipitated silica into the melted phenolic resin, and stirring for 10-15 min to fully and uniformly mix the components;
then adding peptiser into the mixture, stirring for 10-15 min, then preserving heat for 3-6 min, and naturally cooling to room temperature;
s2, crushing the mixture obtained in the step S1 into particles with the diameter of 0.5-1 mm, adding low-polycyclic aromatic hydrocarbon oil, a silane coupling agent and 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ] into the mixture particles, and stirring and mixing for 8-12 min at the temperature of 30-35 ℃;
s3, preparing cobalt stearate:
s3-1, heating stearic acid to 95-110 ℃, and continuously stirring the stearic acid in the melting process until the stearic acid is completely melted;
s3-2, adjusting air pressure to enable the melted stearic acid to be in a condition of 0.6-0.8 standard atmospheric pressure, adding cobalt hydroxide and dimethylbenzene into the melted stearic acid while stirring, and enabling the stearic acid to fully react with the cobalt hydroxide to obtain cobalt stearate;
the addition of cobalt hydroxide is 25-30% of stearic acid, and the addition of dimethylbenzene is 35-40% of stearic acid;
firstly, heating to 135-155 ℃ at the speed of 10-15 ℃/min, fully reacting for 50-90 min, then heating to 190-215 ℃ at the speed of 10-15 ℃/min, and continuing to react for 80-150 min;
s3-3, distilling the compound obtained in the step S3-2, removing water and dimethylbenzene in the mixture to obtain the required cobalt stearate, and drying the obtained cobalt stearate for 10-15 min to thoroughly remove water;
s4, under the condition of 40-60 ℃, firstly adding cobalt stearate prepared in the step S3 into the mixture obtained in the step S2, stirring and mixing by using ultrasonic vibration with the frequency of 30-45 kHz, and adding (2, 4-trimethyl-1, 2-dihydroquinoline), resorcinol and hexamethoxymethyl melamine in TMQ into the mixture after 1-3 min, and continuously stirring and mixing for 5-8 min;
s5, adding fatty acid, paraffin and DCBS into the mixture prepared in the step S4, and stirring and mixing for 5-8 min by using ultrasonic vibration with the frequency of 30-45 kHz;
s6, preserving heat of the mixture prepared in the step S5 at 40-60 ℃ for 10-15 min to obtain the adhesive capable of improving the adhesive property of the rubber and the copper-plated steel wire.
Preferably, the peptiser, znO, N carbon black used in step S1 is a solid powder.
Preferably, the fatty acid used in the step S1 is any one or a combination of two or more of palm oil, castor oil, rapeseed oil, peanut oil, beef tallow, mutton tallow, lard, and fish oil.
Preferably, the phenolic resin used in step S1 is a phenolic resin particle having a particle size of 1 to 2 mm.
Preferably, the adhesive prepared in the step S6 is contained in a sealed container and stored in a dark and cool environment.
Compared with the prior art, the invention has the beneficial effects that: the invention has reasonable design and obvious gain effect, the adhesive force between the rubber and the steel wire of the tire can be obviously enhanced, the safety of the tire in the use process is improved, meanwhile, the quality of a rubber finished product can be improved after the adhesive is used, the durability of the rubber of the tire is obviously improved, and the tire produced by the adhesive is beneficial to keeping a certain adhesive force between the aged rubber and the steel wire, and the use safety of the tire finished product is further improved.
Drawings
FIG. 1 is a process flow diagram of a method of preparing an adhesive according to the present invention.
Detailed Description
Example 1:
an adhesive for improving the adhesive property of rubber and copper-plated steel wires, which comprises the following components in parts by weight: 1 part of pepiser (peptide), 2 parts of ZnO, 30 parts of N326 carbon black, 5 parts of low polycyclic aromatic hydrocarbon oil, 1 part of phenolic resin, 1 part of precipitated silica, 0.1 part of 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ], 0.1 part of silane coupling agent, 0.1 part of fatty acid, 0.05 part of paraffin wax, 0.5 part of TMQ (rubber anti-aging agent) and 1 part of DCBS (rubber vulcanization accelerator).
The TMQ comprises the following components in parts by weight: 0.1 part of (2, 4-trimethyl-1, 2-dihydroquinoline), 0.2 part of cobalt stearate, 0.1 part of resorcinol and 0.1 part of hexamethoxymethyl melamine.
The DCBS comprises the following components in parts by weight: 0.6 part of dicyclohexyl-2-benzothiazole sulfonamide and 0.4 part of cyclohexylthiophene carboxamide.
The low polycyclic aromatic hydrocarbon oil is toluene.
The fatty acid is palm oil.
Example 2:
an adhesive for improving the adhesive property of rubber and copper-plated steel wires, which comprises the following components in parts by weight: 2.5 parts of pepter (peptide), 3.5 parts of ZnO, 37 parts of N326 carbon black, 10 parts of low polycyclic aromatic hydrocarbon oil, 3 parts of phenolic resin, 2.5 parts of precipitated silica, 0.3 part of 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ], 0.15 part of silane coupling agent, 0.2 part of fatty acid, 0.1 part of paraffin wax, 1.8 parts of TMQ (rubber antioxidant) and 3 parts of DCBS (rubber vulcanization accelerator).
The TMQ comprises the following components in parts by weight: 0.3 part of (2, 4-trimethyl-1, 2-dihydroquinoline), 0.8 part of cobalt stearate, 0.3 part of resorcinol and 0.4 part of hexamethoxymethyl melamine.
The DCBS comprises the following components in parts by weight: 1.8 parts of dicyclohexyl-2-benzothiazole sulfonamide and 1.2 parts of cyclohexylthiophene carboxamide.
The low-polycyclic aromatic hydrocarbon oil is benzene and toluene which are combined according to the mass ratio of 1:1.
The fatty acid is beef tallow and mutton tallow which are combined according to a mass ratio of 1:1.
Example 3:
an adhesive for improving the adhesive property of rubber and copper-plated steel wires, which comprises the following components in parts by weight: 4 parts of pepiser (peptide), 5 parts of ZnO, 45 parts of N326 carbon black, 15 parts of low polycyclic aromatic hydrocarbon oil, 5 parts of phenolic resin, 4 parts of precipitated silica, 0.5 part of 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ], 0.2 part of silane coupling agent, 0.3 part of fatty acid, 0.2 part of paraffin wax, 3 parts of TMQ (rubber antioxidant) and 5 parts of DCBS (rubber vulcanization accelerator).
The TMQ comprises the following components in parts by weight: 0.8 part of (2, 4-trimethyl-1, 2-dihydroquinoline), 1 part of cobalt stearate, 0.5 part of resorcinol and 0.7 part of hexamethoxymethyl melamine.
The DCBS comprises the following components in parts by weight: 3 parts of dicyclohexyl-2-benzothiazole sulfonamide and 2 parts of cyclohexylthiophene carboxamide.
The low-polycyclic aromatic hydrocarbon oil is toluene and dimethylbenzene which are combined according to a mass ratio of 2:1.
The fatty acid is rapeseed oil and peanut oil which are combined according to a mass ratio of 2:1.
Example 4:
an adhesive for improving the adhesive property of rubber and copper-plated steel wires, which comprises the following components in parts by weight: 3 parts of pepiser (peptide), 4 parts of ZnO, 40 parts of N326 carbon black, 13 parts of low polycyclic aromatic hydrocarbon oil, 4 parts of phenolic resin, 3 parts of precipitated silica, 0.4 part of 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ], 0.18 part of silane coupling agent, 0.26 part of fatty acid, 0.18 part of paraffin wax, 2.5 parts of TMQ (rubber anti-aging agent) and 4 parts of DCBS (rubber vulcanization accelerator).
The TMQ comprises the following components in parts by weight: 0.7 part of (2, 4-trimethyl-1, 2-dihydroquinoline), 0.8 part of cobalt stearate, 0.4 part of resorcinol and 0.6 part of hexamethoxymethyl melamine.
The DCBS comprises the following components in parts by weight: 2.5 parts of dicyclohexyl-2-benzothiazole sulfonamide and 1.5 parts of cyclohexylthiophene carboxamide.
The low-polycyclic aromatic hydrocarbon oil is formed by combining benzene, toluene and xylene according to a mass ratio of 5:3:4.
The fatty acid is palm oil, castor oil and rapeseed oil which are combined according to a mass ratio of 4:3:4.
Example 5:
an adhesive for improving the adhesive property of rubber and copper-plated steel wires, which comprises the following components in parts by weight: 1.5 parts of peptiser (peptide), 2.5 parts of ZnO, 33 parts of N326 carbon black, 7 parts of low polycyclic aromatic hydrocarbon oil, 2.2 parts of phenolic resin, 1.6 parts of precipitated silica, 0.2 part of 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ], 0.12 part of silane coupling agent, 0.15 part of fatty acid, 0.1 part of paraffin wax, 1 part of TMQ (rubber antioxidant) and 1.8 parts of DCBS (rubber vulcanization accelerator).
The TMQ comprises the following components in parts by weight: 0.2 part of (2, 4-trimethyl-1, 2-dihydroquinoline), 0.4 part of cobalt stearate, 0.2 part of resorcinol and 0.2 part of hexamethoxymethyl melamine.
The DCBS comprises the following components in parts by weight: 1 part of dicyclohexyl-2-benzothiazole sulfonamide and 0.8 part of cyclohexylthiophene carboxamide.
The low-polycyclic aromatic hydrocarbon oil is formed by combining benzene, toluene, dimethylbenzene and ethylbenzene according to a mass ratio of 5:3:4:2.
The fatty acid is beef fat, mutton fat and lard in a mass ratio of 3:4:2.
Example 6:
the preparation method of the adhesive for improving the adhesive property of the rubber and the copper-plated steel wire according to the above embodiments 1 to 5 comprises the following steps:
s1, weighing peptiser, znO, N carbon black, phenolic resin and precipitated silica, firstly heating the phenolic resin to 80 ℃ in a container, adding N326 carbon black, znO and the precipitated silica into the melted phenolic resin, and stirring for 10min to fully and uniformly mix the components;
then adding peptiser into the mixture, stirring for 10min, then preserving heat for 3min, and naturally cooling to room temperature;
peptiser, znO, N326 the carbon black is solid powder, and the phenolic resin adopts phenolic resin particles with the particle size of 1 mm.
S2, crushing the mixture obtained in the step S1 into 0.5mm particles, adding low-polycyclic aromatic hydrocarbon oil, a silane coupling agent and 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ] into the mixture particles, and stirring and mixing for 8min at the temperature of 30 ℃;
s3, preparing cobalt stearate:
s3-1, heating stearic acid to 95 ℃, and continuously stirring the stearic acid until the stearic acid is completely melted in the melting process of the stearic acid;
s3-2, adjusting air pressure to enable the melted stearic acid to be in a condition of 0.6 standard atmospheric pressure, adding cobalt hydroxide and dimethylbenzene into the melted stearic acid while stirring, and enabling the stearic acid to fully react with the cobalt hydroxide to obtain cobalt stearate;
the addition amount of cobalt hydroxide is 25% of the mass of stearic acid, and the addition amount of dimethylbenzene is 35% of the mass of stearic acid;
heating to 135 ℃ at the speed of 10 ℃/min, fully reacting for 50min, heating to 190 ℃ at the speed of 10 ℃/min, and continuing reacting for 80min;
s3-3, distilling the compound obtained in the step S3-2, removing water and dimethylbenzene in the mixture to obtain the required cobalt stearate, and drying the obtained cobalt stearate for 10min to thoroughly remove the water;
s4, under the condition of 40 ℃, firstly adding cobalt stearate prepared in the step S3 into the mixture obtained in the step S2, stirring and mixing by using ultrasonic vibration with the frequency of 30kHz, and adding (2, 4-trimethyl-1, 2-dihydroquinoline), resorcinol and hexamethoxymethyl melamine in TMQ into the mixture after 1min, and continuously stirring and mixing for 5min;
s5, adding fatty acid, paraffin and DCBS into the mixture prepared in the step S4, and stirring and mixing for 5min by using ultrasonic vibration with the frequency of 30 kHz;
s6, preserving heat of the mixture prepared in the step S5 at 40 ℃ for 10min to obtain the adhesive capable of improving the adhesive property of the rubber and the copper-plated steel wire;
and (3) placing the prepared adhesive in a sealed container, and storing in a dark and cool environment.
Example 7:
the preparation method of the adhesive for improving the adhesive property of the rubber and the copper-plated steel wire according to the above embodiments 1 to 5 comprises the following steps:
s1, weighing peptiser, znO, N carbon black, phenolic resin and precipitated silica, firstly heating the phenolic resin to 120 ℃ in a container, adding N326 carbon black, znO and the precipitated silica into the melted phenolic resin, and stirring for 15min to fully and uniformly mix the components;
then adding peptiser into the mixture, stirring for 15min, then preserving heat for 6min, and naturally cooling to room temperature;
peptiser, znO, N326 the carbon black is solid powder, and the phenolic resin adopts phenolic resin particles with the particle size of 2 mm.
S2, crushing the mixture obtained in the step S1 into 1mm particles, adding low polycyclic aromatic hydrocarbon oil, a silane coupling agent and 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ] into the mixture particles, and stirring and mixing for 12min at 35 ℃;
s3, preparing cobalt stearate:
s3-1, heating stearic acid to 110 ℃, and continuously stirring the stearic acid until the stearic acid is completely melted in the melting process of the stearic acid;
s3-2, adjusting air pressure to enable the melted stearic acid to be in a condition of 0.8 standard atmospheric pressure, adding cobalt hydroxide and dimethylbenzene into the melted stearic acid while stirring, and enabling the stearic acid to fully react with the cobalt hydroxide to obtain cobalt stearate;
the addition amount of cobalt hydroxide is 30% of the mass of stearic acid, and the addition amount of dimethylbenzene is 40% of the mass of stearic acid;
heating to 155 ℃ at a speed of 15 ℃/min, fully reacting for 90min, heating to 215 ℃ at a speed of 15 ℃/min, and continuing reacting for 150min;
s3-3, distilling the compound obtained in the step S3-2, removing water and dimethylbenzene in the mixture to obtain the required cobalt stearate, and drying the obtained cobalt stearate for 15min to thoroughly remove the water;
s4, under the condition of 40-60 ℃, firstly adding cobalt stearate prepared in the step S3 into the mixture obtained in the step S2, stirring and mixing by using ultrasonic vibration with the frequency of 45kHz, adding (2, 4-trimethyl-1, 2-dihydroquinoline), resorcinol and hexamethoxymethyl melamine in TMQ into the mixture after 3min, and continuously stirring and mixing for 8min;
s5, adding fatty acid, paraffin and DCBS into the mixture prepared in the step S4, and stirring and mixing for 8min by using ultrasonic vibration with the frequency of 45 kHz;
s6, preserving heat of the mixture prepared in the step S5 at 60 ℃ for 15min to obtain the adhesive capable of improving the adhesive property of the rubber and the copper-plated steel wire;
and (3) placing the prepared adhesive in a sealed container, and storing in a dark and cool environment.
Example 8:
the preparation method of the adhesive for improving the adhesive property of the rubber and the copper-plated steel wire according to the above embodiments 1 to 5 comprises the following steps:
s1, weighing peptiser, znO, N carbon black, phenolic resin and precipitated silica, firstly heating the phenolic resin to 100 ℃ in a container, adding N326 carbon black, znO and the precipitated silica into the melted phenolic resin, and stirring for 12min to fully and uniformly mix the components;
then adding peptiser into the mixture, stirring for 12min, then preserving heat for 4min, and naturally cooling to room temperature;
peptiser, znO, N326 the carbon black is solid powder, and the phenolic resin adopts phenolic resin particles with the particle size of 1 mm.
S2, crushing the mixture obtained in the step S1 into 1mm particles, adding low polycyclic aromatic hydrocarbon oil, a silane coupling agent and 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ] into the mixture particles, and stirring and mixing for 10min at the temperature of 32 ℃;
s3, preparing cobalt stearate:
s3-1, heating stearic acid to 102 ℃, and continuously stirring the stearic acid until the stearic acid is completely melted in the melting process of the stearic acid;
s3-2, adjusting air pressure to enable the melted stearic acid to be in a condition of 0.7 standard atmospheric pressure, adding cobalt hydroxide and dimethylbenzene into the melted stearic acid while stirring, and enabling the stearic acid to fully react with the cobalt hydroxide to obtain cobalt stearate;
the addition amount of cobalt hydroxide is 27% of the mass of stearic acid, and the addition amount of dimethylbenzene is 37% of the mass of stearic acid;
heating to 145 ℃ at a speed of 12 ℃/min, fully reacting for 70min, heating to 205 ℃ at a speed of 12 ℃/min, and continuing reacting for 115min;
s3-3, distilling the compound obtained in the step S3-2, removing water and dimethylbenzene in the mixture to obtain the required cobalt stearate, and drying the obtained cobalt stearate for 12min to thoroughly remove the water;
s4, under the condition of 50 ℃, firstly adding cobalt stearate prepared in the step S3 into the mixture obtained in the step S2, stirring and mixing by using ultrasonic vibration with the frequency of 35kHz, and adding (2, 4-trimethyl-1, 2-dihydroquinoline), resorcinol and hexamethoxymethyl melamine in TMQ into the mixture after 2min, and continuously stirring and mixing for 6min;
s5, adding fatty acid, paraffin and DCBS into the mixture prepared in the step S4, and stirring and mixing for 6min by using ultrasonic vibration with the frequency of 35 kHz;
s6, preserving heat of the mixture prepared in the step S5 at 50 ℃ for 12min to obtain the adhesive capable of improving the adhesive property of the rubber and the copper-plated steel wire;
and (3) placing the prepared adhesive in a sealed container, and storing in a dark and cool environment.
Test example 1:
the control compound was prepared from 95 parts by weight of a low polycyclic aromatic hydrocarbon oil composed of benzene, toluene, xylene, ethylbenzene in a mass ratio of 5:3:4, 2.2 parts of a phenolic resin, 1.6 parts of precipitated silica, 0.2 part of 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ], 0.12 part of a silane coupling agent, 0.15 part of a fatty acid composed of tallow, mutton fat, and lard in a mass ratio of 3:4:2, 0.1 part of paraffin wax, 0.2 part of (2, 4-trimethyl-1, 2-dihydroquinoline), 0.2 part of cyclohexane, 0.2 parts of cyclohexane-dimethyiamide, and 0.8 parts of a sample of cyclohexane, and 8.8 parts of a sample of a melamine.
Test example 2:
preparation of Compound 1A control compound was prepared from 95 parts by weight of a low polycyclic aromatic hydrocarbon oil composed of benzene, toluene, xylene, ethylbenzene in a mass ratio of 5:3:4:2, 2.2 parts of a phenolic resin, 1.6 parts of precipitated silica, 0.2 part of 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ], 0.12 part of a silane coupling agent, 0.15 part of a fatty acid composed of tallow, mutton tallow, and lard in a mass ratio of 3:4:2, 0.1 part of paraffin wax, 0.2 part of (2, 4-trimethyl-1, 2-dihydroquinoline), 0.2 part of cyclohexane, and 0.8 parts of a cyclohexanecarboxylic acid, and 0.8 parts of a sample of a melamine, based on parts by weight of a control compound, which has a Mooney viscosity (ML (1+4), 100C) of 91MU NR (natural rubber), 33 parts of a Mooney viscosity (ML (1+4), 100C) of 91MU RSS #4 (tobacco flake rubber), 19 parts of a Mooney viscosity (ML (1+4), and 100C) of 86 MU-20 (silicone rubber).
Test example 3:
the compound 2 was prepared from 95 parts by weight of a low polycyclic aromatic hydrocarbon oil composed of benzene, toluene, xylene, ethylbenzene in a mass ratio of 5:3:4, 2.2 parts of a phenolic resin, 1.6 parts of precipitated silica, 0.2 part of 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ], 0.12 part of a silane coupling agent, 0.15 part of a fatty acid composed of tallow, mutton tallow, and lard in a mass ratio of 3:4:2, 0.1 part of paraffin wax, 0.2 part of (2, 4-trimethyl-1, 2-dihydroquinoline), 0.2 part of cyclohexane-dimethy-l-thiophene, and 0.8 parts of a sample of a melamine.
Test example 4:
compound 3 was prepared from, by weight, 95 parts of NR (natural rubber) having a Mooney viscosity (ML (1+4), 100C) of 91MU, 33 parts of RSS#4 (tobacco flake gum) having a Mooney viscosity (ML (1+4), 100C) of 91MU, 19 parts of Mooney viscosity (ML (1+4), 100C) a rubber sample prepared from SIR-20 (silicone rubber) of 86MU, 1.5 parts peptiser, 2.5 parts ZnO, 33 parts N326 carbon black, 7 parts low polycyclic aromatic hydrocarbon oil formed by combining benzene, toluene, xylene and ethylbenzene according to a mass ratio of 5:3:4:2, 2.2 parts phenolic resin, 1.6 parts precipitated silica, 0.2 part 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ], 0.12 parts silane coupling agent, 0.15 parts fatty acid formed by combining tallow, mutton tallow and lard according to a mass ratio of 3:4:2, 0.1 part paraffin wax, 0.2 parts (2, 4-trimethyl-1, 2-dihydroquinoline), 0.2 parts hexamethoxy methyl melamine, 1 part dicyclohexyl-2-benzothiazole sulfonamide and 0.8 parts cyclohexylthiophene carboxamide.
Test example 5:
preparation of Compound 4A control compound was prepared from 95 parts by weight of a low polycyclic aromatic hydrocarbon oil composed of benzene, toluene, xylene, ethylbenzene in a mass ratio of 5:3:4:2, 2.2 parts of a phenolic resin, 0.2 part of 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ], 0.12 part of a silane coupling agent, 0.15 part of a fatty acid composed of tallow, mutton tallow, lard in a mass ratio of 3:4:2, 0.1 part of paraffin wax, 0.2 part of (2, 4-trimethyl-1, 2-dihydroquinoline), 0.4-dicyclohexyl-1, 0.2 part of cyclohexane, 0.2 part of a phenylmethane-2-cyclohexyl rubber, and 8.8 parts of a sample of melamine, based on parts by weight of a control compound, which has a Mooney viscosity (ML (1+4), 100C) of 91MU NR (natural rubber), 33 parts of a Mooney viscosity (ML (1+4), 100C) of 91MU RSS #4 (tobacco flake rubber), 19 parts of a Mooney viscosity (ML (1+4), and 100C) of 86 MU) of a fatty acid composed of 86MU, 0.1.2 part of paraffin wax, 0.2 part of a cyclohexane, 0.4 part of cyclohexane, 0.2 part of cyclohexane-methyl-2 part of cyclohexane, 0.2 part of cyclohexane-butyl amide, 0.2 part of 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -2-sulfide, 0.2 part of methyl-1.
Test analysis:
the cure characteristics of each of the compounds prepared in test examples 1 to 5 above were measured using a rubber process analyzer, a rheology curve was obtained by testing the compound at 145 ℃ for 60 minutes using an STM D5289 instrument, and the optimum cure time for each compound was calculated from the graph;
forming each rubber compound in an electric heating hydraulic press using compression forming technique according to ASTM D3182 method, curing the formed tensile sheet at 145 ℃, and evaluating curing time of each rubber compound using rheometer;
t tensile adhesion test was performed according to ASTM D2229, wherein the present study used a 3+9+15×0.175+0.15 plain tensile cord with a brass coating containing 63.5wt% copper, the rubber wire bonded composite cured at 145℃for 60 minutes; these unaged samples were tested at 150mm/min using a Z010 UTM tester, the samples were aged in a humidity cabinet at 93.3C with a relative humidity of 95%, the samples were kept in an oven for 21 days, and then a T-tensile adhesion test was performed using Z010 UTM.
Cure parameters measured at 145℃for each of the compounds of Table 1
Effect of different adhesive components on the rheological properties of the compounds:
as shown in table 1, the CRI measured with each compound was used to interpret the rheology of the compound, and the results indicate that cobalt stearate, hexamethoxymethyl melamine (HMMM), resorcinol, and silica have a significant effect on the degree of cure;
the rheological comparison between the control compounds shows that the CRI without the addition of the cobalt stearate compound is much lower than the control compound, indicating that the lack of cobalt stearate slows down the curing reaction, because the accelerator moiety (essentially anion) in cobalt stearate releases Co at the early stage of curing 3+ Ion, co 3+ The ions affect the cure rate, cure state, and activation energy of the cure reaction;
thus, in the case of compound 1 lacking cobalt stearate, the rate of the curing reaction of the compound is significantly reduced; this explains that compounds without added cobalt stearate and resorcinol show lower CRI;
the CRI of compound 2 is greatest, which may be due to the absence of cobalt stearate and HMMM and resorcinol in compound 3;
the presence of HMMM and resorcinol in compound 1 results in a reduction in cure rate compared to compound 2, mainly due to HMMM entraining amine generated during the DCBS accelerator to 2-Mercaptobenzothiazole (MBT), thus HMMM and resorcinol act as pre-cure inhibitors, retarding the cure reaction and reducing the cure rate;
on the other hand, the presence of stearic acid anions in cobalt stearate can stimulate the accelerator and increase the rate of the curing reaction in compound 2, so from this result it can be inferred that the presence of cobalt stearate and the absence of HMMM help to make the compound exhibit a higher CRI;
finally, silica is extracted from compound 4, the effect of silica on the CRI of compound is studied, the presence of silica in compound 3 leading to a slower curing speed compared to compound 4, while the other components remain unchanged, which can be well explained by the presence of silanol groups, which strongly adsorb or react with amine groups present in the accelerator system, leading to a reduced degree of curing, and similar effects can be observed from the reaction of zinc ions with silanol groups present on the silicon surface, the reactive silanol groups reacting with zinc stearate to form two known reaction products, one being a zinc stearate complex and the other being bridging of zinc across the two silanol groups.
Effect of different binder components on the physical properties of the compounds:
the extraction of each adhesive component from the formulation has an impact on the physical properties, traditionally, a resin system is introduced into the rubber-based skim to improve adhesion, a combination of methylene donor (HMMM) and methylene acceptor (resorcinol) is used, which react together to form a highly crosslinked polymer network, the modulus of compound 1 is increased compared to the control compound due to the increased resin content and lack of synergistic effect between cobalt stearate and the resin system, the absence of HMMM and resorcinol in compound 3 results in a decrease in modulus at 300% elongation for compound (2-4), the maximum adhesion (12% no aging and 11% wet aging) is obtainable for compound 2, and the CRI and elongation at break of compound 2 are maximized, these results indicate that break, elongation and CRI can be considered as symptomatic parameters of adhesion performance.
Effect of different adhesive compositions on adhesion:
our results indicate that the synergistic effect of HMMM/resorcinol/cobalt stearate on bond strength is comparable to a system consisting of HMMM and resorcinol but without cobalt stearate, probably due to the three-dimensional network structure of HMMM and resorcinol, which is formed from rubber;
in several sets of experiments, compound 2 achieved maximum bond strength, where cobalt stearate was present but HMMM and resorcinol were absent, clearly indicating that cobalt stearate had a greater impact on bond strength than HMMM resorcinol combination, due to the presence of the organic cobalt salt increasing the amount of carbon and sulfur at the wire-rubber interface and decreasing the copper and oxygen content in the system, and therefore the Cu to S and Zn to S ratios decreased and the Zn to O ratio increased, and furthermore, cobalt stearateCu at the wire-rubber interface when present x The development of three-dimensional networks is faster because copper and sulfur migrate rapidly to the surface and, therefore, the layer becomes amorphous in nature, which further promotes adhesion between the rubber and the steel wire in the non-aged and wet aged state.
It has also been shown that cobalt (Co) acts as an adhesion promoter in the rubber-steel wire (brass coating) adhesion phenomenon, and that, first, these ions fill Cu X S interstitial lattice, cu is reduced X The growth rate of the S layer, as this affects the stability of the adhesion; secondly, in the use process, zn 2+ And electrons (e) - ) Surface entering, zn 2+ React with sulfur and moisture to form ZnS and Zn (OH) 2 Through C UX ，Cu X The retention of the S layer is the most important parameter affecting the adhesion properties of rubber to metal.
Thus, in ZnS and Zn (OH) 2 Between them, zn (OH) 2 After dissolution of ZnS, another component, co in Co salt 3+ Reducing ZnS to ZnO and helping Cu X The S layer remains in the steel-rubber interface, a phenomenon known as "dezincification", which in fact inhibits corrosion and provides better ageing properties, on the other hand, cu for other compounds due to slower migration of copper and sulfur X The S dendrites have enough time to crystallize, resulting in lower bond strength.
For compounds 3 and 4, the adhesion of both samples (no ageing and wet ageing) was lower, indicating that the silica alone has less effect on adhesion, however, when combined with other binder ingredients (such as HMMM, resorcinol and cobalt stearate), it has a significant synergistic effect on adhesion, furthermore, the combined effect of cobalt stearate on bond strength is greater compared to the synergistic effect of silica with HMMM and resorcinol, the presence of silica reduces the availability of S at the wire-rubber interface, increasing the ratio of Cu: S to Zn: S, and therefore the presence of silica promotes the formation of ZnO at the wire-rubber interface, providing better adhesion after ageing. In addition, znS formation prevents copper diffusion, thereby limitingCu at the interface of steel wire and rubber X The formation of the S layer helps to maintain a certain adhesion between the aged rubber and the steel wire.
Appearance rating after T-pull adhesion:
after the T-pull adhesion test, all samples were rated for the percent appearance of the rubber coated steel wire samples (after the unaged T-pull adhesion test), which was consistent with the adhesion results, compound 2 exhibited the greatest adhesion (no aging and wet aging), and also exhibited the greatest rubber coating, and the appearance of the other tested wires also followed the same trend as the adhesion, so the T-pull adhesion strength was used as an indicator of the appearance of the steel wire after the adhesion test.
Line scanning analysis of the glue coated steel wire after aging-free T-pull adhesion test:
t-tension adhesion test A line scan analysis was performed on the rubber coated steel wire obtained from the T-tension adhesion test sample, the two samples were analyzed without aging and wet aging, the highest concentrations of copper, zinc and iron were detected from the bare steel wire, and in addition, a small amount of carbon and oxygen were obtained;
on the other hand, sulfur and more carbon are available from the composite rubber, and it is observed that the bare area of the wire-rubber interface is mainly Fe, since this is the main component of the wire, while Cu and Zn are the second and third most abundant metals on the surface, carbon being the main contributor element in all samples when scanning the rubber covered parts.
The experimental study analyzes the bonding mechanism of the steel wire-rubber interface and the influence of each component on the bonding strength, measures the T-tensile force adhesive force, and ranks the samples according to the appearance;
the adhesion of the cobalt stearate-added compound was improved by 12% (unaged) and 11% (wet aged), respectively, compared to the control group, and furthermore, the advantage of the cobalt stearate-containing compound in adhesion was related to CuxS film depth before and after aging.
Claims (9)
1. An adhesive for improving the adhesive property of rubber and copper-plated steel wires is characterized by comprising the following components in parts by weight: 1 to 4 parts of pepter, 2 to 5 parts of ZnO, 30 to 45 parts of N326 carbon black, 5 to 15 parts of low polycyclic aromatic hydrocarbon oil, 1 to 5 parts of phenolic resin, 1 to 4 parts of precipitated silica, 0.1 to 0.5 part of 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ], 0.1 to 0.2 part of silane coupling agent, 0.1 to 0.3 part of fatty acid, 0.05 to 0.2 part of paraffin, 0.5 to 3 parts of TMQ and 1 to 5 parts of DCBS.
2. An adhesive for improving the adhesion of rubber to copper-plated steel wire according to claim 1, wherein: the TMQ comprises the following components in parts by weight: 0.1 to 0.8 part of (2, 4-trimethyl-1, 2-dihydroquinoline), 0.2 to 1 part of cobalt stearate, 0.1 to 0.5 part of resorcinol and 0.1 to 0.7 part of hexamethoxy methyl melamine.
3. An adhesive for improving the adhesion of rubber to copper-plated steel wire according to claim 1, wherein: the DCBS comprises the following components in parts by weight: 0.6 to 3 parts of dicyclohexyl-2-benzothiazole sulfonamide and 0.4 to 2 parts of cyclohexylthiophene carboxamide.
4. An adhesive for improving the adhesion of rubber to copper-plated steel wire according to claim 1, wherein: the low-polycyclic aromatic hydrocarbon oil is any one or the combination of any two or more of benzene, toluene, dimethylbenzene and ethylbenzene.
5. The method for preparing an adhesive for improving the adhesion property of rubber to copper-plated steel wire according to any one of claims 1 to 4, comprising the steps of:
s1, weighing peptiser, znO, N carbon black, phenolic resin and precipitated silica, firstly heating the phenolic resin to 80-120 ℃ in a container, adding N326 carbon black, znO and the precipitated silica into the melted phenolic resin, and stirring for 10-15 min to fully and uniformly mix the components;
then adding peptiser into the mixture, stirring for 10-15 min, then preserving heat for 3-6 min, and naturally cooling to room temperature;
s2, crushing the mixture obtained in the step S1 into particles with the diameter of 0.5-1 mm, adding low-polycyclic aromatic hydrocarbon oil, a silane coupling agent and 6PPD [ N-phenyl-N0- (1, 3-dimethyl-butyl) -p-phenylenediamine ] into the mixture particles, and stirring and mixing for 8-12 min at the temperature of 30-35 ℃;
s3, preparing cobalt stearate:
s3-1, heating stearic acid to 95-110 ℃, and continuously stirring the stearic acid in the melting process until the stearic acid is completely melted;
s3-2, adjusting air pressure to enable the melted stearic acid to be in a condition of 0.6-0.8 standard atmospheric pressure, adding cobalt hydroxide and dimethylbenzene into the melted stearic acid while stirring, and enabling the stearic acid to fully react with the cobalt hydroxide to obtain cobalt stearate;
the addition of cobalt hydroxide is 25-30% of stearic acid, and the addition of dimethylbenzene is 35-40% of stearic acid;
firstly, heating to 135-155 ℃ at the speed of 10-15 ℃/min, fully reacting for 50-90 min, then heating to 190-215 ℃ at the speed of 10-15 ℃/min, and continuing to react for 80-150 min;
s3-3, distilling the compound obtained in the step S3-2, removing water and dimethylbenzene in the mixture to obtain the required cobalt stearate, and drying the obtained cobalt stearate for 10-15 min to thoroughly remove water;
s4, under the condition of 40-60 ℃, firstly adding cobalt stearate prepared in the step S3 into the mixture obtained in the step S2, stirring and mixing by using ultrasonic vibration with the frequency of 30-45 kHz, and adding (2, 4-trimethyl-1, 2-dihydroquinoline), resorcinol and hexamethoxymethyl melamine in TMQ into the mixture after 1-3 min, and continuously stirring and mixing for 5-8 min;
s5, adding fatty acid, paraffin and DCBS into the mixture prepared in the step S4, and stirring and mixing for 5-8 min by using ultrasonic vibration with the frequency of 30-45 kHz;
s6, preserving heat of the mixture prepared in the step S5 at 40-60 ℃ for 10-15 min to obtain the adhesive capable of improving the adhesive property of the rubber and the copper-plated steel wire.
6. The method for preparing the adhesive for improving the adhesion property of rubber and copper-plated steel wires according to claim 5, wherein the method comprises the following steps: the peptiser, znO, N326 carbon black adopted in the step S1 is solid powder.
7. The method for preparing the adhesive for improving the adhesion property of rubber and copper-plated steel wires according to claim 5, wherein the method comprises the following steps: the fatty acid adopted in the step S1 is any one or the combination of two or more of palm oil, castor oil, rapeseed oil, peanut oil, beef tallow, mutton tallow, lard and fish oil.
8. The method for preparing the adhesive for improving the adhesion property of rubber and copper-plated steel wires according to claim 5, wherein the method comprises the following steps: the phenolic resin used in step S1 is a phenolic resin particle having a particle diameter of 1 to 2 mm.
9. The method for preparing the adhesive for improving the adhesion property of rubber and copper-plated steel wires according to claim 5, wherein the method comprises the following steps: and (3) placing the adhesive prepared in the step S6 in a sealed container, and storing in a dark and cool environment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211099795.7A CN116218464A (en) | 2022-09-07 | 2022-09-07 | Adhesive for improving adhesive property of rubber and copper-plated steel wire and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211099795.7A CN116218464A (en) | 2022-09-07 | 2022-09-07 | Adhesive for improving adhesive property of rubber and copper-plated steel wire and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116218464A true CN116218464A (en) | 2023-06-06 |
Family
ID=86587994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211099795.7A Pending CN116218464A (en) | 2022-09-07 | 2022-09-07 | Adhesive for improving adhesive property of rubber and copper-plated steel wire and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116218464A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4068041A (en) * | 1975-09-18 | 1978-01-10 | The B. F. Goodrich Company | Method for rubberizing steel cords |
| US20020192489A1 (en) * | 2001-03-16 | 2002-12-19 | Yen-How Huang | Method of treating metallic cord |
| CN103497710A (en) * | 2013-10-14 | 2014-01-08 | 无锡通用钢绳有限公司 | High-temperature-resisting steel cord conveyor belt glue and preparation method thereof |
| CN103881593A (en) * | 2014-02-21 | 2014-06-25 | 德瑞宝轮胎有限公司 | Method for preparing rubber-metal adhesive for all-steel radial truck tire |
| CN103881592A (en) * | 2014-02-21 | 2014-06-25 | 德瑞宝轮胎有限公司 | Preparation method of rubber-metal adhesive for semi-steel radial tyre |
| CN112469795A (en) * | 2018-07-26 | 2021-03-09 | 朗盛德国有限责任公司 | Adhesive mixture for uncured rubber |
-
2022
- 2022-09-07 CN CN202211099795.7A patent/CN116218464A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4068041A (en) * | 1975-09-18 | 1978-01-10 | The B. F. Goodrich Company | Method for rubberizing steel cords |
| US20020192489A1 (en) * | 2001-03-16 | 2002-12-19 | Yen-How Huang | Method of treating metallic cord |
| CN103497710A (en) * | 2013-10-14 | 2014-01-08 | 无锡通用钢绳有限公司 | High-temperature-resisting steel cord conveyor belt glue and preparation method thereof |
| CN103881593A (en) * | 2014-02-21 | 2014-06-25 | 德瑞宝轮胎有限公司 | Method for preparing rubber-metal adhesive for all-steel radial truck tire |
| CN103881592A (en) * | 2014-02-21 | 2014-06-25 | 德瑞宝轮胎有限公司 | Preparation method of rubber-metal adhesive for semi-steel radial tyre |
| CN112469795A (en) * | 2018-07-26 | 2021-03-09 | 朗盛德国有限责任公司 | Adhesive mixture for uncured rubber |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ooij | Fundamental aspects of rubber adhesion to brass-plated steel tire cords | |
| CN108192169B (en) | Anti-slippery safety tire tread rubber and preparation method thereof | |
| JP4431618B2 (en) | Rubber composition for covering tire cord | |
| Fulton | Steel tire cord-rubber adhesion, including the contribution of cobalt | |
| EP0148782B1 (en) | Adhesion promoter improving the adhesion of rubber to metals | |
| JP3891643B2 (en) | Method of bonding galvanized steel cord and rubber and conveyor belt using the bonding method | |
| CN103146084A (en) | Composition as well as preparation method and application thereof | |
| JP2006124474A (en) | Rubber composition for covering steel cord and steel cord covered with the same | |
| CN116218464A (en) | Adhesive for improving adhesive property of rubber and copper-plated steel wire and preparation method thereof | |
| JP2002194139A (en) | Rubber composition and tire containing polymaleimide | |
| CN110776584B (en) | Damping additive, high-performance rubber material prepared from damping additive and preparation method of high-performance rubber material | |
| CN111295418B (en) | Rubber composition, metal-rubber composite, and tire | |
| EP4015704A1 (en) | Steel cord/rubber composite, tire, conveyor belt, hose, and rubber crawler | |
| JPH0354974B2 (en) | ||
| CN110591235A (en) | Ethylene propylene diene monomer based wire and cable rubber protective sleeve and preparation method thereof | |
| CA1247822A (en) | Method for improved metal adhesion and metal adhesion retention | |
| JP5848095B2 (en) | Rubber composition for breaker / ply strip layer and pneumatic tire | |
| CN113185756A (en) | Magnetic sensitive rubber composition and preparation method thereof | |
| JPH01257043A (en) | Manufacture of rubber/metal composite material having strong rubber/metal bond | |
| Jeon | Enhancing the adhesion retention by controlling the structure of the adhesion interphase between rubber compound and metal. Part I. Effect of cobalt salt | |
| CN116731405B (en) | Tire cord fabric sizing composition, mixing method thereof and all-steel radial tire | |
| US11433706B2 (en) | Composite and pneumatic tire | |
| CN114672074B (en) | Rubber composition containing xylene modified phenolic resin and application thereof | |
| CN115895175A (en) | Rubber adhesive, rubber composition and non-tire rubber product | |
| JP2016008244A (en) | Rubber composition for tire and pneumatic tire using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |