KR102624900B1 - Single layer flooring material and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a single-layer flooring and a method of manufacturing the same. The single-layer flooring of the present invention is a single layer comprising styrene-butadiene copolymer, styrene-(meth)acrylate copolymer, and thermoplastic polyurethane (TPU). It relates to layered flooring and its manufacturing method.

Description

Single layer flooring material and method for manufacturing the same}

The present invention relates to a single-layer flooring and a method of manufacturing the same. The single-layer flooring of the present invention is a single layer comprising styrene-butadiene copolymer, styrene-(meth)acrylate copolymer, and thermoplastic polyurethane (TPU). It relates to layered flooring and its manufacturing method.

In general, flooring materials are mainly used to finish the floors of residential or commercial buildings. They provide a hygienic space by blocking dust and cold from the cement floor, and are printed with beautiful patterns in various colors to suit customer tastes. It also has a decorative effect, such as changing the indoor atmosphere to a cozy atmosphere.

Polyvinyl chloride or rubber materials are widely used as the flooring material.

For example, Republic of Korea Patent Publication No. 10-2013-0026629 shows a homogeneous type flooring material in FIG. 2, that is, a single-layer flooring material having a polyvinyl chloride chip layer and an ultraviolet curing paint layer applied to the surface of the polyvinyl chloride chip layer. A single-layer flooring structure has been disclosed.

However, flooring materials made of polyvinyl chloride as described above have serious problems in that a large amount of total volatile organic compounds are emitted and phthalate-based plasticizers added to provide flexibility are leached out, greatly adversely affecting human safety.

In addition, flooring materials made of polyvinyl chloride have a glass transition temperature (Tg) of 15-30°C, so they become hard at low temperatures and have the problem of deteriorating constructability in low-temperature conditions such as winter.

On the other hand, as the processability of the flooring material made of rubber is reduced due to crosslinking through the vulcanization process, it is inevitably made of single-colored, monotonous chips, which deteriorates the beauty of the exterior, and not only is it impossible to recycle, but additional products are generated by the vulcanization process. Accordingly, there was a problem that eco-friendliness was deteriorated.

Therefore, in order to solve the above problems, there is an urgent need for the development of a single-layer flooring material made of non-polyvinyl chloride material and non-rubber material.

KR 10-2013-0026629A (2013.03.14.)

In order to solve the above problems, the purpose of the present invention is to provide a single-layer flooring material composed of a non-polyvinyl chloride material and a non-rubber material and a method for manufacturing the same.

In order to achieve the above object, the present invention is 5-30% by weight of styrene-butadiene copolymer, 3-20% by weight of styrene-(meth)acrylate copolymer, and 3-20% by weight of thermoplastic polyurethane (TPU). %, but provides a single-layer flooring material in which the total volatile organic compound emission (Small Chamber) is 0.1 mg/m ² h or less.

In addition, the present invention includes the steps of producing two or more sheet compositions each having different colors (S1); Manufacturing a sheet by rolling the two or more sheet compositions prepared above with a plywood calender (S3); Grinding the sheet to produce chips (S5); And a step (S7) of manufacturing a single-layer flooring by rolling the manufactured chips, wherein the single-layer flooring contains 5-30% by weight of styrene-butadiene copolymer and styrene-(meth). ) Contains 3-20% by weight of acrylate copolymer and 3-20% by weight of thermoplastic polyurethane (TPU), but the total volatile organic compound emission (Small Chamber) is 0.1 mg/m ² h or less, A method for manufacturing a single-layer flooring material is provided.

The single-layer flooring of the present invention is made of non-polyvinyl chloride material and non-rubber material, so it is environmentally friendly, has excellent (low-temperature) flexibility, has excellent constructability, has a beautiful appearance, and has improved other physical properties.

1 is a cross-sectional view schematically showing an example of a single-layer flooring material of the present invention.
Figure 2 is a cross-sectional view schematically showing an example of a single-layer flooring material in which a UV paint layer is further added to the upper surface of the single-layer flooring material of the present invention.

Hereinafter, the present invention will be described in detail along with the accompanying drawings.

The present invention includes 5-30% by weight of styrene-butadiene copolymer, 3-20% by weight of styrene-(meth)acrylate copolymer, and 3-20% by weight of thermoplastic polyurethane (TPU), but the total volatile organic It relates to a single-layer flooring material (10) in which the emission amount of the compound (Small Chamber) is 0.1 mg/m ² h or less (see FIG. 1).

The styrene-butadiene copolymer can be used to ensure (low-temperature) flexibility, compression recovery, and abrasion resistance of the single-layer flooring (10).

In the present invention, (low temperature) flexibility means both flexibility at room temperature and flexibility in the low temperature range (0-10°C).

The styrene-butadiene copolymer may be polymerized using at least a styrene-based monomer and a butadiene-based monomer. Optionally, the styrene-butadiene copolymer may be polymerized using other comonomers in addition to the styrene-based monomer and butadiene-based monomer.

The styrene-based monomers include, for example, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl- It may be one or more selected from the group consisting of 4-benzylstyrene and 4-(phenylbutyl)styrene. As a specific example, the styrene-based monomer may be styrene.

For example, the butadiene-based monomer may be one or more selected from the group consisting of butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. As a specific example, the butadiene-based monomer may be 1,3-butadiene.

For example, the other comonomer may be one or more selected from the group consisting of ethylene, propylene, vinyl chloride, vinyl fluoride, polyvinyl alcohol, or vinyl acetate.

In the styrene-butadiene copolymer, the bonding form of the styrene-based monomer and the butadiene-based monomer is not particularly limited, and the bonding form may be, for example, one or more types selected from the group consisting of straight chain, branched, and radial. there is.

In the styrene-butadiene copolymer, the copolymerization form may be, for example, one or more types selected from the group consisting of alternating, random, and block.

As a specific example, the styrene-butadiene copolymer may be a block copolymer of styrene and butadiene having viscoelasticity suitable for calendering. In a more specific example, the styrene-butadiene copolymer includes 50-90% by weight, 60-80% by weight, or 65-75% by weight of styrene and 10-50% by weight, 20-40% by weight, or 25-35% by weight of butadiene. doing It may be a block copolymer.

Optionally, when the styrene-butadiene copolymer is polymerized using another comonomer, the content of the other comonomer may be 10% by weight or less, 5% by weight or less, or 1% by weight or less.

The styrene-butadiene copolymer may have a melt volume rate of 5-20 cm ³ /10 min or 7-15 cm ³ /10 min. The melt volume rate may be measured by ISO 1133 (200°C, 5kg). If the melt volume rate of the styrene-butadiene copolymer is below the above range, compatibility with other components may be reduced, and if it is above the above range, processability may be reduced.

The styrene-butadiene copolymer may have a hardness of 40-80 or 50-70. The hardness may be Shore D hardness measured by ISO 868. If the hardness of the styrene-butadiene copolymer is below the above range, dimensional stability and scratch resistance may be reduced, and if it is above the above range, (low temperature) flexibility, compression recovery, and abrasion resistance may be reduced.

The styrene-butadiene copolymer may have a Vicat softening point of 20-60°C or 30-50°C. The Vicat softening point of the styrene-butadiene copolymer may be measured by ISO 306 (50N, 50°C/h).

The styrene-butadiene copolymer may have a flexural strength of 5-30 MPa, or 10-25 MPa. The flexural strength may be measured by ISO 178 (23°C). If the flexural strength of the styrene-butadiene copolymer is below the above range, dimensional stability may be reduced, and if it is above the above range, (low temperature) flexibility and compression recovery may be reduced.

The styrene-butadiene copolymer may have a weight average molecular weight of 100,000-250,000 g/mol or 150,000-200,000 g/mol. If the weight average molecular weight of the styrene-butadiene copolymer is less than the above range, moldability, compression recovery, and dimensional stability may be reduced, and if it exceeds the above range, processability and lightness may be reduced. Here, the weight average molecular weight refers to the average molecular weight obtained by averaging the molecular weights of the component molecular species of a polymer compound with molecular weight distribution by weight fraction. The weight average molecular weight can be measured by methods known in the art.

The styrene-butadiene copolymer may be included in an amount of 5-30% by weight or 8-25% by weight in the single-layer flooring (10). If the styrene-butadiene copolymer is contained in an amount below the above range, (low temperature) flexibility, compression recovery, and abrasion resistance may be reduced, and if the styrene-butadiene copolymer is contained in an amount exceeding the above range, dimensional stability and scratch resistance may be reduced.

The styrene-(meth)acrylate copolymer is intended to secure mechanical properties such as dimensional stability and scratch resistance, and may be polymerized using a styrene-based monomer and a (meth)acrylate compound.

Since the styrene-based monomer has been described above, repeated descriptions are omitted.

The (meth)acrylate compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, 2-methyl-2-nitropropyl ( Meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, s-butyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, t -Pentyl (meth)acrylate, 3-pentyl (meth)acrylate, 2,2-dimethylbutyl (meth)acrylate, n-hexyl (meth)acrylate, cetyl (meth)acrylate, n-octyl (meth)acrylate ) It may be one or more types selected from the group consisting of acrylate, 2-ethylhexyl (meth)acrylate, 4-methyl-2-propylpentyl (meth)acrylate, and n-octadecyl (meth)acrylate. As a specific example, the (meth)acrylate compound may be methyl (meth)acrylate.

In the styrene-(meth)acrylate copolymer, the bonding form of the styrene-based monomer and the (meth)acrylate compound is not particularly limited, and the bonding form is, for example, straight chain, branched, and radial. There may be one or more types selected from.

In the styrene-(meth)acrylate copolymer, the form of the copolymerization of the styrene-based monomer and the (meth)acrylate compound is not particularly limited, and for example, alternating, random, and block. It may be one or more types selected from the group consisting of:

As a specific example, the styrene-(meth)acrylate copolymer may be a random copolymer of styrene and methyl(meth)acrylate suitable for improving the dimensional stability and scratch resistance of a single-layer flooring material. In a more specific example, the styrene-(meth)acrylate copolymer is 50-90% by weight, 60-80% by weight, or 70-80% by weight of styrene and 10-50% by weight, 20-40% by weight of methyl (meth)acrylate. % or 20-30% by weight of random copolymer.

The styrene-(meth)acrylate copolymer may have a melt volume rate of 10-50cm ³ /10min or 20-40cm ³ /10min. The melt volume rate may be measured by ISO 1133 (220° C., 10 kg). If the melt volume rate of the styrene-(meth)acrylate copolymer is below the above range, compatibility with other components may be reduced, and if it is above the above range, processability may be reduced.

The styrene-(meth)acrylate copolymer may have a hardness of 150-190 MPa or 160-180 MPa. The hardness may be ball indentation measured by ISO 2039-1. If the hardness of the styrene-(meth)acrylate copolymer is less than the above range, dimensional stability and scratch resistance may be reduced, and if it is greater than the above range, (low temperature) flexibility, compression recovery, and abrasion resistance may be reduced.

The styrene-(meth)acrylate copolymer may have a Vicat softening point of 80-120°C or 90-110°C. The Vicat softening point of the styrene-(meth)acrylate copolymer may be measured by ISO 306 (50N, 50°C/h).

The styrene-(meth)acrylate copolymer may have a flexural strength of 80-120 MPa, or 90-110 MPa. The flexural strength may be measured by ISO 178 (23°C). If the flexural strength of the styrene-(meth)acrylate copolymer is below the above range, dimensional stability may be reduced, and if it is above the above range, (low temperature) flexibility and compression recovery may be reduced.

The styrene-(meth)acrylate copolymer may have a weight average molecular weight of 100,000-250,000 g/mol or 120,000-200,000 g/mol. If the weight average molecular weight of the styrene-(meth)acrylate copolymer is less than the above range, moldability, compression recovery, and dimensional stability may be reduced, and if it exceeds the above range, processability and lightness may be reduced.

The styrene-(meth)acrylate copolymer may be included in an amount of 3-20% by weight or 5-18% by weight in the single-layer flooring (10). If the styrene-(meth)acrylate copolymer is contained below the above range, dimensional stability and scratch resistance may be reduced, and if contained above the above range, (low temperature) flexibility, compression recovery, and abrasion resistance may be reduced. there is.

The thermoplastic polyurethane (TPU) is used to ensure chemical resistance and compression recovery, and is, for example, selected from the group consisting of polyester, polyether, and polycaprolactone. There may be more than one type. As a specific example, the thermoplastic polyurethane may be a polyester-based polyurethane with excellent chemical resistance.

The thermoplastic polyurethane may have a hardness of 75-95 or 80-90. The hardness may be Shore A hardness measured by ASTM D2240. Since the thermoplastic polyurethane has a hardness in the above range, it can have excellent (low temperature) flexibility, compression recovery, and dimensional stability.

The thermoplastic polyurethane may have an ultimate elongation of 350-550% or 400-500%. The maximum elongation may be measured by ASTM D412. Since the thermoplastic polyurethane has a maximum elongation within the above range, it can have excellent (low-temperature) flexibility and compression recovery.

The thermoplastic polyurethane may be included in 3-20% by weight or 5-18% by weight in the single-layer flooring (10). If the thermoplastic polyurethane is included in an amount less than the above range, chemical resistance and compression recovery may be reduced, and if the thermoplastic polyurethane is contained in an amount exceeding the above range, the processability may be reduced, such as chips detaching during molding of the single-layer flooring 10.

The single-layer flooring 10 may further include a filler. The filler is for compression recovery, dimensional stability, and flame retardancy, and may be, for example, one or more types selected from the group consisting of coal, talc, fly ash, and blast furnace slag. The filler may be isotropic, and in this case, particles of an appropriate size may be selected and used taking into account both the economic effect and the effect of improving physical properties. As a specific example, the filler may be carbon dioxide (CaCO ₃ ), which is advantageous in terms of price and versatility and can increase durability.

The filler may be included in 40-80% by weight or 45-78% by weight in the single-layer flooring (10). If the filler is included in amounts below the above range, compression recovery, flame retardancy and dimensional stability may be reduced, and pulverization during chip molding may be reduced, and if the filler is contained in excess of the above range, (low temperature) flexibility, wear resistance and lightness may be reduced. This may deteriorate.

The single-layer flooring 10 may further include mineral oil. The mineral oil acts as a softener and may be used to control moldability and hardness. For example, the mineral oil may be one or more selected from the group consisting of paraffinic, naphthenic, and aromatic oils. As a specific example, the mineral oil may be a paraffin-based oil with excellent weather resistance and light resistance.

The mineral oil may have a kinematic viscosity of 50-150mm ² /s or 70-130mm ² /s at 40°C. The kinematic viscosity may be measured according to ASTM D 445. If the kinematic viscosity of the mineral oil is below the above range, moldability and (low-temperature) flexibility may be reduced, and if it is above the above range, mechanical properties such as dimensional stability may be reduced.

The mineral oil may be contained in 0.1-10% by weight or 0.5-5% by weight in the single-layer flooring (10). If the mineral oil is contained below the above range, workability and wear resistance may be reduced due to reduced flexibility (at low temperatures), and if contained above the above range, compression recovery, dimensional stability and scratch resistance may be reduced.

The single-layer flooring 10 may optionally further include one or more selected from the group consisting of flame retardants, antioxidants, lubricants, and pigments, and the content is not particularly limited.

For example, the flame retardant may be at least one selected from the group consisting of metal hydroxides including aluminum hydroxide and magnesium hydroxide, phosphorus-based flame retardants, and ammonium pyrophosphate.

For example, the antioxidant may be one or more types selected from the group consisting of phenol-based, sulfur-based, and phosphorus-based antioxidants.

For example, the lubricant can be used alone or in combination with stearic acid, a saturated higher fatty acid with 18 carbon atoms corresponding to an eco-friendly lubricant, or higher fatty acids.

For example, the pigment may be one or more types selected from the group consisting of colored pigments of various colors such as white, blue, black, and yellow.

In addition to the additives listed above, if necessary to adjust physical properties, etc., various additives known in the art can be used, and their type and content are not particularly limited.

The single-layer flooring 10 may have a thickness of 1-5 mm, or 1.5-3.5 mm. If the thickness of the single-layer flooring 10 is less than the above range, the feeling of walking may be reduced, and if the thickness is more than the above range, the manufacturing cost may increase.

The single-layer flooring 10 may optionally further include a UV paint layer 20 on its top (see FIG. 2). The UV paint layer 20 can be formed by applying UV curable paint to the entire top of the single-layer flooring 10 and then irradiating it with ultraviolet rays.

The UV paint layer 20 can prevent contaminants from penetrating into the single-layer flooring 10 and can have the advantage of facilitating removal of surface contamination when it occurs.

The UV paint layer 20 may have a thickness of 0.001-1.0 mm or 0.005-0.5 mm. The UV paint layer 20 may have an excellent anti-pollution effect by having a thickness within the above range.

The single-layer flooring 10 of the present invention may have a Total Volatile Organic Compounds (TVOC) of 0.1 mg/m ² h or less or 0.08 mg/m ² h or less. The TVOC can be measured by the small chamber method. The lower limit of the TVOC is not particularly limited, but may be, for example, 0.002 mg/m ² h or more. The single-layer flooring material 10 of the present invention can realize excellent eco-friendliness by having a TVOC in the above range.

In addition, the single-layer flooring 10 of the present invention may have a Young's modulus of 3,500 kgf/cm ² or less or 3,300 kgf/cm ² or less. The Young's modulus is measured in the low temperature range (0-10℃) according to the tensile specimen standard ASTM D 638. It can be measured. The lower limit of the Young's modulus is not particularly limited, but may be, for example, 500 kgf/cm ² or more. The single-layer flooring material 10 of the present invention has a Young's modulus in the above range and has excellent flexibility (at low temperatures), enabling excellent constructability even under low temperature conditions.

In addition, the single-layer flooring material (10) of the present invention may have an oil resistance of 0 or 1 (where 0 points mean no change, 1 point means slight change, 2 points mean moderate change, and 3 points mean severe change. box). The oil resistance may be evaluated by spraying kerosene on the top of the single-layer flooring (10) according to the ASTM F925 standard, wiping the surface 1 hour later, and visually observing whether damage to the surface of the single-layer flooring (10) has occurred. . The single-layer flooring material 10 of the present invention can realize excellent chemical resistance by having chemical resistance in the above range.

In addition, the single-layer flooring (10) has a residual indentation rate of 0.08 mm or less. Or it may be 0.06mm or less. The residual indentation rate can be measured according to EN 433. The lower limit of the residual indentation ratio is not particularly limited, but may be, for example, 0.001 mm or more. The single-layer flooring material 10 of the present invention can achieve excellent compression recovery by having a residual indentation rate in the above range.

In addition, the single-layer flooring 10 has a smoke density of 700 or less or 500 or less (when heat irradiated at 25 kW/m ² in the presence of a flame), 350 or less or 300 or less (25 kW/m ² without a flame), 900 or less. Or it may be 700 or less (when heat irradiated at 50kW/m ² in the presence of a flame). The smoke density can be measured according to IMO FTP CODE PART 2: 2010 Appendix 1 standards. The lower limit of the smoke density is not particularly limited, but for example, 0 or more or 100 or more (when heat irradiated at 25 kW/m ² in the presence of a flame), 0 or more or 100 or more (25 kW/m ² without a flame), 0 or more. Or it may be 100 or more (when heat irradiated at 50kW/m ² in the presence of a flame). The single-layer flooring material 10 of the present invention can achieve excellent flame retardancy by having a smoke density in the above range.

In addition, it contains 5-30% by weight of the styrene-butadiene copolymer of the present invention, 3-20% by weight of styrene-(meth)acrylate copolymer, and 3-20% by weight of thermoplastic polyurethane (TPU). The method for manufacturing a single-layer flooring (10) in which the emission amount of volatile organic compounds (small chamber) is 0.1 mg/m ² h or less includes the steps of producing two or more sheet compositions each having different colors (S1); Manufacturing a sheet by rolling the two or more sheet compositions prepared above with a plywood calender (S3); Grinding the sheet to produce chips (S5); And it may include a step (S7) of manufacturing a single-layer flooring material 10 by rolling the manufactured chip.

The (S1) step includes, for example, 5-30% by weight of styrene-butadiene copolymer, 3-20% by weight of styrene-(meth)acrylate, and 3-20% by weight of thermoplastic polyurethane (TPU). The sheet composition may be prepared by kneading the composition at 140-180°C or 150-170°C with a Banbari mixer.

The sheet composition may further include filler or mineral oil. At this time, the filler in the sheet composition may be included at 40-80% by weight or 45-78% by weight, and the mineral oil may be included at 0.1-10% by weight or 0.5-5% by weight.

In addition, the sheet composition may further include, for example, one or more selected from the group consisting of flame retardants, antioxidants, lubricants, and pigments, and the content is not particularly limited.

The styrene-butadiene copolymer, styrene-(meth)acrylate copolymer, thermoplastic polyurethane, filler, mineral oil, flame retardant, antioxidant, lubricant, and pigment have been described above, and repeated descriptions will be omitted.

In the step (S3), the two or more sheet compositions are gelled for 250-350 seconds or 280-320 seconds, respectively, at 80-100°C or 85-95°C and 1.5-3 kg/cm ² or 1.8-2.5 kg/cm ² Rolled from 1.0-3.5cm or 2-3cm After manufacturing each first sheet of thickness, the two or more first sheets are rolled with a plywood calender at 60-150°C or 80-130°C and 3-6 kg/cm ² or 3.5-5.5 kg/cm ² to obtain a thickness of 0.5 -3.5mm or 1-3mm It may be manufacturing a second sheet of different thickness.

The second sheet may have a shape in which a plurality of colors are not completely mixed but border each other.

The step (S5) may be to manufacture chips by grinding the second sheet to a length of 0.5-7.0 mm or 1.0-5.0 mm.

In step (S7), the chip is heated to 200-250°C or 200-230°C in an oven, and then heated to 80-130°C or 90-120°C and 2.5-6 kg/cm ² in the first and second calenders. Rolled at 2.5-5kg/cm ² to 1-5mm or 1.5-3.5mm It may be to manufacture a thick single-layer flooring material (10).

The method of manufacturing the single-layer flooring 10 includes optionally coating a UV curing paint on the upper surface of the single-layer flooring 10 after the step (S7) and then curing it to form a UV paint layer 20 (S8). ) may further include.

The UV paint layer 20 has been described above, and repeated descriptions will be omitted.

Below, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are merely illustrative of the present invention, and it is clear to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. It is natural that such changes and modifications fall within the scope of the attached patent claims.

[Example]

Each component used in the examples and comparative examples described below is shown in Table 1 below.

type manufacturer and grade characteristic Styrene-butadiene copolymer ¹⁾ (SBC) Ineos Styrolution, Styrolution SBC KR-40 Block copolymer of styrene and butadiene, melt volume rate (ISO 1133 (200℃, 5kg)) 9 cm ³ /10min, hardness (Shore D (ISO 868)) 55, Vicat softening point (ISO 306 (50N, 50℃/h) ) 40℃, bending strength (ISO 178 (23℃)) 17Mpa Styrene-butadiene copolymer ²⁾ (SBC) LG Chem, SBR 1502 Ethenylbenzene polymer with 1,3-butadiene Styrene-(meth)acrylate copolymer (SMMA) Ineos Styrolution, Styrolution NAS-30 Random copolymer of styrene and methyl (meth)acrylate, melt volume rate (ISO 1133 (220℃, 10kg) 30cm ³ /10min, hardness (ISO 2039-1, ball indentation hardness) 169MPa, Vicat softening point (ISO 306 (50N) , 50℃/h)) 98℃, bending strength (ISO 178 (23℃)) 100MPa Thermoplastic polyurethane (TPU) Songwon Industry, Songstomer P-8185AC Polyester-based thermoplastic polyurethane, hardness (Shore A (ASTM D2240)) 87±2, maximum elongation (ASTM D412) 450% Polyvinyl chloride resin (PVC) LG Chem, LS 080 Polyvinyl chloride homopolymer filler Lexem, S1000 coal stone mineral oil Hyundai Oilbank, LTP 500 Paraffinic oil, kinematic viscosity (ASTM D445) 95mm ² /s Antioxidant ^{1 )} Songwon Industrial, songnox 1076 Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate Antioxidant ^{2 )} Dongnam Synthetic, WESTON-399 Trisnonylphenyl Phosphite Antioxidant ^{3 )} BASF, Tinuvin 622 Poly-(N-Beta-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy-piperidyl succinate) active Songwon Industries, SL-29 stearic acid Pigment ¹⁾ Daewon Pigment, DVM NP Blue blue pigment Pigment ²⁾ Daewon Pigment, DVM NP White white pigment Plasticizer ¹⁾ LG Chem, GL300 Non-phthalate plasticizer Plasticizer ²⁾ LG Chem, GL520 Non-phthalate plasticizer heat stabilizer CNA, BZ-0110 Barium-zinc heat stabilizer Processing aid LG Chem, PA828 Methacrylate Butadiene Styrene (MBS) clay Choyang Chemical, snobrite kaolin clay vulcanizing agent Ilshin Chemtech - Vulcanizing agent Ilshin Chemtech, TT/ Ilshin Chemtech, NS Thioperoxydicarbonic Diamide/2-Benzothiazolesulfenamide,N-(1,1-Dimethylethyl) softener Ilshin Chemtech, WB16F Mixture of calcium soap and N-substituated amides of fatty acids UV curable paint Jogwang Paint -

<Example 1>

Step (S1) of producing two or more sheet compositions each having different colors

Styrene-butadiene copolymer ^{1 )} 250 parts by weight of carbonite, 5 parts by weight of mineral oil, based on 100 parts by weight of resin containing 40% by weight of styrene-(meth)acrylate copolymer and 30% by weight of thermoplastic polyurethane, Sheet composition ¹ was prepared by kneading a composition containing 3 parts by weight of antioxidant 1 ⁾ , 1 part by weight of lubricant, and 2 parts by weight of pigment ^{1 )} at 160°C with a Banbari mixer.

Additionally, sheet composition ² having ^the same composition as sheet composition 1 was prepared except that it included 2 parts by weight of pigment 2 of a different color.

Plying two or more separately manufactured sheet compositions With calendar Step of manufacturing a sheet by rolling (S3)

The sheet composition 1 and sheet composition 2 were each gelled for 290 seconds and heated to 90°C. and rolling at 2 kg/cm ² to produce first sheets with a thickness of 2.5 cm, respectively, and then heat the two first sheets at 90°C using a plywood calender. and rolling at 4-5 kg/cm ² to produce a second sheet with a thickness of 2 mm.

Step of producing chips by crushing the sheet (S5)

The second sheet was ground into chips 1.0-5.0 mm long.

By rolling the manufactured chips single layer Step of manufacturing flooring (S7)

The chips were heated to 210°C in an oven, scattered on a carrier belt, and then rolled at 110°C and 3-4 kg/cm ² in the first and second calenders to produce a single-layer flooring material with a thickness of 2.5 mm.

Step of forming a UV paint layer on the upper surface of the single-layer flooring (S9)

After the UV curable paint was applied to the entire surface of the single-layer flooring, ultraviolet rays were irradiated to form a UV paint layer with a thickness of 0.01 mm.

<Example 2>

In step (S1) of Example 1, 250 carbon stones were used based on 100 parts by weight of the resin containing 30% by weight of styrene-butadiene copolymer ^{1 )} , 40% by weight of styrene-(meth)acrylate copolymer, and 30% by weight of thermoplastic polyurethane. A composition containing 5 parts by weight of mineral oil, 3 parts by weight of antioxidant ^{1 )} , 1 part by weight of lubricant, and 2 parts by weight of pigment ^{1 )} was kneaded at 160°C with a Banbari mixer to prepare sheet composition 3, and different colors were prepared. A single ^- layer flooring material was prepared in the same manner as in Example ¹ , except that sheet composition 4 was prepared with the same composition as sheet composition 3, except that it contained 2 parts by weight of pigment 2).

[Comparative example]

<Comparative Example 1>

In step (S1) of Example ¹ , 100 parts by weight ^of PVC resin, 36 parts by weight of plasticizer, 250 parts by weight of carbon stone, 1 part by weight of lubricant, 2 parts by weight of heat stabilizer, 2 parts by weight of processing aid, and ^{1 )} 2 parts by weight of pigment. Sheet composition 5 was prepared by kneading the composition containing the composition at 160°C with a Banbari mixer, and the sheet composition except that it included 2 parts by weight of pigment ^{2 )} A single-layer flooring material was prepared in the same manner as in Example 1, except that sheet composition 6, which was the same as 5, was prepared.

<Comparative Example 2>

Step of preparing sheet composition (S1)

Styrene-butadiene copolymer ^{2 )} 100 parts by weight, plasticizer ^{2 )} 5 parts by weight, clay 200 Parts by weight, vulcanizing agent and vulcanizing aid Sheet composition 7 was prepared by kneading a composition containing 5 parts by weight of antioxidant ^{2 )} , 2 parts by weight of antioxidant ^{3 )} , 3 parts by weight of softener, and ^{1 )} 2 parts by weight of pigment with a Banbari mixer at 130°C.

Extrusion of the prepared sheet composition T- die Step of manufacturing a sheet through (S3)

The sheet composition 7 was gelled for 200 seconds in a Banbari mixer and extruded through an extrusion T-die with an internal temperature of 80°C to prepare a 3 mm thick sheet.

By hardening the sheet single layer Step of manufacturing flooring (S5)

The sheet was calendered at 120°C and 3-5kg/cm ² to produce a 2.5mm thick sheet, which was then rolled at 180°C and 5-10kg/cm ² A single-layer flooring material was manufactured by curing with Calender Rotorcure.

<Comparative Example 3>

In step (S1) of Example 1, 250 parts by weight of coal and 5 parts by weight of mineral oil based on 100 parts by weight of resin containing 70% by weight of styrene-butadiene copolymer ^{1 )} and 30% by weight of styrene-(meth)acrylate copolymer. Sheet composition 8 was prepared by kneading a composition containing ^{1 )} 3 parts by weight of antioxidant, 1) part by weight of lubricant, and 2) parts by weight of pigment ^{1 )} at 160°C with a Banbari mixer, and ^{2 )} 2 parts by weight of pigments of different colors. A single-layer flooring material was manufactured in the same manner as in Example 1, except that sheet composition 9 was prepared with the same composition as sheet composition 8.

The compositions of the single-layer flooring materials of Example 1-2 and Comparative Example 1-3 are summarized in Table 2 below.

(weight%) Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 SBC 11.1 8.3 - - 19.4 SMMA 8.3 11.1 - - 8.3 TPU 8.3 8.3 - - - PVC - - 25.4 - - SBR - - - 31.5 - coal stone 69.3 69.3 63.6 - 69.3 mineral oil 1.4 1.4 - - 1.4 plasticizer - - 9.2 1.6 - antioxidant 0.8 0.8 - 0.6 0.8 active 0.2 0.2 0.3 - 0.2 heat stabilizer - - 0.5 - - Processing aid - - 0.5 - - clay - - - 63.1 - Vulcanizing agents and vulcanizing aids - - - 1.6 - softener - - - 1.0 - pigment 0.6 0.6 0.5 0.6 0.6

[Test example]

1. Eco-friendliness

After cutting the single-layer flooring to a size of 165mm x 165mm x 2mm (width x height x thickness), TVOC was measured by the small chamber method using a TVOC (total volatile organic compounds) meter.

The smaller the TVOC, the more environmentally friendly it is.

2. Low-temperature flexibility (Young's modulus)

According to the ASTM D638 standard, a doggy bone-shaped specimen with a width of 13 mm and a length of 57 mm was subjected to a tensile test in a low temperature range (0-10℃) using UTM equipment (LLOYD Instrument, LRX Plus) at a stretching speed of 50 mm/min. When doing so, the ratio of force to deformation in the length/width direction was measured.

The smaller the Young's modulus, the better the low-temperature flexibility.

3. Chemical resistance

In accordance with ASTM F925, kerosene was sprayed on the top of the single-layer flooring, the surface was wiped 1 hour later, and the surface damage of the single-layer flooring was visually observed to evaluate oil resistance based on the following criteria.

The smaller the oil resistance evaluation score, the better the chemical resistance.

0 points: no change, 1 point: slight change, 2 points: moderate change, 3 points: severe change

4. Pressure recovery

As specified in EN 433, a load of 51 kg was applied to the single-layer flooring material with a hemispherical steel bar with a diameter of 11.3 mm and released after 150 minutes. After 150 minutes, the residual indentation rate was determined through the change in the thickness of the specimen as follows. Saved.

Residual indentation rate = (T ₀ - T ₁ )mm

T ₀ : Thickness before pressurization, T ₁ : Thickness after pressurization

The smaller the residual indentation rate, the better the indentation recovery ability.

5. Flame retardant

IMO FTP CODE PART2: 2010 Appendix 1 The smoke density was measured by heat irradiation of the single-layer flooring in a closed cabinet according to the standard. The heat irradiation was conducted at an irradiation intensity of 25 kW/m ² with a flame, 25 kW/m ² without a flame, and 50 kW/m ² with a flame.

The smaller the smoke density, the better the flame retardancy.

Eco-friendliness (TVOC, mg/m ² h) Low-temperature flexibility (Young’s modulus, kgf/cm ² ) Chemical resistance (oil resistance, score) pressed
Stability (residual indentation rate, mm) Flame retardant 25(kW/ ^m2 )
There is a flame 25(kW/ ^m2 )
no flame 50(kW/ ^m2 )
There is a flame Example 1 0.052 2,000-2,500 0 0.03-0.05 320 265 405 Example 2 0.054 2,500-3,300 0 0.04-0.06 310 260 405 Comparative Example 1 0.150 3,500-4,500 0 0.08-0.10 782 358 924 Comparative Example 2 0.920 1,500-2,500 One 0.03-0.05 755 402 963 Comparative Example 3 0.054 2,000-2,500 2 0.08-0.10 318 267 403

It was confirmed that the single-layer flooring materials of Examples 1 and 2 had excellent physical properties such as eco-friendliness, low-temperature flexibility, chemical resistance, compression recovery, and flame retardancy.

On the other hand, it was confirmed that the single-layer flooring of Comparative Example 1 was made of polyvinyl chloride material and contained plasticizers, so that eco-friendliness, low-temperature flexibility, compression recovery, and flame retardancy were reduced compared to the Example.

On the other hand, it was confirmed that the single-layer flooring of Comparative Example 2 was made of a rubber material, and its eco-friendliness, chemical resistance, and flame retardancy were reduced compared to the Example.

On the other hand, it was confirmed that the single-layer flooring of Comparative Example 3 did not contain thermoplastic polyurethane, and thus its chemical resistance and compression recovery properties were lowered compared to the Examples.

10: single layer flooring 20: UV paint layer

Claims (15)

A single-layer flooring material composed of non-polyvinyl chloride material and non-rubber material, 5-30% by weight of styrene-butadiene block copolymer, 3-20% by weight of styrene-(meth)acrylate random copolymer, and thermoplastic polyurethane. It is characterized by being calendered and containing 3-20% by weight of (Thermoplastic Polyurethane, TPU), 40-80% by weight of filler, and 0.1-10% by weight of mineral oil.
The styrene-butadiene block copolymer has a melt volume rate of 5 to 20 cm3/10 min as measured by ISO 1133 (200 ° C., 5 kg), Shore D hardness of 40 to 80 as measured by ISO 868, and ISO 868. 306 (Vicat softening point measured by 50N, 50°C is 20 to 60°C, ISO 178 (flexural strength measured by 23°C is 5 to 30MPa, weight average molecular weight is 100,000 to 250,000 g/mol,
The styrene-(meth)acrylate random copolymer has a melt volume rate of 20 to 40 cm3/10min as measured by ISO 1133 (220°C, 10kg) and a Vicat softening point as measured by ISO 306 (50N, 50°C). 80 to 120 ℃, flexural strength measured by ISO 178 (23 ℃) is 80 to 120 MPa, weight average molecular weight is 100,000 to 250,000 g/mol,
The thermoplastic polyurethane has a Shore A hardness of 75 to 95 as measured by ASTM D2240 and a maximum elongation of 350 to 550% as measured by ASTM D412,
The filler is at least one selected from the group consisting of coal, talc, fly ash, and blast furnace slag,
The mineral oil has a kinematic viscosity of 50 to 150 mm2/s at 40°C as measured by ASTM D445,
The single ^- layer flooring was cut to a size of 165mm h or less,
The single-layer flooring has a Young's modulus (ASTM D 638) at 0-10°C of 3,500 kgf/cm ² or less. delete According to clause 1,
The single-layer flooring is a single-layer flooring having a residual indentation rate (EN 433) of 0.08 mm or less. According to clause 1,
The single-layer flooring has an oil resistance (ASTM F925) of 0 or 1. According to clause 1,
The single-layer flooring has a smoke density of 700 or less when heat irradiated at 25 kW/m ² in the presence of a flame, a smoke density of 350 or less when heat irradiated at 25 kW/m ² without a flame, and 50 kW/m ² in the presence of a flame. A single-layer flooring material with a smoke density of 900 or less when subjected to furnace heat irradiation. delete delete According to clause 1,
A single-layer flooring material wherein the thermoplastic polyurethane is polyester-based polyurethane. delete delete According to clause 1,
A single-layer flooring material wherein the mineral oil is a paraffin-based oil. According to clause 1,
The single-layer flooring is a single-layer flooring having a total volatile organic compound emission (Small Chamber) of 0.08 mg/m ² h or less. According to clause 1,
The single-layer flooring has a Young's modulus (ASTM D 638) at 0-10°C of 3,300 kgf/cm ² or less. Producing two or more sheet compositions each having different colors (S1);
Manufacturing a sheet by rolling the two or more sheet compositions prepared above with a plywood calender (S3);
Grinding the sheet to produce chips (S5); and
A method of manufacturing a single-layer flooring comprising a step (S7) of manufacturing a single-layer flooring by rolling the manufactured chips using a calender,
The single-layer flooring is a single-layer flooring made of a non-polyvinyl chloride material and a non-rubber material, and is a single-layer flooring made of a non-polyvinyl chloride material and a non-rubber material, styrene-butadiene block copolymer 5 -30% by weight, 3-20% by weight styrene-(meth)acrylate random copolymer, 3-20% by weight thermoplastic polyurethane (TPU), 40-80% by weight filler, and 0.1-10% by weight mineral oil. It is characterized by calender processing including %,
The styrene-butadiene block copolymer has a melt volume rate of 5 to 20 cm3/10 min as measured by ISO 1133 (200 ° C., 5 kg), Shore D hardness of 40 to 80 as measured by ISO 868, and ISO 868. 306 (Vicat softening point measured by 50N, 50°C is 20 to 60°C, ISO 178 (flexural strength measured by 23°C is 5 to 30MPa, weight average molecular weight is 100,000 to 250,000 g/mol,
The styrene-(meth)acrylate random copolymer has a melt volume rate of 20 to 40 cm3/10min as measured by ISO 1133 (220°C, 10kg) and a Vicat softening point as measured by ISO 306 (50N, 50°C). 80 to 120 ℃, flexural strength measured by ISO 178 (23 ℃) is 80 to 120 MPa, weight average molecular weight is 100,000 to 250,000 g/mol,
The thermoplastic polyurethane has a Shore A hardness of 75 to 95 as measured by ASTM D2240 and a maximum elongation of 350 to 550% as measured by ASTM D412,
The filler is at least one selected from the group consisting of coal, talc, fly ash, and blast furnace slag,
The mineral oil has a kinematic viscosity of 50 to 150 mm2/s at 40°C as measured by ASTM D445,
The single ^- layer flooring was cut to a size of 165mm h or less,
The single-layer flooring has a Young's modulus (ASTM D 638) at 0-10°C of 3,500 kgf/cm ^{2 or} less. According to clause 14,
In the step (S3), the two or more sheet compositions are each gelled for 250-350 seconds and rolled at 80-100° C. and 1.5-3 kg/cm ² to form a sheet of 1.0-3.5 cm. After manufacturing each thick first sheet, the two or more first sheets are heated at 60-150°C using a plywood calender. and 0.5-3.5mm by rolling at 3-6kg/cm ² A method of manufacturing a calendered single-layer flooring material, which is to manufacture a second sheet of thickness.

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