KR101469843B1 - Synthetic Leather For Covering Steering Wheel And Preparation Method Thereof - Google Patents

Abstract

The present invention relates to an artificial leather for a steering wheel cover and a method of manufacturing the same. More particularly, the present invention relates to a synthetic leather for a steering wheel cover, and more particularly to a synthetic leather for a steering wheel cover which comprises a fibrous base material layer including a long fibrous high density microfine nonwoven fabric, a urethane porous layer formed on the fibrous base layer, A skin formed on the pore layer and comprising a polyurethane resin prepared by polymerizing a polyol compound comprising an aliphatic or alicyclic polyisocyanate compound and a polycarbonate-based polyol, a fluorinated polyol, a silicone-based polyol, an ether-based polyol and an ester- Layer and a method of manufacturing the same.

Description

Technical Field [0001] The present invention relates to a synthetic leather for a steering wheel cover,

The present invention relates to an artificial leather which can be used for an automobile interior material, particularly a rim cover of a steering wheel, by improving sensibility such as high light resistance, heat aging resistance, friction coloring property, chemical resistance, And a manufacturing method thereof.

Generally, a steering wheel is provided as an apparatus for applying a steering force when steering a vehicle, such as an automobile, which is called a steering wheel.

The steering wheel transmits the rotational operation force of the driver to the steering device via a steering shaft coupled to the center thereof, thereby performing angular movement of the wheel. The steering wheel is constituted by a circular rim that the driver holds, and a rim support formed at the center of the rim and coupled to the steering shaft at the center thereof. The steering wheel may be formed of various materials. However, the steering wheel may be formed by welding a rim support to a ring formed by a metal pipe, or by a casting method using aluminum, which is a relatively rigid and light non-ferrous metal do. The rim support part of the steering wheel thus manufactured is equipped with an airbag, a horn button, an audio operation button, etc., and then a synthetic resin cover is attached to the rim part. The rim part is covered with a rim cover made of cloth, artificial leather, leather, It is covered.

In general, synthetic leather is manufactured by applying a urethane skin resin mixture containing an organic solvent such as dimethylformamide, methyl ethyl ketone and the like onto a release paper, drying it to form a film, applying an adhesive on the urethane film formed and crosslinking and curing And a method of assembling the fabric with a nonwoven fabric or a textile fiber substrate is used.

For example, Korean Patent Laid-Open Publication No. 10-2012-0133210 relates to a method for manufacturing 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 resin containing water-dispersed polycarbonate urethane on the upper 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 forming an adhesive layer by applying a solvent-free adhesive on an upper surface of the surface layer; And a fourth step of bonding a fabric, a knitted fabric or a nonwoven fabric knitted with synthetic fibers to the upper surface of the adhesive layer to form an artificial layer.

However, the conventional artificial leather has a problem that a skin coating layer is formed on a fibrous substrate such as a short-fiber non-woven fabric or a fabric having a relatively small density and wrinkles are generated when the rim cover of the steering wheel is applied, There is a limitation in showing emotion similar to the volume feeling and touch of natural leather. Also, the conventional polyurethane skin coating layer has disadvantages such as low light resistance, chemical resistance, heat resistance and friction coloring property with respect to a dose of 126 MJ, which makes it difficult to apply the rim cover to the steering wheel.

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

The present inventors have found that when controlling the composition of a polyol used in the production of a polyurethane which forms a skin layer with a long fiber-type high-density microfine nonwoven fabric as a fiber base material, the properties of high light resistance, heat aging resistance, friction coloring resistance, The present invention has been completed on the basis of this fact, and it is confirmed that the wrinkle is good when used as a cover of a steering wheel having many bends, while exhibiting sensitivity similar to that of natural leather, feel and feeling of natural leather.

Accordingly, the object of the present invention is to provide a rim cover for an automobile interior material, particularly a steering wheel, having good physical properties such as high light resistance, heat aging resistance, friction coloring property, chemical resistance and stain resistance, And a method of manufacturing the same.

To this end,

A fibrous base layer comprising a long fibrous high density microfine nonwoven fabric,

A urethane porous layer formed on the fiber substrate layer,

An aliphatic or alicyclic polyisocyanate compound and a polycarbonate-based polyol formed on the urethane porous layer; Fluorinated polyols or silicone-based polyols; Ether-based polyols; And a skin layer comprising a polyurethane resin prepared by polymerizing a polyol compound containing an ester-based polyol. The present invention also provides a synthetic leather for a steering wheel cover.

Also,

Forming a urethane porous layer on a fibrous substrate layer comprising a long fibrous high density microfine nonwoven fabric to produce a first sheet;

Forming a skin layer by coating a release paper with a polyurethane composition for forming a skin layer;

Forming an adhesive layer on the skin layer to produce a second sheet;

Peeling the release paper after laminating the first sheet and the second sheet; And

Coating the surface of the skin layer on which the release paper has been peeled with a surface treatment coating solution to form a polyurethane surface treatment coating layer

The present invention also provides a method of manufacturing a synthetic leather for a steering wheel cover.

According to the present invention, an automotive interior material, particularly a steering wheel rim cover, is excellent in high light resistance, heat aging resistance, friction coloring resistance, chemical resistance, and stain resistance, and durability is improved, thereby improving sensibility such as volume feeling and wrinkle 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.
Fig. 2 is a photograph of a steering wheel manufactured using artificial leather manufactured in Comparative Example 1. Fig.
3 is a photograph of a steering wheel manufactured using artificial leather manufactured in Example 1 of the present invention.
4 is a photograph of a steering wheel manufactured using artificial leather manufactured in Example 3 of the present invention.

Hereinafter, the present invention will be described in more detail.

In the present invention, artificial leather having physical properties suitable for a rim cover of a steering wheel is proposed by newly designing a composition of a polyol used for polymerization reaction of polyurethane forming a skin layer to improve mechanical properties of artificial leather.

Polyurethane is composed of two phases in a polymer: a hard segment (HS) and a soft segment (SS). A hard segment, which serves as a crystalline structure by physical bonding, forms a soft segment domain. As shown in FIG. 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, the skin layer of the artificial leather of the present invention is a polycarbonate-based; Fluorinated polyols or silicone-based polyols; Ether-based polyols; And a polyurethane resin prepared by reacting a polyol compound containing an ester-based polyol with an aliphatic or cycloaliphatic polyisocyanate compound.

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.

1, the artificial leather of the present invention has a structure in which a fibrous base layer 101 containing a long-fiber type high-density micro-nonwoven fabric, a urethane porous layer 102, and a skin layer 104 are sequentially laminated .

The fibrous substrate layer 101 is made of a long fiber-type high-density micro-fiber non-woven fabric as a fibrous base material in order to ensure excellent wrinkling when applied to a rim cover of a steering wheel which exhibits similar sensitivity to natural leather but has many bends.

The long fibrous high density microfine nonwoven fabric of the fiber substrate layer 101 may be a general filament yarn of polyethylene terephthalate (PET) or nylon (PA), polyamide; 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 containing at least one species selected from the group consisting of a filament yarn and a split filament yarn.

The long-fiber type high-density micro-fabric non-woven fabric uses a long-fibrous nonwoven fabric produced by a combination of two or more processes selected from the group consisting of spunbond, needle punching and spun lace. In the present invention, the spun bond / needle punching / spun lace long filament type nonwoven fabric is arranged in a continuous form of fibers unlike the single fiber type nonwoven fabric. In particular, since the nonwoven fabric itself has an apparent density of 0.35 g / cm ³ , preferably an apparent density of 0.35 g / cm ³ To 0.8 g / cm < ³ >, more preferably 0.4 to 0.5 g / cm < ³ >, which is very high in density compared to the conventional needle punching nonwoven fabric. In particular, since the long-fiber type high-density microcellular nonwoven fabric of the present invention can be densified without a separate shrinking process, there is an advantage that it can be impregnated with a water-dispersible polyurethane having no impregnation step or a low concentration. The above-mentioned long-fiber type high-density micro-fabric nonwoven fabric having such properties is superior in strength and density and high in quality to conventional short-fiber type high-density nonwoven fabric, and thus is suitable as a fiber base material of artificial leather.

The long-fiber type high-density micro-yarn nonwoven fabric of the fiber base layer has a tensile strength of 40 to 60 kgf / inch in MD (machine direction) and 50 to 60 kgf / inch in CD (cross direction) when measured according to the ASTM 5035 method May have a tensile strength of MD 42 to 50 kgf / inch and a CD of 52 to 58 kgf / inch. The long-fiber type high-density micro-fiber non-woven fabric has an elongation (elongation) of 60 to 80% and a CD of 100 to 140% as measured according to the ASTM 5035 method, preferably an elongation of 65 to 75% %. ≪ / RTI > Also, the tear strength measured according to the ASTM 5035 method is MD 5.5 to 6.0 kgf and CD 5.2 to 5.8 kgf, preferably tearing strength MD 5.5 to 5.9 kgf and CD 5.3 to 5.7 kgf.

The urethane porous layer 102 is formed with uniform micropores and includes a polyurethane resin. Such a pore layer has a uniform pore formed in a uniform polyurethane resin, which can further increase the volume feeling in artificial leather.

The urethane porous layer has a modulus of 60 to 80 kgf / cm ² , preferably 60 to 75 kgf / cm ² when measured according to KS M 6782. Also, when measured according to ASTM D-412, the tensile strength was 370 to 420 kgf / cm ² in the width direction, Preferably 380 to 400 kgf / cm ² , and a longitudinal direction of 410 to 450 kgf / cm ² , And preferably 420 to 440 kgf / cm ² . The urethane porous layer has an elongation of 430 to 480%, preferably 440 to 480%, and a lengthwise direction of 400 to 450%, preferably 410 to 440%, as measured according to JIS K7311.

The skin layer 104 is formed on the urethane porous layer, and includes an aliphatic or alicyclic polyisocyanate compound and a polycarbonate-based polyol; Fluorinated polyols or silicone-based polyols; Ether-based polyols; And an ester-based polyol; and a polyurethane resin prepared by polymerizing a polyol compound containing an ester-based polyol.

Preferably, the polyurethane resin of the skin layer 104 comprises a polyisocyanate compound and a polycarbonate-based polyol having a number average molecular weight of 800 to 3500; A fluorinated polyol having a number average molecular weight of 200 to 4,000 or a silicon-based polyol having a number average molecular weight of 200 to 4,000; An ether-based polyol having a number average molecular weight of 1,000 to 3,000; And an ester-based polyol having a number average molecular weight of 1,000 to 3,000, and reacting the resultant polyurethane prepolymer with a chain extender.

The polycarbonate-based polyol may be at least one selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butane diol, 1,3-butane diol, Dihydroxyl compounds of 4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol, 1,8-octanediol, or mixtures thereof and diaryl carbonates, dialkyl Carbonate, or condensation reaction of phosgene is used. The polyurethane produced using such a polycarbonate-based polyol is excellent in hydrolysis resistance, weather resistance, and heat resistance.

The use of perfluoropolyether or polytetrafluoroethylene as the fluorinated polyol is useful for improving stain resistance and friction coloring property.

The silicone-based polyol may be any silicone compound having a hydroxyl group on one terminal. For example, α-butyl- ω- {3- {2,2-bis (hydroxymethyl) butoxy} propyl} polydimethylsiloxane, α- {3- (2'-hydroxyethoxy) propyl} (Trimethylsilyloxy) -polydimethylsiloxane,? - {3- (2'-hydroxyethoxy) propyl} -ω-trimethylsilyloxypolyethylenephenylsiloxane, α- {3- (2 ', 3'- ? - {3- (2 ', 3'-dihydroxypropyloxy) propyl} -ω-trimethylsilyoxypolyethylenediphenylsiloxane, α- { 3- (2'-ethyl-2'-hydroxymethyl-3-hydroxypropyl} -ω-trimethylsilyloxypolydimethylsiloxane, α- {3- (2'- Propyl} -? - trimethylsilyloxypolydimethylsilane,? - {3- (2'-hydroxy-3'-isopropylamino) propyl} Siloxane and? - {3- (2'-hydroxy-3'-isopropylamino) propyl} -ω-trimethylsilyoxypolyethyl - it can be used diphenylsiloxane. Such a silicone-based polyol is preferable for improving the stain resistance, the friction coloring property, the chemical resistance, and the like of the polyurethane to be produced.

The types of silicone compounds having a hydroxyl group attached to at least one molecular end are Silaplane (Chisso Corp.) FM-DA11, FM-0411, FM-0413, FM-0415, FM- , FM-D411, FM-D421, FM-D425 (manufactured by Chisso Corp.) and Shin-Etsu Silicone X-22-170A, X-22-170B, X- (Commercially available from Shin-Etsu Chemical Co., Ltd.) such as X-22-176B, X-22-176D, X-22-176DX, X-22-178A, X-22-178B .

The ether-based polyol is a diol having two hydroxyl groups such as polytetramethyleneglycol (PTMG) and polypropyleneglycol (PPG), and polyteramethylene glycol is particularly useful.

Examples of the ester-based polyol include ethylene glycol (EG), 1,4-butanediol (1,4-BD), 1,6-hexanediol (1,6-HD), neopentyl glycol Aliphatic polyester polyols obtained by esterification reaction of a low molecular weight polyol such as ethylene glycol (DEG) and a polycarboxylic acid such as adipic acid (AA), or an aliphatic polyester polyol obtained by esterification of an aliphatic polyester polyol such as epsilon -caprolactone, A polyester polyol obtained by ring-opening polymerization reaction of an ester compound, or copolymerized polyester polyol thereof can be used.

Polycarbonate-based polyols; Fluorinated polyols or silicone-based polyols; Ether-based polyols; And ester polyol are used in a weight ratio of 60 to 95: 0.1 to 20: 1 to 20: 1 to 10. Such use ratio is intended to ensure high light resistance, chemical resistance, heat aging resistance, friction coloring resistance and stain resistance, and is used within the above weight ratio range.

At this time, an adhesive layer 103 may be further included between the urethane porous layer 102 and the skin layer 104.

In the artificial leather of the present invention, the fibrous base layer has an average thickness of 0.7 to 1.3 mm, the urethane porous layer having the micropores has an average thickness of 0.1 to 0.4 mm, and the skin layer has an average thickness of 0.05 to 0.3 mm.

In addition, the artificial leather of the present invention may be formed with a polyurethane surface treatment coating layer to control glossiness on the skin layer 104 and to improve stain resistance.

At this time, the polyurethane surface-treated coating layer can utilize the non-sulfuric modified resin synthesized with a skeleton similar to the polyurethane resin for forming the skin layer as a main raw material. That is, the surface-treated coating layer may be formed of an aliphatic or alicyclic polyisocyanate compound and a polycarbonate-based polyol; Fluorinated polyols or silicone-based polyols; Ether-based polyols; And an ester-based polyol; and a polyurethane resin prepared by polymerizing a polyol compound containing an ester-based polyol.

The artificial leather of the present invention has excellent properties such as light resistance, heat aging resistance, chemical resistance, friction coloring property, stain resistance and sensibility and is useful for automobile interior materials, especially rim cover of steering wheel.

In the artificial leather of the present invention,

Forming a urethane porous layer on a fibrous substrate layer comprising a long fibrous high density microfine nonwoven fabric to produce a first sheet;

Forming a skin layer by coating a release paper with a polyurethane composition for forming a skin layer;

Forming an adhesive layer on the skin layer to produce a second sheet;

Peeling the release paper after laminating the first sheet and the second sheet; And

Coating the surface of the skin layer on which the release paper has been peeled with a surface treatment coating solution to form a polyurethane surface treatment coating layer

Lt; / RTI >

Each step will be described in detail below.

First, a urethane porous layer is formed on a fibrous substrate layer including a long fibrous high density microfine nonwoven fabric to prepare a first sheet.

The urethane porous layer may contain a composition for forming a urethane porous layer containing a polyurethane resin, a solvent, a urethane pore regulator and a toner in a weight ratio of 100: 30 to 60: 0.5 to 2: 0.1 to 1: 5 to 15, And is formed by coating on the surface.

The solvent of the composition for forming a urethane porous layer may include at least one selected from the group consisting of dimethylformamide, dimethylacetamide, ethyl acetate, tetrahydrofuran, ethylene glycol monoethyl ether and ethylene glycol monoether ether acetate. The solvent is used in an amount of 30 to 60 parts by weight, preferably 35 to 45 parts by weight, based on 100 parts by weight of the polyurethane resin. If the amount of the solvent is less than the above range, the viscosity of the solution is high and uniform pore formation is difficult. On the other hand, if the amount of the solvent is more than the above range, the viscosity of the solution is low and it is difficult to precisely control the thickness of the pore layer.

The urethane pore regulator is used to form uniform pores in the urethane porous layer, and an anionic urethane pore regulator or a non-ionic urethane pore regulator can be used. At this time, the urethane pore regulator is preferably used in an amount of 0.5 to 2 parts by weight, preferably 0.5 to 1.5 parts by weight based on 100 parts by weight of the polyurethane resin. If the amount of the urethane pore regulating agent is less than the above-mentioned minimum content, sufficient pores may not be formed in the urethane porous layer, and if it exceeds the above-mentioned maximum content, the processing becomes uneven.

The toner is a pigment that imparts hue to the urethane porous layer. The amount of the toner to be used is 5 to 15 parts by weight, preferably 7 to 12 parts by weight, based on 100 parts by weight of the polyurethane resin. If the upper limit is exceeded, the physical properties of the product may deteriorate.

The polyurethane resin of the composition for forming a urethane porous layer is obtained by reacting a polyurethane prepolymer obtained by reacting a polyisocyanate compound with a polyol compound with a chain extender.

At this time, the polyol may include three kinds of polyols such as a polyester-based polyol (weight average molecular weight: 1,000 to 6,000), a polyether-based polyol (weight average molecular weight: 1,000 to 6,000), and a polycarbonate-based polyol . The polyester polyol, the polyether polyol and the polycarbonate polyol are used at a weight ratio of 10 to 60:20 to 80: 5 to 60, preferably 20 to 40:30 to 65:20 to 50, Water-decomposability and chemical resistance.

The polyisocyanate which reacts with the polyol is selected from the group consisting of 2,4- or 2,6-toluene diisocyanate (TDI), xylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI) , Aromatic diisocyanate having a benzene ring such as 5-naphthalene diisocyanate, hexamethylene diisocyanate (HDI), propylene diisocyanate, lysine diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate Alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate, isophorone diisocyanate (IPDI) and 4,4'-dicyclohexylmethane diisocyanate (H ₁₂ MDI); And a combination thereof.

The chain extender is not particularly limited as long as it can use those known in the art. (EG), 1,4-butanediol (1,4-BD), 1,6-hexanediol, 1,4-butanediol and 1,4-butanediol are preferably used as the low molecular weight diol or diamine having an even number of repeating units advantageous for increasing the crystallinity. One selected from hexanediol (1,6-HD), neopentyl glycol (NPG), diethylene glycol (DEG) and isophoronediamine (IPDA) is used. The amount of the chain extender used is 1 to 15 parts by weight, preferably 2 to 10 parts by weight based on 100 parts by weight of the polyol. If the amount of the chain extender is less than the above range, there is a problem that the heat resistance and the adhesive strength are poor. On the contrary, when the amount exceeds the above range, the unreacted chain extender is excessively generated.

The preparation of the polyurethane prepolymer is not particularly limited in the present invention, and any of the methods commonly used for the reaction of a polyol and a polyisocyanate can be used, and can be found in various related documents. These polymerization methods include emulsion polymerization, suspension polymerization, photopolymerization, bulk polymerization, solution polymerization, and the like, and the use of dispersants, stabilizers, surfactants, chain transfer agents, It is possible.

Next, a polyurethane composition for forming a skin layer is coated on a release paper and dried to form a skin layer.

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 polyurethane composition for forming the skin layer includes a polyurethane resin for forming a skin layer, a solvent and a toner.

At this time, the polyurethane resin, the solvent and the toner for forming the skin layer are as described above.

Next, an adhesive layer is formed on the skin layer to produce a second sheet.

The adhesive layer can be formed by applying an adhesive on the skin layer. The adhesive may be a general adhesive used in the art and is not particularly limited. It is preferable to use a two-component type urethane adhesive to which a urethane-based adhesive agent, more preferably a phosphorus-based or nitrogen-based flame retardant agent, is added, from the viewpoint that adhesion and flame retardancy of the artificial leather can be imparted. The second sheet thus manufactured has a structure in which a skin layer and an adhesive layer are sequentially laminated on a release paper.

Then, the first sheet and the second sheet are laminated together and then the release paper is peeled off.

A first sheet on which a porous layer is laminated on a fibrous base layer containing a long fibrous high density microcellular nonwoven fabric and a second sheet laminated on the second sheet with an adhesive layer interposed therebetween,

Finally, the surface treatment coating liquid is coated on the surface of the skin layer on which the releasing paper has been peeled off to form a polyurethane surface treatment coating layer for adjusting the gloss.

In the practice of the present invention, the coating may be carried out by a conventional coating method such as an air knife method, a gravure method, a reverse roll method, a reverse gravure method, a spray method, a slot die coating method, a blade method, And there is no particular limitation.

Wherein the surface treatment coating solution comprises a non-substituted polyurethane resin, a polish remover, and a solvent. Antioxidants, defoamers, UV absorbers, and the like, if necessary.

Conventional dispersants, antioxidants, antifoaming agents, UV absorbers and the like in the present invention can be used.

The gloss removing agent may be an organic fine powder or an inorganic fine powder. 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, polyurethane resin particles, polyester resin particles, nylon resin particles, , And polyethylene resin particles. The inorganic fine powder may be at least one selected from the group consisting of talc, mica, calcium carbonate, barium sulfate, magnesium carbonate, mud, alumina, silica, carbon fiber, glass fiber, metal fiber, carbon black, titanium oxide, molybdenum, magnesium hydroxide, bentonite, Can be used. Such a powder can be used without limitation as long as the average particle diameter of the particles is 10 탆 or less.

At this time, the amount of the degreaser may be in the range of 1 to 10 parts by weight based on 100 parts by weight of the surface-treatment coating liquid. 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.

Examples of the solvent include dimethylformamide, dimethylsulfoxide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, methylethylketone, isopropyl alcohol and the like. The content of the polyurethane resin for surface treatment in the surface-treated coating solution using a solvent is preferably 3 to 60% by weight. When the content of the resin is less than the above minimum value, the film formability and the friction coloring property are inferior. When the resin content is more than the maximum value, formation of the film after drying is incomplete and problems such as residual organic solvent in the film may occur. not.

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.

compare Preparation Example  One: For textile base layer  Production of nonwoven fabric

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.

Before shrinkage After shrinking After weight loss Weight (g / m ² ) 230 310 248 Thickness (mm) 1.06 1.03 0.98 Density (g / cm ³⁾ 0.21 0.30 0.25 Cotton shrinkage (%) 28

As shown in Table 1, the density of the nonwoven fabric increases by 41.9% at 0.21 g / cm ³ to 0.30 g / cm ³ after shrinkage treatment. Also, the surface contraction ratio due to shrinkage in the longitudinal and transverse directions is shown to be shrunk by 28%. It is difficult to develop a density of 0.3 g / cm < ³ > or more even if the density is increased by shrinking. Also, after the weight loss, the fiber is partially damaged and the density is decreased by 0.25 g / cm ³ .

Preparation Example  One: Long fiber type  High density Microfiber The fibrous substrate layer  Produce

Fineness 3 deniers, even type (PET / Co-PET, 70/30 , 25 islands) the long-fiber-type high-density micro-fiber non-woven fabric by the filament yarns in a spunbond / spunlaced composite continuous process width 1950mm, the average weight of 450g / m ^3, and The average thickness was 1.13 mm, and a long fiber-spun microfiber nonwoven fabric was produced by a reduction process in a 3% NaOH aqueous solution for 30 minutes. The results are shown in Table 2.

division
Before weight loss After weight loss Weight (g / m ² )
450 410 Thickness (mm) 1.13 0.98 Density (g / m ³ )
0.40 0.42 The tensile strength
(kgf / inch)
MD 45.0 44.5 CD 55.5 55.0 Shindo
(%)
MD 87 70 CD 96 120 Tear strength (kgf)

MD 5.7 5.75 CD 5.5 5.40 MD: machine direction (portrait orientation)
CD: cross direction

As shown in Table 2, the density of the long-fiber nonwoven fabric had a very high apparent density compared to the density of the ordinary nickel-punched nonwoven fabric (generally about 0.21) and exhibited high density characteristics without a separate shrinking process. In the case of long-fiber type nonwoven fabric, since the fiber tends to return to its original shape, even after heat or physical force is applied in a post-process such as weight loss, the density after the weight loss tends to be similar to that before the weight loss so that a stable high density nonwoven fabric can be provided .

compare Preparation Example  2: urethane Pore layer  Polyurethane resin for forming

110 parts by weight of a polyester polyol having a weight average molecular weight of 2,000 (K-340 (EG / 1.4 BD / AA) manufactured by Dongsung Chemical), 50 parts by weight of a polyether polyol (PTMEG 2000, produced by Korea PTG), 15 parts by weight of ethylene glycol, And 100 parts by weight of a solvent of dimethylformamide (DMF) were initially charged into the reaction vessel, stirred at the temperature of 50 ° C for 1 hour, and then 80 parts by weight of 4.4'-diphenylmethane diisocyanate (MDI) 23 times so as not to occur. The reaction is carried out so that the NCO / OH ratio of the polyol and the diisocyanate is 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. 1 part by weight of methanol and 190 parts by weight of dimethylformamide (DMF) were added as a blocking agent at a reaction temperature of 75 ° C or lower, and NCO groups were 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 for forming a urethane porous layer of a general type in which a terminal NCO group was blocked.

Preparation Example  2: urethane Polyurethane resin for forming pore layer

(EG / 1.4BD / AA), a polyether polyol having a weight average molecular weight of 2,000 (PTMEG 2000, manufactured by Korea PTG), a polycarbonate having a weight average molecular weight of 2,000 16 parts by weight of ethylene glycol and 270 parts by weight of dimethylformamide were initially charged into 100 parts by weight of a polyol containing polyol (T-6002, product of Asahi Kasei, Japan) at a weight ratio of 30:50:20, After stirring for 1 hour at a temperature of 50 ° C, 90 parts by weight of 4,4'-diphenylmethane diisocyanate (MDI) was added in three divided portions in order to prevent rapid reaction. 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 within the range of 80 ° C so as not to be overheated due to the temperature rise due to the reaction heat. When the temperature of the reaction was 70 ° C, , 0.01 part by weight of methanol and 270 parts by weight of dimethylformamide were added thereto, and the NCO group was masked. Thereafter, it was confirmed that no NCO group was present, and the reaction was terminated. In the above 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: Urethane For forming pore layer Polyurethane resin

A polyurethane resin composition was prepared in the same manner as in Preparation Example 2 except that the polyol was changed to a polyester polyol having a weight average molecular weight of 2,000 (K-340 (EG / 1.4BD / AA) A polyol was used in an amount of 20: 30: 50 by weight of an ether polyol (PTMEG 2000, manufactured by PTG Korea) and a polycarbonate polyol having a weight average molecular weight of 2,000 (T-6002, manufactured by Asahi Kasei, Japan).

Experimental Example  1: urethane Pore layer  Property measurement

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 resistance Aging

The sheet was subjected to a heat resistance test at 100 DEG C for 168 hours based on MS 300-31, and the tensile properties were measured as described above.

3. I hydrolyse

The sheet was immersed in distilled water at 85 캜 according to MS 300-31, heated for 96 hours, taken out and allowed to stand at room temperature for 1 hour, and the tensile properties were measured as described above.

4. Peel strength

A hot melt cloth tape having a width of 25 mm was thermally fused to both surfaces of the sheet at 130 DEG C for 5 seconds to measure the interlaminar peeling strength of the sheet based on KS M 0533 and JIS K 6854.

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

Comparative Preparation Example 2 Preparation Example 2 Preparation Example 3 Tensile Properties Modulus
(Kg _f / cm ² ) 55 70 65 The tensile strength
(Kgf / cm ² ) W  350  380 390 L  400 420 430 Elongation (%) W  500 450 470 L  450 420 440 Heat aging resistance
after the test Modulus
(Kgf / cm ² ) 48 67 64 The tensile strength
(Kgf / cm ² ) W 270 360 370 L 310 390 400 Elongation (%) W 460 420 450 L 410 410 420 I can
Degradability
after the test Modulus
(Kgf / cm ² ) 45 68 64 The tensile strength
(Kgf / cm ² ) W 240 350 360 L 280 380 400 Elongation (%) W 440 430 450 L 400 410 420 Peel strength (Kgf / cm) 2.6 3.0 3.3

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 .

compare Preparation Example  3: Skin layer  Polyurethane resin for forming

100 parts by weight of a polycarbonate polyol having a number average molecular weight of 2,000 (T-6002, manufactured by Asahi Kasei, Japan), 3 parts by weight of 1,4-butanediol and 190 parts by weight of a solvent of dimethylformamide (DMF) The mixture was stirred for 1 hour while maintaining the temperature of the reaction mixture at room temperature, and 30 parts by weight of isophorone diisocyanate (IPDI) was added to the reaction mixture twice or three times in order to prevent a rapid reaction. 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, 60 parts by weight of methyl ethyl ketone (MEK) and 100 parts by weight of isopropyl alcohol (IPA) were added as a blocking agent at a temperature of the reaction product of 75 ° C or lower, and the NCO group was masked. Terminated.

Next, in the course of the reaction, 0.3 part by weight of an anti-yellowing agent and 0.3 parts by weight of an antioxidant were added, respectively, to prepare a polyurethane for forming a skin layer of a polycarbonate type having a terminal NCO group blocked.

Preparation Example  4: Skin layer  Polyurethane for forming

100 parts by weight of a polycarbonate polyol having a number average molecular weight of 2,000 (T-6002, manufactured by Asahi Kasei), 2 parts by weight of a silicone polyol having a number average molecular weight of 1,000 (FM-4411, product of CHISSO) (PTMEG 1000, manufactured by Korea PTG), number average molecular weight 2000 ester-based polyol 10 parts by weight (K-320 (1.4 BD / AA) manufactured by Dongsung Chemical), ethylene glycol 2 parts, dimethylformamide (DMF) And 40 parts by weight of dicyclohexylmethane-4,4 diisocyanate (H12MDI) were added to the reaction vessel at a temperature of 50 DEG C for 1 hour, followed by addition of 40 parts by weight of dicyclohexylmethane- The reaction was divided into two or three times to prevent the reaction. The polyol and diisocyanate were reacted for 2 hours. 10 parts by weight of isophoronediamine (IPDA) To prevent overheating due to the temperature rise due to the reaction heat, the viscosity is increased by adding 3 ~ 4 times while maintaining the temperature at 80 캜. When the temperature of the reaction mixture reached a suitable viscosity, 1 part by weight of methanol, 180 parts by weight of dimethylformamide (DMF), 40 parts by weight of methyl ethyl ketone (MEK) and 140 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, 0.3 parts by weight of a yellowing inhibitor and 0.3 parts by weight of an antioxidant were added, respectively, to prepare a polyurethane for forming a skin layer having a blocked NCO group.

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. The polyurethane adhesive solution was prepared by mixing 100 parts by weight of urethane adhesive (Polycarbonate polyol / 1,4BG / TDI / MDI reaction mixture, 70% solids, 80,000 100,000 cps / 25), 10 parts by weight of dimethylformamide and 30 parts by weight of methyl ethyl ketone Then, 13 parts by weight of a crosslinking agent was added to prepare an adhesive composition.

Preparation Example  5: Preparation of surface treatment coating solution

(T-6002, product of Asahi Kasei) having a number average molecular weight of 2,000, a fluorinated polyol having a number average molecular weight of 580 (FC-502, manufactured by 3M), isophorone diisocyanate (IPDI) and 4,4- in muhwang modified polyurethane resin 100 parts by weight of cyclohexyl methane (H ₁₂ MDI) as the main ingredient of dimethylformamide (DMF) 50 parts by weight of methyl ethyl ketone (MEK) 20 parts by weight of isopropyl alcohol (IPA) 30 parts by weight And the mixture was stirred at room temperature for 2 hours at a low speed to prepare a urethane coating liquid having a solid content of 15%. 6 parts by weight of a hydroxy-modified polyacrylate (BYK-SILCLEAN 3700, manufactured by BYK Korea) as a reactive additive was added and stirred for about 1 hour. Then, 0.2 part by weight of a defoaming agent (BYK-066N, BYK Korea) 0.5 parts by weight of an inhibitor (Irganox 1135, manufactured by BASF), and 0.15 parts by weight of a yellowing inhibitor (ZIKASORB BS, Zico) were added and stirred. Then, 0.5 part by weight of silica (Deggusa TS-100) and 1.0 part by weight of urethane beads (C-800T, produced by Doosung Chemicals) were added in turn and mixed. Then, 15 parts by weight of a melamine resin (CYMEL325, manufactured by Allnex) was added and stirred at a low speed for about 20 minutes. 20 parts by weight of p-toluene sulfonic acid as a reaction promoter was mixed to prepare a surface-treated coating solution.

Comparative Example 1: Production of artificial leather

After preparing the fabric prepared in Comparative Preparation Example 1, the composition for skin layer formation according to Comparative Preparation Example 3 was skin-coated on a release paper to form a skin layer having a thickness of 0.09 mm (based on the thickness after drying) Lt; / RTI > A two-component adhesive according to Comparative Preparation Example 3 was coated on top of the dried skin layer to form an adhesive layer having a thickness of 0.12 mm (based on the thickness after drying), followed by curing at 90 DEG C for 1 minute. Then, the fabric prepared in Comparative Preparation Example 1 was laminated on the adhesive layer, aged for 48 hours while maintaining the temperature at 80 ° C, and the artificial leather laminated on the release paper was peeled off to form a skin layer on the single fiber microfine fiber substrate Artificial leather was produced.

Example 1: Production of artificial leather

A polyurethane resin for forming a urethane porous layer, dimethylformamide, a urethane pore-controlling agent (a polyether-modified polysiloxane solution, BYK-L 9525, manufactured by Uni-Material Co., Ltd.) prepared in Preparative Example 2, ), A surfactant (DISPERBYK-130, manufactured by BYK Korea), and toner (SBW-7388-Black, manufactured by Iseumu Co., Ltd.) in a ratio of 100: 40: 1: 0.5: 5 parts by weight to prepare an aqueous solution of dimethylformamide , A wet silver layer coated surface having a urethane microporous layer was formed through a coagulation and washing process and dried through a thermal tenter to prepare a first sheet having a fiber substrate layer-urethane porous layer laminated thereon.

Then, the composition for forming a skin layer according to Preparation Example 4 was skin-coated on a release paper to form a skin layer having a thickness of 0.09 mm (based on the thickness after drying), followed by drying at 100 ° C for 5 minutes. The dried skin layer was coated with a two-component adhesive according to Preparation Example 4 to form an adhesive layer having a thickness of 0.12 mm (based on the thickness after drying), and then heated at 90 DEG C for 1 minute to cure the adhesive layer to prepare a second sheet . The first sheet laminated with the fiber substrate layer-urethane porous layer prepared above was laminated on the adhesive layer of the second sheet, aged for 48 hours while maintaining the temperature at 80 ° C, and the artificial leather laminated on the release paper was peeled off, .

Example 2: Production of artificial leather

An artificial leather was produced in the same manner as in Example 1 except that the polyurethane resin for forming a pore layer prepared in Preparative Example 3 was used.

Example 3: Production of artificial leather

The surface-treated coating solution prepared in Preparation Example 5 was coated with 20 g / m ² of artificial leather of Example 1 using a gravure coater and dried at 100 ° C for 2 minutes.

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

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

One. Light resistance

Light resistance characteristics were evaluated under the conditions of a total irradiation dose of 126 mJ / m ² and a use light source Xenon-ARC-Lamp at a temperature of 90 ° C, a humidity of 50%, and an illumination intensity of 65100 W / m ² based on MS-210-05 and ISO 105.

2. Heat aging resistance

     The heat resistance test was carried out at 100 ° C for 144 hours by the test method of 3.8 based on MS 322-05.

3. Friction coloring

The friction coloring property was evaluated by the test method of 3.12 based on MS 322-05.

4. Chemical resistance

The chemical resistance was evaluated by the test method of 4.7 based on MS 210-05.

Comparative Example 1 Example 1 Example 2 Example 3 Light fastness, degree 2.5 to 3 3 to 4 3 to 4 Level 4 or higher Dry / wet friction coloring Slight peeling Level 4 or higher Level 4 or higher Level 4 or higher Chemical resistance Slightly peeled off clear clear clear Heat aging resistance 3.5 or less Level 4 or higher Level 4 or higher Level 4 or higher Stain resistance 25% or more 25% or less 20% or less 17% or less Wrinkle Poor Good Good Good Emotion such as volume feeling, touch feeling △ ◎ ◎ ◎ △: Bad feeling such as volume feeling and touch feeling after production
◎: Excellence in emotion such as volume feeling and touch after commercialization

       As can be seen from the above Table 4, the artificial leather of Examples 1 and 2 of the present invention exhibited excellent properties such as light resistance, chemical resistance, and heat aging resistance as compared with Comparative Example 1, and excellent sensitivity Which is similar to the texture of natural leather.

FIG. 2 is a photograph of a steering wheel manufactured using artificial leather manufactured in Comparative Example 1, FIG. 3 is a photograph showing a steering wheel manufactured using artificial leather manufactured in Example 1 of the present invention And FIG. 4 is a photograph of a steering wheel manufactured using artificial leather manufactured in Example 3 of the present invention.

In particular, as shown in Figs. 3 and 4, in the case of Examples 1 and 3, the seam strength and the wrinkles of the curved portions are very good as compared with Comparative Example 1 shown in Fig.

Claims (17)

A fibrous base layer comprising a long fibrous high density microfine nonwoven fabric,
A urethane porous layer formed on the fiber substrate layer,
An aliphatic or alicyclic polyisocyanate compound and a polycarbonate-based polyol formed on the urethane porous layer; Fluorinated polyols or silicone-based polyols; Ether-based polyols; And a skin layer comprising a polyurethane resin prepared by polymerizing a polyol compound containing an ester-based polyol
Wherein the synthetic leather is a synthetic leather. The artificial leather according to claim 1, further comprising an adhesive layer between the urethane porous layer and the skin layer. The artificial leather according to claim 1, wherein the long-fiber type high-density micro-fiber non-woven fabric has an apparent density of 0.35 to 0.8 g / cm ³ . The polyurethane resin composition according to claim 1, wherein the polyurethane resin
An aliphatic or alicyclic polyisocyanate compound and a polycarbonate-based polyol having a number average molecular weight of 800 to 3,500; A fluorinated polyol having a number average molecular weight of 200 to 4,000 or a silicon-based polyol having a number average molecular weight of 200 to 4,000; An ether-based polyol having a number average molecular weight of 1,000 to 3,000; And a polyol compound containing an ester-based polyol, and reacting the resultant polyurethane prepolymer with a chain extender. The method of claim 4, wherein the polycarbonate-based polyol; Fluorinated polyols or silicone-based polyols; Ether-based polyols; And the ester-based polyol are used in a weight ratio of 60 to 95: 0.1 to 20: 1 to 20: 1 to 10. The fluorine-containing polyol according to claim 4,
A perfluoropolyether, or a polytetrafluoroethylene. ≪ RTI ID = 0.0 > 11. < / RTI > The method of claim 4, wherein the silicone-
? - {3- (2'-hydroxyethoxy) propyl} - omega-trimethylsilane,? - {- 3- {2,2-bis (hydroxymethyl) butoxy} propyl} polydimethylsiloxane, (2 ', 3'-dihydroxypropyl) -? - trimethylsiloxypolyethylenepropylsiloxane,? - {3- (2', 3'-dihydroxypropyl) Oxypropyl} -ω-trimethylsilyoxypolydimethylsiloxane, α- {3- (2 ', 3'-dihydroxypropyloxy) propyl} -ω-trimethylsilyoxypolyethylenephenylsiloxane, α- {3- (2'-ethyl-2'-hydroxymethyl-3-hydroxypropyl} -ω-trimethylsilyloxypolydimethylsiloxane, α- {3- (2'- Propyl} -? - trimethylsilyloxypolydimethylsiloxane and? - {3- (2'-hydroxy-3'-isopropylamino) propyl} α- {3- (2'-hydroxy-3'-isopropylamino) propyl} -ω-trimethylsilyoxypolyethylene-diphe Artificial leather, characterized in that one member selected from the group consisting of siloxane. The artificial leather according to claim 1, wherein the skin layer is formed of a polyurethane surface-treated coating layer. The polyurethane resin composition according to claim 8, wherein the polyurethane surface-
Aliphatic or alicyclic polyisocyanate compounds and polycarbonate-based polyols; Fluorinated polyols or silicone-based polyols; Ether-based polyols; And a polyurethane resin prepared by polymerizing a polyol compound containing an ester-based polyol. Forming a urethane porous layer on a fibrous substrate layer comprising a long fibrous high density microfine nonwoven fabric to produce a first sheet;
Forming a skin layer by coating a release paper with a polyurethane composition for forming a skin layer;
Forming an adhesive layer on the skin layer to produce a second sheet;
Peeling the release paper after laminating the first sheet and the second sheet; And
Coating the surface of the skin layer on which the release paper has been peeled with a surface treatment coating solution to form a polyurethane surface treatment coating layer
The method of claim 1, [Claim 11] The method according to claim 10, wherein the nonwoven fabric produced by the combined process of two or more selected from the group consisting of spunbond, needle punching, and spun lace process is miniaturized through a weight reduction process. The polyurethane composition for forming a skin layer according to claim 10,
A polyurethane resin for forming a skin layer, a solvent, and a toner. 13. The method according to claim 12, wherein the polyurethane resin for forming the skin layer
An aliphatic or alicyclic polyisocyanate compound and a polycarbonate-based polyol having a number average molecular weight of 800 to 3,500; A fluorinated polyol having a number average molecular weight of 200 to 4,000 or a silicon-based polyol having a number average molecular weight of 200 to 4,000; An ether-based polyol having a number average molecular weight of 1,000 to 3,000; And a polyol compound containing an ester-based polyol having a number average molecular weight of 1,000 to 3,000, and reacting the resultant polyurethane prepolymer with a chain extender. 14. The method according to claim 13, wherein the polycarbonate-based polyol; Fluorinated polyols or silicone-based polyols; Ether-based polyols; And the ester-based polyol are used in a weight ratio of 60 to 95: 0.1 to 20: 1 to 20: 1 to 10. 14. The fluorine-containing polyol according to claim 13,
Perfluoropolyether or polytetrafluoroethylene. ≪ RTI ID = 0.0 > 11. < / RTI > 14. The method of claim 13, wherein the silicone-
? - {3- (2'-hydroxyethoxy) propyl} - omega-trimethylsilane,? - {- 3- {2,2-bis (hydroxymethyl) butoxy} propyl} polydimethylsiloxane, (2 ', 3'-dihydroxypropyl) -? - trimethylsiloxypolyethylenepropylsiloxane,? - {3- (2', 3'-dihydroxypropyl) Oxypropyl} -ω-trimethylsilyoxypolydimethylsiloxane, α- {3- (2 ', 3'-dihydroxypropyloxy) propyl} -ω-trimethylsilyoxypolyethylenephenylsiloxane, α- {3- (2'-ethyl-2'-hydroxymethyl-3-hydroxypropyl} -ω-trimethylsilyloxypolydimethylsiloxane, α- {3- (2'- Propyl} -? - trimethylsilyloxypolydimethylsiloxane and? - {3- (2'-hydroxy-3'-isopropylamino) propyl} α- {3- (2'-hydroxy-3'-isopropylamino) propyl} -ω-trimethylsilyoxypolyethylene-diphe Production process, characterized in that one member selected from the group consisting of siloxane. 11. The coating solution according to claim 10, wherein the surface-treating coating liquid comprises:
Aliphatic or alicyclic polyisocyanate compounds and polycarbonate-based polyols; Fluorinated polyols or silicone-based polyols; Ether-based polyols; And a polyurethane resin prepared by polymerizing a polyol compound containing an ester-based polyol.

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