CN111321608A - Skin layer composition, foaming layer composition and environment-friendly PVC artificial leather formed by same - Google Patents
Skin layer composition, foaming layer composition and environment-friendly PVC artificial leather formed by same Download PDFInfo
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- CN111321608A CN111321608A CN202010157239.5A CN202010157239A CN111321608A CN 111321608 A CN111321608 A CN 111321608A CN 202010157239 A CN202010157239 A CN 202010157239A CN 111321608 A CN111321608 A CN 111321608A
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- 239000000203 mixture Substances 0.000 title claims abstract description 52
- 239000002649 leather substitute Substances 0.000 title claims abstract description 49
- 238000005187 foaming Methods 0.000 title claims abstract description 21
- 239000004014 plasticizer Substances 0.000 claims abstract description 71
- 239000011347 resin Substances 0.000 claims abstract description 51
- 229920005989 resin Polymers 0.000 claims abstract description 51
- 235000012424 soybean oil Nutrition 0.000 claims abstract description 19
- 239000003549 soybean oil Substances 0.000 claims abstract description 19
- -1 trimellitic anhydride ester Chemical class 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 18
- 239000004088 foaming agent Substances 0.000 claims abstract description 7
- 239000004744 fabric Substances 0.000 claims description 21
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 239000006260 foam Substances 0.000 claims description 10
- 229920000742 Cotton Polymers 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 4
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 239000011846 petroleum-based material Substances 0.000 abstract description 7
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 113
- 239000004800 polyvinyl chloride Substances 0.000 description 113
- 239000010410 layer Substances 0.000 description 75
- 210000003491 skin Anatomy 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 24
- 239000003208 petroleum Substances 0.000 description 21
- 238000009472 formulation Methods 0.000 description 16
- 239000003973 paint Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 238000000576 coating method Methods 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000002344 surface layer Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004049 embossing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical class OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/06—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
- D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
- D06N3/0036—Polyester fibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
- D06N3/005—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by blowing or swelling agent
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
- D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The present invention relates to a skin layer composition for forming an environment-friendly PVC artificial leather, comprising: 44-50 parts by weight of PVC resin; more than 50 and less than or equal to 56 parts by weight of plasticizer; based on 100 parts by weight of the total weight of the PVC resin and the plasticizer, 2-6 parts by weight of the stabilizer, the plasticizer is an environment-friendly plasticizer compounded by epoxidized soybean oil and trimellitic anhydride ester. And also relates to a foaming layer composition for forming an environment-friendly PVC artificial leather, comprising: 44-50 parts by weight of PVC resin; more than 50 and less than or equal to 56 parts by weight of plasticizer; based on 100 parts of the total weight of the PVC resin and the plasticizer, 2-6 parts of the stabilizer and 1-3 parts of the foaming agent by weight, and the plasticizer is an environment-friendly plasticizer compounded by epoxidized soybean oil and trimellitic anhydride ester. Also relates to an environment-friendly PVC artificial leather which improves the proportion of non-petroleum-based materials so as to meet the requirements of environmental protection and regeneration.
Description
Technical Field
The present invention relates to a skin layer composition, a foaming layer composition for forming an environmentally friendly PVC artificial leather, and an environmentally friendly PVC artificial leather comprising a skin layer formed of the skin layer composition and a foaming layer formed of the foaming layer composition.
Background
Polyvinyl chloride (i.e., PVC) is a main raw material in the production and development of artificial leather, and is widely used in automotive interiors. PVC artificial leather generally comprises a skin layer and a foam layer, and a paint layer is usually further provided on the skin layer side, and a base cloth layer is usually adhered on the foam layer side.
The traditional PVC material contains many petroleum raw materials, such as PVC powder, plasticizer, polyester material in base cloth, and the like. In the prior art, the main component of the PVC skin layer, the PVC foaming layer and the PVC adhesive layer is PVC paste resin, and the content of the PVC paste resin is usually more than 50 percent. For example, CN109208340A discloses PVC artificial leather comprising a skin layer, a foamed layer and a glue layer, wherein both the skin layer and the foamed layer contain 100phr of PVC powder.
In order to ensure the coating effect, a low-viscosity PVC paste resin or a mixture of a low-viscosity PVC paste resin and a high-viscosity PVC paste resin is generally selected. Because the viscosity is too high, the coating process is more difficult to accomplish. However, petroleum raw materials such as PVC powder, a plasticizer, a polyester material in base cloth and the like are too much to recycle, and the requirements of the society on higher environmental protection and renewable concepts of products are not met.
Therefore, there is a need to develop PVC artificial leather more satisfying the environmental protection and renewable requirements.
Disclosure of Invention
Based on the prior art, the present invention is to provide a skin layer composition and a foam layer composition, which can form an environmentally friendly PVC skin layer and a PVC foam layer, respectively. Furthermore, the invention provides an environment-friendly PVC artificial leather comprising the PVC skin layer and the PVC foaming layer. The PVC artificial leather improves the proportion of non-petroleum-based materials, thereby being capable of meeting the requirements of environmental protection and reproducibility.
To achieve the above technical objects, the present invention first proposes a skin layer composition for forming environment-friendly PVC artificial leather, comprising:
44 parts by weight or more and less than 50 parts by weight of PVC resin, preferably 44-46 parts by weight;
greater than 50 parts by weight and less than or equal to 56 parts by weight of a plasticizer, preferably 54 to 56 parts by weight;
2 to 6 parts by weight of a stabilizer based on 100 parts by weight of the total weight of the PVC resin and the plasticizer,
wherein, the plasticizer is an environment-friendly plasticizer compounded by epoxidized soybean oil and trimellitic anhydride ester.
In the present invention, in order to reduce the use ratio of petroleum-based raw materials, the plasticizer content in the skin layer composition is increased and the PVC resin content is decreased. In conventional PVC compositions, the PVC resin is generally present in an amount of 50-65% of the main formulation (based on 100 parts by weight of the total weight of PVC resin and plasticizer), and the present invention reduces the PVC resin content to less than 50%. If the content of the PVC resin is 50 parts by weight or more, the environmental friendliness cannot be ensured. The lower limit of the PVC resin content is 44 parts by weight, and if it is less than 44 parts by weight, the viscosity is too low to be processed. Accordingly, the plasticizer content in the present invention is increased to more than 50 parts by weight. If the content is less than 50 parts by weight, the environmental protection property cannot be ensured. The upper limit of the plasticizer content is 56 parts by weight, and if it exceeds the upper limit, the fluidity becomes too large and the processing becomes difficult.
In addition to adjusting the content of PVC resin and plasticizer, in order to reduce the use proportion of petroleum-based raw materials, the key point of the invention is to use the environment-friendly plasticizer compounded by epoxidized soybean oil and trimellitic anhydride ester as the plasticizer. Wherein trimellitic anhydride ester is the primary plasticizer, and 80.5% of trimellitic anhydride ester is non-petroleum based material; epoxidized soybean oil is used as an auxiliary plasticizer, and 100% of the epoxidized soybean oil is non-petroleum-based material. Trimellitic anhydride esters belong to the group of high-viscosity biphenyl plasticizers, which have a higher molecular weight than conventional biphenyl plasticizers. And trimellitic anhydride esters are more environmentally friendly than conventional ortho-benzene plasticizers because the non-petroleum based materials of conventional ortho-benzene plasticizers constitute only 50-60%.
In order to ensure the heat resistance of the material, a stabilizer is generally required to be added to the skin layer composition. The grade and amount of stabilizer depends on the heat resistance requirements of the customer. Calcium zinc stabilizers are generally preferred under high heat resistance requirements; organic epoxy stabilizers or organic tin stabilizers are preferably selected for general heat resistance requirements.
Preferably, the viscosity of the PVC resin is 6000-. Particularly when the PVC resin is present in an amount of 44 to 46 parts by weight, and the plasticizer is present in an amount of 54 to 56 parts by weight, respectively, by selecting the viscosity of the PVC resin to be 6000-8000mpa.s as measured according to ASTM D1824, such a high viscosity PVC resin can compensate for the reduction in viscosity caused by the excessive liquid plasticizer, thereby ensuring that the viscosity of the material is suitable for processing. At this time, if the viscosity of the PVC paste is too low, it may result in non-workability.
Preferably, among the environmentally friendly plasticizers, epoxidized soybean oil: the content ratio of trimellitic anhydride ester is 2:9 to 4: 6. If the epoxidized soybean oil is too much, the viscosity is too low, the processing cannot be performed, and the material performance cannot be met; if the amount of trimellitic anhydride ester is too high, a higher non-petroleum based content results.
In addition, other components, for example, a color paste of 1 to 5% (100 based on the total weight of the PVC resin and the plasticizer) can be added to the skin layer composition as needed, thereby realizing a desired color.
Secondly, the present invention also provides a foaming layer composition for forming an environment-friendly PVC artificial leather, comprising:
44 parts by weight or more and less than 50 parts by weight of PVC resin, preferably 44-46 parts by weight;
greater than 50 parts by weight and less than or equal to 56 parts by weight of a plasticizer, preferably 54 to 56 parts by weight;
based on the total weight of 100 parts by weight of PVC resin and plasticizer, 2-6 parts by weight of stabilizer and 1-3 parts by weight of foaming agent,
wherein, the plasticizer is an environment-friendly plasticizer compounded by epoxidized soybean oil and trimellitic anhydride ester.
Preferably, the viscosity of the PVC resin is 6000-. Particularly when the PVC resin is present in an amount of 44 to 46 parts by weight, and the plasticizer is present in an amount of 54 to 56 parts by weight, respectively, by selecting the viscosity of the PVC resin to be 6000-8000mpa.s as measured according to ASTM D1824, such a high viscosity PVC resin can compensate for the reduction in viscosity caused by the excessive liquid plasticizer, thereby ensuring that the viscosity of the material is suitable for processing. At this time, if the viscosity of the PVC paste is too low, it may result in non-workability.
Preferably, among the environmentally friendly plasticizers, epoxidized soybean oil: the content ratio of trimellitic anhydride ester is 2:9 to 4: 6.
Here, the reason for the limitation of the PVC resin, plasticizer and stabilizer is consistent with those in the skin layer composition, and will not be described again.
The foaming agent in the composition for the foamed layer may use a conventional chemical foaming agent, such as azo-based chemical foaming agents; conventional physical blowing agents, such as physical blowing agents in the microsphere class, may also be used. The particular choice depends on the thickness requirements for the product. When azo-based chemical blowing agents are used, it is also necessary to add, for example, 0.5% (based on 100% by weight of the total weight of the PVC resin and plasticizer) of a catalyst, such as a zinc oxide catalyst, to promote foaming. In addition, other ingredients, for example, a mill base of 1% (based on 100% by weight of the total of the PVC resin and the plasticizer), can also be added to the foaming layer composition as needed, thereby realizing a desired color.
Finally, the present invention provides an environment-friendly PVC artificial leather comprising a skin layer formed of the skin layer composition according to the present invention and a foamed layer formed of the foamed layer composition according to the present invention.
Preferably, a base cloth layer is combined on one side of the foaming layer, and the base cloth layer is made of polyester-cotton blended base cloth, preferably polyester: the content ratio of cotton is 6: 4 to 8: 2. Here, the use of a polyester-cotton blended base fabric as the base fabric is another key to increase the non-petroleum-based content. Wherein, the terylene is a petroleum-based material, and the cotton is a non-petroleum-based material. The strength can be improved by using the polyester-cotton blended base fabric. Thus, even in the case of reducing the content of the PVC resin as compared with the conventional one, the strength required for artificial leather can be maintained.
The foamed layer and the base fabric layer are bonded together by an adhesive, and here, an adhesive conventionally used for PVC artificial leather, such as a polyurethane adhesive, etc., may be used. In the present invention, the adhesive is preferably a PVC adhesive comprising:
44 parts by weight or more and less than 50 parts by weight of PVC resin, preferably 44-46 parts by weight;
greater than 50 parts by weight and less than or equal to 56 parts by weight of a plasticizer, preferably 54 to 56 parts by weight;
2-6 parts by weight of a stabilizer, based on 100 parts by weight of the total weight of the PVC resin and the plasticizer;
wherein, the plasticizer is an environment-friendly plasticizer compounded by epoxidized soybean oil and trimellitic anhydride ester.
Preferably, the viscosity of the PVC resin in the PVC adhesive is 6000-8000mpa.s as determined according to ASTM D1824.
Preferably, among the environmentally friendly plasticizers for the PVC adhesive, epoxidized soybean oil: the content ratio of trimellitic anhydride ester is 2:9 to 4: 6.
Here, the definition of the PVC resin, plasticizer and stabilizer in the PVC binder is consistent with that in the skin layer composition, and the description thereof will not be repeated. In addition, the characteristics and technical effects of the composition for the skin layer and the composition for the foaming layer are also applicable to the environment-friendly PVC artificial leather, and are not described again here in order to avoid redundancy.
Preferably, a paint layer, typically a polyurethane type paint, preferably an aqueous polyurethane paint, is provided over the skin layer. The gloss, feel, and light, heat, dirt, abrasion, scratch, and other functionalities of the surface of the obtained PVC artificial leather can be advantageously improved by performing the surface treatment by printing paint over the skin layer. The paint layer may include, for example: 70-130 parts of polycarbon type aqueous polyurethane dispersoid, 0.1-20 parts of hand feeling agent, 0.05-5 parts of defoaming agent, 0.01-5 parts of flatting agent and 0.5-15 parts of curing agent.
There is no particular requirement for the thickness of each layer constituting the PVC artificial leather of the present invention. One skilled in the art can select the appropriate thickness according to the particular requirements. According to one embodiment of the present invention, the paint layer is 1-4% of the total weight of the product, the PVC skin layer is 25-45% of the total weight of the product, the PVC foam layer is 25-45% of the total weight of the product, the adhesive layer is 10-15% of the total weight of the product, and the base cloth layer is 15-20% of the total weight of the product.
In order to prepare the environment-friendly PVC artificial leather according to the present invention, a method comprising the steps of:
(A) preparing a PVC surface layer and a foaming layer, wherein the surface layer contains PVC resin, a plasticizer and a stabilizer, and the foaming layer contains the PVC resin, the plasticizer, the stabilizer and a foaming agent, and the surface layer and the foaming layer are combined together;
(B) adhering a base fabric layer on the foaming layer through an adhesive;
(C) printing a paint layer on the PVC surface layer, wherein the surface treatment has the effects of protecting the PVC surface layer from abrasion and pollution, adjusting the glossiness and the like;
(D) embossing the paint layer at high temperature to endow the PVC artificial leather with different patterns on the surface;
(E) and finishing the cutting and packaging of the finished product with different sizes according to the requirements of customers.
The PVC artificial leather obtained according to the invention can be applied to automotive interiors such as seats, trim panels, armrests, consoles and the like by a process of cutting seams and coating.
The invention has the advantages that: compared with the traditional PVC interior material, the proportion of the non-petroleum-based raw materials in the PVC artificial leather obtained by the invention is greatly improved. In the traditional PVC material, the renewable non-petroleum-based raw material only accounts for 0-6%, and the petroleum raw material accounts for 64-70%; in the environment-friendly PVC material obtained by the invention, the renewable non-petroleum-based raw materials can be improved to about 50% at most, and the petroleum raw materials are reduced to 21%, so that the environment-friendly PVC material conforms to the concept of environment-friendly sustainable development. In addition, the invention also greatly reduces the problem of carbon emission generated in the production process of the traditional PVC interior material.
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
The environment-friendly PVC artificial leather is prepared according to the following steps:
mixing the slurry: a slurry of the PVC skin layer, a slurry of the PVC foam layer and a slurry of the PVC adhesive were prepared respectively by conventional mixing with stirring according to the formulations of the PVC skin layer, foam layer and adhesive shown in table 1.
Coating: sending release paper, after the sent release paper is stored by the release paper (through the storage of the release paper, the machine does not need to be stopped when the release paper is replaced, thereby realizing continuous production), firstly coating the sizing agent of the PVC epidermal layer on one station of a coating machine, and drying for 30 seconds in a drying pipeline at 180 ℃. After cooling, the mixture was further sent to a two-station foam coater and dried in a drying tunnel at 190 ℃ for 20 seconds. And (3) after cooling, conveying the PVC foaming layer to a three-station glue base cloth coating machine, and then drying the PVC leather coated with the PVC adhesive and the base cloth in a drying oven at 210 ℃ for 60 seconds to complete the whole plasticization of the PVC leather and obtain the finally required hardness. After cooling, the release paper was peeled from the formed laminate and wound up, and the artificial leather produced was wound up.
Printing: the artificial leather is uncoiled and sent, preheating is carried out, the preheated artificial leather is subjected to 3 times of printing of waterborne polyurethane system paint, the waterborne polyurethane system paint is printed on the surface of a PVC surface layer, and the waterborne polyurethane system paint is dried for 10 seconds through an inter-plate drying oven at 90 ℃ between each time of printing of the paint, is dried for 40 seconds through an oven at 140 ℃ after all the 3 times of printing of the paint is finished, and is coiled after cooling.
Embossing: and (3) unwinding and sending the artificial leather, sending the artificial leather to a heating cylinder for preheating, further performing air heating, pressing patterns on the surface of the painted artificial leather at the embossing temperature of 190 ℃, giving the patterns, cooling, inspecting, storing and winding.
Cutting: the artificial leather coiled material obtained after the preparation can be cut and packaged according to the required size.
Table 1: each layer formulation of example 1 (content unit: parts by weight)
Example 2
PVC artificial leather was prepared according to the formulation shown in table 2 by the method of example 1.
Table 2: each layer formulation of example 2 (content unit: parts by weight)
Example 3
PVC artificial leather was prepared according to the formulation shown in table 3 by the method of example 1.
Table 3: each layer formulation of example 3 (content unit: parts by weight)
Comparative example 1
PVC artificial leather was prepared according to the formulation shown in table 4 by the method of example 1.
Table 4: formulation of each layer of comparative example 1 (content unit: parts by weight)
Comparative example 2
PVC artificial leather was prepared according to the formulation shown in table 5 by the method of example 1.
Table 5: formulation of each layer of comparative example 2 (content unit: parts by weight)
Comparative example 3
PVC artificial leather was prepared according to the formulation shown in table 6 by the method of example 1.
Table 6: formulation of each layer of comparative example 3 (content unit: parts by weight)
Comparative example 4
PVC artificial leather was prepared according to the formulation shown in table 7 by the method of example 1.
Table 7: formulation of each layer of comparative example 4 (content unit: parts by weight)
It is noted here that the formulation of comparative example 4 obtained a slurry with a very low viscosity, resulting in no processability, and thus no further production of PVC artificial leather was possible. This is because, although in comparative example 4, the PVC, the content of the plasticizer and the compounding ratio of the plasticizer are set within the preferable range of the present invention, the non-petroleum-based ratio of the product is achieved as low as possible. However, the viscosity of PVC resin is set low as in the conventional art, thereby resulting in insufficient viscosity of the slurry for normal processing.
The non-petroleum-based ratio of the products was calculated for the PVC artificial leathers obtained from examples 1 to 3 and comparative examples 1 to 3, and the calculation process and results are shown in table 8.
Table 8: calculation and comparison of non-petroleum based proportions of products
| a* | b* | c* | d* | |
| Example 1 | 83％*56％*(2/11+9/11*70％)＝34.9％ | 0 | 17％*0.2＝3.4％ | 38.3％ |
| Example 2 | 83％*55％*(3/10+7/10*70％)＝36.1％ | 0 | 17％*0.3＝5.1％ | 41.2％ |
| Example 3 | 83％*54％*(4/10+6/10*70％)＝36.7％ | 0 | 17％*0.4＝6.8％ | 43.5％ |
| Comparative example 1 | 83％*45％*(2/11+9/11*70％)＝28.2％ | 0 | 17％*0.2＝3.4％ | 31.6％ |
| Comparative example 2 | 83％*56％*70％＝32.5％ | 0 | 17％*0.2＝3.4％ | 35.9％ |
| Comparative example 3 | 83％*56％*2/11＝8.45％ | 0 | 17％*0.2＝3.4％ | 11.85％ |
-a*、b*、c*、d*Respectively representing the non-petroleum base proportion in the plasticizer, the non-petroleum base proportion in the PVC, the non-petroleum base proportion in the base cloth and the total non-petroleum base proportion in the product;
the plasticizer + PVC + base fabric is taken as 100 parts, and other stabilizers and additives are omitted. Wherein the plasticizer and the PVC account for 83 percent, and the base cloth accounts for 17 percent of the total weight.
As can be seen from the results in table 8, the total non-petroleum-based proportion in the products obtained in examples 1 to 3 of the present invention can approach 50%, which is significantly improved compared to comparative example 1(PVC resin content higher than 50 parts by weight) and comparative example 3 (compounded plasticizer using epoxidized soybean oil and dialkyl phthalate), and is also partially improved compared to comparative example 2 (pure trimellitic anhydride ester plasticizer). A high non-petroleum based proportion of the product represents better environmental protection and renewability.
Hand feeling test was performed according to GM3390 on the PVC artificial leathers obtained from examples 1 to 3 and comparative examples 1 to 3, and the results are shown in Table 9.
Table 9: hand feel testing of products
| Hand feeling test | |
| Example 1 | 48 |
| Example 2 | 51 |
| Example 3 | 55 |
| Comparative example 1 | 80 |
| Comparative example 2 | 48 |
| Comparative example 3 | 48 |
From the results of Table 9, it can be seen that the hand (stiffness) of the products obtained in examples 1 to 3 of the present invention was remarkably improved as compared with that of comparative example 1 (the content of PVC resin was more than 50 parts by weight).
Finally, the mechanical properties of the PVC artificial leather obtained from examples 1-3 were examined: thickness was measured according to DIN EN ISO2286 part 3; weight was measured according to DIN EN ISO2286 part 2; flame retardancy was tested according to VW TL 1010; static elongation according to PV3909, permanent stretchability according to PV3909, tear strength according to DIN 53356, substrate adhesion according to DIN 53357, tensile strength according to PV 3909. The results are shown in table 10.
Table 10: product mechanical property detection result
As can be seen from Table 10, the mechanical properties of the products obtained in examples 1 to 3 all meet the standard values. This shows that the PVC artificial leather obtained in examples 1 to 3 of the present invention retains the original level of desired mechanical properties while remarkably increasing the non-petroleum-based ratio and improving the hand feeling, compared to comparative example 1.
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 (11)
1. A skin layer composition for forming an environmentally friendly PVC artificial leather comprising:
44 parts by weight or more and less than 50 parts by weight of PVC resin, preferably 44-46 parts by weight;
greater than 50 parts by weight and less than or equal to 56 parts by weight of a plasticizer, preferably 54 to 56 parts by weight;
2 to 6 parts by weight of a stabilizer based on 100 parts by weight of the total weight of the PVC resin and the plasticizer,
wherein, the plasticizer is an environment-friendly plasticizer compounded by epoxidized soybean oil and trimellitic anhydride ester.
2. A skin composition as claimed in claim 1, wherein the PVC resin has a viscosity of 6000-8000mpa.s as determined according to astm d 1824.
3. A skin composition according to claim 1, wherein the environmentally friendly plasticizer comprises, in weight percent, epoxidized soybean oil: the content ratio of trimellitic anhydride ester is 2:9 to 4: 6.
4. A foaming layer composition for forming an environment-friendly PVC artificial leather, comprising:
44 parts by weight or more and less than 50 parts by weight of PVC resin, preferably 44-46 parts by weight;
greater than 50 parts by weight and less than or equal to 56 parts by weight of a plasticizer, preferably 54 to 56 parts by weight;
based on the total weight of 100 parts by weight of PVC resin and plasticizer, 2-6 parts by weight of stabilizer and 1-3 parts by weight of foaming agent,
wherein, the plasticizer is an environment-friendly plasticizer compounded by epoxidized soybean oil and trimellitic anhydride ester.
5. The foam layer composition according to claim 4, wherein the viscosity of the PVC resin is 6000-8000mpa.s as determined according to ASTM D1824.
6. The foam layer composition as claimed in claim 4, wherein, among the environmentally friendly plasticizers, epoxidized soybean oil: the content ratio of trimellitic anhydride ester is 2:9 to 4: 6.
7. An environment-friendly PVC artificial leather comprising a skin layer formed of the skin layer composition according to any one of claims 1 to 3 and a foamed layer formed of the foamed layer composition according to any one of claims 4 to 6.
8. The environment-friendly PVC artificial leather according to claim 7, wherein a base cloth layer is bonded to one side of the foaming layer, and the base cloth layer is made of polyester-cotton blended base cloth, preferably polyester: the content ratio of cotton is 6: 4 to 8: 2.
9. The environment-friendly PVC artificial leather according to claim 8, wherein the foaming layer and the base fabric layer are bonded together by an adhesive, preferably a PVC adhesive, comprising:
44 parts by weight or more and less than 50 parts by weight of PVC resin, preferably 44-46 parts by weight;
greater than 50 parts by weight and less than or equal to 56 parts by weight of a plasticizer, preferably 54 to 56 parts by weight;
2-6 parts by weight of a stabilizer, based on 100 parts by weight of the total weight of the PVC resin and the plasticizer;
wherein, the plasticizer is an environment-friendly plasticizer compounded by epoxidized soybean oil and trimellitic anhydride ester.
10. The environment-friendly PVC artificial leather according to claim 9, wherein the viscosity of the PVC resin in the PVC adhesive is 6000-8000mpa.s as measured according to ASTM D1824.
11. The environment-friendly PVC artificial leather according to claim 9, wherein the weight ratio of epoxidized soybean oil among environment-friendly plasticizers used in the PVC adhesive is: the content ratio of trimellitic anhydride ester is 2:9 to 4: 6.
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