KR20230094232A - Bio artificial leather - Google Patents

Abstract

Provided is eco-friendly bio-artificial leather with reduced risk to a human body and an antibacterial effect. The bio-artificial leather according to the present invention comprises: a fiber base layer; and a foam layer which is disposed on the fiber base layer. The foam layer includes a first polyvinyl chloride resin and a first bioplasticizer.

Description

Bio artificial leather {BIO ARTIFICIAL LEATHER}

The present invention relates to bio-artificial leather, and more particularly, to eco-friendly bio-artificial leather having an effect of reducing harmfulness to the human body and having an antibacterial effect.

Leather commonly encountered in real life is classified into natural leather and artificial leather. Natural leather is derived from animals, has excellent texture and is highly preferred, but has disadvantages such as high price and limited production. Accordingly, artificial leather that is economical, has no restrictions on size and shape, is easy to wash, and is easy to dye is widely used throughout the industrial field.

In particular, in the field of automobiles, functional seats are in the limelight for comfortable and pleasant driving in the interior space of automobiles. Natural leather, polyvinyl chloride, and artificial leather such as polyurethane are widely used as materials for automobile seats. In particular, artificial leather using polyvinyl chloride resin as a base resin (hereinafter, referred to as PVC artificial leather) generally includes a foam layer and a skin layer.

A plasticizer added to the foam layer and the skin layer is added to the polyvinyl chloride resin to improve moldability by imparting flexibility and elasticity. In particular, there are various representative plasticizers applied to polyvinyl chloride resins, such as diethylhexyl phthalate (DEHP), dibutyl phthalate (DBP), and butylbenzyl phthalate (BBP). Since phthalate is a plasticizer whose use is restricted worldwide, countries around the world made a tentative decision that six types of phthalate-based plasticizers, including DEHP, are harmful to the human body, and have been managing them as endocrine disruptor presumptive substances since 1999.

Long-term exposure to phthalates can cause premature puberty in girls and genital malformations or azoospermia in boys. In particular, three types of phthalate-based plasticizers consisting of DEHP, DBP, and BBP have been confirmed to be carcinogenic, mutagenic, and regenerative toxic, and their use is subject to great restrictions. The remaining three types, diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP) and di-n-octyl phthalate (DNOP) are known to be particularly harmful to the human body.

On the other hand, antimony trioxide (Sb ₂ O ₃ ), which is used as a flame retardant in the field of artificial leather for automobiles, is classified as a suspected human carcinogen, and exhibits disorders such as irritation, nosebleeds, dyspnea, and heart failure when exposed for a short period of time, and chronic exposure Blood disorders, liver abnormalities, and cancer may occur. Therefore, research to replace these flame retardants has been continuously conducted in the field of artificial leather.

In addition, since an antibacterial agent is not added to the surface treatment layer constituting the conventional artificial leather, when the artificial leather is applied to a car and implemented as an actual product, there is a problem that it is vulnerable to strains. Even if artificial leather contains an antibacterial agent, it is difficult to actually implement artificial leather that exhibits an antibacterial effect even under conditions after heat resistance, moisture resistance, and light resistance.

An object of the present invention is to provide an eco-friendly bio artificial leather that is not harmful to the human body and has a CO ₂ reducing effect in order to solve the above problems.

Another object of the present invention is to provide a bio-artificial leather with improved cold resistance and flame retardancy and reduced harmfulness to the human body.

Another object of the present invention is to provide a bio-artificial leather containing a durability additive in order to compensate for the problem of poor cold resistance due to an increase in the content of an inorganic composite flame retardant.

Another object of the present invention is to provide bio-artificial leather that exhibits an antibacterial effect even after heat resistance, moisture resistance and light resistance.

The objects of the present invention are not limited to the above-mentioned objects, and other objects and advantages of the present invention not mentioned above can be understood by the following description and will be more clearly understood by the examples of the present invention. It will also be readily apparent that the objects and advantages of the present invention may be realized by means of the instrumentalities and combinations indicated in the claims.

Bio-artificial leather according to an embodiment of the present invention for achieving the above object includes a fiber base layer and a foam layer disposed on the fiber base layer, wherein the foam layer includes a first polyvinyl chloride resin and a first polyvinyl chloride resin. 1 Contains bioplasticizer. In detail, the first bioplasticizer may include a first non-phthalate-based compound and a first trimellitate-based compound. The first bioplasticizer may further include a first natural oil-derived compound. Based on the total weight of the first bioplasticizer, the content of the first natural oil-derived compound is 18 to 49% by weight, the content of the first non-phthalate-based compound is 18 to 49% by weight, and the first tree The content of the melitate-based compound may be 18 to 49% by weight.

Bio-artificial leather according to another embodiment of the present invention for achieving the above object may further include a skin layer disposed on the foam layer. Specifically, the skin layer may include a second polyvinyl chloride resin and a second bioplasticizer. The second bioplasticizer includes a second non-phthalate-based compound and a second trimellitate-based compound. can do. The second bioplasticizer may further include a second natural oil-derived compound. Based on the total weight of the second bioplasticizer, the content of the second natural oil-derived compound is 18 to 49% by weight, the content of the second non-phthalate-based compound is 18 to 49% by weight, and the second The content of the trimellitate-based compound may be 18 to 49% by weight.

According to one embodiment of the present invention, by excluding the use of a phthalate-based plasticizer and antimony trioxide, which is a carcinogen, it is possible to provide an eco-friendly bio-artificial leather having reduced harmfulness to the human body and having an effect of reducing CO ₂ . In addition, according to the present invention, it is possible to provide bio-artificial leather having improved flame retardancy and cold resistance and antibacterial effect while satisfying the physical properties of artificial leather applied to the automobile field.

In addition to the above effects, specific effects of the present invention will be described together while explaining specific details for carrying out the present invention.

1 is a cross-sectional view of a bio-artificial leather according to an embodiment of the present invention.

Hereinafter, each configuration of the present invention will be described in more detail so that those skilled in the art can easily practice it, but this is only one example, and the scope of the present invention is Not limited.

Bio artificial leather according to one aspect of the present invention includes a fiber base layer and a foam layer disposed on the fiber base layer, and the foam layer includes a first polyvinyl chloride resin and a first bio plasticizer.

Hereinafter, for convenience of description, the stacking order will be described, and the configuration of the present invention will be described in more detail with reference to the drawings.

1. Bio artificial leather 100 and its manufacturing method

1 is a cross-sectional view of a bio-artificial leather according to an embodiment of the present invention.

Referring to FIG. 1 , the bio-artificial leather 100 according to the present invention may include a fiber base layer 10, a foam layer 20, a skin layer 30, and a surface treatment layer 40.

(1) fiber base layer (10)

The fiber base layer 10 according to the present invention may correspond to one selected from the group consisting of nonwoven fabric, knitted fabric, fabric, PU impregnated fabric, and PU impregnated knitted fabric. In this specification, the PU impregnated fabric is defined to mean a fabric impregnated with a polyurethane resin, and the PU impregnated knitted fabric is defined to mean a knitted fabric impregnated with a polyurethane resin.

The yarn constituting the fabric as described above may correspond to any one selected from the group consisting of natural fibers, synthetic fibers, regenerated fibers, and combinations thereof.

The natural fiber may correspond to any one selected from the group consisting of cotton fiber, hemp fiber, wool fiber, silk fiber, wool fiber, and combinations thereof.

The synthetic fibers may correspond to any one selected from the group consisting of polyester fibers, nylon fibers, polyolefin fibers, polyvinyl alcohol fibers, polyamide fibers, polyurethane fibers, polyvinylidene chloride fibers, and combinations thereof.

The regenerated fibers may be rayon fibers or cupra fibers.

According to one embodiment of the present invention, the thickness of the weft and warp yarns constituting the fabric may correspond to 75 to 150 Denier, preferably 75 to 120 Denier, and more preferably 75 to 100 Denier may correspond to

According to another embodiment of the present invention, the thickness of the yarn constituting the circular knitting may correspond to 75 to 150 Denier, preferably 75 to 120 Denier, and more preferably 75 to 100 Denier. can The thickness of the yarn constituting the circular knit may have excellent strength within the above range.

The circular piece according to an embodiment of the present invention may be coated with the polyurethane resin on its surface. Impregnating and coating the circular piece with the polyurethane resin is to have shape retention that can withstand repeated stretching. Specifically, in order to realize the suitable circular piece, after impregnating the circular piece with an impregnation solution containing the polyurethane resin or its copolymer, coating the impregnated piece with a coating solution, solidifying it in a coagulation bath And it may be necessary to go through a water washing step to remove the organic solvent (eg, DMF) present in the circular piece.

The polyurethane resin (or impregnation solution) according to the present invention may correspond to any one selected from the group consisting of polycarbonate-based polyurethane resins, polyester-based polyurethane resins, polyether-based polyurethane resins, and mixtures thereof. .

The polyurethane resin can be prepared by reacting a polyol with a diisocyanate and a chain extender.

The diisocyanate is 4,4'-diphenylmethane diisocyanate (MDI), xylene diisocyanate (XDI), aromatic diisocyanate having a benzene ring such as 1,5-naphthalene diisocyanate, hexamethylene diisocyanate (HDI) A group consisting of aliphatic diisocyanates such as propylene diisocyanate and alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate, isophorone diisocyanate (IPDI), and 4,4'-dicyclohexylmethane diisocyanate (H12MDI) It may be at least one selected from, preferably 4,4-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and dicyclohexyl methane diisocyanate (H12MDI) It may be one or more selected from the group consisting of.

The chain extender may be one generally used in the technical field to which the present invention pertains, and preferably may be a low molecular weight diol compound or diamine compound having an even number of repeating units, which is advantageous for increasing crystallinity. The chain extender is preferably ethylene glycol (EG), diethylene glycol (DEG), propylene glycol (PG), 1,4-butanediol (1,4-BD), 1,6-hexanediol (1,6 -HD), methylpentanediol, and isophoronediamine (IPDA). The chain extender may be included in an amount of 1 to 15 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the polyol.

The polyurethane resin may be prepared by the reaction of a soft segment containing a hydroxyl group (-OH) at both ends and a hard segment containing an isocyanate group at both ends. there is.

Specifically, the polycarbonate-based polyurethane resin may correspond to a polyurethane resin using polycarbonate diol as a reactant as a soft segment, and the polyester-based polyurethane resin may correspond to a polyester die as a soft segment. It may correspond to a polyurethane resin using ol as a reactant, and the polyether-based polyurethane resin may correspond to a polyurethane resin using polyether diol as a reactant as a soft segment.

The fiber base layer 10 according to the present invention may further include additives. The additive is added to the polyurethane resin impregnated into the fabric, and may include 10 to 100 parts by weight, preferably 20 to 80 parts by weight, more preferably 30 to 50 parts by weight based on 100 parts by weight of the polyurethane resin. It may contain parts by weight.

The additive according to the present invention may correspond to any one selected from the group consisting of calcium carbonate, flame retardants, surfactants, toners, and combinations thereof. In particular, by using the calcium carbonate as a filler, it is possible to increase the tensile strength of the circular piece, and by using the flame retardant, it is possible to delay the progress of the combustion reaction by igniting the vehicle.

The flame retardant applied to the fiber base layer may be, for example, a water-soluble phosphorus-based flame retardant. The water-soluble phosphorus-based flame retardant may be, for example, Ammonium PolyPhosphate (APP) or Mono-Ammonium Phosphate (MAP).

As the surfactant, it is preferable to use at least one selected from anionic surfactants and nonionic surfactants. However, the technical spirit of the present invention is not limited to the type of surfactant, and any surfactant usable in the technical field to which the present invention belongs may be used.

The fiber base layer 10 according to the present invention may include 10 to 50 parts by weight of the solvent based on 100 parts by weight of the polyurethane resin, preferably 10 to 30 parts by weight.

The solvent may preferably correspond to any one selected from the group consisting of dimethylformamide, methylethylketone, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, ethyl acetate, and mixtures thereof. However, the technical spirit of the present invention is not limited to the type of the solvent, and all solvents capable of dissolving the polyurethane resin may be used.

The thickness of the fiber base layer 10 according to the present invention may correspond to 7 to 14 mm (millimeter), preferably 7 to 12 mm (millimeter), more preferably 7 to 10 mm (millimeter). . When the thickness of the fiber base layer 10 is less than the above numerical range, the durability of artificial leather may decrease, and when it exceeds the above numerical range, stiffness may increase due to high thickness, and softness may be excessive. can rise up In this specification, 'thickness' means the thickness of the fabric, and 'strengthness' means the brittleness of the soft fabric, a measuring device with one end having a 45° inclined surface and a smooth top surface. can be measured using

The thickness of the fiber base layer 10 can be measured by the thickness of the cut section using a scanning electron microscope (SEM) after vertically cutting the bio-artificial leather. As a specific example, the bio-artificial leather After cutting it vertically, draw a vertical line at five equally spaced points at the top of the fiber base layer, measure the distance to the bottom of the fiber base layer meeting the vertical line, and then obtain an average value of them.

(2) foam layer 20

The foam layer 20 according to the present invention may be disposed on the fiber base layer 10, and may be specifically disposed directly on the fiber base layer 10. In this specification, the meaning of 'another member is disposed immediately above one member' is defined as no member intervening between one member and another member.

The foam layer 20 according to the present invention is a layer that imparts a three-dimensional or cushioning feeling to the bio-artificial leather 100, and may be manufactured by foaming a film molded from a composition for forming a foam layer.

The foam layer 20 according to the present invention may include a first polyvinyl chloride resin and a first bio-plasticizer.

The degree of polymerization of the first polyvinyl chloride resin may be 1000 to 3000, preferably 1000 to 1700, and more preferably 1000 to 1300. When the degree of polymerization of the first polyvinyl chloride resin is out of the above numerical range, it may be difficult to realize cold resistance and mechanical properties of artificial leather at the same time.

The first bioplasticizer according to an embodiment of the present invention may include a first non-phthalate-based compound and a first trimellitate-based compound.

The first non-phthalate-based compound is a non-phthalate compound that does not contain a phthalate-based compound, and includes dioctyl terephthalate (DOTP), dioctyl isophthalate (DOIP) and their It may include any one selected from the group consisting of combinations.

The first trimellitate-based compound is composed of tris (2-ethylhexyl) trimellitate (TOTM), triisononyl trimellitate (TINTM), and combinations thereof. It may contain any one selected from the group. The first trimellitate-based compound has excellent mechanical properties and excellent characteristics such as heat resistance, migration resistance, and volatility resistance.

The first bioplasticizer according to another embodiment of the present invention may further include a first natural oil-derived compound.

Based on the total weight of the first bioplasticizer, the content of the first natural oil-derived compound may be 18 to 49% by weight, preferably 25 to 45% by weight, more preferably 30 to 40% by weight. When the content of the first natural oil-derived compound is less than the above numerical range, the content of the first non-phthalate-based compound and the trimellitate-based compound may relatively increase, causing an insignificant CO ₂ reduction effect. If it exceeds , the content of the first non-phthalate-based compound and the trimellitate-based compound may be relatively reduced, resulting in poor soaking retention (or fogging property) and volatility resistance of artificial leather. In the present specification, 'fogging property' is defined as a phenomenon in which liquid plasticizers, liquid stabilizers, and additives included in the polyvinyl chloride resin matrix volatilize.

Based on the total weight of the first bioplasticizer, the content of the first non-phthalate-based compound may be 18 to 49% by weight, preferably 25 to 45% by weight, more preferably 30 to 40% by weight. . When the content of the first non-phthalate-based compound is less than the above numerical range, the soaking retention rate (or fogging property) of bio-artificial leather may be lowered, and when the content exceeds the above numerical range, the first natural oil-derived compound and the above As the content of the first trimellitate-based compound decreases, performance such as mechanical properties and volatility resistance may deteriorate.

Based on the total weight of the first bioplasticizer, the content of the first trimellitate-based compound may be 18 to 49% by weight, preferably 25 to 45% by weight, and more preferably 30 to 40% by weight. . When the content of the first trimellitate-based compound is less than the above numerical range, mechanical properties and volatility resistance may be deteriorated, and when the content of the first trimellitate-based compound exceeds the above numerical range, gloss retention and CO ₂ reduction effect may be insignificant.

Phthalate-based plasticizers such as DINP, DIDP, and DPHP, which are applied as plasticizers in the field of conventional artificial leather and used for the purpose of facilitating moldability, are harmful to the human body due to carcinogenicity, mutagenicity, and regenerative toxicity. According to the present invention, by applying the first bio-plasticizer to the foam layer instead of the phthalate-based plasticizer harmful to the human body, it is possible to provide an eco-friendly bio-artificial leather with reduced harmfulness to the human body while having a CO ₂ reduction effect.

Therefore, when only the first natural oil-derived compound is used as a plasticizer, moldability performance may be poor and the purpose of the plasticizer may not be sufficiently achieved. Measurement problems may occur, and when only the first trimellitate-based compound is used, although mechanical properties may be excellent, moldability and cold resistance may not be secured.

The compound derived from the first natural oil may be a compound derived from the first natural oil. The first natural oil is soybean oil, palm oil, olive oil, tall oil, cottonseed oil, linseed oil, safflower oil, sunflower oil, canola oil, rapeseed oil, jatropha oil, algae oil, corn oil, tung oil, and these It may include any one selected from the group consisting of a mixture of.

The compound derived from the first natural oil may correspond to, for example, epoxidized soybean oil or epoxidized palm oil. The epoxidized soybean oil or epoxidized palm oil is a bio compound obtained by epoxidizing oil collected from soybeans or various plants.

The first bioplasticizer according to another embodiment of the present invention may include any one selected from the group consisting of myristic acid, lauric acid, adipic acid, and combinations thereof. The myristic acid, lauric acid and adipic acid are compounds extracted from palm oil. According to the present invention, even if only one of the compounds extracted from palm oil is used as the first bioplasticizer, artificial leather having physical properties and softness equal to or higher than that of artificial leather using a phthalate-based plasticizer can be implemented.

The foam layer 20 according to the present invention may include 20 to 80 parts by weight of the first bioplasticizer, preferably 20 to 40 parts by weight, more preferably, based on 100 parts by weight of the first polyvinyl chloride resin. It may include 20 to 30 parts by weight. When the content of the first bioplasticizer is less than the above numerical range, moldability of artificial leather may be lowered, and when the content of the first bioplasticizer exceeds the above numerical range, mechanical properties may not be improved.

The foam layer 20 according to the present invention may further include a first composite flame retardant. The first composite flame retardant may include a first hypophosphate-based flame retardant and a first phosphorus-nitrogen-based flame retardant. In the present specification, a phosphorus-nitrogen-based flame retardant is defined as a compound containing both a phosphorus atom and a nitrogen atom, and a hypophosphate-based flame retardant is defined as a flame retardant containing a hypophosphate functional group.

The content of the first composite flame retardant may be 1 to 40 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 20 parts by weight based on 100 parts by weight of the first polyvinyl chloride resin. When the content of the first composite flame retardant is less than the above numerical range, flame retardant performance of artificial leather may be lowered, and when the content exceeds the above numerical range, cold resistance performance may be lowered.

The weight ratio of the first hypophosphate-based flame retardant and the first phosphorus-nitrogen-based flame retardant may be 1:1 to 1:5 (w/w).

The first phosphorus-nitrogen-based flame retardant may be, for example, a compound represented by Formula 1 below.

[Formula 1]

In addition to the compound represented by Formula 1, the first phosphorus-nitrogen-based flame retardant may be any one selected from the group consisting of phosphazene, ammonium polyphosphate, ammonium phosphinate, magnesium hydroxide, and aluminum hydroxide.

The first hypophosphate-based flame retardant may correspond to, for example, metal hypophosphate, preferably selected from the group consisting of aluminum hypophosphate, calcium hypophosphate and sodium hypophosphate, more preferably aluminum hypophosphate It may correspond to phosphate.

As shown in Scheme 1 below, the mechanism by which aluminum hypophosphate acts as a flame retardant depending on the temperature can delay combustion mainly by endothermic heat due to dehydration reaction.

[Scheme 1]

The metal hypophosphate is generally prepared through a hypophosphate reaction with a metal hydroxide, or may be prepared by an exchange reaction with a water-soluble metal salt (hypophosphorous acid and its salt).

The first composite flame retardant may include aluminum hydroxide and magnesium hydroxide. Specifically, the first composite flame retardant may be a mixture of aluminum hydroxide and magnesium hydroxide (Al(OH) _3- Mg(OH) ₂ ). At this time, the weight ratio of the aluminum hydroxide and magnesium hydroxide may be 1: 1 to 1: 5 (w / w).

When only one of the first phosphorus-nitrogen-based flame retardant and the first hypophosphate-based flame retardant is used as the flame retardant applied to the foam layer 20 according to the present invention, flame retardancy may not be improved. In addition, according to the present invention, by using the first phosphorus-nitrogen-based flame retardant, the content of the inorganic flame retardant is significantly reduced, so that cold resistance can be improved.

Antimony trioxide (Sb ₂ O ₃ ), which is used as a flame retardant in the field of conventional artificial leather for automobiles, is classified as a suspected human carcinogen, and exhibits disorders such as irritation, nosebleeds, dyspnea, and heart failure when exposed for a short period of time. There were problems such as blood disorders, liver abnormalities, and cancer. According to the present invention, by using the first phosphorus-nitrogen-based flame retardant and the first hypophosphate-based flame retardant instead of antimony trioxide, bio-artificial leather with reduced harmfulness to the human body can be implemented.

The foam layer 20 according to the present invention may further include 2 to 8 parts by weight of a foaming agent, preferably 2 to 6 parts by weight, more preferably 2 to 8 parts by weight, based on 100 parts by weight of the first polyvinyl chloride resin. It may further include 4 parts by weight. When the content of the foaming agent is less than the above numerical range, foam cells are not sufficiently formed, and thus the tactile feel or ductility of artificial leather may be lowered. Mechanical properties may not be satisfied.

The foaming agent according to the present invention may correspond to a capsule foaming agent or a chemical foaming agent, and preferably may correspond to a capsule foaming agent. The capsule foaming agent is in the form of a foaming agent contained in a fine spherical thermoplastic cell structure having a size of 1 to 1000 μm (micrometer). When the capsule foaming agent is heated, the thermoplastic plastic cell is softened, and the foaming agent contained therein is vaporized to increase internal pressure, thereby expanding the capsule and forming a foam layer.

As the blowing agent, azodicarbonamide (ADCA), p,p'-oxybisbenzenesulfonyl hydrazide (p,p'-oxybis(benzenesulfonyl hydrazide)), p-toluenesulfonyl hydrazide (p- toluenesulfonyl hydrazide) and sodium bicarbonate, etc. may be used, but the technical spirit of the present invention is not limited thereto.

The thickness of the foam layer 20 according to the present invention may correspond to 2.5 to 4.0 mm, preferably 2.5 to 3.5 mm, and more preferably 2.5 to 3.0 mm.

The foam layer 20 according to another embodiment of the present invention may further include chlorinated polyethylene as a durability additive. The chlorinated polyethylene does not contain a double bond in its molecular chain and is embedded in the first polyvinyl chloride resin matrix to increase durability such as impact resistance of the foam layer. The content of the chlorinated polyethylene may be 3 to 10 parts by weight based on 100 parts by weight of the first polyvinyl chloride resin. When the content of the chlorinated polyethylene is out of the above numerical range, cold resistance is weakened when it is less than 3 parts by weight, and when it exceeds 10 parts by weight, odor may cause a problem that the odor specification is exceeded. The weight average molecular weight of the chlorinated polyethylene may be 90 to 130 g / mol, and the content of chlorine may be 25 to 45% by weight.

The foam layer 20 according to another embodiment of the present invention may further include a first polyester-based plasticizer. The first polyester-based plasticizer may be, for example, any one selected from the group consisting of poly-2-ethylhexyl glycol adipate, adipic acid polyester, citric acid polyester, and combinations thereof. The first polyester-based plasticizer may be, for example, P2600 from Songwon Industry. The amount of the first polyester-based plasticizer may be 3 to 20 parts by weight based on 100 parts by weight of the first polyvinyl chloride resin. If the content of the first polyester-based plasticizer is less than 3 parts by weight, endurance fatigue may be weakened, and if it exceeds 20 parts by weight, cold resistance may be deteriorated.

The chlorinated polyethylene or the first polyester-based plasticizer may be added to solve the problem of low cold resistance due to an increase in the content of the first composite flame retardant, which is an inorganic material.

(3) Skin layer (30)

The skin layer 30 according to the present invention may be disposed on the foam layer 20, and specifically may be disposed directly on the foam layer 20. Therefore, the foam layer 20 may be disposed between the skin layer 30 and the fiber base layer 10 . The foregoing parts and repeated descriptions are briefly described or omitted.

The skin layer 30 according to the present invention may include a second polyvinyl chloride resin.

The polymerization degree of the second polyvinyl chloride resin according to the present invention may be 1000 to 3000, preferably 1000 to 1700, more preferably 1000 to 1300. When the degree of polymerization of the second polyvinyl chloride resin is out of the above numerical range, the hardness of the artificial leather increases and pattern transfer may not be possible in the embossing process.

The skin layer 30 according to the present invention comprises 60 to 90 parts by weight, preferably 60 to 80 parts by weight, more preferably 60 to 70 parts by weight of the second bioplasticizer based on 100 parts by weight of the second polyvinyl chloride resin. can include When the content of the second bio-plasticizer is less than the above numerical range, moldability of artificial leather may be lowered, and when the content of the second bio-plasticizer exceeds the above numerical range, mechanical properties may not be improved.

The second bioplasticizer according to an embodiment of the present invention may include a second non-phthalate-based compound and a second trimellitate-based compound. The second non-phthalate-based compound may include any one selected from the group consisting of dioctyl terephthalate, dioctyl isophthalate, and combinations thereof. The second trimellitate-based compound is any one selected from the group consisting of tris (2-ethylhexyl) trimellitate, triisononyl trimellitate, and combinations thereof. may contain one.

The second bioplasticizer according to another embodiment of the present invention may further include a second natural oil-derived compound. The compound derived from the second natural oil may be a compound derived from the second natural oil.

The second natural oil is soybean oil, palm oil, olive oil, tall oil, cottonseed oil, linseed oil, safflower oil, sunflower oil, canola oil, rapeseed oil, jatropha oil, algae oil, corn oil, tung oil and these It may include any one selected from the group consisting of a mixture of.

Based on the total weight of the second bioplasticizer, the content of the second natural oil-derived compound is 25 to 35% by weight, the content of the second non-phthalate compound is 35 to 45% by weight, and the second tree The content of the melitate-based compound may be 25 to 35% by weight.

The second bioplasticizer according to another embodiment of the present invention may include any one selected from the group consisting of myristic acid, lauric acid, adipic acid, and combinations thereof.

The second bioplasticizer may be the same as or different from the first bioplasticizer.

The skin layer 30 according to the present invention may further include a second composite flame retardant. The second composite flame retardant may include a second phosphorus-nitrogen-based flame retardant and a second hypophosphate-based flame retardant.

The content of the second composite flame retardant may be 1 to 40 parts by weight, preferably 5 to 30 parts by weight, more preferably 10 to 20 parts by weight based on 100 parts by weight of the second polyvinyl chloride resin. When the content of the second composite flame retardant is less than the above numerical range, flame retardant performance of artificial leather may be lowered, and when the content exceeds the above numerical range, cold resistance performance may be lowered. The second composite flame retardant may be the same as or different from the first composite flame retardant. The second phosphorus-nitrogen-based flame retardant may be the same as or different from the first phosphorus-nitrogen-based flame retardant. The second hypophosphate-based flame retardant may be the same as or different from the first hypophosphate-based flame retardant.

The thickness of the skin layer 30 according to the present invention may correspond to 0.12 to 0.3 mm, preferably 0.12 to 0.25 mm, and more preferably 0.12 to 0.20 mm.

The skin layer 30 according to another embodiment of the present invention may further include chlorinated polyethylene as a durability additive. The chlorinated polyethylene may be embedded in the second polyvinyl chloride resin matrix to increase durability such as impact resistance of the skin layer. The content of the chlorinated polyethylene may be 3 to 10 parts by weight based on 100 parts by weight of the second polyvinyl chloride resin. The weight average molecular weight of the chlorinated polyethylene may be 90 to 130 g / mol, and the content of chlorine may be 25 to 45% by weight.

The skin layer 30 according to another embodiment of the present invention may further include a second polyester-based plasticizer. The second polyester plasticizer may be the same as or different from the first polyester plasticizer described above. The content of the second polyester-based plasticizer may be 3 to 20 parts by weight based on 100 parts by weight of the second polyvinyl chloride resin.

The chlorinated polyethylene or the second polyester-based plasticizer may be added to solve a problem in that cold resistance properties are lowered due to an increase in the content of the second composite flame retardant, which is an inorganic material.

(4) surface treatment layer 40

The surface treatment layer 40 according to the present invention may be disposed on the skin layer 30, and specifically may be disposed directly on the skin layer 30. Therefore, the skin layer 30 may be disposed between the surface treatment layer 40 and the foam layer 20 .

The surface treatment layer 40 according to the present invention may have a thickness of 0.001 to 0.02 mm (millimeter), preferably 0.001 to 0.01 mm (millimeter), more preferably 0.001 to 0.008 mm (millimeter). can do. When the thickness of the surface treatment layer 40 satisfies the above numerical range, abrasion resistance, light resistance, hydrolysis resistance and chemical resistance may be excellent while maintaining an appropriate cost.

The surface treatment layer 40 can improve functions such as light resistance, hydrolysis resistance, and chemical resistance of artificial leather. Specifically, the surface treatment layer 40 may be formed by coating a surface treatment agent on top of the skin layer 30 . The surface treatment agent may be classified as an aqueous surface treatment agent or an oil-based surface treatment agent according to the nature (aqueous or oily) of a solvent serving as a dispersion medium.

In particular, when the surface treatment layer is coated with an aqueous surface treatment agent, odor and volatile organic compounds are reduced, so that bio-artificial leather can be realized. For example, the aqueous surface treatment agent may include a polyurethane dispersion and carbodiimide as a two-component aqueous surface treatment agent.

The surface treatment layer 40 may preferably be formed by including a crosslinking agent and a silicone compound in a polyurethane resin, more preferably including a crosslinking agent, a reactive silicone compound, a polyolefin wax, and a polyurethane bead in a polyurethane resin. It may be formed, and in this case, there is a more excellent effect of sound absorption and luxury.

The crosslinking agent is preferably 3 to 7 parts by weight, more preferably 4 to 6 parts by weight, still more preferably 4 to 5 parts by weight based on 100 parts by weight of the polyurethane resin, and within this range, sound absorption and luxury It has an excellent effect.

The crosslinking agent is not particularly limited if it is a crosslinking agent commonly used in the art to which the present invention pertains, but is preferably selected from compounds containing at least one selected from the group consisting of an aziridine group, an isocyanate group, and a carbodiimide group in a molecule. It can be, and in this case, there is an advantage of better sound absorption and luxury.

The content of the silicone compound is 5 to 20 parts by weight, more preferably 5 to 15 parts by weight, and even more preferably 8 to 10 parts by weight based on 100 parts by weight of the polyurethane resin, and within this range, the surface feel is There are great advantages.

The silicone compound may be preferably polysiloxane, more preferably polysiloxane that is liquid at room temperature, polysiloxane in the form of beads, or a mixture thereof, more preferably polysiloxane that is liquid at room temperature, in which case the surface texture is There are great advantages.

The surface treatment layer 40 according to another embodiment of the present invention may have an embossed pattern engraved on its surface.

The surface treatment layer 40 according to another embodiment of the present invention may include a polyurethane resin and 1 to 10 parts by weight of an antibacterial agent based on 100 parts by weight of the polyurethane resin. The antibacterial agent may be a silver-zeolite compound.

Specifically, the silver-zeolite compound is a compound in which silver ions (Ag ⁺ ), which have strong antibacterial activity and high stability, are supported on zeolite, and can be produced by exchanging silver ions (Ag ⁺ ) with an alkali metal in zeolite. In general, silver-zeolite compounds have better antibacterial activity than zinc-zeolite compounds or copper-zeolite compounds, and in the process of adding and dispersing them in a composition for forming a surface treatment layer, the silver-zeolite compounds become zinc-zeolite. Its dispersibility is better than that of the zeolite-based compound or the copper-zeolite-based compound, so that the antibacterial effect can be well maintained even after heat resistance, moisture resistance, or light resistance.

The average particle size of the antimicrobial agent according to the present invention may correspond to 1 to 10 μm (micrometer), preferably 2 to 8 μm (micrometer), more preferably 3 to 5 μm (micrometer). can When the average particle size of the antimicrobial agent exceeds the above range, it is difficult to disperse in the composition for forming a surface treatment layer.

Specifically, the antimicrobial agent may be included in 4 to 6 parts by weight based on 100 parts by weight of the polyurethane resin, more specifically 5 to 6 parts by weight. When the content of the antimicrobial agent is less than the above numerical range based on 100 parts by weight of the polyurethane resin, the antibacterial effect may be less than 90% according to the ISO 22196 method, and when it exceeds the above numerical range, toxicity is strong and adversely affects the human skin. In addition to the problem, there may be a problem of work defect during the coating operation.

The antibacterial agent according to the present invention may have an antibacterial effect against any one selected from the group consisting of pneumoniae , Staphylococcus , Escherichia coli and combinations thereof. Specifically, Pneumococcus is the most powerful bacteria among respiratory disease causing bacteria, and Staphylococcus aureus is one of bacteria widely distributed in nature, and Staphylococcus aureus in particular can produce enterotoxin. These toxins can cause vomiting, diarrhea and abdominal pain as they are absorbed into the stomach or intestines. Escherichia coli is one of the enteric bacteria belonging to bacillus.

The bio-artificial leather according to the present invention may have an antibacterial effect of 90% or more, preferably 95 to 99.999%, and more preferably 99 to 99.9% according to ISO 22196.

The bio-artificial leather according to the present invention has an antibacterial effect of 80% or more, preferably 90 to 99.99%, more preferably 90 to 99.99% according to ISO 22196 after at least one surface treatment selected from the group consisting of heat treatment, water treatment, and light treatment. may correspond to 95 to 99.9%.

In the method for manufacturing bio-artificial leather according to another embodiment of the present invention, (S1) forming a foam layer on a fiber base layer, (S2) forming a skin layer on the foam layer, (S3) the skin A step of forming a surface treatment layer on the layer may be included.

Hereinafter, an embodiment of the present invention will be described in detail so that those skilled in the art can easily practice it, but this is only one example, and the scope of the present invention is Not limited.

[Preparation Example 1: Preparation of plasticizer]

As shown in Tables 1 to 3 below, plasticizers according to Comparative Preparation Examples and bioplasticizers according to Preparation Examples were prepared. Specifically, the bio carbon content ( ¹⁴ C/ ¹² C) of the plasticizer was measured according to ASTM D6866.

unit:
weight% Comparative preparation example 1 Comparative preparation example 2 Comparative preparation example 3 Comparative preparation example 4 Comparative preparation example 5 Implementation Example 1 Implementation Example 2 Preparation Example 3 Implementation Example 4 Preparation example 5 ESO ^1-1) - 100 - - - 30 30 30 30 - EPO ^1-2) - - - - 100 - - - - 30 DOTP ²⁾ - - 100 - - 40 40 - - - DOIP ³⁾ - - - - - - - 40 40 40 TOTM ⁴⁾ - - - 100 - 30 - 30 - - TITM ⁵⁾ - - - - - - 30 - 30 30 DINP ⁶⁾ 100 - - - - - - - - - 1-1) epoxidized soybean oil/bio carbon content ( ¹⁴ C/ ¹² C): 30%
1-2) Epoxidized palm oil/bio carbon content ( ¹⁴ C/ ¹² C): 30%
2) Dioctyl terephthalate/bio carbon content ( ¹⁴ C/ ¹² C): 0%
3) Dioctyl isophthalate/bio carbon content ( ¹⁴ C/ ¹² C): 0%
4) tris(2-ethylhexyl)trimellitate with a molecular weight of 547/bio carbon content ( ¹⁴ C/ ¹² C): 0%
5) triisononyl trimellitate with a molecular weight of 588/bio carbon content ( ¹⁴ C/ ¹² C): 0%
6) Diisononyl Phthalate/Bio Carbon Content ( ¹⁴ C/ ¹² C): 0%

unit:
weight% Preparation Example 6 Preparation Example 7 Preparation Example 8 Preparation Example 9 DOTP ²⁾ 50 50 - - DOIP ³⁾ - - 50 50 TOTM ⁴⁾ 50 - 50 - TITM ⁵⁾ - 50 - 50

unit:
weight% Preparation Example 10 Preparation Example 11 Example 12 of preparation myristic acid 100 - - lauric acid - 100 - adipic acid - - 100

[Manufacture Example 1: Manufacture of artificial leather]

Artificial leather was manufactured according to the following Preparation Example.

<Example 1-1>

A foam layer was formed on the fiber base layer made of Maryas terry woven fabric woven with 35% Rayon fiber. After forming a skin layer on the foam layer, a surface treatment layer containing a water-based polyurethane resin (trade name: UT-66 manufactured by Unitech Industries) was formed on the skin layer to manufacture artificial leather.

The foam layer according to Example 1-1 is a first polyvinyl chloride resin (polymerization degree: 1000) and 30 parts by weight of the plasticizer according to Preparation Example 1, a foaming agent (azo dicarbonamide) 2.5 parts by weight, calcium carbonate (H-type) 5 parts by weight.

The skin layer according to Example 1-1 is a second polyvinyl chloride resin (polymerization degree: 1300) and 80 parts by weight of the plasticizer according to Preparation Example 1 based on 100 parts by weight of the second polyvinyl chloride resin, calcium carbonate ( H-type) 5 parts by weight and Ba-Zn heat-resistant stabilizer (KBZ-270) 2.5 parts by weight.

<Example 1-2>

Artificial leather was manufactured in the same manner as in Example 1-1, but instead of the foam layer according to Example 1-1, the foam layer according to Example 1-2 was made of phosphorus-nitrogen-based flame retardant represented by Chemical Formula 1 Further comprising 10 parts by weight of a first composite flame retardant prepared by mixing the compound and aluminum hypophosphite in a weight ratio of 1: 1 based on 100 parts by weight of the first polyvinyl chloride resin, according to Example 1-1 The skin layer further includes 10 parts by weight of a second composite flame retardant prepared by mixing the compound represented by Formula 1 and aluminum hypophosphite in a weight ratio of 1: 1 based on 100 parts by weight of the second polyvinyl chloride resin . In order to compensate for the decrease in cold resistance due to the increase in the content of the inorganic flame retardant, the foam layer according to Example 1-2 is chlorinated polyethylene (chlorine content: 25 parts by weight) based on 100 parts by weight of the first polyvinyl chloride resin. %, weight average molecular weight 100 g / mol) and further comprises 5 parts by weight, and the skin layer according to Example 1-2, based on 100 parts by weight of the second polyvinyl chloride resin, chlorinated polyethylene (chlorine content: 25% by weight , weight average molecular weight 100 g / mol) and further includes 5 parts by weight.

<Example 1-3>

Artificial leather was manufactured in the same manner as in Example 1-2, but instead of the first composite flame retardant according to Example 1-2, a first composite flame retardant prepared by mixing aluminum hydroxide and magnesium hydroxide in a weight ratio of 1: 1 ( Al(OH) _3- Mg(OH) ₂ ) was used, and instead of the second composite flame retardant according to Example 1-2, a second composite flame retardant prepared by mixing aluminum hydroxide and magnesium hydroxide at a weight ratio of 1: 1 (Al(OH) _3- Mg(OH) ₂ ) was used.

<Example 1-4>

Artificial leather was prepared in the same manner as in Example 1-1, but the surface treatment layer contained 5 parts by weight of a silver-zeolite compound (trade name: silver-based inorganic antibacterial agent Zeomic) based on 100 parts by weight of the aqueous polyurethane resin. include

<Example 2-1>

Artificial leather was manufactured in the same manner as in Example 1-1, but the bioplasticizer according to Preparation Example 2 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 2-2>

Artificial leather was manufactured in the same manner as in Example 1-2, but the bioplasticizer according to Preparation Example 2 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 2-3>

Artificial leather was manufactured in the same manner as in Examples 1-3, but the bioplasticizer according to Preparation Example 2 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 2-4>

Artificial leather was manufactured in the same manner as in Examples 1-4, but the bioplasticizer according to Preparation Example 2 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 3-1>

Artificial leather was manufactured in the same manner as in Example 1-1, but the bioplasticizer according to Preparation Example 3 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 3-2>

Artificial leather was manufactured in the same manner as in Example 1-2, but the bioplasticizer according to Preparation Example 3 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 3-3>

Artificial leather was manufactured in the same manner as in Examples 1-3, but the bioplasticizer according to Preparation Example 3 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 3-4>

Artificial leather was manufactured in the same manner as in Examples 1-4, but the bioplasticizer according to Preparation Example 3 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 4-1>

Artificial leather was manufactured in the same manner as in Example 1-1, but the bioplasticizer according to Preparation Example 4 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 4-2>

Artificial leather was manufactured in the same manner as in Example 1-2, but the bioplasticizer according to Preparation Example 4 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 4-3>

Artificial leather was manufactured in the same manner as in Examples 1-3, but the bioplasticizer according to Preparation Example 4 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 4-4>

Artificial leather was manufactured in the same manner as in Examples 1-4, but the bioplasticizer according to Preparation Example 4 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 5-1>

Artificial leather was manufactured in the same manner as in Example 1-1, but the bioplasticizer according to Preparation Example 5 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 5-2>

Artificial leather was manufactured in the same manner as in Example 1-2, but the bioplasticizer according to Preparation Example 5 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 5-3>

Artificial leather was manufactured in the same manner as in Examples 1-3, but the bioplasticizer according to Preparation Example 5 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 5-4>

Artificial leather was manufactured in the same manner as in Examples 1-4, but the bioplasticizer according to Preparation Example 5 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 6-1>

Artificial leather was manufactured in the same manner as in Example 1-1, but the bioplasticizer according to Preparation Example 6 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 6-2>

Artificial leather was manufactured in the same manner as in Example 1-2, but the bioplasticizer according to Preparation Example 6 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 6-3>

Artificial leather was manufactured in the same manner as in Examples 1-3, but the bioplasticizer according to Preparation Example 6 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 6-4>

Artificial leather was manufactured in the same manner as in Examples 1-4, but the bioplasticizer according to Preparation Example 6 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 7-1>

Artificial leather was manufactured in the same manner as in Example 1-1, but the bioplasticizer according to Preparation Example 7 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 7-2>

Artificial leather was manufactured in the same manner as in Example 1-2, but the bioplasticizer according to Preparation Example 7 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 7-3>

Artificial leather was manufactured in the same manner as in Examples 1-3, but the bioplasticizer according to Preparation Example 7 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 7-4>

Artificial leather was manufactured in the same manner as in Examples 1-4, but the bioplasticizer according to Preparation Example 7 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 8-1>

Artificial leather was manufactured in the same manner as in Example 1-1, but the bioplasticizer according to Preparation Example 8 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 8-2>

Artificial leather was manufactured in the same manner as in Example 1-2, but the bioplasticizer according to Preparation Example 8 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 8-3>

Artificial leather was manufactured in the same manner as in Examples 1-3, but the bioplasticizer according to Preparation Example 8 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 8-4>

Artificial leather was manufactured in the same manner as in Examples 1-4, but the bioplasticizer according to Preparation Example 8 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 9-1>

Artificial leather was manufactured in the same manner as in Example 1-1, but the bioplasticizer according to Preparation Example 9 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 9-2>

Artificial leather was manufactured in the same manner as in Example 1-2, but the bioplasticizer according to Preparation Example 9 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 9-3>

Artificial leather was manufactured in the same manner as in Examples 1-3, but the bioplasticizer according to Preparation Example 9 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 9-4>

Artificial leather was manufactured in the same manner as in Examples 1-4, but the bioplasticizer according to Preparation Example 9 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 10-1>

Artificial leather was manufactured in the same manner as in Example 1-1, but the bioplasticizer according to Preparation Example 10 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 10-2>

Artificial leather was manufactured in the same manner as in Example 1-2, but the bioplasticizer according to Preparation Example 10 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 10-3>

Artificial leather was manufactured in the same manner as in Examples 1-3, but the bioplasticizer according to Preparation Example 10 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 10-4>

Artificial leather was manufactured in the same manner as in Examples 1-4, but the bioplasticizer according to Preparation Example 10 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 11-1>

Artificial leather was manufactured in the same manner as in Example 1-1, but the bioplasticizer according to Preparation Example 11 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 11-2>

Artificial leather was manufactured in the same manner as in Example 1-2, but the bioplasticizer according to Preparation Example 11 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 11-3>

Artificial leather was manufactured in the same manner as in Examples 1-3, but the bioplasticizer according to Preparation Example 11 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 11-4>

Artificial leather was manufactured in the same manner as in Examples 1-4, but the bioplasticizer according to Preparation Example 11 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 12-1>

Artificial leather was manufactured in the same manner as in Example 1-1, but the bioplasticizer according to Preparation Example 12 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 12-2>

Artificial leather was manufactured in the same manner as in Example 1-2, but the bioplasticizer according to Preparation Example 12 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 12-3>

Artificial leather was manufactured in the same manner as in Examples 1-3, but the bioplasticizer according to Preparation Example 12 was used instead of the bioplasticizer according to Preparation Example 1.

<Example 12-4>

Artificial leather was manufactured in the same manner as in Examples 1-4, but the bioplasticizer according to Preparation Example 12 was used instead of the bioplasticizer according to Preparation Example 1.

<Reference Example 1>

Artificial leather was manufactured in the same manner as in Example 1-2, but instead of the bioplasticizer according to Example 1, a phthalate-based plasticizer, DINP (Di-(iso-nonyl) phthalate) was used, and the first and second Instead of 2 composite flame retardants, 5 parts by weight of Sb ₂ O ₃ were used, respectively.

<Comparative Example 1-1>

Artificial leather was manufactured in the same manner as in Example 1-1, but the plasticizer according to Comparative Preparation Example 1 was used instead of the bioplasticizer according to Example 1.

<Reference example 2>

Artificial leather was manufactured in the same manner as in Example 1-2, but antimony trioxide (Sb ₂ O ₃ ) was used as both the first composite flame retardant and the second composite flame retardant.

<Comparative Example 2-1>

Artificial leather was manufactured in the same manner as in Example 2-1, but the plasticizer according to Comparative Preparation Example 2 was used instead of the bioplasticizer according to Example 2.

<Reference Example 3>

Artificial leather was manufactured in the same manner as in Example 2-2, but antimony trioxide (Sb ₂ O ₃ ) was used as both the first composite flame retardant and the second composite flame retardant.

<Comparative Example 3-1>

Artificial leather was manufactured in the same manner as in Example 3-1, but the plasticizer according to Comparative Preparation Example 3 was used instead of the bioplasticizer according to Example 3.

<Reference example 4>

Artificial leather was manufactured in the same manner as in Example 3-2, but antimony trioxide (Sb ₂ O ₃ ) was used as both the first composite flame retardant and the second composite flame retardant.

<Comparative Example 4-1>

Artificial leather was manufactured in the same manner as in Example 4-1, but the plasticizer according to Comparative Preparation Example 4 was used instead of the bioplasticizer according to Example 4.

<Reference Example 5>

Artificial leather was manufactured in the same manner as in Example 4-2, but antimony trioxide (Sb ₂ O ₃ ) was used as both the first composite flame retardant and the second composite flame retardant.

<Comparative Example 5-1>

Artificial leather was manufactured in the same manner as in Example 5-1, but the plasticizer according to Comparative Preparation Example 5 was used instead of the bioplasticizer according to Example 5.

<Reference Example 6>

Artificial leather was manufactured in the same manner as in Example 5-2, but antimony trioxide (Sb ₂ O ₃ ) was used as both the first composite flame retardant and the second composite flame retardant.

[Experimental Example 1: Physical property test of artificial leather specimen]

The physical properties of the artificial leather specimen according to the Preparation Example were evaluated by MS 321-08.

1) Tensile strength (kgf/30mm)

If it is 24 kgf / 30 mm or more in the longitudinal direction (L) and 12 kgf / 30 mm or more in the width direction (W), it is evaluated as meeting the artificial leather standard for automobiles.

2) Elongation (%)

When it was 25% or more in the longitudinal direction (L) and 120% or more in the width direction (W), it was evaluated as meeting the artificial leather standard for automobiles.

3) Tear strength (kgf)

When it was 1.5 kgf or more in the longitudinal direction (L) and 1.5 kgf or more in the width direction (W), it was evaluated as meeting the artificial leather standard for automobiles.

4) Peel strength (kgf/30mm)

When it was 1.8 kgf/30mm or more in the longitudinal direction (L) and 1.8 kgf/30mm or more in the width direction (W), it was evaluated as meeting the artificial leather standard for automobiles.

5) Burst strength (kgf/cm ² )

When 9 kgf/cm ² or more was satisfied, it was evaluated as meeting the standard value for artificial leather for automobiles.

6) Surface hardness (Shore A)

When the Shore A hardness range of 40 to 70 was satisfied, it was evaluated as meeting the standard value for artificial leather for automobiles.

direction Example 1-1 Example 1-2 Example 1-3 Example 1-4 Comparative Example 1-1 Comparative Example 1-2 Seal
robbery
(kg/30mm) L 26.95 25.60 28.30 25.87 27.49 25.41 W 17.41 16.54 18.28 16.71 17.76 17.77 elongation
(%) L 62.15 59.04 65.26 59.66 63.39 59.54 W 180.63 171.60 189.66 173.40 184.24 177.57 tear strength
(kgf) L 3.71 3.52 3.90 3.56 3.78 3.56 W 4.21 4.00 4.42 4.04 4.29 3.98 peel strength
(kg/30mm) L 3.88 3.69 4.07 3.72 3.96 3.54 W 3.45 3.28 3.62 3.31 3.52 3.28 burst strength
(kgf/cm ² ) 12.5 11.88 13.13 12.00 12.75 11.84 Surface hardness (Shore A) 45 47 52 50 50 48

As shown in Table 4, Examples 1-1 to 1-4 are evaluated to conform to the physical properties of artificial leather for automobiles, and the rest of the Examples also use the same fiber base layer, so Example 1-4 It can be inferred that they exhibit mechanical properties similar to those of 1 to 1-4.

[Experimental Example 2: Test for fogging, cold resistance, combustibility, smell and detection of artificial leather specimens]

Fogging test, cold resistance test, combustibility, odor grade evaluation, and detection of phthalate-based compound and Sb ₂ O ₃ were evaluated for the artificial leather specimen according to the preparation example.

1) Fogging test (soaking value spec)

A fogging test was performed using an immersion tester and an integrating sphere-type light transmittance measuring device according to MS300-54 of the artificial leather according to the above preparation example. Specifically, the immersion test apparatus includes a beaker and an oil bath capable of heating the beaker. The fogging test measurement method is the step of putting the artificial leather specimen according to the preparation example into the beaker with the film side up, covering the top of the beaker with a steel lid having a round hole with a diameter of 40 mm, and the hole part is 50 wide Placing a transparent glass plate (soaked at 1% or less) with a length of 50 mm and a thickness of 3 to 5 mm, and after heating at 100 ° C. for 5 hours in an oil bath, take out the glass plate and use the integrating sphere type light transmittance measuring device It consists of a step of measuring three places in the central part of the glass plate according to the order of Table 5, and a step of calculating the soaking (%) according to Equation 1 below.

[Equation 1]

Fogging% = (T4/T2-T3/T1) X 100

If the impregnation of the artificial leather specimen according to the Preparation Example is 'exceeding 15%', it is unsuitable for artificial leather for automobiles, and if it is 'less than 15%', it is suitable for artificial leather for automobiles.

order glass plate TRAP With standard white plate Galvanometer scale measurement One unused unused attachment use T1 (aligned to 100) amount of incident light 2 attachment use unused attachment use T2 total light transmittance 3 unused attachment use unused T3 The amount of light scattered by the device 4 attachment use attachment use unused T4 The amount of light scattered by the device and the glass plate

2) Cold resistance test (bally flex/standard: MS 300-31)

The gap between the upper clamp and the lower clamp is widened so that the thickness of the artificial leather specimen according to the manufacturing example is twice or more. After mounting the artificial leather specimen according to the manufacturing example to the upper clamp and the lower clamp, respectively, the artificial leather specimen is tightened so as to be fixed. A bending test is performed on the fixed artificial leather specimen 5 or more times, and the presence or absence of cracks or fine cracks in the bent portion is recorded with the naked eye and a magnifying glass. When any one of cracks, microcracks, and whitening occurred, it was marked as X, and when cracks, fine cracks, and whitening did not occur, it was marked as O.

3) Flammability test (standard: MS300-08)

The measured value (mm/min) of Equation 2 below was measured in the length direction (L) and width direction (W) of the artificial leather specimen according to the above Preparation Example to confirm whether the standard was satisfied. Specifically, when the combustion speed was 80 mm / min or less, it was evaluated as meeting the criteria, when it met the criteria, it was evaluated as O, and when it did not meet the criteria, it was evaluated as X.

[Equation 2]

4) Odor level (standard: MS 321-08)

If the grade 3 or higher was satisfied, it was evaluated as meeting the standard value of artificial leather for automobiles.

5) Confirmation of detection of phthalate compounds

IEC 62321-8 ; 2017 GC / MS evaluated whether at least one of DEHP, DBP, BBP, DIBP, DIBP, DIDP, DINP, DNOP, DEP, DPP and DNHP, which are phthalate compounds, was detected. When at least one of the phthalate-based compounds was detected, it was evaluated as 'O', and when it was not detected, it was evaluated as 'X'.

6) Detection of Sb ₂ O ₃

When the Sb ₂ O ₃ flame retardant was not used, it was marked as 'X' because it was not detected, and when the Sb ₂ O ₃ flame retardant was used, it was marked as 'O'.

Fogging (%) cold resistance combustibility odor rating Detection of phthalates Sb ₂ O ₃
detection Reference example 1 3 O X 3 O O Comparative Example 1-1 3 O X 3 O X Reference example 2 3 O O 3 X O Example 1-1 5 O X 3 X X Example 1-2 5 O O 3 X X Example 1-3 5 O O 3 X X Comparative Example 2-1 16 X X 4 X X Reference example 3 16 X O 4 X O Example 2-1 5 O X 3 X X 2-2 on implementation 5 O O 3 X X Example 2-3 5 O O 3 X X Comparative Example 3-1 25 O X 3 X X Reference example 4 25 O O 3 X O Example 3-1 5 O X 3 X X Example 3-2 5 O O 3 X X Example 3-3 5 O O 3 X X

Fogging (%) cold resistance combustibility odor rating Detection of phthalates Sb ₂ O ₃
detection Comparative Example 4-1 2 X X 3 X X Reference Example 5 2 X O 3 X O Example 4-1 5 O X 3 X X Example 4-2 5 O O 3 X X Example 4-3 5 O O 3 X X Comparative Example 5-1 16 X X 4 X X Reference example 6 16 X O 4 X O Example 5-1 5 O X 3 X X Example 5-2 5 O O 3 X X Example 5-3 5 O O 3 X X Example 6-1 9 O X 3 X X Example 6-2 10 O O 3 X X Example 6-3 8 O O 3 X X Example 7-1 8 O X 3 X X Example 7-2 10 O O 3 X X Example 7-3 6 O O 3 X X

Fogging (%) cold resistance combustibility odor rating Detection of phthalates Sb ₂ O ₃
detection Example 8-1 9 O X 3 X X Example 8-2 11 O O 3 X X Example 8-3 13 O O 3 X X Example 9-1 10 O X 3 X X Example 9-2 9 O O 3 X X Example 9-3 12 O O 3 X X Example 10-1 11 O X 3 X X Example 10-2 10 O O 3 X X Example 10-3 11 O O 3 X X Example 11-1 9 O X 3 X X Example 11-2 10 O O 3 X X Example 11-3 10 O O 3 X X Example 12-1 8 O X 3 X X Example 12-2 9 O O 3 X X Example 12-3 10 O O 3 X X

Referring to Tables 6 to 8, unlike Comparative Examples, all examples do not use phthalate-based compounds and Sb ₂ O ₃ flame retardants, so harmless to the human body and eco-friendly artificial leather can be implemented. In addition, it can be seen that the wetness of all examples is less than 15, which is suitable for artificial leather for automobiles, and the cold resistance and odor ratings are all evaluated as suitable. In the case of combustibility, it was confirmed that the flame retardant, in the case of the embodiment using the first or second composite flame retardant, satisfies all of the combustion rate standards.

[Experimental Example 3: Antibacterial effect test of artificial leather specimen]

Staphylococcus aureus ATCC ^® 6538P as strain 1 and E. coli ( Escherichia coli ATCC ^® 8739) as strain 2 were applied to the artificial leather specimen (100 mm x 100 mm) according to the preparation example prepared using the hot press equipment (CARVER). and strain 3, Klebsiella pneumoniae ATCC ^® 4352, were respectively inoculated to conduct an antibacterial test (inoculation amount: 0.4 mL) according to the ISO 22196 method.

Antibacterial activity was calculated according to Equation 3 and shown in Tables 9 to 11 below. It can be seen that the higher the antibacterial activity, the better the antibacterial effect.

[Equation 3]

Antimicrobial activity (%) = (M _b -M _c /M _b ) X 100

In Equation 3, M _b means the number of colonies (unit: number of bacteria/cm ² ) after 24 hours of the artificial leather specimen according to the control group, and M _c is the number of colonies after 24 hours of the artificial leather specimen according to the above preparation example. After that, it means the number of colonies (unit: number of bacteria/cm ² ). The control group (blank) is an artificial leather specimen not treated with an antimicrobial agent.

1) Antibacterial effect in initial conditions

The number of bacteria immediately after inoculating the inoculation solution on the artificial leather specimen according to the Preparation Example was compared with that of the control group, and an antibacterial test was conducted according to the ISO 22196 method.

2) Heat aging resistance

An antibacterial test was conducted according to the ISO 22196 method to see if the antibacterial effect was maintained even after the artificial leather specimen according to the Preparation Example was left in an 80 ° C. thermostat (oven) for 300 hours.

3) Moisture aging resistance

An antibacterial test was conducted according to the ISO 22196 method to see if the antibacterial effect was maintained even after the artificial leather specimen according to the Preparation Example was left in a constant temperature and humidity chamber at a temperature of 50 ± 2 ° C and a humidity of 98 ± 2% for 168 hours.

4) Light aging resistance

Light of 84 MJ/m ² (300 to 400 nm) is irradiated to the artificial leather specimen according to the Preparation Example placed in the chamber (internal humidity: 50 ± 5 ° C) (irradiance: 65.5 ± 2.5 W / m ² (300 to 400 nm)) ), an antibacterial test was conducted according to the ISO 22196 method to see if the antibacterial effect was maintained even after light resistance.

Unit: Antibacterial activity (%) Example
1-1 Example 1-4 Example 2-1 Example 2-4 Example 3-1 Example 3-4 Example 4-1 Example 4-4 Example 5-1 Example 5-4 Early strain 1 0 99.99 0 99.99 0 99.99 0 99.99 0 99.99 strain 2 0 99.99 0 99.99 0 99.99 0 99.99 0 99.99 strain 3 0 99.99 0 99.99 0 99.99 0 99.99 0 99.99 after heat resistance strain 1 0 99.9 0 99.9 0 99.9 0 99.9 0 99.9 strain 2 0 99.9 0 99.9 0 99.9 0 99.9 0 99.9 strain 3 0 99.9 0 99.9 0 99.9 0 99.9 0 99.9 inroad
after strain 1 0 99 0 99 0 99 0 99 0 99 strain 2 0 99 0 99 0 99 0 99 0 99 strain 3 0 99 0 99 0 99 0 99 0 99 After lightening strain 1 0 99.9 0 99.9 0 99.9 0 99.9 0 99.9 strain 2 0 99.9 0 99.9 0 99.9 0 99.9 0 99.9 strain 3 0 99.9 0 99.9 0 99.9 0 99.9 0 99.9 1) Strain 1: Staphylococcus aureus ATCC ^® 6538P
2) Strain 2: Escherichia coli ATCC ^® 8739
3) Strain 3: Klebsiella pneumoniae ATCC ^® 4352

Unit: Antibacterial activity (%) Example 6-1 Example 6-4 Example
7-1 Example
7-4 Example
8-1 Example
8-4 Example
9-1 Example 9-4 Early strain 1 0 99.99 0 99.99 0 99.99 0 99.99 strain 2 0 99.99 0 99.99 0 99.99 0 99.99 strain 3 0 99.99 0 99.99 0 99.99 0 99.99 heat resistance
after strain 1 0 99.9 0 99.9 0 99.9 0 99.9 strain 2 0 99.9 0 99.9 0 99.9 0 99.9 strain 3 0 99.9 0 99.9 0 99.9 0 99.9 inroad
after strain 1 0 99 0 99 0 99 0 99 strain 2 0 99 0 99 0 99 0 99 strain 3 0 99 0 99 0 99 0 99 lightproof
after strain 1 0 99.9 0 99.9 0 99.9 0 99.9 strain 2 0 99.9 0 99.9 0 99.9 0 99.9 strain 3 0 99.9 0 99.9 0 99.9 0 99.9 1) Strain 1: Staphylococcus aureus ATCC ^® 6538P
2) Strain 2: Escherichia coli ATCC ^® 8739
3) Strain 3: Klebsiella pneumoniae ATCC ^® 4352

Unit: Antibacterial activity (%) Example
10-1 Example
10-4 Example
11-1 Example
11-4 Example
12-1 Example
12-4 Early strain 1 0 99.99 0 99.99 0 99.99 strain 2 0 99.99 0 99.99 0 99.99 strain 3 0 99.99 0 99.99 0 99.99 heat resistance
after strain 1 0 99.9 0 99.9 0 99.9 strain 2 0 99.9 0 99.9 0 99.9 strain 3 0 99.9 0 99.9 0 99.9 inroad
after strain 1 0 99 0 99 0 99 strain 2 0 99 0 99 0 99 strain 3 0 99 0 99 0 99 lightproof
after strain 1 0 99.9 0 99.9 0 99.9 strain 2 0 99.9 0 99.9 0 99.9 strain 3 0 99.9 0 99.9 0 99.9 1) Strain 1: Staphylococcus aureus ATCC ^® 6538P
2) Strain 2: Escherichia coli ATCC ^® 8739
3) Strain 3: Klebsiella pneumoniae ATCC ^® 4352

Referring to Tables 9 to 11, in the case of Example n-4, it can be confirmed that the antibacterial effect is significantly superior to that of Example n-1 in which the antimicrobial agent is not treated (where n is a natural number and is 1 to 12) .

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concept of the present invention defined in the following claims are also present. It falls within the scope of the right of invention.

10: fiber base layer
20: foam layer
30: skin layer
40: surface treatment layer
100: bio artificial leather

Claims (24)

a fiber base layer; and
A foam layer disposed on the fiber base layer; including,
The foam layer,
A first polyvinyl chloride resin and
Comprising a first bioplasticizer
Bio artificial leather. According to claim 1,
The foam layer,
Further comprising a first composite flame retardant
Bio artificial leather. According to claim 2,
The first composite flame retardant,
A first hypophosphate-based flame retardant and a first phosphorus-nitrogen-based flame retardant comprising
Bio artificial leather. According to claim 2,
The first composite flame retardant,
containing aluminum hydroxide and magnesium hydroxide
Bio artificial leather. According to claim 1,
The first bioplasticizer,
A first non-phthalate-based compound and
Comprising a first trimellitate-based compound
Bio artificial leather. According to claim 5,
The first non-phthalate-based compound,
Containing any one selected from the group consisting of dioctyl terephthalate, dioctyl isophthalate, and combinations thereof,
The first trimellitate-based compound,
Tris (2-ethylhexyl) trimellitate (tris (2-ethylhexyl) trimellitate), triisononyl trimellitate (triisononyl trimellitate), and any one selected from the group consisting of combinations thereof
Bio artificial leather. According to claim 5,
The first bioplasticizer,
Further comprising a first natural oil-derived compound
Bio artificial leather. According to claim 7,
Based on the total weight of the first bioplasticizer
The content of the first natural oil-derived compound is 18 to 49% by weight,
The content of the first non-phthalate-based compound is 18 to 49% by weight,
The content of the first trimellitate-based compound is 18 to 49% by weight
Bio artificial leather. According to claim 7,
The first natural oil-derived compound,
A compound derived from a first natural oil,
The first natural oil,
selected from the group consisting of soybean oil, palm oil, olive oil, tall oil, cottonseed oil, linseed oil, safflower oil, sunflower oil, canola oil, rapeseed oil, jatropha oil, algae oil, corn oil, tung oil and mixtures thereof including any
Bio artificial leather. According to claim 1,
The foam layer,
Based on 100 parts by weight of the first polyvinyl chloride resin, comprising 20 to 80 parts by weight of the first bioplasticizer
Bio artificial leather. According to claim 1,
a skin layer disposed on the foam layer; further comprising
Bio artificial leather. According to claim 11,
The skin layer,
a second polyvinyl chloride resin; and
Comprising a second bioplasticizer
Bio artificial leather. According to claim 12,
The second bioplasticizer,
a second non-phthalate-based compound and
Including the second trimellitate-based compound
Bio artificial leather. According to claim 13,
The second non-phthalate-based compound,
Containing any one selected from the group consisting of dioctyl terephthalate, dioctyl isophthalate, and combinations thereof,
The second trimellitate-based compound,
Tris (2-ethylhexyl) trimellitate (tris (2-ethylhexyl) trimellitate), triisononyl trimellitate (triisononyl trimellitate), and any one selected from the group consisting of combinations thereof
Bio artificial leather. According to claim 13,
The second bioplasticizer,
Further comprising a second natural oil-derived compound
Bio artificial leather. According to claim 15,
The second natural oil-derived compound,
A compound derived from a second natural oil,
The second natural oil,
selected from the group consisting of soybean oil, palm oil, olive oil, tall oil, cottonseed oil, linseed oil, safflower oil, sunflower oil, canola oil, rapeseed oil, jatropha oil, algae oil, corn oil, tung oil and mixtures thereof including any
Bio artificial leather. According to claim 15,
Based on the total weight of the second bioplasticizer
The content of the second natural oil-derived compound is 18 to 49% by weight,
The content of the second non-phthalate-based compound is 18 to 49% by weight,
The content of the second trimellitate-based compound is 18 to 49% by weight,
Bio artificial leather. According to claim 12,
The skin layer,
Further comprising a second composite flame retardant
Bio artificial leather. According to claim 11,
a surface treatment layer disposed on the skin layer; further comprising
Bio artificial leather. According to claim 19,
The surface treatment layer,
polyurethane resin
1 to 10 parts by weight of an antimicrobial agent based on 100 parts by weight of the polyurethane resin,
The antibacterial agent is a silver-zeolite compound
Bio artificial leather. According to claim 1,
The first bioplasticizer is
Containing any one selected from the group consisting of myristic acid, lauric acid and adipic acid, and combinations thereof
Bio artificial leather. According to claim 12,
The second bioplasticizer,
Containing any one selected from the group consisting of myristic acid, lauric acid and adipic acid, and combinations thereof
Bio artificial leather. According to claim 2,
The foam layer,
Further comprising a chlorinated polyethylene or first polyester plasticizer
Bio artificial leather. According to claim 18,
The skin layer,
Further comprising chlorinated polyethylene or a second polyester plasticizer
Bio artificial leather.

Images