KR101030313B1 - Artificial leather and method of manufacturing the same - Google Patents

Abstract

The present invention relates to a vehicle artificial leather having excellent flame retardancy and a manufacturing method thereof, wherein the vehicle artificial leather is impregnated with a polymer elastomer containing a phosphate ester flame retardant in a nonwoven fabric in which microfibers having a single yarn fineness of 0.001 to 0.3 denier are intertwined with each other. It has a structure, the content of phosphorus (P) atom is 4,500-15,000 ppm, and stiffness is 120 mm or less, It is characterized by the above-mentioned.

Since the present invention does not undergo a separate process of imparting flame retardancy after dyeing, there is no deterioration in touch, appearance, and wear strength, and the flame retardancy can be greatly improved without problems of environmental pollution such as environmental hormone generation.

Artificial leather, vehicle, automobile, flame retardant, wear strength, touch, phosphate ester.

Description

Artificial leather and method of manufacturing the same

The present invention relates to a vehicle artificial leather excellent in flame retardancy and a method of manufacturing the same, and more specifically, since it does not undergo a separate process of imparting flame retardancy after dyeing, there is no deterioration of touch, appearance and wear strength, and environmental hormone generation. The present invention relates to a vehicle artificial leather and a method of manufacturing the same, which can greatly improve flame retardancy without a problem of environmental pollution.

Artificial leather is composed of a nonwoven fabric in which microfibers are intertwined three-dimensionally and a polymer elastomer impregnated in the nonwoven fabric. The artificial leather has excellent feel, light effect and drape, and has a soft texture and unique appearance similar to that of natural leather. BACKGROUND ART It is widely used as a sheet skin material or interior material of a vehicle (hereinafter, referred to as "vehicle") for transportation such as trains and ships.

Artificial leather is usually manufactured by manufacturing a nonwoven fabric with island-in-the-sea composite fiber, impregnating a polymer elastic body in the nonwoven fabric, and treating it with an aqueous alkali solution to minimize the island-in-the-sea composite fiber, followed by buffing and dyeing.

Artificial leather (abbreviated as "vehicle artificial leather") used as a vehicle material is required for durability and form stability against friction and external force, and is suitable for bending and mounting. This is required. In addition, recently, the artificial leather material is recognized as a highly sensitive material, and the application to the vehicle is increasing day by day, and aesthetic elements such as a soft lighting effect are becoming very important.

In particular, artificial leather is very vulnerable to fire due to its structural properties and composition.

Specifically, since artificial leather is composed of a nonwoven fabric made of ultrafine fibers and a porous polyurethane resin impregnated in the nonwoven fabric, oxygen is smoothly supplied during combustion, and the microfine fiber plays a role as a wick, and a porous polyurethane Softeners act as oil and are very vulnerable to fire.

As a conventional technique for solving the problems of artificial leather lacking flame retardancy as described in the Republic of Korea Patent Publication No. 199595-8855 discloses a method of padding the artificial leather in a halogen-based flame retardant solution, Korean Patent No. 0616738 bromine A method of coating a surface containing a flame retardant and an antimony trioxide flame retardant on artificial leather is disclosed, and Japanese Patent Laid-Open No. 2004-68205 discloses a method of applying a halogen flame retardant to a back surface of a vehicle interior agent instead of artificial leather. We publish.

In the conventional methods, halogen-based flame retardants, bromine-based flame retardants, and antimony-based flame retardants are toxic and have environmental problems, such as generating environmental hormones.

In addition, the above-mentioned conventional methods perform a process of imparting flame retardancy after the dyeing process of the product, and in order to obtain a desired flame retardancy, a large amount of flame retardant must be used, so that the touch becomes hard, the appearance worsens, and the flame retardant is eliminated when worn. There arises a problem that the flame retardancy is lowered.

Since the present invention does not go through a separate process of imparting flame retardancy after dyeing, there is no deterioration of touch, appearance and wear strength, and to provide artificial leather for vehicles that can greatly improve flame retardancy without environmental pollution problems such as environmental hormone generation. do.

In addition, the present invention is to provide a method for manufacturing the vehicle artificial leather.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

First, the vehicle artificial leather according to the present invention has a structure in which a polymer elastic body containing a phosphate-based flame retardant is impregnated in a nonwoven fabric in which fine fibers having a single yarn fineness of 0.001 to 0.3 denier are intertwined with each other, and the content of phosphorus (P) atoms is increased. It is 4,500-15,000ppm, and stiffness is 120 mm or less, It is characterized by the above-mentioned.

It is preferable that the said phosphate ester flame retardant has a structure of the following general formula (I) or general formula (II).

[In the general formula (I) or (II), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are alkyl groups or aliphatic compounds.]

The content of phosphorus (P) atoms contained in the vehicle artificial leather according to the present invention is 4,500 ~ 15,000ppm.

When the content of phosphorus (P) atoms is less than 4,500 ppm, the effect of improving flame retardancy is lowered. When the content of phosphorus (P) is higher than 15,000 ppm, only the manufacturing cost is increased without further improving the flame retardancy.

Automotive artificial leather according to the present invention has a ductility of 120 mm or less, when the ductility exceeds 120 mm, the touch is greatly reduced.

The ultrafine fibers are polyamide fibers, polyester fibers and the like, but in the present invention, the type of the ultrafine fibers is not particularly limited.

Single yarn fineness of the ultrafine fibers is 0.001 ~ 0.3 denier.

If the single yarn fineness is less than 0.001 denier, the strength of the artificial leather is lowered. If the single yarn fineness is more than 0.3 denier, the touch and lighting effect of the artificial leather is lowered.

In addition, the artificial leather for vehicles according to the present invention is excellent in flame retardancy as the combustion evaluation results by FMVSS-302 No. 50 mm / min or less.

The present invention includes a vehicle artificial leather in which the phosphate ester flame retardant is contained in the ultrafine fibers.

In the present invention, flame retardancy was evaluated by the vehicle horizontal method according to the FMVSS-302 standard. In detail, it is as follows. Width 100mm, length 350mm, thickness are taken as the thickness of a component. The test apparatus shall comply with the requirements of KS B 9152-1978 [Testing method for Combustibility of Organic Materials for Automobile Interior] or shall have equivalent performance. The specimens are allowed to stand for at least 24 hours at a temperature of 16∼21 ℃ and a relative humidity of 55 ± 5%, and then again in a drying furnace at a temperature of 80 ± 3 ℃ for 168 hours before use in the test. The specimen is sandwiched between two specimen fittings specified in KS B 9152. The test piece fitting shall be marked with a mark at a position of 38 mm at the opening and at a position of 254 mm at the site. The inner diameter of the discharge tube of the Bunsen burner used for the test piece ignition is 9.5 ± 0.5 mm. The gas supplied to the Bunsen burner uses, in principle, natural gas having a heat capacity of 35,000 to 38000 kj / m 3 (8361 to 9078 kcal / m 3). However, liquefied petroleum gas (LP gas) having a heat of vaporization equal to or higher than that of the natural gas may be used. The test piece faces downwards with the spark of the Bunsen burner. Put the Bunsen burner on a horizontal track with the air inlet closed and ignite it to adjust the flame height to approximately 38 mm from the tip of the discharge tube. Bring the flame of the Bunsen burner to the specimen for 15 seconds and immediately turn off the flame of the Bunsen burner. When combustion reaches the mark A (38 mm from the end of the specimen), start the time measurement and measure the time required to reach the mark B (254 mm from the A mark). However, if the combustion does not reach the B mark, the combustion time and the combustion length to the position where the progress of combustion has stopped are measured. At each test, the combustion gas in the test chamber is evacuated and adjusted to the condition.

Calculate the combustion rate according to the following equation.

B = 60 × D ÷ T

B: burning speed (mm / min)

D: combustion length (mm)

T: Burning time (seconds)

Non-combustible flames that do not burn at all for 15 seconds.

Although ignition occurs, when the combustion does not reach the A mark or when it is turned off within 50 mm or within 60 seconds beyond the A mark, it is set as [self-extinguishing].

The calculation of the combustion speed is made up to an integer and the less than it is cut up.

In the burning rate column, enter [S.E] for self-extinguishing.

However, if it is nonflammable, record [0].

Lecture was evaluated by the following method.

In general, the most commonly used cantilever method was evaluated. The test apparatus uses a flat bar with a smooth top surface, equipped with a ruler, with a 45-degree inclined surface at one end, like a typical stiffness tester. Five test pieces of 25 mm in width and 200 mm in length are taken in the longitudinal and transverse directions, respectively, and the short side is placed on the horizontal line in accordance with the reference line of the ruler. Press the specimen with the same size pressing plate as the specimen, and slide it at a speed of approximately 10 mm / sec in the direction of the inclined surface, and read the position of the other end when the one end of the specimen contacts the inclined surface. Lecture degree is represented by moving distance (mm) from baseline, and it measures and shows five surface and back surface in both length and width, and shows it with the average value.

Peel strength is made of FABRIC, urethane foam and fabric under the same conditions as mass production and left for more than 24 hours in a standard state to make it a specimen. Three specimens 25 mm wide and 150 mm long were taken from the specimens, and one end was peeled off about 30 mm. After leaving for 72 hours at 50 ° C 95% RH, the specimens were tested and peeled at a rate of 200 mm / min. Find the average.

However, in the case of the denshiron type, it is represented by the average of the maximum values.

Method for producing artificial leather for vehicles according to the present invention is a process for producing a non-woven fabric with island-in-the-sea composite fiber in which island components having a single yarn fineness of 0.001 ~ 0.3 denier dispersed in a sea component of an alkali-soluble polyester, and a polymer in the nonwoven fabric Phosphoric acid in the polymer elastomer solution when manufacturing artificial leather through a process of impregnating an elastomer solution, treating the nonwoven fabric with an aqueous alkali solution to elute the sea component, and buffing and dyeing the nonwoven fabric impregnated with the polymer elastomer. It is characterized in that the ester-based flame retardant is added so that the content of phosphorus (P) atoms to the total weight of the artificial leather for vehicles is 4,500 ~ 15,000ppm.

Next, an example of a method of manufacturing the vehicle artificial leather according to the present invention will be described in detail.

First, in the present invention, the island-in-the-sea composite fiber composed of sea component which is an alkali-soluble copolyester and island components having a single yarn fineness of 0.001 to 0.3 denier is dispersed in the sea component, and then opened, carded, cross-wrapped and Needle punching produces a nonwoven fabric.

The phosphate ester flame retardant described above may be added to the island component.

Next, the composite sheet is impregnated with a polymer elastomer solution in the nonwoven fabric and then treated with an aqueous alkali solution to elute the sea component to impregnate the polymer elastomer in a nonwoven fabric in which microfibers having a single yarn fineness of 0.001 to 0.3 denier are intertwined with each other. To prepare.

At this time, the phosphate ester flame retardant in the polymer elastomer solution is added so that the content of phosphorus (P) atoms to the total weight of the vehicle artificial leather is 4,500 ~ 15,000ppm.

Meanwhile, in the present invention, the nonwoven fabric prepared as described above may be first treated with an aqueous alkali solution to elute the sea component, and then impregnated with the polymer elastomer.

Alkali-soluble copolyester as the sea component has polyethylene terephthalate as a main component, and is an additional component with a molecular weight of 400 to 20000, most preferably 1000 to 4000 polyethylene glycol, polypropylene glycol, 1,4-cyclohexanedicar Acids, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedicarboxylate, 2,2-dimethyl-1,3-propanediol, 2,2-dimethyl-1,4-butanediol, 2, 2,4-trimethyl 1,3-propanediol and copolyester obtained by copolymerizing 25% by weight or less of one or two or more selected from adipic acid.

Polyurethane resins, polyurea resins, polyacrylic acid resins, and the like may be used as the polymer elastomer, but polyurethane resins are preferable in terms of processed tablets, abrasion resistance, and hydrolysis resistance.

The weight ratio of the fibrous base composed of the polymer elastomer / fine fiber is preferably 10/90 to 70/30.

When the weight ratio of the polymer elastomer is less than 10% by weight, the cushioning property is too low, and when it exceeds 70% by weight, the feel and light effect are too low.

The method of filling the polymer elastomer may be applied by wet coagulation or dry coagulation after impregnating and / or applying the organic solvent solution or the aqueous dispersion of the polymer elastomer to the nonwoven fabric.

As an organic solvent of a high molecular elastic body, toluene, acetone, methyl ethyl ketone, etc. other than polar solvents, such as dimethylformamide, dimethylacetamide, and dimethyl sulfoxide, can be used.

Next, as described above, by buffing and dyeing a composite sheet impregnated with a polymer elastic body in a microfiber nonwoven fabric to produce a vehicle artificial leather with a wool formed on the surface.

Vehicle artificial leather of the present invention described above does not go through a separate process of imparting flame retardancy after dyeing, so there is no deterioration in touch, appearance, and wear strength, and it is possible to greatly improve flame retardancy without environmental pollution problems such as environmental hormone generation. have.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

However, the present invention is not limited by the following examples.

Example  One

The island-in-the-sea composite fiber (single-fiber fineness of 0.10 denier of the island component) consisting of the sea component of the alkali-soluble copolyester and 70 polyester components dispersed and arranged in the sea component is cut to a length of 50 mm to form a short fiber. After the lamination web of the islands-in-the-sea composite short fibers was manufactured through a carding and cross wrapper process, needle punching was performed to prepare a nonwoven fabric of the island-in-the-sea composite fiber.

Next, the prepared nonwoven fabric was impregnated with 40% by weight of the polyurethane resin to the nonwoven fabric, and then wet coagulated. Prepared.

In the polyurethane resin, a phosphate ester flame retardant having the structural formula of Formula (I) described above was added so that the content of phosphorus (P) atoms relative to the total weight of artificial leather for vehicles is 7,000 ppm.

Next, the artificial sheet was manufactured by buffing and dyeing the composite sheet using a brush.

The results of evaluating various physical properties of the manufactured vehicle artificial leather are shown in Table 1.

Comparative Example  One

Vehicle artificial leather was manufactured in the same manner as in Example 1, except that the phosphate ester flame retardant of formula (I) was not added to the polyurethane resin.

The results of evaluating various physical properties of the manufactured vehicle artificial leather are shown in Table 1.

division Burning speed Ductility (mm) Peel Strength of Coating Layer (gf) touch Example 1 34 102 270 Great Comparative Example 1 240 138 340 usually

The combustibility was evaluated by the FMVSS-302 method.

Feeling was classified as excellent if 10 or more of the 10 people rated the skin as good after the sensory test of 10 experts, and 5 to 7 people rated the skin as good. .

Since the present invention does not undergo a separate process of imparting flame retardancy after dyeing, there is no deterioration in touch, appearance, and wear strength, and the flame retardancy can be greatly improved without problems of environmental pollution such as environmental hormone generation.

Claims (7)

Microfibers with a single yarn fineness of 0.001 to 0.3 denier have a structure in which a polymer elastic body containing a phosphate-based flame retardant is impregnated in a nonwoven fabric interwoven with each other, and a phosphorus (P) atom content is 4,500 to 15,000 ppm and stiffness is 120 Artificial leather, characterized in that it is mm or less. The artificial leather according to claim 1, wherein the phosphate ester flame retardant is at least one selected from flame retardants having the structures of the following general formulas (I) to (II).

[In the general formula (I) or (II), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are alkyl groups or aliphatic compounds.] The artificial leather according to claim 1, wherein the microfine fiber contains a phosphate ester flame retardant. The artificial leather according to claim 1, wherein the evaluation result of the combustibility by the FMVSS-302 method is 50 mm / min or less. A process for producing a nonwoven fabric with island-in-the-sea composite fiber in which island components having a single yarn fineness of 0.001 to 0.3 denier are dispersed in a sea component which is an alkali-soluble polyester, a process of impregnating the nonwoven fabric with a polymer elastomer solution, and In the manufacture of artificial leather through the process of eluting sea component by treatment with aqueous alkali solution, and the process of buffing and dyeing the nonwoven fabric impregnated with the polymer elastomer, the phosphate ester flame retardant in the polymer elastomer solution to the total weight of the artificial leather for the vehicle Method for producing artificial leather, characterized in that the content of the phosphorus (P) is added to 4,500 ~ 15,000ppm. The method for producing artificial leather according to claim 5, wherein the phosphate ester flame retardant is at least one selected from flame retardants having the structures of the following general formulas (I) to (II).

[In the general formula (I) or (II), R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are alkyl groups or aliphatic compounds.] The method of manufacturing artificial leather for vehicles having excellent flame retardancy according to claim 5, wherein a phosphate ester flame retardant is added to the island component.