KR101582573B1 - Complex functional synthetic leather for crash pad covering and Preparation method thereof - Google Patents

Abstract

The present invention relates to a composite functional artificial leather for a crash pad cover and a method of manufacturing the same. More particularly, the present invention relates to a composite functional artificial leather for a crash pad cover, which comprises a fibrous substrate layer 101 composed of a long fibrous high density microfine nonwoven fabric, A polyurethane skins layer 104 formed on the polyurethane porous layer and made by polymerizing a polyol compound comprising a polyisocyanate compound and a carbonate polyol and an ester polyol; And a polyurethane adhesive layer (103) for adhering the layer and the skin surface layer, and a method for manufacturing the same.

Description

Technical Field [0001] The present invention relates to a composite functional synthetic leather for crash pad cover and a manufacturing method thereof,

The present invention relates to a cover for an automobile interior material improved in moldability such as durability and crease resistance such as high light resistance, heat aging resistance, chemical resistance, friction coloring resistance and hydrolysis resistance, The present invention relates to useful multifunctional artificial leather and a method for producing the same.

The automotive interior parts, called crash pads, are mounted on the bottom of the front glass, and are manufactured in such a shape as to integrate instrument panels such as a speedometer, a fuel system, etc., instrument panel, audio and navigation. Particularly, for safety, a skin layer is formed so as to show various patterns on a urethane foam layer which absorbs impact and imparts complete layering property. A typical crash pad is composed of a product surface-treated with a spray method on a urethane foam layer.

However, the above method has limitations in showing various surface patterns, and also has disadvantages such as difficulty in realizing a luxurious automobile interior atmosphere such as touch feeling of high sensitivity.

In recent years, crush pads have been developed in the form of crush pads which are wrapped around natural leather for the feeling of high sensibility and for expressing a luxurious interior atmosphere of a car. The natural leather material has a disadvantage in that wrinkles, shrinkage, and deformation are generated depending on the management method due to a large deviation according to the bare parts of the bark. In addition, since it depends on imports and the price is too high, it is limited to high-end cars, so there is a limit to expanding to various models. Accordingly, there is a desperate need to develop artificial leather that exhibits similar sensibility, touch, and appearance as natural leather, while exhibiting complex functionality and high physical properties, and a crash pad utilizing the same.

In the process for producing artificial leather for general automobile interior materials, an organic solvent type urethane compound liquid containing an organic solvent such as an aqueous urethane resin, dimethyl formamide, methyl ethyl ketone or the like is applied on a release paper and dried to form a film of the surface layer, A method in which an adhesive is applied on the surface layer thus formed, crosslinked and cured, and then a fiber material such as a monofilament-type microfibre nonwoven fabric or a fabric is laminated.

For example, Korean Patent Laid-Open Publication No. 10-2012-0133210 (Patent Document 1) relates to a method for producing a polyurethane artificial leather for automobile interior materials, comprising: a first step of preparing a release paper; A second step of repeatedly applying and drying a polyurethane blend liquid containing an aqueous dispersion type polycarbonate urethane on the top surface of the release paper a plurality of times to form a surface layer to be laminated with a plurality of layers; A third step of applying an urethane adhesive to the upper surface of the surface layer to form an adhesive layer; And a fourth step of adhering a fabric, a knitted fabric or a nonwoven fabric knitted with synthetic fibers to the upper surface of the adhesive layer to form artificial leather.

However, the artificial leather disclosed in Patent Document 1 has only a surface coating layer of a water-dispersible urethane on a fiber substrate such as a short-fiber non-woven fabric or fabric having a relatively small density, and wrinkles are generated when applied as a covering material for a crash pad And there is a limitation in showing emotion similar to the volume feeling and touch of natural leather.

In addition, the conventional surface coating layer is resistant to the light resistance by the 84 MJ irradiation dose, which is the property of general car seat and door trim application. However, for the 126 MJ irradiation dose of the crash pad covering material, the light resistance is insufficient and the chemical resistance, heat aging resistance, , And exhibits a disadvantage that the physical properties such as hydrolysis resistance are low, and thus it is difficult to apply the material as a covering material for a crash pad.

Korean Patent Laid-Open No. 10-2012-0133210

The present inventors have found that when controlling the composition of a polyol used for the production of a polyurethane which forms a skin layer and a surface treatment coating layer with a long fiber type high density microfine nonwoven fabric as a fiber base material, It is possible to improve the physical properties such as water resistance and water repellency and to improve the wrinkling property when using as a covering material of a crash pad, while showing a sensibility similar to that of natural leather, volume feeling, and feel.

Accordingly, a problem to be solved by the present invention is to provide an antifogging agent which has good durability properties such as high light resistance, heat aging resistance, friction coloring property, chemical resistance and hydrolysis resistance while exhibiting sensitivity similar to that of natural leather, And to provide a composite functional artificial leather which can be used as a covering material of a composite functional artificial leather.

Another problem to be solved by the present invention is to provide a polyurethane resin composition comprising a urethane porous layer, a urethane adhesive layer and a polyurethane skin layer sequentially laminated on a fiber substrate layer of a long-fiber type high-density micro- And to provide a method for manufacturing artificial leather in which the polyol component is specifically formed to control physical properties.

Another problem to be solved by the present invention is to provide a crash pad overlaid with artificial leather.

In order to solve the above-mentioned problems, the present invention provides a fibrous substrate comprising a fibrous substrate layer 101 comprising a long fibrous high density microfine nonwoven fabric; A polyurethane porous layer 102 having micropores; A non-sulfur-modified polyurethane adhesive layer 103 comprising a polyurethane-based adhesive for adhering the polyurethane porous layer and the polyurethane skin layer; A polyurethane resin prepared by reacting a polyurethane prepolymer prepared by polymerizing a polyisocyanate compound and a polyol compound containing a carbonate polyol and an ester polyol with an aliphatic amine chain chain extender or an alicyclic amine chain chain extender And a polyurethane skin layer on the surface of the impact pad cover, which are laminated in this order, to provide a highly functional artificial leather for a crash pad cover.

The present invention also relates to a method of producing a polyurethane foam, comprising the steps of: i) forming a first sheet by forming a polyurethane porous layer 102 having fine pores on a fiber substrate layer 101 containing a long fiber type high density microcellular nonwoven fabric; (Ii) a polyurethane resin prepared by reacting a polyurethane prepolymer prepared by polymerizing a polyisocyanate compound and a polyol compound containing a carbonate-based polyol and an ester-based polyol with an aliphatic amine-based chain extender or an alicyclic amine- Coating the release paper on a release paper sheet to form a polyurethane skin layer; Iii) forming a second sheet by forming a polyurethane adhesive layer on the skin layer 104; And iv) laminating the first sheet and the second sheet together, followed by peeling the release paper from the skin layer, thereby providing a method of manufacturing a highly functional artificial leather for a crash pad cover.

In addition, the present invention provides a crash pad cover and a crash pad cover which are covered with the artificial leather.

INDUSTRIAL APPLICABILITY According to the present invention, durability such as high light resistance, heat aging resistance, friction coloring property, chemical resistance, and hydrolysis resistance, which are the main required properties of automobile interior materials, especially crash pad covering materials, An effect of improving the moldability can be obtained.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a photograph of a cut surface of a synthetic leather produced in Example 1 of the present invention by a scanning electron microscope (SEM). Fig.
2 is a photograph of a section of a conventional artificial leather produced in Comparative Example 1 of the present invention by scanning electron microscopy (SEM).
Fig. 3 is a photograph of a cut surface of a nonwoven fabric constituting the fiber substrate layer observed by a scanning electron microscope (SEM), wherein (A) is a typical single-fiber type high-density micro-fiber nonwoven fabric photograph, (B) This is a high density microfiber nonwoven fabric photo.
4A to 4C are photographs of a crash pad manufactured using the artificial leather manufactured in Example 1 of the present invention.
5A to 5C are photographs of a crash pad manufactured using the artificial leather manufactured in Comparative Example 1. FIG.

The present invention relates to a synthetic leather for a crash pad cover and a method of producing the same, and as shown schematically in Fig. 1, the artificial leather of the present invention comprises a polyurethane (Defined as a PU porous layer 102), a polyurethane adhesive layer 103 (hereinafter referred to as a PU adhesive layer), and a polyurethane skin layer 104 (hereinafter, referred to as a PU skin layer) (Hereinafter referred to as " PU surface treatment coating layer ") is formed on the polyurethane skin layer.

In addition, the present invention controls the physical properties suitable for the crash pad cover by newly designing the composition of the polyol used in the polymerization reaction of the polyurethane resin forming the PU porous layer 102 and the PU skin layer 104.

In general, polyurethane is composed of two phases in a polymer: a hard segment (HS) and a soft segment (SS), and a rigid segment serving as a crystalline structure by physical bonding is composed of a soft segment domain domain). The physical properties and rigidity of the polyurethane vary not only with the cohesive force of the hard segment but also with the type of the soft segment. Depending on the type of the polyol used as the soft segment, the mechanical properties, thermal properties, hydrolysis resistance and chemical resistance are different.

Accordingly, in the present invention, in forming the PU skin layer 104 of artificial leather, a polyurethane resin prepared by polymerizing a polyol compound containing an aliphatic or alicyclic polyisocyanate compound together with a carbonate polyol, a fluorinated polyol and an ester polyol Resin. This has the effect of simultaneously improving the high durability such as high light resistance, heat aging resistance, chemical resistance, friction coloring property and hydrolysis resistance for application to a crash pad cover.

Each layer constituting the artificial leather according to the present invention will be described in more detail as follows.

a) the fiber substrate layer (101)

In the present invention, when the fiber base layer 101 is used as a crash pad covering material while exhibiting a similar sensation to natural leather, a fiber base material is applied to a long-fiber type high-density micro-fiber non-woven fabric in order to ensure excellent formability without wrinkles .

The long-fiber type high-density microfine nonwoven fabric is a long-fiber type nonwoven fabric produced by a combined process of two or more selected from spunbond, needle punching and spun lace. The long-fiber type high-density microcellular nonwoven fabric has an apparent density of 0.30 g / cm ³ or more, preferably 0.30 to 0.60 g / cm ³ , and more preferably 0.40 to 0.50 g / cm ³ , The impregnation process can be performed without using a shrinking process or the impregnation process can be performed by utilizing a polyurethane resin blend liquid having a low concentration. The above-mentioned long-fiber type high-density micro-fabric nonwoven fabric having such characteristics has higher strength and density than the conventional short-fiber type high-density nonwoven fabric and has excellent quality, and is suitable for a fiber substrate for automobile interior materials such as crash pad. 3 shows a scanning electron microscope (SEM) observing the internal structures of the conventional single-fiber type high-density nonwoven fabric A and the long-fiber type high-density microcellular nonwoven fabric B, Can be confirmed.

Also, the long-fiber type high-density micro-fiber nonwoven fabric may include at least one general-purpose filament yarn selected from the group consisting of polyethylene terephthalate (PET) and polyamide (PA); Or PET / PA (polyethylene terephthalate / polyamide), PET / PLA (polyethylene terephthalate / polylactic acid), PET / Co-PET (polyethylene terephthalate / co-polyethylene terephthalate) Or a segmented filament yarn including at least one species selected from the group consisting of the sea-island filament yarns and the split-type filament yarns. Preferably, sea-island filament yarns are used for application to a crash pad cover.

According to one embodiment for producing the long-fiber micro-woven high-density non-woven fabric, a long-fiber micro-woven high-density non-woven fabric is manufactured from a sea-island filament yarn having an average fineness of 2.0 to 5.0 denier, preferably, preferably 2.5 to 3.8 denier, Molecular weight thermoplastic resin such as polyamide (PA), polyamide (PA), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT) and the like, as a component, and a low molecular weight polyethylene terephthalate (Co-PET, co-polyethylene terephthalate) and polylactic acid (PLA, polylactic acid).

The sea-island filament yarn having an average fineness of 2.0 to 5.0 denier was spun by a spinning method at a mixing ratio of 60 to 80% by weight of the island component and 20 to 40% by weight of the sea component (3,000 to 7,000 m / min) 30 to 50 g / cm < ² >). Next, after performing calendering using a cold calendaring method in which the surface is treated without applying heat for the shape stability of the web, the web is subjected to a calendering process in the case of a heavy weight (300 to 600 g / cm ² ) , A long-fiber type high density nonwoven fabric can be manufactured by crosslapping and drafting, treating with a penetration per square centimeter (PPSC) of 100 to 800 ea / cm ² by needle punching,

A nonwoven fabric is produced by a composite spinning method using a high molecular weight thermoplastic resin and a low molecular weight resin and the spinning is carried out at a spinning speed of 3,000 to 7,000 m / min, preferably 4,000 to 5,000 m / min It is excellent in quality.

For example, a web is formed by spunbonding a sea-island filament yarn having an average fineness of 2.0 to 5.0 denier; Performing cold calendaring of the web; Laminating and stretching a web subjected to a knife-rendering process, performing a needle punching process at 100 to 800 ea / cm < ² > And a step of reducing the nonwoven fabric in a NaOH aqueous solution having a concentration of 2% to 10% for 5 minutes to 30 minutes, preferably 5 minutes to 20 minutes.

The long-fiber microfine high-density nonwoven fabric used as the fibrous substrate layer of the present invention has a tensile strength measured according to the ASTM 5035 method in a machine direction of 40 to 60 kgf / inch and a CD (cross direction) of 50 to 60 kgf / inch, preferably from 42 to 50 kgf / inch of MD and 52 to 58 kgf / inch of CD. In addition, the long fibrous high density nonwoven fabric has 60 to 80% of MD and 100 to 140% of CD, preferably 65 to 75% of MD and 110 to 130% of CD in terms of elongation (elongation) measured according to the ASTM 5035 method. Lt; / RTI > It may also be between MD 5.5 to 6.0 kgf and CD 5.2 to 5.8 kgf, preferably MD 5.5 to 5.9 kgf and CD 5.3 to 5.7 kgf for the tear strength measured according to the ASTM 5035 method. If the elongation is too low, it is difficult to pull the leather during the covering process of the crash pad, resulting in poor workability and wrinkles on the curved surface. If the elongation is too high, the surface is stretched and the physical properties become uneven. Also, if the tear strength is low, a problem of breakage may occur during the manufacturing process of the crash pad, so that a synthetic leather fiber substrate exhibiting physical properties within the above range is suitable.

The fiber base layer 101 constituting the artificial leather of the present invention may have an average thickness of 0.5 to 1.3 mm, preferably 0.7 to 1.0 mm.

b) Polyurethane porous layer 102

As shown in FIG. 1, since uniform pores are formed in the polyurethane resin, the PU pore layer 102 can further increase soft feel and volume feeling on artificial leather.

Wherein the PU pore layer comprises a polyurethane porous layer composition comprising a polyurethane resin, a solvent, a urethane pore regulator and toner in a weight ratio of 100: 30 ~ 60: 0.5 ~ 2: 0.1 ~ 1: 5 ~ Layer on the surface of the substrate.

In the PU pore layer composition, the polyurethane resin is preferably a mixture of a polyisocyanate compound and an ester-based polyol having a weight average molecular weight of 1,000 to 4,000, preferably 1,200 to 2,500, an ether-based polyol having a weight average molecular weight of 1,500 to 3,000, 1,800 to 2,500) and a carbonate-based polyol (weight average molecular weight: 1,000 to 3,500, preferably 1,500 to 3,000), and reacting the obtained polyurethane prepolymer with a chain extender.

The polyurethane polymerization method is not particularly limited in the present invention, and any method can be used as long as it is usually used in the reaction of a polyol and a polyisocyanate, and can be found in various related documents.

The polyisocyanate compound used to polymerize the polyurethane resin may be any of those commonly used in the art and includes, but is not limited to, 4,4'-diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI) , 1,5-naphthalene diisocyanate and the like; aromatic diisocyanates having a benzene ring; Aliphatic diisocyanates such as hexamethylene diisocyanate (HDI) and propylene diisocyanate; And alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate, isophorone diisocyanate (IPDI) and 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI); (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane diisocyanate (H ₁₂ MDI), preferably at least one selected from the group consisting of 4,4-diphenylmethane diisocyanate And the like.

The polyol compound used for polymerizing the polyurethane resin is prepared by polymerizing the ester polyol, the ether polyol and the carbonate polyol in a weight ratio of 100: 100 to 150: 110 to 200, preferably 100: 105 to 125: 115 to 185 Is preferable in terms of improving hydrolysis resistance and chemical resistance while maintaining excellent mechanical properties. The polymerization may further include a flame-retardant polyol such as a reaction-type phosphoric acid ester-based polyol as the polyol component.

The chain extender used in the production of the polyurethane resin is a component commonly used in the art. The present invention is not particularly limited to the use of the chain extender, but preferably includes an even number of repeating units A low molecular weight diol compound or a diamine compound having a low molecular weight can be used. Specifically, the chain extender may be selected from the group consisting of ethylene glycol (EG), diethylene glycol (DEG), propylene glycol (PG), 1,4-butanediol (1,4-BD), 1,6- HD), methylpentanediol and isophoronediamine (IPDA), preferably at least one selected from ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol and methylpentanediol Can be used. The amount of the chain extender may be 1 to 15 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the polyol.

The amount of the polyisocyanate compound and polyol compound used for polymerizing the polyurethane resin is preferably such that the molar ratio of NCO / OH is 0.95 to 1.05, preferably 1.0.

In the PU porous layer composition, the solvent includes at least one selected from the group consisting of dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO) And it is preferable to use 100 to 180 parts by weight, preferably 110 to 150 parts by weight, based on 100 parts by weight of the polyol. If the amount of the solvent used is less than 100 parts by weight, the viscosity of the solution is high and uniform pore formation is difficult. If the amount of the solvent is more than 180 parts by weight, the viscosity of the solution is too low to control the thickness precisely.

In the porous layer composition, the urethane porous regulator is used to form uniform pores in the urethane porous layer. Although not specifically limited, the urethane porous regulator may include one or more surfactants selected from anionic and non- It is good to use. The amount of the urethane pore regulator used is preferably from 100: 0.5 to 2: 1 by weight, more preferably from 100: 0.5 to 1.5: 1 by weight, based on the polyurethane resin (polyol compound, chain extender, solvent and polyisocyanate compound- If it is less than 0.5 weight ratio, it may not be possible to form sufficient pores in the urethane porous layer. If it exceeds 2 weight ratio, the pores may be uneven.

In the above-mentioned porous layer composition, the toner is a pigment that imparts the color of the urethane porous layer. The amount of the toner to be used is preferably in the range of 100: 5 to 15, more preferably 100: 7 to 12, by weight of the polyurethane resin. If the amount of the toner is less than 5 parts by weight, There may be a problem of deteriorating all properties, so it is preferable to use within the above range.

The polyurethane resin further contains 0.1 to 1 part by weight, preferably 0.1 to 0.5 part by weight, and 0.05 to 0.5 part by weight, preferably 0.1 to 0.3 part by weight, of a yellowing inhibitor per 100 parts by weight of the polyol can do.

The PU porous layer constituting the artificial leather of the present invention has a modulus of 65 to 87 kgf / cm ² , preferably 68 to 85 kgf / cm ² when measured according to KS M 6782.

Further, when measured according to ASTM D-412, the tensile strength was 350 to 450 kgf / cm ² in the width direction, Preferably 380 to 400 kgf / cm ² , and a longitudinal direction of 390 to 430 kgf / cm ² , Preferably 405 to 425 kgf / cm < ^{2 &} gt ;.

The polyurethane porous layer has an elongation of 415 to 460%, preferably 425 to 460%, and a lengthwise direction of 420 to 465%, preferably 420 to 450%, in the width direction when measured according to JIS K7311.

The polyurethane porous layer is formed into a sheet, and then a hot-melt cloth tape having a width of 25 mm is thermally fused at 130 DEG C for 5 seconds. When measured based on KS M 0533, the peel strength is 3.0 Kgf / cm or more, And preferably 3.5 to 4.5 Kgf / cm.

The PU pore layer 102 constituting the artificial leather of the present invention may have an average thickness of 0.1 to 0.6 mm, preferably 0.15 to 0.45 mm, and more preferably 0.15 to 0.35 mm.

c) the PU adhesive layer 103,

In the artificial leather of the present invention, an adhesive layer 103 is formed between the PU porous layer 102 and the PU skin layer 104. The PU adhesive layer may be a non-porous deformable adhesive used in the art, It is preferable to use a hexamethylene diisocyanate (HDI) urethane-based adhesive, and it is also preferable to use a two-component type urethane adhesive to which a phosphorus-based, nitrogen-based flame retardant is added to impart flame retardancy to an artificial leather.

Specific examples thereof include a urethane adhesive (a non-sulfur modified reaction product (containing 65 to 80 wt% solids, 70,000 to 90,000 cps / 25 属 C) of a carbonate polyol, 1,4-butylene glycol hexa and hexylene diisocyanate 5 to 20 parts by weight, preferably 8 to 12 parts by weight of dimethylformamide and 20 to 40 parts by weight, preferably 27 to 32 parts by weight of methyl ethyl ketone are mixed with 10 to 15 parts by weight of a crosslinking agent By weight, preferably 11 to 14 parts by weight, based on 100 parts by weight of the polyurethane adhesive.

The PU adhesive layer 103 constituting the artificial leather of the present invention may have an average thickness of 0.06 to 0.5 mm, preferably 0.15 to 0.45 mm.

d) PU skin layer 104,

The PU skin layer 104 may be prepared by reacting a polyurethane prepolymer obtained by polymerizing a polyisocyanate compound and a polyol compound containing a carbonate-based polyol and an ester-based polyol, and a chain extender.

The polyisocyanate compound used to polymerize the polyurethane resin contained in the PU skin layer 104 is hexamethylene diisocyanate (HDI), propylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate (IPDI ) And 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI), preferably isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) and 4, 4-diaminodicyclohexylmethane (H ₁₂ MDI) may be used alone or in admixture of two or more.

The polyol compound used for polymerizing the polyurethane resin is preferably a carbonate-based polyol having a weight average molecular weight of 1,200 to 3,500, preferably a weight average molecular weight of 1,500 to 2,500, and an ester type polyol having a weight average molecular weight of 1,000 to 3,000, Average molecular weight 1,500 to 2,800). If a polyol compound having a low molecular weight is used, the modulus of the skin layer is increased, and the elongation of the skin layer is lowered, so that the surface feeling may be deteriorated and the product may become stiff. On the other hand, when a polyol compound having a very high molecular weight is used, the skin layer may be smooth, but the surface may become sticky and mechanical properties may deteriorate.

The carbonate polyol and ester polyol used as the polyol compound for polymerizing the polyurethane resin are preferably used in a weight ratio of 100: 2 to 30, preferably 100: 7 to 20, by weight. When the use ratio of the polyol compound is in the above-mentioned weight ratio, high light resistance, hydrolysis resistance, heat aging resistance and excellent friction coloring property can be ensured.

The carbonate-based polyol as the polyol compound may be at least one selected from the group consisting of ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), propylene glycol (PG), 1,4- 1,3-BD, 1,5-PD, 1,6-HD, 1,4-cyclohexanediol, 1,4-cyclohexanediol, -Cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol, and 1,8-octanediol, with at least one dihydroxyl compound selected from the group consisting of diaryl carbonate, dialkyl carbonate, or phosgene A polyol synthesized by a known synthesis method such as a condensation reaction can be used. The polyurethane produced using such a polycarbonate-based polyol is excellent in hydrolysis resistance, weather resistance, and heat resistance.

As the polyol compound, the ester-based polyol may be at least one selected from the group consisting of ethylene glycol (EG), 1,4-butanediol (1,4-BD), 1,6-hexanediol (1,6-HD), and diethylene glycol Or an aliphatic polyester polyol obtained by esterifying a low molecular weight polyol and a polycarboxylic acid such as adipic acid (AA), or the ester polyol may be a ring-opening ester compound such as? -Caprolactone, Or a polyester polyol obtained by a reaction.

The polyol compound used for polymerizing the polyurethane resin may further include a flame-retardant polyol such as a reaction-type phosphoric acid ester-based polyol.

The chain extender used for polymerizing the polyurethane resin may be an aliphatic amine-based chain extender or alicyclic amine-based extender which is not used in the glycol system used conventionally to improve heat resistance, hydrolysis resistance and chemical resistance Chain extenders may be used, and preferably at least one selected from hexamethylenediamine, dicyclohexylamine and isophoronediamine.

The PU skin layer 104 constituting the artificial leather of the present invention may have an average thickness of 0.05 to 0.5 mm, preferably 0.05 to 0.30 mm, more preferably 0.08 to 0.15 mm.

e) PU surface treatment The coating layer (105)

The artificial leather of the present invention forms a PU surface treatment coating layer 105 on the surface of the PU skin layer 104 in order to adjust the gloss and color, and to improve functions such as light resistance, hydrolysis resistance and chemical resistance, The PU surface treatment coating layer 105 can be produced as a main raw material by using an anion-free modified urethane resin. That is, a surface treatment coating liquid containing non-yellowing polyurethane resin, a polish remover, and a solvent may be coated on the surface of the polyurethane skin layer 104.

The resin contained in the PU surface treatment coating liquid is a non-sulfur-modified polyurethane resin which is a non-sulfur-modified polyurethane resin, which is obtained by reacting a polyisocyanate compound, a carbonate polyol (weight average molecular weight 1,200 to 3,500, preferably weight average molecular weight 1,500 to 2,500) A polyol compound having a molecular weight of 400 to 1,500, preferably a weight average molecular weight of 450 to 900) and an ester-type polyol (weight average molecular weight 1,000 to 3,000, preferably weight average molecular weight 1,500 to 2,800) Is prepared by reacting a prepolymer with a chain extender. The prepared polyurethane resin may have a solid content of 10 to 40% by weight, preferably 13 to 32% by weight.

As the polyol compound, the fluorinated polyol is useful for improving the stain resistance and the friction coloring property by using a mixture of at least one selected from the group consisting of perfluoropolyether and polytetrafluoroethylene.

The polyisocyanate compound may be a mixture of at least one selected from isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) and 4,4-diaminodicyclohexylmethane (H ₁₂ MDI) And preferably two kinds of them may be mixed in a weight ratio of 1: 0.5 to 1.5, preferably 1: 0.8 to 1.2.

The chain extender may contain at least one selected from hexamethylenediamine, dicyclohexylamine and isophoronediamine for improving heat resistance, hydrolysis resistance, chemical resistance and the like.

The amount of the carbonate-based polyol, the fluorinated polyol, and the ester-based polyol used as the polyol compound used to polymerize the polyurethane resin used in the coating liquid for forming the PU surface-treated coating layer is preferably 100: 5 to 30: 1 to 10: It is preferable to use it in a weight ratio of 100: 8 to 15: 3 to 8.

An organic fine powder or an inorganic fine powder may be used as the luster removing agent included in the PU surface treatment coating liquid. Herein, the organic fine powder may be at least one selected from the group consisting of acrylic resin particles, styrene resin particles, styrene-acrylic resin particles, phenol resin particles, melamine resin particles, acrylic-polyurethane resin particles, polyester resin particles, nylon resin particles, silicone resin particles, Urethane beads, and the like. Examples of the inorganic fine powder include talc, mica, calcium carbonate, magnesium carbonate, alumina, silica, carbon black, titanium oxide, magnesium hydroxide, bentonite and graphite. Such a powder can be used without limitation as long as the average particle diameter of the particles is 10 μm or less. If the average particle diameter is more than 10 μm, when the product is dispersed in the surface-treating coating liquid and thin-coated on the surface of the product, the scratch resistance is deteriorated and the appearance of the product may be deteriorated.

The amount of the degreasing agent may be 5 to 20 parts by weight, preferably 10 to 18 parts by weight, based on 100 parts by weight of the non-sulfur-modified polyurethane resin. When the amount is less than the above range, the effect for extinguishing the gloss is not sufficient, and if it exceeds the above range, the physical properties of the artificial leather are lowered.

The solvent contained in the PU surface treatment coating solution may be at least one selected from the group consisting of dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-ethylpyrrolidone, dimethylsulfoxide (DMSO) (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), ethyl acetate, methyl ethyl Ketone, and isopropyl alcohol. These solvents may be used alone or in admixture of two or more. More preferably, they may be used in admixture of two or more kinds. More preferred are dimethylformamide, methyl ethyl ketone, and isopropyl Alcohol may be mixed in a weight ratio of 50:15 to 25: 25 to 35.

The amount of the solvent used in the PU surface-treatment coating liquid is preferably 70 to 200 parts by weight, and preferably 90 to 150 parts by weight, based on 100 parts by weight of the non-sulfur-modified polyurethane resin. When the amount of the solvent used is less than 70 parts by weight, the film formability and the friction coloring property are poor. When the amount exceeds 200 parts by weight, formation of the film after drying is incomplete and problems such as residual organic solvent in the coating film may occur I do not.

The PU surface treatment coating solution may further contain reactive additives, dispersants, antioxidants, antifoaming agents, yellowing inhibitors, reaction promoters, UV absorbers, and the like which are conventionally used in the art depending on the purpose. As an example of the reactive additive, hydroxy silicone polyacrylate may be used in an amount of 2 to 10 parts by weight, preferably 3 to 8 parts by weight, based on 100 parts by weight of the non-sulfur-modified polyurethane resin. As the reaction accelerator, 10 to 25 parts by weight, preferably 15 to 23 parts by weight, of p-toluenesulfonic acid may be used per 100 parts by weight of the polyurethane resin.

The PU surface treatment coating layer 105 constituting the artificial leather of the present invention may have an average thickness of 0.005 to 0.03 mm, preferably 0.008 to 0.01 mm.

A method of manufacturing artificial leather according to the present invention will be described below.

The artificial leather of the present invention comprises the steps of: i) preparing a first sheet by forming a PU porous layer having fine pores on a fibrous substrate layer containing a long fibrous high density microcellular nonwoven fabric; (Ii) a polyurethane resin prepared by reacting a polyurethane prepolymer prepared by polymerizing a polyisocyanate compound and a polyol compound containing a carbonate-based polyol and an ester-based polyol with an aliphatic amine-based chain extender or an alicyclic amine- On a release paper to form a PU skin layer; Iii) forming a PU adhesive layer on one surface of the PU skin layer to produce a second sheet; And iv) laminating the first sheet and the second sheet, followed by peeling the release paper from the PU skin layer.

And (v) coating the surface of the PU skin layer on which the release paper has been peeled with the PU surface treatment coating liquid to form a PU surface treatment coating layer.

In the artificial leather manufacturing method of the present invention, the fiber base layer, the PU pore layer, the PU skin layer, the components used in the manufacture of the PU surface treatment coating layer, the composition ratios, the physical properties and the characteristics thereof, .

The release paper may be made of paper or a film, and various types can be used. In particular, it is preferable that the release paper has a constant thickness and high dimensional stability so as not to be deformed by heat and pressure .

The coating for forming each layer by the above-described method of producing artificial leather is carried out by a usual coating method. For example, the coating method may be applied to various layers such as air knife method, gravure method, reverse roll method, reverse gravure method, Or spray coating method, and there is no particular limitation.

According to another aspect of the present invention, the present invention is characterized by using artificial leather described above as a crash pad covering material. Accordingly, the present invention includes the crash pad covering the above-described artificial leather as a right scope.

3 and 4 are photographs of a crash pad manufactured using the artificial leather according to the present invention. Compared with the artificial leather of Comparative Example 1 shown in FIG. 5, the artificial leather of the present invention has durability And particularly excellent in sensibility such as wrinkle and volatility.

The artificial leather of the present invention thus prepared was irradiated with a light intensity of 126 MJ / m ² under a black panel temperature of 90 ° C and a humidity resistance of 50% RH by a testing machine specified in accordance with ISO 105, When the difference in discoloration caused by the naked eye is judged to be the gray scale specified in ISO 105-A02, the fastness to light fastness can have an excellent light fastness of 3 to 5, preferably 4 to 5 .

Hereinafter, preferred embodiments and experimental examples of the present invention will be described. The following examples and experimental examples are provided for the purpose of more clearly expressing the present invention, but the present invention is not limited to the following examples and experimental examples.

[Example]

Comparative Preparation Example 1: Fabrication of nonwoven fabric for textile base layer

A fabric having a fineness of 1.4 denier, a fiber length of 51 mm, a polyester of 50%, a fineness of 2 denier and a fiber length of 51 mm and a nylon of 50% was produced and shrunk to 230 g / m ² according to a conventional method of producing a needle punching nonwoven fabric. % NaOH aqueous solution for 30 minutes. The results are shown in Table 1 below.

[Table 1]

As shown in Table 1, the density of the nonwoven fabric increased by 0. 41 g% at 0.21 g / cm ³ to 0.30 g / cm ³ after shrinkage treatment. In addition, the contraction rate of contraction due to longitudinal and transverse contraction was 28% shrunk. It is difficult to develop a density of 0.3 g / cm < ³ > or more even if the density is increased by shrinking. After the weight loss, the fiber was partially damaged and the density decreased by 0.25 g / cm ³ .

Preparation Example 1: Production of long-fiber type high-density microfine fiber base layer

(PET / Co-PET, 70/30, 25 islands) filament yarn with a fineness of 3.0 denier and a sea level of 38 to 40 g / cm ² by a spunbond process, followed by cold calendaring ), and then, after the web was performed knife render that the multi-layer stack and stretching, 330 ~ 350 ea / cm after ² performs a needle punching process, the by current coupling, width 1950mm, average weight of 450g / m ^3, and performing A nonwoven fabric having an average thickness of 0.98 mm was produced.

Next, this was subjected to a reduction process for 30 minutes in an aqueous 3% NaOH solution to prepare a long-fiber type high-density microfine nonwoven fabric. The results are shown in Table 2.

[Table 2]

As shown in Table 2, the density of the long-fiber type nonwoven fabric has a very high apparent density compared to the density of the ordinary nickel-punched nonwoven fabric (generally about 0.21 g / cm ³ ), and the high density characteristics Respectively. In the case of long-fiber type nonwoven fabric, since the fiber tends to return to its original form, even after application of heat or physical force in the post-process such as loss reduction, the density after the reduction shows a tendency similar to that before the weight loss, so that a stable high density nonwoven fabric can be provided .

Comparative Preparation Example 2: Polyurethane resin for forming PU pore layer

50 parts by weight of an ester polyol having an average molecular weight of 2,000 (K-340 (EG / 1.4BD / AA), manufactured by Dongsung Chemical), 50 parts by weight of an ether polyol (PTMEG 2000, produced by Korea PTG), 7.0 parts by weight of ethylene glycol, And 120 parts by weight of a solvent of dimethylformamide (DMF) were initially charged into the reaction vessel and stirred at a temperature of 50 ° C for 1 hour. Secondarily, 4.4'-diphenylmethane diisocyanate (MDI) 3 times.

Next, the reaction was carried out so that the NCO / OH ratio of the polyol and the diisocyanate became 1.0 for 6 hours while maintaining the temperature at 80 ° C so as not to be overheated by the temperature rise due to the reaction heat.

Then, 1 part by weight of methanol and 100 parts by weight of dimethylformamide (DMF) were added as a blocking agent at a temperature of the reaction product of 75 DEG C or less, and the NCO group was masked after completion of the reaction.

Next, in the course of the reaction, 0.3 part by weight of a yellowing inhibitor and 0.3 parts by weight of an antioxidant were added, respectively, to prepare a polyurethane resin for forming a urethane porous layer of a general type in which a terminal NCO group was blocked.

Preparation Example 2: Polyurethane resin for forming PU pore layer

An ester polyol having an average molecular weight of 2,000 (K-340 (EG / 1.4BD / AA), a homogeneous chemical), an ether polyol having an average molecular weight of 2,000 (PTMEG 2000, manufactured by PTG Korea), a carbonate polyol having an average molecular weight of 2,000 7 parts by weight of ethylene glycol and 120 parts by weight of dimethylformamide were initially charged into 100 parts by weight of a polyol having a weight ratio of 100: 120: 110 (product of Asahi Kasei, Japan) in a reaction vessel, After stirring for 1 hour, 4,4'-diphenylmethane diisocyanate (MDI) was added to the reaction mixture in three portions in order to prevent rapid reaction.

The reaction was carried out at a temperature of 70 ° C. so that the NCO / OH ratio of the polyol and the diisocyanate was 1.0 for 6 hours while maintaining the temperature within the range of 80 ° C. so as not to be overheated due to the temperature rise due to the reaction heat. 0.01 part by weight of methanol and 200 parts by weight of dimethylformamide were added to the parts by weight, and the NCO groups were masked to confirm that no NCO groups were present, and the reaction was terminated.

In the reaction, 0.3 parts by weight of each of the yellowing inhibitor and the antioxidant and 0.2 parts by weight of the cell controlling agent were added to prepare a polyurethane resin having a blocked NCO group.

Preparation Example 3: Polyurethane resin for forming PU urethane porous layer

A polyurethane resin composition was prepared in the same manner as in Preparation Example 2 except that an ester polyol having an average molecular weight of 2,000 (K-340 (EG / 1.4BD / AA), homogeneous chemical) and an ether polyol having an average molecular weight of 2,000 2000, manufactured by PTG Korea), and a carbonate polyol having an average molecular weight of 2,000 (T-6002, manufactured by Asahi Kasei, Japan) at a weight ratio of 100: 130: 170.

Comparative Preparation Example 3: Polyurethane resin for forming PU skin layer

100 parts by weight of a carbonate polyol having a weight average molecular weight of 2,000 (T-6002, manufactured by Asahi Kasei, Japan), 3 parts by weight of 1,4-butanediol and 110 parts by weight of a solvent of dimethylformamide (DMF) The mixture was stirred for 1 hour while maintaining the temperature of the reaction mixture, and isophorone diisocyanate (IPDI) was added in two or three divided portions so that no rapid reaction occurred. The reaction was carried out so that the NCO / OH ratio of the polyol and the diisocyanate was 1.0 for 6 hours while maintaining the temperature at 80 ° C so as not to overheat due to the temperature rise due to the reaction heat. 1 part by weight of methanol was added as a blocking agent at a temperature of 75 ° C or lower and 100 parts by weight of dimethylformamide (DMF), 60 parts by weight of methyl ethyl ketone (MEK) and 60 parts by weight of isopropyl alcohol (IPA) After masking the NCO group, it was confirmed that there was no -NCO group and the reaction was terminated.

Next, in the course of the reaction, a yellowing agent and 0.3 part by weight of an antioxidant were added, respectively, to prepare a polyurethane for forming a carbonate type skin layer.

Preparation Example 4: Polyurethane resin for forming a PU skin layer

8 parts by weight of a carbonate polyol having a weight average molecular weight of 2,000 (T-6002, manufactured by Asahi Kasei), an ester polyol having a weight average molecular weight of 2,000 (K-340 (EG / 1.4BD / AA) And 110 parts by weight of a solvent of formaldehyde (DMF) were initially charged into the reaction vessel, stirred at a temperature of 50 캜 for 1 hour, and then dicyclohexylmethane-4,4-diisocyanate (H ₁₂ MDI) It was divided into 2 ~ 3 times so as not to cause a rapid reaction. The polyol and diisocyanate were reacted for 2 hours. 6 parts by weight of isophoronediamine (IPDA) The viscosity was increased by keeping the temperature at 80 캜 so as not to overheat due to the temperature rise due to the reaction heat. 1 part by weight of methanol was added as a blocking agent at a temperature of the reaction product of 75 ° C or lower and 100 parts by weight of dimethylformamide (DMF), 60 parts by weight of methyl ethyl ketone (MEK), 60 parts by weight of isopropyl alcohol (IPA) And the NCO group was masked. Then, it was confirmed that there was no -NCO group, and the reaction was terminated.

15 parts by weight of dimethylformamide. 30 parts by weight of methyl ethyl ketone and 15 parts by weight of a color developing toner were mixed and mixed for about 30 minutes by a high-speed stirrer to prepare a polyurethane skin coating solution.

Preparation Example 5: Preparation of coating liquid for PU surface treatment

100 parts by weight of a carbonate polyol having a weight average molecular weight of 2,000 (T-6002, manufactured by Asahi Kasei), 8 parts by weight of a fluorinated polyol having a weight average molecular weight of 580 (FC-502 manufactured by 3M Co.) 100 parts by weight of a solvent of dimethylformamide (DMF) was added to the polyol mixture as a main raw material in an amount of 5 parts by weight per 100 parts by weight of a polyvinyl alcohol (polyvinyl alcohol), 3,000 (EG / 1.4BD / AA) And the mixture was stirred for 1 hour. Secondarily, isophorone diisocyanate (IPDI) was added in two or three divided portions so as not to cause a rapid reaction. The polyol and diisocyanate were reacted for 2 hours. 5 parts by weight of cyclohexyldiamine in tertiary order The viscosity was increased by keeping the temperature at 80 캜 so as not to overheat due to the temperature rise due to the reaction heat. 1 part by weight of methanol was added as a blocking agent at a temperature of the reaction product of 75 ° C or lower and 100 parts by weight of dimethylformamide (DMF), 60 parts by weight of methyl ethyl ketone (MEK), 60 parts by weight of isopropyl alcohol (IPA) And the NCO group was masked. Then, it was confirmed that there was no -NCO group, and the reaction was terminated. Next, 0.3 parts by weight of an antifogging agent and 0.3 parts by weight of an antioxidant were added to the polyurethane for surface treatment in the course of the reaction.

Next, a solvent of dimethylformamide (DMF) / methyl ethyl ketone (MEK) / isopropyl alcohol (IPA) was added to 100 parts by weight of the polyurethane resin at a weight ratio of 50: 20: 30 and the mixture was stirred at room temperature for 2 hours , And a solid content of 15 wt%.

Subsequently, 6 parts by weight of a hydroxy-modified polyacrylate (BYK-SILCLEAN 3700, manufactured by BYK Korea) as a reactive additive was added to the coating solution, and the mixture was stirred for about 1 hour to 100 parts by weight of the surface- , 0.5 part by weight of an antioxidant (Irganox 1135, manufactured by BASF), and 0.15 part by weight of a yellowing inhibitor (ZIKASORB BS, manufactured by Zico Co.) were added and stirred.

Next, 0.5 parts by weight of silica (Deggusa TS-100) and 1.0 part by weight of urethane beads (C-800T, manufactured by Dojung Chemis Co., Ltd.) were added in turn to the surface treatment coating solution and mixed by stirring.

Next, 15 parts by weight of melamine resin particles (CYMEL325, product of Allnex) was added to the above surface treatment coating liquid and stirred at a low speed for about 20 minutes. Then, 20 parts by weight of p-toluenesulfonic acid as a reaction accelerator was added and mixed to prepare a PU surface treatment coating solution .

Preparation Example 6: Preparation of PU Adhesive

10 parts by weight of dimethylformamide was added to 100 parts by weight of a urethane adhesive (non-sulfur modified reaction product of a carbonate polyol / 1,4-butylene glycol / hexamethylene diisocyanate (HDI), 70% solids, 70,000 to 90,000 cps / 25) And 30 parts by weight of methyl ethyl ketone were mixed, and then 13 parts by weight of a cross-linking agent was added to prepare a two-part polyurethane adhesive.

Example 1: Production of artificial leather

The polyurethane resin for forming the PU porous layer, dimethylformamide, a urethane pore-controlling agent (polyether-modified polysiloxane solution, BYK-L 9525, manufactured by Univ.) Prepared in Preparative Example 2, (DPP), a surfactant (DISPERBYK-130, BYK Korea), and a toner (SBW-7388-Black, manufactured by Sunshin Chemical Co., Ltd.) were coated with a coating liquid for forming a PU porous layer in a weight ratio of 100: 40: 1: 0.5: A wet silver layer coated surface on which a microporous layer was formed was formed by a coagulation and washing process in an aqueous amide solution and dried through a thermal tenter to prepare a first sheet in which a fiber substrate layer-urethane porous layer was laminated.

Then, the polyurethane resin for forming the PU skin layer prepared in Preparation Example 4 was skin coated on the release paper to form a PU skin layer having a thickness of 0.09 mm (based on the thickness after drying), followed by drying at 100 ° C for 5 minutes.

Next, a two-component polyurethane adhesive prepared in Preparation Example 6 was coated on the dried skin layer to form an adhesive layer having a thickness of 0.13 mm (based on the thickness after drying), followed by heating at 90 DEG C for 1 minute to harden the PU adhesive layer To prepare a second sheet.

Then, the first sheet laminated with the fiber substrate layer-PU pore layer prepared above was laminated on the PU adhesive layer of the second sheet and aged for 48 hours while maintaining the temperature at 80 DEG C, and the artificial leather laminated on the release paper was peeled off , PU porous layer (average thickness: 0.25 mm), PU adhesive layer (average thickness: 0.13 mm), and PU skin layer (average thickness: 0.09 mm).

Fig. 1 shows an SEM measurement photograph of the cut surface of the manufactured artificial leather.

Example 2: Production of artificial leather

(Average thickness 0.98 mm) -PU porous layer (average thickness 0.23 mm) was obtained in the same manner as in Example 1, except that the polyurethane resin for forming the PU porous layer prepared in Preparation Example 3 was used. ) -PU adhesive layer (average thickness 0.13 mm) -PU skin layer (average thickness 0.09 mm).

Example 3: Production of artificial leather

The PU surface treatment coating liquid prepared in Preparation Example 5 was coated on the upper surface of the PU skin layer of the artificial leather of Example 1 at 20 g / m ² using a gravure coater and dried at 100 ° C for 2 minutes, PU skin layer (average thickness 0.09 mm) -PU surface treatment coating layer (average thickness 0.009 mm) -PU air layer (average thickness 0.23 mm) -PU adhesive layer (average thickness 0.13 mm) In artificial leather.

Comparative Example 1: Production of artificial leather

After preparing the fabric prepared in Comparative Preparation Example 1, the polyurethane resin for forming the PU skin layer prepared in Comparative Preparation Example 3 was skin-coated on the release paper to obtain a PU skin layer having a thickness of 0.09 mm And then dried at 100 DEG C for 5 minutes.

Next, a PU adhesive layer having a thickness of 0.12 mm (based on the thickness after drying) was formed on the top of the dried PU skin layer by coating with the PU adhesive prepared in Preparation Example 6, and then cured by heating at 90 ° C for 1 minute.

Then, the fabric prepared in Comparative Preparation Example 1 was laminated on the PU adhesive layer and aged for 48 hours while maintaining the temperature at 80 ° C. Thereafter, the artificial leather laminated on the release paper was peeled off to form a skin layer on the single- To thereby produce artificial leather. FIG. 2 shows an SEM photograph of a section of the manufactured artificial leather.

[Experimental Example]

Experimental Example 1: Measurement of physical properties of urethane porous layer

The polyurethane resin compositions prepared in Comparative Preparation Example 2, Preparation Example 2 and Preparation Example 3 were each prepared in the form of a sheet having an average thickness of 0.25 mm through wet processing, and then the properties of the sheet were measured by the following method. The results are shown in Table 3 below.

(1) Tensile properties: The tensile properties of the sheet were measured based on KS M 6782, ASTM D-412, and JIS K7311.

(2) Heat aging resistance: The sheet was held in a hot-air circulating oven maintained at a temperature of 100 캜 for 168 hours, and then the tensile properties were measured as described above.

(3) Hydrolysis resistance: According to DIN EN ISO 2440, the sheet was held for 168 hours in saturated water vapor at 72 ° C and 2% RH, taken out and allowed to stand at room temperature for 1 hour, Respectively.

(4) Peeling strength: A hot-melt cloth tape having a width of 25 mm was thermally fused to both surfaces of the sheet at 130 캜 for 5 seconds, and the interlaminar peeling strength of the sheet was measured based on KS M 0533.

In the following Table 3, W denotes a width, and L denotes a length.

[Table 3]

As a result of physical properties of the urethane porous sheet shown in Table 3, when the degree of change in physical properties after the hydrolysis resistance test and the heat aging resistance test was compared, the preparation examples 2 and 3 of the present invention had excellent characteristics .

Experimental Example 2: Measurement of physical properties of artificial leather products

The physical properties of the artificial leather prepared in Examples 1 to 3 and Comparative Example 1 were measured by the following methods, and the results are shown in Table 4 below.

(1) Light fastness

A test device specified in ISO 105 is used to measure the difference in fade caused by the naked eye after the black panel is irradiated with 126 MJ / m ² at a temperature of 90 ° C and a humidity resistance of 50% RH in accordance with ISO 105-A02 (Gray Scale).

(2) Heat aging resistance

The sheet was held in a hot-air circulating oven maintained at a temperature of 140 캜 for 96 hours, and the difference in discoloration due to the naked eye was judged to be a gray scale specified in ISO 105-A02 to obtain a grade.

(3) Friction coloring property

The test piece was fixed on a test stand of a friction tester (type II friction tester for dyeing fastness of JIS L 0823), and the friction surface of the test piece was covered with a friction surface. The surface of the specimen was reciprocated 100 times at a reciprocating speed of 30 rpm at a reciprocating speed of 100 rpm under a load of 4.9 N (500 gf), and then the degree of contamination of the white cotton cloth was measured with a grayscale for contaminant (JIS L0805, Scale). Further, the white cotton cloth was immersed in the artificial perspiration liquid for 10 minutes, and lightly squeezed to perform a friction test. The artificial perspiration fluid was prepared by mixing 8 g of first grade or more of JIS K 9019 (sodium phosphate 12 hydrate), 8 g of first grade or more of JIS K 8150 (sodium chloride) and 5 g of first grade or more of JIS K 8355 (glacial acetic acid) And the volume was adjusted to 1 L. (pH 4.5)

(4) Chemical resistance

The surface of the skin was wiped and wiped 10 times with a gauze moistened with a test solution (a weak alkaline glass cleaner, a mixture of 95% distilled water and a 5% neutral detergent, a mixture of 50% isopropyl alcohol and 50% distilled water, unleaded gasoline) And the difference in fade caused by the naked eye was judged to be gray scale (gray scale) defined in ISO 105-A02.

(5) emotion

The softness of the sense of volume and touch was evaluated by the test method based on EN ISO 17235.

[Table 4]

As can be seen from the above Table 4, the artificial leather of Examples 1, 2 and 3 of the present invention exhibited excellent properties such as light resistance, chemical resistance, heat aging resistance and friction coloring property as compared with Comparative Example 1, And the sensibility of the leather is excellent, showing a tendency similar to the texture of natural leather.

Production Example 1 and Comparative Production Example 1

A crash pad of an automobile was covered with artificial leather manufactured in Example 1, and photographs thereof are shown in FIGS. 4A to 4C.

In addition, the crash pad of an automobile was covered using artificial leather manufactured in Comparative Example 1, and photographs thereof are shown in Figs. 5A to 5C.

Comparing FIG. 4 and FIG. 5, it can be seen that, in the case of Example 1, the formability such as corrugation is very good as compared with Comparative Example 1.

Although the preferred embodiments of the artificial leather according to the present invention have been described above, the scope of the present invention is not limited to the above-described embodiments and the following claims. Those skilled in the art will appreciate that, Various modifications and equivalent embodiments are possible.

101: long fiber high density micro-woven fabric (fiber substrate layer) 102: microporous layer
103. 202: adhesive layer 104, 203: skin layer
201: Short fiber high density nonwoven fabric (fiber substrate layer)

Claims (22)

delete delete delete delete delete delete delete delete delete delete delete delete I) the density is 0.30 ~ 0.60 g / cm ³ Preparing a first sheet by forming a urethane porous layer having micropores on a fibrous substrate layer containing a long fibrous high density microcellular nonwoven fabric;
(Ii) a polyurethane resin prepared by reacting a polyurethane prepolymer prepared by polymerizing a polyisocyanate compound and a polyol compound containing a carbonate-based polyol and an ester-based polyol with an aliphatic amine-based chain extender or an alicyclic amine- Coating the release paper on a release paper sheet to form a polyurethane skin layer;
Iii) forming a second sheet by forming a polyurethane adhesive layer on one surface of the skin layer; And
Iv) laminating the first sheet and the second sheet, and peeling the release paper from the polyurethane skin layer,
Wherein the long-fiber type high-density micro-fiber non-woven fabric has a web of a sea-island filament yarn having an average fineness of 2.0 to 5.0 denier by a spunbond method; Performing cold calendaring of the web; Laminating and stretching a web subjected to a knife-rendering process, performing a needle punching process at 100 to 800 ea / cm < ² > And a step of reducing the nonwoven fabric in an aqueous NaOH solution at a concentration of 2% to 10% for 5 minutes to 20 minutes. 14. The method of claim 13, further comprising: v) coating a surface of the skin layer on which the release paper has been peeled with a polyurethane surface treatment coating liquid to form a polyurethane surface treatment coating layer;
The method of claim 1, further comprising: delete 14. The method according to claim 13, wherein the sea-island filament yarn is produced by spinning at a spinning rate of 3,000 to 7,000 m / min at a mixing ratio of 60 to 80% by weight of a flour component and 20 to 40% by weight of a sea component,
Wherein the web of the web forming step has a basis weight of 30 to 50 g / cm < ² >. delete 14. The method of claim 13, wherein the polyol compound in the step of forming the polyurethane skin layer comprises
A carbonate-based polyol having a weight-average molecular weight of 800 to 3,500 and an ester-based polyol having a weight-average molecular weight of 1,000 to 3,000 at a weight ratio of 100: 2 to 30. 15. The polyurethane coating solution according to claim 14, wherein the polyurethane surface-treating coating liquid comprises 5 to 20 parts by weight of a degreasing agent and 70 to 150 parts by weight of a solvent, based on 100 parts by weight of the non-
The non-sulfur-modified polyurethane resin is prepared by mixing a carbonate-based polyol having a weight average molecular weight of 800 to 3500, a fluorinated polyol having a weight average molecular weight of 200 to 4,000 and an ester polyol having a weight average molecular weight of 1,000 to 3,000 at a weight ratio of 100: 5 to 30: Which is produced by polymerizing a polyol compound and a polyisocyanate compound,
The degreasing agent includes an organic or inorganic fine powder having an average particle diameter of 10 mu m or less and the solvent is selected from the group consisting of two kinds selected from dimethylformamide, dimethylsulfoxide, dimethyl acetate, N-methylpyrrolidone, methylethylketone and isopropyl alcohol The method as claimed in claim 1, 20. The crash pad cover of claim 19, wherein the polyurethane surface treatment coating liquid further comprises at least one selected from the group consisting of a reactive additive, a dispersant, an antioxidant, a defoamer, a yellowing inhibitor, a reaction promoter, ≪ / RTI > 21. The method of claim 20, wherein the solvent comprises dimethylformamide, methyl ethyl ketone, and isopropyl alcohol in a weight ratio of 50:15 to 25:25 to 35:50. delete

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