CN111361244A - Warping-resistant TPO artificial leather and preparation method and application thereof - Google Patents
Warping-resistant TPO artificial leather and preparation method and application thereof Download PDFInfo
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- CN111361244A CN111361244A CN202010142764.XA CN202010142764A CN111361244A CN 111361244 A CN111361244 A CN 111361244A CN 202010142764 A CN202010142764 A CN 202010142764A CN 111361244 A CN111361244 A CN 111361244A
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- 239000002649 leather substitute Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 41
- 229920001971 elastomer Polymers 0.000 claims abstract description 26
- 239000000806 elastomer Substances 0.000 claims abstract description 26
- 239000004088 foaming agent Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000004743 Polypropylene Substances 0.000 claims description 48
- 239000004698 Polyethylene Substances 0.000 claims description 26
- 238000004049 embossing Methods 0.000 claims description 20
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 14
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 10
- 238000003475 lamination Methods 0.000 claims description 3
- 238000010030 laminating Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 9
- 238000009966 trimming Methods 0.000 abstract description 8
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- 238000003878 thermal aging Methods 0.000 description 3
- 238000007666 vacuum forming Methods 0.000 description 3
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- 206010040829 Skin discolouration Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
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- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
- 239000000289 melt material Substances 0.000 description 1
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- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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Classifications
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
-
- 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
- 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
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/06—Embossing
-
- 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
- B32B5/18—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 features of a layer of foamed material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
- B60R13/0237—Side or rear panels
- B60R13/0243—Doors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
- B60R13/0256—Dashboard liners
-
- 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
- B32B2266/00—Composition of foam
- B32B2266/02—Organic
- B32B2266/0214—Materials belonging to B32B27/00
- B32B2266/025—Polyolefin
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Laminated Bodies (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention relates to a warping-resistant TPO artificial leather, which comprises a TPO skin layer and a sponge layer, wherein the TPO skin layer comprises 30-40 parts by weight of PP, 30-40 parts by weight of PE and 20-40 parts by weight of elastomer, based on 100 parts by weight of the total weight of the PP, the PE and the elastomer in the skin layer; the sponge layer comprises more than 90 parts by weight of PP and 3-5 parts by weight of foaming agent, and TPO artificial leather has a warping degree of less than or equal to 1cm at normal temperature and less than or equal to 2cm after 10min at 120 ℃, based on 100 parts by weight of the total weight of the sponge layer. The invention also relates to a manufacturing method of the warp-resistant TPO artificial leather, and the traction tension in the process is required to be less than or equal to 30N. And finally relates to the application of the warping-resistant TPO artificial leather in the precise trimming and laminating technology.
Description
Technical Field
The present invention relates to a warpage-resistant thermoplastic polyolefin elastomer (also called TPO) artificial leather, and a method for manufacturing the TPO artificial leather, and uses of the TPO artificial leather.
Background
TPO can be widely used in automobile interior as skin, and has the advantages of environmental protection, no halogen and no plasticizer compared with the interior material of traditional polyvinyl chloride. TPO artificial leather is generally formed by compounding a TPO skin layer and a sponge layer.
Various methods have been disclosed in the prior art to improve TPO automotive interior materials. For example, CN107351495A discloses a multicolor TPO automotive interior material, which comprises, from bottom to top, a polyolefin sponge layer, a multicolor TPO skin layer and an aqueous polyurethane coating, wherein the skin layer is formed by compositely splicing at least two single-color TPO skins, and each single-color TPO skin comprises 20-40 parts by weight of high-density polyethylene, 20-40 parts by weight of polypropylene, 5-10 parts by weight of ethylene-acrylic acid copolymer, 30-50 parts by weight of ethylene propylene diene monomer, and the like. CN106380819A discloses a super-soft TPO material, which comprises a matrix layer, a sponge layer, a TPO skin layer and a paint layer from bottom to top, wherein the TPO skin layer comprises 25-45 parts by weight of thermoplastic elastomer, 10-20 parts by weight of polyolefin, 25-40 parts by weight of tackifying resin, 1-5 parts by weight of ethylene-vinyl acetate copolymer, 8-15 parts by weight of foaming agent and the like.
Need be in the same place TPO synthetic leather and skeleton laminating in automotive interior field, at this laminating in-process, the processing mode that is most used at present has vacuum forming, female die shaping and three kinds of processing techniques of low pressure injection moulding. In vacuum forming, the artificial leather with leather grains is preheated, and then is subjected to vacuum adsorption, so that the side with patterns back to the framework is subjected to thermal compounding with the framework, and the interior trim part with a multilayer structure is obtained. The product patterns obtained by the method often have certain loss. In the female die forming, the artificial leather without dermatoglyph is preheated and then is absorbed on a die with reverse patterns through vacuum, after the die with the framework at the other end is closed, the pressure is maintained for a certain time, then the upper die and the lower die are separated, and the compounded part is taken out. The method has high requirement on the tensile property of the surface skin, the investment cost of the die is high, and the process is relatively complex. In the low-pressure injection molding, the artificial leather with the existing leather grains is placed in an injection mold, and then the molten framework material is combined with the surface skin through the low-pressure injection molding to form the automotive interior part with the multilayer structure. The combined action of stretching and melt material extrusion on artificial leather can cause the problems of seeping materials, perforation, wrinkles, uneven skin lines and the like.
The three forming methods of vacuum forming, female die forming and low-pressure injection molding all require that the artificial leather material is fed by a coiled material or a sheet material, the formed parts contain a large amount of leftover materials and need to be cut off, and the material utilization rate is low.
On the basis, a new process using an accurate trimming and film covering technology is newly developed. The technology level of pressure laminating and edge covering is improved by an accurate edge cutting laminating technology (ESL). The accurate trimming and laminating process uses the fabric which is accurately cut and matched with the geometric figure of the finished product part, the accurate covering of the fabric on a grinding tool in the pressure laminating process is realized through a servo-controlled gripper system, and then the automatic edge covering process is directly completed at one time. The ESL technology has the advantages that the waste of the fabric is reduced through an optimal fabric cutting method, and therefore the epidermis can be used at the maximum utilization rate, the utilization rate exceeds 95%, and the utilization rate of the epidermis in the three methods is less than 80%; can meet increasing quality requirements, such as limiting the stretching of the particles; and labor cost is reduced by integrating processing flows. The ESL process has high requirements on the heated forming of materials, requires the materials to have good thermal stability, and has no problems of shrinkage, warping and the like during heating.
However, existing conventional TPO materials have drawbacks in terms of hot processing. The TPO artificial leather becomes warped after the hot melt adhesive is coated for bonding the skeleton. Warped TPO leather cannot be used for compounding because it curls at the part corners. Therefore, the existing TPO material is not suitable for the precise trimming and laminating technology. In order to be applied to a technique of processing favorable accurate trimming and coating, TPO artificial leather needs to be further improved.
Disclosure of Invention
Based on the above prior art, the present invention aims to provide a TPO artificial leather resistant to warping, which does not have the problems of shrinkage, warping, etc. It is also an object of the present invention to provide a method for manufacturing a warp-resistant TPO artificial leather. Finally, the present invention aims to provide the use of such a TPO artificial leather resistant to warping.
In order to achieve the above technical objects, the present invention provides a warp-resistant TPO artificial leather comprising a TPO skin layer and a sponge layer, wherein,
the TPO skin layer comprises polypropylene (PP), Polyethylene (PE) and elastomer, and contains 30-40 parts by weight of PP, 30-40 parts by weight of PE and 20-40 parts by weight of elastomer based on 100 parts by weight of the total weight of PP, PE and elastomer in the skin layer;
the sponge layer comprises > 90 parts by weight of PP and 3-5 parts by weight of a foaming agent, based on 100 parts by weight of the total sponge layer,
the TPO artificial leather has the warping degree of less than or equal to 1cm at normal temperature and less than or equal to 2cm after being heated at 120 ℃ for 10 min.
The PP in the TPO skin layer is preferably an extrusion/calendering type PP, which is used primarily to improve the heat resistance of the TPO skin layer. When the PP content is too high (more than 40 parts by weight), the skin layer of the TPO tends to be too hard, and the soft touch of the skin is lost. PE in the skin layer of TPO is mainly used to improve the strength and feel of the material. When the PE content is too high (more than 40 parts by weight), the heat resistance of the TPO skin layer is lowered.
An index that can clearly characterize the warpage resistance of a material is the warpage of the material. Here, warpage is defined as: the vertical distance between the highest point of warpage and the horizontal plane when a sample block with dimensions of 10cm x 10cm is laid on the horizontal plane. Compared with the conventional TPO artificial leather, the TPO artificial leather has low normal temperature and high temperature warping degree, specifically has the warping degree less than or equal to 1cm at normal temperature and has the warping degree less than or equal to 2cm after 10min at 120 ℃.
In order to improve the warpage resistance of TPO artificial leather, one of the keys in the present invention is: the content of PP, PE in the TPO skin is higher than conventional, while the content of elastomer is as low as possible.
Preferably, the TPO skin layer comprises 20 to 25 parts by weight of elastomer, based on 100 parts by weight of the combined weight of PP, PE and elastomer in the skin layer.
To improve the warpage resistance, elastomers in the TPO skin layer are required to be not too elastic and not easily deformable upon heating. In this regard, polyolefin elastomers (POE) are not used as the elastomer in the skin layer of the TPO of this invention because POE has a generally low melting point and the raw materials tend to agglomerate, resulting in a finished product that has poor thermal stability and pattern retention and tends to stick to the mold. Elastomers that can be used in the skin layers of the TPO of this invention are, for example: SBES (styrene block copolymer), TPS (thermoplastic styrene), TPV (thermoplastic vulcanizate), and the like.
Preferably, the elastomer in the skin layer of the TPO of this invention is TPV. TPV is selected as the elastomer in the TPO skin layer, and the content of TPV is lower than that of TPO skin layer, so that the good matching of the shrinkage rates of the TPO skin layer and the sponge layer can be realized, and the warpage and shrinkage are effectively reduced.
Preferably, the PP in the TPO skin layers of this invention has an elongation at break of > 300% and the PE in the TPO skin layers is a linear low density polyethylene and has an elongation at break of > 300%.
In addition, the TPO skin layer of this invention can be added with small amount of heat stabilizer and color master batch based on 100 weight parts of total weight of PP, PE and elastomer to improve light and heat aging property and skin coloring property.
PP is the main raw material of sponges. Preferably, the PP in the sponge layer is homopolymeric PP and impact-resistant PP, wherein the impact-resistant PP is contained in an amount of 5 to 10 parts by weight, based on 100 parts by weight of the total weight of the sponge layer. The heat resistance of the sponge can be optimized by homopolymerization PP and impact-resistant PP.
Preferably, the sponge layer also comprises ≦ 5 parts by weight of Polyethylene (PE), preferably Linear Low Density Polyethylene (LLDPE). The PE can improve the softness of the sponge layer.
Preferably, a stabilizer, for example, 1 part by weight, can also be added to the sponge layer as needed to further improve heat resistance; and color concentrates, for example 0 to 2 parts by weight.
In the sponge layer, two kinds of PP (homopolymerized PP and impact-resistant PP), linear low-density polyethylene, a foaming agent, a stabilizer and color master batches are uniformly mixed and then extruded to obtain a compact layer film, and then, electrons are crosslinked to form action points inside the compact layer film. The compact film is foamed into the polyolefin sponge through a foaming furnace, and the foaming rate has influence on the performance of the material. The properties of the raw materials PP, LLDPE will influence the thermodynamic behaviour of the polyolefin sponge, for example: shrinkage, cohesion, warpage, elongation at break and tensile strength.
Preferably, a paint layer is provided on the TPO skin layer. The surface coating may be carried out using conventional paints known in the art. Aqueous polyurethane paints are preferably used in the present invention. The surface treatment by printing paint on the surface of the TPO material can advantageously improve the gloss, hand feel, and light, heat, dirt, abrasion, scratch, and other functionalities of the obtained TPO artificial leather surface. The paint layer can for example comprise the following components: 60-75 parts of aqueous polyurethane dispersoid, 0.5-1.5 parts of polyurethane thickener, 0.1-0.5 part of isocyanate curing agent, 10-40 parts of water and 0.5-2 parts of silicon dioxide.
The thickness of each layer constituting the TPO artificial leather of the present invention is not particularly required. One skilled in the art can select the appropriate thickness according to the particular requirements.
Accordingly, the present invention also provides a method for manufacturing a warp-resistant TPO artificial leather, comprising the following steps
(A) Providing a TPO skin layer comprising PP, PE and an elastomer, comprising 30 to 40 parts by weight PP, 30 to 40 parts by weight PE and 20 to 40 parts by weight elastomer, based on 100 parts by weight total of PP, PE and elastomer in the skin layer;
(B) providing a sponge layer comprising > 90 parts by weight PP and 3-5 parts by weight of a foaming agent, based on 100 parts by weight of the total sponge layer;
(C) and combining the TPO skin layer and the sponge layer together through composite embossing, wherein the traction tension is less than or equal to 30N.
In order to improve the warpage resistance of the manufactured TPO artificial leather, in addition to the product formulation of TPO, it is another key that the traction tension during the composite embossing process is as low as possible. It is desirable according to the present invention that neither the TPO skin layer nor the sponge layer have a control system tension (tension pulled by the traction device) in excess of 30N, preferably in excess of 25N. The low tension minimizes the stretching deformation of the TPO artificial leather.
Preferably, the embossing temperature is 175-. If the embossing temperature is too low, e.g., < 155 ℃, the pattern is difficult to press on the TPO skin and the product cannot be used in a precision trim lamination technique. If the embossing temperature is more than 155 ℃ and less than 175 ℃, although the pattern can be formed, the pattern retention is not so good in the post-processing formation, and the pattern forming appearance fluctuates depending on the depth. In addition, if the temperature is too high, the product will appear too bright and have a high gloss during embossing, typically exceeding 220 ℃, and the TPO will melt completely and fail to emboss properly.
According to the invention, after the TPO skin layer and the sponge layer are compounded, the TPO material is cooled by sequentially cooling.
Preferably, the TPO artificial leather manufactured according to the above method is the aforementioned TPO artificial leather resistant to warping according to the present invention. Thus, the aforementioned characteristics of TPO artificial leather are also applicable to the preparation method, and will not be described repeatedly.
Finally, the invention also provides the application of the warping-resistant TPO artificial leather, which can be applied to the precise edge cutting and laminating technology. Compared with the conventional process, the precise trimming and laminating technology can more favorably perform part forming. For this, after TPO artificial leather is manufactured by compounding a TPO skin layer with a polyolefin sponge layer by infrared heating, it is pre-cut into a skin of an irregular shape which is precise and slightly larger than a part by a cutter. Then carry out the hot melt adhesive coating to irregular shape's TPO synthetic leather, the hot melt adhesive is accurately coated on sponge layer one side surface. The hot melt adhesive can be selected from a reactive type or a non-reactive type, the reactive type is generally not more than 12 hours, and the non-reactive type product can be stored for 2-3 months at most. And finally, the irregular TPO artificial leather precoated with the hot melt adhesive is precisely attached to the framework through a precise film laminating machine to form an automotive interior part, such as an automotive interior decoration area of an instrument panel, a door panel and the like. Alternatively, the hot melt adhesive can be coated on the back of the sponge in advance through a roll gluing machine, then the TPO artificial leather is cut into a designed shape by a precise mould and then is attached to the framework, and the using amount of the hot melt adhesive is slightly larger than that of the scheme of cutting irregular skins and then coating the hot melt adhesive.
The TPO artificial leather according to the present invention has advantages in that: has good dimensional stability, the dimensional change of the foam layer relative to the TPO skin layer is less than or equal to 1mm, the warp degree at normal temperature is less than or equal to 1cm, the warp degree after 10min at 120 ℃ is less than or equal to 2cm, and in addition, the shrinkage rate at high temperature is reduced compared with the traditional TPO, for example, the shrinkage rates in the machine direction (longitudinal direction) and the breadth direction (transverse direction) tested after 168h at 80 ℃ according to GMW4217 are less than or equal to 2 percent, and the shrinkage rates in the machine direction (longitudinal direction) and the breadth direction (transverse direction) tested after 168h at 120 ℃ according to GMW4217 are less than or equal to 3 percent. Therefore, after the hot melt adhesive is coated for adhering the framework, the TPO material cannot be warped, and the method can be well applied to an accurate film laminating technology; and the flatness of the TPO material can be adjusted. Meanwhile, the thermal aging resistance and compression resilience of the TPO artificial leather of the invention both keep expected requirements, for example, when the thermal aging resistance is measured after 500 hours at 120 ℃ according to GMW141223.2.9.3, the gray level is more than or equal to 4; the compression resilience was tested according to DBL5306.15.2 and was 0.1mm or more in rebound at 10N and 0.4mm or more in rebound at 40N.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following description will be made for clarity and completeness in combination with examples and comparative examples, and it is obvious that the described examples are a part of the examples of the present invention, but not all of the examples. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1：
TPO artificial leather was prepared according to the following method:
the method comprises the following steps: 40 parts by weight of PP (Bolu chemical), 40 parts by weight of LLDPE (Dow chemical), 20 parts by weight of TPV (gold hair), 3 parts by weight of color master batch and 1 part by weight of stabilizer are mixed uniformly by a double screw extruder at 210 ℃ to extrude a TPO skin layer of 0.5 mm.
Step two: and (3) performing coating treatment of polyurethane paint on the surface of the TPO film obtained according to the step one by a printing machine.
Step three: 90 parts by weight of homopolymerized PP, 6 parts by weight of impact-resistant PP, 2 parts by weight of linear low-density polyethylene, 1.5 parts by weight of foaming agent and 0.5 part by weight of stabilizer are mixed and extruded to obtain a 1.0mm sponge template.
Step four: a1.0 mm sponge template was foamed in a foaming oven at 250 ℃ to give a 2.0mm sponge layer.
Step five: the TPO skin layer and the sponge layer coated with the paint coating are subjected to composite embossing at 185 ℃ under a limit tension of 25N by an embossing laminator to obtain a sample.
Example 2：
TPO artificial leather was prepared according to the following method:
the method comprises the following steps: 35 parts by weight of PP (Bolu chemical), 35 parts by weight of LLDPE (Dow chemical), 30 parts by weight of TPV (gold hair), 3 parts by weight of color master batch and 1 part by weight of stabilizer are mixed uniformly by a double screw extruder at 210 ℃ to extrude a TPO skin layer of 0.5 mm.
Step two: and (3) performing coating treatment of polyurethane paint on the surface of the TPO film obtained according to the step one by a printing machine.
Step three: 88 parts by weight of homopolymerized PP, 8 parts by weight of impact-resistant PP, 2 parts by weight of linear low-density polyethylene, 1.5 parts by weight of foaming agent and 0.5 part by weight of stabilizer are mixed and extruded to obtain a 1.0mm sponge template.
Step four: a1.0 mm sponge template was foamed in a foaming oven at 250 ℃ to give a 2.0mm sponge layer.
Step five: and (3) carrying out composite embossing on the TPO skin layer and the sponge layer coated with the paint coating at 180 ℃ under the ultimate tension of 30N by using an embossing laminator to obtain a sample.
Example 3：
TPO artificial leather was prepared according to the following method:
the method comprises the following steps: 40 parts by weight of PP (Bolu chemical), 35 parts by weight of LLDPE (Dow chemical), 25 parts by weight of TPV (gold hair), 3 parts by weight of color master batch and 1 part by weight of stabilizer are mixed uniformly by a double screw extruder at 210 ℃ to extrude a TPO skin layer of 0.5 mm.
Step two: and (3) performing coating treatment of polyurethane paint on the surface of the TPO film obtained according to the step one by a printing machine.
Step three: 90 parts by weight of homopolymerized PP, 8 parts by weight of impact-resistant PP, 1.5 parts by weight of foaming agent and 0.5 part by weight of stabilizer are mixed and extruded to obtain a 1.0mm sponge template.
Step four: a1.0 mm sponge template was foamed in a foaming oven at 250 ℃ to give a 2.0mm sponge layer.
Step five: the TPO skin layer and the sponge layer coated with the paint coating are subjected to composite embossing at 175 ℃ under a limiting tension of 30N by an embossing laminator to obtain a sample.
Comparative example 1：
TPO artificial leather was prepared according to the following method:
the method comprises the following steps: 30 parts by weight of PP (Bolu chemical), 25 parts by weight of LLDPE (Dow chemical), 45 parts by weight of TPV (gold hair), 3 parts by weight of color master batch and 1 part by weight of stabilizer are mixed uniformly by a double screw extruder at 210 ℃ to extrude a TPO skin layer of 0.5 mm.
Step two: and (3) performing coating treatment of polyurethane paint on the surface of the TPO film obtained according to the step one by a printing machine.
Step three: 90 parts by weight of homopolymerized PP, 6 parts by weight of impact-resistant PP, 2 parts by weight of linear low-density polyethylene, 1.5 parts by weight of foaming agent and 0.5 part by weight of stabilizer are mixed and extruded to obtain a 1.0mm sponge template.
Step four: a1.0 mm sponge template was foamed in a foaming oven at 250 ℃ to give a 2.0mm sponge layer.
Step five: the TPO skin layer and the sponge layer coated with the paint coating are subjected to composite embossing at 185 ℃ under a limit tension of 25N by an embossing laminator to obtain a sample.
Comparative example 2：
TPO artificial leather was prepared according to the following method:
the method comprises the following steps: 40 parts by weight of PP (Bolu chemical), 40 parts by weight of LLDPE (Dow chemical), 20 parts by weight of TPV (gold hair), 3 parts by weight of color master batch and 1 part by weight of stabilizer are mixed uniformly by a double screw extruder at 210 ℃ to extrude a TPO skin layer of 0.5 mm.
Step two: and (3) performing coating treatment of polyurethane paint on the surface of the TPO film obtained according to the step one by a printing machine.
Step three: 90 parts by weight of homopolymerized PP, 6 parts by weight of impact-resistant PP, 2 parts by weight of linear low-density polyethylene, 1.5 parts by weight of foaming agent and 0.5 part by weight of stabilizer are mixed and extruded to obtain a 1.0mm sponge template.
Step four: a1.0 mm sponge template was foamed in a foaming oven at 250 ℃ to give a 2.0mm sponge layer.
Step five: the TPO skin layer and the sponge layer coated with the paint coating are subjected to composite embossing at 185 ℃ under 50N ultimate tension by an embossing laminator to obtain a sample.
Performance detection：
The TPO samples obtained in examples 1-3 and comparative examples 1-2 were tested for dimensional change, warpage, thermal aging resistance, shrinkage, and compression resilience, and specific test methods or standards are as described below. And the test results are shown in table 1.
1. Dimensional Change testing of sponge layer versus TPO skin layer
The test method comprises the following steps:
sampling in a whole width of an embossing machine, wherein the sampling is 50cm long (the first roll, the second roll and the last roll), and sampling is carried out at three positions of the left, the middle and the right (the sampling at the left and the right sides needs to be more than 10cm away from the edge);
cutting out test pieces with the length of 200mm and the width of 20 mm;
under the protection of gloves, using an art knife to slowly separate the sponge layer from one section, and only leaving about 10mm at the tail end;
the length of the sponge layer shrunk relative to the TPO skin layer was tested and recorded.
2. Degree of warp at normal temperature
The test method comprises the following steps: 10 x 10cm blocks of material were cut from the TPO samples, laid flat on a horizontal test bed, and then the vertical distance between the highest point of the warped edge and the test bed was measured with a straight ruler.
3. Warping degree after 10min at 120 DEG C
The test method comprises the following steps: 10cm by 10cm squares were cut from the TPO samples, aged in an oven at 120 ℃ for 10min, cooled to room temperature, placed on a horizontal test stand and the vertical distance between the highest point of the edge of the crimp and the test stand measured with a ruler.
4. According to GMW141223.2.9.3 heat aging resistance after 500h at 120 DEG C
5. Testing of shrinkage in Machine Direction (MD) and breadth direction (AMD) according to GMW4217 after 168h at a temperature of 40 deg.C
6. Testing of shrinkage in Machine Direction (MD) and breadth direction (AMD) according to GMW4217 at 80 ℃ after 168h
7. Testing of shrinkage in Machine Direction (MD) and breadth direction (AMD) according to GMW4217 after 168h at 120 deg.C
8. Testing of compression Resilience under 10N and 40N conditions according to DBL5306.15.2
Table 1: results of examining samples of examples 1 to 3 and comparative examples 1 to 2
The data shown in table 1 gave:
compared with the comparative examples 1-2, the TPO artificial leather obtained in the examples 1-3 has obviously improved dimensional stability, wherein the dimensional changes of the sponge layer relative to the TPO skin layer are less than or equal to 1mm, the warpage at normal temperature is less than or equal to 1cm, and the warpage at 120 ℃ for 10min is less than or equal to 2 cm;
comparative example 1 has increased the TPV content in the TPO skin layer, correspondingly reduced the PP and PE content, resulting in a significant deterioration in dimensional stability of the final product, as embodied by the dimensional change of the sponge layer relative to the TPO skin layer increased to 2.8mm, the warpage at room temperature increased to 2.5cm, the warpage at 120 ℃ for 10min increased to 3.0 cm;
comparative example 2 increased the traction tension during the composite embossing process with respect to example 1, thereby resulting in a significant deterioration in dimensional stability of the finally obtained product, in particular, the dimensional change of the sponge layer with respect to the TPO skin layer was increased to 2.3mm, the warpage at room temperature was increased to 2.7cm, and the warpage at 120 ℃ for 10min was increased to 4.5 cm.
Finally, an example of a precision trimming lamination is given: the TPO material prepared by the method is subjected to accurate trimming to obtain the shape of a door panel; coating hot melt adhesive on the surface of the pre-cut TPO sponge, wherein the TPO after being coated with the adhesive has no warpage; compounding the TPO material and the interior framework by a 3CON ESL compounding machine; finally, the composite TPO material door panel is obtained.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (10)
1. A warp-resistant TPO artificial leather comprising a TPO skin layer and a sponge layer, wherein,
the TPO skin layer comprises PP, PE and elastomer, and contains 30-40 parts by weight of PP, 30-40 parts by weight of PE and 20-40 parts by weight of elastomer based on 100 parts by weight of the total weight of PP, PE and elastomer in the skin layer;
the sponge layer comprises > 90 parts by weight PP and 3-5 parts by weight of a foaming agent, based on 100 parts by weight of the total sponge layer,
the TPO artificial leather has the warping degree of less than or equal to 1cm at normal temperature and less than or equal to 2cm after being heated at 120 ℃ for 10 min.
2. The TPO artificial leather of claim 1, comprising 20 to 25 parts by weight of the elastomer, based on 100 parts by weight of the combined weight of PP, PE and elastomer in the skin layer.
3. The TPO artificial leather of claim 1, the elastomer being TPV.
4. The TPO artificial leather of claim 1, the PP in the TPO skin layer having an elongation at break of > 300% and the PE in the TPO skin layer being linear low density polyethylene and having an elongation at break of > 300%.
5. The TPO artificial leather according to claim 1, the PP in the sponge layer is homo PP and impact PP, wherein the impact PP is contained in an amount of 5 parts by weight to 10 parts by weight based on 100 parts by weight of the total weight of the sponge layer.
6. The TPO artificial leather of claim 1, wherein the sponge layer further comprises 5 parts by weight or less of PE, preferably linear low density polyethylene.
7. A method for manufacturing a warp-resistant TPO artificial leather comprising the following steps
(A) Providing a TPO skin layer comprising PP, PE and an elastomer, comprising 30 to 40 parts by weight PP, 30 to 40 parts by weight PE and 20 to 40 parts by weight elastomer, based on 100 parts by weight total of PP, PE and elastomer in the skin layer;
(B) providing a sponge layer comprising > 90 parts by weight PP and 3-5 parts by weight of a foaming agent, based on 100 parts by weight of the total sponge layer;
(C) and combining the TPO skin layer and the sponge layer together through composite embossing, wherein the traction tension is less than or equal to 30N, preferably less than or equal to 25N.
8. The method as claimed in claim 7, wherein the embossing temperature is 175-185 ℃.
9. The method of claim 7, wherein the TPO artificial leather is the TPO artificial leather of any one of claims 1 to 6.
10. Use of TPO artificial leather manufactured according to the method of any one of claims 7 to 9, which is suitable for a precise edge trim lamination technique.
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Address after: No. 108 Jianghai South Road, Jingang Town, Zhangjiagang City, Suzhou City, Jiangsu Province, 215632 Patentee after: Benecke Changshun automotive interior materials (Zhangjiagang) Co.,Ltd. Country or region after: China Address before: 215632 No.1 Jianghai South Road, Jingang town, Zhangjiagang City, Jiangsu Province Patentee before: BENECKE-CHANGSHUN AUTO TRIM (ZHANGJIAGANG) Co.,Ltd. Country or region before: China |