Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
  • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
• • 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
  • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
  • D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
• • 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
• • 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
  • D06N3/12—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 otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
  • D06N3/14—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 otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/35—Abrasion, pilling or fibrillation resistance
• • 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
  • D06N2203/00—Macromolecular materials of the coating layers
  • D06N2203/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06N2203/045—Vinyl (co)polymers
• • 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
  • D06N2203/00—Macromolecular materials of the coating layers
  • D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06N2203/068—Polyurethanes
• • 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
  • D06N2209/00—Properties of the materials
  • D06N2209/16—Properties of the materials having other properties
  • D06N2209/1685—Wear resistance
• • 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
  • D06N2211/00—Specially adapted uses
  • D06N2211/12—Decorative or sun protection articles
  • D06N2211/28—Artificial leather

Definitions

• the present invention by using water-dispersible polyurethane as the binder resin, reduces the amount of organic solvent used in the production process, and in an environmentally friendly sheet, achieves both good flexibility and high quality appearance,
• the present invention also relates to a method for producing a sheet having good wear resistance.
• a sheet-like material mainly composed of a fibrous base material and polyurethane has excellent characteristics not found in natural leather, and is widely used in various applications.
• leather-like sheet materials using a polyester-based fibrous base material are excellent in light resistance, and thus their use has been spreading yearly for use in clothing, upholstery, and automotive interior materials.
• a fibrous base material is impregnated with an organic solvent solution of polyurethane, and then the resulting fibrous base material is mixed with a non-solvent of polyurethane or a mixed solution of organic solvent / water.
• a process of immersing the polyurethane therein to wet coagulate the polyurethane is generally employed.
• a water-miscible organic solvent such as N, N-dimethylformamide (hereinafter, referred to as "DMF" is used as an organic solvent as a solvent for such a polyurethane.
• DMF N, N-dimethylformamide
• a nonwoven fabric is impregnated with an aqueous solution of polyvinyl alcohol.
• the fiber sheet is immersed in a polyurethane impregnating solution, and the polyurethane is wet-coagulated in a 45% DMF aqueous solution at 20 ° C.
• a method for producing a sheet-like material by removing alcohol has been proposed (see Patent Document 1).
• a sheet-like material in which a conventional fibrous base material is impregnated with a water-dispersible polyurethane and is provided with polyurethane has a problem in that the polyurethane becomes strongly bonded to the fibers of the fibrous base material, and the texture becomes hard.
• Patent Document 2 attempts to suppress polyvinyl alcohol from falling into water by using a polyvinyl alcohol aqueous solution having a degree of saponification of 98% or more and a degree of polymerization of 800 to 3500 and containing few impurities.
• polyvinyl alcohol having a high degree of polymerization has a problem that the viscosity of the aqueous polyvinyl alcohol solution becomes high, and the impregnation into the fibrous base material and the handleability of the aqueous polyvinyl alcohol solution are reduced.
• the present invention reduces the use of organic solvents in the manufacturing process and considers the environment, and achieves both an elegant appearance with raised hair and a soft texture, even when using a low polymerization degree, low viscosity polyvinyl alcohol aqueous solution.
• Another object of the present invention is to provide a sheet-shaped material having good abrasion resistance.
• a sheet-like material having excellent flexibility is obtained by applying a polyvinyl alcohol having a high degree of saponification and applying a polyurethane after applying the polyvinyl alcohol.
• a polyvinyl alcohol having a high degree of saponification was obtained, and it was found that the solubility of polyvinyl alcohol in water can be effectively reduced by making the stereoregularity of polyvinyl alcohol a structure having a higher syndiotactic property.
• the present invention is to solve the above-mentioned problems, and the present invention is a method for producing a sheet-like material containing a fibrous base material containing ultrafine fibers and polyurethane, and comprises the following (1) This is a method for producing a sheet-like material including the steps (4) to (4).
• a polyvinyl alcohol aqueous solution which is an aqueous solution of polyvinyl alcohol having the following characteristics to a fibrous base material containing ultrafine fiber-expressing fibers as a main component, the fiber mass contained in the fibrous base material is reduced.
• a polyvinyl alcohol providing step of providing the polyvinyl alcohol in an amount of 0.1 to 50% by mass (Polyvinyl alcohol: The degree of saponification is 90% or more, and the rrr composition abundance ratio is 14.5% or more in a stereoregularity measurement measured by 13C-NMR in a heavy water solvent.)
• the ultrafine fiber expressing type fiber of the fibrous base material is converted into an ultrafine fiber having an average single fiber diameter of 0.1 to 10 ⁇ m, (3) a polyurethane applying step of applying an aqueous dispersion type polyurethane to the fibrous base material to which the polyvinyl alcohol has been applied after the step;
• a polyvinyl alcohol removing step of removing the polyvinyl alcohol from the fibrous base material to which the water-dispersed polyurethane has been applied.
• the degree of polymerization of the polyvinyl alcohol is 200 to 3,500.
• the fibrous base material containing the ultrafine fiber-expressing fibers as a main component is treated with an aqueous alkaline solution.
• heating is performed at 80 to 190 ° C.
• the fibrous base material having the ultrafine fiber-expressing fiber as a main component is entangled and integrated with the fiber and the woven and / or knitted fabric. Use what was done.
• an environmentally friendly manufacturing process achieves an elegant appearance and a soft texture even when a low-polymerization aqueous solution having high solubility in water and low viscosity is used. And a sheet having good abrasion resistance can be obtained.
• the method for producing a sheet material of the present invention includes the following steps (1) to (4).
• a polyvinyl alcohol aqueous solution which is an aqueous solution of polyvinyl alcohol having the following characteristics to a fibrous base material containing ultrafine fiber-expressing fibers as a main component, the fiber mass contained in the fibrous base material is reduced.
• a polyvinyl alcohol providing step of providing the polyvinyl alcohol in an amount of 0.1 to 50% by mass (Polyvinyl alcohol: The degree of saponification is 90% or more, and the rrr composition abundance ratio is 14.5% or more in a stereoregularity measurement measured by 13C-NMR in a heavy water solvent.)
• the ultrafine fiber expressing type fiber of the fibrous base material is converted into an ultrafine fiber having an average single fiber diameter of 0.1 to 10 ⁇ m, (3) a polyurethane applying step of applying an aqueous dispersion type polyurethane to the fibrous base material to which the polyvinyl alcohol has been applied after the step;
• a polyvinyl alcohol removing step of removing the polyvinyl alcohol from the fibrous base material to which the water-dispersed polyurethane has been applied.
• the steps (1) to (4) are performed in this order.
• a step of expressing ultrafine fibers from the ultrafine fiber-expressing fibers for example, sea-island type fibers
• a sea removing step for example, a sea removing step
• both voids caused by the removal of the polyvinyl alcohol and voids caused by the sea components removed from the sea are generated between the polyurethane and the ultrafine fibers. Therefore, the area where the surface of the ultrafine fiber is directly gripped by the polyurethane is further reduced. The texture of the sheet-like material becomes soft, but characteristics such as abrasion resistance tend to deteriorate.
• a fibrous base material containing ultrafine fiber-expressing fibers as a main component is provided with a polyvinyl alcohol aqueous solution which is an aqueous solution of polyvinyl alcohol having the following characteristics.
• the polyvinyl alcohol providing step of providing 0.1 to 50% by mass of the polyvinyl alcohol with respect to the mass of the fiber contained in the above is described.
• the polyvinyl alcohol used here has a degree of saponification of 90% or more and an rrr composition existence ratio of 14.5% or more.
• the polyvinyl alcohol to be applied to the fibrous base material preferably uses polyvinyl acetate as a raw material. Further, those using poly (vinyl trifluoroacetate) as a raw material are also preferable.
• Polyvinyl alcohol has a degree of saponification of 90% or more. It is preferably at least 95%, more preferably at least 98%. By setting the degree of saponification of polyvinyl alcohol to a certain value or more, after the polyvinyl alcohol is applied to the fibrous base material, the polyvinyl alcohol is prevented from being dissolved in the water-dispersed polyurethane liquid when applying the water-dispersed polyurethane. be able to.
• the saponification degree of polyvinyl alcohol can be calculated as follows as described in 3.5 "Saponification degree" of JIS K6726: 1994 "Testing method of polyvinyl alcohol”.
• Polyvinyl alcohol is weighed and placed in an Erlenmeyer flask, and water and a phenolphthalein solution are added, and completely dissolved at a temperature of 90 ° C. or higher.
• an aqueous solution of sodium hydroxide is added with a burette, shaken well, and kept at room temperature for 2 hours or more.
• the saponification degree is less than 97%, 0.5 mol / L is used, and when it is 97% or more, a 0.1 mol / L aqueous sodium hydroxide solution is used.
• Sulfuric acid or hydrochloric acid having the same molar concentration (unit mol / L) as the aqueous sodium hydroxide solution is added to the same amount of the aqueous sodium hydroxide solution as a burette and shaken well.
• the saponification degree H is calculated from the following equation.
• X 1 amount of acetic acid (%) corresponding to residual acetic acid groups
• X 2 residual acetic acid group (mol%)
• H Saponification degree (mol%)
• a Usage amount of sodium hydroxide aqueous solution in (4) (mL)
• b Usage amount (mL) of aqueous sodium hydroxide solution in blank test of (5)
• f Factor of aqueous sodium hydroxide solution
• D Concentration of aqueous sodium hydroxide solution (mol / L)
• S Polyvinyl alcohol collection amount (g)
• P Pure content (%) of polyvinyl alcohol.
• X 1 amount of carboxylic acid corresponding to residual carboxylic acid group (%)
• X 2 residual carboxylic acid group (mol%)
• Request X 2 using molecular weight of the carboxylic acid constituting the carboxylic acid vinyl ester in place of 60.05 (the molecular weight of acetic acid) of the formula.
• the polyvinyl alcohol applied to the fibrous base material has an rrr composition abundance of 14.5% or more in a stereoregularity measurement measured by 13 C-NMR in a heavy water solvent.
• a repeating structure of “r” in which adjacent hydroxyl groups are in different directions from each other is partially a syndiotactic structure.
• hydroxyl groups are alternately arranged up and down with respect to the plane formed by the carbon chains in the polymer, so it is easy to form a large number of hydrogen bonds due to hydroxyl groups in the polyvinyl alcohol molecule of the syndiotactic structure. Become. As a result, the number of hydroxyl groups that contribute to the formation of hydrogen bonds with water molecules decreases, so that the solubility in water decreases and the solubility in warm water also decreases.
• Polyvinyl alcohol in which the ratio of the rrr structure having the highest syndiotactic property is 14.5% or more can effectively lower the solubility in water.
• the existence ratio of the rrr structure is preferably 14.7% or more, more preferably 15.0% or more.
• the existence ratio of the rrr structure is less than 14.5%, the formation of hydrogen bonds between polyvinyl alcohols is reduced, and the polyvinyl alcohol dissolves and drops in water in a sea removing step, etc., and the polyurethane directly forms fibers.
• the number of parts to be gripped increases, and the flexibility and surface appearance of the sheet-like material decrease.
• the ratio of the mrr structure other than the rrr structure is 25% or more. It is more preferably at least 25.5%, further preferably at least 26%. In addition, it is preferable that the sum of the existence ratio of the rrr structure and the existence ratio of the mrr structure is 39.5% or more. It is more preferably at least 40%, further preferably at least 40.5%. On the other hand, the sum of the existence ratio of the mmr structure and the existence ratio of the mmr structure is preferably 50% or less. It is more preferably at most 48%, further preferably at most 45%.
• rrr structure there is no particular upper limit for the rrr structure, but it is preferably 28.0% or less, more preferably 20.0% or less, from the viewpoint of availability or production.
• polyvinyl alcohol is dissolved in a heavy water solvent at a temperature of 80 ° C., and 13 C-NMR measurement at a measurement temperature of 80 ° C. and a resonance frequency of 100 MHz is performed.
• the peak group observed at 45 to 49 ppm is the peak group corresponding to the methylene carbon in the polyvinyl alcohol skeleton.
• the peak group on the low magnetic field side is a methine carbon peak group to which a hydroxyl group in the polyvinyl alcohol skeleton is bonded.
• the peaks of the five peaks detected in the group of carbon peaks constituting the methylene group overlap, the peaks are vertically divided at the valleys of the peaks, the integrated value is calculated, and the abundance ratio of each sequence is calculated as a percentage.
• the peak of the rrr structure is the peak observed in the lowest magnetic field side in the peak group.
• the ratio of the rrr structure can be adjusted by appropriately changing the polymerization conditions and polymerization catalyst for polyvinyl alcohol or polyvinyl acetate that can be a raw material.
• the solubility of polyvinyl alcohol in water and the viscosity of an aqueous solution of polyvinyl alcohol vary depending on the degree of polymerization.
• the higher the degree of polymerization of polyvinyl alcohol the lower the solubility in water.
• the dissolution of polyvinyl alcohol in the water-dispersed polyurethane liquid can be further suppressed.
• the polyvinyl alcohol of the present invention has a high rrr composition abundance ratio, even when the degree of polymerization of polyvinyl alcohol is low, the dissolution of polyvinyl alcohol in the water-dispersed polyurethane liquid can be effectively suppressed. Therefore, the average degree of polymerization of polyvinyl alcohol is preferably 200 or more, more preferably 300 or more, and still more preferably 400 or more. By setting the degree of polymerization of polyvinyl alcohol to 200 or more, dissolution of polyvinyl alcohol in water can be suppressed.
• the average degree of polymerization of polyvinyl alcohol is preferably 3500 or less, more preferably 2500 or less, further preferably 1500 or less, and particularly preferably 1000 or less.
• the average degree of polymerization of polyvinyl alcohol is measured as in the following (1) to (7) according to 3.7 "average degree of polymerization" of JIS K6726: 1994 "Testing method for polyvinyl alcohol”.
• the average degree of polymerization calculated in the present invention is used.
• Polyvinyl alcohol is put in an Erlenmeyer flask, methanol is added, and then an aqueous sodium hydroxide solution is added and stirred.
• the polyvinyl alcohol is not the polyvinyl alcohol having the average polymerization degree specified in the present invention.
• the viscosity of a polyvinyl alcohol aqueous solution having a concentration of 4% by mass is measured as follows in 3.11.1 "Rotational viscometer method" of JIS K6726: 1994 "Testing method for polyvinyl alcohol”. Is the viscosity at 20 ° C. (1) Weigh polyvinyl alcohol and place in an Erlenmeyer flask. Prepare these three. (2) Water is added so that the concentration becomes 3.8% by mass, 4.0% by mass, and 4.2% by mass, and the mixture is completely heated and dissolved, and is allowed to cool to a temperature of 20 ° C., and is completely defoamed. I do.
• the polyvinyl alcohol has a viscosity of 2 to 70 mPa ⁇ s at 20 ° C. in a 4% by mass aqueous solution of the polyvinyl alcohol.
• the viscosity of the polyvinyl alcohol is within this range, an appropriate migration structure can be obtained inside the fibrous base material during drying, and the balance between the flexibility and surface appearance of the sheet-like material and physical properties such as abrasion resistance can be obtained. can get.
• the viscosity is 2 mPa ⁇ s or more, more preferably 3 mPa ⁇ s or more, and still more preferably 4 mPa ⁇ s or more, an extreme migration structure can be suppressed.
• the fibrous base material can be easily impregnated with polyvinyl alcohol.
• the glass transition temperature (Tg) of polyvinyl alcohol is preferably 70 to 100 ° C. or less.
• Tg glass transition temperature
• the glass transition temperature of polyvinyl alcohol is preferably 70 to 100 ° C. or less.
• the melting point of polyvinyl alcohol is preferably from 200 to 250 ° C.
• the melting point of polyvinyl alcohol is preferably from 200 to 250 ° C.
• the melting point of polyvinyl alcohol is preferably from 200 ° C. or higher, more preferably 210 ° C. or higher, softening in the drying step can be prevented, dimensional stability of the fibrous base material can be obtained, and the surface appearance of the sheet-shaped material deteriorates. Can be suppressed.
• the melting point of the polyvinyl alcohol to 250 ° C. or lower, more preferably 240 ° C. or lower, it is possible to prevent the fibrous base material from becoming too hard and deteriorating the handleability.
• the glass transition point and the melting point of polyvinyl alcohol are defined as the glass transition temperature and the melting temperature measured by differential scanning calorimetry (DSC) of JIS K7121: 1987 "Method for measuring the transition temperature of plastic", respectively.
• DSC differential scanning calorimetry
• an aqueous solution of polyvinyl alcohol is applied to a fibrous base material containing ultrafine fiber-expressing fibers as a main component, whereby the polyvinyl alcohol is added to the fibrous base material in an amount of 0.1 to 50 wt.
• the polyvinyl alcohol application step for applying the mass% will be described.
• the fibrous base material of the present invention contains ultrafine fiber-expressing fibers as main components.
• the content of the ultrafine fiber-expressing fibers in the fibrous equipment is preferably 50 to 100% by mass.
• the ultrafine fiber-expressing fiber in the fibrous base material is more preferably 60% by mass or more, and even more preferably 70% by mass or more, since an excellent surface appearance of the sheet material can be obtained.
• the fiber can be made ultrafine through a subsequent fiber ultrafineness step, and an elegant surface appearance can be obtained.
• thermoplastic resin of two components having different solvent solubility is made into a sea component and an island component, and the sea component is dissolved and removed using a solvent or the like, so that the island component is converted into the ultrafine fiber.
• "Sea-island type fiber” can be used.
• two-component thermoplastic resin may be alternately arranged radially or in a multilayer shape on the fiber cross section, and each component may be separated and split into ultrafine fibers by splitting to separate fibers. it can.
• the sea-island type fiber is preferably used from the viewpoint of the flexibility and texture of the sheet-like material because the sea component can be removed to remove the sea component, thereby providing an appropriate space between the island components, that is, between the ultrafine fibers. .
• sea-island type fiber for example, a sea-island type composite fiber or a sea-island type composite fiber obtained by mutually arranging and spinning the two components of the sea component and the island component, and the two components of the sea component and the island component were mixed and spun.
• the former sea-island composite fiber is preferably used in that ultrafine fibers having a uniform fineness can be obtained, and ultrafine fibers having a sufficient length can be obtained, which contributes to the strength of the sheet-like material.
• the island component of the sea-island fiber is not particularly limited, the following are exemplified.
• Polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate and polylactic acid.
• Polyamides such as polyamide 6 and polyamide 66; acrylics; polyethylene; And thermoplastic resins that can be melt-spun, such as thermoplastic cellulose.
• polyester fibers from the viewpoints of strength, dimensional stability and light resistance. Further, from the viewpoint of environmental consideration, it is preferable that the fiber is obtained from a recycled material or a plant-derived material. Further, the fibrous base material may be formed by mixing fibers of different materials.
• sea component of the sea-island fiber is not particularly limited, the following are exemplified.
• Hydrocarbon addition polymers such as polyethylene, polypropylene, and polystyrene.
• Copolymerized polyester obtained by copolymerizing sodium sulfoisophthalate, polyethylene glycol, etc.
• Polylactic acid Polyvinyl alcohol.
• copolymerized polyester or polylactic acid which is copolymerized with alkali-decomposable sodium sulfoisophthalate or polyethylene glycol, which can be decomposed without using an organic solvent, and hot water-soluble polyvinyl alcohol are used. preferable.
• the cross-sectional shape of the fiber constituting the fibrous base material is not particularly limited, and may be a round cross-section. However, an elliptic shape, a polygonal shape such as a flat shape and a triangular shape, and a modified cross-sectional shape such as a fan shape and a cross shape are employed. Is also good.
• a woven fabric, a knitted fabric, a nonwoven fabric and the like can be adopted.
• a nonwoven fabric is preferably used because the surface appearance of the sheet-like material after the surface raising treatment is good.
• the nonwoven fabric may be either a short fiber nonwoven fabric or a long fiber nonwoven fabric.
• the number of fibers in the thickness direction of the sheet-like material that becomes raised when raised is shorter than that of short-fiber nonwoven fabrics, and the dense appearance of the raised fibers tends to be low, resulting in poor surface appearance.
• a fibrous nonwoven fabric is preferably used.
• the short fiber length of the short fiber nonwoven fabric is preferably 25 to 90 mm.
• the fiber length is at least 25 mm, more preferably at least 30 mm, a sheet-like material having excellent abrasion resistance due to entanglement can be obtained.
• the fiber length is set to 90 mm or less, more preferably 80 mm or less, a sheet-like material excellent in texture and quality can be obtained.
• Needle punching or water jet punching can be used as a method of entanglement of the fibers or fiber bundles of the nonwoven fabric.
• the fibrous base material composed of the ultrafine fiber-expressing fibers is a nonwoven fabric
• the ultrafine fiber-expressing fibers of the nonwoven fabric are intertwined with each other in advance.
• the fibrous base material made of the ultrafine fibers has a structure in which the bundles of the ultrafine fibers are entangled, and the ultrafine fibers are entangled in a bundle, so that the sheet-like material is formed. The strength is improved.
• the fibrous base material containing the microfiber-expressing fiber as a main component is a nonwoven fabric
• the fibrous base material may be further entangled and integrated with a woven or knitted fabric for the purpose of improving strength or the like.
• a woven fabric plain weave, twill weave, satin weave and the like can be mentioned, and plain weave is preferably used in terms of cost.
• a knitted material circular knitting, tricot, Russell and the like can be mentioned.
• the average single fiber diameter of the fibers constituting such a woven or knitted fabric is preferably 0.3 to 20 ⁇ m.
• the amount of polyvinyl alcohol applied to the fibrous base material is 0.1 to 50% by mass based on the mass of the fibrous base material.
• the applied amount of polyvinyl alcohol is 0.1% by mass or more, preferably 1% by mass or more, a sheet having good flexibility and texture is obtained, and the applied amount of polyvinyl alcohol is 50% by mass or less, preferably By setting it to 45% by mass or less, a sheet-like material having good workability and good physical properties such as abrasion resistance can be obtained.
• the method for applying polyvinyl alcohol to the fibrous base material is not particularly limited, and various methods usually used in this field can be adopted. Among them, a method in which polyvinyl alcohol is dissolved in water, impregnated into a fibrous base material, and dried by heating is preferred from the viewpoint of uniform application. When the drying temperature is too low, a long drying time is required. When the temperature is too high, the polyvinyl alcohol is insolubilized and it is difficult to dissolve and remove it later. Therefore, the drying temperature is preferably from 80 to 140 ° C, and the drying temperature is more preferably from 110 to 130 ° C.
• the drying time is usually 1 to 20 minutes, preferably 1 to 10 minutes, more preferably 1 to 5 minutes from the viewpoint of processability.
• a heat treatment may be performed after drying.
• the preferred temperature of the heat treatment is 80 to 190 ° C.
• the second step ie, the step of expressing ultrafine fibers having an average single fiber diameter of 0.1 to 10 ⁇ m from a fibrous base material containing ultrafine fiber-expressing fibers, will be described.
• the ultrafine fiber-expressing fibers are preferably sea-island fibers.
• the ultrafine fiber development treatment of a fibrous base material containing such fibers as a main component is a sea removal treatment. This can be performed by immersing the fibrous base material in a solvent, dissolving the sea component in the solvent, and squeezing the fibrous base material.
• the solvent is an organic solvent such as toluene or trichloroethylene when the sea component is polyethylene, polypropylene or polystyrene, and when the sea component is copolyester or polylactic acid.
• An aqueous solution of an alkali such as sodium hydroxide can be used.
• the sea component is polyvinyl alcohol
• hot water can be used. From the viewpoint of environmental considerations in the process, a sea removal treatment with an aqueous alkali solution such as sodium hydroxide or hot water is preferred.
• the average single fiber diameter of the ultrafine fibers obtained from the ultrafine fiber-expressing fibers through the fiber ultrafine-coating step is 0.1 to 10 ⁇ m.
• the average single fiber diameter is 10 ⁇ m or less, more preferably 7 ⁇ m or less, and still more preferably 5 ⁇ m or less, it is possible to obtain a sheet having excellent flexibility and nap quality.
• the average single fiber diameter is 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, and still more preferably 0.7 ⁇ m or more, the color development after dyeing or the bundling at the time of napping treatment such as grinding with sandpaper etc. It has excellent fiber dispersibility and is easy to judge.
• the average single fiber diameter adopts a value obtained by the following procedure.
• a portion to be a sample is cut out from a fibrous base material, a desealed sheet, or a sheet.
• the diameter of a single fiber of the extracted 50 ultrafine fibers is measured in ⁇ m units to the first decimal place.
• the fibers having a fiber diameter of more than 50 ⁇ m are mixed, the fibers are clearly excluded from ultrafine fibers and are excluded from the measurement target of the average fiber diameter.
• the cross-sectional area (S) of the single fiber is first measured, and the diameter (D) of a circle corresponding to the cross-sectional area is calculated as follows to obtain the diameter of the single fiber.
• the average value is calculated using the population as a population, and is defined as the average single fiber diameter.
• a third step that is, a polyurethane applying step of applying a water-dispersible polyurethane to a fibrous base material containing ultrafine fibers to which polyvinyl alcohol has been added as a main component will be described.
• the water-dispersed polyurethane is (I) a forced emulsified polyurethane which is forcibly dispersed and stabilized in water using a surfactant, and (II) a hydrophilic structure in the polyurethane molecular structure, and the surfactant is Although it is classified as a self-emulsifying polyurethane which disperses and stabilizes in water even if it does not exist, any of them may be used in the present invention.
• the method of applying the water-dispersible polyurethane to the fibrous base material is not particularly limited.
• a method of impregnating and applying a water-dispersed polyurethane liquid to a fibrous base material, coagulating, and then heating and drying can be uniformly applied.
• the concentration of the polyurethane is preferably from 10 to 50% by mass, more preferably from 15 to 40% by mass in the water-dispersed polyurethane liquid.
• the water-dispersible polyurethane liquid used in the present invention may contain a water-soluble organic solvent in an amount of 40% by mass or less based on the polyurethane liquid in order to improve storage stability and film-forming properties. It is preferable that the content of the organic solvent be 1% by mass or less from the viewpoint of preservation and the like.
• the water-dispersible polyurethane liquid used in the present invention is preferably one having heat-sensitive coagulability.
• polyurethane can be applied uniformly in the thickness direction of the fibrous base material.
• the thermosetting property refers to a property that when the polyurethane liquid is heated, when the temperature reaches a certain temperature, the fluidity of the polyurethane liquid decreases and solidifies.
• the temperature at which this occurs is called the heat-sensitive coagulation temperature.
• a polyurethane liquid is applied to a fibrous base material, it is coagulated by dry coagulation, wet heat coagulation, wet coagulation, or a combination thereof, and then dried. Is given.
• dry coagulation is practical in industrial production.
• the heat-sensitive coagulation temperature of the water-dispersed polyurethane liquid is preferably 40 to 90 ° C.
• the heat-sensitive coagulation temperature is preferably 40 to 90 ° C.
• a heat-sensitive coagulant may be appropriately added in order to keep the heat-sensitive coagulation temperature as described above.
• the heat-sensitive coagulant include inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, magnesium sulfate, calcium sulfate and calcium chloride; sodium persulfate, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, and peroxide.
• examples include a radical reaction initiator such as benzoyl.
• the polyurethane liquid can be coagulated by impregnating or applying a polyurethane liquid to a fibrous base material, by dry coagulation, wet heat coagulation, wet coagulation, or a combination thereof.
• the temperature of the wet heat coagulation is preferably equal to or higher than the heat coagulation temperature of polyurethane, and more preferably 40 to 200 ° C.
• the temperature of the wet heat coagulation is preferably equal to or higher than the heat coagulation temperature of polyurethane, and more preferably 40 to 200 ° C.
• the wet coagulation temperature is equal to or higher than the heat-sensitive coagulation temperature of polyurethane, and is preferably 40 to 100 ° C.
• the temperature of the dry coagulation and the drying temperature are preferably from 80 to 140 ° C.
• productivity is excellent.
• a heat treatment may be performed after the polyurethane is solidified.
• the interface between the polyurethane molecules is reduced, resulting in a stronger polyurethane.
• Heat treatment after removing polyvinyl alcohol from the sheet provided with the water-dispersed polyurethane is also a preferred embodiment.
• the temperature of the heat treatment is preferably from 80 to 170 ° C.
• a polyurethane obtained by reacting a polymer diol, an organic diisocyanate, and a chain extender is preferable.
• the polymer diol is not particularly limited, but, for example, polycarbonate-based, polyester-based, polyether-based, silicone-based, and fluorine-based diols can be used, and a copolymer of these diols may be used.
• polycarbonate-based and polyether-based diols are preferably used.
• polycarbonate and polyester are preferably used.
• polycarbonate-based and polyester-based diols are more preferred, and polycarbonate-based diols are particularly preferred.
• the polycarbonate diol can be produced by a transesterification reaction between an alkylene glycol and a carbonate, or a reaction between phosgene or chloroformate and an alkylene glycol.
• alkylene glycol examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol.
• Examples of the branched alkylene glycol include neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, and the like.
• Other examples include alicyclic diols such as 1,4-cyclohexanediol, aromatic diols such as bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.
• polyester diol examples include polyester diols obtained by condensing various low molecular weight polyols with polybasic acids.
• the low-molecular-weight polyol is not particularly limited.
• Adducts obtained by adding various alkylene oxides to bisphenol A can also be used.
• the polybasic acid is not particularly limited, for example, succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, phthalic acid, isophthalic acid, One or two or more selected from terephthalic acid and hexahydroisophthalic acid are exemplified.
• the polyether diol is not particularly limited, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolymerized diols obtained by combining them.
• the number average molecular weight of the polymer diol used in the present invention is preferably from 500 to 4,000. By setting the number average molecular weight to 500 or more, more preferably 1500 or more, it is possible to prevent the texture from becoming hard. Further, by setting the number average molecular weight to 4000 or less, more preferably 3000 or less, the strength as polyurethane can be maintained.
• the organic diisocyanate is not particularly limited, for example, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, aliphatic diisocyanate such as xylylene diisocyanate, diphenylmethane diisocyanate, and aromatic diisocyanate such as tolylene diisocyanate. And these may be used in combination. Among them, aliphatic diisocyanates such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate are preferably used from the viewpoint of light resistance.
• the chain extender is not particularly limited, but an amine-based chain extender such as ethylenediamine and methylenebisaniline, and a diol-based chain extender such as ethylene glycol can be used. Further, a polyamine obtained by reacting a polyisocyanate with water can be used as a chain extender.
• a crosslinking agent may be used in combination with the polyurethane for the purpose of improving water resistance, abrasion resistance, hydrolysis resistance and the like.
• the cross-linking agent may be an external cross-linking agent added as a third component to the polyurethane, or may be an internal cross-linking agent that introduces a reaction site that becomes a cross-linked structure in the polyurethane molecular structure in advance.
• crosslinking agent a compound having an isocyanate group, an oxazoline group, a carbodiimide group, an epoxy group, a melamine resin, a silanol group, or the like can be used.
• the crosslinking proceeds excessively, the polyurethane tends to be hardened and the texture of the sheet-like material tends to be hard. Therefore, those having a silanol group are preferably used in terms of the balance between the reactivity and the flexibility.
• the polyurethane used in the present invention preferably has a hydrophilic group in the molecular structure.
• a hydrophilic group in the molecular structure By having a hydrophilic group in the molecular structure, the dispersion and stability of the water-dispersible polyurethane can be improved.
• hydrophilic group examples include a cationic group such as a quaternary amine salt, an anionic group such as a sulfonate and a carboxylate, a nonionic group such as polyethylene glycol, a combination of a cationic group and a nonionic group, and an anionic group and a nonionic group.
• a cationic group such as a quaternary amine salt
• an anionic group such as a sulfonate and a carboxylate
• nonionic group such as polyethylene glycol
• a combination of a cationic group and a nonionic group a nonionic hydrophilic group which does not cause yellowing due to light or adverse effects due to a neutralizing agent is particularly preferably used.
• a neutralizing agent is required.
• the neutralizing agent is a tertiary amine such as ammonia, triethylamine, triethanolamine, triisopropanolamine, trimethylamine and dimethylethanolamine.
• amines are generated and volatilized by heat during film formation and drying, and are released outside the system. Therefore, in order to suppress the release to the atmosphere and the deterioration of the working environment, it is necessary to introduce a device for recovering the volatile amine. Further, when the amine is not volatilized by heating and remains in a sheet material as a final product, the amine may be discharged to the environment when the product is incinerated.
• a nonionic hydrophilic group there is no need to introduce an amine recovery device because a neutralizing agent is not used, and there is no fear of amine remaining in the sheet-like material. it can.
• the neutralizing agent for the anionic hydrophilic group is an alkali metal such as sodium hydroxide, potassium hydroxide, and calcium hydroxide, or a hydroxide of an alkaline earth metal
• the polyurethane portion may be wet with water. Although it shows alkalinity, in the case of a nonionic hydrophilic group, there is no need to worry about deterioration due to hydrolysis of the polyurethane because no neutralizing agent is used.
• the water-dispersed polyurethane used in the present invention may optionally contain various additives, for example, pigments such as carbon black, phosphorus-based, halogen-based, silicone-based and inorganic-based flame retardants, phenol-based, sulfur-based and phosphorus-based.
• additives for example, pigments such as carbon black, phosphorus-based, halogen-based, silicone-based and inorganic-based flame retardants, phenol-based, sulfur-based and phosphorus-based.
• Antioxidants such as benzotriazoles, benzophenones, salicylates, cyanoacrylates and oxalic acid anilides, etc.
• UV absorbers such as hindered amines and benzoates
• light stabilizers such as polycarbodiimide, etc.
• Fillers such as stabilizers, plasticizers, antistatic agents, surfactants, softeners, water repellents, coagulation regulators, viscosity regulators, dyes, preservatives, antibacterial agents, deodorants, cellulose particles, microballoons, etc.
• inorganic particles such as silica and titanium oxide.
• an inorganic material such as sodium hydrogen carbonate or an organic material such as 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] is used.
• a foaming agent may be contained.
• the content ratio of polyurethane to the fibrous base material containing the ultrafine fiber of the present invention as a main component is preferably 1 to 80% by mass.
• the ratio of the polyurethane is preferably 1% by mass or more, more preferably 5% by mass or more, it is possible to obtain sheet strength and prevent the fibers from falling off.
• the mixing ratio of the polyurethane is 80% by mass or less, more preferably 70% by mass or less, it is possible to prevent the texture from becoming hard and obtain a good nap quality.
• a flexible sheet is obtained by removing polyvinyl alcohol from the fibrous base material after the polyurethane is applied.
• the method for removing the polyvinyl alcohol is not particularly limited.
• the sheet is immersed in hot water at 60 to 100 ° C. and, if necessary, squeezed with a mangle or the like to dissolve and remove the sheet.
• the method for producing a sheet-like material of the present invention may include a step of half-cutting in the thickness direction after applying the water-dispersible polyurethane to at least the fibrous base material to which polyvinyl alcohol has been applied.
• a large amount of polyvinyl alcohol adheres to the surface layer of the fibrous base material due to migration, and the amount of polyvinyl alcohol adhered to the inner layer is small.
• the water-dispersed polyurethane is applied and then cut in half in the thickness direction, so that the water-dispersed polyurethane is adhered less on the side where the amount of polyvinyl alcohol is attached, and the water-dispersed polyurethane is attached on the side where the amount of polyvinyl alcohol is less.
• the surface to which a large amount of polyvinyl alcohol adheres in other words, the surface to which a small amount of water-dispersed polyurethane adheres is used as the napped surface of the sheet-like material, the following effects can be obtained.
• the polyvinyl alcohol Since the polyvinyl alcohol is provided, a large gap is generated between the polyurethane and the ultrafine fibers constituting the nap. As a result, the fibers constituting the nap are given a degree of freedom, the surface texture becomes soft, and a good appearance quality and a soft touch are obtained.
• the surface on which the polyvinyl alcohol adheres little that is, the surface on which the water-dispersed polyurethane adheres frequently is used as the napped surface of the sheet-like material
• the following effects can be obtained.
• the fibers constituting the nap are strongly gripped by the polyurethane.
• the nap length is short, a good appearance quality with a dense feeling is obtained, and the abrasion resistance is further improved.
• the production efficiency can be improved by including the step of half-cutting in the sheet thickness direction.
• the sheet-like material may be raised to form raised hairs on the surface.
• the method for forming the nap is not particularly limited, and various methods commonly used in the art, such as buffing with sandpaper or the like, can be used. If the nap length is too short, it is difficult to obtain an elegant appearance, and if the nap length is too long, pilling tends to occur. Therefore, the nap length is preferably 0.2 to 1 mm.
• silicone or the like may be applied as a lubricant to the sheet before the raising treatment.
• the addition of the lubricant is preferable because raising the surface by grinding easily becomes possible and the surface quality becomes very good.
• an antistatic agent may be applied before the raising treatment. This is a preferred embodiment because the application of the antistatic agent makes it difficult for grinding powder generated from the sheet-like material to be deposited on sandpaper by grinding.
• the sheet material can be dyed.
• various methods usually used in this field can be employed.However, since a sheet-like material can be softened by giving a rubbing effect at the same time as dyeing the sheet-like material, a liquid jet dyeing machine is used. The method used is preferred.
• the dyeing temperature is preferably from 80 to 150 ° C, although it depends on the type of fiber. By setting the dyeing temperature at 80 ° C. or higher, more preferably at 110 ° C. or higher, it is possible to efficiently dye the fibers. On the other hand, by setting the dyeing temperature to 150 ° C. or lower, more preferably 130 ° C. or lower, it is possible to prevent the deterioration of the polyurethane.
• the dye used in the present invention may be selected according to the type of fiber constituting the fibrous base material, and is not particularly limited.
• a disperse dye can be used as long as it is a polyester fiber, and a polyamide fiber can be used. If so, an acid dye or a gold-containing dye can be used, and further, a combination thereof can be used.
• reduction washing may be performed after dyeing.
• a dyeing assistant at the time of dyeing.
• the uniformity and reproducibility of the dyeing can be improved.
• a finishing agent treatment using a softener such as silicone, an antistatic agent, a water repellent, a flame retardant, a light resistant agent, an antibacterial agent, or the like can be performed.
• the sheet-like material obtained by the above-mentioned production method achieves an elegant appearance and a soft texture, and has good abrasion resistance.
• the surface appearance of the sheet is evaluated by the following method.
• the surface appearance of the sheet was evaluated by visual and sensory evaluation on a five-point scale, assuming a total of 20 evaluators, 10 male and 10 female adults in good health, as follows.
• the surface appearance is preferably grade 3 to grade 5.
• Grade 5 Uniform fiber napping, good dispersion of fibers, good appearance.
• Grade 4 An evaluation between grades 5 and 3.
• Grade 3 The dispersion state of the fibers is slightly poor, but the fibers are raised and the appearance is fairly good.
• Grade 2 An evaluation between Grade 3 and Grade 1.
• Grade 1 The dispersion state of the fiber is very poor as a whole, or the nap of the fiber is long and the appearance is poor.
• the flexibility of the sheet-shaped material is determined in accordance with JIS L1096: 2010 “Method for testing the fabric of woven and knitted fabrics”, 8.21 “Bending softness”, and “A method (45 ° cantilever method)” described in 8.21.1. )),
• the evaluation is made based on the magnitude of the softness (mm) measured as follows. (1) A test piece of 2 cm ⁇ 15 cm is created in each of the vertical direction and the horizontal direction. (2) Place on a horizontal platform having a 45 ° slope. (3) The test piece is slid, and the position of the other end when the center point of one end of the test piece contacts the slope is read by a scale. (4) The length of movement of the test piece at this time is represented by (mm), and the average value of the movement length of the five test pieces is determined and defined as the softness (mm).
• the bending resistance of the sheet is preferably 20 to 45 mm. It is more preferably at least 25 mm. In addition, it is preferably 40 mm or less where the bending resistance is high.
• the abrasion resistance shall be evaluated by the small amount of abrasion loss (mg) measured by the following method.
• a circular sample (45 mm in diameter) of a sheet is cut out and its mass is measured.
• a bundle of polyamide fibers made of polyamide 6 having a diameter of 0.4 mm and cut to a length of 11 mm perpendicular to the longitudinal direction of the fibers is arranged in a bundle of 100 pieces.
• the wear loss of the sheet is preferably 30 mg or less. More preferably, it is 25 mg or less.
• the density of the sheet obtained by the above-mentioned production method is preferably 0.2 to 0.7 g / cm 3 .
• the density is 0.2 g / cm 3 or more, more preferably 0.3 g / cm 3 or more, the surface appearance becomes dense and high quality can be exhibited.
• the density is 0.7 g / cm 3 or less, more preferably 0.6 g / cm 3 or less, it is possible to prevent the texture of the sheet from becoming hard.
• Example 1 (Process for forming nonwoven fabric for fibrous base material) Polyethylene terephthalate prepared by copolymerizing 8 mol% of sodium 5-sulfoisophthalate as a sea component and polyethylene terephthalate as an island component were prepared. A sea-island composite fiber having 36 islands / 1 filament and an average single fiber diameter of 17 ⁇ m was obtained at a composite ratio of 45% by mass of the sea component and 55% by mass of the island component. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to obtain a staple. A fibrous web was formed through a card and a cross wrapper, and was formed into a nonwoven fabric by needle punching. The nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink, and dried at a temperature of 100 ° C. for 5 minutes to obtain a nonwoven fabric for a fibrous base material.
• Polyvinyl alcohol aqueous solution preparation step Polyvinyl alcohol having a saponification degree of 98%, an rrr composition abundance ratio of 15.5%, and a polymerization degree of 450 obtained from polyvinyl acetate was prepared. It was added to water at 25 ° C., heated to 90 ° C., and kept at 90 ° C. with stirring for 2 hours to prepare an aqueous solution having a solid content of 10% by mass to obtain an aqueous polyvinyl alcohol solution.
• Polyvinyl alcohol application step The above-mentioned nonwoven fabric for a fibrous base material was impregnated with the above-mentioned aqueous solution of polyvinyl alcohol, heated and dried at a temperature of 140 ° C for 10 minutes, and then subjected to a heat treatment at a temperature of 160 ° C for 5 minutes. A polyvinyl alcohol-added sheet was obtained in which the amount of polyvinyl alcohol attached to the fiber mass of the nonwoven fabric for a fibrous base material was 30% by mass.
• the polyvinyl alcohol-coated sheet was immersed in an aqueous solution of sodium hydroxide having a concentration of 10 g / L and heated to a temperature of 60 ° C. and treated for 30 minutes to obtain a sea-removed sheet from which the sea component of the sea-island composite fiber was removed.
• the average single fiber diameter of the cross section of the desealing sheet was 3 ⁇ m.
• Polyurethane liquid preparation step 1 part by weight of magnesium sulfate as a heat-sensitive coagulant is added to 100 parts by weight of a solid content of a polycarbonate-based self-emulsifying polyurethane liquid in which polyhexamethylene carbonate is applied to a polyol and dicyclohexylmethane diisocyanate is applied to an isocyanate, and the whole is mixed with water.
• the heat-sensitive coagulation temperature was 65 ° C.
• Example 2 (Process for forming nonwoven fabric for fibrous base material) Polyethylene terephthalate prepared by copolymerizing 8 mol% of sodium 5-sulfoisophthalate as a sea component and polyethylene terephthalate as an island component were prepared. A sea-island composite fiber having 16 islands / 1 filament and an average single fiber diameter of 12 ⁇ m was obtained at a composite ratio of 45% by mass of the sea component and 55% by mass of the island component. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to obtain a staple. It was formed into a fibrous web through a card and a cross wrapper, and subjected to a needle punch treatment to obtain a nonwoven fabric. The nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink, and dried at a temperature of 100 ° C. for 5 minutes to obtain a nonwoven fabric for a fibrous base material.
• Polyvinyl alcohol application step The same polyvinyl alcohol aqueous solution as in Example 1 was used to obtain a polyvinyl alcohol-coated sheet in which the amount of polyvinyl alcohol attached was 30% by mass based on the mass of the fibers of the nonwoven fabric for a fibrous base material.
• Example 2 (Extra fine fiber development process) The above nonwoven fabric for a fibrous base material was treated in the same manner as in Example 1 to obtain a sea-removed sheet from which the sea component of the sea-island composite fiber was removed.
• the average single fiber diameter of the cross section of the desealed sheet was 2 ⁇ m.
• Polyurethane application step A polyurethane-coated sheet was obtained in the same manner as in Example 1.
• Example 3 (Process for forming nonwoven fabric for fibrous base material) Polyethylene terephthalate prepared by copolymerizing 8 mol% of sodium 5-sulfoisophthalate as a sea component and polyethylene terephthalate as an island component were prepared. A sea-island composite fiber having 16 islands / 1 filament and an average single fiber diameter of 20 ⁇ m was obtained at a composite ratio of 20% by mass of the sea component and 80% by mass of the island component. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to obtain a staple. It was formed into a fibrous web through a card and a cross wrapper, and subjected to a needle punch treatment to obtain a nonwoven fabric. The nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink, and dried at a temperature of 100 ° C. for 5 minutes to obtain a nonwoven fabric for a fibrous base material.
• Polyvinyl alcohol application step The same polyvinyl alcohol aqueous solution as in Example 1 was used to obtain a polyvinyl alcohol-coated sheet in which the amount of polyvinyl alcohol attached was 30% by mass based on the mass of the fibers of the nonwoven fabric for a fibrous base material.
• Example 2 (Extra fine fiber development process) The above nonwoven fabric for a fibrous base material was treated in the same manner as in Example 1 to obtain a sea-removed sheet from which the sea component of the sea-island composite fiber was removed.
• the average single fiber diameter of the cross section of the desealing sheet was 4.4 ⁇ m.
• Polyurethane application step A polyurethane-coated sheet was obtained in the same manner as in Example 1.
• Example 4 (Process for forming nonwoven fabric for fibrous base material) Polyethylene terephthalate prepared by copolymerizing 8 mol% of sodium 5-sulfoisophthalate as a sea component and polyethylene terephthalate as an island component were prepared. A sea-island composite fiber having 16 islands / 1 filament and an average single fiber diameter of 24 ⁇ m was obtained at a composite ratio of 10% by mass of sea component and 90% by mass of island component. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to obtain a staple. It was formed into a fibrous web through a card and a cross wrapper, and subjected to a needle punch treatment to obtain a nonwoven fabric. The nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink, and dried at a temperature of 100 ° C. for 5 minutes to obtain a nonwoven fabric for a fibrous base material.
• Polyvinyl alcohol application step The same polyvinyl alcohol aqueous solution as in Example 1 was used to obtain a polyvinyl alcohol-coated sheet in which the amount of polyvinyl alcohol attached was 30% by mass based on the mass of the fibers of the nonwoven fabric for a fibrous base material.
• Example 2 (Extra fine fiber development process) The above nonwoven fabric for a fibrous base material was treated in the same manner as in Example 1 to obtain a sea-removed sheet from which the sea component of the sea-island composite fiber was removed.
• the average single fiber diameter of the cross section of the sea-removed sheet was 5.5 ⁇ m.
• Polyurethane application step A polyurethane-coated sheet was obtained in the same manner as in Example 1.
• Example 2 (Half-cut / napping / dyeing / reduction cleaning process) A sheet was obtained in the same manner as in Example 1. The surface appearance of the obtained sheet was good, had a soft texture, and also had good abrasion resistance.
• Example 5 (Nonwoven fabric for fibrous base material) The same nonwoven fabric for a fibrous base material as in Example 1 was used.
• a polyvinyl alcohol-applied sheet was obtained in the same manner as in Example 1 except that the same polyvinyl alcohol aqueous solution as in Example 1 was used, and the amount of polyvinyl alcohol attached was changed by adjusting the squeezing after impregnation.
• the sheet had an adhesion amount of polyvinyl alcohol of 20% by mass relative to the fiber mass of the nonwoven fabric for a fibrous base material.
• Polyurethane application step A polyurethane-coated sheet was obtained in the same manner as in Example 1.
• Example 6 (Process for forming nonwoven fabric for fibrous base material) Polyethylene terephthalate prepared by copolymerizing 8 mol% of sodium 5-sulfoisophthalate as a sea component and polyethylene terephthalate as an island component were prepared. A sea-island composite fiber having 16 islands / 1 filament and an average single fiber diameter of 20 ⁇ m was obtained at a composite ratio of 20% by mass of the sea component and 80% by mass of the island component. The obtained sea-island type composite fiber was cut into a fiber length of 51 mm to obtain a staple. It was formed through a card and a cross wrapper to form a fibrous web.
• PET polyethylene terephthalate
• a plain woven fabric using a strong twist yarn of 2,000 T / m in number of twists were laminated and subjected to a needle punch treatment to obtain a nonwoven fabric.
• the nonwoven fabric thus obtained was immersed in hot water at a temperature of 98 ° C. for 2 minutes to shrink, and dried at a temperature of 100 ° C. for 5 minutes to obtain a nonwoven fabric for a fibrous base material.
• Polyvinyl alcohol application step A polyvinyl alcohol-applied sheet was obtained in the same manner as in Example 1 except that the same polyvinyl alcohol aqueous solution as in Example 1 was used, and the amount of polyvinyl alcohol attached was changed by adjusting the squeezing after impregnation.
• the sheet had an amount of polyvinyl alcohol attached of 15% by mass based on the mass of fibers of the nonwoven fabric for a fibrous base material.
• Example 2 (Extra fine fiber development process) The above nonwoven fabric for a fibrous base material was treated in the same manner as in Example 1 to obtain a sea-removed sheet from which the sea component of the sea-island composite fiber was removed.
• the average single fiber diameter of the cross section of the sea-removing sheet was 4.4 ⁇ m.
• Polyurethane application step A polyurethane-coated sheet was obtained in the same manner as in Example 1.
• Example 7 (Process for forming nonwoven fabric for fibrous base material) The same nonwoven fabric for a fibrous base material as in Example 1 was used.
• Polyvinyl alcohol aqueous solution preparation step Polyvinyl alcohol having a saponification degree of 98%, an rrr composition abundance of 15.2%, and a polymerization degree of 1000, obtained from polyvinyl acetate, was prepared. It was added to 25 ° C. water, heated to 90 ° C., and kept at 90 ° C. with stirring for 2 hours to obtain a polyvinyl alcohol aqueous solution having a solid content of 10% by mass.
• Polyvinyl alcohol application step A polyvinyl alcohol-coated sheet was obtained in the same manner as in Example 1 except that the aqueous polyvinyl alcohol solution was used, in which the amount of polyvinyl alcohol attached was 30% by mass based on the mass of the fibers of the nonwoven fabric for a fibrous base material.
• Polyurethane application step A polyurethane-coated sheet was obtained in the same manner as in Example 1.
• Example 8 Provides for forming nonwoven fabric for fibrous base material. In the same manner as in Example 6, a nonwoven fabric for a fibrous base material was obtained.
• Polyvinyl alcohol application step A polyvinyl alcohol-coated sheet was obtained in the same manner as in Example 6 except that the aqueous polyvinyl alcohol solution of Example 7 was used, in which the amount of polyvinyl alcohol attached was 15% by mass relative to the fiber mass of the nonwoven fabric for a fibrous base material.
• Polyurethane application step A polyurethane-coated sheet was obtained in the same manner as in Example 1.
• Example 1 Provides for forming nonwoven fabric for fibrous base material. The same nonwoven fabric for a fibrous base material as in Example 1 was used.
• Polyvinyl alcohol aqueous solution preparation step Polyvinyl alcohol having a saponification degree of 98%, an rrr composition existence ratio of 14.1%, and a polymerization degree of 400 obtained from polyvinyl acetate was prepared. It was added to water at 25 ° C., heated to 90 ° C., and kept at 90 ° C. with stirring for 2 hours to prepare an aqueous solution having a solid content of 10% by mass to obtain an aqueous polyvinyl alcohol solution.
• Polyvinyl alcohol application step A polyvinyl alcohol-coated sheet was obtained in the same manner as in Example 1 except that the aqueous polyvinyl alcohol solution was used, in which the amount of polyvinyl alcohol attached was 30% by mass based on the mass of the fibers of the nonwoven fabric for a fibrous base material.
• Polyurethane application step A polyurethane-coated sheet was obtained in the same manner as in Example 1.
• the obtained sheet-like material does not have a uniform imparted state due to the partial dissolution of polyvinyl alcohol in an aqueous alkali solution or a water-dispersed polyurethane liquid, and the surface appearance is poor in the dispersion state of fibers and there is no dense feeling of nap. It was poor and the texture was hard.
• a polyvinyl alcohol-coated sheet was obtained in the same manner as in Example 6 except that the aqueous polyvinyl alcohol solution of Comparative Example 1 was used, in which the amount of polyvinyl alcohol attached to the nonwoven fabric for a fibrous base material was 15% by mass based on the fiber mass.
• Polyurethane application step A polyurethane-coated sheet was obtained in the same manner as in Example 1.
• the obtained sheet-like material does not have a uniform imparted state due to the partial dissolution of polyvinyl alcohol in an aqueous alkali solution or a water-dispersed polyurethane liquid, and the surface appearance is poor in the dispersion state of fibers and there is no dense feeling of nap. It was poor and the texture was hard.
• Polyvinyl alcohol aqueous solution preparation step Polyvinyl alcohol having a saponification degree of 98%, an rrr composition abundance ratio of 13.9%, and a polymerization degree of 500 obtained from polyvinyl acetate was prepared. It was added to water at 25 ° C., heated to 90 ° C., and kept at 90 ° C. with stirring for 2 hours to prepare an aqueous solution having a solid content of 10% by mass to obtain an aqueous polyvinyl alcohol solution.
• Polyvinyl alcohol application step A polyvinyl alcohol-coated sheet was obtained in the same manner as in Example 1 except that the aqueous polyvinyl alcohol solution was used, in which the amount of polyvinyl alcohol attached was 30% by mass based on the mass of the fibers of the nonwoven fabric for a fibrous base material.
• Polyurethane application step A polyurethane-coated sheet was obtained in the same manner as in Example 1.
• the obtained sheet-like material does not have a uniform imparted state due to the partial dissolution of polyvinyl alcohol in an aqueous alkali solution or a water-dispersed polyurethane liquid, and the surface appearance is poor in the dispersion state of fibers and there is no dense feeling of nap. It was poor and the texture was hard.
• Polyvinyl alcohol aqueous solution preparation step A polyvinyl alcohol having a degree of saponification of 99%, a composition ratio of rrr of 14.4%, and a degree of polymerization of 500 obtained from polyvinyl acetate was prepared. It was added to water at 25 ° C., heated to 90 ° C., and kept at 90 ° C. with stirring for 2 hours to prepare an aqueous solution having a solid content of 10% by mass to obtain an aqueous polyvinyl alcohol solution.
• Polyvinyl alcohol application step A polyvinyl alcohol-coated sheet was obtained in the same manner as in Example 1 except that the aqueous polyvinyl alcohol solution was used, in which the amount of polyvinyl alcohol attached was 30% by mass based on the mass of the fibers of the nonwoven fabric for a fibrous base material.
• Polyurethane application step A polyurethane-coated sheet was obtained in the same manner as in Example 1.
• the obtained sheet-like material does not have a uniform imparted state due to the partial dissolution of polyvinyl alcohol in an aqueous alkali solution or a water-dispersed polyurethane liquid, and the surface appearance is poor in the dispersion state of fibers and there is no dense feeling of nap. It was poor and the texture was hard.
• Polyvinyl alcohol aqueous solution preparation step Polyvinyl alcohol having a degree of saponification of 88%, a composition ratio of rrr of 14.2%, and a degree of polymerization of 500 obtained from polyvinyl acetate was prepared. It was added to water at 25 ° C., heated to 90 ° C., and kept at 90 ° C. with stirring for 2 hours to prepare an aqueous solution having a solid content of 10% by mass to obtain an aqueous polyvinyl alcohol solution.
• Polyvinyl alcohol application step A polyvinyl alcohol-coated sheet was obtained in the same manner as in Example 1 except that the aqueous polyvinyl alcohol solution was used, in which the amount of polyvinyl alcohol attached was 30% by mass based on the mass of the fibers of the nonwoven fabric for a fibrous base material.
• Polyurethane application step A polyurethane-coated sheet was obtained in the same manner as in Example 1.
• the obtained sheet-like material does not have a uniform imparted state due to the partial dissolution of polyvinyl alcohol in an aqueous alkali solution or a water-dispersed polyurethane liquid, and the surface appearance is poor in the dispersion state of fibers and there is no dense feeling of nap. It was poor and the texture was hard.
• Polyurethane application step A polyurethane-coated sheet was obtained in the same manner as in Example 1.
• the surface appearance of the obtained sheet was good and had a soft texture, but the amount of abrasion loss was large.
• Polyurethane application step A polyurethane-coated sheet was obtained in the same manner as in Example 1.
• Table 1 shows the test conditions and the evaluation results of the sheet-like material of each Example and Comparative Example.
• Sheets obtained by the present invention are furniture, chairs and wall materials, and interior materials having a very elegant appearance as skin materials such as seats in car interiors such as cars, trains and aircraft, ceilings and interiors, shirts, Jackets, casual shoes, sports shoes, men's shoes, women's shoes, and other shoe uppers, trims, bags, belts, wallets, etc., and clothing materials, wiping cloths, polishing cloths, CD curtains, etc. used for some of them Can be suitably used as an industrial material.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Dispersion Chemistry (AREA)
• Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)
• Diaphragms For Electromechanical Transducers (AREA)
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• 2019
  • 2019-06-18 CN CN201980038469.5A patent/CN112262238A/zh active Pending
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