Polyvinyl chloride artificial leather without foaming structure and manufacturing method thereof

Abstract

The invention discloses polyvinyl chloride artificial leather without a foaming structure and a manufacturing method thereof. The polyvinyl chloride artificial leather comprises a base cloth layer and a fabric layer. The fabric layer is formed by a fabric composition containing polyvinyl chloride resin and a polymer plasticizer. The polymer plasticizer is formed by carrying out a polycondensation reaction on a dibasic acid raw material and a dibasic alcohol raw material and blocking the dibasic acid raw material through a blocking fatty acid. The end-capped fatty acid is a biomass-derived fatty acid, the chemical structure of the end-capped fatty acid has a long carbon chain with a carbon number between C8 and C22, one end of the long carbon chain has a carboxyl group, and the other end of the long carbon chain does not have a carboxyl group. The residual quantity of the dihydric alcohol raw material in the polymer plasticizer is controlled to be less than 300ppm, and the acid value of the polymer plasticizer is less than 1mg KOH / g. Therefore, the artificial leather with better odor quality can be produced. Therefore, the biomass content ratio of the polyvinyl chloride artificial leather is increased, and the odor emitted by the polyvinyl chloride artificial leather can be improved in an auxiliary manner.

Description

Technical Field

[0001] The invention relates to a polyvinyl chloride artificial leather, in particular to a polyvinyl chloride artificial leather without a foaming structure and a manufacturing method thereof. Background Art

[0002] Polyvinyl chloride (PVC) is the main raw material in the production and development of artificial leather and is widely used in the interior of automobiles. Polyvinyl chloride with a high degree of polymerization has a high melting point and poor fluidity of the melt, which leads to the problem of difficulty in processing.

[0003] In order to improve the fluidity of the melt of polyvinyl chloride, reduce the processing temperature and facilitate production and processing, plasticizers must be added to the polyvinyl chloride material. However, the acid plasticizers used in the prior art emit a pungent odor, and other additives added during the processing of polyvinyl chloride, such as foaming agents, may also emit a pungent odor.

[0004] In addition, in order to improve the surface properties of artificial leather, the surface of artificial leather is usually treated. The existing surface treatment method mainly uses a solvent-based surface treatment agent.

[0005] However, the disadvantage of solvent-based surface treatment agents is that the odor level is relatively high. The odor level of existing surface-treated artificial leather measured according to Volkswagen's odor test method PV3900C3 is not less than level 4.0, which seriously affects the user's use pleasure. Furthermore, most of the existing solvent-based surface treatment agents contain irritating solvents (such as toluene and xylene), which may cause certain harm to human health.

[0006] Further, the polyvinyl chloride artificial leather (also known as PVC artificial leather) of the prior art usually comprises a dense fabric layer and a foaming layer providing a leather feel. However, the existing foaming layer may still emit a pungent odor due to the use of a foaming agent to produce a foaming structure.

[0007] In recent years, many studies have also been devoted to improving the odor level of PVC artificial leather.

[0008] CN107190521A discloses a polyvinyl chloride artificial leather with low odor, which comprises a base fabric layer, a PVC skin layer, and a paint layer in sequence. The plasticizer used in the patent comprises epoxy soybean oil and an acid plasticizer. In order to provide a leather feel, the patented technology still uses a foaming agent to produce a foaming structure. CN107366166A discloses a polyvinyl chloride artificial leather without reproductive toxicity, which comprises a polyvinyl chloride epidermis layer, a polyvinyl chloride foaming layer, and a water paint layer coated on the polyvinyl chloride epidermis layer, the water paint layer does not contain N-methylpyrrolidone and N-ethylpyrrolidone, and can meet the environmental protection requirements of low VOC and low odor. However, in order to provide a leather feel, the patented technology still uses a foaming agent to produce a foaming structure.

[0009] The above-mentioned prior art still uses a foaming agent (especially chemical foaming) in the polyvinyl chloride artificial leather to produce a foamed structure, so the polyvinyl chloride artificial leather produced by the above-mentioned prior art may still emit a pungent odor.

[0010] In the technical field of polyvinyl chloride artificial leather, there is a need to further develop technical solutions to reduce the odor level of polyvinyl chloride artificial leather in order to improve the in-car environment and thus meet the requirements of most mid- to high-end cars.

[0011] Furthermore, improving the use of non-petrochemical materials in polyvinyl chloride artificial leather is also a goal that the art is committed to developing. Summary of the invention

[0012] The technical problem to be solved by the present invention is to provide a polyvinyl chloride artificial leather without a foaming structure and a manufacturing method thereof in view of the deficiencies of the prior art.

[0013] In order to solve the above technical problems, one of the technical solutions adopted by the present invention is to provide a polyvinyl chloride artificial leather without a foaming structure, comprising: a base fabric layer; and a fabric layer formed on the base fabric layer; wherein the fabric layer is formed by a fabric composition, and based on the total weight of the fabric composition being 100 parts by weight, the fabric composition comprises: 25 parts by weight to 65 parts by weight of a polyvinyl chloride resin; and 20 parts by weight to 60 parts by weight of a polymer plasticizer. wherein the polymer plasticizer is formed by a polycondensation reaction of a dibasic acid raw material and a diol raw material, and is capped by a capped fatty acid; wherein the capped fatty acid is a fatty acid derived from biomass, and its chemical structure has a long carbon chain with a carbon number between C8 and C22, and has a carboxyl group at one end of the long carbon chain, and does not have a carboxyl group at the other end of the long carbon chain. The residual amount of the diol raw material in the polymer plasticizer is less than 300 parts per million (ppm), and the acid value of the polymer plasticizer is less than 1 mg KOH / g.

[0014] Preferably, the capped fatty acid is at least one selected from the group consisting of lauric acid, stearic acid, palmitic acid, linoleic acid, n-caprylic acid, capric acid, and myristic acid.

[0015] Preferably, in the polycondensation reaction, a first initial molar number of the dibasic acid raw material is lower than a second initial molar number of the diol raw material.

[0016] Preferably, the fabric composition further comprises 3 to 5 parts by weight of a stabilizer; wherein the stabilizer is at least one selected from the following materials: lithium stearate, magnesium stearate, calcium stearate, barium stearate, zinc stearate, magnesium laurate, barium laurate, zinc laurate, calcium ricinoleate, barium ricinoleate, zinc ricinoleate, and zinc octanoate.

[0017] Preferably, there is no foaming layer between the fabric layer and the base fabric layer, and the fabric layer does not have any foaming pores.

[0018] In order to solve the above technical problems, another technical solution adopted by the present invention is to provide a method for manufacturing polyvinyl chloride artificial leather without a foaming structure, comprising: providing a base fabric layer; forming a fabric layer on one side surface of the base fabric layer, and the fabric layer is formed by a fabric composition; based on the total weight of the fabric composition being 100 parts by weight, the fabric composition comprises: 25 parts by weight to 65 parts by weight of polyvinyl chloride resin and 20 parts by weight to 60 parts by weight of a polymer plasticizer; wherein the polymer plasticizer is formed by a polycondensation reaction of a dibasic acid raw material and a diol raw material, and then capped by a capped fatty acid; wherein the capped fatty acid is a fatty acid of a biomass source, and its chemical structure has a long carbon chain with a carbon number between C8 and C22, and has a carboxyl group at one end of the long carbon chain, and has no carboxyl group at the other end of the long carbon chain. The residual amount of the diol raw material in the polymer plasticizer is less than 300 parts per million (ppm), and the acid value of the polymer plasticizer is less than 1 mg KOH / g.

[0019] Preferably, the polymer plasticizer is formed by the following steps: an esterification step: mixing the dibasic acid raw material and the diol raw material to form a reaction liquid, and heating to carry out the polycondensation reaction to form a polymer polyester polyol, the end of which has an excess of hydroxyl groups (-OH groups) at the end of the chemical structure; and an end-capping step: adding a biomass-derived blocked fatty acid to the reaction liquid to cap the excess hydroxyl groups on the polymer polyester polyol, thereby terminating the polycondensation reaction and forming the polymer plasticizer.

[0020] Preferably, a first initial molar number of the dibasic acid raw material when fed into the esterification step is lower than a second initial molar number of the diol raw material when fed into the esterification step.

[0021] Preferably, a third starting molar number of the capped fatty acid when fed in the capping step is higher than the difference between the second starting molar number of the diol raw material and the first starting molar number of the dibasic acid raw material, and the third starting molar number is 1.5 to 3 times the difference.

[0022] Preferably, the molar ratio of the first starting molar number of the dibasic acid raw material: the second starting molar number of the diol raw material: the third starting molar number of the capped fatty acid is 0.27-0.31: 0.32-0.35: 0.06-0.09.

[0023] The beneficial effect of the present invention is that according to the molecular weight design and molecular structure design of the polymer plasticizer of the present invention, the polymer plasticizer can replace the use of the existing low molecular weight plasticizer and avoid the use of the foaming agent. It not only improves the odor level of the polyvinyl chloride artificial leather, but also the molecular structure of the polymer plasticizer can make the fabric layer of the polyvinyl chloride artificial leather have a leather feel.

[0024] Furthermore, since the chemical structure end of the polymer plasticizer of the present invention is a capped fatty acid of biomass origin, the biomass content ratio of polyvinyl chloride artificial leather is increased. Furthermore, since the capped fatty acid of biomass origin has a natural fragrance (such as natural soap flavor), it can assist in improving the odor emitted by polyvinyl chloride artificial leather. In addition, the technical solution provided in the embodiment of the present invention can further effectively reduce the residual amount of diols in the reaction liquid compared to the method of removing diols only by general vacuum distillation.

[0025] To further understand the features and technical contents of the present invention, please refer to the following detailed description and drawings of the present invention. However, the drawings provided are only for reference and description and are not intended to limit the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is a schematic diagram of the laminated structure of polyvinyl chloride artificial leather in the prior art.

[0027] Figure 2 Schematic diagram of the laminated structure of polyvinyl chloride artificial leather according to an embodiment of the present invention. DETAILED DESCRIPTION

[0028] The following is an explanation of the disclosed embodiments of the present invention through specific embodiments. Those skilled in the art can understand the advantages and effects of the present invention from the contents disclosed in this specification. The present invention can be implemented or applied through other different specific embodiments, and the details in this specification can also be modified and changed in various ways based on different viewpoints and applications without departing from the concept of the present invention. In addition, the drawings of the present invention are only simple schematic illustrations and are not depicted according to actual dimensions. It is stated in advance. The following embodiments will further explain the relevant technical contents of the present invention in detail, but the disclosed contents are not intended to limit the scope of protection of the present invention.

[0029] It should be understood that although the terms "first", "second", "third" and the like may be used herein to describe various materials or parameters, these materials or signals should not be limited by these terms. These terms are mainly used to distinguish one material from another material, or one parameter from another parameter. In addition, the term "or" used herein may include any one or more combinations of the associated listed items depending on the actual situation.

[0030] [PVC artificial leather]

[0031] like Figure 2 As shown, an embodiment of the present invention provides a polyvinyl chloride artificial leather 100, and in particular provides a polyvinyl chloride artificial leather 100 without a foaming structure, the composition of which includes biomass-derived materials.

[0032] The polyvinyl chloride artificial leather 100 of the embodiment of the present invention can provide the leather feel required by general artificial leather without having a foaming structure.

[0033] More specifically, the polyvinyl chloride artificial leather 100 of the embodiment of the present invention comprises, from bottom to top, a base fabric layer 1 , a top fabric layer 2 , and a surface treatment layer 3 that is selectively coated.

[0034] The fabric layer 2 is directly formed on one side surface of the base fabric layer 1, and the surface treatment layer 3 is formed on one side surface of the fabric layer 2 away from the base fabric layer 1. The polyvinyl chloride artificial leather 100 of the embodiment of the present invention does not have a foam structure.

[0035] More specifically, in this embodiment, a solid structure (ie, the main body structure of the fabric layer 2 ) is formed extending from the surface of one side of the fabric layer 2 away from the base fabric layer 1 to the base fabric layer 1 .

[0036] Furthermore, the solid structure of the fabric layer 2 is in direct contact with the base fabric layer 1, and there is no foaming layer between the fabric layer 2 and the base fabric layer 1. The solid structure of the fabric layer 2 is not foamed and does not have any foaming structure such as foam pores, and can provide the leather feel required by general artificial leather without having a foaming structure.

[0037] It should be noted that the "solid structure" referred to in this article refers to a continuous phase resin structure that has not been foamed by a foaming agent and has no foaming pores. However, in the manufacturing process of artificial leather, due to the compatibility between different polymer materials or additives, or due to process parameters, the solid structure still has some pores, but they are not foamed pores.

[0038] Furthermore, the "leather feel" herein refers to the feel that the user feels when the polyvinyl chloride artificial leather is touched, which is similar to the feel that natural leather can provide.

[0039] In order to achieve the above technical objectives, the solid structure of the fabric layer 2 of the embodiment of the present invention is formed by a fabric composition.

[0040] The fabric composition includes: a polyvinyl chloride resin and a polymer plasticizer.

[0041] Based on the total weight of the fabric composition being 100 parts by weight, the amount of the polyvinyl chloride resin used is between 25 parts by weight and 65 parts by weight, and preferably between 35 parts by weight and 55 parts by weight. The amount of the polymer plasticizer used is between 20 parts by weight and 60 parts by weight, and preferably between 30 parts by weight and 50 parts by weight.

[0042] Furthermore, the polyvinyl chloride resin is the matrix material of the fabric composition, which is used to provide the mechanical strength required by the artificial leather. The polymer plasticizer is a high molecular weight plasticizer, which not only improves the odor level of the artificial leather, but also allows the fabric layer 2 to have a leather feel.

[0043] The polyvinyl chloride resin of the embodiment of the present invention has a weight average molecular weight (Mw) ranging from 30,000 to 200,000 g / mol and a glass transition temperature (Tg) ranging from 80° C. to 85° C.

[0044] The polymer plasticizer of the embodiment of the present invention has special material properties, so that the polyvinyl chloride artificial leather can have a low odor level, and the polyvinyl chloride artificial leather can provide the leather feel required by general artificial leather without a foaming structure.

[0045] More specifically, the polymer plasticizer of the embodiment of the present invention has a first weight average molecular weight between 1,500 g / mol and 6,000 g / mol, and preferably between 2,000 g / mol and 5,000 g / mol, but the present invention is not limited thereto.

[0046] It is worth mentioning that the polymer plasticizer used in the embodiment of the present invention has a much higher molecular weight than conventional plasticizers (the weight average molecular weight of conventional plasticizers is approximately between 300 g / mol and 800 g / mol).

[0047] Specifically, the polymer plasticizer according to the embodiment of the present invention has at least one linear soft segment in its molecular structure, and the soft segment has an ether group.

[0048] Furthermore, a concentration range of the soft segment having the ether group in the polymer plasticizer is between 10 wt % and 50 wt %, preferably between 10 wt % and 40 wt %, and particularly preferably between 10 wt % and 30 wt %.

[0049] According to the special molecular weight design and molecular structure design of the above-mentioned polymer plasticizer, the polymer plasticizer can replace the existing low molecular weight plasticizer and avoid the use of foaming agent. It not only improves the odor level of polyvinyl chloride artificial leather, but also the molecular structure of the polymer plasticizer can make the fabric layer 2 of the polyvinyl chloride artificial leather 100 have a leather feel.

[0050] In addition, in the molecular structure of the polymer plasticizer, the linear soft segment having the ether group can soften the resin material and provide a leather feel within the above concentration range.

[0051] Since the fabric layer 2 of the embodiment of the present invention can provide a leather feel without a foaming structure, the polyvinyl chloride artificial leather can also avoid the high-temperature process of chemical foaming.

[0052] In terms of thickness, the fabric layer 2 has a thickness D between 100 micrometers and 600 micrometers, and preferably between 150 micrometers and 350 micrometers, so as to provide sufficient leather feel.

[0053] In one embodiment of the present invention, the soft segment having the ether group is embedded in the middle or terminal part of the molecular structure of the polymer plasticizer. Furthermore, the soft segment having the ether group is on the main chain of the molecular structure of the polymer plasticizer, not in the form of a side chain, but the present invention is not limited thereto.

[0054] Specifically, the polymer plasticizer is a polymer polyester formed by a polycondensation reaction of a dibasic acid raw material and a diol raw material. Furthermore, the soft segment having the ether group is composed of at least one of a dibasic acid raw material and a diol raw material.

[0055] The dibasic acid raw material may be, for example, at least one selected from the group consisting of adipic acid (AA), succinic acid (SA), maleic acid (MA), decanedioic acid, and dodecanedioic acid.

[0056] Furthermore, the diol raw material may be, for example, at least one selected from the group consisting of diethylene glycol (DEG), triethylene glycol (TEG), tetraethylene glycol (TEG), polytetrahydrofuran (PTMEG), propane-1,2-diol (1,2-PG), 2-methyl-1,3-propanediol (MPO), neopentyl glycol (NPG), and 1,4-cyclohexanedimethanol ([4-(hydroxymethyl)cyclohexyl]methanol, CHDM). In some embodiments of the present invention, the dibasic acid raw material for synthesizing the polymer plasticizer may be adipic acid (AA). The diol raw material for synthesizing the polymer plasticizer may be: diethylene glycol (DEG) and optionally 2-methyl-1,3-propanediol (MPO) and / or polytetramethylene glycol (PTMEG).

[0057] In the polycondensation reaction, the polymer plasticizer is further capped by an end-capped fatty acid to terminate the polycondensation reaction. The end-capped fatty acid is a monobasic fatty acid of biomass origin (e.g., plant origin), and its chemical structure has only a single carboxyl group (-COOH group).

[0058] In some embodiments of the present invention, the chemical structure of the end-capped fatty acid has a long carbon chain with a carbon number between C8 and C22, and preferably between C12 and C18, and has a carboxyl group (-COOH group) at one end of the long carbon chain and no carboxyl group at the other end.

[0059] In some embodiments of the present invention, the capped fatty acid is at least one selected from the group consisting of lauric acid, stearic acid, palmitic acid, linoleic acid, n-caprylic acid, capric acid, and myristic acid.

[0060] For example, the biomass-derived lauric acid may be derived from at least one of coconut milk, coconut oil, laurel oil, and palm oil, and preferably coconut milk, but the present invention is not limited thereto.

[0061] For example, the biomass-derived stearic acid may be derived from at least one of tea oil, cocoa butter, and palm oil, and preferably tea oil, but the present invention is not limited thereto.

[0062] For example, the biomass-derived palmitic acid is derived from at least one of palm oil and palm kernel oil, and preferably palm oil, but the present invention is not limited thereto.

[0063] For example, the biomass-derived linoleic acid is derived from at least one of safflower oil, sunflower seed oil, corn oil, and linseed oil, and preferably safflower oil, but the present invention is not limited thereto.

[0064] The chemical structures of biomass-derived capped fatty acids are as follows.

[0065]

[0066] In the polycondensation reaction, relative to the stoichiometric number of the entire reaction, the dibasic acid raw material is the limiting reactant (also referred to as the limiting reagent), and the diol raw material is the excess reactant (also referred to as the excess reagent).

[0067] That is, in the polycondensation reaction, a first initial molar number of the dibasic acid raw material when fed is lower than a second initial molar number of the diol raw material when fed.

[0068] After the dibasic acid raw material and the diol raw material are polymerized to a number average molecular weight between 500 g / mol and 2,000 g / mol, preferably between 800 g / mol and 1,500 g / mol, through a polycondensation reaction, the dibasic acid raw material is completely reacted, and the chemical structure terminal of the high molecular weight polyester has an excess of hydroxyl groups (-OH groups). Residual diol raw materials exist in the reaction liquid of the polycondensation reaction.

[0069] In this embodiment, the polycondensation reaction is terminated by capping the excess hydroxyl groups with the capped fatty acid to terminate the polycondensation reaction and finally form the polymer plasticizer. Furthermore, the capped fatty acid also reacts with the residual diol raw material in the reaction liquid, thereby reducing the residual amount of diol in the polymer plasticizer to less than 300 parts per million (ppm).

[0070] In addition, the acid value of the polymer plasticizer is adjusted to less than 1 mg KOH / g to improve the rubber odor.

[0071] The acid value indicates the number of milligrams of potassium hydroxide (KOH) required to neutralize 1 gram of the chemical substance. The test standard may be, for example, ASTM D664.

[0072] According to the above configuration, since the chemical structure terminal of the polymer plasticizer in the embodiment of the present invention is a capped fatty acid derived from biomass, the biomass content ratio of the polyvinyl chloride artificial leather is increased.

[0073] Furthermore, since the biomass-derived capped fatty acids have a natural aroma (such as a natural soap smell), they can help improve the odor emitted by polyvinyl chloride artificial leather.

[0074] In addition, the technical solution provided by the embodiment of the present invention can further effectively reduce the amount of residual diol in the reaction liquid compared to the method of removing diol only by general vacuum distillation.

[0075] Furthermore, since the viscosity of the polymer plasticizer may be relatively viscous, it is difficult to uniformly mix the polymer plasticizer with the polyvinyl chloride resin during processing, thereby causing difficulty in processing.

[0076] In order to solve the above technical problems, the fabric composition further comprises: a processing aid in an amount not greater than 10 parts by weight.

[0077] For example, the fabric composition may include 1 part by weight, 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, or 10 parts by weight of the processing aid, but the present invention is not limited thereto.

[0078] The processing aid is a linear aliphatic dibasic acid ester and has a second weight average molecular weight between 300 and 800. That is, the weight average molecular weight of the processing aid is less than the weight average molecular weight of the polymer plasticizer.

[0079] In terms of material types, the processing aid is at least one selected from the group consisting of di-2-ethylhexyl sebacate (DOS), di-2-ethylhexyl adipate (DOA), di-isononyl adipate (DINA), di-isodecyl adipate (DIDA), and di-isononyl sebacate (DINS), and is preferably di-2-ethylhexyl sebacate (DOS).

[0080] According to the above configuration, the processing aid can help reduce the viscosity of the fabric composition, thereby improving the processability of the fabric composition.

[0081] Furthermore, the processing aid can also play the role of a plasticizer and enhance the leather feel of the fabric layer.

[0082] However, the amount of the processing aid should not be too high. If the amount of the processing aid is too high (eg, greater than 15 parts by weight), the fabric layer 2 may not be able to present the desired leather feel or odor level.

[0083] In one embodiment of the present invention, the fabric composition further comprises 3 to 5 parts by weight of a stabilizer, which can provide heat-resistant stability to the rubber and reduce the odor level of the artificial leather.

[0084] Wherein, the stabilizer is at least one selected from the following materials: lithium stearate, magnesium stearate, calcium stearate, barium stearate, zinc stearate, magnesium laurate, barium laurate, zinc laurate, calcium ricinoleate, barium ricinoleate, zinc ricinoleate, and zinc caprylate.

[0085] In some embodiments of the present invention, the stabilizer is a metal alkali compound, and is at least one of calcium ricinoleate, barium ricinoleate, and zinc ricinoleate.

[0086] It is worth mentioning that, in the process of introducing the polymer plasticizer of the present invention into the production of polyvinyl chloride artificial leather, since the rubber will have more acidic substances (such as blocked fatty acids) remaining, it will be unfavorable for the processing of artificial leather.

[0087] In order to improve this technical problem, the present invention increases the amount of stabilizer (such as calcium ricinoleate and / or zinc ricinoleate) in the fabric layer composition to improve the processability of artificial leather.

[0088] For example, in one specific embodiment of the present invention, when calcium ricinoleate and zinc ricinoleate are used simultaneously, the polyvinyl chloride artificial leather is subjected to a thermal stability test (i.e., the discoloration of the polyvinyl chloride artificial leather is tested at 190°C), and the amount of the stabilizer is increased to 3 parts by weight. The polyvinyl chloride artificial leather does not change color after being heated for 80 to 85 minutes, but the present invention is not limited thereto.

[0089] In one embodiment of the present invention, the fabric composition further comprises: 0 to 10 parts by weight of a filler. The filler is an inorganic granular material.

[0090] The filler is at least one of the following materials: calcium carbonate, silicon dioxide, alumina, clay, talc, diatomaceous earth, fertilizer and other metal oxides. Alternatively, the filler is at least one of the following materials: glass, carbon black, metal fibers and powders; glass balls, graphite, aluminum hydroxide, barium sulfate, magnesium oxide, magnesium carbonate, magnesium silicate, calcium silicate.

[0091] Wherein, the filler is preferably calcium carbonate, but the present invention is not limited thereto.

[0092] In one embodiment of the present invention, the fabric composition further comprises: 2 to 8 parts by weight of a flame retardant. The flame retardant is at least one selected from the following materials: aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, cresyl diphenyl phosphate, tris(2-chloroethyl)phosphate, tris(1-chloropropan-2-yl)phosphate, phosphoric acid tris(2-chloro-1-methylethyl)ester, chlorinated paraffin wax. The flame retardant is preferably antimony trioxide.

[0093] It is worth mentioning that in one embodiment of the present invention, the fabric composition does not contain any foaming agent, such as a chemical foaming agent or a physical foaming agent. The fabric layer 2 of the embodiment of the present invention can provide the leather feel required by general artificial leather without having a foaming structure or using a foaming agent. In other words, the pungent smell that may be caused by the use of a foaming agent or a foaming structure can be avoided in the present invention.

[0094] Please continue reading Figure 2 As shown, the base fabric layer 1 may be, for example, a woven fabric or a non-woven fabric (eg, non-woven fabric). The fabric layer 2 may be, for example, formed on the base fabric layer 1 in an artificial synthetic manner to form an artificial leather that looks like natural leather.

[0095] In this embodiment, the polyvinyl chloride artificial leather 100 further includes a surface treatment layer 3, which is formed by coating an aqueous surface treatment agent on the surface of the fabric layer 2 on the side away from the base fabric layer 1. The surface treatment layer 3 can improve the gloss, feel, light resistance, heat resistance, dirt resistance, wear resistance, and scratch resistance of the polyvinyl chloride artificial leather 100.

[0096] The surface of the surface treatment layer 3 on the side away from the fabric layer 2 can be subjected to high temperature embossing treatment, thereby forming different patterns on the surface of the artificial leather. In this embodiment, the water-based surface treatment agent is a water-based polyurethane system treatment agent that does not contain N-ethylpyrrolidone. Thereby, the material formula of the surface treatment layer 3 can also make the polyvinyl chloride artificial leather 100 have a lower odor level, thereby improving the user's use pleasure.

[0097] The water-based surface treatment agent adopts water-based polyurethane without N-ethylpyrrolidone, which abandons the traditional solvent-based treatment agent and can avoid solvent substances such as toluene and xylene that have pungent odors and are harmful to the human body. At the same time, by adopting the water-based polyurethane system treatment agent of this embodiment, it can also be achieved without N-ethylpyrrolidone to reduce the pungent odor.

[0098] It is worth mentioning that, in the present embodiment, there is no foaming layer or foaming structure between the surface treatment layer 3 and the fabric layer 2, and the surface treatment layer 3 does not include any foaming pores, but the present invention is not limited thereto.

[0099] According to the above configuration, the polyvinyl chloride artificial leather 100 without a foaming structure in the embodiment of the present invention can be used in automobile interior decoration, such as automobile door panels, dashboards, consoles, pillars, seat back panels, seat fabrics, etc.

[0100] Of course, the polyvinyl chloride artificial leather 100 without a foaming structure according to the embodiment of the present invention can also be applied to other fields such as automobile interiors.

[0101] [Method for producing polyvinyl chloride artificial leather]

[0102] The above is a description of the material characteristics of the polyvinyl chloride artificial leather of the embodiment of the present invention. The following will introduce the manufacturing method of the polyvinyl chloride artificial leather, which includes step S110, step S120, and step S130. It should be noted that the order of each step and the actual operation method in this embodiment can be adjusted according to needs, and the present invention is not limited to the embodiment.

[0103] The step S110 includes: providing a base fabric layer 1. The base fabric layer 1 can be, for example, a woven fabric or a non-woven fabric (eg, non-woven fabric).

[0104] The step S120 includes: forming a fabric layer 2 on a side surface of the base fabric layer 1 .

[0105] The fabric layer 2 is formed by a fabric composition comprising a polyvinyl chloride resin and a polymer plasticizer.

[0106] Based on the total weight of the fabric composition being 100 parts by weight, the amount of the polyvinyl chloride resin used is between 25 parts by weight and 65 parts by weight, and preferably between 35 parts by weight and 55 parts by weight. The amount of the polymer plasticizer used is between 20 parts by weight and 60 parts by weight, and preferably between 30 parts by weight and 50 parts by weight.

[0107] The polymer plasticizer has a first weight average molecular weight between 1,500 g / mol and 6,000 g / mol, and preferably between 2,000 g / mol and 5,000 g / mol, but the present invention is not limited thereto. Further, the polymer plasticizer is a polymer polyester formed by a polycondensation reaction of a dibasic acid raw material and a diol raw material. The material types of the dibasic acid raw material and the material types of the diol raw material have been described above and will not be described here.

[0108] In the polycondensation reaction, the polymer plasticizer is further capped by an end-capped fatty acid to terminate the polycondensation reaction. The end-capped fatty acid is a monoacid of biomass origin (e.g., plant origin), and its chemical structure has only a single carboxyl group (-COOH group).

[0109] In some embodiments of the present invention, the chemical structure of the end-capped fatty acid has a long carbon chain with a carbon number between C8 and C22, and preferably between C12 and C18, and has a carboxyl group (-COOH group) at one end of the long carbon chain and no carboxyl group at the other end. In some embodiments of the present invention, the end-capped fatty acid is at least one of the material groups consisting of lauric acid, stearic acid, palmitic acid, linoleic acid, n-caprylic acid, capric acid, and myristic acid. In the polycondensation reaction, relative to the stoichiometric number of the entire reaction, the dibasic acid raw material is the limiting reactant (also referred to as the limiting reagent), and the diol raw material is the excess reactant (also referred to as the excess reagent). That is, a first starting molar number of the dibasic acid raw material at the time of feeding is lower than a second starting molar number of the diol raw material at the time of feeding.

[0110] After the dibasic acid raw material and the diol raw material are polymerized to a number average molecular weight between 500 g / mol and 2000 g / mol, and preferably between 800 g / mol and 2000 g / mol, through a polycondensation reaction, the dibasic acid raw material is completely reacted, and the chemical structure terminal of the polymer polyester has an excess of hydroxyl groups (-OH groups). Residual diol raw materials exist in the reaction liquid of the polycondensation reaction.

[0111] In this embodiment, the polycondensation reaction is terminated by capping the excess hydroxyl groups with the capped fatty acid to terminate the polycondensation reaction and finally form the polymer plasticizer. Furthermore, the capped fatty acid also reacts with the residual diol raw material in the reaction liquid, thereby reducing the residual amount of diol in the reaction liquid to less than 300 parts per million (ppm).

[0112] In addition, the acid value of the polymer plasticizer is adjusted to less than 1 mg KOH / g to improve the rubber odor. The acid value is the number of milligrams of potassium hydroxide (KOH) required to neutralize 1 gram of chemical substances. The test standard can be, for example, ASTM D664.

[0113] According to the above configuration, since the chemical structure end of the polymer plasticizer of the embodiment of the present invention is a biomass-derived blocked fatty acid, the biomass content ratio of the polyvinyl chloride artificial leather is increased. Furthermore, since the biomass-derived blocked fatty acid has a natural fragrance (such as a natural soap smell), it can help improve the odor emitted by the polyvinyl chloride artificial leather.

[0114] In addition, the technical solution provided by the embodiment of the present invention can further effectively reduce the amount of residual diol in the reaction liquid compared to the method of removing diol only by general vacuum distillation.

[0115] Specifically, the polymer plasticizer can be prepared, for example, by the following preparation method. The preparation method sequentially comprises: an esterification step, an end-capping step, and a decompression step.

[0116] The esterification step includes: mixing a dibasic acid raw material (such as AA) and a diol raw material (such as MPO, DEG, PTMEG) to form a reaction liquid.

[0117] Then, the reaction liquid is heated to a first temperature (eg, 110° C. to 150° C., and preferably 120° C. to 140° C.), and maintained at the first temperature for 0.5 hour to 2 hours to perform a polycondensation reaction.

[0118] Then, the reaction liquid is heated to a second temperature (e.g., 190° C. to 200° C., and preferably 195° C.), and maintained at the temperature for 2 to 4 hours, wherein the dibasic acid raw material and the diol raw material are polymerized to a number average molecular weight between 500 g / mol and 2,000 g / mol, and preferably between 800 g / mol and 1,500 g / mol, through a polycondensation reaction, to form a high molecular weight polyester polyol.

[0119] As described above, in the polycondensation reaction, the dibasic acid raw material is the limiting reactant and the diol raw material is the excess reactant relative to the stoichiometric amount of the entire reaction.

[0120] That is, a first initial molar number of the dibasic acid raw material when it is fed is lower than a second initial molar number of the diol raw material when it is fed.

[0121] The end-capping step includes: adding a biomass-derived end-capped fatty acid (such as lauric acid) to the reaction liquid to end-cap the polymer polyester polyol formed in the esterification step, thereby terminating the polycondensation reaction and forming the polymer plasticizer of the embodiment of the present invention in the reaction liquid. In the end-capping step, the reaction liquid is heated to a third temperature (such as 200° C. to 210° C., and preferably 205° C.), and the temperature is maintained for 2 to 4 hours to continuously distill out the water in the reaction liquid and increase the concentration of the polymer plasticizer.

[0122] It is worth mentioning that the third initial molar number of the end-capped fatty acid when it is fed in the end-capping step is higher than the difference between the second initial molar number of the diol raw material and the first initial molar number of the dibasic acid raw material, and the third initial molar number is preferably 1.5 to 3 times the aforementioned difference. Thereby, the end-capped fatty acid can effectively cap the excess hydroxyl groups on the polymer polyester polyol to terminate the polycondensation reaction, and can also react with the residual diol raw material in the reaction liquid, thereby reducing the residual amount of diol in the reaction liquid, and can also avoid excessive residual end-capped fatty acids.

[0123] In some embodiments of the present invention, the molar ratio between the first starting molar number of the dibasic acid raw material: the second starting molar number of the diol raw material: the third starting molar number of the capped fatty acid can be, for example, 0.27-0.31: 0.32-0.35: 0.06-0.09, preferably 0.28-0.30: 0.32-0.34: 0.07-0.09, and specifically can be, for example, 0.29: 0.33: 0.08, but the present invention is not limited thereto.

[0124] The decompression step includes: reducing the pressure of the reaction liquid containing the polymer plasticizer in the end-capping step from normal pressure (i.e., 760 torr) to a low pressure of 50 to 150 torr, and cooling to a fourth temperature (e.g., 190° C. to 200° C., and preferably 195° C.) and maintaining the temperature for 1 to 3 hours. In the decompression step, the acid value of the polymer plasticizer is adjusted to less than 1 mg KOH / g to reach the reaction endpoint and complete the preparation of the polymer plasticizer.

[0125] According to the above configuration, the terminal of the chemical structure of the polymer plasticizer has a capped fatty acid of biomass origin, thereby increasing the proportion of biomass content in the polyvinyl chloride artificial leather and improving the odor of the polyvinyl chloride artificial leather.

[0126] The step S130 includes: forming a surface treatment layer 3 on the surface of the fabric layer 2 away from the base fabric layer 1. The surface treatment layer 3 is formed on the surface of the fabric layer 2 by coating with a water-based surface treatment agent to complete the polyvinyl chloride artificial leather. In this embodiment, the water-based surface treatment agent is a water-based polyurethane system treatment agent that does not contain N-ethylpyrrolidone.

[0127] [Experimental data test]

[0128] Hereinafter, the content of the present invention will be described in detail with reference to Examples 1 to 3 and Comparative Example 1. However, the following examples are only provided to help understand the present invention, and the scope of the present invention is not limited to these examples.

[0129] Example 1: The fabric composition in Example 1 in Table 1 below is sequentially mixed and melted at high temperature by a small mixer and a 10,000 horsepower machine; then the fabric composition is calendered by a calender to form the fabric composition into a fabric layer, and the fabric layer is attached to a base fabric layer by the calender; then, an aqueous polyurethane system treatment agent is applied to the surface of the fabric layer and dried to form a surface treatment layer. The polyvinyl chloride artificial leather of Example 1 is tested for physical and chemical properties, and the test results are shown in Table 1 below. Among them, the polymer plasticizer is prepared by mixing a dibasic acid raw material (such as AA) and a diol raw material (such as MPO, DEG, PTMEG mixed in a molar ratio of 2:1:0.05), and heating to 130°C, holding the temperature for 1 hour, and then heating to 195°C and holding the temperature for 3 hours to perform a polycondensation reaction (esterification reaction) and form a polyester polyol. A biomass-derived capped fatty acid (e.g., lauric acid) is added to the reaction liquid to cap the polyester polyol. The temperature is raised to 205° C. and maintained for 3 hours to distill off water and form a high molecular plasticizer in the reaction liquid with a weight average molecular weight of 3,845 g / mol.

[0130] In Example 1, the molar ratio of the dibasic acid raw material: the diol raw material: the capped fatty acid is 0.29:0.33:0.08.

[0131] Finally, the reaction liquid containing the polymer plasticizer is introduced into a decompression section (760-100 torr) and reacted at 195°C for 2 hours. The acid value of the polymer plasticizer is adjusted to less than 1 mg KOH / g to reach the end point of the reaction and complete the preparation of the polymer plasticizer.

[0132] The preparation methods of Examples 2 and 3 are roughly the same as those of the above-mentioned Examples. The differences between Examples 2 and 3 and Example 1 lie in the formulation of the fabric composition and the selection of the material of the end-capped fatty acid of the synthetic polymer plasticizer.

[0133] In addition, the end-capping material of the polymer plasticizer of Comparative Example 1 is isooctyl alcohol (monohydric alcohol) instead of end-capping fatty acid (monohydric fatty acid).

[0134] Next, the PVC artificial leathers prepared in Examples 1 to 3 and Comparative Example 1 were tested for physical and chemical properties to obtain the physical and chemical properties of the PVC artificial leathers, such as odor level, residual amount of low boiling point alcohols (ppm), and odor type. The relevant test results are summarized in Table 1.

[0135] The odor level is based on Volkswagen's odor test standard PV3900C3, tested at 80°C for 2 hours. The odor rating system is divided into 6 levels: 1 = no odor; 2 = odor but not disturbing; 3 = obvious odor but no disturbing odor; 4 = disturbing odor; 5 = strong disturbing odor; 6 = unbearable odor.

[0136] The residual amount (ppm) of low-boiling alcohols is tested using the headspace method, in which one gram of the product is placed in a test bottle and heated at 120°C for 30 minutes, and the top gas is extracted with a syringe needle for quantitative analysis.

[0137] [Table 1 Experimental conditions and test results]

[0138]

[0139]

[0140]

[0141] From the experimental results in Table 1, it can be seen that the odor levels of Examples 1 to 3 are all 3, which is less than 3.5 of Comparative Example 1. The residual alcohol low-boiling substances of Examples 1 to 3 are all less than 300 ppm, which is less than 2,242 of Comparative Example 1. The odor types of Examples 1 to 3 are all natural gas odors, which are different from the chemical odor of Comparative Example 1. Furthermore, in the experimental results not recorded in Table 1, the amount of stabilizer in Examples 1 to 3 is increased to 3 parts by weight, and accordingly, the final polyvinyl chloride artificial can be heated for 80 to 85 minutes without changing color.

[0142] [Beneficial Effects of Embodiments]

[0143] The beneficial effect of the present invention is that according to the molecular weight design and molecular structure design of the polymer plasticizer of the present invention, the polymer plasticizer can replace the use of the existing low molecular weight plasticizer and avoid the use of the foaming agent. It not only improves the odor level of the polyvinyl chloride artificial leather, but also the molecular structure of the polymer plasticizer can make the fabric layer of the polyvinyl chloride artificial leather have a leather feel.

[0144] Furthermore, since the chemical structure end of the polymer plasticizer of the present invention is a biomass-derived blocked fatty acid, the biomass content of the polyvinyl chloride artificial leather is increased. Furthermore, since the biomass-derived blocked fatty acid has a natural fragrance (such as a natural soap smell), it can help improve the odor emitted by the polyvinyl chloride artificial leather.

[0145] In addition, the technical solution provided by the embodiment of the present invention can further effectively reduce the amount of residual diol in the reaction liquid compared to the method of removing diol only by general vacuum distillation.

[0146] The contents disclosed above are only preferred feasible embodiments of the present invention, and are not intended to limit the scope of the present invention. Therefore, all equivalent technical changes made using the contents of the present invention's specification and drawings are included in the scope of the present invention.

Claims

1. A polyvinyl chloride artificial leather without a foaming structure, characterized in that: The polyvinyl chloride artificial leather without a foaming structure comprises: a base fabric layer; and A fabric layer is formed on the base fabric layer; wherein the fabric layer is formed by a fabric composition, and based on 100 parts by weight of the total weight of the fabric composition, the fabric composition comprises: 25 to 65 parts by weight of a polyvinyl chloride resin; and 20 to 60 parts by weight of a polymer plasticizer; The polymer plasticizer is formed by a polycondensation reaction of a dibasic acid raw material and a diol raw material, and is capped by a capped fatty acid; wherein the capped fatty acid is a biomass-derived fatty acid, and its chemical structure has a long carbon chain with a carbon number between C8 and C22. And there is a carboxyl group at one end of the long carbon chain, and there is no carboxyl group at the other end of the long carbon chain; wherein the residual amount of the diol raw material in the polymer plasticizer is less than 300 parts per million (ppm), and the acid value of the polymer plasticizer is less than 1 mgKOH / g.

2. The polyvinyl chloride artificial leather without a foaming structure according to claim 1, characterized in that: The capped fatty acid is at least one selected from the group consisting of lauric acid, stearic acid, palmitic acid, linoleic acid, n-caprylic acid, capric acid, and myristic acid.

3. The polyvinyl chloride artificial leather without a foaming structure according to claim 1, characterized in that: In the polycondensation reaction, a first starting molar number of the dibasic acid raw material is lower than a second starting molar number of the diol raw material.

4. The polyvinyl chloride artificial leather without a foaming structure according to claim 1, characterized in that: The fabric composition further comprises 3 to 5 parts by weight of a stabilizer; wherein the stabilizer is at least one selected from the following materials: lithium stearate, magnesium stearate, calcium stearate, barium stearate, zinc stearate, magnesium laurate, barium laurate, zinc laurate, calcium ricinoleate, barium ricinoleate, zinc ricinoleate, and zinc octanoate.

5. The polyvinyl chloride artificial leather without a foaming structure according to claim 1, characterized in that: There is no foaming layer between the fabric layer and the base fabric layer, and the fabric layer does not have any foaming pores.

6. A method for producing polyvinyl chloride artificial leather without a foaming structure, characterized in that: The method for manufacturing the polyvinyl chloride artificial leather without a foaming structure comprises: providing a base fabric layer; A fabric layer is formed on one side surface of the base fabric layer, wherein the fabric layer is formed of a fabric composition; Based on the total weight of the fabric composition being 100 parts by weight, the fabric composition comprises: 25 parts by weight to 65 parts by weight of a polyvinyl chloride resin and 20 parts by weight to 60 parts by weight of a polymer plasticizer; The polymer plasticizer is formed by a polycondensation reaction of a dibasic acid raw material and a diol raw material, and then capped by a capped fatty acid; The capped fatty acid is a fatty acid from a biomass source, and its chemical structure has a long carbon chain with a carbon number between C8 and C22, and has a carboxyl group at one end of the long carbon chain and no carboxyl group at the other end of the long carbon chain; The residual amount of the diol raw material in the fabric layer is less than 300 parts per million (ppm), and the acid value of the polymer plasticizer is less than 1 mg KOH / g.

7. The method for producing polyvinyl chloride artificial leather without a foaming structure according to claim 6, characterized in that: The polymer plasticizer is formed by the following steps: an esterification step: mixing the dibasic acid raw material and the diol raw material to form a reaction liquid, and heating to perform the polycondensation reaction to form a high molecular weight polyester polyol having an excess of hydroxyl groups (-OH groups) at the ends of its chemical structure; and End-capping step: adding a biomass-derived blocked fatty acid into the reaction liquid to cap the excess hydroxyl groups on the polymer polyester polyol, thereby terminating the polycondensation reaction and forming the polymer plasticizer.

8. The method for producing polyvinyl chloride artificial leather without a foaming structure according to claim 7, characterized in that: A first initial molar number of the dibasic acid raw material when fed into the esterification step is lower than a second initial molar number of the diol raw material when fed into the esterification step.

9. The method for producing polyvinyl chloride artificial leather without a foaming structure according to claim 8, characterized in that: A third starting molar number of the capped fatty acid when fed in the capping step is higher than a difference between the second starting molar number of the diol raw material and the first starting molar number of the dibasic acid raw material, and the third starting molar number is 1.5 to 3 times the difference.

10. The method for producing polyvinyl chloride artificial leather without a foaming structure according to claim 9, characterized in that: A molar ratio of the first starting molar number of the dibasic acid raw material: the second starting molar number of the diol raw material: the third starting molar number of the capped fatty acid is 0.27-0.31: 0.32-0.35: 0.06-0.09.

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