CN112895668B - Glue-free TPO artificial leather and manufacturing method thereof - Google Patents

Glue-free TPO artificial leather and manufacturing method thereof Download PDF

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Publication number
CN112895668B
CN112895668B CN201911134777.6A CN201911134777A CN112895668B CN 112895668 B CN112895668 B CN 112895668B CN 201911134777 A CN201911134777 A CN 201911134777A CN 112895668 B CN112895668 B CN 112895668B
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weight
parts
tpo
artificial leather
ethylene
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CN112895668A (en
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李帅
刘海洋
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Benecke Changshun Automotive Interior Materials Zhangjiagang Co ltd
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Benecke Changshun Auto Trim Zhangjiagang Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/026—Knitted fabric

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  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The invention relates to a glue-free TPO artificial leather, which at least comprises a base cloth layer and a TPO skin layer from bottom to top, wherein the TPO skin layer comprises: 10 to 30 parts by weight of polyethylene, 10 to 30 parts by weight of polypropylene, 20 to 70 parts by weight of elastomer, 5 to 40 parts by weight of olefin tackifying resin. The invention also relates to a manufacturing method of the glue-free TPO artificial leather. The TPO product obtained by the invention can improve the adhesion between the base cloth layer and the TPO skin layer without glue, so that the TPO skin layer is more easily and reliably adhered to the base cloth.

Description

Glue-free TPO artificial leather and manufacturing method thereof
Technical Field
The present invention relates to a glue-free TPO artificial leather and a method for manufacturing the same, wherein the TPO artificial leather can be sewn and is suitable for an automobile seat.
Background
Various artificial leathers are widely used as automotive interior materials. Currently, automotive seat fabrics basically adopt polyvinyl chloride (PVC) artificial leather or Polyurethane (PU) artificial leather. The structure of the PVC seat material is generally divided into four layers, namely a base cloth, a PVC foaming layer, a PVC compact layer and a surface paint layer from bottom to top. Because the PVC product contains the plasticizer, the plasticizer is easy to move and migrate out, so that the material becomes hard and brittle, and surface cracks, particularly the problem of embrittlement aggravated at low temperature, are easy to occur when the PVC product is broken and fatigued. In addition, the PVC artificial leather has poor high temperature resistance and is easy to generate yellowing because the high temperature PVC can be degraded.
To avoid the above-mentioned drawbacks of PVC artificial leather, attempts have been made to develop other kinds of artificial leather, such as TPO artificial leather. In this regard, different methods are disclosed in the prior art for making various TPO automotive interior materials with improved properties.
CN107351495a discloses a multicolor TPO automotive interior material, which comprises a polyolefin sponge layer, a multicolor TPO skin layer and a water-based polyurethane coating layer from bottom to top, wherein the multicolor TPO skin layer is formed by compounding and splicing at least two monochromatic TPO skins. The personalized requirements on the interior material can be realized by freely combining and collocating various colors.
CN106380772a discloses an environment-friendly TPO automotive interior material based on SEBS, which comprises a TPO skin layer and a sponge layer, wherein the TPO skin layer comprises 50 to 80 parts of SEBS, 10 to 20 parts of polypropylene, 10 to 20 parts of tackifying resin and 5 to 20 parts of homo-polypropylene; the sponge layer comprises 35-60 parts of polypropylene, 40-55 parts of toughening material, 15-25 parts of rubber and 20-30 parts of foaming agent. The TPO interior material has the characteristics of low odor and low VOC.
CN106393890a discloses a soft environment-friendly TPO automotive interior material, which comprises a TPO skin layer and a sponge layer, wherein the TPO skin layer comprises 10 to 40 parts of low-density polyethylene, 10 to 40 parts of polypropylene, 10 to 40 parts of tackifying resin and 30 to 60 parts of rubber; the sponge layer comprises 35 to 60 parts of polypropylene, 40 to 55 parts of toughening material, 15 to 25 parts of rubber and 20 to 30 parts of foaming agent. The TPO interior material reduces the content of Volatile Organic Compounds (VOC) and improves the environmental protection of products.
However, these conventional TPO products of the prior art are only useful for door panels and dashboards and do not meet the standards and performance of automotive seat facings. This is because, on the one hand, the sponge layer results in a material that is not soft enough to the seat shell and is not easily hand-wrapped, and TPO interior trim materials containing sponge layers are typically used for thermoplastic processing; on the other hand, even if the sponge layer is simply replaced by the base cloth layer, so that the sewing can be performed, but the conventional sewing TPO is too large in hardness and rigidity, and is poor in toughness and crumple resistance, difficult to manually cover, easy to produce crease and the like, and cannot meet the test standard of the seat performance.
In addition, in order to improve the bonding force between the TPO skin layer and the base cloth, glue is required to be added between the common sewing TPO and the base cloth. However, the addition of the glue layer can harden the material hand feeling, and VOC can be improved; on the other hand, glue is added in the production line, so that the cost is increased and the operation is not easy.
Disclosure of Invention
Based on the prior art, the invention aims to provide glue-free TPO artificial leather. The TPO artificial leather can improve the adhesion between the base cloth layer and the TPO skin layer under the condition that glue is not needed, so that the TPO skin layer is more easily and reliably attached to the base cloth. It is also an object of the present invention to provide a process for manufacturing the glue free TPO.
The above object is achieved by the TPO artificial leather and the manufacturing method thereof according to the present invention.
In view of this, the present invention firstly proposes a glue-free TPO artificial leather, which comprises, from bottom to top, at least a base cloth layer and a TPO skin layer, the TPO skin layer comprising:
10 to 30 parts by weight, for example 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight or a polyethylene in a range between any two of these,
10 to 30 parts by weight, for example 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight or polypropylene in a range between any two of these,
20 to 70 parts by weight, for example, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight, 41 parts by weight, 42 parts by weight, 43 parts by weight, 44 parts by weight, 45 parts by weight, 46 parts by weight, 47 parts by weight, 48 parts by weight, 49 parts by weight, 50 parts by weight, 51 parts by weight, 52 parts by weight, 53 parts by weight, 54 parts by weight, 55 parts by weight, 56 parts by weight, 57 parts by weight, 58 parts by weight, 59 parts by weight, 60 parts by weight, 61 parts by weight, 62 parts by weight, 63 parts by weight, 64 parts by weight, 65 parts by weight, 66 parts by weight, 67 parts by weight, 68 parts by weight, 69 parts by weight, 70 parts by weight, or an elastomer in a range between any two of these,
5 to 40 parts by weight, for example, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, 31 parts by weight, 32 parts by weight, 33 parts by weight, 34 parts by weight, 35 parts by weight, 36 parts by weight, 37 parts by weight, 38 parts by weight, 39 parts by weight, 40 parts by weight of the olefin-based tackifying resin.
Here, the key to improving the adhesion between the TPO skin layer and the base fabric is the addition of tackifying resins, especially olefinic tackifying resins. The tackifying resin can also improve softness. The olefin tackifying resin has particularly good compatibility, and the obtained TPO artificial leather has a smooth surface. If the content of tackifying resin is too low, the viscosity of the system is improved insufficiently, and the requirement of cohesive force cannot be met; if the content of the tackifying resin is too high, the viscosity of the system is too high, the processability is poor, and the heat resistance and the like of the product are poor.
According to a preferred embodiment of the present invention, the olefin-based tackifying resin is an ethylene-vinyl acetate copolymer (EVA) or an ethylene-acrylic acid copolymer (EAA). Ethylene-vinyl acetate copolymers (EVA) and ethylene-acrylic acid copolymers (EAA) can effectively increase the viscosity of the system, increasing adhesion to the substrate.
According to a preferred embodiment of the present invention, when the olefin-based tackifying resin is an ethylene-vinyl acetate copolymer, the ethylene-vinyl acetate copolymer has a Vinyl Acetate (VA) content of 5 to 45 wt%; when the olefin-based tackifying resin is an ethylene-acrylic acid copolymer, the Acrylic Acid (AA) content in the ethylene-acrylic acid copolymer is 5 to 45% by weight. The amounts mentioned here are based on the total amount of tackifying resin. The VA content in EVA and AA content in EAA have a significant impact on the performance of the product. If the VA content in EVA or the AA content in EAA is too low, the viscosity of the system is not improved enough, and the adhesive force requirement cannot be met; if the content is too high, the viscosity of the system may be too high, the processability may be poor, and extrusion molding may not be performed.
The polyethylene in the TPO skin layer of the present invention may in principle be any conventional polyethylene, such as high density polyethylene, low density polyethylene, etc. According to a preferred embodiment of the invention, the polyethylene is a linear low density polyethylene. The incorporation of Linear Low Density Polyethylene (LLDPE) in the TPO skin layer enables significantly improved softness due to its lower density and lower hardness compared to non-linear LDPE and HDPE.
The polypropylene in the TPO skin layer in the present invention includes homo-polypropylene and co-polypropylene, and may involve isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene, etc. According to a preferred embodiment of the present invention, the polypropylene is a random copolymer polypropylene, such as an ethylene propylene random copolymer polypropylene or the like. The lower stiffness of random copolymer polypropylene relative to other types of polypropylene can help achieve improved softness.
The elastomer in the TPO skin layer in the present invention may in principle be any conventionally known elastomer such as EPDM rubber, polyurethane elastomer, SBS elastomer, POE elastomer, etc. According to a preferred embodiment of the invention, the elastomer comprises a thermoplastic vulcanizate (TPV) and an ethylene-alpha olefin copolymer elastomer (POE), preferably containing from 10 to 30 parts by weight of thermoplastic vulcanizate and from 20 to 50 parts by weight of ethylene-alpha olefin copolymer elastomer. The thermoplastic vulcanized rubber can provide good retention of gloss and patterns of the artificial leather and improve ageing resistance.
According to a preferred embodiment of the invention, the thermoplastic vulcanizate has a Shore hardness of 45-75A. The shore a hardness of TPV (measured according to ISO 868) has a significant impact on product performance. If the Shore hardness A of the TPV is too large, the TPV can cause hard handfeel and large rigidity, so that the performance of the automobile seat fabric cannot be met; if the shore A hardness of the TPV is too small, the product becomes tacky and oily, and the processability is deteriorated. In addition, the shore hardness of the TPV also affects the adhesion between the TPO skin layer and the base fabric, with the adhesion increasing as the TPV hardness decreases.
According to a preferred embodiment of the present invention, the ethylene-alpha olefin interpolymer elastomer has a Shore hardness of 45-70A. The shore hardness a of POE (measured according to ISO 868) also has an important impact on the product properties, and good softness and processability can be ensured at the same time only if the shore hardness a of POE is within the limits of the present invention. In addition, the shore hardness of POE affects the adhesion between the TPO skin layer and the base fabric, and the adhesion increases as the POE hardness decreases.
Preferably, a thermoplastic vulcanizate (preferably an oil extended gel) and an ethylene-alpha olefin copolymer elastomer are added simultaneously, in which case the toughness of the product is improved while the hardness is reduced and the softness is improved compared to conventional formulations, thereby improving the crumple and buckle resistance properties, from a significant improvement in breaking from 1 to 2 ten thousand crumples at normal temperature to 10 ten thousand non-breaks at normal temperature, completely reaching or exceeding the requirements for car seats. The softness of the surface skin is reduced from 100-120mm to 50-80mm through sagging test, the rigidity is obviously reduced, the hand feel is softened, and thus the performance standard of the seat fabric is achieved.
According to a preferred embodiment of the invention, the thermoplastic vulcanizate is extended with an oil extender, in particular a low hardness oil extender, preferably with paraffinic or paraffinic oil at an oil filling level of 10-30% (based on the total amount of TPV). If other non-oil-extended glue is used, or other oil-extended types or oil-extended amounts are used, the VOC content may be increased, which is not satisfactory and is easy to separate out.
According to a preferred embodiment of the present invention, the content of alpha olefin monomers in the ethylene-alpha olefin copolymer elastomer, preferably octene, is from 30 to 60% by weight based on the total weight of POE. The content of alpha olefin monomers has a significant impact on the hardness of POE. If the alpha olefin monomer content is too low, the polyethylene PE fraction in POE increases, which results in increased crystallinity, hardness and stiffness; if the content of the alpha olefin monomer is too high, PE in the POE is excessively broken, so that the copolymerization difficulty is increased, and the processing is difficult. In addition, octene provides particularly desirable plasticity and softness as an alpha olefin monomer.
According to a preferred embodiment of the present invention, the TPO skin layer comprises 2 to 10 parts by weight, for example 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight or an additive in the range between any two of these values. The additives mainly include heat-resistant stabilizers and processing aids, such as lubricants, etc., and conventional materials well known to those skilled in the art may be selected as needed.
According to a preferred embodiment of the present invention, the TPO skin layer comprises 2 to 8 parts by weight of color master batch, for example 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight or a range between any two of these values of color master batch. The additional optional addition of color master batches to the TPO composition, as desired, can help meet different color requirements of the product.
According to a preferred embodiment of the present invention, a paint layer is provided over the TPO skin layer. The surface coating may be performed using conventional paints known in the art. In the present invention, an aqueous polyurethane paint is preferably used, which contains 10 to 30 parts by weight of water, 30 to 60 parts by weight of polyurethane, 5 to 10 parts by weight of a curing agent, and 5 to 15 parts by weight of an auxiliary agent. The gloss, feel and light, heat, dirt, abrasion, scratch and other functionalities of the resulting TPO imitation leather surface can be advantageously improved by surface treatment by printing paint on the TPO material surface.
According to a preferred embodiment of the present invention, the base fabric layer is a knitted or nonwoven fabric, preferably a double-sided knitted fabric. The base fabric layer can improve the softness of the leather, so that the leather is easy to manually wrap at normal temperature. Among them, knitted fabrics have softer hand feel than other fabrics such as woven fabrics.
Accordingly, the present invention also proposes a method for manufacturing the aforementioned TPO imitation leather according to the present invention, comprising the steps of:
extruding a TPO skin comprising
10 to 30 parts by weight of a polyethylene, preferably a linear low density polyethylene,
10 to 30 parts by weight of polypropylene, preferably random copolymer polypropylene,
20 to 70 parts by weight of an elastomer,
5 to 40 parts by weight of an olefin tackifying resin,
-a base fabric layer of composite bottom.
The compounding of the TPO skin layer and the base cloth layer can be directly realized by hot-pressing compounding.
The various features of the aforementioned TPO artificial leather are applicable to the method of manufacturing the same.
There is no particular requirement for the thickness of each layer constituting the TPO artificial leather of the present invention. One skilled in the art can select an appropriate thickness according to specific requirements.
The TPO artificial leather can be applied to automobile interiors, and particularly meets the performance requirements of automobile seat fabrics. Of course, the TPO artificial leather according to the present invention can be applied to other fields like automotive interiors.
The invention has the advantages that:
firstly, compared with the traditional formula, the adhesion between the surface skin and the base cloth can be obviously improved by adding the olefin tackifying resin into the system. In the conventional technology, the bonding force between the TPO skin layer and the base cloth layer is generally about 10-20N/5cm under the condition that no additional glue is applied. The improved binding force can reach more than 30N/5cm, even close to 50N/5cm or can not be torn. Thus, even if no glue is used, the adhesion is comparable to the case of using glue. Moreover, the glue is abandoned, so that the TPO artificial leather has good hand feeling, the VOC is reduced, and the cost is reduced.
Second, the TPO seating material obtained according to the present invention has the following performance improvements over conventional PVC seating:
since the TPO product contains no plasticizer, there is no plasticizer migration and precipitation problem;
the melting point of the TPO material is high, so that the product has good high-temperature heat resistance;
low temperature PVC products are prone to embrittlement, the products are prone to breakage at low temperatures, while TPO products perfectly avoid this problem;
PVC products with small molecular plasticizers and poor VOC emission properties, TPO with good odor and emission properties, adjusted hardness according to the elastomer, can meet various standards in terms of domestic and foreign odor emission.
In addition, the optimized TPO formula of the invention has better flexibility, crumple resistance, heat resistance and softness, can be cut and sewn, and is easy to manually cover at normal temperature. The TPO artificial leather obtained according to the present invention has a softness of 60-80mm through sagging test; according to the ball-flex test, the normal-temperature crumple-resistant performance can reach 10 ten thousand times, the low-temperature (-30 ℃) crumple-resistant performance can reach more than 3 ten thousand times, and even can reach 10 ten thousand times; in addition, the crease is hardly visible to the naked eye.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description will clearly and completely describe the technical solutions of the present invention with reference to examples and comparative examples, and it is apparent that the described examples are some, but not all, examples of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
TPO artificial leather was prepared as follows:
I. TPO compositions were prepared according to the skin layer formulations shown in Table 1;
from the obtained TPO composition, a film having a thickness of 0.5mm was melt-extruded by a laboratory extruder (labtech LTE 20) having a temperature of 160℃and 180℃and 180-190℃in this order from the inlet to the outlet, to obtain a TPO skin layer.
The surface corona treatment is carried out on the surface of the film material to increase the polarity of the surface, thereby facilitating the next surface treatment.
II, coating a paint layer
The paint comprises the following components in parts by weight: 70 parts of aqueous polyurethane dispersion, 1 part of polyurethane thickener, 0.2 part of isocyanate curing agent, 45 parts of water and 1 part of silicon dioxide;
uniformly mixing and stirring the aqueous polyurethane dispersion, silicon dioxide and water to obtain a mixed solution;
adding a polyurethane thickener, and fully and uniformly stirring to obtain a mixed solution;
adding isocyanate curing agent, and stirring thoroughly and uniformly;
uniformly coating a layer of the obtained aqueous polyurethane coating on the surface of the prepared TPO epidermis layer, and then drying.
III preparing the final product
Heating the TPO skin layer with the paint in a compounding machine, and then compounding with a base fabric to obtain a final product.
Table 1: TPO formulation of example 1
Figure BDA0002279292260000081
Figure BDA0002279292260000091
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Example 2:
TPO artificial leather was prepared according to the skin layer formulation shown in Table 2 by the same method as in example 1.
Table 2: example 2 TPO formulation
Linear low density polyethylene (Exxon Mobil) 15 parts by weight
Random copolymer polypropylene (Korea Dalin) 15 parts by weight
POE (Shore hardness: 63A) (America Dow) 30 parts by weight
TPV (Shore hardness: 70A) (Ekesen Mobil) 20 parts by weight
Tackifying resin EVA (VA content 35%) (DuPont U.S.A.) 20 parts by weight
Additive agent 5 parts by weight
Color master batch 4 parts by weight
Example 3:
TPO artificial leather was prepared according to the skin layer formulation shown in Table 3 by the same method as in example 1.
Table 3: example 3 TPO formulation
Linear low density polyethylene (Exxon Mobil) 15 parts by weight
Random copolymer polypropylene (Korea Dalin) 15 parts by weight
POE (Shore hardness: 63A) (America Dow) 30 parts by weight
TPV (Shore hardness: 70A) (Ekesen Mobil) 30 parts by weight
Tackifying resin EAA (AA content 10%) (DuPont U.S.A.) 10 parts by weight
Additive agent 5 parts by weight
Color master batch 4 parts by weight
Example 4:
TPO artificial leather was prepared according to the skin layer formulation shown in Table 4 by the same method as in example 1.
Table 4: example 4 TPO formulation
Figure BDA0002279292260000092
Figure BDA0002279292260000101
Example 5:
TPO artificial leather was prepared according to the skin layer formulation shown in Table 5 by the same method as in example 1.
Table 5: example 5 TPO formulation
Linear low density polyethylene (Exxon Mobil) 15 parts by weight
Random copolymer polypropylene (Korea Dalin) 15 parts by weight
POE (Shore hardness: 50A) (America Dow) 30 parts by weight
TPV (Shore hardness: 50A) (Exxon Mobil) 20 parts by weight
Tackifying resin EVA (VA 13%) (DuPont U.S.A.) 20 parts by weight
Additive agent 5 parts by weight
Color master batch 4 parts by weight
Comparative example 1: POE hardness is too high
TPO artificial leather was prepared according to the skin layer formulation shown in Table 6 by the same method as in example 1.
Table 6: TPO formulation of comparative example 1
Linear low density polyethylene (Exxon Mobil) 15 parts by weight
Random copolymer polypropylene (Korea Dalin) 15 parts by weight
POE (Shore hardness: 80A) (Mitsubishi Japanese) 30 parts by weight
TPV (Shore hardness: 60A) (Exxon Mobil) 20 parts by weight
Tackifying resin EVA (VA content 35%) (DuPont U.S.A.) 20 parts by weight
Additive agent 5 parts by weight
Color master batch 4 parts by weight
Comparative example 2: TPV with too high a hardness
TPO artificial leather was prepared according to the skin layer formulation shown in Table 7 by the same method as in example 1.
Table 7: TPO formulation of comparative example 2
Linear low density polyethylene (Exxon Mobil) 15 parts by weight
Random copolymer polypropylene (Korea Dalin) 15 parts by weight
POE (Shore hardness: 60A) (America Dow) 30 parts by weight
TPV (Shore hardness: 80A) (Japanese Mitsubishi) 20 parts by weight
Tackifying resin EVA (VA content 35%) (DuPont U.S.A.) 20 parts by weight
Additive agent 5 parts by weight
Color master batch 4 parts by weight
Comparative example 3: glue containing water
TPO artificial leather was prepared according to the skin layer formulation shown in Table 8 by substantially the same method as in example 1. The production method differs from that of example 1 in that, in comparative example 3, a solvent-based polyurethane glue (95 parts by weight of solvent-based polyurethane dispersion, 2 parts by weight of curing agent) was further applied to the back surface of the TPO skin layer before compounding the TPO skin layer and the base fabric.
Table 8: TPO formulation of comparative example 3
Linear low density polyethylene (Exxon Mobil) 15 parts by weight
Random copolymer polypropylene (Korea Dalin) 15 parts by weight
POE (Shore hardness: 60A) (America Dow) 30 parts by weight
TPV (Shore hardness: 70A) (Ekesen Mobil) 20 parts by weight
Additive agent 5 parts by weight
Color master batch 4 parts by weight
Comparative example 4: does not contain tackifying resin
TPO artificial leather was prepared according to the skin layer formulation shown in Table 9 by the same method as in example 1.
Table 9: TPO formulation of comparative example 4
Figure BDA0002279292260000111
Figure BDA0002279292260000121
Performance tests were performed on the TPO artificial leathers obtained in examples 1 to 5 and comparative examples 1 to 4. The results of the measurements are shown in tables 10-11 and compared.
Table 10: results of the tests of examples 1 to 5
Figure BDA0002279292260000122
Table 11: results of the tests of comparative examples 1 to 4
Figure BDA0002279292260000123
Figure BDA0002279292260000131
The specific results are described below:
the TPO artificial leather obtained in examples 1 to 5 all met the aesthetic requirements in appearance, and had no surface defects such as pits, bright lines, wrinkles, and the like. No adverse phenomena such as large roll stickiness and the like occur in the production process.
As can be seen from the results in table 10, the adhesive force of the products according to examples 1-5 of the present invention without glue was comparable to, or even better than, the adhesive force of the product of comparative example 3 with glue. The VOC content of the artificial leather is obviously reduced compared with that of comparative example 3 containing glue water due to the fact that the artificial leather does not contain glue, and the influence on the environment is further reduced. Meanwhile, the Shore hardness of the examples 1-5 is not more than 70A, and meets the hardness requirement of the seat fabric; the softness and sagging degree are all in the range of 60-70mm, and the soft and sagging degree has proper rigidity; can bear 15 ten thousand times of crumpling at normal temperature, and can bear 10 ten thousand times of crumpling at the low temperature of minus 30 ℃. Wherein, as the VA content in the tackifying resin EVA increases, the adhesive force of the product increases as demonstrated by examples 1 and 2; it is demonstrated by examples 1, 4, 5 that as POE and TPV hardness decrease, product hardness decreases and product cohesion increases.
In contrast, the hardness of POE or TPV used in comparative examples 1 and 2 is too high. This resulted in the TPO artificial leather obtained in comparative examples 1-2 having significantly greater hardness; a greater sag indicates too little stiffness; can only bear 5 ten thousand times of crumpling at normal temperature, and does not meet the requirement of the automobile seat on at least 10 ten thousand times of crumpling resistance at normal temperature.
In comparative example 3, since there is also a solvent type glue between the base fabric layer and the TPO skin layer, the stiffness is increased compared with examples 1 to 3 without glue, the softness is deteriorated, the crumple resistance is also reduced, and the VOC content is remarkably increased.
Comparative example 4 was free of tackifying resin, and the product adhesion was significantly poor.
It is to be understood that the above embodiments are merely illustrative of the application of the principles of the present invention, but not in limitation thereof. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the invention, and are also considered to be within the scope of the invention.

Claims (12)

1. A glue-free TPO imitation leather comprising, from bottom to top, at least a base fabric layer and a TPO skin layer, the TPO skin layer comprising:
10 to 30 parts by weight of polyethylene,
10 to 30 parts by weight of polypropylene,
20 to 70 parts by weight of an elastomer comprising 10 to 30 parts by weight of a thermoplastic vulcanizate having a Shore hardness of 45-75A and 20 to 50 parts by weight of an ethylene-alpha olefin co-elastomer having a Shore hardness of 45-70A,
5 to 40 parts by weight of an olefin-based tackifying resin.
2. The TPO artificial leather according to claim 1, wherein the olefin-based tackifying resin is an ethylene-vinyl acetate copolymer or an ethylene-acrylic acid copolymer.
3. The TPO artificial leather according to claim 2, wherein when the olefin-based tackifying resin is an ethylene-vinyl acetate copolymer, the vinyl acetate content in the ethylene-vinyl acetate copolymer is 5 to 45 wt%; when the olefin-based tackifying resin is an ethylene-acrylic acid copolymer, the acrylic acid content in the ethylene-acrylic acid copolymer is 5 to 45% by weight.
4. A TPO artificial leather according to any of claims 1 to 3, characterized in that the polyethylene is a linear low density polyethylene.
5. A TPO artificial leather according to any of claims 1 to 3, characterized in that the polypropylene is a random copolymer polypropylene.
6. The TPO artificial leather according to claim 1, wherein the thermoplastic vulcanizate uses an oil extended gel.
7. The TPO artificial leather according to claim 6, wherein the thermoplastic vulcanizate is oil extended with paraffin oil or alkane oil at an oil extension of 10-30%.
8. The TPO artificial leather of claim 1, wherein the alpha olefin monomer in the ethylene-alpha olefin co-elastomer is present in an amount of 30 to 60% by weight based on the total weight of the co-elastomer.
9. The TPO artificial leather of claim 8, wherein the alpha olefin monomer in the ethylene-alpha olefin co-elastomer is octene.
10. A process for manufacturing the TPO artificial leather according to any one of claims 1 to 9, comprising the steps of:
extruding a TPO skin comprising
10 to 30 parts by weight of polyethylene,
10 to 30 parts by weight of polypropylene,
20 to 70 parts by weight of an elastomer comprising 10 to 30 parts by weight of a thermoplastic vulcanizate having a Shore hardness of 45-75A and 20 to 50 parts by weight of an ethylene-alpha olefin co-elastomer having a Shore hardness of 45-70A,
5 to 40 parts by weight of an olefin tackifying resin,
-a base fabric layer of composite bottom.
11. The method of claim 10, wherein the polyethylene is a linear low density polyethylene.
12. The method of claim 10, wherein the polypropylene is a random copolymer polypropylene.
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