CN101389806A - Artificial leather and method for producing the same - Google Patents
Artificial leather and method for producing the same Download PDFInfo
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- CN101389806A CN101389806A CNA2007800068750A CN200780006875A CN101389806A CN 101389806 A CN101389806 A CN 101389806A CN A2007800068750 A CNA2007800068750 A CN A2007800068750A CN 200780006875 A CN200780006875 A CN 200780006875A CN 101389806 A CN101389806 A CN 101389806A
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Abstract
An artificial leather includes an entangled body made of bundles of microfine fibers and an elastic polymer impregnated into the entangled body. A part of the elastic polymer penetrates into the bundles of microfine fibers. The degree of penetration of the elastic polymer is from 1 to 30% by area when measured on a cross section which is taken along a direction perpendicular to a lengthwise direction of the bundles of microfine fibers. The fiber-holding property is improved by the elastic polymer which partly penetrates into the bundles of microfine fibers, and therefore, the artificial leather has good hand without deteriorating the surface quality.
Description
Technical field
The present invention relates to dermatine and preparation method thereof.
Background technology
In the past, extensively known in fiber pseudoconjugants such as nonwoven fabric, braided fabric, their tablets such as various processed goods impregnation be the high polymer elastic liquid solution or the dispersion liquid of representative with polyurethane etc., prepare the leather-like sheet of functional excellence, but industrializing implementation.
For example, impregnation polyurethane in the fibrous substrate of the superfine fibre generation fiber type that contains island structure, this polyurethane is solidified, generate to extract the fiber type from superfine fibre then and remove sea component, can obtain soft leather-like sheet (for example with reference to patent documentation 1) thus.Also disclose: contain the blend spinning fiber of the good sea component polymer of solvent extraction by use, do not have between the superfine fibre after can obtaining extracting deadlocked, open the good superfine fibre of fibre (for example with reference to patent documentation 2).But, in the above-mentioned leather-like sheet, macromolecular elastomer with and the superfine fibre bundle between possess the space state be present in around the fibre bundle.Therefore therefore, though feel is soft, macromolecular elastomer does not directly contact with fiber, to the gripping deficiency of fiber.
After sea component is removed in extraction from the superfine fibre generation fiber type of island structure in addition, fibrous substrate is provided the technology of macromolecular elastomer.In this technology, macromolecular elastomer directly contacts with fiber, therefore to the gripping raising of fiber, still, owing to be direct contact, the problem of feel hardening is arranged.For improving this problem, people have proposed polyvinyl alcohol was provided before sea component is removed in extraction, regulate the method for the amount that macromolecular elastomer and fiber directly contact; In order to replenish owing to move the deficiency of the middle body that causes, secondary provides the method (for example with reference to patent documentation 3) of polyvinyl alcohol etc.But even adopt said method, the adjusting macromolecular elastomer directly grips the amount of fibre bundle and is adjusted to the superfine fibre group that grips thickness direction equably all also is very difficult.
In recent years, consider the harmful effect of organic solvent to human body or environment, people wish to set up solvent-free preparation technology in the dermatine preparation.For example, people remove superfine fibre that component of polymer obtains to available extraction with aqueous solution and generate the application of fiber type and the aqueous dispersions of macromolecular elastomer is contained the inside that is immersed in the fiber pseudoconjugant and study.But, compare with the situation that with an organic solvent is macromolecular elastomer, if use the macromolecular elastomer aqueous dispersions, then be difficult to form the pantostrat of macromolecular elastomer usually, fiber gripping property variation.If the amount of providing of macromolecular elastomer aqueous dispersions is provided in order to form pantostrat, then gained dermatine hardening, feel variation.For improving the problems referred to above, someone has proposed to provide macromolecular elastomer to the fiber pseudoconjugant, make superfine fibre generate the fiber type super-refinement, and then the impregnation of macromolecular elastomer aqueous dispersions is provided in the fiber pseudoconjugant, the macromolecular elastomer that is provided by impregnation once more directly grips the method (for example with reference to patent documentation 4) of superfine fibre.But in this method, macromolecular elastomer moves, and exceedingly grips fiber easily, therefore makes the feel of gained dermatine impaired easily.
More than, in the dermatine that uses the macromolecular elastomer aqueous dispersions to obtain, do not obtain fully to satisfy the material of fiber gripping property and feel as yet.
Patent documentation 1: Japanese Patent Publication 41-9315 communique (1～3 page)
Patent documentation 2: Japanese kokai publication hei 5-59615 communique (1～3 page)
Patent documentation 3: Japanese Patent Publication 49-10633 communique (1～3 page)
Patent documentation 4: TOHKEMY 2003-306878 (1～4 page)
Summary of the invention
The invention provides use macromolecular elastomer aqueous dispersions dermatine that obtain, that can fully satisfy fiber gripping property and feel and preparation method thereof.
Promptly, the present invention relates to a kind of dermatine, this dermatine contains the obvolvent structure that is formed by the superfine fibre bundle and contains the macromolecular elastomer that is immersed in this obvolvent structure inside, the part of this macromolecular elastomer exists with the form of infiltration in this superfine fibre bundle inside, in the arbitrary section vertical of this superfine fibre bundle with length direction, the infiltration ratio of this macromolecular elastomer according to area than the scope of counting 1～30%.
The invention still further relates to imitative chamois leather dermatine by this dermatine preparation.
The invention further relates to the preparation method of dermatine, this preparation method may further comprise the steps:
(1) inside of the fiber pseudoconjugant that formed by composite fibre is provided the step of macromolecular elastomer aqueous dispersions, wherein, described composite fibre contains water-soluble polymer composition and slightly water-soluble component of polymer;
(2), make the surface that provides the fiber of above-mentioned macromolecular elastomer aqueous dispersions pseudoconjugant be warming up to step than the high temperature more than 10 ℃ of gelling temperature of this macromolecular elastomer aqueous dispersions by infrared radiation;
(3) make the gelling temperature high temperature 10 ℃ or more of the surface maintenance of above-mentioned fiber pseudoconjugant than this macromolecular elastomer aqueous dispersions, the moisture rate that makes this fiber pseudoconjugant simultaneously is the following steps of 50 quality %;
(4) moisture drying that will remain in the above-mentioned fiber pseudoconjugant is removed, and makes above-mentioned macromolecular elastomer be adhered to step in this fiber pseudoconjugant;
(5) remove the water-soluble polymer composition with extracting in the composite fibre of hot water from the fiber pseudoconjugant that is bonded with above-mentioned macromolecular elastomer, this composite fibre is transformed to the step of superfine fibre bundle.
The best mode that carries out an invention
Below describe the present invention in detail.
The superfine fibre bundle that constitutes dermatine of the present invention can be selected arbitrarily according to the purposes of dermatine, is not particularly limited, and preferably generates the superfine fibre bundle that fiber type generates by superfine fibre.Consider from the angle that the appearance of the feel that makes the gained dermatine or imitative chamois leather dermatine improves, preferred 0.0001～0.5 dtex of the single fiber degree of each superfine fibre, more preferably 0.001～0.45 dtex, consider preferred especially 0.002～0.4 dtex from the angle of the gripping of colour rendering or macromolecular elastomer.Preferred 2～10 dtexs of the fiber number of superfine fibre bundle, more preferably 3～8 dtexs preferably contain 10～100 superfine fibres.
Superfine fibre generates fiber type and is made of water-soluble polymer composition and slightly water-soluble component of polymer, and this is very important.Adopt above-mentioned macromolecule component to constitute and then need not with an organic solvent promptly can generate superfine fibre, can reduce pressure environment.By being used in combination the macromolecular elastomer aqueous dispersions, can obtain the structure of macromolecular elastomer described later to the specific infiltration of superfine fibre Shu Jinhang.Among the present invention, " water-soluble " is meant in the water of 60 ℃ of 100g and dissolves more than the 10g that " slightly water-soluble " is meant in the water of 60 ℃ of 100g can only dissolve 0.1g at most.
Superfine fibre generates fiber type so long as formed by at least a water-soluble polymer composition and at least a slightly water-soluble component of polymer that becomes superfine fibre and to get final product, can use islands-in-sea type fibres such as sea-island-type composite spun fiber, fabric of island-in-sea type blend spinning fiber, or multicomponents such as petal-shaped cross section or laminate-type fiber be composite fibre any.But be extracted the composition of removing is the water soluble polymer composition of spinning, and this is very important.The water-soluble polymer composition can use the available water or the aqueous solution (hereinafter referred to as water solvent) to extract the known polymer of removing, the preferred polyvinyl alcohol copolymer class (being designated hereinafter simply as PVA) that is dissolvable in water water solvent of using.PVA can easily remove with the hot water dissolving, when extracting processing, the decomposition reaction that superfine fibre forms composition or macromolecular elastomer does not take place in fact.Therefore, thermoplastic resin that uses in the superfine fibre composition and macromolecular elastomer are not limited to specific kind, and the pressure to environment is also little in addition.
Above-mentioned PVA can be homopolymerization PVA, also can be the modified PVA that has imported copolymerization units, and the shrinkage character equal angles when melt spinning, water-soluble, fibrous physical property and extraction are handled is considered preferred modified PVA.Copolymerization units is preferably from being selected from the alpha-olefines of carbon number below 4 such as ethene, propylene, 1-butylene, isobutene; At least a compound of alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether.Preferably there is 1～20mol% in copolymerization units in PVA.Owing to fibrous physical property is improved, therefore more preferably contain the modified PVA of 4～15mol% ethylene unit.
Preferred 90～the 99.99mol% of the saponification degree of PVA, more preferably 92～99.98mol%, further preferred 94～99.96mol%, preferred especially 95～99.95mol%.Saponification degree is more than the 90mol%, and then good thermal stability can carry out the composite molten spinning under the situation that thermal decomposition or gelation do not take place.Be difficult to the PVA of stable preparation saponification degree greater than 99.99mol%.
The slightly water-soluble component of polymer be so long as can form the known resin of superfine fibre, and the polymer of for example polyamide-based, polyesters, TPO etc. gets final product, and is not particularly limited.Wherein, preferred polyethylene terephthalate, polybutylene terephthalate (PBT), copolymerization have the polyethylene terephthalate of M-phthalic acid or the polyesters such as polybutylene terephthalate (PBT) that copolymerization has M-phthalic acid, and nylon 6, nylon 11, nylon 12 etc. are polyamide-based.At high temperature, then cause the spinnability variation easily with the water-soluble polymer spinning of PVA etc.Therefore, the stability of spinning process angle that generates fiber type from superfine fibre considers, the slightly water-soluble component of polymer of the fusing point in the fusing point+60 ℃ scope of preferred fusing point～water-soluble polymer composition of selecting to have the water-soluble polymer composition.Consider preferred 160～230 ℃ of the fusing point of water-soluble polymer composition from the spinnability equal angles.
The scope of the water-soluble polymer composition of formation superfine fibre generation fiber type and the mass ratio preferred 10/90～60/40 of slightly water-soluble high polymer composition.In above-mentioned scope, then superfine fibre generates the good dispersion of water-soluble polymer composition and slightly water-soluble component of polymer in the cross section of fiber type, therefore superfine fibre and the superfine fibre bundle that is produced is even, the feel excellence of gained dermatine can obtain having the imitative chamois leather dermatine that plays velvet uniformly.
Superfine fibre can contain pigment.In order to make in the superfine fibre dispersing of pigments good, preferably in mixing device such as extruder that slightly water-soluble component of polymer and pigment is mixing, add pigment by granular colour masterbatch mode then.In addition, in the scope of not damaging purpose of the present invention and effect, can be when polymerisation or after step in the slightly water-soluble component of polymer, add stabilizing agent, colouring agent, ultra-violet absorber, light stabilizer, antioxidant, antistatic additive, fire retardant, plasticizer, lubricant, crystallization rate delayed-action activator such as copper compound.And, for example can also add inert particulates such as silica, aluminium oxide, titanium oxide, calcium carbonate, barium sulfate.They can use separately, also can be used in combination two or more, and this can improve spinnability, draftability.
Above-mentioned superfine fibre generates fiber type and is stretched to 1.5～4 times usually.Stretching is after being sprayed by spinning-nozzle, can carry out after reeling, and also can carry out before reeling.Stretch and preferably under 50～110 ℃ heating, carry out, also can use arbitrary forms such as hot blast, hot plate, hot-rolling, water-bath.Preferably stretch by the few hot blast of the moisture content change of water-soluble polymer composition.
Superfine fibre generates makes web of staple fibers after fiber type is made long fibre net or staple by spun-bond process etc.For example, superfine fibre is generated the curling segment afterwards of fiber type, by carding machine, cross lapping machine, random web-laying equipment etc. is made net.Long fibre net or web of staple fibers can form the fiber pseudoconjugant by acupuncture.Also can carry out acupuncture then as required at the laminated braided fabric in top layer, lower floor or intermediate layer of net.Acupuncture is through under the condition of net surface and preferred 400～5000 thorn/cm at pinhock
2, more preferably 1000～2000 thorn/cm
2Needling density under carry out.
When using braided fabric, for net form all-in-one-piece structure, the twisting count that preferably constitutes the silk of braided fabric is 10～650T/ rice, more preferably 15～500T/ rice.More than 10T/ rice, then under the situation about can not scatter, generate the fiber type obvolvent with superfine fibre at the monofilament of braided fabric, therefore can prevent the more bad order of exposing the silk of damage and causing on fiber pseudoconjugant surface.Twisting count is below the 650T/ rice, then generates the firm obvolvent of fiber type with superfine fibre, can obtain the structure of net and braided fabric one.The weight per unit area of braided fabric is suitably selected according to purpose, preferred 20～200g/m
2, more preferably 30～150g/m
2Weight per unit area is 20g/m
2More than, then the form retentivity of braided fabric is good, mesh displacement etc. can not take place.Weight per unit area is 200g/m
2Below, then constituting the interval appropriateness of the silk of braided fabric, superfine fibre generates fiber type can fully run through braided fabric, and net and the obvolvent of braided fabric height can obtain unseparated incorporate net/basketwork structure body.The kind of braided fabric is not particularly limited, can use through compile, section is basic various braided fabrics through weft knittings such as volume, petinet ocular tissue and with these knitting technology weaves in the spy, or plain weave, twill-weave, satin weave and with these woven basic various woven fabrics etc. that are organized as.Tissue, density etc. can suitably be selected according to purpose.
In gained fiber pseudoconjugant, when dry then, if elevate the temperature, then the fiber pseudoconjugant may significantly shrink with the impregnation of high polymer elastic liquid solution.During contraction, reduce fiber pseudoconjugant inner space, contains the macromolecular elastomer that is immersed in inside and be expressed into the top layer, makes the elastomeric even distribution of molecule impaired.For avoiding the problems referred to above, preferably the fiber pseudoconjugant after making acupuncture before the impregnation high polymer elastic liquid solution carries out thermal contraction.Thermal contraction can make the fibre density of fiber pseudoconjugant increase, obtain fine and close napping outward appearance or the good imitative chamois leather dermatine of feel when handling, therefore preferred.In order to improve the surface smoothing of dermatine, after thermal contraction, can carry out hot pressing as required.
The weight per unit area of gained fiber pseudoconjugant can be selected arbitrarily according to the purposes of gained dermatine, is not particularly limited, but preferred 300～1500g/m
2Preferred 0.20～the 0.80g/cm of apparent density
3, more preferably 0.25～0.70g/cm
3Be 0.20g/cm
3More than, then a velvet or the mechanical properties of imitative chamois leather dermatine are good, are 0.80g/cm
3Below, then can avoid the feel hardening.As long as the thickness of fiber pseudoconjugant satisfies this weight per unit area scope and density range, be not particularly limited.
Among the present invention, the macromolecular elastomer that is contained in the fiber pseudoconjugant is known in the dermatine field.For example can be to contain the various polyurethane that at least a mean molecule quantity is 500～3000 polymer polyatomic alcohol, at least a polyisocyanate and the composition with at least a low molecular compound of two above active hydrogen atoms divides a step or multistep reaction to obtain.Polymer polyatomic alcohol is selected from polyester-diol, PTMEG, polyether ester glycol, PCDL etc.Polyisocyanate is selected from 4, the vulcabond of the aromatics system of 4 '-methyl diphenylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate etc., alicyclic ring family, aliphatic series etc.Low molecular compound with 2 above active hydrogen atoms is selected from ethylene glycol, ethylenediamine etc.The mixture that can contain different types of polyurethane also can make it contain different types of polyurethane several times.Except that polyurethane, can also contain the elastomeric polymeric elastomer compositions of macromolecule such as having added synthetic rubber, polyester elastomer, acrylic resin as required.
Among the present invention, use water soluble polymer composition such as above-mentioned PVA to generate a kind of composition of fiber type, aqueous dispersions that therefore must the impregnation macromolecular elastomer as superfine fibre.Use aqueous dispersions, then contain be immersed in after the fiber pseudoconjugant inside and make the macromolecular elastomer gelation, solidify, when dry, constitute water soluble polymer composition that superfine fibre generates fiber type with in a certain amount of water that is dissolved in aqueous dispersions, macromolecular elastomer is penetrated into its inside by the periphery that superfine fibre generates fiber type.Thus, after step in when making superfine fibre generate the fiber type super-refinement, then can obtain a part bonding structure that is present in superfine fibre bundle inside in particular range of macromolecular elastomer.
When the aqueous dispersions of the inside of fiber pseudoconjugant impregnation macromolecular elastomer, can adopt dip nip technique known such as (clamping dippings), because the pressure that clamping is handled, the water-soluble polymer composition in the composite fibre is squeezed out, and may pollute the macromolecular elastomer aqueous dispersions.Therefore, do not adopt dip nip mode among the present invention, and utilize the permeability of macromolecular elastomer aqueous dispersions to the water-soluble polymer composition, need not big pressurization, only control the method that the quantity delivered of macromolecular elastomer aqueous dispersions and concentration promptly can the impregnation ormal weights, for example preferred method of using with lip coater impregnations such as (lip type coating machines).
After bonding, macromolecular elastomer is in the discontinuous in fact existence in the inside of fiber pseudoconjugant, having macromolecular elastomer concurrently to preferred aspect the gripping of fiber and the soft hand feeling, therefore, preferred macromolecular elastomer aqueous dispersions is according to macromolecular elastomer: the mass ratio of fiber pseudoconjugant=5:95～60:40 provides.In the dermatine, macromolecular elastomer plays the adhesive effect that makes the collection of filaments.The ratio of macromolecular elastomer then can be given full play to adhesive effect in above-mentioned scope, in addition, rerum naturas such as tearing strength and TENSILE STRENGTH are good, and feel is also soft.Preferred 5～40 quality % of high polymer elastic bulk concentration in the aqueous dispersions.
Among the present invention, the final structure that must obtain is: in the fiber pseudoconjugant behind the impregnation macromolecular elastomer aqueous dispersions, suppress it and move, the part of macromolecular elastomer exists to the internal penetration of fibre bundle than 1～30% the scope peripheral part by the superfine fibre bundle with area in fact.By this structure, can keep feel and can improve the gripping of macromolecular elastomer fiber.For obtaining this structure, must make before moisture evaporates fully, a part that makes superfine fibre generate the water-soluble polymer composition of fiber type is dissolved in the water, and makes the rapid gelation of macromolecular elastomer aqueous dispersions simultaneously.Among the present invention,, can carry out ultrared treatment with irradiation for the fiber pseudoconjugant Fast Heating that the macromolecular elastomer aqueous dispersions will be provided in inside heats up, simultaneously the water-soluble polymer component portion dissolved for this reason.From surface and the inner favourable angle that heats up to the fiber pseudoconjugant, and the infrared ray absorbing wavelength of water be 2.6 μ m, for the very favorable angle of the intensification of macromolecular elastomer aqueous dispersions, and infrared ray absorbing and the angle consideration preferably of transmission balance that the fiber pseudoconjugant of macromolecular elastomer aqueous dispersions is provided, preferably using the ceiling capacity wavelength is the infrared ray of 2～6 μ m.Preferred irradiation infrared ray, make the surface temperature of fiber pseudoconjugant be warming up to the high temperature more than 10 ℃ of gelling temperature than macromolecular elastomer aqueous dispersions, the moisture rate that makes the fiber pseudoconjugant is below the 50 quality %, remove remaining moisture, bonding polymer elastomer 130～160 ℃ of following dryings then.
The surface of fiber pseudoconjugant is the high temperature more than 10 ℃ of gelling temperature that was warming up in 1 minute than macromolecular elastomer aqueous dispersions, preferably is warming up to gelling temperature+10 ℃～gelling temperature+50 ℃.The surface temperature of fiber pseudoconjugant is in above-mentioned scope, and then fiber pseudoconjugant temperature inside reaches more than the gelling temperature of macromolecular elastomer aqueous dispersions, promotes the sensible heat gelation of macromolecular elastomer.The time that the surface temperature of fiber pseudoconjugant is warming up in the above-mentioned scope was controlled in 1 minute, like this, the macromolecular elastomer aqueous dispersions cause move before sensible heat gelation easily, therefore preferred.In the intensification of infrared radiation, the water-soluble polymer composition is partly dissolved by the moisture of macromolecular elastomer aqueous dispersions, and slightly water-soluble component of polymer appropriateness is exposed.Therefore, macromolecular elastomer can directly contact with the slightly water-soluble component of polymer, obtain easily following structure, promptly the part of macromolecular elastomer is penetrated in the integral body in fact of the dermatine that ultra fine obtains than the scope that is 1～30% with area by the peripheral part of superfine fibre bundle to the inside of fibre bundle.
By infrared radiation heated up in the surface of fiber pseudoconjugant, in 0.3～1.5 minute this surface temperature is remained in the above-mentioned scope then, making the moisture rate of this fiber pseudoconjugant during this period is below the 50 quality %.If surpass 50 quality %, the water-soluble polymer composition dissolves to such an extent that surpass requiredly during heat drying after then, and the ratio rising that macromolecular elastomer directly contacts with the slightly water-soluble component of polymer is moved in addition easily.As a result, obtain macromolecular elastomer with the structure of area than 30% infiltration that surpasses fibre bundle, the feel hardening of dermatine.The lower limit of moisture rate is not particularly limited, and considers from the angle of drying efficiency, and is preferred more than 10%.Two surfaces of fiber pseudoconjugant need evenly heating, therefore preferably carry out infrared radiation according to the same terms by two faces.For moisture is evenly volatilized from two faces, preferred vertical infrared radiation.
Above-mentioned moisture rate can be obtained by following formula.
Moisture rate (%)=(I-J)/J * 100
I: the weight per unit area (g/m of the fiber pseudoconjugant after impregnation macromolecular elastomer aqueous dispersions, the infrared radiation
2)
J: impregnation macromolecular elastomer aqueous dispersions also solidifies the weight per unit area (g/m of dried fiber pseudoconjugant
2)
After infrared radiation is handled, bonding more firmly in order to make the water evaporates that remains in the fiber pseudoconjugant in order to make bonding macromolecular elastomer, can under 110～170 ℃, carry out heat drying and handle 1～10 minute.If not carrying out heat drying handles, then extract the superfine fibre processing remove the water-soluble polymer composition or the dyeing macromolecular elastomer swelling that hot water causes when handling, come off, surface fibre can't fully be gripped by macromolecular elastomer, and the exterior quality of the imitative chamois leather dermatine of gained is poor.The heat drying processing method can be known method such as heated-air drying, damp and hot drying.Heat drying treatment temperature and time can be set arbitrarily according to the adhesion properties of macromolecular elastomer, preferably carry out under 110～160 ℃ 1～9 minute.
Then, with the non-solvent of slightly water-soluble component of polymer and macromolecular elastomer and be the treatment fluid of the solvent of water-soluble polymer composition (composition is removed in extraction), promptly water or acidity or alkaline aqueous solution extract and remove the water-soluble polymer composition.By this operation, superfine fibre can be generated fiber type and be transformed into the superfine fibre bundle, obtain dermatine.Particularly environmental pressure is little, therefore preferred hot water extracting.Preferred 60～100 ℃ of the temperature of hot water, more preferably 80～95 ℃.Be then can shorten extraction time more than 60 ℃.Therefore, the hot water temperature is high more preferred more.Be that then the adhering state of macromolecular elastomer that is provided and superfine fibre is difficult to become flexible below 100 ℃, can keep the gripping of macromolecular elastomer fiber.
Superfine fibre bundle inside in the gained dermatine has the infiltration of part macromolecular elastomer to exist.In the arbitrary section vertical of superfine fibre bundle with length direction, the amount of the macromolecular elastomer of infiltration according to area than the scope that is 1～30%.By said structure, can obtain soft, superfine fibre by the macromolecular elastomer good grip, the dermatines such as imitative chamois leather dermatine that reduce of the quality that do not have young pilose antler to come off etc. to cause.Above-mentioned area is than preferred 1.5～25%, and more preferably 2～20%.In above-mentioned scope, then the superfine fibre bundle is by the macromolecular elastomer secure grip, and the superfine fibre that can obtain the surface is not decoherenced, imitative chamois leather dermatine superfine fibre fibrillation, that have good appearance on surface.Preferred especially superfine fibre bundle central part (from the center～length surface direction at center 80% in) do not have a macromolecular elastomer.
This area is lower than at 1% o'clock, and the amount that is penetrated into superfine fibre macromolecular elastomer intrafascicular, that directly contact with superfine fibre is few, and therefore, though that the feel of gained dermatine can keep is soft, sense of fulfillment (body bone) reduces.And the superfine fibre amount that is gripped by macromolecular elastomer is few, therefore, decoherences the exterior quality variation easily in the imitative chamois leather dermatine of gained.Surpass at 30% o'clock, can prevent to decoherence, presentation quality is improved, but the amount of the macromolecular elastomer that directly contacts with superfine fibre is too much, so the feel hardening.Macromolecular elastomer is also discontinuous on the length direction of superfine fibre bundle, is discontinuous infiltration, and this can keep good hand feeling, and is therefore preferred.On the arbitrary section vertical of superfine fibre bundle, can be non-continuous state, also can be partial continuous state infiltration with length direction.
Above-mentioned area than, promptly, macromolecular elastomer is penetrated into the intrafascicular ratio A of superfine fibre (%) and calculates by following formula:
A＝B/C×100
B: the area that is present in the macromolecular elastomer on the arbitrary section vertical of superfine fibre bundle with length direction
C: the area of the arbitrary section vertical of superfine fibre bundle with length direction.
Area B is obtained by the electron micrograph of the arbitrary section vertical with length direction of superfine fibre bundle with C.Above-mentioned cross section is defined as the zone that the center that will constitute a plurality of superfine fibres of superfine fibre bundle periphery connects gained successively.
Macromolecular elastomer preferably by the periphery of superfine fibre bundle to internal direction, discontinuous infiltration in the scope of average 0.2～7 μ m.Form said structure, then can obtain not have young pilose antler to come off, have the imitative chamois leather dermatine of uniform young pilose antler length.Discontinuous form be meant do not resemble provide organic solvent be macromolecular elastomer such continuously, but provide the state of the macromolecular elastomer of aqueous dispersion with distinctive some line shape.
In the imitative chamois leather dermatine, the part of superfine fibre of formation superfine fibre bundle that preferably is present in napping portion and dermatine boundary vicinity is bonding by macromolecular elastomer.By above-mentioned bonding, can prevent to form the decoherencing of superfine fibre of napping, can obtain the imitative chamois leather dermatine of surface physical property excellence.The part of macromolecular elastomer than the inside that is penetrated into the superfine fibre bundle that is present in dermatine of the present invention inside in 1～30% scope, therefore, has sufficient gripping and feel to fiber concurrently in area.But napping portion may stand bigger power such as frictional force, and the fiber that constitutes napping is decoherenced easily.Therefore, if it is also bonding by macromolecular elastomer to be present in the part of superfine fibre napping portion and dermatine boundary vicinity, that constitute the superfine fibre bundle, then collaborative with the grip effect to superfine fibre of inside, can prevent coming off of face fibre, can significantly improve surface physical property.
The boundary vicinity of napping portion and dermatine is meant near the root of the superfine fibre that constitutes the napping of imitating the chamois leather dermatine.As described later, be meant the solution or the existing scope of dispersion liquid of the macromolecular elastomer of artificial leather surface before raised surfaces that imitative chamois leather dermatine is provided or the napping.More particularly, be meant from apart from the 100 μ m depths, surface of dermatine to by the root (surface of dermatine) of the superfine fibre bundle that the constitutes napping portion part till the 100 μ m upwards.
Environmental pressure is little, the water-dispersion type macromolecular elastomer is discontinuous adheres to, the superfine fibre that collects suede by napping processing etc. scatters easily, therefore, the fibrillation of back step (superfine fibre of collection suede is scattered) becomes easily, therefore preferably provides macromolecular elastomer to the raised surfaces of imitative chamois leather dermatine or the dermatine surface before the napping with the form of aqueous dispersions.Heat drying is provided after providing handles (preferred 130～160 ℃ were handled 2～10 minutes), macromolecular elastomer is adhered on the superfine fibre of above-mentioned boundary vicinity securely.Macromolecular elastomer uses and the macromolecular elastomer that contains the identical or homologous ray of the macromolecular elastomer that is immersed in the dermatine, and this considers preferably from cohesiveness or surface physical property equal angles.Only otherwise damage effect of the present invention, can use known macromolecular elastomer.Can add water-soluble high-molecular compounds such as bleeding agent, defoamer, thickener, extender, curing accelerator, antioxidant, ultra-violet absorber, fluorescer, mould inhibitor, polyvinyl alcohol, carboxymethyl cellulose, dyestuff, pigment etc. in right amount in this macromolecular elastomer.Preferred 5～40 quality % of high polymer elastic bulk concentration in this aqueous dispersions.
Provide the macromolecular elastomer aqueous dispersions to the dermatine surface, this can be an any stage so long as get final product after superfine fibreization.For example, can be after the superfine fibreization immediately, napping handles any stage after back, the dyeing.Provide and carry out napping behind macromolecular elastomer aqueous dispersions, the heat drying and handle, this is easily at napping portion and dermatine boundary vicinity bonding polymer elastomer optionally, and is therefore more preferred.The macromolecular elastomer aqueous dispersions can adopt known method such as dipnip mode, heliogravure mode or spray pattern to provide.The heliogravure mode can easily only provide, can obtain excellent feel or surface touch in napping portion and dermatine boundary vicinity bonding polymer elastomer, macromolecular elastomer for discontinuous form, and is therefore preferred especially.The amount of providing of macromolecular elastomer can suitably be selected according to the function that purposes maybe will realize, preferably is provided to above-mentioned boundary vicinity with respect to dermatine with the scope of 0.5～7 quality %.If be that the bonding effect that then is present in the superfine fibre of this boundary vicinity obtains easily, and is below the 7 quality % more than the 0.5 quality %, the amount of macromolecular elastomer that then is present in this boundary vicinity portion is suitable, can obtain excellent outward appearance or surface touch.
Among the present invention, provide macromolecular elastomer to the surface of dermatine after, can handle by pressurized, heated as required or dividing processing etc. obtains desired thickness.In addition, at least one face of dermatine is implemented polishing wait napping to handle, the superfine fibre that forms based on superfine fibre plays matte, makes imitative chamois leather dermatine.The adjusting of thickness can be before superfine fibre is generated the fiber type super-refinement or carry out polishing afterwards.Surface nappy is handled preferred surface to dermatine macromolecular elastomer aqueous dispersions and dry is provided, and carries out after the part of the superfine fibre that makes the superfine fibre bundle that constitutes above-mentioned boundary vicinity is bonding.Like this, not participating in the bonding unwanted macromolecular elastomer of superfine fibre removes easily by the napping processing.The surface treatments such as napping of softening processing, contrary seal plush (シ-Le) such as can also crumple as required.In the dermatine of gained of the present invention, the mobile of macromolecular elastomer is inhibited, and therefore can obtain good hand feeling and outward appearance.
By providing resin bed, can obtain the dermatine of grain or half grain to dermatine.Can also the area of heating surface, push, make it level and smooth, can make dermatine top layer partial melting thus, form resin bed.It is the known macromolecular elastomer of representative that the resin that the surface is provided preferably adopts with polyurethane or polypropylene.Can also on this resin bed, use dyestuff or a spot of pigment coloring of minute quantity.Also can use dermatine of the present invention as required on the upper strata, the applying braided fabric is as lower floor, and perhaps imitative chamois leather dermatine of the present invention is used on the upper strata, and applying contains the layer of the fiber different with the fiber that constitutes this imitative chamois leather dermatine as lower floor.
Embodiment
Specify the present invention by the following examples, but the present invention is not subjected to any qualification of these embodiment.
Embodiment 1
Is sea component with 10mol% M-phthalic acid copolymerization polyethylene terephthalate (234 ℃ of fusing points) as island component, with the polyvinyl alcohol copolymer (the Network ラ レ of Co., Ltd. system エ Network セ バ-Le) that contains 210 ℃ of 10mol% ethylene unit, saponification degree 98.4mol%, fusing point, and the islands-in-sea type fibre on 64 islands of sea component/island component=30/70 (mass ratio) is carried out composite spinning.With its stretching, obtain filament number 5.5dtex, island fiber 0.026dex, density 1.27g/cm
3Superfine fibre generate fiber type.This fiber crimp is handled, be cut into 51mm then, carry out combing and handle, make web of staple fibers.
Then implement the false twisting processing of 84dtex/36f, the gained Polyester Filament is carried out the twisted filament of appending of 600T/m and process, weave with 82 * 76 pieces/inch of loom density then, obtain weight per unit area 55g/m
2Plain cloth.
Above-mentioned net and plain cloth is laminated, then with 1265 thorn/cm
2Density carry out acupuncture and handle, carry out area by 205 ℃ xeothermic contraction and shrink, obtain weight per unit area 580g/m
2, apparent density 0.450g/cm
3, thickness 1.2mm the fiber pseudoconjugant.
Then, at ether is to add the sodium sulphate decahydrate in the polyurethane aqueous dispersion emulsion (the system エ バ of Nicca Chemical Co., Ltd Off ア ノ-Le AP-12), dilute with water, decahydrate/emulsion solid content composition is 3 parts to regulate sodium sulphate, obtaining concentration is 14 quality %, density 1.02g/cm
3The macromolecular elastomer aqueous dispersions.The sensible heat gelling temperature of this macromolecular elastomer aqueous dispersions is 60 ℃.
Then, use lip coater (the ヒ ラ ノ テ of Co., Ltd. Network シ-De system リ Star プ ダ イ レ Network ト mode), impregnation macromolecular elastomer aqueous dispersions makes (dermatine+braided fabric fiber)/macromolecular elastomer=80/20) (mass ratio).Behind the impregnation macromolecular elastomer aqueous dispersions, the infrared ray with 97V irradiation ceiling capacity wavelength 2.6 μ m shone 60 seconds, made fiber pseudoconjugant surface temperature be increased to 100 ℃ within 1 minute, and the moisture rate of infrared radiation after 60 seconds is 30%.Use 155 ℃ air drier heat drying 7 minutes and 30 seconds then, moisture is evaporated fully, macromolecular elastomer is solidified, be adhered on the fiber pseudoconjugant.Use 90 ℃ hot water extracting polyvinyl alcohol copolymer composition then, superfine fibre is generated fiber type be transformed into the superfine fibre bundle, obtain dermatine.The gained dermatine does not have the generation of gauffer, stretching, and outward appearance is good, has the uniform feel or the excellent rerum natura of class leather.
Then, make the surface smoothingization of dermatine, then by heliogravure, under the condition of 140 purpose rollers, speed 8m/ minute the ether of this surface coated 20% be polyurethane aqueous dispersion emulsion (Dainippon Ink Chemicals's system, WLI-612).The high polymer elastic scale of construction of adhering to is 3.5 quality % of dermatine, carries out polishing with No. 320 sand paper then, makes surface nappy.
Then, use Sumikaron UL DISPERSE DYES (Sumitomo Chemical Co's preparation) (the blue GF of red GF, 0.70owf% of 0.24owf% yellow 3RF, 0.34owf%), 2owf%AntifadMC-500 (bright one-tenth KCC preparation) and 1g/LDisper TL (bright one-tenth KCC prepare), 130 ℃ of following high pressure dyeings.The gained dyeing is carried out polishing with No. 400 sand paper, make the whole suede of fiber on top layer, obtain imitative chamois leather dermatine.Confirm the cross section vertical of superfine fibre bundle of central authorities to the lower floor of gained dermatine with length direction by electron microscope, macromolecular elastomer in fibre bundle inside by area than, ratio infiltration with average 3%.In the discontinuous infiltration of length direction.In the fibre bundle on top layer, in inside in area than the macromolecular elastomer that has 10%.The core of fibre bundle is not seen macromolecular elastomer.The imitative chamois leather dermatine of gained does not fracture, gauffer etc., and is soft, very good, and young pilose antler length is neat, has good surface appearance.In addition, use the chair cushion young pilose antler of this imitative chamois leather dermatine preparation to come off few.
Embodiment 2
90 seconds infrared rays of irradiation under 97V, the moisture rate that shines after 90 seconds is 20%, in addition carries out same operation with embodiment 1.It is intrafascicular that macromolecular elastomer is penetrated into superfine fibre in area than 2%.As a result, do not fracture, gauffer etc., feel is soft, very good, and young pilose antler length is neat, obtains having the imitative chamois leather dermatine of good appearance.Use the chair cushion young pilose antler of this imitative chamois leather dermatine preparation to come off few.
Embodiment 3
60 seconds infrared rays of irradiation made fiber pseudoconjugant surface temperature rise to 90 ℃ within 1 minute under 80V, in addition carried out same operation with embodiment 1.It is intrafascicular that macromolecular elastomer is penetrated into superfine fibre in area than 3.5%.The gained dermatine does not fracture, gauffer etc., and is soft, very good, and fiber is by secure grip.Neat by the imitative chamois leather dermatine young pilose antler length that this dermatine obtains, have good surface appearance.Use the chair cushion young pilose antler of this imitative chamois leather dermatine preparation to come off few.
Embodiment 4
The island component that makes ultra-fine generation fiber type is a nylon, in addition carries out same operation with embodiment 1.It is intrafascicular that macromolecular elastomer is penetrated into superfine fibre in area than 3%.The result is not fractureed, gauffer etc., and is soft, very good, and young pilose antler length is neat, has the imitative chamois leather dermatine of good surface appearance.The jacket of this imitative chamois leather dermatine preparation is used in dress, and young pilose antler comes off few as a result.
Comparative example 1
Use the sea component of polyethylene, shrink by hot water and carry out the area contraction, extract with toluene and remove this polyethylene, carry out superfine fibreization, in addition carry out same processing with embodiment 1 as ultra-fine generation fiber type.There is the space in the cross section vertical with length direction by electron microscope affirmation superfine fibre bundle between macromolecular elastomer and fibre bundle external peripheral zone, macromolecular elastomer is not penetrated into fibre bundle inside.Macromolecular elastomer fails fully to grip the superfine fibre bundle, and in the imitative chamois leather dermatine of gained, young pilose antler is decoherenced, and long face fibre is obvious, and young pilose antler length is irregular, and exterior quality is poor.In addition, use the chair cushion of this imitative chamois leather dermatine preparation, young pilose antler comes off many.
Comparative example 2
With 90 ℃ hot water extracting, make superfine fibre, the macromolecular elastomer aqueous dispersions is contained be immersed in the fiber pseudoconjugant then, in addition carry out operation similarly to Example 1.It is intrafascicular that macromolecular elastomer is penetrated into superfine fibre in area than 50%.As a result, in the imitative chamois leather dermatine of gained, fiber is by secure grip, but feel is stone, and is poor.
Comparative example 3
With 60 seconds infrared rays of 30V irradiation, in addition carry out same processing with embodiment 1.Moisture rate behind the irradiation infrared ray is 60%.Macromolecular elastomer moves to the top layer, so the surface fibre of the imitative chamois leather dermatine of gained covered by resin, and young pilose antler is felt non-constant.In addition, macromolecular elastomer is more intrafascicular than near 35% superfine fibre that is penetrated into the imitative chamois leather dermatine top layer in area.As a result, as seen imitative chamois leather dermatine fractures, and Boardy Feeling is poor.
Comparative example 4
Impregnation macromolecular elastomer aqueous dispersions in the fiber pseudoconjugant of embodiment 1 makes (dermatine+braided fabric fiber)/macromolecular elastomer=80/10 (mass ratio).Behind the impregnation macromolecular elastomer aqueous dispersions,, moisture is evaporated fully, macromolecular elastomer is solidified, be adhered on the fiber pseudoconjugant by air drier heat drying 10 minutes.Use 90 ℃ hot water extracting polyvinyl alcohol copolymer composition then, make superfine fibre.Impregnation macromolecular elastomer aqueous dispersions makes (dermatine+braided fabric fiber)/macromolecular elastomer=80/10 (mass ratio) once more.Behind the impregnation macromolecular elastomer aqueous dispersions,, moisture is evaporated fully, macromolecular elastomer is solidified, be adhered on the fiber pseudoconjugant by air drier heat drying 10 minutes.In addition similarly to Example 1, obtain dermatine and imitative chamois leather dermatine.Macromolecular elastomer is more intrafascicular than being penetrated into superfine fibre more than 40% in area, and infiltrates into central part.Near the surface and the back side, the macromolecular elastomer that moves exists with closely knit state.As a result, in the imitative chamois leather dermatine of gained, fiber is by secure grip, but Boardy Feeling is poor.
Industrial applicability
It is good and to the leatheret of the gripping excellence of superfine fibre that the present invention can obtain feel Leather. The imitative chamois leather dermatine that is obtained by this dermatine can not make feel impaired, can suppress The young pilose antler of surface fiber comes off, and has uniform napping outward appearance. Imitative chamois leather leatheret of the present invention Leather can be used for chair cushion, jacket, the garment material take various handbags as representative, furnishings, footwear, The manufacturing of sack etc.
Claims (7)
1. dermatine, this dermatine contains the obvolvent structure that is formed by the superfine fibre bundle and contains the macromolecular elastomer that is immersed in this obvolvent structure inside, the part of this macromolecular elastomer exists with the form of infiltration in this superfine fibre bundle inside, in the arbitrary section vertical of this superfine fibre bundle with length direction, the infiltration ratio of this macromolecular elastomer according to area than the scope of counting 1～30%.
2. the dermatine of claim 1, wherein above-mentioned macromolecular elastomer is in the discontinuous in fact infiltration in the inside of fiber pseudoconjugant.
3. imitative chamois leather dermatine, this imitative chamois leather dermatine is by the dermatine preparation of claim 1 or 2.
4. the imitative chamois leather dermatine of claim 3, it is further bonding by macromolecular elastomer wherein to be present near the boundary of napping portion and dermatine the part of superfine fibre part, that constitute the superfine fibre bundle.
5. the preparation method of dermatine, this method may further comprise the steps:
(1) provide the step of macromolecular elastomer aqueous dispersions in the inside of the fiber pseudoconjugant that is formed by composite fibre, wherein said composite fibre contains water-soluble polymer composition and slightly water-soluble component of polymer;
(2), make the surface that provides the fiber of above-mentioned macromolecular elastomer aqueous dispersions pseudoconjugant be warming up to step than the high temperature more than 10 ℃ of gelling temperature of this macromolecular elastomer aqueous dispersions by infrared radiation;
(3) make the gelling temperature high temperature 10 ℃ or more of the surface maintenance of above-mentioned fiber pseudoconjugant than this macromolecular elastomer aqueous dispersions, the moisture rate that makes this fiber pseudoconjugant simultaneously is the following steps of 50 quality %;
(4) moisture drying that will remain in the above-mentioned fiber pseudoconjugant is removed, and makes above-mentioned macromolecular elastomer be adhered to step in this fiber pseudoconjugant; And
(5) with extracting the water-soluble polymer composition in the composite fibre of hot water from the fiber pseudoconjugant that is bonded with above-mentioned macromolecular elastomer and removing, this composite fibre is transformed to the step of superfine fibre bundle.
6. the preparation method of the dermatine of claim 5, wherein ultrared ceiling capacity wavelength is 2～6 μ m.
7. imitate the preparation method of chamois leather dermatine, this method is that the surface of the dermatine that obtains in the preparation method by claim 5 or 6 provides the macromolecular elastomer aqueous dispersions, carry out drying, use macromolecular elastomer bonding a part that is exposed to the superfine fibre of surperficial formation superfine fibre bundle, carry out napping then and handle.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP052404/2006 | 2006-02-28 | ||
| JP2006052404 | 2006-02-28 | ||
| JP090917/2006 | 2006-03-29 |
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| CN101389806A true CN101389806A (en) | 2009-03-18 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112567092A (en) * | 2018-08-27 | 2021-03-26 | 株式会社可乐丽 | Artificial leather substrate, method for producing same, and raised-hair artificial leather |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112567092A (en) * | 2018-08-27 | 2021-03-26 | 株式会社可乐丽 | Artificial leather substrate, method for producing same, and raised-hair artificial leather |
| CN112567092B (en) * | 2018-08-27 | 2024-01-02 | 株式会社可乐丽 | Artificial leather base material, method for producing same, and standing-hair artificial leather |
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