WO2019054731A1 - 우수한 표면 외관을 갖는 인조가죽 및 그 제조방법 - Google Patents
우수한 표면 외관을 갖는 인조가죽 및 그 제조방법 Download PDFInfo
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- WO2019054731A1 WO2019054731A1 PCT/KR2018/010649 KR2018010649W WO2019054731A1 WO 2019054731 A1 WO2019054731 A1 WO 2019054731A1 KR 2018010649 W KR2018010649 W KR 2018010649W WO 2019054731 A1 WO2019054731 A1 WO 2019054731A1
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- Prior art keywords
- layer
- surface treatment
- artificial leather
- foamed
- weight
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60N—SEATS SPECIALLY ADAPTED FOR VEHICLES; VEHICLE PASSENGER ACCOMMODATION NOT OTHERWISE PROVIDED FOR
- B60N2/00—Seats specially adapted for vehicles; Arrangement or mounting of seats in vehicles
- B60N2/58—Seat coverings
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/06—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
Definitions
- the present invention relates to an artificial leather, and more particularly, to an artificial leather used as an automobile seat cover, which is provided with a surface treatment layer having a uniform thickness by performing surface treatment before embossing, To an artificial leather having excellent surface appearance and a manufacturing method thereof.
- conventional artificial leather comprises a laminated structure including a back layer, a foam layer, a skin layer, and a surface treatment layer from the bottom.
- the surface treatment agent is applied to the upper part of the skin layer on which the emboss is formed to form the surface treatment layer.
- the thickness of the surface treatment layer is not uniform as the amount of the surface treatment agent applied to the embossed bone and the floor is significantly different.
- the bone or floor portion is visibly brighter than other regions due to the difference in gloss between the bone and the floor.
- Patent Document 1 KR 10-1361535 B (public announce date: 2014. 02. 13)
- An object of the present invention is to provide an artificial leather having an excellent surface appearance.
- the present invention provides a synthetic leather having a ratio of the thickness of the surface treatment layer formed on the embossed floor to the thickness of the surface treatment layer formed on the embossed bone of 0.7-1.
- an embossing step of vacuum-forming an emboss using vacuum on the skin layer and the surface treatment layer heated by the infrared ray irradiation is performed.
- the artificial leather of the present invention has an effect of having excellent surface appearance because the thickness of the surface treatment layer formed on the embossed corrugation and the floor is uniform.
- the artificial leather of the present invention has an effect of having a texture similar to that of natural leather and a soft touch.
- the artificial leather of the present invention can prevent the foamed cell constituting the foamed layer from being crushed or broken, thereby realizing an excellent cushioning effect.
- FIG. 1 is a side sectional view showing a laminated structure of artificial leather according to the present invention.
- FIG. 2 is a flow chart showing a process of manufacturing artificial leather according to the present invention.
- FIG. 3 is a photograph showing the surface (emboss) of the artificial leather of the present invention.
- FIG. 4 is a photograph showing a surface (emboss) of an artificial leather coated with a surface treatment agent after emboss molding using a conventional roller pressing method.
- Fig. 5 is a view schematically showing a method of measuring the gloss difference of the appearance of the synthetic leather surface.
- Fig. 1 is a sectional side view showing a laminated structure of artificial leather according to the present invention.
- Fig. 1 is a side sectional view showing a laminated structure of artificial leather according to the present invention.
- the artificial leather 10 of the present invention is characterized in that the surface treatment layer formed on the crest 19b of the emboss 19 with respect to the thickness of the surface treatment layer formed on the valley 19a of the emboss 19
- the thickness ratio of the layer (that is, the thickness of the surface treatment layer formed on the floor ⁇ the thickness of the surface treatment layer formed on the valley) may be 0.7-1 or 0.8-1, There is an effect that it is possible to provide an artificial leather excellent in appearance since the surface of the treated layer does not appear to be uneven because the difference in gloss of the treated layer is small.
- the valley of the embossment is a recessed concave portion of the concave and convex portion, which means the lowest point, and the crest of the embossed portion is a convex convex portion, (See FIG. 3).
- the ratio of the thickness of the surface treatment layer formed on the trough 19a of the emboss 19 to that of the surface 19b is obtained by cutting the artificial leather 10 in the vertical direction,
- the thickness can be calculated as the thickness of the surface treatment layer formed on the floor / the thickness of the surface treatment layer formed on the valley.
- the artificial leather 10 of the present invention is characterized in that the difference in thickness between the trough 19a of the emboss 19 and the surface treatment layer formed on the floor 19b is less than 5 ⁇ ⁇ or 3 ⁇ ⁇ or less, Since there is little difference in gloss of the surface treatment layer formed on the surface 19a and the floor 19b, the surface does not appear to be mottled, so that an artificial leather excellent in appearance can be provided.
- the surface treatment agent In order to prevent damage to the surface treatment layer, the surface treatment agent must be applied after embossing, so that the tread 19a of the embossing 19 and the surface
- the difference in the thickness of the surface treatment layer formed on the base 19b is 5 ⁇ ⁇ or more and the difference in gloss of the surface treatment layer formed on the trough 19a and the floor 19b is large, Since the surface treatment of the embossing 19 can be performed before the embossing 19 is formed, the thickness of the surface treatment layer formed on the trough 19a and the floor 19b of the embossing 19 can be uniform, There is an effect that can be done.
- the region where the ratio of the thickness of the surface treatment layer formed on the valley 19a of the embossment 19 and the thickness of the surface treatment layer formed on the floor 19b satisfies the above range is not less than 80% Or more.
- the difference in thickness between the tread 19a of the emboss 19 and the surface treatment layer formed on the floor 19b is less than 5 ⁇ ⁇ , There is no difference in gloss between the trough 19a and the floor 19b.
- the gloss difference is caused by a difference in gloss between the valley 19a of the emboss 19 and the floor 19b due to the difference in reflectivity when the artificial leather specimen is tilted at 30-60 degrees from the light incident angle of light in the wavelength of 380-800 nm
- the difference in brightness caused by the light is qualitatively measured by eyes.
- a panel composed of ten evaluators was used to determine whether visually recognizing the difference in gloss between the trough 19a of the emboss 19 and the floor 19b with respect to the artificial leather specimen, When there are 5 or more people, it is defined as having a difference in gloss, and it is described as X (appearance deterioration). When there are less than 5 persons who said that there is a difference in gloss, it is defined that there is no difference in gloss and it is described as ⁇ (excellent appearance).
- a method for measuring the difference in gloss between the valley 19a of the emboss 19 and the floor 19b in the artificial leather specimen is as follows.
- the light (light source), the artificial leather specimen and the eyes of the evaluator are placed at right angles, The eyes of the psalm and the evaluator should be on the same line.
- the artificial leather specimen is repeatedly tilted at 30-60 degrees with respect to incident light of light, and visibility of the gloss difference is measured based on the valley 19a of the emboss 19 as shown in Figs. 3 and 4 (See FIG. 5).
- the distance between the eyes of the artificial leather specimen and the eyes of the evaluator may be 30 cm or less, or 20 cm or less. It is difficult to measure the gloss difference between the valley 19a of the emboss 19 and the floor 19b and only the overall gloss increase of the artificial leather specimen is visually recognized.
- the artificial leather 10 of the present invention can be subjected to surface treatment before embossing, the surface treatment layer is processed with the embossing at the time of embossing so that the embossing (Ra) is formed by embossing.
- the conventional artificial leather formed by embossing has a higher surface roughness Ra than the artificial leather 10 according to the present invention because the surface treatment agent is applied more to the valley than the embossed floor when the surface treatment agent is applied after the embossing, ). ≪ / RTI >
- the artificial leather 10 of the present invention may have a microhardness of 45-59, or 50-57.
- the microhardness is a local hardness for a minute specimen such as a thickness of about 0.5-1.5 mm and is measured in a peak hold mode at a pressing speed of 1 mm / s using a microhardness tester (Asker Micro Durometer, Model: MD-1 CAPA) The maximum value was measured immediately after the needle was in contact with the leather, that is, when the load holding time of the needle was 1s.
- hardness shore 'HS'
- hardness rock 'HR'
- hardness vickers 'HV'
- Hardness Knoop 'HK'
- microhardness a hardness measuring method
- shore hardness is commonly used for measuring hardness of artificial leather.
- Shore hardness is a method of measuring a specimen having a thickness of 5 mm or more, and is not suitable for measuring the hardness of a minute specimen having a thickness of less than 5 mm.
- MD-1 CAPA of Asker Micro Durometer may be used as an example of a microhardness hardness of less than 5 mm, for example, a hardness of 0.5 to 1.5 mm have.
- microhardness exceeds the above range, the touch feeling is not general and smooth. If the microhardness is less than the above range, the mechanical properties such as abrasion and the like are lowered, so that the microhardness within the above range can be obtained.
- a method of manufacturing the artificial leather 10 is as follows.
- the present invention includes a backside layer coating step (S1) of coating one side of a backing layer, which is a woven fabric or a nonwoven fabric, with a coating solution;
- the backside layer The coating step (S1)
- the step (S1) may be for increasing the peeling strength between the back layer 11 and the foam layers 13b and 13b 'on the back layer 11 by coating one surface of the back layer 11 with a coating solution .
- the backside layer 11 of the present invention may be formed by coating one side of the backside layer 11 with the coating solution to enhance the peeling strength with the foam layers 13b and 13b ', followed by gelling through heat treatment at 120-150 ° C. have.
- the coating solution may be an acrylic adhesive, a polyurethane adhesive, or a polyvinyl chloride plastisol.
- acrylic adhesive has a disadvantage in that the micro hardness of the artificial leather is increased due to hardness after drying, the polyurethane adhesive is relatively expensive and the material cost is increased, and the micro hardness of the artificial leather is increased
- Polyvinyl chloride plastisols can be used.
- the polyvinyl chloride plastisol may be formed by stirring 70 to 130 parts by weight of a plasticizer and 0.5 to 10 parts by weight of a curing agent at room temperature with respect to 100 parts by weight of a polyvinyl chloride resin.
- the polyvinyl chloride resin may be a mixed resin composed of 60-90% by weight of a homopolymer of vinyl chloride and 10-40% by weight of a copolymer of vinyl chloride and vinyl acetate.
- the vinyl chloride homopolymer is a paste polyvinyl chloride resin prepared by emulsion polymerization and may be contained in the mixed resin in an amount of 60-90% by weight or 65-85% by weight. If it is less than the above range, the peeling strength between the back layer 11 and the foam layers 13b and 13b 'may be lowered. If the above range is exceeded, odor may be undesirable.
- the copolymer of vinyl chloride and vinyl acetate is a resin that imparts excellent adhesion to the backing layer 11, which is woven or nonwoven fabric, and the content of vinyl acetate in the copolymer may be 1-15% by weight or 3-10% by weight have.
- the amount is less than the above range, the adhesive strength is lowered and the peeling strength between the back layer 11 and the foam layer 13b is lowered. If the above range is exceeded, the hydrolysis resistance is lowered.
- the copolymer of vinyl chloride and vinyl acetate may be contained in the mixed resin in an amount of 10-40 wt% or 15-35 wt%. If it is less than the above range, the peel strength between the back layer 11 and the foam layer 13b is lowered, and if it exceeds the above range, the mechanical properties such as heat resistance are lowered.
- the plasticizer contained in the coating solution may be at least one selected from a phthalate plasticizer, a terephthalate plasticizer, a benzoate plasticizer, a citrate plasticizer, a phosphate plasticizer or an adipate plasticizer.
- a terephthalate plasticizer which is environmentally friendly and excellent in heat resistance.
- the terephthalate-based plasticizer for example, dioctyl terephthalate can be used, but is not limited thereto.
- the plasticizer may be contained in an amount of 70-130 parts by weight or 80-120 parts by weight based on 100 parts by weight of the mixed resin. When the amount is less than the above range, the viscosity of the coating solution may be increased and the processability may be deteriorated. If the amount is more than the above range, the adhesive force may decrease due to migration of the plasticizer.
- the curing agent contained in the coating solution may be a low-temperature curing type curing agent for enhancing energy efficiency and productivity, and a block isocyanate curing agent blocked with a blocking agent in part or all of the isocyanate group may be used.
- the blocking agent may be selected from the group consisting of phenol, ⁇ -caprolactam, methyl ethyl ketone oxime, 1,2-pyrazole, diethyl malonate, malonate, diisopropylamine, triazole, imidazole, and 3,5-dimethylpyrazole may be used as the starting material. .
- the blocked isocyanate curing agent blocks the isocyanate group so that the isocyanate group (-NCO) does not react with the hydroxyl group (-OH) or the amino group (-NH) at room temperature.
- the blocked isocyanate curing agent reaches a certain temperature region, And the curing reaction proceeds.
- the dissociation temperature of the curing agent may be 100 ° C or higher or 110-130 ° C.
- the curing agent may be added in an amount of 0.5-10 parts by weight or 1-5 parts by weight based on 100 parts by weight of the mixed resin. If it is less than the above range, the peeling strength between the backing layer 11 and the foam layers 13b and 13b 'is lowered due to the lowering of the degree of crosslinking. If the above range is exceeded, the unreacted curing agent remains impurities, Can be used within.
- the coating solution may further optionally contain at least one other additive selected from the group consisting of a stabilizer, a filler, a pigment, a viscosity reducing agent and a dispersing agent.
- the content of the coating solution may be adjusted so long as it does not affect the physical properties of the coating solution There is no restriction.
- the viscosity of the coating solution may be 80-140 seconds or 100-120 seconds at 25 ° C in the viscosity of cup (# 3 cup). If the amount of the coating solution is less than the above range, the coating solution may flow down to lower the coating efficiency. If the amount exceeds the above range, the coating solution may not be impregnated into the backing layer 11, And stable processability can be ensured.
- the backside layer 11 coated with the coating solution assists mechanical properties and plays a role of maintaining the shape of the artificial leather and preventing wrinkles.
- the backside layer 11 is made of cotton, rayon, silk, polyolefin (for example, polyethylene, polypropylene, , Nonwoven fabrics, knitted fabrics, plain weaves, spunbond fabrics, and the like, and may further include natural fibers and / or synthetic fibers.
- the backside layer 11 can easily secure mechanical properties such as strength and flame retardancy, and has an advantage that a sewing performance and a clean appearance can be realized in relation to the foam layers 13b and 13b '
- a woven fabric or a nonwoven fabric containing rayon and polyester in a weight ratio of 30-40: 60-70 can be used.
- the thickness of the coating formed on the backside layer 11 may be 1-10 ⁇ ⁇ or 2-5 ⁇ ⁇ , for example.
- the thickness of the coating means the thickness including the coating solution impregnated into the backside layer 11. If the thickness of the coating is less than the above range, the peel strength of the back layer 11 and the foam layers 13b and 13b 'decreases. If the thickness exceeds the above range, the microhardness of the synthetic leather increases, So that it can be coated with a thickness within the above range.
- the peeling strength between the backside layer and the foam layer may be 2.5-6 kgf / 30 mm, or 2.5-5.5 kgf / 30 mm. If it is less than the above range, the back layer 11 and the foam layers 13b and 13b 'are easily peeled off and the quality of the artificial leather is deteriorated. If it exceeds the above range, the microhardness is increased and the touch feeling is lowered. It is desirable to maintain the peel strength.
- the thickness of the backside layer 11 may be 0.4-0.7 mm. If the thickness is less than the above range, the mechanical strength of the backside layer 11 may deteriorate. If the backside layer 11 is thicker than the above range, material cost may be increased.
- the step (S3) may be a step of extrusion molding or calendering molding the prefoamed foam layer 13a or the foamed layer 13b and the skin layer 15.
- the extrusion molding may be a T-die extrusion process using a T-die extruder after melting the prefoamed or foamed layer and the composition for preparing the skin layer, respectively, in an extruder, and the calendered molding is carried out using the pre- And the composition for preparing the skin layer are kneaded in a mixer, respectively, and then passed through a calender roll at 160 to 170 ° C.
- the pre-foamed layer 13a is formed into a sheet shape by extrusion molding or calendering, and then foamed in a foam molding step S8 to form a foamed layer 13b '
- the layer 13a may have a thickness of 0.2-0.35 mm or 0.25-0.3 mm.
- the foamed layer 13b may be formed into a sheet through extrusion or calendering, then passed through an oven at 220-260 ° C to complete foaming, and may have a thickness of 0.4-0.8 mm or 0.4-0.7 mm If it is less than the above range, the feeling of cushioning deteriorates. If it exceeds the above range, it may be formed to be thicker than required.
- the pre-foamed layer 13a or the foamed layer 13b is prepared by mixing 100 parts by weight of a polyvinyl chloride resin with 60-120 parts by weight of a plasticizer and 5-15 parts by weight of a foaming agent, ≪ / RTI >
- the polyvinyl chloride resin contained in the pre-foamed layer 13a or the foamed layer 13b is a straight polyvinyl chloride resin (polyvinyl chloride resin) formed by suspension polymerization capable of ensuring excellent cushioning, high elongation and high durability at the same time Lt; / RTI >
- the degree of polymerization of the polyvinyl chloride resin may be 900-1200, or 950-1150. If it is less than the above range, the durability is deteriorated. If it exceeds the above range, the hardness of the prefoamed foam layer 13a or the foamed layer 13b is increased and the cushion feeling is lowered, so that polyvinyl chloride resin having the polymerization degree within the above range can be used.
- the pre-foamed layer 13a or the foamed layer 13b of the present invention may be formed by adding a copolymer of vinyl chloride and vinyl acetate to the polyvinyl chloride resin 100 5-20 parts by weight or 5-15 parts by weight based on 100 parts by weight of the base layer 11, and the peeling strength with the back layer 11 is excellent within the above range.
- the content of vinyl acetate in the copolymer of vinyl chloride and vinyl acetate may be 0.5-10 wt% or 1-5 wt%.
- the pre-foamed layer 13a or the foamed layer 13b of the present invention may be formed by applying a thermoplastic polyurethane (TPU) resin, polyvinylidene chloride (PVDC) resin, polyvinylidene fluoride (PVDF) (PE) resin, a poly (ethylene terephthalate) resin, and a polypropylene (PP) resin.
- TPU thermoplastic polyurethane
- PVDC polyvinylidene chloride
- PVDF polyvinylidene fluoride
- PE poly (ethylene terephthalate) resin
- PP polypropylene
- the resin is preferably selected from the group consisting of chlorinated polyvinyl chloride (CPVC) resin, polyvinyl alcohol (PVA) resin, polyvinyl acetate (PVAc) resin, polyvinyl butyrate , And the like.
- the plasticizer may be at least one selected from the phthalate plasticizer, the terephthalate plasticizer and the epoxy plasticizer.
- the phthalate plasticizer may be one selected from the group consisting of dibutyl phthalate, diethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate and butyl benzyl phthalate as plasticizers that are highly compatible with the polyvinyl chloride resin , Preferably diisodecyl phthalate which is a low volatile plasticizer can be used.
- the terephthalate plasticizer is an environmentally friendly plasticizer such as dioctyl terephthalate, but is not limited thereto.
- the epoxy plasticizers are epoxidized double bonds of unsaturated fatty acid glycerol esters with hydrogen peroxide or peracetic acid, for example, epoxidized soybean oil or epoxidized linseed oil, but are not limited thereto.
- the plasticizer may be used in an amount of 60-120 parts by weight, or 70-100 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin. If the amount is less than the above range, the processability and ductility are lowered, and the microhardness is increased. When the amount exceeds the above range, bleeding phenomenon of the plasticizer occurs.
- the foaming agent is not particularly limited as long as it can form fine bubbles that give necessary elasticity and thickness to the foam layer 13b.
- Examples of the foaming agent include azodicarbonamide (ADCA), p, p'-oxybisbenzene
- a chemical foaming agent such as p-toluidine sulfonyl hydrazide, sodium bicarbonate, and the like can be used.
- the foaming agent may be used in an amount of 5-15 parts by weight, or 5-10 parts by weight, based on 100 parts by weight of the polyvinyl chloride resin. If it is less than the above range, the softness and cushion feeling of the artificial leather deteriorates, and if it exceeds the above range, the foaming cells of the foam layer 13b are excessively produced, and the physical properties and durability of the surface are lowered.
- the foaming rate of the foam layer 13b may be 100-500% or 150-300%.
- the foaming ratio within the above range, it is possible to secure a sense of volume, a cushion feeling, and a smooth surface feel.
- the artificial leather is hardened due to an increase in the microhardness thereof, and when it exceeds the above range, the artificial leather is weakened in durability and strength in the case of excessive foaming, and the physical properties are deteriorated.
- the foamed cells formed in the foamed layer 13b may be spherical foamed cells.
- the spherical foam cell is not necessarily a geometrically perfect spherical shape as it is distorted by the external pressure or is in contrast to the shape of the foam cell having a pointed shape.
- the spherical foam cell is generally referred to as spherical But also the level of inclusiveness. Therefore, in the present specification, it is to be understood that a spherical foam cell does not deform its shape due to a physical external force, but maintains a spherical shape at the time of formation.
- the foam cells may be included in the foam layer 13b at a side end face or at a flat face of 10 to 30, or 15 to 20 per unit area of 1 mm 2 . If it is less than the above range, the ductility and cushion feeling will be lowered. If it exceeds the above range, the surface durability will be lowered and the physical properties such as surface feeling and cushion feeling will decrease.
- the number of the foam cells was measured by using an optical microscope after the artificial leather was cut in the vertical direction or the horizontal direction and then the number of foam cells formed on the end face of the foam layer 13b or 1 mm 2 of the flat face was measured.
- the average diameter of the foamed cells may be 120-250 ⁇ ⁇ , or 135-200 ⁇ ⁇ .
- the average diameter represents an average value of the diameter of one foam cell. More specifically, when the foam cell is geometrically spherical, it means an average diameter. In the case of a shape other than a geometric sphere, And the average length of the axis.
- the average diameter of the foam cells satisfies the above range, and by maintaining the shape of the sphere, the artificial leather can secure high ductility and workability, and can exhibit excellent cushioning feeling.
- the average diameter of the foamed cells is obtained by cutting the synthetic leather in the vertical direction or the horizontal direction and then measuring the average diameter of the foamed cells formed on the end face on the side of the foam layer 13b or on the area of 1 mm 2 of the flat face by the scale bar of the optical microscope Lt; / RTI >
- the foamed layer 13b may have a specific gravity of 0.7-0.9, or 0.7-0.8. If it is less than the above range, the durability is deteriorated. If the above range is exceeded, the ductility and cushion feeling may be deteriorated.
- the foam layer 13b is formed of a spherical foamed cell, which is not deformed by the external pressure and is included in the foam layer side end face or 10-30 per 1 mm 2 unit area of the flat face, and has a specific gravity of 0.7-0.9 So that the cushioning feeling and the smooth surface feeling of the artificial leather according to the present invention can be remarkably improved.
- the skin layer 15 may be formed from 100 to 20 parts by weight of a polyvinyl chloride resin, 60 to 120 parts by weight of a plasticizer, and a composition for preparing a skin layer including a pigment.
- the polyvinyl chloride resin contained in the skin layer 15 has a higher degree of polymerization than the polyvinyl chloride resin contained in the prefoamed layer 13a or the foamed layer 13b is used in the foam molding step S8 ) Or the skin layer 15 is prevented from popping out during the embossing step S13.
- the polyvinyl chloride resin included in the skin layer 15 may be a straight polyvinyl chloride resin prepared by suspension polymerization.
- the degree of polymerization of the polyvinyl chloride resin contained in the skin layer 15 may be 1250-3000 or 1250-2000. If it is less than the above range, the skin layer 15 may burst during the foaming molding step (S8) or the embossing step (S13) which will be described later. If it exceeds the above range, the surface feeling and ductility are lowered, Polyvinyl chloride resin can be used.
- the plasticizer contained in the composition for preparing the skin layer 15 is the same as the plasticizer contained in the pre-foamed layer 13a or the foamed layer 13b, so repeated descriptions are omitted.
- the pre-foamed layer or the composition for preparing the foam layer and the skin layer may further comprise at least one member selected from the group consisting of a heat stabilizer, a flame retardant and a filler for controlling melt strength and physical properties, There is no limit.
- the thickness of the skin layer 15 may be 100-300 ⁇ ⁇ or 120-200 ⁇ ⁇ .
- the amount is less than the above range, the surface smoothness and workability are lowered.
- the material cost is increased due to an increase in the amount of pigment added to realize the color, and when it exceeds the above range, the cushioning feeling of artificial leather is lowered, Can take a lot of time.
- the step (S5) may be a step of heat-laminating the back layer 11 coated on the bottom surface of the pre-foamed layer 13a or the foamed layer 13b.
- the step (S7) may be performed by heat-laminating the skin layer 15 on the pre-foamed layer 13a or the foamed layer 13b on which the back layer 11 is laminated.
- the back layer 11 coated with one side is laminated on the bottom surface of the pre-foam layer 13a or the foam layer 13b, and the pre-foam layer 13a or the foam layer 13b,
- the reason why the skin layer 15 is laminated on the upper portion 13b is that the back layer 11 has excellent mechanical strength and each layer holds the physical properties in the process. If the pre-foamed layer 13a or the foamed layer 13b and the skin layer 15 are first laminated, bending of the two layers 13a / 13b and 15 during thermal lamination, or curling such as bending of the layer It is possible to preferentially heat-laminate the back layer 11 having excellent mechanical strength on the bottom surface of the pre-expanded layer 13a or the foam layer 13b.
- the prefoamed foam layer 13a is passed through the oven at 220-230 ° C and foamed after the step (S7) to form a backing layer 11; A foam layer 13b '; And a foaming molding step (S8) of forming a semi-finished product in which the skin layer 15 is laminated.
- a surface treatment layer 17 is formed by applying and drying an aqueous surface treatment agent on the skin layer of the semi-finished product, and may be a single layer or a multilayer coating of two or more layers.
- the aqueous surface treatment agent may be a two-part type aqueous surface treatment agent containing, in 100 parts by weight of the subject, 1-25 parts by weight of a hardening agent, 1-25 parts by weight of an aqueous solvent, and 1-15 parts by weight of a silicone compound.
- the subject may be, but is not limited to, a water-dispersed polycarbonate-based polyurethane resin.
- the curing agent may contain, per molecule, at least one functional group selected from the group consisting of an aziridine group, an isocyanate group, and a carbodiimide group.
- the silicone compound may be in the form of a liquid in which the polysiloxane is dispersed in water or may be a polysiloxane in the form of beads, but may be in the form of a liquid, preferably dispersed in water with better surface feel.
- the aqueous solvent may be water or an alcohol or a mixture of water and an alcohol.
- the silicone compound may be in the form of a liquid in which the polysiloxane is dispersed in water or may be a polysiloxane in the form of beads, but may be in the form of a liquid, preferably dispersed in water with better surface feel.
- the above-described aqueous surface treatment agent can be applied.
- a composition excluding the silicone compound in the aqueous surface treatment agent described above can be applied to the base, The above-mentioned aqueous surface treating agent as described above can be applied.
- the drying may be performed at 110-150 ° C or 130-150 ° C for 80-120 seconds.
- the aqueous solvent remains not evaporated.
- whitening occurs on the surface of the artificial leather due to uncracking, and the surface properties are deteriorated.
- the temperature exceeds the above temperature range, So that it can be dried within the above temperature and time range.
- the whitening phenomenon refers to a white dot defect of a white dot appearing in the middle of the surface of the artificial leather after application of the aqueous surface treatment agent.
- the surface treatment layer 17 may have a thickness of 4-30 ⁇ or 4-20 ⁇ . By keeping the thickness of the surface treatment layer 17 within the above-mentioned range, the stain resistance can be secured simultaneously while maintaining the flexibility of the artificial leather. When the thickness is less than the above range, the thickness is too thin and durability is deteriorated. If it exceeds the above range, the material cost may be increased due to an increase in the requirement of the aqueous surface treatment agent.
- the step (S11) may include irradiating the surface of the skin layer (15) of the semi-finished product having the surface treatment layer (17) formed in step (S9) with infrared rays at 150-180 ⁇ for 5-15 seconds or 10-15 seconds .
- infrared rays When the infrared ray is irradiated at less than the above temperature and time, the skin layer 15 is not softened, so embossing is not performed well in the embossing step S13 to be described later.
- infrared rays are irradiated over the temperature and time, The infrared ray 15 can be melted and the infrared ray can be irradiated within the time.
- the process speed may be 10-20 m / min or 12-15 m / min.
- infrared may be irradiated for 14 seconds.
- the step (S13) may be performed at a vacuum of 0.02-0.08 MPa or 0.04-0.07 MPa for adsorbing and molding the embossment 19 using vacuum.
- a vacuum pressure range When the step is performed at a pressure lower than the vacuum pressure range, it is difficult to form the embossment 19, and the cushion feeling may be deteriorated. If the step is performed in excess of the above range, the surface treatment layer 17 may be damaged, So that it can be performed within the vacuum pressure range.
- the step (S13) may be performed at a temperature of 160-180 DEG C or 170-180 DEG C. It is difficult to sufficiently form the embossing 19 when the process is performed at a temperature lower than the above temperature range. When the process is performed at a temperature lower than the above range, the surface properties of the artificial leather may become rough or torn, .
- the foaming molding step S8, the surface treatment layer forming step S9, the infrared irradiation step S11 and the embossing step S13 may be selectively performed in-line have.
- the artificial leather of the present invention has an effect of having excellent surface appearance because the thickness of the formed surface treatment layer formed on the embossed bone and the floor is uniform.
- the artificial leather of the present invention has an effect of having a texture similar to that of natural leather and a soft touch.
- the artificial leather of the present invention can prevent the foamed cell constituting the foamed layer from being crushed or broken, thereby realizing an excellent cushioning effect.
- Paste 100 parts by weight of a mixed resin composed of 75% by weight of a vinyl chloride homopolymer and 25% by weight of a copolymer of vinyl chloride and vinyl acetate (vinyl acetate content: 6% by weight), 100 parts by weight of a plasticizer and 3 parts by weight of a curing agent
- the coating composition was thoroughly stirred at room temperature to prepare a coating solution having a cup viscosity (Zahn cup, # 3 cup) at 25 ⁇ for 110 seconds.
- a composition for preparing a skin layer containing 95 parts by weight of a plasticizer, 2 parts by weight of a pigment and 2 parts by weight of a heat stabilizer was kneaded with respect to 100 parts by weight of a straight polyvinyl chloride having a degree of polymerization of 1,300, and the kneaded raw material was passed through a calender roll To prepare a skin layer having a thickness of 150 mu m.
- the skin layer 15 was heat-laminated on the pre-foamed layer 13a on which the backside layer 11 was laminated.
- the skin layer the amount of 40-50g / m 2 of an aqueous surface treating agent containing 15 to a polycarbonate-based polyurethane resin based on 100 parts by weight of a curing agent, 5 parts by weight of a water-based solvent 20 parts by weight, and 5 parts by weight of a silicon compound , followeded by drying at 140 ⁇ to evaporate the aqueous solvent to form a surface treatment layer 17 having a thickness of 15 ⁇ .
- the surface of the semi-finished product on which the surface treatment layer 17 was formed was irradiated with infrared rays at 150-180 ⁇ ⁇ for 14 seconds and heated to about 170 ⁇ ⁇ and then exposed to the surface of the skin layer 15 and the surface treatment layer 17 at a vacuum system pressure of 0.06 Mpa And the emboss 19 was adsorbed and formed to complete the production of artificial leather according to the present invention.
- the artificial leather prepared in Example 1 was cut to any other position and an evaluation sample for measuring the difference in gloss between the valley 19a of the emboss 19 and the floor 19b was prepared.
- embossing molding step (S8) in Example 1 embossing was performed on the surface of the skin layer 15 using an embossing roll having an embossing pattern at a pressure of 4 Mpa to form an embossing, and the surface of the skin layer 15 In the same manner as in Example 1 except that an aqueous surface treatment agent was applied in the same amount as in Example 1 to form a surface treatment layer.
- the artificial leather prepared in Comparative Example 1 was cut into arbitrary different positions to prepare evaluation samples for measuring the difference in gloss between the valleys 19a of the embossments 19 and the floor 19b.
- the synthetic leather of Example 1 and Comparative Example 1 prepared above was cut in the vertical direction and the thickness of the surface treatment layer formed on the embossed bone and floor was measured using a high magnification optical microscope and the results are shown in Table 1 .
- Example 1 Comparative Example 1 Thickness ( ⁇ m) of the surface treatment layer formed on the embossed bone 15 15 The thickness ( ⁇ ) of the surface treatment layer formed on the embossed floor 15 10
- Example 1 of the artificial leather according to the present invention the thickness of the surface treatment layer formed on the embossed corrugation and the floor was uniform to 15 ⁇ , the thickness of the surface treatment layer formed on the embossed corrugation
- the ratio of the thickness of the surface treatment layer formed on the embossed floor to the surface of the embossed layer is 1, which satisfies a specific range of 0.7 to 1, so that there is little difference in gloss of the surface treatment layer, 1, the difference between the thickness of the surface treatment layer formed on the embossed corrugation and the thickness of the surface treatment layer formed on the floor is large, and the embossed floor
- the ratio of the thickness of the surface treatment layer formed on the base and the surface treatment layer formed on the floor was large and the difference in gloss of the surface treatment layer was large.
- the above gloss difference is defined as a gloss difference when there are five or more persons who answered that there is a difference in luster with respect to a synthetic leather sample constituting a panel with a panel of 10 persons and write it as X (appearance deterioration) When the number of respondents is less than 5, it is defined that there is no gloss difference and it is marked as ⁇ (excellent appearance).
- the artificial leather of Examples 2 to 10 according to the present invention had the artificial leather of Conventional Comparative Examples 2 to 10, in which the embossing was performed through the roller pressing method and the surface treatment agent was applied, It was confirmed that most of the evaluators did not feel the difference in gloss between the corrugated floor and the floor so that the surface appearance of the artificial leather according to the present invention was superior to that of the artificial leather of the comparative examples.
- microhardness was measured immediately after the needle contacted the artificial leather at a pressing speed of 1 mm / s in peak hold mode using a micro-hardness tester (Asker Micro Durometer, model: MD-1 CAPA) The maximum value was measured.
- a specimen having a width of 30 mm and a length of 150 mm was prepared from the artificial leather prepared in the above step 1, five samples were taken in each of the transverse direction and the longitudinal direction, and the bubble side was impregnated with a solvent such as methyl ethyl ketone (MEK) (Foam layer) and air bubbles (back layer) are forcedly peeled by a length of 50 mm in parallel with the short side, taking care not to apply stress to the bubbles.
- MEK methyl ethyl ketone
- test piece was allowed to stand in the room for 2 hours or more, the solvent was sufficiently volatilized, and the peeled skin (foam layer) and bubbles (back layer) were fixed to the clamp of the tensile tester and then peeled off at a rate of 200 mm / min Is obtained as an average value of the maximum value.
- the test results are the average of five specimens.
- 5 pieces of artificial leather specimens having a pi (pi) of 100 mm were prepared by using a softness measuring instrument (SDL Atlas, ST300D) at a temperature of 23 ⁇ 2 ° C. and a relative humidity of 50 ⁇ 5% Measurements were made by reading the numerical value of the scale moved for 15 seconds by pushing it with the instrument.
- SDL Atlas, ST300D softness measuring instrument
- the specimen is pressed with a pressing plate of the same size as the specimen and slid at a speed of about 10 mm / sec in the direction of the slope, and the position (B) of the other end when the one end of the specimen comes into contact with the slope is read as SCALE .
- the lecture figure is expressed by the moving distance (scale of B point) (mm), and it shows the average value of five surface and back surface in both length and width.
- Example One Comparative Example One Micro hardness 54 66 Peel strength [kgf / 30mm] 3 3 Softness 3.8 3.3 Sensibility (touch feeling) O ⁇ Lecture (mm) 52 76
- the artificial leather of Example 1 according to the present invention has a lower microhardness, higher ductility, and a soft touch feeling than artificial leather of Comparative Example 1 in which embossing is performed by a roller pressing method, It can be confirmed that the surface sensitivity is excellent.
- the artificial leather of Example 1 according to the present invention has low flexibility as compared with artificial leather of Comparative Example 1, so that it can be confirmed that flexibility is high.
- the average diameter of the foamed cells formed in a unit area of 1 mm 2 on the end face of the foam layer 13b 'after cutting the artificial leather in the vertical direction was measured using a scale bar of an optical microscope Respectively.
- the number of foam cells was measured by using an optical microscope after the artificial leather was cut in the vertical direction, and the number of foam cells formed in a unit area of 1 mm 2 on the cross section of the foam layer (13b ') side was measured.
- Example 1 Comparative Example 1 Foam cell size [ ⁇ ] 135-200 100-400 Foam cell number [pieces / mm 2 ] 15-20 5-10 Foam cell shape rectangle Unevenness Foaming layer thickness (mm) 0.5 0.3
- the artificial leather of Example 1 retains the spherical shape of the foamed cells in the foamed layer even after forming the embossed body by calendering and vacuuming, (Average diameter) of 135-200 ⁇ ⁇ , and the number of foam cells on the cross-section of the foam layer is 15-20 pieces / mm 2 , thereby realizing excellent cushioning feeling, high ductility and excellent sensitivity.
- embossing is performed by a roller pressing method, and the shape of the foam cells is irregular such as elongated and distorted, and the size and number of the foam cells are small. Softness, sensibility and the like are all lower than those of the artificial leather of Example 1.
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Abstract
Description
실시예 1 | 비교예 1 | |
엠보의 골에 형성된 표면처리층의 두께(㎛) | 15 | 15 |
엠보의 마루에 형성된 표면처리층의 두께(㎛) | 15 | 10 |
실시예 2 | 실시예 3 | 실시예 4 | 실시예 5 | 실시예 6 | 실시예 7 | 실시예 8 | 실시예 9 | 실시예 10 | 비교예 2 | 비교예 3 | 비교예 4 | 비교예 5 | 비교예 6 | 비교예 7 | 비교예 8 | 비교예 9 | 비교예 10 | |
광택 차이가 있다고 답한 인원 | 1 | 0 | 0 | 0 | 1 | 0 | 0 | 0 | 0 | 9 | 10 | 9 | 9 | 9 | 10 | 10 | 9 | 9 |
표면 외관 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | X | X | X | X | X | X | X | X | X |
실시예 1 | 비교예 1 | |
미소경도 | 54 | 66 |
박리강도 [kgf/30mm] | 3 | 3 |
연성(Softness) | 3.8 | 3.3 |
감성 (터치감) | ⓞ | △ |
강연도(mm) | 52 | 76 |
실시예 1 | 비교예 1 | |
발포 셀 크기[㎛] | 135-200 | 100-400 |
발포 셀 숫자[개/mm2] | 15-20 | 5-10 |
발포 셀 모양 | 구형 | 불균일 |
발포층 두께(mm) | 0.5 | 0.3 |
Claims (20)
- 엠보의 골에 형성되는 표면처리층의 두께에 대한 엠보의 마루에 형성되는 표면처리층의 두께의 비는 0.7-1인 것인 인조가죽.
- 제 1항에 있어서,상기 엠보의 골과 마루에 형성되는 표면처리층의 두께의 차가 5㎛미만인 것인 인조가죽.
- 제 1항에 있어서,상기 엠보의 골에 형성되는 표면처리층의 두께에 대한 엠보의 마루에 형성되는 표면처리층의 두께의 비가 0.7-1인 영역이 인조가죽 표면 전체의 80%이상인 것인 인조가죽.
- 제 1항에 있어서,상기 인조가죽은 하부에서 상부로 이면층, 발포층, 스킨층 및 표면처리층을 포함하고,상기 스킨층 및 표면처리층 상부에 형성된 엠보를 포함하는 것인 인조가죽.
- 제 1항에 있어서,상기 인조가죽은 미소경도가 45-59인 것인 인조가죽으로, 상기 미소경도는 미소경도계(Asker Micro Durometer社, 모델명 : MD-1 CAPA)를 이용하여 피크홀드 모드에서 압입속도 1mm/s로 상기 인조가죽에 바늘이 접촉한 직후, 즉 바늘의 부하유지시간이 1s일 때의 최대값을 측정한 것인, 인조가죽.
- 제 1항 내지 5항 중 어느 한 항의 인조가죽을 제조하는 방법으로서,직포 또는 부직포인 이면층의 일면을 코팅 용액으로 코팅하는 이면층 코팅단계(S1);예비발포층 또는 발포층 및 스킨층을 각각 성형하는 예비발포층 또는 발포층 및 스킨층 형성단계(S3);상기 예비발포층 또는 발포층의 저면에 일면이 코팅된 상기 이면층을 적층하는 이면층 적층단계(S5);상기 이면층이 형성된 예비발포층 또는 발포층의 상부에 상기 스킨층을 적층하는 스킨층 적층단계(S7);상기 스킨층 상부에 상기 수성 표면처리제를 코팅하여 표면처리층을 형성하는 표면처리층 형성단계(S9);상기 표면처리층 상부에 적외선을 조사하는 적외선 조사단계(S11);상기 적외선 조사를 통해 가열된 스킨층 및 표면처리층 상부에 진공을 이용하여 엠보를 흡착 성형해주는 엠보 성형단계(S13);를 포함하는 인조가죽 제조방법.
- 제 6항에 있어서,상기 (S1)단계의 코팅 용액은 폴리염화비닐 수지 100중량부에 대해, 가소제 70-130중량부 및 경화제 0.5-10중량부를 상온에서 교반하여 형성된 것인 인조가죽 제조방법.
- 제 7항에 있어서,상기 폴리염화비닐 수지는 염화비닐의 단독중합체 60-90중량% 및 염화비닐과 비닐 아세테이트의 공중합체 10-40중량%로 이루어진 혼합수지인 것인 인조가죽 제조방법.
- 제 6항에 있어서,상기 (S1)단계의 코팅 용액의 점도는 좐컵(Zahn cup, #3번 cup) 점도로 25℃에서 80-140초인 것인 인조가죽 제조방법.
- 제 6항에 있어서,상기 이면층과 발포층의 박리강도는 2.5-6kgf/30mm인 것인 인조가죽 제조방법.
- 제 6항에 있어서,상기 (S3)단계는 상기 예비발포층 또는 발포층 및 스킨층을 압출 성형 또는 캘린더링 성형하여 형성하는 단계인 것인 인조가죽 제조방법.
- 제 6항에 있어서,상기 예비발포층 또는 발포층은 폴리염화비닐 수지 100중량부에 대해, 가소제 60-120중량부 및 발포제 5-15중량부를 포함한 예비발포층 또는 발포층 제조용 조성물로부터 형성되는 것인 인조가죽 제조방법.
- 제 12항에 있어서,상기 폴리염화비닐 수지의 중합도는 900-1200인 스트레이트(straight) 폴리염화비닐 수지인 것인 인조가죽 제조방법.
- 제 6항에 있어서,상기 발포층의 발포율은 100-500%인 것인 인조가죽 제조방법.
- 제 6항에 있어서,상기 발포층에 형성된 발포 셀은 평균 직경은 120-250㎛인 구형의 발포 셀로, 상기 발포 셀은 발포층 측단면 또는 평단면의 1mm2의 단위면적 당 10-30개로 포함된 것인 인조가죽 제조방법.
- 제 6항에 있어서,상기 (S3)단계의 상기 스킨층은 폴리염화비닐 수지 100중량부에 대해, 가소제 60-120중량부 및 안료를 포함한 스킨층 제조용 조성물로부터 형성되는 것인 인조가죽 제조방법.
- 제 16항에 있어서,상기 폴리염화비닐 수지는 중합도가 1250-3000인 것인 인조가죽 제조방법.
- 제 6항에 있어서,상기 (S3)단계에서 예비발포층(13a) 및 스킨층(15)을 각각 형성하고, 상기 (S7)단계 이후에 상기 예비발포층(13a)을 발포시켜 발포층(13b')을 형성하는 발포 성형단계(S8)을 더 포함하는 것인 인조가죽 제조방법.
- 제 6항에 있어서,상기 (S11)단계는 150-180℃의 온도에서 5-15초 동안 적외선을 조사하는 단계인 것인 인조가죽 제조방법.
- 제 6항에 있어서,상기 (S13)단계는 진공을 이용하여 엠보(19)를 흡착 성형하는 단계로 0.02-0.08Mpa의 진공계 압력 및 160-180℃의 온도에서 수행되는 것인 인조가죽 제조방법.
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US16/641,956 US12024817B2 (en) | 2017-09-14 | 2018-09-11 | Artificial leather having excellent surface appearance and method of manufacturing the same |
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KR1020180098244A KR102080403B1 (ko) | 2017-09-14 | 2018-08-22 | 우수한 표면 외관을 갖는 인조가죽 및 그 제조방법 |
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KR20130130224A (ko) * | 2012-04-09 | 2013-12-02 | 한화엘앤씨 주식회사 | 자동차 시트커버용 인조가죽 및 그 제조방법 |
KR20170018580A (ko) * | 2015-08-10 | 2017-02-20 | (주) 정산인터내셔널 | 폴리에스터를 이용한 인조피혁 및 이의 제조 방법 |
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