CN111733606A - High-strength polyvinyl chloride artificial leather and preparation method thereof - Google Patents

Abstract

The invention discloses high-strength polyvinyl chloride artificial leather which comprises base cloth and a PVC surface layer, wherein the base cloth is woven by adopting lining warp yarns, lining weft yarns, oblique lining yarns and looping yarns; the lining warp yarns, the lining weft yarns and the oblique lining yarns adopt polyester yarns, the looping yarns adopt polyester-nylon superfine fibers, the looping yarns are woven into warp knitting ground tissues, and the looping yarns bind the lining warp yarns which are lined in parallel along the warp direction, the lining weft yarns which are lined in parallel along the weft direction and the oblique lining yarns which are lined in obliquely; the PVC surface layer is prepared from the following raw materials: 100 parts of PVC resin, 20-50 parts of plasticizer, 5-15 parts of wollastonite powder, 0.2-0.5 part of modified multi-walled carbon nanotube, 1-3 parts of stabilizer and 0-2 parts of foaming agent; the modified multi-walled carbon nanotube is prepared by modifying the surface of the multi-walled carbon nanotube by using MMA-BA-GMA terpolymer treating fluid. The artificial leather has high strength, is not easy to crack when being punched or cut, is not easy to tear in the using process, and has good structure retentivity and high strength retention rate.

Description

High-strength polyvinyl chloride artificial leather and preparation method thereof

Technical Field

The invention belongs to the technical field of artificial leather, and particularly relates to high-strength polyvinyl chloride artificial leather and a preparation method thereof.

Background

Since the last 90 s, the polyvinyl chloride (PVC) artificial leather product, which is the first generation artificial leather, is gradually replaced by Polyurethane (PU) artificial leather due to its disadvantages of poor air permeability and hygroscopicity, no recyclability, no environmental protection requirement, etc., and the PVC artificial leather is reduced to less than 40% from the initial almost 100% market share. However, in recent years, due to the rising price of raw materials of PU artificial leather and the poor performance of partial properties such as hydrolysis resistance and weather resistance, the advantages of hydrolysis resistance, wear resistance, scratch resistance, acid and alkali resistance, flame retardance and the like of PVC artificial leather are exerted, and in addition, the use of environment-friendly plasticizers and various processing aids, the improvement of PVC resin recycling technology and the improvement of waste gas recycling efficiency and the like, the main environmental protection problem is basically solved. Most importantly, the PVC artificial leather has the advantage of relatively low price, so that new vitality and vitality are revived in recent years.

The artificial leather generally comprises a base fabric and a resin layer, wherein the base fabric is generally woven fabric or knitted fabric. When the artificial leather product is produced, holes need to be punched or the synthetic leather material needs to be cut into a required size or pattern, and when the holes are punched or the pattern is cut, yarns of the base cloth are easy to pull out, so that the artificial leather is cracked, the structure cannot be maintained, and the artificial leather product is easy to tear under the action of external force in the using process; in addition, the strength of the resin layer of artificial leather is not ideal, and problems such as cracking are easily caused; therefore, the strength of the existing artificial leather needs to be improved to meet the processing requirements of subsequent products.

Disclosure of Invention

In order to solve the above problems, it is an object of the present invention to provide a high-strength polyvinyl chloride artificial leather and a method for preparing the same, which has high strength, is less likely to crack when punched or cut, is less likely to tear during use, and has good structure retentivity and high strength retention rate.

In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:

a high-strength polyvinyl chloride artificial leather comprises a base cloth and a PVC surface layer;

the base cloth is a warp knitted fabric which is knitted by adopting lining warp yarns, lining weft yarns, oblique lining yarns and looping yarns; the warp lining yarns, the weft lining yarns and the oblique lining yarns adopt polyester yarns, the looping yarns adopt polyester-nylon superfine fibers, the looping yarns are woven into warp knitting ground tissues, the warp lining yarns are lined in parallel along the warp direction of the fabric, the weft lining yarns are lined in parallel along the weft direction of the fabric, the oblique lining yarns are lined in parallel along the oblique direction of the fabric, the warp lining yarns, the weft lining yarns and the oblique lining yarns are not looped, the looping yarns are woven into loops, and the warp lining yarns, the weft lining yarns and the oblique lining yarns are bound;

the PVC surface layer is prepared from the following raw materials in parts by weight: 100 parts of PVC resin, 20-50 parts of plasticizer, 5-15 parts of wollastonite powder, 0.2-0.5 part of modified multi-walled carbon nanotube, 1-3 parts of stabilizer and 0-2 parts of foaming agent; the modified multi-walled carbon nanotube is prepared by modifying the surface of the multi-walled carbon nanotube by using MMA-BA-GMA terpolymer treating fluid.

Furthermore, the specification of the polyester yarn is 35D/36F, and the specification of the polyester-nylon ultrafine fiber yarn is 35D/72F.

Further, the warp knitting ground structure is a warp flat structure or a warp pile structure.

Furthermore, the oblique angle of the oblique lining yarn is within-45 degrees to +45 degrees.

Further, the plasticizer is selected from one or a combination of two or more of phthalate, phosphate and epoxy plasticizers.

Further, the stabilizer is selected from one or a combination of two or more of calcium and zinc, metal soap and rare earth stabilizer.

The invention also provides a preparation method of the high-strength polyvinyl chloride artificial leather, which comprises the following steps:

(1) putting the preparation raw materials of the PVC surface layer into a high-speed stirrer according to the mass part ratio for high-speed mixing and stirring, wherein the stirring temperature is 80-110 ℃, and the stirring time is 100-200 s, so as to obtain a mixed material;

(2) discharging the mixed material obtained in the step (1) into an internal mixer for mixing at the mixing temperature of 100-150 ℃, discharging the mixed material into an open mill after mixing is finished, plasticating the mixed material at the temperature of 100-150 ℃ through two open mills in sequence, conveying the plasticated mixed material to a calender for calendering to obtain a sheet material, wherein the calendering temperature is 120-180 ℃, attaching the sheet material obtained after calendering to base cloth to prepare a semi-finished product, conveying the semi-finished product to a foaming embossing machine, and performing foaming embossing treatment at the temperature of 160-210 ℃.

The invention has the beneficial effects that:

the base fabric is a multi-axial warp knitted fabric, the warp knitted fabric is knitted by lining warp yarns, lining weft yarns, oblique lining yarns and loop-forming yarns, wherein the loop-forming yarns are knitted into warp knitted ground texture, the lining warp yarns are parallel along the warp direction of the fabric and are inserted in a straightened state in the knitting process of the loop-forming yarns, the lining weft yarns are parallel along the weft direction of the fabric and are inserted in a straightened state, the oblique lining yarns are parallel along the oblique direction of the fabric and are inserted in a straightened state, the lining warp yarns, the lining weft yarns and the oblique lining yarns are not looped, the loop-forming yarns are knitted into loops, and the loop-forming yarns bind the lining warp yarns, the lining weft yarns and the oblique lining yarns; therefore, the weave structure of the base cloth is a structure with mutually locked and enhanced yarns, and when the base cloth is subjected to external force effects such as breakdown and the like, the yarns are not easy to take out and take off, so that the problems of cracking, tearing and the like can be avoided, the strength of the whole synthetic leather is improved, and the processing requirements of subsequent products can be better met.

In the aspect of raw materials of the base cloth, the warp and weft interlinings and the oblique interlining in the base cloth adopt polyester yarns, and the looping yarns adopt polyester-nylon ultrafine fiber yarns; the polyester yarn and the polyester-nylon ultrafine fiber yarn are matched, and the friction force among a plurality of fibers in the yarn is increased from the raw materials, so that the strength of the base cloth is increased, and the structure retentivity and the strength retentivity of the base cloth are improved.

In addition, the modified multi-walled carbon nanotube is added into the PVC surface layer, and is prepared by modifying the multi-walled carbon nanotube by using MMA-BA-GMA terpolymer treating fluid; the epoxy group on the MMA-BA-GMA terpolymer reacts with-OH and-COOH functional groups on the multi-walled carbon nanotube, so that the multi-walled carbon nanotube is coated with an MMA-BA-GMA organic layer after modification; under the action of an MMA-BA-GMA organic layer, the dispersibility and stability of the modified multi-walled carbon nano tube in a PVC resin matrix are greatly enhanced, a three-dimensional network particle structure is formed in the PVC resin matrix, a larger external force can be borne, the effect of reinforcing and toughening is achieved, and the mechanical properties such as the tensile strength, the fracture productivity and the like of a PVC surface layer can be improved. Wollastonite powder is added into the PVC surface layer of the invention and is used as an inorganic filler, so that the impact strength, the tensile strength and the like of the PVC surface layer can be improved.

Drawings

Fig. 1 is a schematic view of the weave structure of the base fabric in the high-strength polyethylene artificial leather of example 1.

Detailed Description

The technical solutions in the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides high-strength polyvinyl chloride artificial leather, which comprises base cloth and a PVC surface layer;

the base cloth is a warp knitted fabric which is knitted by adopting lining warp yarns, lining weft yarns, oblique lining yarns and looping yarns; the method comprises the following steps that polyester yarns are adopted as lining warp yarns, lining weft yarns and oblique lining yarns, polyester-nylon superfine fibers are adopted as looping yarns, the looping yarns are woven into warp knitting ground tissues, the lining warp yarns are parallel to the warp direction of a fabric and are inserted in a straightened state in the weaving process of the looping yarns, the lining weft yarns are parallel to the weft direction of the fabric and are inserted in a straightened state, the oblique lining yarns are parallel to the oblique direction of the fabric and are inserted in a straightened state, the lining warp yarns, the lining weft yarns and the oblique lining yarns are not looped, the looping yarns are woven into loops, and the lining warp yarns, the lining weft yarns and the oblique lining yarns are bound;

the PVC surface layer is prepared from the following raw materials in parts by weight: 100 parts of PVC resin, 20-50 parts of plasticizer, 5-15 parts of wollastonite powder, 0.2-0.5 part of modified multi-walled carbon nanotube, 1-3 parts of stabilizer and 0-2 parts of foaming agent; the modified multi-walled carbon nanotube is prepared by modifying the surface of the multi-walled carbon nanotube by using MMA-BA-GMA terpolymer treating fluid.

Wherein the specification of the polyester yarn is 35D/36F, and the specification of the polyester-nylon superfine fiber yarn is 35D/72F.

Wherein the warp knitting ground structure is a warp flat structure or a warp pile structure.

Wherein the oblique angle of the oblique lining yarn is within-45 degrees to +45 degrees.

Wherein the plasticizer is selected from one or a combination of two or more of phthalate, phosphate and epoxy plasticizers.

Wherein the stabilizer is one or the combination of two or more of calcium and zinc, metal soap and rare earth stabilizer.

Wherein the modification process of the modified multi-walled carbon nanotube comprises the following steps: ultrasonically dispersing a proper amount of carbon nano tube in an acetone solution, adding an MMA (methyl methacrylate) -BA (butyl acrylate) -GMA (glycidyl methacrylate) terpolymer treating solution which accounts for 7% of the mass of the carbon nano tube, then dropwise adding 2-3 drops of triethylamine as a catalyst, heating to 75 ℃ under the protection of nitrogen, carrying out heat preservation reaction for 3 hours, neutralizing the triethylamine with hydrochloric acid after the reaction is finished, washing the reaction solution with deionized water, and drying to obtain the modified multi-wall carbon nano tube.

Hereinafter, the high strength polyvinyl chloride artificial leather and the method for manufacturing the same according to the present invention will be described with reference to specific examples.

Example 1

A high-strength polyvinyl chloride artificial leather comprises a base cloth and a PVC surface layer;

as shown in fig. 1, the base fabric is a warp knitted fabric which is knitted by using warp interlining yarns 1, weft interlining yarns 2, oblique interlining yarns 3 and loop-forming yarns 4; the warp interlining yarns 1, the weft interlining yarns 2 and the oblique interlining yarns 3 adopt polyester yarns, the looping yarns 4 adopt polyester-nylon superfine fibers, the looping yarns 4 are woven into a warp plain weave, in the weaving process of the looping yarns 4, the warp interlining yarns 1 are parallel along the warp direction of the fabric and are inserted in a straightened state, the weft interlining yarns 2 are parallel along the weft direction of the fabric and are inserted in a straightened state, the oblique interlining yarns 3 are parallel along the oblique direction of the fabric and are inserted in a straightened state, the warp interlining yarns 1, the weft interlining yarns 2 and the oblique interlining yarns 3 are not looped, the looping yarns 4 are woven into loops, and the warp interlining yarns 1, the weft interlining yarns 2 and the oblique interlining yarns 3 are bound; wherein the specification of the polyester yarn is 35D/36F, and the specification of the polyester-nylon superfine fiber yarn is 35D/72F. In this example 1, the bias interlining 3 is interlined in one layer, and the layer of bias interlining 3 is at 45 ° to the weft direction of the fabric.

The PVC surface layer comprises the following raw materials in parts by weight: 100 parts of PVC resin, 20 parts of phthalate plasticizer, 10 parts of wollastonite powder, 0.5 part of modified multi-walled carbon nanotube and 1 part of metal soap stabilizer; the modified multi-walled carbon nanotube is prepared by modifying the surface of the multi-walled carbon nanotube by using MMA-BA-GMA terpolymer treating fluid.

The method for preparing high-strength polyvinyl chloride artificial leather of example 1 includes the steps of:

(1) putting the preparation raw materials of the PVC surface layer into a high-speed stirrer according to the mass part ratio for high-speed mixing and stirring, wherein the stirring temperature is 100 ℃, and the stirring time is 150s, so as to obtain a mixed material;

(2) discharging the mixed material obtained in the step (1) into an internal mixer for mixing at the mixing temperature of 120 ℃, discharging the mixed material into an open mill after mixing is finished, plasticating the mixed material at the temperature of 120 ℃ sequentially through two open mills, conveying the mixed material to a calender for calendering into a sheet at the calendering temperature of 140 ℃, attaching the sheet obtained after calendering to base cloth to prepare a semi-finished product, conveying the semi-finished product into a foaming embossing machine, and performing foaming embossing treatment at the temperature of 160 ℃ to prepare the polyvinyl chloride artificial leather.

Example 2

A high-strength polyvinyl chloride artificial leather comprises a base cloth and a PVC surface layer;

the base cloth is a warp knitted fabric which is knitted by adopting lining warp yarns, lining weft yarns, oblique lining yarns and looping yarns; the method comprises the following steps that polyester yarns are adopted as lining warp yarns, lining weft yarns and oblique lining yarns, polyester-nylon superfine fibers are adopted as looping yarns, the looping yarns are woven into a warp plain weave, the lining warp yarns are lined in parallel along the warp direction of a fabric, the lining weft yarns are lined in parallel along the weft direction of the fabric, the oblique lining yarns are lined in parallel along the oblique direction of the fabric, the lining warp yarns, the lining weft yarns and the oblique lining yarns are not looped, the looping yarns are woven into loops, and the lining warp yarns, the lining weft yarns and the oblique lining yarns are bound; wherein the specification of the polyester yarn is 35D/36F, and the specification of the polyester-nylon superfine fiber yarn is 35D/72F. In this example 2, the bias liner yarns are laid in one layer at-45 ° to the fill of the fabric.

The PVC surface layer comprises the following raw materials in parts by weight: 100 parts of PVC resin, 35 parts of phthalate plasticizer, 15 parts of wollastonite powder, 0.3 part of modified multi-walled carbon nanotube, 2 parts of rare earth stabilizer and 1 part of foaming agent; the modified multi-walled carbon nanotube is prepared by modifying the surface of the multi-walled carbon nanotube by using MMA-BA-GMA terpolymer treating fluid.

The preparation method of the high-strength polyvinyl chloride artificial leather of example 2 includes the steps of:

(1) putting the preparation raw materials of the PVC surface layer into a high-speed stirrer according to the mass part ratio for high-speed mixing and stirring, wherein the stirring temperature is 110 ℃, and the stirring time is 150s, so as to obtain a mixed material;

(2) discharging the mixed material obtained in the step (1) into an internal mixer for mixing at the mixing temperature of 130 ℃, discharging the mixed material into an open mill after mixing is finished, plasticating the mixed material at the temperature of 130 ℃ sequentially through two open mills, conveying the mixed material to a calender for calendering into a sheet material at the calendering temperature of 150 ℃, attaching the sheet material obtained after calendering to base cloth to prepare a semi-finished product, conveying the semi-finished product into a foaming embossing machine, and performing foaming embossing treatment at the temperature of 200 ℃.

Example 3

A high-strength polyvinyl chloride artificial leather comprises a base cloth and a PVC surface layer;

the base cloth is a warp knitted fabric which is knitted by adopting lining warp yarns, lining weft yarns, oblique lining yarns and looping yarns; the method comprises the following steps that polyester yarns are adopted as lining warp yarns, lining weft yarns and oblique lining yarns, polyester-nylon superfine fibers are adopted as looping yarns, the looping yarns are woven into a warp plain weave, the lining warp yarns are lined in parallel along the warp direction of a fabric, the lining weft yarns are lined in parallel along the weft direction of the fabric, the oblique lining yarns are lined in parallel along the oblique direction of the fabric, the lining warp yarns, the lining weft yarns and the oblique lining yarns are not looped, the looping yarns are woven into loops, and the lining warp yarns, the lining weft yarns and the oblique lining yarns are bound; wherein the specification of the polyester yarn is 35D/36F, and the specification of the polyester-nylon superfine fiber yarn is 35D/72F. In this example 3, the bias liner yarns are laid in one layer at 45 ° to the fill of the fabric.

The PVC surface layer comprises the following raw materials in parts by weight: 100 parts of PVC resin, 50 parts of epoxy plasticizer, 5 parts of wollastonite powder, 0.2 part of modified multi-walled carbon nanotube, 3 parts of rare earth stabilizer and 2 parts of foaming agent; the modified multi-walled carbon nanotube is prepared by modifying the surface of the multi-walled carbon nanotube by using MMA-BA-GMA terpolymer treating fluid.

The preparation method of the high-strength polyvinyl chloride artificial leather of example 3 includes the steps of:

(1) putting the preparation raw materials of the PVC surface layer into a high-speed stirrer according to the mass part ratio for high-speed mixing and stirring, wherein the stirring temperature is 110 ℃, and the stirring time is 150s, so as to obtain a mixed material;

(2) discharging the mixed material obtained in the step (1) into an internal mixer for mixing at the mixing temperature of 130 ℃, discharging the mixed material into an open mill after mixing is finished, plasticating the mixed material at the temperature of 130 ℃ sequentially through two open mills, conveying the mixed material to a calender for calendering into a sheet material at the calendering temperature of 150 ℃, attaching the sheet material obtained after calendering to base cloth to prepare a semi-finished product, conveying the semi-finished product into a foaming embossing machine, and performing foaming embossing treatment at the temperature of 210 ℃.

Performance testing

The polyvinyl chloride artificial leathers of examples 1 to 3 were subjected to performance tests according to QB/T2710 and QB/T2779, respectively. The test results showed that the polyvinyl chloride artificial leather samples of examples 1-3, having a thickness of 1.4mm, had a tensile load of not less than 450N, a tear load of not less than 35N, and an elongation at break of not less than 45%.

The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents made by the contents of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.

Claims (7)

1. A high-strength polyvinyl chloride artificial leather comprises a base cloth and a PVC surface layer, and is characterized in that,

the base cloth is a warp knitted fabric which is knitted by adopting lining warp yarns, lining weft yarns, oblique lining yarns and looping yarns; the warp lining yarns, the weft lining yarns and the oblique lining yarns adopt polyester yarns, the looping yarns adopt polyester-nylon superfine fibers, the looping yarns are woven into warp knitting ground tissues, the warp lining yarns are lined in parallel along the warp direction of the fabric, the weft lining yarns are lined in parallel along the weft direction of the fabric, the oblique lining yarns are lined in parallel along the oblique direction of the fabric, the warp lining yarns, the weft lining yarns and the oblique lining yarns are not looped, the looping yarns are woven into loops, and the warp lining yarns, the weft lining yarns and the oblique lining yarns are bound;

the PVC surface layer is prepared from the following raw materials in parts by weight: 100 parts of PVC resin, 20-50 parts of plasticizer, 5-15 parts of wollastonite powder, 0.2-0.5 part of modified multi-walled carbon nanotube, 1-3 parts of stabilizer and 0-2 parts of foaming agent; the modified multi-walled carbon nanotube is prepared by modifying the surface of the multi-walled carbon nanotube by using MMA-BA-GMA terpolymer treating fluid.

2. The high-strength polyvinyl chloride artificial leather according to claim 1, wherein: the specification of the polyester yarn is 35D/36F, and the specification of the polyester-nylon superfine fiber yarn is 35D/72F.

3. The high-strength polyvinyl chloride artificial leather according to claim 1, wherein: the warp knitting ground tissue is a warp flat tissue or a warp velvet tissue.

4. The high-strength polyvinyl chloride artificial leather according to claim 1, wherein: the oblique angle of the oblique lining yarn is-45 degrees to +45 degrees.

5. The high-strength polyvinyl chloride artificial leather according to claim 1, wherein: the plasticizer is selected from one or a combination of two or more of phthalate, phosphate and epoxy plasticizers.

6. The high-strength polyvinyl chloride artificial leather according to claim 1, wherein: the stabilizer is one or the combination of two or more of calcium and zinc, metal soap and rare earth stabilizer.

7. The method of preparing high-strength polyvinyl chloride artificial leather according to any one of claims 1 to 6, comprising the steps of:

(1) putting the preparation raw materials of the PVC surface layer into a high-speed stirrer according to the mass part ratio for high-speed mixing and stirring, wherein the stirring temperature is 80-110 ℃, and the stirring time is 100-200 s, so as to obtain a mixed material;

(2) discharging the mixed material obtained in the step (1) into an internal mixer for mixing at the mixing temperature of 100-150 ℃, discharging the mixed material into an open mill after mixing is finished, plasticating the mixed material at the temperature of 100-150 ℃ through two open mills in sequence, conveying the plasticated mixed material to a calender for calendering to obtain a sheet material, wherein the calendering temperature is 120-180 ℃, attaching the sheet material obtained after calendering to base cloth to prepare a semi-finished product, conveying the semi-finished product to a foaming embossing machine, and performing foaming embossing treatment at the temperature of 160-210 ℃.

Images