KR101863618B1 - Artificial leather sheet and manufacturing method thereof - Google Patents
Artificial leather sheet and manufacturing method thereof Download PDFInfo
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- KR101863618B1 KR101863618B1 KR1020160180238A KR20160180238A KR101863618B1 KR 101863618 B1 KR101863618 B1 KR 101863618B1 KR 1020160180238 A KR1020160180238 A KR 1020160180238A KR 20160180238 A KR20160180238 A KR 20160180238A KR 101863618 B1 KR101863618 B1 KR 101863618B1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/06—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
- D06N3/065—PVC together with other resins except polyurethanes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
- D06N3/183—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Laminated Bodies (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
An example of the present invention is a base fabric comprising: a base fabric; A foam layer formed on the surface of the base fabric; A surface layer formed on the surface of the foam layer; And a surface treatment layer formed on the surface layer surface. The artificial leather sheet according to one embodiment of the present invention is a plasticizer for a polyvinyl chloride film for a foamed layer and a polyvinyl chloride film for a surface layer, which is a non-toxic bis (2-propylheptyl) phthalate, DPHP], it has a human-friendly and excellent softness and flexibility. Therefore, the artificial leather sheet according to one example of the present invention can be applied to infants, children's products.
Description
The present invention relates to an artificial leather sheet, and more particularly, to a artificial leather sheet excellent in softness and at the same time non-toxic, and a method for producing the same.
Normally, what we call leather is largely divided into natural leather and artificial leather. Natural leather is made of animal leather and has a limited production volume. It is expensive, and it can not be continuously processed, and it is difficult to expect color diversification and quality uniformity. Artificial leather, on the other hand, is made as close to natural leather as possible using textile materials such as nonwoven fabrics and woven fabrics, and serves to compensate for the above disadvantages of natural leather. Artificial leather is generally used as a surface material for automobile interior materials, electronic products, furniture and other products.
PVC (polyvinyl chloride) foam artificial leather has a wide range of uses, and is widely used in furniture, wall / door interior, household / office furniture fabric, bag, automobile seat cover, and shoe fabrics. The PVC foam artificial leather generally comprises a base fabric, a PVC foam sheet bonded to the surface of the base fabric, a PVC film bonded to the surface of the PVC foam sheet, and a surface coating layer formed on the surface of the PVC film. Korean Patent Registration No. 10-0873655 discloses a PVC artificial leather which is formed by laminating a fabric layer, an adhesive layer, a foam layer and a label layer in this order, wherein the foam layer or the label layer contains a flame retardant substance, PVC artificial leather characterized in that the adhesive layer is composed of 36 kg of PVC resin with a polymerization degree of 1,600, 24 kg of PVC resin with a polymerization degree of 1,350, 39 kg of alkylaryl phosphate and 1 kg of K-Zn stabilizer Lt; / RTI > Also, Korean Patent Registration No. 10-0515621 discloses a method for producing a polyvinyl alcohol copolymer, which comprises mixing a raw material mixture in which 0.5 to 5% by weight of dicumyl peroxide is added to an ethylene vinyl acetate copolymer having a vinyl acetate content of 20 to 50% by weight; A mixture extruding step of extruding the mixture into an extruder; An ethylene vinyl acetate copolymer coating process for coating the compact on one side of the fabric to form a semi-finished product; And a foaming step of adding steam generated in the foaming machine or adding an organic foaming agent to form a foamed layer in the semi-finished product. [5] In the method of manufacturing artificial leather using the ethylene vinyl acetate copolymer, Korean Patent Registration No. 10-0936326 discloses a substrate layer; Foam layer; A surface layer containing 85 to 95% by weight of a polyvinyl chloride resin and 5 to 15% by weight of soybean protein crumbs having an average diameter of 5 to 75 탆; And a coating layer containing a pulverized soybean protein having an average diameter of 5 to 75 占 퐉 and a water-based adhesive at a weight ratio of 70:30 to 60:40. The polyvinyl chloride artificial leather having improved water absorption is disclosed . Korean Patent No. 10-0992734 discloses a surface layer comprising a polyvinyl chloride resin, a black pigment obtained by mixing a perylene black pigment and a carbon black pigment, and a plasticizer; A foam layer comprising a polyvinyl chloride resin, a titanium dioxide pigment, and a plasticizer; And a base layer comprising a polyester fiber containing a titanium dioxide pigment. The present invention also provides an infrared high reflection polyvinyl chloride artificial leather characterized by comprising:
A plasticizer of PVC (polyvinyl chloride) is used to form a foam layer or surface layer (also referred to as a label layer) constituting PVC (polyvinyl chloride) foamed artificial leather in the above prior art. Examples of plasticizers commonly used in the manufacture of PVC (polyvinyl chloride) foamed artificial leather include diisodecyl phthalate (DIDP), diisononyl phthalate (DINP), diisobutyl phthalate DIBP, Di-n-octyl phthalate (DnOP), etc. These plasticizers are suspected of environmental hormones, which are poor in human affinity and give stiffness to artificial leather, .
The present invention has been made under the conventional technical background, and an object of the present invention is to provide an artificial leather sheet that is non-toxic and is human-friendly and at the same time exhibits excellent softness characteristics. Another object of the present invention is to provide a process for producing a synthetic leather sheet which is almost non-toxic and which is human-friendly and shows excellent softness characteristics.
According to an aspect of the present invention, A foam layer formed on the surface of the base fabric; A surface layer formed on the surface of the foam layer; And a surface treatment layer formed on the surface of the surface layer, wherein the foam layer is made of a foamed product of a polyvinyl chloride film formed from a composition for a foam layer containing a polyvinyl chloride resin, a plasticizer, a foaming agent, a pigment and a flame retardant, Wherein the surface layer comprises a polyvinyl chloride film formed from a composition for a surface layer comprising a polyvinyl chloride resin, a plasticizer, a pigment and a flame retardant, wherein the plasticizer constituting the composition for the foam layer and the composition for the surface layer is bis (2-propylhexyl) phthalate, bis (2-ethylhexyl) phthalate, DEHP], or a combination thereof. The present invention also provides an artificial leather sheet .
According to an aspect of the present invention, there is provided a method of manufacturing a foamed product, including: bonding a foamed layer film to a surface of a base fabric; Bonding the surface layer film to the surface of the foam layer film to form a surface layer; Applying a composition for a surface treatment layer to the surface of the surface layer and drying to form a surface treatment layer; And forming a foam layer by foaming the film for the foam layer, wherein the film for the foam layer is a polyvinyl chloride film formed from a composition for a foam layer comprising a polyvinyl chloride resin, a plasticizer, a foaming agent, a pigment and a flame retardant , The surface layer film is a polyvinyl chloride film formed from a composition for a surface layer containing a polyvinyl chloride resin, a plasticizer, a pigment and a flame retardant, and the plasticizer constituting the composition for the foam layer and the composition for the surface layer is bis Bis (2-ethylhexyl) phthalate, DEHP], or a combination thereof. The synthetic leather sheet according to claim 1, wherein the synthetic resin is selected from the group consisting of bis (2-propylheptyl) phthalate and DPHP. ≪ / RTI >
Another object of the present invention is to provide a method for manufacturing a foam layer, comprising: forming a surface layer by bonding a surface layer film to an upper surface of a film for a foam layer; Bonding the base fabric to the lower surface of the film for foam layer; Applying a composition for a surface treatment layer to the surface of the surface layer and drying to form a surface treatment layer; And forming a foam layer by foaming the film for the foam layer, wherein the film for the foam layer is a polyvinyl chloride film formed from a composition for a foam layer comprising a polyvinyl chloride resin, a plasticizer, a foaming agent, a pigment and a flame retardant , The surface layer film is a polyvinyl chloride film formed from a composition for a surface layer containing a polyvinyl chloride resin, a plasticizer, a pigment and a flame retardant, and the plasticizer constituting the composition for the foam layer and the composition for the surface layer is bis Bis (2-ethylhexyl) phthalate, DEHP], or a combination thereof. The synthetic leather sheet according to claim 1, wherein the synthetic resin is selected from the group consisting of bis (2-propylheptyl) phthalate and DPHP. ≪ / RTI >
The artificial leather sheet according to one embodiment of the present invention is a plasticizer for a polyvinyl chloride film for a foamed layer and a polyvinyl chloride film for a surface layer, which is a non-toxic bis (2-propylheptyl) phthalate, DPHP], it has a human-friendly and excellent softness and flexibility. Therefore, the artificial leather sheet according to one example of the present invention can be applied to infants, children's products.
1 is a sectional view of an artificial leather sheet according to an example of the present invention.
Fig. 2 is a schematic view showing a process for producing an artificial leather sheet according to an embodiment of the present invention.
3 schematically shows a manufacturing process of a synthetic leather sheet according to another example of the present invention.
Hereinafter, the present invention will be described in detail.
One aspect of the present invention relates to an artificial leather sheet that is non-toxic and is human-friendly and at the same time exhibits excellent softness characteristics. 1 is a sectional view of an artificial leather sheet according to an example of the present invention. As shown in FIG. 1, an
Base fabric
The base fabric, which is one component of the artificial leather sheet according to an example of the present invention, is not limited to a known fabric used as a substrate layer in PVC artificial leather. For example, the base fabric may be a woven fabric, a nonwoven fabric or a woven fabric made of natural fibers or synthetic fibers; Mesh fabrics (e.g., double lacquer mesh fabrics), and the like. The synthetic fibers forming the woven fabric, nonwoven fabric, knitted fabric or mesh fabric may be selected from polyester fibers, nylon fibers or blend fibers. The blended fibers are preferably fibers containing 1 to 10 parts by weight of nylon or polyurethane per 100 parts by weight of polyester.
Foam layer
The foam layer, which is one component of the artificial leather sheet according to one example of the present invention, is a layer that gives a three-dimensional feeling or a cushion feeling to the artificial leather sheet. In the artificial leather sheet according to an example of the present invention, the lower surface of the foam layer is bonded to the base fabric, and the upper surface of the foam layer is bonded to the surface layer described later. The lower surface of the foam layer and the upper surface of the base fabric or the foam layer and the surface layer are preferably joined together by calendaring. The term " calendering "used in the present invention refers to a processing method in which a thermoplastic resin is put between two heated rolls and rolled to form a film or a sheet-like molded product. In addition, the calendering process includes coating the surface of cloth, paper or the like with plastic.
The foam layer is composed of a foamed polyvinyl chloride film formed from a composition for a foam layer containing a polyvinyl chloride resin, a plasticizer, a foaming agent, a pigment and a flame retardant. Specifically, the foam layer is formed by molding a composition for a foam layer containing a polyvinyl chloride resin, a plasticizer, a foaming agent, a pigment and a flame retardant into a polyvinyl chloride film for a foam layer by calendering, Followed by foaming by applying a predetermined heat and pressure. The content of the polyvinyl chloride resin in the composition for the foam layer is 35 to 55 wt%, preferably 40 to 50 wt%, based on the total weight. The composition for the foam layer preferably contains 65 to 100 parts by weight of a plasticizer, 0.2 to 6 parts by weight of a foaming agent, 0.5 to 10 parts by weight of a pigment and 5 to 35 parts by weight of a flame retardant per 100 parts by weight of a polyvinyl chloride resin, 75 to 95 parts by weight of a plasticizer, 0.5 to 4 parts by weight of a foaming agent, 1 to 8 parts by weight of a pigment and 10 to 30 parts by weight of a flame retardant per 100 parts by weight of a polyvinyl chloride resin. Further, the composition for the foam layer may further comprise at least one selected from a processing aid, a foam stabilizer, and a heat stabilizer. Specifically, the composition for the foam layer preferably further comprises 0.2 to 8 parts by weight of the processing aid, 0.1 to 6 parts by weight of the foam stabilizer, and 0.5 to 10 parts by weight of the heat stabilizer per 100 parts by weight of the polyvinyl chloride resin, 1 to 4 parts by weight of the processing aid, 0.5 to 3 parts by weight of the foam stabilizer and 1 to 5 parts by weight of the heat stabilizer per 100 parts by weight of the polyvinyl chloride resin. Among the components constituting the composition for the foamed layer, polyvinyl chloride (PVC) resins preferably have a degree of polymerization of 900 to 1500, preferably 1000 to 1400. If the degree of polymerization of the polyvinyl chloride resin is less than 900, excessive flow may occur and molding into a film may not be desired. If the degree of polymerization exceeds 1500, excessive load may be applied to the processing machine during film formation. Among the components constituting the composition for the foamed layer, the plasticizer is preferably bis (2-propylheptyl) phthalate (DPHP), bis (2-propylheptyl) phthalate or the like in consideration of human affinity, softness, (2-ethylhexyl) phthalate, DEHP] or a combination thereof, and is preferably bis (2-propylheptyl) phthalate (DPHP). Components other than the polyvinyl chloride resin and the plasticizer among the components constituting the composition for the foam layer are described later.
Surface layer
The surface layer, which is one component of the artificial leather sheet according to an example of the present invention, is composed of a polyvinyl chloride film formed from a composition for a surface layer containing a polyvinyl chloride resin, a plasticizer, a pigment and a flame retardant. Specifically, the surface layer is formed by forming a surface layer composition containing a polyvinyl chloride resin, a plasticizer, a pigment and a flame retardant into a polyvinyl chloride film for surface layer by calendering, and then fusing the polyvinyl chloride film for the surface layer to a poly And then joining to the upper surface of the vinyl chloride film. The content of the polyvinyl chloride resin in the composition for the surface layer is 40 to 60 wt%, preferably 45 to 55 wt%, based on the total weight. The composition for the surface layer preferably comprises 60 to 95 parts by weight of a plasticizer, 1 to 15 parts by weight of a pigment and 1 to 8 parts by weight of a flame retardant per 100 parts by weight of a polyvinyl chloride resin, more preferably 100 parts by weight of a polyvinyl chloride resin 70 to 90 parts by weight of a sugar plasticizer, 2 to 12 parts by weight of a pigment and 1.5 to 6 parts by weight of a flame retardant. The composition for the surface layer may further comprise at least one selected from a processing aid, a heat stabilizer, and an ultraviolet absorber. Specifically, the composition for the surface layer preferably further comprises 1 to 8 parts by weight of a processing aid, 1 to 12 parts by weight of a heat stabilizer and 0.01 to 3 parts by weight of an ultraviolet absorber per 100 parts by weight of a vinyl chloride resin, 1.5 to 6 parts by weight of a processing aid, 2 to 10 parts by weight of a heat stabilizer and 0.1 to 2 parts by weight of an ultraviolet absorber per 100 parts by weight of the polyvinyl chloride resin. Among the components constituting the composition for the surface layer, polyvinyl chloride (PVC) resin preferably has a degree of polymerization of 900 to 1500, preferably 1000 to 1400. If the degree of polymerization of the polyvinyl chloride resin is less than 900, excessive flow may occur and molding into a film may not be desired. If the degree of polymerization exceeds 1500, excessive load may be applied to the processing machine during film formation. Among the components constituting the composition for the surface layer, the plasticizer is selected from bis (2-propylheptyl) phthalate (DPHP), bis (2-propylheptyl) phthalate and the like, in consideration of human affinity, softness, (2-ethylhexyl) phthalate, DEHP] or a combination thereof, and is preferably bis (2-propylheptyl) phthalate (DPHP). Components other than the polyvinyl chloride resin and the plasticizer among the components constituting the composition for the surface layer are described later.
Surface treatment layer
The surface treatment layer, which is one component of the artificial leather sheet according to one example of the present invention, is a layer that protects the surface layer or imparts various physical properties such as antifouling property and gloss to the artificial leather sheet surface. The surface treatment layer may be composed of a single layer or a multilayer of different components. Also, the surface treatment layer may be formed with a leather texture grain design through embossing.
Wherein the surface treatment layer comprises 1 to 5 wt% of a vinyl chloride / vinyl acetate copolymer, 5 to 10 wt% of a methyl methacrylate polymer, 3 to 5 wt% of a silica powder, 1 to 5 wt% of cyclohexanone, To 80% by weight and methyl isobutyl ketone in an amount of 2 to 5% by weight based on the total weight of the composition. The surface treatment layer may contain 10 to 25 wt% of polyurethane resin, 1 to 5 wt% of silica powder, 1 to 7 wt% of ethylene glycol propyl ether, 30 to 60 wt% of methyl ethyl ketone, 1 to 7 wt% of butyl acetate, , And 10 to 20% by weight of N, N-dimethylformamide. The surface treatment layer may be formed of a composition for a surface treatment layer comprising 20 to 30 wt% of polyurethane, 1 to 10 wt% of a curing agent, 60 to 75 wt% of a diluting solvent, and 1 to 10 wt% of an auxiliary additive . The surface treatment layer may be formed of a composition for a surface treatment layer comprising 40 to 60% by weight of a polyurethane, 1 to 10% by weight of a curing agent, 20 to 50% by weight of a diluting solvent and 1 to 10% by weight of an auxiliary additive . In consideration of durability and stain resistance, the surface treatment layer preferably comprises 6 to 18% by weight of a polycarbonate urethane resin, 6 to 18% by weight of a hydroxyl acrylic resin, 20% by weight of a surfactant and 55 to 80% by weight of a diluting solvent. The polycarbonate-based urethane resin is formed by a polymerization reaction of a polyisocyanate and a polycarbonate polyol. The polyisocyanate forming the polycarbonate-based urethane resin may be selected from polyisocyanates which form ordinary polyurethanes, and is preferably selected from the group consisting of p-phenylene diisocynate, 1,6-hexamethylene diisocyanate Butadiene diisocyanate, 1,6-hexamethylene diisocyanate, toluene diisocyanate, 1,5-naphthalene diisocyanate, isoporone diisocyanate, 4,4-diphenylmethane diisocyanate, cyclohexymethane diisocyanate, and the like. The polycarbonate polyol for forming the polycarbonate-based urethane resin is a polymer having a carbonate group [-O- (C = O) -O-] in the main chain and a hydroxyl group at the end, Is formed by polymerization of a carbonate and a diol. For example, the polycarbonate polyol may contain at least one carbonate compound selected from ethylene carbonate, propylene carbonate, and diphenyl carbonate, and at least one compound selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, Cyclohexanedimethanol, and the like. ≪ / RTI > Further, in the present invention, the polycarbonate polyol is preferably formed by polymerization of carbonic acid, dimethyl ester, and 1,6-hexanediol, It is preferably a polycarbonate diol having a hydroxyl group (CAS Registration Number: 101325-00-2). The polycarbonate polyol used in the present invention is commercially available, and commercial polycarbonate polyol products include Oxymer (TM) polycarbonate polyol, ETERNACOLL (UBE), and Duranol (TM) polycarbonate polyol (Asahi Kasei). The weight-average molecular weight (Mw) of the polycarbonate diol used for forming the polycarbonate-based urethane resin in the present invention is preferably 500 to 2000. In addition, the polycarbonate-based urethane resin may include a polymer formed by a polymerization reaction between at least one polyisocyanate and at least one polycarbonate polyol, as well as a form in which the polymer reacts with a chain extender to extend the chain. The chain extender may be selected from known materials used in the production of polyurethane. For example, the chain extender may be selected from the group consisting of mono ethylene glycol, 1,2-propylene glycol, 1,3-butane diol, 1,4 1,4-butane diol, neopentyl glycol, diethylene glycol, 3-methyl-1,5-pentane diol, 1,6-hexane diol, trimethylol propane, and the like. The chain extender may also be selected from the group consisting of hydrazine, ethylenediamine, 1,4-cyclohexanediamine, 2,4-toluenediamine, Isophorone diamine, diethyltoluene diamine, 4,4-diamino dicyclohexyl methane, 4,4-methylene bis (2-chloroaniline ) [4,4-Methylene bis (2-chloro aniline)], and the like. The hydroxyl group-containing acrylic resin is formed by a polymerization reaction of a monomer having a hydroxyl group and an ethylenic unsaturated bond with a (meth) acrylic monomer. The type of the hydroxyl group-containing acrylic resin is not limited as long as it is a polymer formed by a polymerization reaction of a monomer having a hydroxyl group and an ethylenic unsaturated bond with a (meth) acrylic monomer. The term '(meth) acryl' is an idiomatic expression that simultaneously expresses methacrylic and acrylic. Since the hydroxyl group-containing acrylic resin can form a crosslinking bond with the polyisocyanate, the coating film can be smoothly formed upon application and drying of the composition for surface treatment according to one embodiment of the present invention. For example, the monomer having a hydroxyl group and an ethylenically unsaturated bond may be selected from hydroxyalkyl (meth) acrylate, allyl alcohol, alkoxylated allyl alcohol, and the like, and the (meth) (Meth) acrylate having 1 to 20 carbon atoms, an aryl (meth) acrylate having 1 to 20 carbon atoms, a carboxylic acid having a vinyl group or an allyl group, and the like. The hydroxyl group-containing acrylic resin is preferably selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl acrylate, methacrylate, allyl alcohol, methallyl alcohol, 2-ethyl-2-propen-1-ol, Is preferably an acrylic copolymer formed by polymerization of at least one species selected from the group consisting of acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate and butyl methacrylate. The hydroxyl group-containing acrylic resin is commercially available, and commercially available hydroxyl group-containing acrylic resin products include MACRYNAL®, DOMACRYL (Helios), Elvacite® (Lucite International Inc.), OTTOPOL (Gellner Industrial LLC ), And Dianal Hydroxyl Functional Acrylic Resins (Dianal America, Inc.).
The foam layer and the surface layer, which are components of the artificial leather sheet according to the present invention, are each formed by a composition for a foam layer and a composition for a surface layer, and the compositions include pigments, flame retardants, processing aids and heat stabilizers as common components.
The kind of the pigment is not particularly limited, and examples thereof include phthalocyanine blue, phthalocyanine green, carbon black, disazo yellow, crystal violet, titanium dioxide and the like. The pigments usable in the present invention can be represented by a color index number. For example, red pigments for forming red filter segments include CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 81, 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, 272, etc., and can be used in combination with yellow or orange pigments. As the yellow color pigment for forming the yellow filter segment, for example, C.I.
The flame retardant may be selected from a variety of known materials, and preferably is a non-halogen flame retardant in consideration of human affinity. For example, the flame retardant may be selected from the group consisting of trimethyl phosphate, triethyl phosphate, triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate phosphate, TXP), resorcinol bis (diphenyl phosphate), RDP, phenyl diresorcinol phosphate, bisphenol diphenyl phosphate (BDP) But are not limited to, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, phenyl di (isopropylphenyl) phosphate, triisophenyl phosphate, (Diphenyl Phosphate), Resorcinol di Phosphate, Aromatic Polyphosphate, Phosphoric Acid Nidin may be (Guanidine phosphate), ammonium phosphate, melamine phosphate, ammonium polyphosphate, phosphorus-based flame retardant and at least one selected from the group consisting of a mixture thereof. The flame retardant may also be a poly [[6- [1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6 -Tetramethyl-4-piperidinyl) imino] -1,6-hexanediyl [(2,2,6,6-tetramethyl-4-pyrrolidinyl) imino]]; Poly [[6-morphine-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] Diyl [(2,2,6,6-tetramethyl-4-pyrrolidinyl) imino]]; Poly [[6- [1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(1,2,2,6,6- -4-piperidinyl) imino] -1,6-hexanediyl [(2,2,6,6-tetramethyl-4-pyrrolidinyl) imino]]; Poly [[6-morphine-1,3,5-triazine-2,4-diyl] [(1,2,2,6,6-pentamethyl-4-piperidinyl) imino] - hexanediyl [(2,2,6,6-tetramethyl-4-pyrrolidinyl) imino]]; Poly [[6- [1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl- -Piperidinyl) imino] -1,5-pentanediyl [(2,2,6,6-tetramethyl-4-pyrrolidinyl) imino]]; Poly [[6-morphine-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] Diyl [(2,2,6,6-tetramethyl-4-pyrrolidinyl) imino]]; Poly [[6- [1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(1,2,2,6,6- -4-piperidinyl) imino] -1,5-pentanediyl [(2,2,6,6-tetramethyl-4-pyrrolidinyl) imino]]; Poly [[6-morphine-1,3,5-triazine-2,4-diyl] [(1,2,2,6,6-pentamethyl-4-piperidinyl) imino] - pentanediyl [(2,2,6,6-tetramethyl-4-pyrrolidinyl) imino]]; Poly [[6- [1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl- -Piperidinyl) imino] -1,4-butanediyl [(2,2,6,6-tetramethyl-4-pyrrolidinyl) imino]]; Poly [[6-morphine-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] Diyl [(2,2,6,6-tetramethyl-4-pyrrolidinyl) imino]]; Poly [[6- [1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(1,2,2,6,6- -4-piperidinyl) imino] -1,4-butanediyl [(2,2,6,6-tetramethyl-4-pyrrolidinyl) imino]]; Poly [[6-morphine-1,3,5-triazine-2,4-diyl] [(1,2,2,6,6-pentamethyl-4-piperidinyl) imino] -Butanediyl [(2,2,6,6-tetramethyl-4-pyrrolidinyl) imino]]; N, N ', N' ', N' '' - tetrakis {2,4-bis [(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin- -s-triazin-6-yl} -3,3'-ethylenediminodipropylamine; Bis {N - [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin- - (2-hydroxymethylamino) -s-triazine; (1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin-4-yl) alkylamino] -6- (2-hydroxyethylamino) -s-tri Azine; 2,4-bis [(1-hydrocarbyloxy-2,2,6,6-piperidin-4-yl) alkylamino] -6-chloro-s-triazine; Or N, N ', N "' -tris {2,4-bis [(1-hydrocarbyloxy-2,2,6,6-tetramethylpiperidin- (Hindered Amine Light Stabilizer, HALS) -based flame retardant selected from the group consisting of HALS (triazine-6-yl) -3,3'-ethylene diaminodipropylamine, In the flame retardant, hydrocarbyloxy mainly refers to methoxy, cyclohexyloxy, octyloxy and the like. The alkyl of alkylamino means mainly an alkyl group having 1 to 12 carbon atoms. Further, commercially available hals (HALS ) Flame retardants include FLAMESTAB NOR 116 (Ciba chemical), HALS 944 (Yantai Yusheng Chemical), etc. The flame retardant may be selected from aluminum hydroxide, magnesium hydroxide, antimony trioxide and the like.
The processing aids improve the processability when the composition for a foamed layer and the composition for a surface layer are formed into a film to have a smooth surface, a good gloss or a uniform foam cell structure. The type of the processing aid is not particularly limited as long as it is known in the art of known polyvinyl chloride resins. Examples of the processing aid include paraffin wax, acrylic resin added with aluminum hydroxide, styrene series resin disclosed in Korean Patent Registration No. 10-1556447 50 to 90 wt% of an ethylenically unsaturated nitrile-based copolymer; And 50 to 10 wt% of an alkyl methacrylate-alkyl acrylate-based copolymer; and a foaming processing aid for polyvinyl chloride resin in the methyl methacrylate-based polymer fine particles disclosed in Korean Patent Registration No. 10-0752503 At least one member selected from the group consisting of fatty acid ester derivatives, C10-C20 fatty acid derivatives and metal salts thereof, C6-C20 fatty acid alcohols and metal salts thereof, ester compounds of polyols and fatty acids, and fatty acid amide derivatives of C10- Selected), and the like. Commercially available processing aids include CPE-135A (Chlorinated polyethylene), Acryloid K-125, and Paraloid (TM) K-445 (Rohm and Haas).
The heat stabilizer is selected from various known heat stabilizers such as a binder stabilizer, an organotin stabilizer, and a complex stabilizer such as a component preventing the degradation of the polyvinyl chloride film during heat treatment or a heat-induced degradation of the produced polyvinyl chloride film. And it is preferable that lead is not included in consideration of human affinity. Specific examples of the heat stabilizer include barium stearate, zinc stearate, magnesium stearate, calcium stearate, mercaptide stabilizers, maleate stabilizers, carboxylate stabilizers, Ba-Zn based organic complexes and Ca-Zn based organic composites . BZ-128T, BZ-210T, BZ-608, BZ-609 and BZ-806F (manufactured by Songwon Industrial Co., Ltd.); KBZ-250G, KBZ-260G, and KBZ-557 (hereinafter, referred to as manufacturer: Kolon oil); LOX-3, LOX-3C, LOX-101, LOX-300C and LOX-708 (hereinafter, Commercially available Ca-Zn thermal stabilizers include CZ-200 and CZ-400 (hereinafter referred to as "Songwon Industrial"); KCZ-252KA (hereinafter referred to as " Kolon Oil "); LOX-80, LOX-901 and LTX-616 (hereinafter referred to as " K-DICHEM ").
The foam layer, which is a component of the artificial leather sheet according to the present invention, is formed by a composition for a foam layer, and the composition includes a foaming agent and a foam stabilizer. As the foaming agent, it is preferable to use a thermally decomposable foaming agent. Examples of the thermally decomposable foaming agent include azo compounds such as azobutane copolymer, azodicarbonamide (ADCA) and azobis formamide, oxybenzene sulfonyl hydrazide, OBSH), and palladium toluene sulfonyl hydrazide, and the like can be used. The foam stabilizer promotes the decomposition of the foaming agent to further enhance the foaming effect, and may be variously selected depending on the kind of the foaming agent. For example, when azodicarbonamide (ADCA) is used as a foaming agent, a foam stabilizer such as adipic acid hydrazide, hydrazide hydrazide such as hydrous acid hydrazide, zinc oxide, , Zinc stearate and the like can be used.
The surface layer which is a component of the artificial leather sheet according to the present invention is formed by a composition for a surface layer, and the composition includes an ultraviolet absorber. The ultraviolet absorber is also expressed as a light stabilizer and can be selected from a variety of known materials. For example, the ultraviolet absorber may be a benzotriazole type ultraviolet absorber or a triazine type ultraviolet absorber. Examples of benzotriazole type ultraviolet absorbers include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3,5- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-sec-butyl-5-tert-butylphenyl) benzotriazole and 2- (2-hydroxy- Phenol, 2,2'-methylenebis [6-2H-benzotriazol-2-yl) -4- (1,1,3,3-tetra Methylbutyl)]. Examples of triazine-type ultraviolet absorbers include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxy- (2-hydroxy-3-dodecyloxypropyl) -oxyl-2-hydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-3-tridecyloxypropyl) -oxyl-2-hydroxyphenyl) -4,6-bis (2,4- (4 - ((2-hydroxy-3-isooctyloxypropyl) -oxyl-2-hydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine .
The surface treatment layer, which is a component of the artificial leather sheet according to the present invention, is formed by a composition for a surface treatment layer, and the composition for the surface treatment layer includes a curing agent, a diluting solvent, and an auxiliary additive.
The curing agent may be selected from known curing agents used for curing the polyurethane. Examples of such a known curing agent include an isocyanate curing agent, an epoxy curing agent, a melamine curing agent, a carbodiimide curing agent, an oxazoline curing agent, and an aziridine curing agent, and is preferably compatible with other constituents An isocyanate-based curing agent in the form of a polyisocyanate may be mentioned. The curing agent in the polyisocyanate form may be selected from aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates and aromatic polyisocyanates used for polyurethane formation, more preferably trimethylene diisocyanate, tetramethylene diisocyanate , Hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, 1,12-dodecamethylene diisocyanate, lysine ester triisocyanate, 1,4,8-triisocyanate octane , 1,6,11-triisocyanate undecane, 1,8- Aliphatic polyesters such as isocyanate-4-isocyanate methyloctane, 1,3,6-triisocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyloctane, and hexamethylene diisocyanate homopolymer. Can be selected from isocyanates. As the curing agent, aliphatic polyisocyanate and ethyl acetate may be mixed in a weight ratio of 1: 1 to 9: 1.
The diluting solvent serves to adjust the viscosity of the composition to impart an appropriate level of application. The diluting solvent used in the present invention is not limited in its kind as long as it is capable of uniformly dispersing or dissolving urethane resin or acrylic resin, and examples thereof include ethylene glycol, propylene glycol, diethylene glycol, But are not limited to, ethylene glycol, hexylene glycol, 1,5-pentanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, diethylene glycol dimethyl ether, Propylene glycol Dimethylformamide, monoethylformamide, diethylformamide, acetamide, monomethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, N , N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, dimethylsulfone, diethylsulfone, bis (2-hydroxysulfone), tetramethylene sulfone, acetone, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, pentane, hexane, dodecane, tetradecane, benzene, trimethylbenzene, butylbenzoate, dodecylbenzene, xylene, toluene, tetrahydrofuran, Dioxane, tetrahydrofuran, 1,3-dioxane, methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, hexanol, Propanol, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl cellosolve, butyl cellosolve, butyl cellosolve, butyl cellosolve, butyl cellosolve, Propyl acetate, isopropyl acetate, ethyl propionate, butyl acetate, isobutyl acetate, diethyl adipate, diisopropyl ethyl ketone, methyl ethyl ketone, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, Monoethyl ether acetate and 3-methoxypropyl acetate, naphtha Selected one kinds or more can be configured. The diluent solvent used in the present invention may be selected from the group consisting of dimethylformamide, methyl ethyl ketone, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, cyclohexanone, and the like in consideration of compatibility with other components, Hexanone, naphtha, and combinations thereof.
The auxiliary additive may be at least one selected from the group consisting of a gloss-imparting agent, a light-quenching agent, a scratch-preventive agent, a crosslinking agent, a defoaming agent, a slip agent, a coupling agent and a dispersant. The glossing agent may be selected from known ones and may be at least one selected from the group consisting of, for example, polyacrylates, polyurethanes, silicones, waxes, paraffins and paraffin / mineral oil blends. The quencher may be selected from known ones, for example, precipitated silica, amorphous silica obtained by treating particles of silica with a hydrophilic polyolefin wax, PLAMAT, silane-based coupling Modified zeolite, zeolite modified silica, titanium dioxide, polyimide powder, ester amide condensation product, and the like. Further, the anti-scratch agent may be selected from known ones, for example, 7-hydroxy-5-methyl-1,3,4-triazaindolizine, 5-amino- 1,2,4-triazole, 1-phenyl-5-mercapto-1H-tetrazole, 5-methyl-1H-benzotriazole and the like. Further, the crosslinking agent is an additive for promoting the formation of the polyurethane film and improving the strength of the formed film. Examples of the additives include ethylene diamine, propylene diamine-1,2 and -1,3, tetramethylene diamine- Isomer mixtures of hexamethylene diamine-1,6, 2,2,4- and 2,4,4-trimethyl hexamethylene diamine, 2-methylpentamethylene diamine and bis- (beta -aminoethyl) amine Aliphatic polyamine based crosslinking agents such as ethylenetriamine, ethylenetriamine, etc .; aliphatic polyamine based crosslinking agents such as triethylamine, triisobutylamine, trioctylamine, triisodecylamine, triethanolamine, 4,4-diphenylmethane, And ethyl acetate in a weight ratio of 4: 1 to 6: 1 may be used. The antifoaming agent is used to remove harmful foam, and includes silicone antifoaming agents such as dimethylpolysiloxane, methylethylpolysiloxane, and diethylpolysiloxane, and non-silicone antifoaming agents such as mineral oil, alcohol, organic phosphate, etc. . These antifoaming agents may be in powder form, in emulsion form, in oil form, in compound form and the like, and are not greatly restricted. Specific examples of antifoaming agents include CELANT-DF3, CELANT-DF18, CELANT-EF23, CELANT-DF600, KF96 series, FK-150 and FK-500 products. As the slip agent, oleic acid, LC-102N, LC-104N, LC-140B / P, LC-402F and the like may be used as a preparation for improving the friction resistance by smoothing the ink coating. The coupling agent may be a reaction agent (for example, a vinyl group, a methacrylate group, a methacrylate group, or a methacrylate group) which bonds with an organic material such as a synthetic resin, An epoxy group, an amino group, a methacryl group, and a thiol group) at both terminals is not limited. Examples thereof include silane series, titanate series, chromium series, aluminum series and zirconium series. Specific examples of the silane-based coupling agent include 2- (3,4-epoxycyclohexyl) -ethyltrimethoxysilane, 3-glycidoxytrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, Aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) 3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, Siloxane-containing silanes such as ethoxysilane, isocyanates such as 3-isocyanate propyltriethoxysilane, Silane containing vinyl groups such as silane, vinyl trichlorosilane, vinyltri (2-methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane And silane containing a methacryl group such as methoxy silane, etc. These may be used singly or in combination of two or more kinds. Further, the dispersant is a preparation for helping the powder components and the like to be uniformly dispersed in the composition, for example, a commercial product such as a TEGO® Dispers 610, BYK 4130 product, etc., and a polyether-modified silicone oil, an aralkyl- , Long chain alkyl-modified silicone oils, polyalkyl chain-modified alkyl silicone oils, long chain alkyl-alkyl modified silicone oils, high fatty acid amide modified silicone oils, Ether-modified silicone oil, polyether methoxy-modified silicone oil, polyimide siloxane, polyamideimide siloxane, polyamide siloxane, polyester siloxane, and the like.
Another aspect of the present invention relates to a method of producing a synthetic leather sheet that is non-toxic and is human-friendly and exhibits excellent softness characteristics. FIG. 2 is a schematic view illustrating a process for producing a synthetic leather sheet according to an embodiment of the present invention, and FIG. 3 is a schematic view illustrating a process for manufacturing an artificial leather sheet according to another example of the present invention. As shown in FIG. 2, a method of manufacturing an artificial leather sheet according to an embodiment of the present invention includes: bonding a film for a foam layer to a surface of a base fabric; Bonding the surface layer film to the surface of the foam layer film to form a surface layer; Applying a composition for a surface treatment layer to the surface of the surface layer and drying to form a surface treatment layer; And foaming the film for a foam layer to form a foam layer. Further, as shown in FIG. 3, a method of manufacturing an artificial leather sheet according to another embodiment of the present invention includes: forming a surface layer by bonding a surface layer film to an upper surface of a film for a foam layer; Bonding the base fabric to the lower surface of the film for foam layer; Applying a composition for a surface treatment layer to the surface of the surface layer and drying to form a surface treatment layer; And foaming the film for a foam layer to form a foam layer. In the method for producing a synthetic leather sheet according to one embodiment of the present invention and another example, the film for a foam layer is a polyvinyl chloride film formed from a composition for a foam layer containing a polyvinyl chloride resin, a plasticizer, a foaming agent, a pigment and a flame retardant, The surface layer film is a polyvinyl chloride film formed from a composition for a surface layer comprising a polyvinyl chloride resin, a plasticizer, a pigment, and a flame retardant. For a detailed description of the composition for the foam layer and the composition for the surface layer, refer to the above description. In addition, the manufacturing method of artificial leather sheet according to one example and another example of the present invention may further include the step of forming a design of leather texture on the surface treatment layer, preferably after forming the foam layer.
In the method of manufacturing an artificial leather sheet according to one example of the present invention and another example, the bonding between the base fabric and the film for the foam layer and the bonding between the film for the foam layer and the film for the surface layer are preferably bonded by calendering. The calendering processing temperature at joining by calendering is preferably 150 to 200 ° C, more preferably 160 to 190 ° C.
Further, in the method of manufacturing an artificial leather sheet according to one example of the present invention and another example, the step of forming the foam layer may preferably be performed by a hot press or the like, It is preferably carried out at a temperature of 200 to 250 DEG C and a pressure of 150 to 250 kgf / cm < 2 > for 30 seconds to 3 minutes. Further, in the method of manufacturing an artificial leather sheet according to one example of the present invention and another example, the step of forming the design of the leather texture on the surface treatment layer may be performed by using the embossing process immediately after forming the foam layer.
Hereinafter, the present invention will be described more specifically by way of examples. However, the following examples are intended to clearly illustrate the technical features of the present invention and do not limit the scope of protection of the present invention.
1. Manufacture of artificial leather sheets
Production Example 1
65 parts by weight of bis (2-propylheptyl) phthalate (DPHP), 8 parts by weight of a processing aid, 6 parts by weight of a foam stabilizer, 10 parts by weight of a heat stabilizer , 6 parts by weight of a blowing agent, 10 parts by weight of a pigment and 35 parts by weight of a flame retardant were added and mixed at about 110 DEG C to prepare a composition for a foamed layer. Thereafter, the composition for the foam layer was calendered to form a film for a foam layer having a thickness of about 0.3 mm and bonded to a H / Knit base fabric of a PET material to prepare a first laminate composed of a base fabric and a film for a foam layer. During calendering for the production of the first laminate, the roll temperature was 168 ± 5 ° C and the porosity was 25 ± 2 m / min. 95 parts by weight of bis (2-propylheptyl) phthalate (DPHP), 1 part by weight of a processing aid, 1.1 parts by weight of a heat stabilizer, 100 parts by weight of an ultraviolet absorber 0.01 part by weight, pigment 1 part by weight and flame retardant 1 part by weight were added and mixed at about 110 DEG C to prepare a composition for a surface layer. Thereafter, the composition for the surface layer was calendered to form a film for a surface layer having a thickness of about 0.2 mm, and this was laminated to the film for a foam layer of the first laminate to prepare a second laminate composed of a base fabric, a film for a foam layer and a surface layer . During calendering for the production of the second laminate, the roll temperature was 172 ± 5 ° C and the porosity was 30 ± 2 m / min. Thereafter, an acrylic resin surface treatment agent was applied to the surface layer of the second laminate and dried at 80 캜 to prepare a third laminate composed of base fabric, film for foam layer, surface layer and first surface treatment layer. Thereafter, the third layered product was foamed in a foaming chamber at about 190 to 230 DEG C for about 2 minutes to form a foamed layer, and the third layered product was pressed with an emboss roll engraved with a grain of leather with the film having fluidity A grain of leather texture was imparted to the surface. Thereafter, a polyurethane resin surface treatment agent was applied to the first surface treatment layer of the third layered body and dried at 130 캜 to obtain a PVC foaming agent composed of a base fabric, a foam layer, a surface layer, a first surface treatment layer and a second surface treatment layer Leather sheets were produced. Wherein the acrylic resin surface treatment agent comprises 1 to 5 wt% of a vinyl chloride / vinyl acetate copolymer, 5 to 10 wt% of a methyl methacrylate polymer, 3 to 5 wt% of a silica powder, 1 to 5 wt% of cyclohexanone, 70 to 80 wt% and methyl isobutyl ketone 2 to 5 wt%. The polyurethane resin surface treatment agent may be prepared by mixing 10 to 25 wt% of polyurethane resin, 1 to 5 wt% of silica powder, 1 to 7 wt% of ethylene glycol propyl ether, 30 to 60 wt% of methyl ethyl ketone, By weight, and 10 to 20% by weight of N, N-dimethylformamide.
Production Example 2
100 parts by weight of bis (2-propylheptyl) phthalate (DPHP), 0.2 part by weight of a processing aid, 0.1 part by weight of a foam stabilizer, and 0.1 part by weight of a heat stabilizer were added to 100 parts by weight of a polyvinyl chloride resin having a degree of polymerization of about 1,300. 0.5 part by weight of a blowing agent, 0.5 part by weight of a pigment and 5 parts by weight of a flame retardant were added and mixed at about 110 DEG C to prepare a composition for a foamed layer. Thereafter, the composition for the foam layer was calendered to form a film for a foam layer having a thickness of about 0.3 mm. 60 parts by weight of bis (2-propylheptyl) phthalate (DPHP), 8 parts by weight of a processing aid, 12 parts by weight of a heat stabilizer, 100 parts by weight of an ultraviolet absorber 3 parts by weight, pigment 15 parts by weight and flame retardant 8 parts by weight were added and mixed at about 110 DEG C to prepare a composition for a surface layer. Thereafter, the composition for the surface layer was calendered to form a film for a surface layer having a thickness of about 0.2 mm and bonded to the upper surface of the film for a foamed layer to prepare a first laminate composed of a film for a foamed layer and a surface layer. During calendering for the production of the first laminate, the roll temperature was 172 +/- 5 DEG C and the porosity was 30 +/- 2 m / min. Thereafter, the H / Knit base fabric of the PET material was bonded to the lower surface of the film for the foam layer of the first laminate to prepare a second laminate composed of the base fabric, the film for the foam layer and the surface layer. At the time of calendering for the production of the second laminate, 168 ± 5 ° C and a porosity of 25 ± 2 m / min. Thereafter, to the surface layer of the second laminate, 13.5 wt% of polycarbonate urethane resin, 13.5 wt% of hydroxyl group-containing acrylic resin, 20.25 wt% of cyclohexanone, 24 wt% of methyl ethyl ketone, A composition for a surface treatment layer composed of 4.5 wt% of amide, 4.5 wt% of propylene glycol monomethyl ether acetate, 2.25 wt% of naphtha, 4.5 wt% of silica powder, and 13 wt% of hexamethylene diisocyanate as a curing agent was applied, And dried for 2 minutes and 30 seconds to prepare a third laminate composed of a base fabric, a film for a foam layer, a surface layer and a first surface treatment layer. Thereafter, the third layered product was foamed in a foaming chamber at about 190 to 230 DEG C for about 2 minutes to form a foamed layer, and the third layered product was pressed with an emboss roll engraved with a grain of leather with the film having fluidity A grain of leather texture was imparted to the surface. Thereafter, 13.5 wt% of a polycarbonate urethane resin, 13.5 wt% of a hydroxyl group-containing acrylic resin, 20.25 wt% of cyclohexanone and 24 wt% of methyl ethyl ketone were added to the first surface-treated layer of the third layered product, , 4.5 wt% of dimethylformamide, 4.5 wt% of propylene glycol monomethyl ether acetate, 2.25 wt% of naphtha, 4.5 wt% of silica powder, and 13 wt% of hexamethylene diisocyanate as a curing agent And dried at 110 ° C for 2 minutes and 30 seconds to prepare a PVC foamed artificial leather sheet composed of a base fabric, a foam layer, a surface layer, a first surface treatment layer and a second surface treatment layer. The polycarbonate urethane resin used to form the surface treatment layer was prepared by polymerizing carbonic acid, dimethyl ester and 1,6-hexanediol (CAS Registry No. 101325-00-2) and a polyisocyanate selected from trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and the like, and a polycarbonate diol having a hydroxyl group at the end formed by the polyisocyanate ≪ / RTI > The hydroxyl group-containing acrylic resin used for forming the surface treatment layer is an acrylic copolymer formed by polymerization reaction of hydroxyethyl methacrylate and methacrylic acid.
Comparative Production Example 1
65 parts by weight of diisodecyl phthalate (DIDP), 8 parts by weight of a processing aid, 6 parts by weight of a foam stabilizer, 10 parts by weight of a heat stabilizer, 6 parts by weight of a foaming agent, 10 parts by weight of a pigment and 35 parts by weight of a flame retardant were added and mixed at about 110 DEG C to prepare a composition for a foamed layer. Thereafter, the composition for the foam layer was calendered to form a film for a foam layer having a thickness of about 0.3 mm and bonded to a H / Knit base fabric of a PET material to prepare a first laminate composed of a base fabric and a film for a foam layer. During calendering for the production of the first laminate, the roll temperature was 168 ± 5 ° C and the porosity was 25 ± 2 m / min. To 100 parts by weight of a polyvinyl chloride resin having a degree of polymerization of about 1,300, 95 parts by weight of diisodecyl phthalate (DIDP), 1 part by weight of a processing aid, 1.1 parts by weight of a heat stabilizer, 0.01 part by weight of an ultraviolet absorber, And 1 part by weight of a flame retardant were added and mixed at about 110 DEG C to prepare a composition for a surface layer. Thereafter, the composition for the surface layer was calendered to form a film for a surface layer having a thickness of about 0.2 mm, and this was laminated to the film for a foam layer of the first laminate to prepare a second laminate composed of a base fabric, a film for a foam layer and a surface layer . During calendering for the production of the second laminate, the roll temperature was 172 ± 5 ° C and the porosity was 30 ± 2 m / min. Thereafter, an acrylic resin surface treatment agent was applied to the surface layer of the second laminate and dried at 80 캜 to prepare a third laminate composed of base fabric, film for foam layer, surface layer and first surface treatment layer. Thereafter, the third layered product was foamed in a foaming chamber at about 190 to 230 DEG C for about 2 minutes to form a foamed layer, and the third layered product was pressed with an emboss roll engraved with a grain of leather with the film having fluidity A grain of leather texture was imparted to the surface. Thereafter, a polyurethane resin surface treatment agent was applied to the first surface treatment layer of the third layered body and dried at 130 캜 to obtain a PVC foaming agent composed of a base fabric, a foam layer, a surface layer, a first surface treatment layer and a second surface treatment layer Leather sheets were produced. Wherein the acrylic resin surface treatment agent comprises 1 to 5 wt% of a vinyl chloride / vinyl acetate copolymer, 5 to 10 wt% of a methyl methacrylate polymer, 3 to 5 wt% of a silica powder, 1 to 5 wt% of cyclohexanone, 70 to 80 wt% and methyl isobutyl ketone 2 to 5 wt%. The polyurethane resin surface treatment agent may be prepared by mixing 10 to 25 wt% of polyurethane resin, 1 to 5 wt% of silica powder, 1 to 7 wt% of ethylene glycol propyl ether, 30 to 60 wt% of methyl ethyl ketone, By weight, and 10 to 20% by weight of N, N-dimethylformamide.
Comparative Preparation Example 2
100 parts by weight of diisodecyl phthalate (DIDP), 0.2 parts by weight of a processing aid, 0.1 parts by weight of a foam stabilizer, 0.5 parts by weight of a heat stabilizer, 0.2 parts by weight of a foaming agent, 0.5 parts by weight of a pigment and 5 parts by weight of a flame retardant were added and mixed at about 110 DEG C to prepare a composition for a foamed layer. Thereafter, the composition for the foam layer was calendered to form a film for a foam layer having a thickness of about 0.3 mm. 60 parts by weight of diisodecyl phthalate (DIDP), 8 parts by weight of a processing aid, 12 parts by weight of a heat stabilizer, 3 parts by weight of an ultraviolet absorber, 15 parts by weight of a pigment and 100 parts by weight of a polyvinyl chloride resin having a degree of polymerization of about 1,300, And 8 parts by weight of a flame retardant were added and mixed at about 110 DEG C to prepare a composition for a surface layer. Thereafter, the composition for the surface layer was calendered to form a film for a surface layer having a thickness of about 0.2 mm and bonded to the upper surface of the film for a foamed layer to prepare a first laminate composed of a film for a foamed layer and a surface layer. During calendering for the production of the first laminate, the roll temperature was 172 +/- 5 DEG C and the porosity was 30 +/- 2 m / min. Thereafter, the H / Knit base fabric of the PET material was bonded to the lower surface of the film for the foam layer of the first laminate to prepare a second laminate composed of the base fabric, the film for the foam layer and the surface layer. At the time of calendering for the production of the second laminate, 168 ± 5 ° C and a porosity of 25 ± 2 m / min. Thereafter, to the surface layer of the second laminate, 13.5 wt% of polycarbonate urethane resin, 13.5 wt% of hydroxyl group-containing acrylic resin, 20.25 wt% of cyclohexanone, 24 wt% of methyl ethyl ketone, A composition for a surface treatment layer composed of 4.5 wt% of amide, 4.5 wt% of propylene glycol monomethyl ether acetate, 2.25 wt% of naphtha, 4.5 wt% of silica powder, and 13 wt% of hexamethylene diisocyanate as a curing agent was applied, And dried for 2 minutes and 30 seconds to prepare a third laminate composed of a base fabric, a film for a foam layer, a surface layer and a first surface treatment layer. Thereafter, the third layered product was foamed in a foaming chamber at about 190 to 230 DEG C for about 2 minutes to form a foamed layer, and the third layered product was pressed with an emboss roll engraved with a grain of leather with the film having fluidity A grain of leather texture was imparted to the surface. Thereafter, 13.5 wt% of a polycarbonate urethane resin, 13.5 wt% of a hydroxyl group-containing acrylic resin, 20.25 wt% of cyclohexanone and 24 wt% of methyl ethyl ketone were added to the first surface-treated layer of the third layered product, , 4.5 wt% of dimethylformamide, 4.5 wt% of propylene glycol monomethyl ether acetate, 2.25 wt% of naphtha, 4.5 wt% of silica powder, and 13 wt% of hexamethylene diisocyanate as a curing agent And dried at 110 ° C for 2 minutes and 30 seconds to prepare a PVC foamed artificial leather sheet composed of a base fabric, a foam layer, a surface layer, a first surface treatment layer and a second surface treatment layer. The polycarbonate urethane resin used to form the surface treatment layer was prepared by polymerizing carbonic acid, dimethyl ester and 1,6-hexanediol (CAS Registry No. 101325-00-2) and a polyisocyanate selected from trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, and the like, and a polycarbonate diol having a hydroxyl group at the end formed by the polyisocyanate ≪ / RTI > The hydroxyl group-containing acrylic resin used for forming the surface treatment layer is an acrylic copolymer formed by polymerization reaction of hydroxyethyl methacrylate and methacrylic acid.
The processing aid, foam stabilizer, foaming agent, heat stabilizer, flame retardant and ultraviolet absorber used in Production Example 1, Production Example 2, Comparative Production Example 1 and Comparative Production Example 2 are as follows.
* Processing aid: Paraloid ™ K-445 (Rohm and Haas)
* Foam stabilizer: Zinc oxide
* Foaming agent: Azodicarbonamide (ADCA)
* Heat stabilizer: CINASTAB-5010 (Ba-Zn organic complex)
* Flame retardant: Poly [[6- [1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetra Methyl-4-piperidinyl) imino] -1,6-hexanediyl [(2,2,6,6-tetramethyl-4-pyrrolidinyl) imino]
* Ultraviolet absorber: 2- (2-hydroxy-5-methylphenyl) benzotriazole
2. Measurement of physical properties of artificial leather sheet
(1) Softness and lubrication measurement
The softness and firmness of the synthetic leather sheets prepared in Production Example 1, Production Example 2, Comparative Production Example 1 and Comparative Production Example 2 were measured using the standard test method of MS300-31, which is an internal standard of Hyundai Motor Company (Korea) ), And the results are shown in Table 1 below. In Table 1, the softness indicates that the higher the value, the smoother the firmness is, and the lower the firmness, the more flexible.
Width: 62
Width: 65
Width: 83
Width: 86
* How to measure softness of artificial leather sheet
- Test equipment is ST300D.
- Take 5 sheets of Φ100 mm test specimens and measure the softness with a tester (15 second delay method).
- The tester ring SiZE shall be 25 mm.
* How to measure the firmness of synthetic leather sheets
- The test equipment has a 45 ° slope on one end and a smooth horizontal surface on the top as shown below.
- Take 5 specimens, 25 mm wide and 200 mm long, in each of the longitudinal and transverse directions and align the short side of the test rig with the baseline (A) of the scale. Press the specimen with a pressure plate of the same size as the specimen, slide it at a speed of about 10 mm / sec in the direction of the slope, and read the SCALE position (B) of the other end when one end of the specimen comes into contact with the slope. The lecture figure is represented by the moving distance (scale of point B) (mm), and five surface and back surface in both length and width are measured and shown with their average value.
[Lecture test equipment]
(2) Determination of the content of 6 kinds of phthalate substances and ROHS 6 heavy metals prescribed as suspected substances of environmental hormones
The presence or absence of six phthalate-based substances defined as suspected substances of environmental hormones were measured on the artificial leather sheets prepared in Production Example 1, Production Example 2, Comparative Production Example 1 and Comparative Production Example 2, The results are shown in Table 2 below.
* N.D: Not detect
* DnBP: Di-n-butyl phthalate
* BBP: Butyl benzyl phthalate
* DnOP: Di-n-octyl phthalate
* DOP: Di-2-ethylhexyl-phthalate
* DINP: Diisononyl phthalate
* DIDP: Diisodecyl phthalate
The presence or absence and presence of 6 ROHS heavy metals were measured on the artificial leather sheets prepared in Production Example 1, Production Example 2, Comparative Production Example 1 and Comparative Production Example 2, and the results are shown in Table 3 Respectively.
* N.D: Not detect
While the present invention has been described in connection with the exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Therefore, the scope of the present invention should be construed as including all embodiments falling within the scope of the appended claims.
10: Base fabric
20: foam layer
30: Surface layer
40: Surface treatment layer
100: artificial leather sheet
Claims (10)
Wherein the foam layer is made of a foamed polyvinyl chloride film formed from a composition for a foam layer containing a polyvinyl chloride resin, a plasticizer, a foaming agent, a pigment and a flame retardant,
Wherein the surface layer comprises a polyvinyl chloride film formed from a composition for a surface layer comprising a polyvinyl chloride resin, a plasticizer, a pigment and a flame retardant,
Wherein the plasticizer constituting the composition for the foamed layer and the composition for the surface layer is bis (2-propylheptyl) phthalate (DPHP).
Wherein the first surface treatment layer comprises 1 to 5 wt% of a vinyl chloride / vinyl acetate copolymer, 5 to 10 wt% of a methyl methacrylate polymer, 3 to 5 wt% of a silica powder, 1 to 5 wt% of cyclohexanone, A composition for a first surface treatment layer comprising 70 to 80% by weight of a canon and 2 to 5% by weight of methyl isobutyl ketone,
Wherein the second surface treatment layer comprises 10 to 25 wt% of a polyurethane resin, 1 to 5 wt% of silica powder, 1 to 7 wt% of ethylene glycol propyl ether, 30 to 60 wt% of methyl ethyl ketone, 1 to 7 wt% And 10 to 20% by weight of N, N-dimethylformamide, based on the total weight of the composition.
The film for a foam layer is a polyvinyl chloride film formed from a composition for a foam layer containing a polyvinyl chloride resin, a plasticizer, a foaming agent, a pigment and a flame retardant,
Wherein the surface layer film is a polyvinyl chloride film formed from a composition for a surface layer comprising a polyvinyl chloride resin, a plasticizer, a pigment, and a flame retardant,
Wherein the plasticizer constituting the composition for the foamed layer and the composition for the surface layer is bis (2-propylheptyl) phthalate (DPHP).
The film for a foam layer is a polyvinyl chloride film formed from a composition for a foam layer containing a polyvinyl chloride resin, a plasticizer, a foaming agent, a pigment and a flame retardant,
Wherein the surface layer film is a polyvinyl chloride film formed from a composition for a surface layer comprising a polyvinyl chloride resin, a plasticizer, a pigment, and a flame retardant,
Wherein the plasticizer constituting the composition for the foamed layer and the composition for the surface layer is bis (2-propylheptyl) phthalate (DPHP).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200060224A (en) | 2018-11-22 | 2020-05-29 | (주)엘지하우시스 | Artificial leather for automobile interior materials and manufacturing method thereof |
| US20210046728A1 (en) * | 2018-02-12 | 2021-02-18 | Omnova Solutions Inc. | Discoloration resistant fabric |
| KR20220169157A (en) * | 2021-06-18 | 2022-12-27 | 희성폴리머 주식회사 | Coating Composition of Building Membrane Structures with improved fire resistance, contamination, durability, and weather resistance |
| KR102515389B1 (en) * | 2022-06-28 | 2023-03-30 | 조앤리코퍼레이션 주식회사 | UV blocking-coating agent, anti-discoloration and anti-bacterial mat using the same and Manufacturing method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR930005780B1 (en) * | 1988-12-21 | 1993-06-24 | 주식회사 금성사 | Optical head |
| JPH06116875A (en) * | 1992-10-01 | 1994-04-26 | Achilles Corp | Pvc leather cloth |
| KR20010002269A (en) * | 1999-06-14 | 2001-01-15 | 서상우 | Preparation Method for Far Infrared Ray Irradiating Artificial Leather |
| KR20020092077A (en) * | 2001-06-02 | 2002-12-11 | 조성식 | Scent PVC leather and manufacturing method thereof |
| KR100873655B1 (en) * | 2007-07-27 | 2008-12-12 | (주)아이앤에스 | Flame retarded pvc foam artificial leather and manufacturing method thereof |
| KR20090131529A (en) * | 2008-06-18 | 2009-12-29 | 에스케이에너지 주식회사 | A plasticizer and the composition of polyvinylchloride resin comprised the same |
| KR101084958B1 (en) * | 2003-08-07 | 2011-11-23 | 에보니크 옥세노 게엠베하 | Foamable compositions which comprise isononyl benzoate |
-
2016
- 2016-12-27 KR KR1020160180238A patent/KR101863618B1/en active IP Right Grant
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR930005780B1 (en) * | 1988-12-21 | 1993-06-24 | 주식회사 금성사 | Optical head |
| JPH06116875A (en) * | 1992-10-01 | 1994-04-26 | Achilles Corp | Pvc leather cloth |
| KR20010002269A (en) * | 1999-06-14 | 2001-01-15 | 서상우 | Preparation Method for Far Infrared Ray Irradiating Artificial Leather |
| KR20020092077A (en) * | 2001-06-02 | 2002-12-11 | 조성식 | Scent PVC leather and manufacturing method thereof |
| KR101084958B1 (en) * | 2003-08-07 | 2011-11-23 | 에보니크 옥세노 게엠베하 | Foamable compositions which comprise isononyl benzoate |
| KR100873655B1 (en) * | 2007-07-27 | 2008-12-12 | (주)아이앤에스 | Flame retarded pvc foam artificial leather and manufacturing method thereof |
| KR20090131529A (en) * | 2008-06-18 | 2009-12-29 | 에스케이에너지 주식회사 | A plasticizer and the composition of polyvinylchloride resin comprised the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210046728A1 (en) * | 2018-02-12 | 2021-02-18 | Omnova Solutions Inc. | Discoloration resistant fabric |
| KR20200060224A (en) | 2018-11-22 | 2020-05-29 | (주)엘지하우시스 | Artificial leather for automobile interior materials and manufacturing method thereof |
| KR20220169157A (en) * | 2021-06-18 | 2022-12-27 | 희성폴리머 주식회사 | Coating Composition of Building Membrane Structures with improved fire resistance, contamination, durability, and weather resistance |
| KR102594053B1 (en) | 2021-06-18 | 2023-10-25 | 희성폴리머 주식회사 | Coating Composition of Building Membrane Structures with improved fire resistance, contamination, durability, and weather resistance |
| KR102515389B1 (en) * | 2022-06-28 | 2023-03-30 | 조앤리코퍼레이션 주식회사 | UV blocking-coating agent, anti-discoloration and anti-bacterial mat using the same and Manufacturing method thereof |
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