CN115287902A - Semi-hard thread rope and fabric, elastic product and surface treatment agent thereof - Google Patents

Abstract

The invention belongs to the field of composite materials, and in particular relates to a semi-hard cord and an elastomer product treated with a surface treatment agent. The semi-rigid cord is treated with a surface treatment agent, and the specific stiffness of the semi-rigid cord is less than or equal to 12 mgf/dtex; the components of the surface treatment agent include an aqueous dispersion of blocked aliphatic isocyanate, and/or An aqueous dispersion of blocked aliphatic isocyanate, the components of the aqueous dispersion of blocked aliphatic isocyanate include blocked aliphatic isocyanate and water. By treating the cord with a self-emulsifying, blocked aliphatic isocyanate-containing aqueous dispersion surface treatment, the cord has a stiffness equivalent to that of an aromatic isocyanate-treated cord treated with an organic solvent, equivalent to that of a solvent-based Aromatic isocyanate cord.

Description

A kind of semi-rigid cord and its fabric and elastic product, surface treatment agent

technical field

The invention belongs to the field of cords for rubber reinforcement, in particular to a semi-hard cord, its fabric, elastic products, and a surface treatment agent.

Background technique

The rubber-based transmission belt used to transmit power, also known as V-belt, is reinforced with continuous long fibers. As in the patent US9927002B2, the cord made of continuous long fiber twisting. The reinforcing cords need to be surface treated with an adhesive to provide the necessary bond to the rubber matrix.

Among rubber products, for example, tires, tapes, hoses and air springs are composed of rubber and reinforcing fibers, threads or fabrics such as cord fabric or canvas. The rubber matrix must have good adhesion with reinforcing fibers and other materials to ensure that cavitation delamination and other failure phenomena will not occur during use.

Usually there are soft ropes and hard ropes. Soft cords are mainly used on cloth-wrapped tapes where the finished tape is wrapped with a layer of rubber-coated fabric, while hard cords are mainly used on cut-edge tapes that do not require wrapping. However, some wrapped cloth belts, such as the power transmission belt of the washing machine, need to enhance the stiffness of the cord to maintain the stiffness of the rubber belt, and at the same time require the cord to have sufficient softness to maintain a certain elongation. The thread that meets this use requirement The rope is called semi-hardened rope.

At present, the surface treatment agent using semi-hardened cords is made of aromatic polyisocyanate dissolved in diphenylmethane diisocyanate, or polyaromatic isocyanate dissolved in organic solvent toluene, but it is not safe to use organic solvents such as toluene. It is easy to burn or explode, and is harmful to the environment and health. Therefore, it is necessary to develop an inorganic solvent-based hardening agent.

Contents of the invention

The application provides a surface treatment agent and hard ropes and elastomer products treated with the same, in order to solve the technical problem in the prior art that the raw material of the surface treatment agent for ropes is an organic solvent.

In the first aspect, the application provides a semi-hard cord, the semi-hard cord is treated with a surface treatment agent, and the specific stiffness of the semi-hard cord is ≤12mgf/dtex; the group of the surface treatment agent Parts include aqueous dispersions of blocked aliphatic isocyanates, and/or, aqueous dispersions of blocked aliphatic isocyanates.

Optionally, the raw material of the blocked aliphatic isocyanate includes trimer of hexamethylene diisocyanate; the raw material of the aqueous dispersion of the blocked aliphatic isocyanate also includes butanone oxime, caprolactam and lutim Any of the azoles.

Optionally, the components of the surface treatment agent include: an aqueous dispersion of blocked aliphatic isocyanate, water and a synergist, and the synergist is glycidyl ether and styrene-butadiene-vinyl Any of the pyridine copolymer emulsions.

Optionally, in the surface treatment agent, the mass fraction of blocked aliphatic isocyanate is 0.5-7%, and/or, the mass fraction of aliphatic isocyanate in the surface treatment agent is 0.15%-1.5%.

In a second aspect, the present application provides a fabric, the fabric is composed of the semi-rigid cord described in the first aspect, and the specific stiffness of the semi-rigid cord in the fabric is ≤12mgf/dtex.

In a third aspect, the present application provides an elastomeric product, the components of which include the semi-rigid cord described in the first aspect or the fabric described in the second aspect.

In a fourth aspect, the present application provides an application of a surface treatment agent in the treatment of cords, the application comprising: treating the cords with a surface treatment agent, and the specific stiffness of the cords after the treatment is ≤12mgf/dtex; The component of said surface treatment agent comprises the aqueous dispersion of blocked type aliphatic isocyanate, and/or the aqueous dispersion of blocked type aliphatic isocyanate, and the component of the aqueous dispersion of described blocked type aliphatic isocyanate comprises blocked type aliphatic isocyanate and water;

The raw material of the blocked aliphatic isocyanate comprises a trimer of hexamethylene diisocyanate;

The raw material of the aqueous dispersion of the blocked aliphatic isocyanate also includes any one of butanone oxime, caprolactam and dimethylpyrazole;

and / or,

The components of the surface treatment agent include: blocked aliphatic isocyanate aqueous dispersion, water and synergist, and the synergist is glycidyl ether and styrene-butadiene-vinylpyridine copolymer emulsion any of them.

In a fifth aspect, the present application provides a method for regulating the specific stiffness of a semi-rigid cord, the method comprising the following steps:

Obtain surface treatment agent, the component of described surface treatment agent comprises the water dispersion of blocked type aliphatic isocyanate, and/or the water dispersion of blocked type aliphatic isocyanate, the water dispersion of described blocked type aliphatic isocyanate The components of the body include blocked aliphatic isocyanate and water;

Carry out dipping treatment to the cord with the dipping solution containing the surface treatment agent described in the fourth aspect;

The mass concentration of isocyanate and/or isocyanate in the dipping solution is controlled to a predetermined concentration, so as to realize regulation and control of the specific stiffness of the semi-rigid cord.

Optionally, the mass fraction of isocyanate in the impregnation solution is 0.15%-1.5%.

Optionally, the mass fraction of isocyanate in the dipping solution is 0.5%-7%.

Compared with the prior art, the above-mentioned technical solutions provided by the embodiments of the present application have the following advantages:

The surface treatment agent provided by the embodiment of the present application uses a self-emulsifying aqueous dispersion containing aliphatic isocyanate or an aqueous dispersion surface treatment agent of a blocked aliphatic isocyanate to treat the cord, and the length of the cord is equivalent to The organic solvent dissolves the thread treated with aromatic isocyanate, which solves the problem in the prior art that the aqueous dispersion of blocked aliphatic isocyanate or the aqueous dispersion containing aliphatic isocyanate is too soft to treat the thread with aromatic isocyanate The technical bias of cord hardness has realized that blocked aliphatic isocyanate-treated fibers can reach the hardness of organic solvent solutions of aromatic polyisocyanates.

Description of drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description serve to explain the principles of the invention.

In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, for those of ordinary skill in the art, In other words, other drawings can also be obtained from these drawings without paying creative labor.

Fig. 1 is a schematic flow chart of regulating the specific stiffness of a semi-rigid wire rope provided by the embodiment of the present application;

Fig. 2 is a schematic flow chart of a dipping treatment method provided in the embodiment of the present application;

Fig. 3 is a schematic diagram of the cross-sectional structure of the rubber product provided by the embodiment of the present application.

Detailed ways

In order to make the purposes, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments It is a part of the embodiments of this application, but not all of them. Based on the embodiments in the present application, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present application.

According to a typical embodiment of the present invention, a semi-hard cord is provided, the semi-hard cord is treated with a surface treatment agent, and the specific stiffness of the semi-hard cord is ≤12mgf/dtex; the surface The components of the treating agent include an aqueous dispersion of blocked aliphatic isocyanate, and/or, an aqueous dispersion of blocked aliphatic isocyanate.

Specifically, the components of the aqueous dispersion of blocked aliphatic isocyanate include blocked aliphatic isocyanate and water.

By using the aqueous dispersion of blocked aliphatic isocyanate as a surface treatment agent for the treated cord or fabric, the specific stiffness of the treated semi-rigid cord does not exceed 12 milligram force (mgf)/dtex, after treatment The properties of the obtained semi-rigid cord include: a stiffness of 4-12mgf/dtex and an elongation of ≥4% when the load is 200N, which better meet the application requirements.

In some embodiments, the raw material of the blocked aliphatic isocyanate includes trimer of hexamethylene diisocyanate; the raw material of the aqueous dispersion of the blocked aliphatic isocyanate also includes butanone oxime, caprolactam and dimethyl Any of the base pyrazoles.

Hexamethylene diisocyanate reacts with any one of butanone oxime and dimethylpyrazole to obtain an aqueous dispersion of aliphatic isocyanate, which has self-emulsifying properties and can be used as a surface treatment agent to treat rubber cords.

The mechanism for choosing butanone oxime is that the oxime group of butanone oxime can react with isocyanate, and after the reaction, the isocyanate can be protected at room temperature, but it can dissociate and release isocyanate at about 150 degrees Celsius, and the released isocyanate Can react with the target substance.

The mechanism of choosing dimethylpyrazole lies in the fact that the oxime group of butanone oxime can react with isocyanate. After the reaction, the isocyanate can be protected at room temperature, but it can be dissociated and released at about 130 degrees Celsius. Isocyanate is released, and the released isocyanate can react with the target substance.

Specifically, the mass fraction of the blocked aliphatic isocyanate in the aqueous dispersion of the blocked aliphatic isocyanate can be 44%-46%; The score can be 37%-39%. The raw material in the aqueous dispersion of blocked aliphatic isocyanate includes a trimer of hexamethylene diisocyanate (HDI), part of the isocyanate groups on the trimer and hydrophilic groups such as low molecular weight poly Oxyethylene ether reacts to produce self-emulsifying ability in water, other isocyanate groups react with butanone oxime, emulsify and dilute with water to 44%-46% non-volatile content, preferably 45% non-volatile content ; The isocyanate group in the aqueous dispersion of the blocked aliphatic isocyanate reacts with dimethylpyrazole, emulsifies and dilutes with water to a non-volatile content of 37%-39%.

It should be noted that the blocking group in the blocked aliphatic isocyanate is at least one of dimethylpyrazole, caprolactam or butanone oxime. The liquid of the aqueous dispersion of blocked aliphatic isocyanate contains an epoxy compound and a styrene-butadiene-vinylpyridine copolymer.

In some embodiments, the components of the surface treatment agent include: an aqueous dispersion of blocked aliphatic isocyanate, water and a synergist, and the synergist is glycidyl ether and styrene-butadiene- Any of the vinylpyridine copolymer emulsions.

Specifically, glycidyl ether is a water-soluble epoxy compound, and the EX313 model of Nagase Chemical Company can be used; the mass fraction of non-volatile components in the styrene-butadiene-vinylpyridine copolymer emulsion is 40% , the content of vinylpyridine in the copolymer is 15%, and the model produced by Trinseo can be used, referred to as Pyratex240.

It should be noted that: the preparation method containing blocked aliphatic isocyanate, glycidyl ether, and water can be: first weigh water, then add glycidyl ether, stir to disperse and dissolve, then add the water dispersion of blocked aliphatic isocyanate Stir well.

In addition, the preparation method of the emulsion containing blocked aliphatic isocyanate, water and styrene-butadiene-vinylpyridine copolymer can be: first weigh the water, then add the water dispersion of blocked aliphatic isocyanate, stir and disperse , and then add the emulsion of styrene-butadiene-vinylpyridine copolymer and stir evenly.

The mechanism of choosing glycidyl ether is that this type of epoxy compound has an aqueous solution and can form a uniform solution in water, which is conducive to penetration into the fiber to form better cohesion in the tow.

The reason for choosing the styrene-butadiene-vinylpyridine copolymer emulsion is that it is a commonly used polymer binder for fiber surface treatment, which can enhance the adhesion of the fiber to the matrix material such as rubber.

In some embodiments, in the surface treatment agent, the mass fraction of blocked aliphatic isocyanate is 0.5-7%, and/or, the mass fraction of aliphatic isocyanate in the surface treatment agent is 0.15%-1.5% %.

The mechanism for controlling the mass fraction of blocked aliphatic isocyanate in the water dispersion of blocked isocyanate to not exceed 7% is that too high concentration of blocked isocyanate will lead to too high hardness of the cord after dipping.

In a second aspect, the present application provides a fabric composed of the semi-rigid cord described in the first aspect, and the specific stiffness of the semi-rigid cord in the fabric is ≤12 mgf/dtex.

In a third aspect, the present application provides an elastomeric product, the components of which include the semi-rigid cord described in the first aspect or the fabric described in the second aspect.

In a fourth aspect, the present application provides an application of a surface treatment agent in the treatment of cords, the application comprising: treating the cords with a surface treatment agent, and the specific stiffness of the cords after the treatment is ≤12mgf/dtex; The component of said surface treatment agent comprises the aqueous dispersion of blocked type aliphatic isocyanate, and/or the aqueous dispersion of blocked type aliphatic isocyanate, and the component of the aqueous dispersion of described blocked type aliphatic isocyanate comprises blocked type aliphatic isocyanate and water;

The raw material of the blocked aliphatic isocyanate comprises a trimer of hexamethylene diisocyanate;

The raw material of the aqueous dispersion of the blocked aliphatic isocyanate also includes any one of butanone oxime, caprolactam and dimethylpyrazole;

and / or,

The components of the surface treatment agent include: blocked aliphatic isocyanate aqueous dispersion, water and synergist, and the synergist is glycidyl ether and styrene-butadiene-vinylpyridine copolymer emulsion any of them.

In a fifth aspect, the present application provides a method for regulating the specific stiffness of a semi-rigid cord, as shown in Figure 1, the method comprising the following steps:

Obtain surface treatment agent, the component of described surface treatment agent comprises the water dispersion of blocked type aliphatic isocyanate, and/or the water dispersion of blocked type aliphatic isocyanate, the water dispersion of described blocked type aliphatic isocyanate The components of the body include blocked aliphatic isocyanate and water;

Carry out dipping treatment to the cord with the dipping solution containing the surface treatment agent;

The mass concentration of isocyanate and/or isocyanate in the dipping solution is controlled to a predetermined concentration, so as to realize regulation and control of the specific stiffness of the semi-rigid cord.

In some embodiments, the mass fraction of isocyanate in the impregnating liquid is 0.15%-1.5%, and/or, the mass fraction of isocyanate in the impregnating liquid is 0.5%-7%.

In some embodiments, the mass fraction of blocked aliphatic isocyanate in the surface treatment agent is ≤7%.

In some embodiments, the mass fraction of aliphatic isocyanate in the surface treatment agent is 0.15%-1.5%.

The mechanism for controlling the mass fraction of blocked aliphatic isocyanate in the water dispersion of blocked isocyanate to not exceed 7% is that too high concentration of blocked isocyanate will lead to too high hardness of the cord after dipping.

The mass fraction of aliphatic isocyanate in the surface treatment agent is 0.15%-1.5%. The concentration of isocyanate will cause the hardness of the cord to be too low, which does not achieve the treatment effect, and is still in the soft state when it is not treated. Generally, the materials of the untreated cord include but are not limited to: polyester, aromatic polyamide or polyamide.

According to a typical implementation of the present invention, a method for regulating the specific stiffness of a semi-rigid wire rope is provided, and the method includes the following steps:

Obtain surface treatment agent, the component of described surface treatment agent comprises the aqueous dispersion of blocked type aliphatic isocyanate, and/or, the aqueous dispersion of blocked type aliphatic isocyanate, the water dispersion of described blocked type aliphatic isocyanate The components of the dispersion include blocked aliphatic isocyanate and water;

Dip the wire rope with a dipping solution containing a surface treatment agent;

The mass concentration of isocyanate and/or isocyanate in the dipping solution is controlled to a predetermined concentration, so as to realize regulation and control of the specific stiffness of the semi-rigid cord.

Specifically, the thread can be two strands of 1100dtex polyethylene terephthalate continuous long fibers twisted, the twisting direction is the Z direction, and the twist is 190 twists/meter. Then 3 strands of this twisted fiber are twisted along the reverse S direction, and the twist is 110 twists/meter, and the obtained string product can be expressed as PET1100dtex/2x3. The chemical composition of the cord can be at least one of polyester, aromatic polyamide or polyamide. From the initial soft, with a certain strength, elasticity and elongation, through the method of this application, the specific stiffness of the treated semi-hard cord is ≤12mgf/dtex, and the elongation under the load of 200N is greater than 4%.

By controlling the mass concentration of isocyanate in the impregnation solution, the isocyanate reacts with the fiber, and due to the mechanism of releasing the isocyanate group to react with the fiber at high temperature, the purpose of regulating the specific stiffness of the semi-rigid cord can be achieved.

In some embodiments, the mass fraction of isocyanate in the impregnating liquid is 0.15%-1.5%, and/or, the mass fraction of isocyanate in the impregnating liquid is 0.5%-7%.

By controlling the mass fraction of isocyanate in the impregnating liquid to 0.15%-1.5% and/or by controlling the mass fraction of isocyanate in the impregnating liquid to be 0.5%-7%, it has the positive effect of being able to moderately react with the fiber, so that the cord does not To too soft or too hard.

According to a typical embodiment of the present invention, a semi-rigid cord is provided, the semi-rigid cord is treated with the surface treatment agent described in the first aspect, and the specific stiffness of the semi-rigid cord is ≤12mgf/ dtex.

According to a typical embodiment of the present invention, a fabric is provided, the fabric is treated with the surface treatment agent according to the first aspect, and the specific stiffness of the semi-hard cord in the fabric is ≤12mgf/dtex.

According to a typical embodiment of the present invention, an elastic product is provided, and the components of the elastic product include the semi-rigid cord described in the third aspect or the fabric described in the fourth aspect.

Specifically, elastomeric articles include, but are not limited to, tires or rubber, such as belts, conveyor belts, conveyor belts, drive belts, hoses, straps, conveyor belts, and bellows.

The method of the present invention will be described in detail below in conjunction with examples, comparative examples and experimental data.

Experimental reagents include: IL-6, an aqueous dispersion of caprolactam-blocked diphenylmethane diisocyanate, 50% non-volatile content, produced by EMS AG, Switzerland; WANNATE® PM200, polymerized diphenylmethane diisocyanate, expressed It is pMDI, produced by Wanhua Chemical Company; toluene and water, preferably soft water.

Example 1

The embodiment of the present application provides a semi-rigid cord, the semi-hard cord is treated with a surface treatment agent, and the specific stiffness of the semi-hard cord is ≤12 mgf/dtex; the components of the surface treatment agent include Aqueous dispersion of blocked aliphatic isocyanate.

The components of the aqueous dispersion of blocked aliphatic isocyanate include blocked aliphatic isocyanate and water, and the content of isocyanate in the aqueous dispersion of blocked aliphatic isocyanate is 4.3% by weight. The raw material of the aqueous dispersion of blocked aliphatic isocyanate includes trimer of hexamethylene diisocyanate (HDI), part of the isocyanate group on the trimer and hydrophilic group such as low molecular weight polyoxyethylene ether The reaction results in a self-emulsifying ability in water, where the isocyanate group reacts with butanone oxime and emulsifies and dilutes with water to a non-volatile content of 44%-46%.

Mix the aqueous dispersion of blocked aliphatic isocyanate with water at a mass ratio of 2:98 to obtain an impregnating liquid; use the impregnating liquid containing a surface treatment agent to impregnate the cord, as shown in Figure 2; control the isocyanate in the impregnating liquid The mass concentration of cyanate and/or isocyanate is a predetermined concentration, so as to realize regulation and control of the specific stiffness of the semi-rigid cord; the cut surface of the obtained cord product is shown in FIG. 3 .

Example 2

The embodiment of the present application differs from the embodiment 1 in that: the aqueous dispersion of blocked isocyanate and water are mixed at a mass ratio of 5:95 to obtain an impregnating solution.

Example 3

The embodiment of the present application differs from the embodiment 1 in that: the aqueous dispersion of blocked isocyanate and water are mixed at a mass ratio of 15:85 to obtain an impregnation solution.

Example 4

The difference between the embodiment of the present application and the embodiment 1 is that the aqueous dispersion of blocked isocyanate, glycidyl ether and soft water are mixed in a mass ratio of 5:2:93 to obtain an impregnation solution.

Example 5

The difference between the embodiment of the present application and embodiment 1 is that the aqueous dispersion of blocked isocyanate, styrene-butadiene-vinylpyridine copolymer emulsion and soft water are mixed in a mass ratio of 6:40:54 to obtain impregnated liquid.

Example 6

The difference between the embodiment of the present application and embodiment 1 is that the aqueous dispersion of blocked isocyanate, styrene-butadiene-vinylpyridine copolymer emulsion and soft water are mixed in a mass ratio of 15:40:45 to obtain impregnated liquid.

Example 7

The embodiment of the present application provides a semi-rigid cord, the semi-hard cord is treated with a surface treatment agent, and the specific stiffness of the semi-hard cord is ≤12 mgf/dtex; the components of the surface treatment agent include Aqueous dispersion of blocked aliphatic isocyanate. The component of the aqueous dispersion of described blocked isocyanate comprises blocked isocyanate and soft water, and the content of isocyanate in the aqueous dispersion of blocked isocyanate is 4.3% by weight percentage; The raw material of the aqueous dispersion of blocked aliphatic isocyanate Including the trimer of hexamethylene diisocyanate (HDI), some of the isocyanate groups on the trimer react with hydrophilic groups such as low molecular weight polyoxyethylene ether to produce self-emulsifying ability in water, and the rest The isocyanate group reacts with dimethylpyrazole and emulsifies and dilutes with water to a non-volatile content of 37%-39%.

Comparative example 1

The comparative example of the present application provides an impregnation solution, the chemical composition of the impregnation solution is 3% pMDI/toluene; the toluene solution of pMDI: weigh 47.5 grams of toluene, and then add 2.5 grams of pMDI into toluene to fully dissolve. Expressed as 5% pMDI/toluene, dilute 5% pMDI/toluene with toluene to 3% pMDI/toluene.

Comparative example 2

The comparative example of the present application provides an impregnation solution, the chemical composition of which is an aqueous dispersion of caprolactam-blocked diphenylmethane diisocyanate (IL-6) and water, the mass ratio of which is 2:98.

Comparative example 3

The comparative example of the present application provides an impregnating solution, the chemical composition of which is an aqueous dispersion of caprolactam-blocked diphenylmethane diisocyanate (IL-6) and water, the mass ratio of which is 6:94.

Comparative example 4

The comparative example of the present application provides an impregnation solution, the chemical composition of which is an aqueous dispersion of caprolactam-blocked diphenylmethane diisocyanate (IL-6) and water, the mass ratio of which is 15:85.

Comparative example 5

The comparative example of the present application provides an impregnation solution, the chemical composition of which is caprolactam-blocked diphenylmethane diisocyanate aqueous dispersion (IL-6), water and styrene-butadiene-vinylpyridine Copolymer emulsion (Pyratex 240), its mass ratio is 6:40:54.

Comparative example 6

The comparative example of the present application provides an impregnation solution, the chemical composition of which is caprolactam-blocked diphenylmethane diisocyanate aqueous dispersion (IL-6), water and styrene-butadiene-vinylpyridine Copolymer emulsion (Pyratex 240) with a mass ratio of 15:40:45.

Comparative example 7

The comparative example of the present application provides a dipping solution, the chemical composition of which is caprolactam-blocked diphenylmethane diisocyanate aqueous dispersion (IL-6), water and glycidyl ether, and its mass ratio is 6: 2:92.

The component of the surface treatment agent of embodiment and comparative example is as shown in table 1 and table 2, is configured with dipping solution with the surface treatment agent that makes, and the component of dipping solution comprises blocked type aliphatic isocyanate and water, can further Containing glycidyl ether and/or styrene-butadiene-vinylpyridine polymers, impregnated with impregnating liquid, the method consists of putting PET1100/2x3 cords in a single cord impregnation machine (manufactured by Lizler Fangdian ) is impregnated with the adhesive treatment liquid, then dried at 160 degrees Celsius for 1 minute, and then dried at 247 degrees Celsius for 1 minute before winding.

Test the cord after dipping, and test the hardness, or stiffness, of the cord, according to GB/T 33099-2016. The results obtained are expressed in grams force (gf). The obtained result is converted into milligram force (mgf), and then divided by the total denier of the tested cord expressed in decitex (dtex), to obtain the specific stiffness mgf/dtex. Practical experience has proved that when the specific stiffness of the treated cord does not exceed 12 milligram force (mgf)/dtex, the stiffness and flexibility of the cord can better meet the requirements of the process and application. Generally, when the cord with better stiffness is used for rubber products, the incision of the rubber sample is more neat. For semi-hard cord, both hardness and flexibility should be paid attention to, so as to comprehensively control its specific stiffness to achieve Hardness and flexibility requirements; conventionally, the specific stiffness of the semi-hard cord is not higher than 12mgf/dtex, more preferably 4-10mgf/dtex.

In addition, the wire rope is also subjected to a tensile test according to GB/T 32108-2015, and the elongation at break and the constant load elongation at 200 Newton (N) are obtained according to the standard test. The elongation at break reflects the extent to which the cord can be stretched when it is stretched to break, and the constant load elongation at 200N reflects the extent of the cord's elongation under the load. These two performance indicators reflect the elasticity of the cord. The higher these two numbers, the better the elasticity of the cord.

The test results are shown in Table 1 and Table 2.

Table 1 is the test results of the comparative example.

project Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Isocyanate content in impregnation solution (mass fraction) 5% 1% 3% 7.5% 3% 7.5% 3% Isocyanate content in impregnation solution (mass fraction) 1.55% 0.09% 0.26% 0.66% 0.26% 0.66% 0.26% Stiffness (gf)(GB/T 33099-2016) 32.9 20.2 32.3 56.8 28.3 50.2 35.8 Specific stiffness (mgf/dtex) 5.0 3.0 4.9 8.6 4.3 7.6 5.4 200N constant load elongation 3.74% 3.91% 4.56% 4.25% 4.67% 4.51% 4.71% elongation at break 8.82% 9.21% 9.01% 8.93% 9.21% 9.07% 9.69%

Table 2 is the test result of embodiment.

project Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Isocyanate content in impregnation solution (mass fraction) 0.9% 2.25% 6.75% 2.25% 2.7% 6.75% 5.7% Isocyanate content in impregnation solution (mass fraction) 0.19% 0.47% 1.42% 0.47% 0.56% 1.42% 1.29% Stiffness (gf) (GB/T 33099-2016 28.3 35.7 68.7 39.3 36.1 58.7 59.3 Specific stiffness (mgf/dtex) 4.3 5.4 10.4 5.9 5.5 8.9 9.0 200N constant load elongation 4.61% 4.58% 4.65% 5.21% 4.47% 4.74% 4.69% elongation at break 11.30% 11.10% 9.85% 11.35% 11.31% 11.02% 10.98%

It can be seen from the table that treating fibers with internally emulsified water-based blocked aliphatic isocyanate can achieve the hardness of treating with an organic solvent solution of aromatic polyisocyanate (comparative example 1 and all examples). In addition, comparing the aqueous dispersions of internally emulsified blocked aliphatic isocyanate and blocked aromatic isocyanate, it is generally found that aliphatic compounds are softer than aromatics, but it can be seen from the results that to achieve the same treatment half Hard cord specific stiffness, the consumption of the inner emulsified aliphatic isocyanate of use is lower than the consumption of the water dispersion of blocked type aromatic isocyanate (comparative example 2 is compared with embodiment 1, comparative example 3 is compared with embodiment 2 , Comparative Example 4 is compared with Example 3, Comparative Example 7 is compared with Example 4, Comparative Example 5 is compared with Example 5, and Comparative Example 6 is compared with Example 6.

It should be noted that in this article, relative terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply these No such actual relationship or order exists between entities or operations. Furthermore, the term "comprises", "comprises" or any other variation thereof is intended to cover a non-exclusive inclusion such that a process, method, article, or apparatus comprising a set of elements includes not only those elements, but also includes elements not expressly listed. other elements of or also include elements inherent in such a process, method, article, or device. Without further limitations, an element defined by the phrase "comprising a ..." does not exclude the presence of additional identical elements in the process, method, article or apparatus comprising said element.

The above descriptions are only specific embodiments of the present invention, so that those skilled in the art can understand or implement the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Accordingly, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims (10)

1. The semi-hard wire rope is characterized in that the semi-hard wire rope is treated by a surface treatment agent, the specific stiffness of the semi-hard wire rope is less than or equal to 12mgf/dtex, and the surface treatment agent comprises a water dispersion of blocked aliphatic isocyanate and/or a water dispersion of blocked aliphatic isocyanate.

2. The semi-rigid cord according to claim 1, wherein the blocked aliphatic isocyanate starting material comprises a trimer of hexamethylene diisocyanate; the raw material of the water dispersion of the blocked aliphatic isocyanate also comprises any one of butanone oxime, caprolactam and dimethylpyrazole.

3. The semi-rigid cord according to claim 2, wherein the surface treatment comprises the components of: the water-based emulsion paint comprises a closed aliphatic isocyanate water dispersion, water and a synergist, wherein the synergist is any one of glycidyl ether and styrene-butadiene-vinyl pyridine copolymer emulsion.

4. The semi-hard cord according to claim 1, wherein the surface treatment agent contains 0.5 to 7% by mass of blocked aliphatic isocyanate, and/or the surface treatment agent contains 0.15 to 1.5% by mass of aliphatic isocyanate.

5. A fabric, characterized in that it is composed of semi-stiff cords as claimed in any one of claims 1 to 5, the semi-stiff cords of said fabric having a stiffness of 12mgf/dtex or less.

6. An elastomeric article characterized in that the components of said elastomeric article comprise a semi-rigid cord as claimed in any one of claims 1 to 5 or a fabric as claimed in claim 6.

7. Use of a surface treatment agent for treating a strand, said use comprising: treating the thread rope with a surface treating agent, wherein the specific stiffness of the treated thread rope is less than or equal to 12mgf/dtex, the component of the surface treating agent comprises a water dispersion of blocked aliphatic isocyanate and/or a water dispersion of blocked aliphatic isocyanate, and the component of the water dispersion of blocked aliphatic isocyanate comprises blocked aliphatic isocyanate and water;

the raw material of the blocked aliphatic isocyanate comprises trimer of hexamethylene diisocyanate;

the raw material of the water dispersion of the closed aliphatic isocyanate also comprises any one of butanone oxime, caprolactam and dimethylpyrazole;

and/or the presence of a gas in the gas,

the components of the surface treating agent comprise: the water dispersion of the blocked aliphatic isocyanate, water and a synergist, wherein the synergist is any one of glycidyl ether and styrene-butadiene-vinyl pyridine copolymer emulsion.

8. A method of controlling the stiffness of a semi-rigid cord, comprising the steps of:

obtaining a surface treating agent, wherein the components of the surface treating agent comprise an aqueous dispersion of blocked aliphatic isocyanate and/or an aqueous dispersion of blocked aliphatic isocyanate;

dipping the cord with a dipping solution containing the surface treating agent according to claim 7;

and controlling the mass concentration of isocyanic acid radical and/or isocyanate in the impregnation liquid to be a preset concentration so as to realize the control of the specific stiffness of the semi-rigid cord.

9. The method according to claim 8, wherein the mass fraction of isocyanate groups in the impregnation liquid is 0.15-1.5%.

10. The method as claimed in claim 8, wherein the mass fraction of isocyanate in the impregnation liquid is 0.5% to 7%.

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