CN1985042B - Production of extra-fine filament-interlaced sheet - Google Patents
Production of extra-fine filament-interlaced sheet Download PDFInfo
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- CN1985042B CN1985042B CN200580023582.4A CN200580023582A CN1985042B CN 1985042 B CN1985042 B CN 1985042B CN 200580023582 A CN200580023582 A CN 200580023582A CN 1985042 B CN1985042 B CN 1985042B
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Abstract
A method of producing an entangled sheet of microfine long fibers using long fibers for forming microfine fibers. The method includes a step of forming a long-fiber web made of long fibers for forming microfine fibers, at least one component of the long fibers being a water-soluble, thermoplastic polyvinyl alcohol resin; a step of entangling the long-fiber web to form a long-fiber entangled sheet; a step of shrinking the long-fiber entangled sheet to form a long-fiber shrunk sheet; and a step of converting the long fibers for forming microfine fibers in the long-fiber shrunk sheet to microfine long fibers, thereby producing the entangled sheet of microfine long fibers. The step of entangling is conducted so as to allow the long-fiber entangled sheet to have an interlaminar peel strength of 2 kg/2.5 cm or more. The step of shrinking is conducted so as to shrink in an areal shrinkage of 35% or more.
Description
Technical field
The present invention relates to the production method of extra-fine filament-interlaced sheet, described extra-fine filament-interlaced sheet is suitable for as the substrate of leather-like sheet and the invention further relates to production method with the substrate of the leather-like sheet of elastomeric polymer dipping.
Background technology
Leather-like sheet, for example dermatine is accepted by the consumer, and this is that they have superiority because compare with natural leather: lightweight and processing arbitrarily, and be widely used on clothes, versatile material, motion goods and the other products.
Usually produce known dermatine by the following method of listing: make and form the composite fibre that ultra tiny fiber is used, described ultra tiny fiber is made up of two kinds of polymer that have different solubilities in staple fiber; By carding machine, cross lapping machine or random web-laying equipment; Staple fiber is made fiber web (web); This fiber web of acupuncture, the supatex fabric of formation fibre matting; With elastomeric polymer, for example polyurethane impregnated is in this supatex fabric; By removing a kind of component in the composite fibre, this composite fibre is changed into ultra tiny fiber then, form soft dermatine.
With compare by the supatex fabric of staple fibre manufacturing, be favourable by the supatex fabric of long fiber manufacturing because its production does not need one group of big device, for example supply coarse-fibred device, the device and the carding machine of fiber opening (open).With compare by the supatex fabric of staple fibre manufacturing, also be favourable aspect the intensity by the supatex fabric of long fiber manufacturing.
The substrate that the supatex fabric of attempting to be made by long fiber is produced leather-like sheet.Yet the substrate of the dermatine of particle arrangement (grain-finished) is that 0.5dtex or bigger regular fiber are made by fineness on the market, does not occur the dermatine of being made by fine filament on the market as yet.This may be owing to be difficult to have on the production unit area sheet material that the long fiber of stabilised quality tangles, be difficult to handle the compound long fiber that is spun into long filament (spun) for form ultra tiny fiber and because of the fineness of composite long fiber inhomogeneous and distortion cause product quality inhomogeneous due to.In fact, if with use staple fibre produce in employed same procedure, produce supatex fabric by fine filament, sheet material corrugation in changing into the step of ultra tiny fiber, staining procedure and other step then makes stable production difficulty.
In order to eliminate this inhomogeneities, following method has been proposed, wherein part is cut long fiber, partly to reduce distortion (patent documentation 1).Yet this method reduces improves the advantage of intensity by long fiber length, and in some cases, can't make full use of long fiber.Following method has also been proposed: wherein by weaving or braided fabric strengthens long stapled supatex fabric, with the change of shape (patent documentation 2) that prevents composite sheet.Yet, only use reinforced fiber can not resist the lax of fiber distortion, may cause wrinkling.
Patent documentation 1:JP2000-273769A; Patent documentation 2:JP 64-20368A
Disclosure of the Invention
The purpose of this invention is to provide the method for producing extra-fine filament-interlaced sheet, this method can produced leather-like sheet with using ultramicrofine long fiber in the substrate, although this up to now long fiber is not suitable for this production technology.
To achieve these goals, the inventor furthers investigate, the result has realized the present invention. that is, the invention provides the method for producing extra-fine filament-interlaced sheet, this method comprises the step of the long fibre net that formation is made by the long fiber that is used to form ultra tiny fiber, and at least a component in its medium-length fibre is water miscible thermoplastic polyvinyl alcohol resin; The entanglement long fibre net is with the step of the sheet material of formation long fiber entanglement; The sheet material that long fiber is tangled shrinks to form the step of long stapled contraction sheet material; With will change into the step of fine filament at the long fiber that is used to form ultra tiny fiber in the long stapled contraction sheet material, produce extra-fine filament-interlaced sheet thus, the step of the long fibre net of wherein tangling be the interlaminar strength of the sheet material that tangles with long fiber be that 2kg/2.5cm or bigger mode are carried out and sheet material step of shrinking that long fiber is tangled be with percentage reduction of area (areal shrinkage) be 35% or bigger mode carry out.
The present invention further provides the method for producing the substrate be used for leather-like sheet, this method further comprises elastomeric polymer is impregnated into step in the extra-fine filament-interlaced sheet of producing by said method.
The present invention still further is provided for the substrate of leather-like sheet, and it is by above-mentioned method production, and the leather-like sheet of particle arrangement and the leather-like sheet of suede finish are produced in the substrate that is used for leather-like sheet by processing separately.
Implement optimal mode of the present invention
The production method of extra-fine filament-interlaced sheet of the present invention comprises that long fibre net that formation made by long fiber is for the step that forms ultra tiny fiber, the entanglement long fibre net, form the step of the sheet material of long fiber entanglement, the sheet material that long fiber is tangled shrinks, form the step of long stapled contraction sheet material, with will change into the step of fine filament at the long fiber that is used to form ultra tiny fiber in the long stapled contraction sheet material, so produce extra-fine filament-interlaced sheet.However the extra-fine filament-interlaced sheet of Sheng Chaning can directly be used and act on the substrate of leather-like sheet, but preferably is made into the substrate that is used for leather-like sheet with the elastomeric polymer dipping.The leather-like sheet of particle arrangement and the leather-like sheet of suede finish are processed in the substrate that will be used for leather-like sheet.
In the present invention, term " long fiber " is meant the long fiber of staple fibre that is generally about 10-50mm than length, with the fiber that does not have deliberately cutting (as producing cutting in the staple fibre).For example, long stapled length is preferably 100mm or longer before changing into ultra tiny fiber, and can be several meters, hundreds of meters or thousands of rice, as long as can produce or not have physical rupture technically.
The long fiber of the ultra tiny fiber of formation used in the present invention is selected from sea-island fiber and multi-layer fiber, these fibers are by the class methods production such as blending or composite spinning, wherein preferably form sea-island, the long fiber that ultra tiny fiber is used as sea component and water-insoluble thermoplastic resin as what the island component was formed by water-soluble, thermoplastic polyvinyl alcohol resin.
The preferred embodiment of water-insoluble thermoplastic resin comprises, but be not limited to, mylar, for example polyethylene terephthalate (being called PET in some cases), polytrimethylene terephtalate, polybutylene terephthalate (being called PBT in some cases), and polyester elastomer; Polyamide, for example nylon 6, nylon 66, NYLON610, aromatic polyamides and polyamide elastomer; With the polymer that forms fiber, for example polyurethane resin, vistanex, acrylonitrile resin and modified resin thereof wherein preferably use PET, PBT, nylon 6 and nylon 66, and this is because the final products of sense of touch and function admirable can obtain to use the time.Especially preferred PET and modified resin thereof, the PET of isophthalate modified for example, this is because when use hot water treatment, the shrinkage of the sheet material of long fiber entanglement is good.
In view of shape stability and practicality consideration, the fusing point of water-insoluble thermoplastic resin is preferably 160-350 ℃.The method of measuring fusing point below will be described.
Consider environmental pollution, the shrinkage when removing by dissolving etc., water-soluble, thermoplastic polyvinyl alcohol (hereinafter referred to as " PVA resin ") is preferably used as and forms the long stapled sea component of ultra tiny fiber.The PVA resin shrinks when removing by dissolving significantly, obtains having highdensity extra-fine filament-interlaced sheet, so make the drapability of gained leather-like sheet and sense of touch be similar to natural leather completely.In order to obtain the hide-like sense of touch, the preferred 0.3g/cm of the apparent density of extra-fine filament-interlaced sheet
3Or bigger, and in order to obtain the fine and close sense of touch of good hide-like and performance, more preferably 0.4g/cm
3Or it is bigger.Do not determine the upper limit particularly, but for fear of hard sense of touch, preferred 0.9g/cm
3Or it is lower. in order to realize that apparent density is in above-mentioned scope, the content of PVA resin is preferably 5-70% in the long fiber that the ultra tiny fiber of formation is used, more preferably 10-60%, especially preferred 15-50%, wherein separately based on quality, this is because long fiber entanglement sheet material stably demonstrates 35% or bigger percentage reduction of area in shrink process.
The preferred 200-500 of the viscometric degree of polymerization of PVA resin (hereinafter only being called " degree of polymerization "), more preferably 230-470, still more preferably 250-450.If 200 or higher, then acquisition is enough to the PVA resin is made the melt viscosity of composite fibre.If 500 or lower, then melt viscosity is not too high and the PVA resin ejects from spinneret easily.Have 500 or the PVA resin of lower low polymerization degree be favourable, this be because when the usefulness hot water treatment dissolution velocity height.
Measure the degree of polymerization (P) according to JIS K6726, wherein resaponifying and purifying PVA resin are measured its intrinsic viscosity [η] then in water under 30 ℃.Calculate the degree of polymerization according to following equation:
P＝([η]×10
3/8.29)
(1/0.62)
When the degree of polymerization is in the 200-500 scope, will realize purpose of the present invention well.
The saponification degree of PVA resin is preferably 90-99.99%, more preferably 93-99.98%, and still more preferably 94-99.97% and especially preferred 96-99.96% are wherein separately based on mole.If 90mol% or higher, the Heat stability is good of PVA resin then, and can avoid the defective melt spinning that causes because of thermal decomposition and gelling.In addition, biodegradable is good.In addition, according to the kind of the comonomer of the following stated, the water-soluble of PVA resin do not descend, and makes the long fiber that can steady production be used to form ultra tiny fiber.Be difficult to the PVA of steady production saponification degree greater than 99.99mol%.
The PVA resin can by the activated sludge processing or by underground landfill, biodegradation be also resolved into water and carbon dioxide.Preferred process contains the waste water of PVA, and this is by dissolving, and activated sludge is handled from the PVA resin and removed waste water and realize.When the waste water that contains PVA was handled continuously by activated sludge, the PVA resin decomposed in the time period in January at 2 days.Because the combustion heat is low, therefore the result, after drying contains the waste water of PVA, can burn the PVA resin to burning device generation heat burden seldom.
Fusing point (the T of PVA resin
m) be preferably 160-230 ℃, more preferably 170-227 ℃ and still more preferably 175-224 ℃ and especially be preferably 180-220 ℃.If 160 ℃ or higher, then can avoid the toughness of fibre decline that descends and cause the PVA resin because of degree of crystallinity.In addition, the PVA resin has the performance of good heat endurance and formation fiber.If 230 ℃ or lower, then can stably produce the long fiber that is used to form ultra tiny fiber, this is because can make the melt spinning temperature be lower than the decomposition temperature of PVA fully.The measuring method of fusing point is as described below.
The resin that mainly constitutes by saponification by the vinyl acetate unit, thus the PVA resin produced.The example that is used for the vinyl monomer of vinyl acetate unit comprises vinyl formate, vinyl acetate, propionate, valeric acid vinyl acetate, capric acid vinyl acetate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate, new vinyl acetate acid and branched alkane carboxylic acid's vinyl acetate (vinylversatate), wherein in view of easy production PVA resin, therefore preferred vinyl acetate.
The PVA resin can be homopolymerization PVA or the modified PVA of introducing comonomer unit, wherein in view of good melt spinning, water-soluble and fibre property, and preferred modified PVA.In view of good copolymerization, melt spinning and water-soluble, the preferred embodiment of comonomer is to have 4 or the still less alpha-olefin of carbon atom, for example ethene, propylene, 1-butylene and isobutene; And vinethene, for example ethylene methacrylic ether, ethyl vinyl ether, n-pro-pyl vinethene, isopropyl-ethylene ether and normal-butyl vinethene.The molar content of comonomer unit is preferably 1-20% in PVA, more preferably 4-15% and still more preferably 6-13%.Especially the PVA of optimal ethylene modification, this is because when comonomer unit is ethene, the fibre property raising.The molar content of ethylene unit is preferably 4-15% and more preferably 6-13% in the PVA of ethene modification.
Can be by known method, for example bulk polymerization, polymerisation in solution, suspension polymerization and emulsion polymerisation, thereby produce the PVA resin. there is not solvent in general the use or at solvent, for example bulk polymerization in the alcohol or polymerisation in solution. the example that is used for the solution of polymerisation in solution comprises lower alcohol, methyl alcohol for example, ethanol and propyl alcohol. at known initator, for example azo initiator or peroxide initiator, α for example, α '-azobis isobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), benzoyl peroxide and peroxide carbonic acid n-propyl exist down, carry out copolymerization. and polymerization temperature is not crucial, and recommends 0-150 ℃ scope.
Can be effectively by spunbond method in conjunction with melt spinning, produce the long fibre net of making by the fiber that is used to form ultra tiny fiber.For example, melt-kneaded PVA resin and water-insoluble thermoplastic resin in different extruders respectively.With the nozzle of molten resin flow, be incorporated on the spinning head, and from nozzle, eject by combination.Composite long fiber by the cooling device cooling injection goes out uses aspirator, and employing speed by air flow jetting, is drawn into the fineness of being planned corresponding to the coiling speed of 1000-6000m/min, collects on the surface of moving then.After the long fiber that the part compression is collected, optionally obtain long fibre net.In view of handling easily in this technology, the long stapled fineness that therefore is used to form ultra tiny fiber is preferably 1-5dtex and unit mass is preferably 20-500g/m
2The preferred quantity of adjusting the island, so that the fineness of the average single fiber of gained fine filament preferably drops in the 0.0003-0.5dtex scope, more preferably 0.001-0.2dtex, this is because will obtain favourable leather-like sheet of flexibility and outward appearance and the leather-like sheet with good chromatic suede finish.Can for example pass through under transmission electron microscope, to observe the cross section or the surface of the dermatine of suede finish, thereby measure the average single fiber fineness of the fine filament of the dermatine that constitutes suede finish.
Using oil agent (oiling agent), the anti-broken needle of silicone oil, mineral oil or other type (anti-needle break) oil agent for example, after antistatic oil agent and entanglement oil agent oil to the long fibre net of so producing, the processing of tangling in known manner.For three dimensional entanglement and the easy apparent density that increases resulting sheet, preferred acupuncture.Optionally, oil for lamination (stack), tangle then by using the two-layer or more multi-layered long fibre net of stack such as cross lapping machine to obtain.When using this lamination, preferably reduce the unevenness of mass area ratio.Can come suitably to determine the quantity of long fibre net of stack and the quality of lamination unit are according to the thickness that leather-like sheet is planned.The gross mass of the fiber web unit are of stack is preferably 100-1000g/m
2, this is because handle easily.
In the processing of tangling, the fiber web of the stack of tangling is 2kg/2.5cm or bigger long fiber entanglement sheet material so that produce interlaminar strength.Interlaminar strength is preferably 4kg/2.5cm or bigger, and this is because the sense of touch and the good strength of leather-like sheet.Can estimate the three dimensional entanglement degree by interlaminar strength.If interlaminar strength is less than 2kg/2.5cm, it is not enough then to tangle, and even when by shrink process, when for example hot water shrinks high compaction, also can not obtain to have the leather-like sheet of sufficient intensity and natural leather shape densification sense of touch.In addition, occur because the wrinkle defective that fiber slides and causes.Do not stipulate the upper limit of interlaminar strength particularly, but consider the balance between acupuncture load and the sense of touch, consider the problem such as broken needle, be preferably 30kg/2.5cm or still less.
Do not limit the condition of acupuncture particularly, for example kind of oil agent and consumption, the shape of pin, depth of needling and pin hole quantity are as long as obtain interlaminar strength in above-mentioned scope.For example, although when barb (barb) quantity increases, acupuncture is more effective, and selecting barb quantity is 1-9, so that do not cause broken needle.Can set depth of needling, so that the barb of pin arrives the fibroreticulate surface of stack and do not have tangible acupuncture mark.The quantity of acupuncture is preferably 500-5000 pin hole/cm
2, but this depends on the shape of pin and the kind and the consumption of oil agent.The quality optimization of unit are is at least 1.5 times and more preferably at least 1.7 times of quality before the processing of tangling after entanglement is handled, and this is because can easily prevent wrinkling.The upper limit is not concrete and in view of successfully carrying out this method and avoid increasing because of the process velocity that reduces causes production cost, therefore preferred 4 times or still less.
To handling by tangling, for example the sheet material of the long fiber entanglement of acupuncture production carries out shrink process then.For the substrate as leather-like sheet, the percentage reduction of area in shrink process that requires to represent with following formula is 35% or bigger:
[area before (area after the area-contraction before shrinking)/contraction] * 100
If percentage reduction of area is less than 35%, then the apparent density of gained extra-fine filament-interlaced sheet is not enough height, the feasible shape that is difficult to keep sheet material.This negative effect disposal ability conversely and with the processing effect of the production stage of the substrate that is used for leather-like sheet of elastomeric polymer dipping and the substrate that is used for leather-like sheet that can not get having sufficient intensity.Consider the limit of physics shrinkage factor and sense of touch, the upper limit of percentage reduction of area is preferably 80% or still less.
Can pass through known method, preferably handle, thereby carry out shrink process by hot water treatment or Steam Heating.
Can be by carrying out shrink process and comprise the step that changes into ultra tiny fiber of removing (removing) by dissolving simultaneously by extraction, thus carry out hot water treatment.Preferably, handle this two stage mode with shrink process and extraction and carry out hot water treatment, this is because of shrinking the efficient height and can extracting simultaneously, so that this technology is effective.For example, in the phase I, at preferred 65-85 ℃, more preferably soak the sheet material 5-300 second that long fiber tangles in 70-80 ℃ the hot water, with in second stage,, more preferably soak the sheet material 100-600 second that long fiber tangles in 90-100 ℃ the hot water at preferred 85-100 ℃.
In steam heat is handled, in relative humidity preferred 75% or bigger, more preferably 90% or bigger steam atmosphere in heat treatment long fiber sheet material 60-600 second of tangling.If relative humidity is 75% or bigger, then will prevent to adhere to the rapid draing of the water on the sheet material that long fiber tangles, to guarantee 35% or bigger percentage reduction of area.The temperature of shrink process (temperature of atmosphere) is preferably 60-130 ℃, and this is because the sheet material that this device is operated easily and long fiber tangles shrinks widely.Because the PVA resin is dissolving fully not, therefore, in the production of the little fabric of thickness, use steam heat to handle.According to the kind of device, technology and final products, carry out the heat treated selection of hot water treatment or steam.
Continue shrink process, before the quality of unit are after the shrink process reaches shrink process 1.2-4 times (in mass) of the quality of unit are, be preferably 1.3-4 doubly (in mass), this is because can obtain to have the outward appearance of the suede finish of the fine and close sense of touch of hide-like, high cashmere density, high-quality and good writing effect.By aforesaid shrink process, with percentage reduction of area is 35% or the sheet material that tangles of bigger long fiber and form the fine filament that long fiber that ultra tiny fiber uses changes into the average preferred 0.0003-0.5dtex of single fiber fineness, to obtain extra-fine filament-interlaced sheet of the present invention.Its thickness is preferably 0.2-10mm, and the quality optimization of unit are is 50-3500g/m
2, but this depends on the final use of extra-fine filament-interlaced sheet.
Extra-fine filament-interlaced sheet has the known up to now fine and close sense of touch of being made by fiber only of supatex fabric, and the leather-like sheet that can directly be used as particle arrangement or suede finish is made into the substrate that is used for leather-like sheet with more stable shaped reservation with substrate, preferably by the elastomeric polymer of dipping as adhesive.Weave or braided fabric can pass through known laminating method, be integrated in the extra-fine filament-interlaced sheet, if purpose of the present invention and effect do not have affected words.
Elastomeric polymer (adhesive resin) available among the present invention can be selected from any polymer, as long as they are flexible and can exemplify polyurethane, butadiene-styrene rubber (SBR), acrylonitrile-butadiene rubber (NBR), polyamino acid and acryloid cement, wherein preferably use polyurethane, this is because the sense of touch of leather-like sheet and functional.More preferably use the elastomeric polymer of aqueous emulsion type, this is because it does not need organic solvent and environmental friendliness.
Solution or aqueous emulsion for example by wherein flooding elastomeric polymer, the wet method method of solidifying then, perhaps wherein flood the solution or the aqueous emulsion of elastomeric polymer, dry then for bonding method, thereby flooding. the hot glue of aqueous emulsion coagulates preferred 30 ℃ or higher of temperature, but less than 60 ℃, more preferably 32-58 ℃. can be by selecting the kind of elastomeric polymer, the concentration of emulsion, with hot gelling agent, inorganic salts for example, the addition of sodium sulphate for example, or use known thickener, adjust hot glue and coagulate temperature in above-mentioned scope. in known method, in view of the easy degree of handling, yet it is 60 ℃ or higher that common setting hot glue coagulates temperature., in the present invention, set hot glue and coagulate temperature less than 60 ℃, so that in whole sheet material, distribute elastomeric polymer equably. if hot glue coagulates temperature less than 60 ℃, then can avoid elastomeric polymer uneven distribution on the surface of extra-fine filament-interlaced sheet, this is because will prevent to solidify before elastomeric polymer is moved to inside. in addition, can avoid wrinkling, this is because the elastomeric polymer that distributes prevents to move with intrabasement each fine filament at leather-like sheet equably. if hot glue coagulates temperature is 30 ℃ or higher, then the storage stability of emulsion is good, this is because will prevent emulsion aggregation. the amount of elastomeric polymer to be impregnated is preferably 35% or still less, more preferably 1-35%, more preferably 1-15% still, wherein separately based on the gross mass of gained leather-like sheet with substrate (extra-fine filament-interlaced sheet+elastomeric polymer). if the amount of elastomeric polymer to be impregnated is 35% or still less, then obtain leather-like sheet with flexible touch and sufficient intensity.
By making surface nappy, softening processing and dyeing are handled, thereby leather-like sheet are made the leather-like sheet of suede finish with substrate.By known method, for example use sand paper or card clothing, polishing is handled, thereby carries out napping.Among elastomeric polymer dipping or afterwards, by known method, form epidermal area and the step by subsequently in its surface: embossed technology, softening handle and dyeing is handled, thus extra-fine filament-interlaced sheet is made the leather-like sheet of particle arrangement or the arrangement of half particle.So the leather-like sheet of producing is crease-resistant in its production process, and the drapability that has the fine and close sense of touch of natural hide-like and cause because of long fiber, therefore is suitable as clothes, shoes, gloves and inner furniture, for example sofa material.
In using the sea-island long fiber production leather-like sheet that forms ultra tiny fiber and use, usually be difficult to prevent because of in high-temperature step, for example remove and shrink the long fiber that causes in the step of sea component and the staining procedure and move, the result forms irregular wrinkle in many cases on whole sheet surface.Especially when the content of adhesive resin hanged down, this became more obvious.Producing the leather-like sheet do not contain the extra-fine filament-interlaced sheet of elastomeric polymer or to contain elastomeric polymer in a small amount with in the inventive method of substrate, by under the situation that does not have elastomeric polymer or before elastomeric polymer dipping, remove PVA resin (sea component), thereby change into ultra tiny fiber.Utilize this technology, can relax fully at entanglement step and the distortion that changes into the fine filament (island component) that causes in the step of ultra tiny fiber.In addition, resulting sheet has high apparent density, and this is because entanglement abundance and shrinkage factor are big, and this makes that fine filament and sheet material are difficult to stretch, and the result improves fine filament and leather-like sheet uses the shape of substrate to keep.This improved shape reservation prevents in the production of leather-like sheet wrinkling, and the result obtains having the seldom leather-like sheet of wrinkle.In addition, production method environmental sound of the present invention, this is because under the situation that not have to use the organic solvent harmful to human body and environment, the leather-like sheet that generation has superperformance.
Embodiment
Reference example is described the present invention.Yet, should be noted that scope of the present invention is unlimited to following embodiment.Part among the following embodiment and % are based on quality, except as otherwise noted.
Measure the fineness of average single fiber, the fusing point and the interlaminar strength of PVA resin by following method.
(A) fineness of average single fiber
By ESEM (amplifying: hundreds of), measure the area of section of the fiber that forms sheet material to thousands of times.By the fineness of measured area with the density calculation average single fiber of the resin that forms fiber.
(B) fusing point
Use differential scanning calorimeter (available from the TA3000 of Mettler Inc.), by in nitrogen atmosphere with 10 ℃/minute speed heating resin to 300 ℃, cool to room temperature then heats resin to 300 ℃ once more with 10 ℃/minute speed then, thereby measures the summit temperature of endothermic peak.
(C) interlaminar strength
Becoming length direction by the sheet material that cuts the long fiber entanglement is that 23cm and width are 2.5cm, thus the preparation sample.At sample longitudinally on the end face, by with scraper along the line cutting that is positioned at transverse center, thereby make slit.Then, be releasing sheet the slit of about 10cm from strip length.By the edge of two parts of peeling off of clamp, and use tester for elongation, under the draw rate of 100mm/min, peel away sheet material, to measure peel strength.Flat according to gained load-deformation curve (SS curve) is measured average peel strength.By on three samples, on average obtaining the result.
Production example 1
Produce water-soluble, thermoplastic polyvinyl alcohol resin
In the 100L pressure reactor of being furnished with agitator, nitrogen inlet, ethene inlet and initator inlet, introduce 29.0kg vinyl acetate and 31.0kg methyl alcohol, after elevated temperature to 60 ℃, by nitrogen bubble 30 minutes, use the nitrogen purging reaction system.Then, introduce ethene, so that the pressure of conditioned reaction device is 5.9kgf/cm
2By nitrogen bubble, purge 2.8g/l2,2 '-methanol solution (polymerization initiator) of azo two (4-methoxyl group-2,4-methyl pentane nitrile).After conditioned reaction actuator temperature to 60 ℃, add the 170ml initiator solution, with initiated polymerization.In polymerization process, by introducing ethene, the pressure of keeping reactor is 5.9kgf/cm
2, keep polymerization temperature under 60 ℃, and add initiator solution continuously with the speed of 610ml/h.When the conversion ratio of polymerization after 10 hours reaches 70%, stop polymerization by cooling.After from reactor, discharging ethene,, remove ethene fully by nitrogen bubble.Unreacted vinyl acetate monomer is removed in decompression, obtains the methanol solution of the polyvinyl acetate (modified PVA c) of ethene modification, with methyl alcohol it is diluted to 50% concentration then.PVAc by adding 46.5g aqueous slkali (methanol solution of 10%NaOH) modification (NaOH/ vinyl acetate unit=0.10/1 mole) in the methanol solution of 200g50% modified PVA c, thereby saponification modified PVA c.After about 2 minutes of interpolation aqueous slkali, this system gelling.Pulverize gel by pulverizer, and allow under 60 ℃, to leave standstill 1 hour, saponification is further carried out.Then, add 1000g methyl acetate neutralization bases.After confirming neutralization fully, by isolated by filtration white solid PVA by phenolphthalein indicator.Add white solid PVA and 1000g methyl alcohol, and allow at room temperature to leave standstill 3 hours for washing.After repeating above-mentioned washing operation 3 times, the centrifugal liquid of removing, and, obtain the PVA (modified PVA) of ethene modification at 70 ℃ of dry remaining solids 2 days down.The saponification degree of modified PVA is 98.4mol%.Burn this modified PVA and be dissolved in the acid for by atomic absorption spectroscopy.Based on 100 parts by mass modified PVAs, the content of sodium is 0.03 parts by mass.
Add n-hexane therein to by in the methanol solution of removing the modified PVA c that unreacted vinyl acetate monomer obtains after polymerization, add then after the precipitation again-dissolving operation triplicate of acetone, precipitate 3 days 80 ℃ of following vacuumizes, obtain the modified PVA c of purifying.C is dissolved in the d6-DMSO with modified PVA, and by 500MHz H-NMR (JEOLGX-500), analyzes down at 80 ℃.The content of ethylene unit is 10mol%.At saponification modified PVA c (alkali/vinyl acetate unit=0.5/1 mole) afterwards, pulverize the gained gel, and, allow further to carry out saponification by under 60 ℃, leaving standstill 5 hours.By apparatus,Soxhlet's, use methanol extraction saponification resultant 3 days, and, obtain the modified PVA of purifying extract obtained 3 days of 80 ℃ of following vacuumizes.When measuring according to JIS K6726 method, the average degree of polymerization of the PVA of purifying is 330.In the modified PVA of purifying, 1, the content of the content of 2-diol bond and three continuous hydroxyls is respectively 1.50mol% and 83% when by 5000MHz H-NMR (JEOL GX-500) test.The aqueous solution of the modified PVA of 5% purifying is made the casting films of 10 micron thickness, then 80 ℃ of following vacuumizes 1 day, then to measure fusing point with above-described mode.Fusing point is 206 ℃.
Embodiment 1
Under 260 ℃, sea component) and the polyethylene terephthalate of isophthalate modified (modification degree 6mol%: the island component) in sea component/island component of 30/70 (in mass), be used to melt the bluk recombination spinning eject modified PVA (water-soluble, the thermoplastic polyvinyl alcohol resin: of above production from the spinning head that is used for the melt composite spinning from spinning nozzle ejection, (quantity on island: 25/ fiber). adjust expulsion pressure, collect the long fiber that average fineness is 2.0dtex on the net so that spinning speed is 4500m/min., the acquisition mass area ratio is 30g/m
2Spunbond sheet material (long fibre net).
By 6 blocks of spunbond sheet materials of cross lapping, thereby the gross mass of preparation unit are is 180g/m
2The stack fiber web.Spraying oil agent with after preventing broken needle, by using needle point to the distance of pinhock single crochet hook, at 3600 pin holes/cm as 5mm
2Density and the depth of needling of 10mm under, alternately acupuncture on both sides, the fiber web of the stack of tangling.Handle by acupuncture, percentage reduction of area is 53%.The quality of the sheet material unit are that the long fiber that obtains by acupuncture tangles is 340g/m
2And interlaminar strength is 9.2kg/2.5cm.
In 70 ℃ hot water, soaked long fiber entanglement sheet material 90 seconds, and, in 95 ℃ hot water, soaked 10 minutes then, remove the PVAc of modification, obtain extra-fine filament-interlaced sheet by dissolving because of the stress relaxation of island component causes causing that area shrinks.The percentage reduction of area of measuring after drying is 49%, and the quality of unit are is 490g/m
2, apparent density is 0.55g/cm
3And the average single fiber fineness of fine filament is 0.1dtex.
To the Super Flex E-4800 that is adjusted into 40% hard resin concentration of component (by Dai-Ichi Kogyo Seiyaku Co., Ltd. add sodium sulphate (hot gelling agent) the polyurethane aqueous emulsion of Zhi Zaoing), its consumption is 1 part/40 parts hard resin components, with preparation hot glue curdled milk liquid (hot glue coagulate temperature=55 ℃).This emulsion is impregnated in the extra-fine filament-interlaced sheet, and dry and solidify, the ratio that obtains R/F is 5/95 leather-like sheet with substrate (R is the quality of elastomeric polymer and the quality that F is fine filament).By polishing, make the substrate surface napping, use disperse dyeing, obtain the leather-like sheet of wrinkling less suede finish, it has natural hide-like sense of touch.The intensity of resulting sheet is suitable for being applied on inside, automobile sheet material and the other products.
Embodiment 2
To the Evaphanol AP-12 that is adjusted into 20% hard resin concentration of component (by NiccaChemical Co., Ltd. add sodium sulphate (hot gelling agent) the polyurethane aqueous emulsion of Zhi Zaoing), its consumption is 6 parts/100 parts hard resin components, with preparation hot glue curdled milk liquid (hot glue coagulate temperature=53 ℃).Mode with identical with embodiment 1 is impregnated into this emulsion in the extra-fine filament-interlaced sheet, and is dry and solidify, and obtains leather-like sheet.
Thickness is 1.0mm, and the average single fiber fineness of fine filament is 0.08dtex, and the ratio of R/F is 20/80, and does not observe wrinkling.On sheet material, observe the cross section and show that elastomeric polymer is evenly distributed in transversely.By polishing, make the surface nappy of leather-like sheet, use disperse dyeing, obtaining thickness is the leather-like sheet of the suede finish of 0.9mm.Resulting sheet does not have wrinkle, and has and come from long stapled good overhanging property, good writing effect and be suitable for being applied to intensity on inside, automobile sheet material and the other products.
Embodiment 3
Produce the dermatine of suede finish in the mode identical with embodiment 2, different is that hard resin component concentrations in the emulsion is become 30%, and sulphates content becomes 3 parts/100 parts hard resin components and hot glue and coagulates temperature and become 48 ℃.Resulting sheet does not have wrinkle and has to come from long stapled good drapability, good writing effect and be suitable for being applied to intensity on inside, automobile sheet material and the other products.
Embodiment 4
Produce the dermatine of suede finish in the mode identical with embodiment 2, different is that hard resin component concentrations in the emulsion is become 40%, and sulphates content becomes 1.5 parts/100 parts hard resin components and hot glue and coagulates temperature and become 45 ℃.Resulting sheet does not have wrinkle and has to come from long stapled good drapability, good writing effect and be suitable for being applied to intensity on inside, automobile sheet material and the other products.
Embodiment 5
Produce the dermatine of suede finish in the mode identical with embodiment 2, melt flow rate that different are to use (the spinneret diameter of 255 ℃, 325g load and 2mm φ) for the contractile polyamide of 10g/10min as forming ultra tiny fiber with long stapled island component.Resulting sheet does not have wrinkle and has to come from long stapled good drapability, good writing effect and be suitable for being applied to intensity on inside, automobile sheet material and the other products.
Embodiment 6
Produce the dermatine of suede finish in the mode identical with EXAMPLE l, different is by adjusting the content and the needling density of oil agent, and the preparation interlaminar strength is that 2.3kg/2.5cm and percentage reduction of area are the sheet material that 55% long fiber tangles.Resulting sheet does not have wrinkle and has to come from long stapled good drapability, good writing effect and be suitable for being applied to intensity on inside, automobile sheet material and the other products.
Embodiment 7
Produce the dermatine of suede finish in the mode identical with embodiment 1, different is by adjusting the content and the needling density of oil agent, and the preparation interlaminar strength is that 14kg/2.5cm and percentage reduction of area are the sheet material that 38% long fiber tangles.Resulting sheet does not have wrinkle and has to come from long stapled good drapability, good writing effect and be suitable for being applied to intensity on inside, automobile sheet material and the other products.
Comparative Examples 1
Produce the sheet material that long fiber tangles in the mode identical with embodiment 1, different is that needling density is become 120 pin holes/cm
2The interlaminar strength of the sheet material that long fiber tangles is 0.8kg/2.5cm.In the mode identical the sheet material that the gained long fiber tangles is shunk/conversion processing, obtain extra-fine filament-interlaced sheet with embodiment 1.Percentage reduction of area is 48%.Resulting sheet is not suitable for as the leather-like sheet material, because the sense of touch of its undercapacity and densification is poor.
Comparative Examples 2
The long fiber entanglement sheet material for preparing in the mode identical 170 ℃ of following dry heat 20 minutes with embodiment 1, make the island component lax, in 70 ℃ hot water, soak sheet material 90 seconds for contraction, and in 95 ℃ hot water, soaked 10 minutes, remove the PVA of modification by dissolving, obtain extra-fine filament-interlaced sheet.The percentage reduction of area of measuring after drying is 12%.The gained extra-fine filament-interlaced sheet is not suitable for as the leather-like sheet material.
Comparative Examples 4
Produce leather-like sheet in the mode identical with embodiment 1, different is, and to change the sea component that forms in the long fiber that ultra tiny fiber uses be polyethylene.By being dissolved in the toluene, remove polyethylene, in this process, island component (polyethylene terephthalate of isophthalate modified) swelling, the result increases percentage elongation in the process by this technology, so make difficult treatment.This sheet material is significantly wrinkling, and sense of touch and fine and close sense of touch are poor, makes it be not suitable for as commercial product.
Industrial applicibility
The method according to this invention can be produced the extra-fine filament-interlaced sheet that is suitable for the substrate of leather-like sheet usefulness. By the dipping elastomeric polymer, extra-fine filament-interlaced sheet can be made into the leather-like sheet substrate. By making surface nappy, leather-like sheet can be made into the leather-like sheet of suede finish or velvet leather-arrangement with substrate. In addition, can be by coating resin in its surface or under heating or in the solvent, melting or dissolve its surface in order to form resin bed thereon, thereby will be used for the leather-like sheet that the substrate granulation of leather-like sheet is put in order. These leather-like sheets have the thick and heavy and fine and close sense of touch of natural leather shape, and mechanical performance, and pliability is good and have an outward appearance of aesthetic pleasant. Therefore, this leather-like sheet is suitable for as hide-like product material, for example shoes, sport ball, furniture, vehicle seat, clothes, gloves, baseball glove, briefcase, belt and handbag.
Claims (9)
1. method of producing extra-fine filament-interlaced sheet, this method comprises:
The step of the long fibre net that formation is made by the long fiber that is used to form ultra tiny fiber, the wherein said long stapled length that is used to form ultra tiny fiber is that at least a component in 100mm or longer and the long fiber is water miscible thermoplastic polyvinyl alcohol resin;
The entanglement long fibre net is with the step of the sheet material of formation long fiber entanglement;
The sheet material that long fiber is tangled shrinks to form the step of long stapled contraction sheet material; With
To change into the step of fine filament at the long fiber that is used to form ultra tiny fiber in the long stapled contraction sheet material, produce extra-fine filament-interlaced sheet thus,
Wherein the interlaminar strength of the sheet material that tangles with long fiber is the tangle step of long fibre net and be 35% or bigger mode sheet material step of shrinking that long fiber is tangled with percentage reduction of area of 2kg/2.5cm or bigger mode.
2. the process of claim 1 wherein the two-layer or more multi-layered long fibre net of stack, tangle then, form the sheet material that long fiber tangles.
3. the process of claim 1 wherein the step of tangling by acupuncture.
4. the process of claim 1 wherein by carrying out step of shrinking with hot water or steam treatment.
5. the process of claim 1 wherein that the viscometric degree of polymerization of thermoplastic polyvinyl alcohol resin is 200-500, saponification degree is that 90-99.99mol% and fusing point are 160-230 ℃.
6. the process of claim 1 wherein that the fineness of average single fiber of fine filament is 0.0003-0.5dtex.
7. any one method of claim 1-6 is wherein carried out step of shrinking simultaneously and is changed into the step of fine filament.
8. a production is used for the method for the substrate of leather-like sheet, and this method comprises elastomeric polymer is impregnated into step in the extra-fine filament-interlaced sheet of producing by any one method of claim 1-7.
9. the method for claim 8, wherein coagulating temperature with hot glue is 30 ℃ or bigger, but less than 60 ℃ hot glue curdled milk liquid form dipping elastomeric polymer.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP179682/2004 | 2004-06-17 | ||
| JP2004179682A JP4602001B2 (en) | 2004-06-17 | 2004-06-17 | Method for producing ultra-thin fiber entangled sheet |
| JP2004179683A JP4602002B2 (en) | 2004-06-17 | 2004-06-17 | Leather-like sheet manufacturing method |
| JP179683/2004 | 2004-06-17 | ||
| PCT/JP2005/010937 WO2005124002A1 (en) | 2004-06-17 | 2005-06-15 | Process for producing intertwined ultrafine filament sheet |
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| Publication Number | Publication Date |
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| CN1985042A CN1985042A (en) | 2007-06-20 |
| CN1985042B true CN1985042B (en) | 2010-05-05 |
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| CN200580023582.4A Active CN1985042B (en) | 2004-06-17 | 2005-06-15 | Production of extra-fine filament-interlaced sheet |
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| JP (1) | JP4602001B2 (en) |
| CN (1) | CN1985042B (en) |
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| JP4647295B2 (en) * | 2004-11-29 | 2011-03-09 | 株式会社クラレ | Method for producing flame-retardant sheet |
| WO2008053674A1 (en) | 2006-10-11 | 2008-05-08 | Toray Industries, Inc. | Leather-like sheet and process for production thereof |
| EP2557223A1 (en) * | 2010-03-31 | 2013-02-13 | Kuraray Co., Ltd. | Leather-like sheet |
| CN102587037A (en) * | 2012-02-23 | 2012-07-18 | 昆山胜昱无纺布有限公司 | Imitation inner leather non-woven fabric and preparation method thereof |
| CN115613371B (en) * | 2022-11-04 | 2024-02-23 | 上海华峰超纤科技股份有限公司 | Preparation method of high-wear-resistance waterborne polyurethane microfiber base cloth |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5899785A (en) * | 1996-06-17 | 1999-05-04 | Firma Carl Freudenberg | Nonwoven lap formed of very fine continuous filaments |
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| JP3727181B2 (en) * | 1998-10-02 | 2005-12-14 | 帝人コードレ株式会社 | Method for producing nonwoven fabric for artificial leather |
| JP2001192980A (en) * | 2000-01-05 | 2001-07-17 | Kuraray Co Ltd | Method for producing leather-like sheet |
| JP4021238B2 (en) * | 2002-05-09 | 2007-12-12 | 株式会社クラレ | Artificial leather made of ultra-thin fiber nonwoven fabric and method for producing the same |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5899785A (en) * | 1996-06-17 | 1999-05-04 | Firma Carl Freudenberg | Nonwoven lap formed of very fine continuous filaments |
Non-Patent Citations (2)
| Title |
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| JP平5-71006A 1993.03.23 |
| JP平8-246336A 1996.09.24 |
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| JP4602001B2 (en) | 2010-12-22 |
| JP2006002287A (en) | 2006-01-05 |
| CN1985042A (en) | 2007-06-20 |
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