Polyvinyl chloride-based artificial leather having no foaming structure and manufacturing method thereof

Abstract

To provide a polyvinyl chloride-based artificial leather having no foaming structure, and also to provide a manufacturing method thereof.SOLUTION: A polyvinyl chloride-based artificial leather includes a base layer and a surface layer. The surface layer is formed of a surface composition including polyvinyl chloride resin and polymer plasticizer. The polymer plasticizer is formed by being terminal-blocked with a terminal-blocked fatty acid after polycondensation reaction between dibasic acid raw material and dihydric alcohol raw material. The terminal-blocked fatty acid is a biomass-derived fatty acid and chemical structure thereof has long carbon chain of C8 to C22, carboxyl group at one end of the long carbon chain but no carboxyl group at the other end of the long carbon chain. Residual amount of the dihydric alcohol raw material in the polymer plasticizer is less than 300 ppm and acid number of the polymer plasticizer is less than 1 mg KOH / g in the invention. Accordingly, the artificial leather excellent in smell quality can be manufactured.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a polyvinyl chloride-based artificial leather, and more particularly to a polyvinyl chloride-based artificial leather not having a foamed structure and a method for producing the same. [Background technology]

[0002] Polyvinyl chloride (PVC) is a major raw material in the production and development of artificial leather and is widely used in automotive interiors. Polyvinyl chloride with a high degree of polymerization has a high melting temperature and low melt fluidity, making it difficult to process.

[0003] In order to improve the melt flowability of polyvinyl chloride, lower the processing temperature, and facilitate the production processing, it is necessary to add a plasticizer to polyvinyl chloride materials. However, the phenolic acid plasticizers used in the conventional technology may release pungent odors, and the addition of other additives such as foaming agents during the processing of polyvinyl chloride may also release pungent odors.

[0004] In order to improve the surface properties of the artificial leather, the surface of the artificial leather is usually subjected to a surface treatment. Existing surface treatment methods mainly use solvent-based surface treatment agents.

[0005] However, solvent-based surface treatment agents have a problem with high odor levels. Artificial leather that has been treated with existing surface treatments has an odor level of 4.0 or higher when measured based on PV3900C3, a common automobile odor test method, which significantly affects the comfort of the user. In addition, most existing solvent-based surface treatment agents contain irritating solvents (e.g., toluene and xylene), which may be harmful to physical health.

[0006] In addition, the conventional polyvinyl chloride artificial leather (also called PVC artificial leather) usually includes a dense surface layer and a foam layer to provide the feel of leather. However, since the existing foam layer is a foam structure formed by a foaming agent, it may still emit an irritating odor.

[0007] In recent years, much research has been conducted into improving the odor levels of PVC artificial leather.

[0008] CN107190521A discloses a low odor polyvinyl chloride artificial leather with a base layer, a PVC leather layer, and a paint layer in sequence. The plasticizers used in this patent document include epoxidized soybean oil and phenolic acid plasticizers. In order to provide the feel of leather, this patent document still uses a foaming agent to create a foam structure. CN107366166A discloses a non-reproductively toxic polyvinyl chloride artificial leather including a polyvinyl chloride surface layer, a polyvinyl chloride foam layer, and an aqueous paint layer coated on the polyvinyl chloride surface layer. The aqueous paint layer does not contain N-methylpyrrolidone and N-methylpyrrolidone, and simultaneously meets the environmental protection requirements of low VOC and low odor. However, in order to provide the feel of leather, this patent document still uses a foaming agent to create a foam structure.

[0009] Since the polyvinyl chloride-based artificial leather in the conventional technology still generates a foam structure by foaming (especially chemical foaming) with a foaming agent, the polyvinyl chloride-based artificial leather produced by the conventional technology still may have an irritating odor.

[0010] In the technical field of polyvinyl chloride-based artificial leather, there is a need to further develop a technical solution for further reducing the odor level of polyvinyl chloride-based artificial leather so as to improve the in-car environment and meet the requirements of luxury cars.

[0011] Furthermore, one of our goals in developing this field is to increase the proportion of non-petrochemical-derived materials used in polyvinyl chloride-based artificial leather. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] China Publication No. CN107190521A [Patent Document 2] China Publication No. CN107366166A Summary of the Invention [Problem to be solved by the invention]

[0013] The technical problem to be solved by the present invention is to provide a polyvinyl chloride-based artificial leather that does not have a foamed structure and a manufacturing method thereof in response to the shortcomings of the prior art. [Means for solving the problem]

[0014] In order to solve the above technical problems, one technical means adopted by the present invention is to provide a polyvinyl chloride-based artificial leather having no foamed structure. The polyvinyl chloride-based artificial leather having no foamed structure comprises a base layer and a surface layer formed of the surface composition and formed on the base layer, and the surface composition contains 25 to 65 parts by weight of a polyvinyl chloride resin and 20 to 60 parts by weight of a polymer plasticizer, with the total weight of the surface composition being 100 parts by weight.

[0015] Here, the polymeric plasticizer is formed by performing a polycondensation reaction between a dibasic acid raw material and a dihydric alcohol raw material, followed by end-capping with an end-capping fatty acid, wherein the end-capping fatty acid is a fatty acid derived from biomass, and the chemical structure of the end-capping fatty acid has a long carbon chain of C8 to C22, a carboxyl group at one end of the long carbon chain, and no carboxyl group at the other end of the long carbon chain.

[0016] Here, the residual amount of the dihydric alcohol raw material in the polymer plasticizer is less than 300 ppm, and the acid value of the polymer plasticizer is less than 1 mg KOH / g.

[0017] Preferably, the end-capping 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.

[0018] Preferably, in the polycondensation reaction, the first initiation number of moles of the diacid feedstock is lower than the second initiation number of moles of the dihydric alcohol feedstock.

[0019] Preferably, the surface composition further comprises 3 to 5 parts by weight of a stabilizer, and the stabilizer is at least one selected from the group consisting of 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.

[0020] Preferably, no foam layer is included between the surface layer and the base layer, and the surface layer also does not include foam pores due to foaming.

[0021] In order to solve the above technical problems, another technical means adopted by the present invention provides a method for producing polyvinyl chloride-based artificial leather that does not have a foamed structure. The method for producing the polyvinyl chloride-based artificial leather includes providing a base layer, and forming a surface layer formed of a surface composition on one side of the base layer, the surface composition including 25 to 65 parts by weight of polyvinyl chloride resin and 20 to 60 parts by weight of a polymer plasticizer, the total weight of the surface composition being 100 parts by weight, the polymer plasticizer being formed by performing a polycondensation reaction of a dibasic acid raw material and a dihydric alcohol raw material, followed by terminal blocking with a terminal blocking fatty acid, the terminal blocking fatty acid being a fatty acid derived from biomass, the chemical structure of the terminal blocking fatty acid having a long carbon chain of C8 to C22, 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 dihydric alcohol raw material in the polymer plasticizer being less than 300 ppm, and the acid value of the polymer plasticizer being less than 1 mgKOH / g.

[0022] Preferably, the polymer plasticizer is formed through an esterification process in which the dibasic acid raw material and the dihydric alcohol raw material are mixed to form a reaction liquid and the polycondensation reaction is carried out by heating to form a polymer polyester polyol having an excess amount of hydroxyl groups (-OH groups) at the ends of its chemical structure, and an end-capping process in which a biomass-derived end-capping fatty acid is added to the reaction liquid to end-capping the excess hydroxyl groups in the polymer polyester polyol, thereby terminating the polycondensation reaction and forming the polymer plasticizer.

[0023] Preferably, in the polycondensation reaction, the first initiation mole number when supplied in the esterification step of the dibasic acid raw material is lower than the second initiation mole number when supplied in the esterification step of the dihydric alcohol raw material.

[0024] Preferably, the third initiation mole number of the end-capping fatty acid when supplied in the end-capping step is higher than a value obtained by subtracting the first initiation mole number of the dibasic acid from the second initiation mole number of the dihydric alcohol raw material, and the third initiation mole number is 1.5 to 3 times the subtraction value.

[0025] Preferably, the first initial number of moles of the dibasic acid raw material: the second number of moles of the dihydric alcohol raw material: the third initial number of moles of the end-capping fatty acid (molar ratio) is 0.27-0.31:0.32-0.35:0.06-0.09. Effect of the Invention

[0026] The advantageous effects of the present invention are that, by designing the molecular weight and molecular structure of the polymeric plasticizer of the present invention, the polymeric plasticizer can be used as a substitute for conventional low molecular weight plasticizers, and the use of a foaming agent can be avoided. Not only can the odor level of the polyvinyl chloride-based artificial leather be improved, but the molecular structure of the polymeric plasticizer can also impart a leather feel to the surface layer of the polyvinyl chloride-based artificial leather.

[0027] To explain further, since the end of the chemical structure of the polymer plasticizer of the present invention is a biomass-derived end-capped fatty acid, the proportion of biomass content in polyvinyl chloride-based artificial leather is improved. In addition, since the biomass-derived end-capped fatty acid has a natural scent (e.g., the scent of natural soap), it is useful for improving the odor emitted by polyvinyl chloride-based artificial leather. Furthermore, in the technical means provided in the embodiment of the present invention, the method of reducing the residual amount of dihydric alcohol in the reaction liquid can further reduce the residual amount of dihydric alcohol more effectively than a method of removing dihydric alcohol only by general vacuum distillation. [Brief description of the drawings]

[0028] [Figure 1] FIG. 1 is a schematic diagram of a laminated structure of a polyvinyl chloride-based artificial leather according to the prior art. [Diagram 2] 1 is a schematic diagram of a laminated structure of the polyvinyl chloride-based artificial leather of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] In order to better understand the features and technical contents of the present invention, please refer to the following detailed description of the present invention and the accompanying drawings, which are provided for reference and explanation only and are not intended to limit the scope of the present invention.

[0030] Hereinafter, the embodiments of the present invention will be described in accordance with certain specific embodiments, and those skilled in the art can understand the advantages and effects of the present invention based on the contents disclosed in this specification. The present invention can be implemented or applied in other different specific embodiments, and various modifications and changes can be made to each detail in this specification based on different perspectives and applications without departing from the concept of the present invention. In addition, as described in advance, the accompanying drawings of the present invention are simple schematic illustrations and are not drawn based on actual size. The technical contents of the present invention will be described in more detail based on the following embodiments, but the disclosed contents do not limit the protection scope of the present invention.

[0031] It should be understood that although the present specification may use terms such as "first," "second," and "third" to describe various materials or parameters, these materials or parameters are not limited by these terms, and the term "or" as used herein may include any one or more combinations of the associated listed items, depending on the actual situation.

[0032] [Vinyl chloride-based artificial leather] As shown in Fig. 2, in an embodiment of the present invention, a polyvinyl chloride artificial leather 100 is provided, and in particular, a polyvinyl chloride artificial leather 100 not having a foamed structure is provided. The composition of the polyvinyl chloride artificial leather 100 includes a material derived from biomass.

[0033] The polyvinyl chloride-based artificial leather 100 according to the embodiment of the present invention can provide the leather feel required for ordinary artificial leathers, without having a foamed structure.

[0034] Specifically, the polyvinyl chloride-based artificial leather 100 according to the embodiment of the present invention includes, from bottom to top, a base fabric layer 1, a top fabric layer 2, and a selectively applied surface treatment layer 3.

[0035] The surface layer 2 is formed directly on one side of the base layer 1, and the surface treatment layer 3 is formed on the surface of the surface layer 2 away from the base layer 1. The polyvinyl chloride-based artificial leather 100 according to the embodiment of the present invention does not have a foam structure.

[0036] More specifically, in this embodiment, a solid structure (that is, the main structure of the surface layer 2) is formed so as to extend from the surface of the surface layer 2 away from the base layer 1 to the base layer 1.

[0037] The solid structure of the surface layer 2 is in direct contact with the base layer 1 so as not to provide a foamed layer between the surface layer 2 and the base layer 1. The solid structure of the surface layer 2 is not foamed, and therefore does not include a foamed structure such as foam pores, and can provide the leather feel required for ordinary artificial leathers without including a foamed structure.

[0038] It should be noted that the "solid structure" in this specification refers to a continuous phase resin structure that is not foamed with a foaming agent and does not contain foam pores. However, during the manufacturing process of artificial leather, due to the compatibility between different polymer materials or added materials, or the parameters of the manufacturing method, the solid structure may contain a small amount of pores, but these are not foam pores caused by foaming.

[0039] In this specification, the term "feel of leather" means that the feel felt by a user when touching the polyvinyl chloride-based artificial leather is similar to that of natural leather.

[0040] To achieve the above technical objectives, the solid structure of the surface layer 2 according to the embodiment of the present invention is formed of a fabric composition.

[0041] The surface composition includes a polyvinyl chloride resin and a polymer plasticizer.

[0042] With the total weight of the surface composition being 100 parts by weight, the amount of the polyvinyl chloride resin used is 25 parts by weight to 65 parts by weight, and preferably 35 parts by weight to 55 parts by weight, and the amount of the polymer plasticizer used is 20 parts by weight to 60 parts by weight, and preferably 30 parts by weight to 50 parts by weight.

[0043] To explain further, the polyvinyl chloride resin is a matrix material of the outer layer composition and can provide the mechanical strength required for the artificial leather. The polymer plasticizer is a high molecular weight plasticizer that can not only improve the odor level of the artificial leather but also give the outer layer 2 a leather feel.

[0044] The polyvinyl chloride resin according to the embodiment of the present invention has a weight average molecular weight (Mw) of 30,000 g / mol to 200,000 g / mol, and a glass transition temperature (Tg) of 80°C to 85°C.

[0045] The polymeric plasticizer according to the embodiment of the present invention has specific material properties, so that the polyvinyl chloride-based artificial leather has a low odor level, and can provide the leather feel required for ordinary artificial leathers, provided that the polyvinyl chloride-based artificial leather does not have a foam structure.

[0046] The first weight average molecular weight of the polymeric plasticizer according to the embodiment of the present invention is 1,500 g / mol to 6,000 g / mol, and preferably 2,000 g / mol to 5,000 g / mol, although the present invention is not limited thereto.

[0047] It is noteworthy that the polymeric plasticizers used in the embodiments of the present invention have a much higher molecular weight than existing common plasticizers (the weight average molecular weight of existing plasticizers is generally 300 g / mol to 800 g / mol).

[0048] The molecular structure of the polymeric plasticizer according to the embodiment of the present invention includes a linear soft segment, and the soft segment has an ether group.

[0049] The concentration of the soft segment containing an ether group in the polymer plasticizer is 10 wt % to 50 wt %, preferably 10 wt % to 40 wt %, and particularly preferably 10 wt % to 30 wt %.

[0050] By designing the molecular weight and molecular structure of the above-mentioned polymeric plasticizer, the polymeric plasticizer can be used as a substitute for conventional low molecular weight plasticizers, and the use of a foaming agent can be avoided. Not only does it improve the odor level of the polyvinyl chloride-based artificial leather, but the molecular structure of the polymeric plasticizer also gives the surface layer 2 of the polyvinyl chloride-based artificial leather 100 a leather feel.

[0051] Furthermore, when the molecular structure of the polymer plasticizer contains an ether group and the linear soft segment is in the above-mentioned concentration range, the resin material can be made flexible, providing a leather feel.

[0052] The surface layer 2 of the embodiment of the present invention can provide the feel of leather without having a foamed structure, so that the polyvinyl chloride-based artificial leather can avoid the high-temperature process of chemical foaming.

[0053] Regarding the thickness, the thickness D of the surface layer 2 is 100 μm to 600 μm, preferably 150 μm to 350 μm, so as to provide a sufficient leather feel.

[0054] In one embodiment of the present invention, the soft segment having an ether group is incorporated in the middle or end of the molecular structure of the polymer plasticizer. Note that the soft segment having an ether group is in 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.

[0055] More specifically, the polymer plasticizer is a polymer polyester formed by a poly-condensation reaction between a dibasic acid raw material and a dihydric alcohol raw material, and the soft segment having an ether group is composed of at least one of the dibasic acid raw material and the dihydric alcohol raw material.

[0056] Here, the dibasic acid raw material is, for example, at least one selected from the group consisting of adipic acid (AA), succinic acid (SA), maleic acid (MA), sebacic acid (decanediic acid), and dodecanedioic acid.

[0057] The dihydric alcohol may be at least one selected from the group consisting of diethylene glycol (DEG), triethylene glycol (TEG), tetraethylene glycol, poly-tetrahydrofuran (PTMEG), 1,2-propylene glycol (1,2-PG), 2-methyl-1,3-propanediol (MPO), neopentyl glycol (NPG), and 1,4-cyclohexanedimethanol ([4-(hydroxymethyl)cyclohexyl]methanol (CHDM). In one embodiment of the present invention, the dibasic acid of the polymer plasticizer may be adipic acid (AA). The dihydric alcohol raw material of the polymer plasticizer is selectively selected from diethylene glycol (DEG), 2-methyl-1,3-propanediol (MPO) and / or polytetrahydrofuran (PTMEG).

[0058] In the polycondensation reaction, the polymer plasticizer terminates the polycondensation reaction by capping the end-capped fatty alcohol. The end-capped fatty acid is a monovalent fatty acid derived from biomass, and its chemical structure has only a single carboxyl group (-COOH group).

[0059] In one embodiment of the present invention, the chemical structure of the end-capping fatty acid has a long carbon chain of C8 to C22, preferably C12 to C18, and has a carboxyl group (-COOH group) at one end of the long carbon chain and no carboxyl group at the other end.

[0060] In one embodiment, the end-capping 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.

[0061] For example, the biomass-derived lauric acid may be at least one of coconut milk, coconut oil, bay oil, and palm kernel oil, and is preferably coconut milk, although the invention is not limited thereto.

[0062] For example, the biomass-derived stearic acid may be at least one of tea oil, cocoa butter, and palm oil, and is preferably tea oil, although the present invention is not limited thereto.

[0063] For example, the biomass-derived palmitic acid may be at least one of palm oil and palm kernel oil, and is preferably palm oil, although the invention is not limited thereto.

[0064] For example, the biomass-derived linoleic acid may be at least one of safflower oil, sunflower seed oil, corn oil, and linseed oil, and is preferably safflower oil, although the invention is not limited thereto.

[0065] The chemical structure of the biomass-derived end-capped fatty acid is as follows: [Table 1]

[0066] In the polycondensation reaction, the dibasic acid raw material becomes the limiting reactant (also called the limiting reagent) and the dihydric alcohol raw material becomes the excess reactant (also called the excess reagent) with respect to the stoichiometric number of the entire reaction.

[0067] That is, in the polycondensation reaction, the first initiation mole number when the dibasic acid raw material is supplied is lower than the second initiation mole number when the dihydric alcohol raw material is supplied.

[0068] After carrying out a polycondensation reaction between the dibasic acid raw material and the dihydric alcohol raw material to obtain a number average molecular weight of 500 g / mol to 2,000 g / mol, preferably 800 g / mol to 1,500 g / mol, the dibasic acid raw material is completely reacted, and the polymer polyester has an excess amount of hydroxyl groups (-OH groups) at the ends of its chemical structure. The dihydric alcohol raw material remains in the reaction liquid of the polycondensation reaction.

[0069] In this embodiment, the polymer plasticizer is finally formed by terminally blocking excess hydroxyl groups with terminally blocked fatty acid to terminate the polycondensation reaction. The terminally blocked fatty acid reacts with the dihydric alcohol raw material remaining in the reaction liquid to reduce the residual amount of dihydric alcohol in the polymer plasticizer to less than 300 ppm (parts per million).

[0070] In addition, in order to improve the rubber odor, the acid value of the polymer plasticizer is controlled to less than 1 mgKOH / g.

[0071] Here, acid number refers to the number of milligrams of potassium hydroxide (KOH) required to neutralize one gram of a chemical. The test standard may be, for example, ASTM D664.

[0072] Due to the above-mentioned configuration, the terminal of the chemical structure of the polymer plasticizer according to the embodiment of the present invention is a terminal-capped fatty acid derived from biomass, thereby improving the proportion of biomass content in the polyvinyl chloride-based artificial leather.

[0073] Furthermore, since the end-capped fatty acid derived from biomass has a natural scent (for example, the scent of natural soap), it is useful for improving the odor emitted by polyvinyl chloride-based artificial leather.

[0074] In addition, in the technical means provided in the embodiment of the present invention, the method for reducing the residual amount of dihydric alcohol in the reaction liquid can more effectively reduce the residual amount of dihydric alcohol than the general method of removing dihydric alcohol only by vacuum distillation.

[0075] In further explanation, the viscosity of the polymeric plasticizer may be relatively high, which may make it difficult for the polymeric plasticizer to be mixed uniformly with the polyvinyl chloride resin, resulting in processing difficulties.

[0076] In order to solve the above technical problems, the facing composition further comprises not more than 10 parts by weight of processing aids.

[0077] For example, the facing 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 invention is not limited thereto.

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

[0079] Regarding the material, the processing aid is at least one selected from the group consisting of bis(2-ethylhexyl) sebacate (di-octyl sebacate, DOS), di-2-ethylhexyl adipate (di-octyl adipate, DOA), di-isononyl adipate (dina), di-isodecyl adipate (dida), and di-isononyl sebacate (dins), and is preferably bis(2-ethylhexyl) sebacate (di-octyl sebacate, DOS).

[0080] With the above-mentioned configuration, the processing aid can improve the processability of the surface material composition by reducing the viscosity of the surface material composition.

[0081] The processing aid also functions as a plasticizer and improves the feel of the leather of the surface layer.

[0082] However, the amount of the processing aid used should not be too high: if the amount of the processing aid used is too high (e.g., more than 15 parts by weight), the surface layer 2 may not achieve the required leather feel or odor level.

[0083] In one embodiment of the present invention, the outer material composition further provides 3 to 5 parts by weight of a stabilizer for increasing the heat resistance stability of the rubber and reducing the odor level of the artificial leather.

[0084] Here, the stabilizer is at least one selected from the group consisting of 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 one embodiment of the present invention, the stabilizer is a metal soap compound and at least one selected from the group consisting of calcium ricinoleate, barium ricinoleate, and zinc ricinoleate.

[0086] It is particularly noteworthy that in the manufacturing process for introducing the polymeric plasticizer of the present invention into polyvinyl chloride-based artificial leather, the rubber contains a large amount of acidic substances (such as blocked fatty acids), which are disadvantageous for processing the artificial leather.

[0087] To solve this technical problem, the amount of stabilizer (e.g., calcium ricinoleate and / or zinc ricinoleate) is increased in the outer material composition of the present invention so as to improve the processability of the artificial leather.

[0088] For example, in one embodiment of the present invention, when calcium ricinoleate and zinc ricinoleate are used simultaneously, the thermal stability of the polyvinyl chloride-based artificial leather is measured (i.e., the discoloration of the polyvinyl chloride-based artificial leather is measured at 190°C), and it is found that when the amount of the stabilizer is increased by 3 parts by weight, the polyvinyl chloride-based artificial leather does not discolor even 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 surface composition further comprises 0 to 10 parts by weight of a filler, the filler being an inorganic particulate material.

[0090] Here, the filler may be a metal oxide such as calcium carbonate, silicon dioxide, alumina, clay, talc, diatomaceous earth, and fertilizer. Alternatively, the filler may be at least one selected from the group consisting of glass, carbon black, fibers and powders of metals, glass balls, graphite, aluminum hydroxide, barium sulfate, magnesium oxide, magnesium carbonate, magnesium silicate, and calcium silicate.

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

[0092] In one embodiment of the present invention, the surface composition further includes 2 to 8 parts by weight of a flame retardant. The flame retardant may be at least one selected from the group consisting of 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, and chlorinated paraffin wax. The flame retardant is preferably antimony trioxide.

[0093] It is worth noting that in one embodiment of the present invention, the surface composition does not contain a foaming agent (e.g., a chemical foaming agent or a physical foaming agent). The surface layer 2 of the embodiment of the present invention can provide the leather feel required for ordinary artificial leather, on the premise that it does not have a foamed structure or does not use a foaming agent. That is, the use of a foaming agent or the irritating odor caused by the foamed structure can be avoided in the present invention.

[0094] 2, the base layer may be, for example, a woven or nonwoven fabric. The surface layer 2 may be, for example, formed on the base fabric layer 1 by artificial synthesis to form an artificial leather similar in appearance to natural leather.

[0095] In this embodiment, the polyvinyl chloride-based artificial leather 100 further includes a surface treatment layer 3. The surface treatment layer 3 is formed on the surface of the outer layer 2 away from the base layer so as to be coated with an aqueous surface treatment agent. The surface treatment layer 3 can improve the gloss, feel, light resistance, heat resistance, stain resistance, abrasion resistance, and scratch resistance of the polyvinyl chloride-based artificial leather 100.

[0096] The surface of the surface treatment layer 3 away from the surface layer 2 can be embossed at high temperature to form different patterns on the surface of the artificial leather. In this embodiment, the aqueous surface treatment agent is an aqueous polyurethane-based treatment agent that does not contain N-ethylpyrrolidone. This allows the formulation of the surface treatment layer 3 to reduce the odor level of the polyvinyl chloride-based artificial leather 100, thereby improving the comfort of the user.

[0097] As the aqueous surface treatment agent, the conventional solvent-based treatment agent is discarded, and an aqueous polyurethane-based treatment agent that does not contain N-ethylpyrrolidone is adopted. This can avoid solvent substances such as toluene and xylene that have irritating odors and are harmful to the human body. At the same time, by adopting the aqueous polyurethane-based treatment agent of this embodiment, it is possible to achieve the absence of N-ethylpyrrolidone, and reduce the irritating odor.

[0098] It is noteworthy that in this embodiment, there is no foam layer or foam structure between the surface treatment layer 3 and the outer layer 2, and the surface treatment layer 3 does not contain foam pores due to foaming, but the present invention is not limited to this.

[0099] With the above-mentioned configuration, the polyvinyl chloride-based artificial leather 100 without a foamed structure according to the embodiment of the present invention can be applied to automobile interiors, such as door panels, instrument panels, consoles, columns, seat back panels, and seat fabrics.

[0100] Of course, the polyvinyl chloride-based artificial leather 100 without a foam structure according to the embodiment of the present invention can be applied to other fields similar to automobile interiors.

[0101] [Manufacturing method of polyvinyl chloride-based artificial leather] The above is an explanation of the materials and characteristics of the polyvinyl chloride-based artificial leather according to the present invention. The method for producing the polyvinyl chloride-based artificial leather will be explained below. The method for producing the polyvinyl chloride-based artificial leather includes steps S110, S120, and S130. It should be noted that the order and operation method of each step in this embodiment can be adjusted according to needs, and is not limited thereto.

[0102] The step S110 includes providing a base layer 1. The base layer 1 may be, for example, a woven or non-woven fabric.

[0103] The step S120 includes forming a surface layer 2 directly on one side of the base layer 1.

[0104] Here, the surface layer 2 is formed of a surface composition, which contains a polyvinyl chloride resin and a polymer plasticizer.

[0105] With the total weight of the surface composition being 100 parts by weight, the amount of the polyvinyl chloride resin used is 25 parts by weight to 65 parts by weight, preferably 35 parts by weight to 55 parts by weight, and the amount of the polymer plasticizer used is 20 parts by weight to 60 parts by weight, preferably 30 parts by weight to 50 parts by weight.

[0106] The first weight average molecular weight of the polymer plasticizer is 1,500 g / mol to 6,000 g / mol, preferably 2,000 g / mol to 5,000 g / mol, but the present invention is not limited thereto. More specifically, the polymer plasticizer is a polymer polyester formed by a poly-condensation reaction between a dibasic acid raw material and a dihydric alcohol raw material. The types of the dibasic acid raw material and the dihydric alcohol raw material have already been described above, so they will not be described here again.

[0107] In the polycondensation reaction, the polymeric plasticizer terminates the polycondensation reaction by capping with an end-capped fatty alcohol, where the end-capped fatty acid is a monovalent fatty acid derived from biomass (e.g., plant), the chemical structure of which has only a single carboxyl group (-COOH group).

[0108] In one embodiment of the present invention, the chemical structure of the end-capping fatty acid has a long carbon chain of C8 to C22, preferably C12 to 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 one embodiment, the end-capping 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. In the polycondensation reaction, the dibasic acid raw material is the limiting reactant (also called the limiting reagent) and the dihydric alcohol raw material is the excess reactant (also called the excess reagent) with respect to the stoichiometric number of the entire reaction. That is, the first initial molar number when the dibasic acid raw material is supplied is lower than the second initial molar number when the dihydric alcohol raw material is supplied.

[0109] After carrying out a polycondensation reaction between the dibasic acid raw material and the dihydric alcohol raw material to obtain a number average molecular weight of 500 g / mol to 2,000 g / mol, preferably 800 g / mol to 2,000 g / mol, the dibasic acid raw material is completely reacted, and the polymer polyester has an excess amount of hydroxyl groups (-OH groups) at the end of its chemical structure. The dihydric alcohol raw material remains in the reaction liquid of the polycondensation reaction.

[0110] In this embodiment, the polymer plasticizer is finally formed by terminally blocking excess hydroxyl groups with terminally blocked fatty acid to terminate the polycondensation reaction. The terminally blocked fatty acid reacts with the dihydric alcohol raw material remaining in the reaction liquid to reduce the residual amount of dihydric alcohol in the polymer plasticizer to less than 300 ppm (parts per million).

[0111] In addition, the acid value of the polymer plasticizer is controlled to be less than 1 mgKOH / g to improve the rubber odor. Here, the acid value indicates the number of milligrams of potassium hydroxide (KOH) required to neutralize 1 gram of chemical substance. The test standard may be, for example, ASTM D664.

[0112] The above-mentioned configuration allows the polymeric plasticizer according to the embodiment of the present invention to have a chemical structure in which the terminals are capped fatty acids derived from biomass, thereby improving the biomass content of the polyvinyl chloride-based artificial leather. Since the biomass-derived capped fatty acids have a natural scent (e.g., the scent of natural soap), they are useful for improving the odor emitted by the polyvinyl chloride-based artificial leather.

[0113] In addition, in the technical means provided in the embodiment of the present invention, the method for reducing the residual amount of dihydric alcohol in the reaction liquid can more effectively reduce the residual amount of dihydric alcohol than the general method of removing dihydric alcohol only by vacuum distillation.

[0114] To explain further, the polymeric plasticizer may be formed, for example, by the following manufacturing method: The manufacturing method includes an esterification step, an end-capping step, and a decompression step in this order.

[0115] In the esterification step, a dibasic acid source (eg, AA) and a dihydric alcohol source (eg, MPO, DEG, PTMEG) are mixed to form a reaction liquid.

[0116] Thereafter, the reaction liquid is heated to a first temperature (for example, 110° C. to 150° C., preferably 120° C. to 140° C.) and maintained at that temperature for 0.5 to 2 hours, thereby carrying out a polycondensation reaction.

[0117] Thereafter, the reaction liquid is heated to a second temperature (for example, 190°C to 200°C, preferably 195°C) and maintained for 2 to 4 hours. The dibasic acid raw material and the dihydric alcohol raw material are subjected to a polycondensation reaction to form a polymer polyester polyol having a number average molecular weight of 500 g / mol to 2,000 g / mol, preferably 800 g / mol to 1,500 g / mol.

[0118] As described above, in the polycondensation reaction, the dibasic acid raw material is the limiting reactant and the dihydric alcohol raw material is the excess reactant with respect to the stoichiometric number of the entire reaction.

[0119] That is, the first initial number of moles when the dibasic acid raw material is supplied is lower than the second initial number of moles when the dihydric alcohol raw material is supplied.

[0120] In the end-capping step, a biomass-derived end-capping fatty acid (e.g., lauric acid) is added to the reaction liquid to end-capping the polymer polyester formed in the esterification step, thereby terminating the polycondensation reaction and forming the polymer plasticizer according to the embodiment of the present invention in the reaction liquid. In the end-capping step, the reaction liquid is heated to a third temperature (e.g., 200°C to 210°C, preferably 205°C) and held for 2 to 4 hours, thereby distilling off water in the reaction liquid and increasing the concentration of the polymer plasticizer.

[0121] It is particularly noteworthy that the third initiation mole number of the end-capping fatty acid when supplied in the end-capping step is higher than the value obtained by subtracting the first initiation mole number of the dibasic acid from the second initiation mole number of the dihydric alcohol raw material, and the third initiation mole number is 1.5 to 3 times the subtraction value. As a result, the end-capping fatty acid effectively ends-capping the excess hydroxyl groups in the high molecular weight polyester polyol, terminating the polycondensation reaction, and reacting with the dihydric alcohol raw material remaining in the reaction liquid, reducing the amount of dihydric alcohol remaining in the reaction liquid, and also preventing the excess end-capping fatty acid from remaining.

[0122] In one embodiment of the present invention, the molar ratio of the first starting mole number of dibasic acid raw material:the second starting mole number of dihydric alcohol raw material:the third starting mole number of end-capped fatty acid is, 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 may be, for example, 0.29:0.33:0.08, but the present invention is not limited thereto.

[0123] In the depressurization step, the reaction liquid containing the polymeric plasticizer in the end-capping step is depressurized from normal pressure (i.e., 760 torr) to a low pressure of 50 to 150 torr, and cooled to a fourth temperature (e.g., 190°C to 200°C, preferably 195°C) and maintained for 1 hour to 3 hours. In the depressurization step, the acid value of the polymeric plasticizer is controlled to 1 mgKOH / g, and the reaction reaches the end point, completing the production of the polymeric plasticizer.

[0124] With the above-mentioned configuration, the polymer plasticizer has a terminal-capped fatty acid derived from biomass at the end of its chemical structure, thereby increasing the proportion of biomass content in the polyvinyl chloride-based artificial leather and improving the odor of the polyvinyl chloride-based artificial leather.

[0125] In step S130, the surface treatment layer 3 is formed on the surface of the surface layer 2 away from the base layer 1. The surface treatment layer 3 is formed by applying an aqueous surface treatment agent to the surface of the surface layer 2, thereby completing the polyvinyl chloride-based artificial leather. In this embodiment, the aqueous surface treatment agent is an aqueous polyurethane-based treatment agent that does not contain N-ethylpyrrolidone.

[0126] [Measurement of experimental data] The present invention will be described in detail below with reference to Examples 1 to 3 and Comparative Example 1. However, these Examples are provided for the purpose of understanding the present invention, and the present invention is not limited thereto.

[0127] [Example 1] The surface composition of Example 1 shown in Table 1 below was mixed and melted at high temperature in a small mixer and a Banbury mixer in this order, and then the surface composition was rolled by a rolling machine to form the surface composition as a surface layer, and the surface layer was laminated to the base layer by rolling, and then an aqueous polyurethane treatment agent was applied to the surface of the surface layer and dried to form a surface treatment layer. The physicochemical properties of the polyvinyl chloride-based artificial leather of Example 1 were measured, and the results are shown in Table 1 below. Here, the polymerized material was mixed with a dibasic acid raw material (e.g., AA) and a dihydric alcohol raw material (e.g., MPO:DEG:PTMEG (molar ratio) = 2:1:0.05), heated to 130 ° C and held for 1 hour, and heated to 195 ° C and held for 3 hours, thereby carrying out a polycondensation reaction (esterification reaction) and forming a polyester polyol. The polyester polyol was end-capped by adding a biomass-derived end-capping fatty acid (e.g., lauric acid) to the reaction liquid, and the reaction liquid was heated to 205°C and maintained for 3 hours to distill off water and form a polymeric plasticizer with a weight-average molecular weight of 3,845 g / mol in the reaction liquid.

[0128] In Example 1, the molar ratio of dibasic acid raw material:dihydric alcohol raw material:end-blocked alcohol was 0.29:0.33:0.08.

[0129] Finally, the reaction liquid containing the polymer plasticizer was fed to a reduced pressure section (760-100 Torr) and reacted for 2 hours at 195° C. The acid value of the polymer plasticizer was controlled to less than 1 mg KOH / g, and the reaction was terminated to complete the production of the polymer plasticizer.

[0130] The manufacturing methods of Examples 2 to 3 are basically the same as those of the above-mentioned Example, and the differences between Examples 2 to 3 and Example 1 lie in the formulation of the surface composition and the end-capped fatty acid used to synthesize the polymer plasticizer.

[0131] Furthermore, the end-capping material of the polymeric plasticizer in Comparative Example 1 was isooctanol (monohydric alcohol), not an end-capping fatty acid (monovalent fatty acid).

[0132] Next, the physicochemical properties of the polyvinyl chloride-based artificial leathers produced in Examples 1 to 3 and Comparative Example 1 were measured to obtain the physicochemical properties of those polyvinyl chloride-based artificial leathers, such as odor level, residual amount (ppm) of low boiling point alcohol, odor type, etc. The relevant results are summarized in Table 1.

[0133] Here, the odor level was measured based on PV3900C3, a common automobile odor test method at 80℃ for 2 hours. The odor level system includes six levels: 1=no odor; 2=odor is present but not bothersome; 3=odor is noticeable but not unpleasant; 4=unpleasant odor; 5=strong unpleasant odor; 6=unbearable odor.

[0134] The residual amount (ppm) of low boiling point alcohol was measured by headspace sampling method: 1 g of sample was placed in a test bottle, heated at 120°C for 30 minutes, and the upper gas was extracted using a syringe needle and quantitatively analyzed.

[0135] [Table 2]

[0136] According to the experimental results in Table 1, the odor levels of Examples 1 to 3 were all 3, lower than 3.5 of Comparative Example 1. The residual amount of low boiling point alcohol in Examples 1 to 3 was 300 ppm, lower than 2,242 ppm of Comparative Example 1. The odor levels of Examples 1 to 3 were all natural scents, different from the chemical scent of Comparative Example 1. In the experimental results not shown in Table 1, the amount of stabilizer used in Examples 1 to 3 was increased by 3 parts by weight. As a result, the polyvinyl chloride-based artificial leather finally formed did not discolor even after heating for 80 to 85 minutes.

[0137] [Advantageous Effects of the Embodiments] The advantageous effects of the present invention are that, by designing the molecular weight and molecular structure of the polymeric plasticizer of the present invention, the polymeric plasticizer can be used as a substitute for conventional low molecular weight plasticizers, and the use of a foaming agent can be avoided. Not only can the odor level of the polyvinyl chloride-based artificial leather be improved, but the molecular structure of the polymeric plasticizer can also give the surface layer of the polyvinyl chloride-based artificial leather a leather feel.

[0138] More specifically, the terminal of the chemical structure of the polymeric plasticizer according to the embodiment of the present invention is a biomass-derived end-capped fatty acid, which increases the biomass content of the polyvinyl chloride-based artificial leather. Since the biomass-derived end-capped fatty acid has a natural scent (e.g., a natural soap scent), it is useful for improving the odor emitted by the polyvinyl chloride-based artificial leather.

[0139] In addition, in the technical means provided in the embodiment of the present invention, the method for reducing the residual amount of dihydric alcohol in the reaction liquid can more effectively reduce the residual amount of dihydric alcohol than the general method of removing dihydric alcohol only by vacuum distillation.

[0140] The above disclosure is merely a preferred embodiment of the present invention, and the scope of the claims of the present invention is not limited thereto. Therefore, all equivalent technical modifications made by utilizing the contents of the specification and drawings of the present invention are included in the scope of the claims of the present invention. [Explanation of symbols]

[0141] <Prior Art> 100a...Polyvinyl chloride artificial leather 1a...Base layer 2a...Foam layer 3a...surface layer 4a..Surface treatment layer <Example of the present invention> 100...Polyvinyl chloride artificial leather 1. Base layer 2...Surface layer 3. Surface treatment layer D...Thickness

Claims

1. A base layer; The surface layer is formed of a surface composition and is formed on the base layer. The total weight of the surface composition is 100 parts by weight, and the surface composition is 25 to 65 parts by weight of polyvinyl chloride resin; and 20 parts by weight to 60 parts by weight of a polymer plasticizer; The polymer plasticizer is formed by carrying out a polycondensation reaction between a dibasic acid raw material and a dihydric alcohol raw material, followed by terminal-capping with a terminal-capping fatty acid, The end-capping fatty acid is a fatty acid derived from biomass, and the chemical structure of the end-capping fatty acid has a long carbon chain of C8 to C22, a carboxyl group at one end of the long carbon chain, and no carboxyl group at the other end of the long carbon chain, A polyvinyl chloride-based artificial leather not having a foamed structure, characterized in that the residual amount of the dihydric alcohol raw material in the polymer plasticizer is less than 300 ppm, and the acid value of the polymer plasticizer is less than 1 mg KOH / g.

2. 2. The polyvinyl chloride-based artificial leather not having a foamed structure according to claim 1, wherein the end-capping 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. 2. The polyvinyl chloride-based artificial leather having no foamed structure according to claim 1, wherein in the polycondensation reaction, a first initiation mole number of the dibasic acid raw material is lower than a second initiation mole number of the dihydric alcohol raw material.

4. The surface composition further comprises 3 parts by weight to 5 parts by weight of a stabilizer, 2. The polyvinyl chloride-based artificial leather not having a foamed structure according to claim 1, wherein the stabilizer is at least one selected from the group consisting of 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.

5. 2. The polyvinyl chloride-based artificial leather without a foamed structure according to claim 1, wherein no foam layer is included between the surface layer and the base layer, and the surface layer does not include foam pores due to foaming.

6. Providing a base layer; forming a surface layer formed of a surface composition on one side of the base layer; The surface composition contains 25 to 65 parts by weight of a polyvinyl chloride resin and 20 to 60 parts by weight of a polymer plasticizer, where the total weight of the surface composition is 100 parts by weight, The polymer plasticizer is formed by carrying out a polycondensation reaction between a dibasic acid raw material and a dihydric alcohol raw material, followed by terminal-capping with a terminal-capping fatty acid, The end-capping fatty acid is a fatty acid derived from biomass, and the chemical structure of the end-capping fatty acid has a long carbon chain of C8 to C22, a carboxyl group at one end of the long carbon chain, and no carboxyl group at the other end of the long carbon chain, A method for producing a polyvinyl chloride-based artificial leather not having a foamed structure, characterized in that the residual amount of the dihydric alcohol raw material in the polymer plasticizer is less than 300 ppm, and the acid value of the polymer plasticizer is less than 1 mg KOH / g.

7. The polymer plasticizer is an esterification step in which the dibasic acid raw material and the dihydric alcohol raw material are mixed to form a reaction liquid, and the polycondensation reaction is carried out by heating to form a polymer polyester polyol having an excess amount of hydroxyl groups (—OH groups) at the ends of the chemical structure; an end-capping step of adding a biomass-derived end-capping fatty acid to the reaction liquid to end-capping an excess amount of hydroxyl groups in the polymer polyester polyol, thereby terminating the polycondensation reaction and forming the polymer plasticizer; 7. A method for producing a polyvinyl chloride-based artificial leather having no foamed structure according to claim 6, which is formed by the steps of:

8. 8. The method for producing a polyvinyl chloride-based artificial leather not having a foamed structure according to claim 7, wherein a first initiation molar number when the dibasic acid raw material is supplied in the esterification step is lower than a second initiation molar number when the dihydric alcohol raw material is supplied in the esterification step.

9. a third initiation mole number of the end-capping fatty acid when it is supplied in the end-capping step is higher than a value obtained by subtracting the first initiation mole number of the dibasic acid from the second initiation mole number of the dihydric alcohol raw material; The method for producing a polyvinyl chloride-based artificial leather having no foamed structure according to claim 8, wherein the third initial mole number is 1.5 to 3 times the subtracted value.

10. 10. The method for producing a polyvinyl chloride-based artificial leather not having a foamed structure according to claim 9, wherein the first initiation mole number of the dibasic acid raw material: the second mole number of the dihydric alcohol raw material: the third initiation mole number of the end-capped fatty acid (molar ratio) is 0.27 to 0.31:0.32 to 0.35:0.06 to 0.09.

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