CN100572638C - Micro staple fiber nonwoven fabric and Leathery sheet and manufacture method thereof - Google Patents
Micro staple fiber nonwoven fabric and Leathery sheet and manufacture method thereof Download PDFInfo
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- CN100572638C CN100572638C CNB2004800206579A CN200480020657A CN100572638C CN 100572638 C CN100572638 C CN 100572638C CN B2004800206579 A CNB2004800206579 A CN B2004800206579A CN 200480020657 A CN200480020657 A CN 200480020657A CN 100572638 C CN100572638 C CN 100572638C
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Abstract
Problem of the present invention is to provide a kind of micro staple fiber nonwoven fabric and solid sense excellent leather shape tablet that is suitable for leather-shaped sheets.The present invention has solved above-mentioned problem by providing following micro staple fiber unit to spin cloth, that is, a kind of micro staple fiber nonwoven fabric is characterized in that, contain filament fiber number 0.0001～0.5 dtex, the fibre length staple fibre smaller or equal to 10cm, it is 100～550g/m that order is paid
2, the fiber apparent density is 0.280～0.700g/cm
3, tensile strength is more than or equal to 70N/cm, tearing brute force is 3～50N.
Description
Technical field
The present invention be more particularly directed to be suitable for the micro staple fiber nonwoven fabric and the manufacture method thereof of the base fabric of Leathery sheet, in more detail, relate to the polyurethane amount of paying that can reduce in the Leathery sheet, the micro staple fiber nonwoven fabric that the intensity rerum natura is good.
And then, the present invention relates to can be used for the solid sense excellent leather shape tablet and the manufacture method thereof of footwear, furniture, dress material etc.In more detail, relate to Leathery sheet and the manufacture method thereof that mainly constitutes, has enough feels, rerum natura by fibrous material.
Background technology
By the Leathery sheet that superfine fibre and macromolecular elastomer constitute, have the not available excellent characteristic of natural leather, be widely used for various uses.When making this Leathery sheet, general adopt the high polymer elastic liquid solution that makes fiber tablet impregnation polyurethane etc. after, this fiber tablet is immersed in water or the aqueous solutions of organic solvent, make macromolecular elastomer carry out the method that wet type is solidified.
But owing to using a large amount of polyurethane in order to obtain intensity, DIMENSIONAL STABILITY etc., and because the cost of material of polyurethane, manufacturing technique complicated etc. makes Leathery sheet become expensive article.In addition,, become feel easily, be difficult to obtain the solid sense of similar natural leather like rubber when macromolecular elastomer becomes for a long time.And then, for this polyurethane of impregnation, generally use N, the water miscibility organic solvent of N '-dimethyl formamide etc., but these organic solvents, generally the angle from operating environment is unfavorable.
In addition, in order to protect environment, resource etc., recycle is paid attention to by people,, has for example developed the decomposition method of the decomposition recovery method of polyester (for example, patent documentation 1), polyurethane (for example, patent documentation 2) for this reason in recent years.But these methods all mainly are applicable to the article of single component, do not separate integrated and composite that form for the macromolecular elastomer of as described above fiber and polyurethane etc., because its decomposition method difference, so be difficult to be suitable for.Therefore, must be separated into each composition, but general cost is very big, it also is difficult separating fully in addition.
And then, point out that also polyurethane etc. causes flavescence because of NOx gas etc., is difficult to obtain flock suede formula (suede) tablet of white.
Therefore, expect that a kind of minimizing uses or do not contain the elastomeric Leathery sheet of macromolecule such as polyurethane in fact.
Therefore, in order to solve these problems, the intensity that improves nonwoven fabric self becomes effective method.As the method for the intensity that improves nonwoven fabric self, studied several so far.Nonwoven fabric that a kind of Leathery sheet that is made of fibre bundle and filament uses is for example disclosed (for example, patent documentation 3), it is to form the self-bonded fibre bundle by the self adhesion fiber with cellulose for example etc., after then carry out sheetization with the method for needle point method etc., fluid stream at a high speed is ejected on the sheet material, makes between the fibre bundle, interweaving between fibre bundle and filament and the filament forms.But,, then when dyeing, have the problem that produces degradation under color spot, surperficial grade or the feel if make fibre bundle bonding with this method.In addition because by high-velocity fluid stream peel off the superfine fibre of autoadhesion considerable part, make its complexing, so also the existence meeting owing to handle inequality and make and when peeling off, generate spot, the problem of its control difficulty.
On the other hand, proposed various by after carrying out acupuncture, carry out the method that high-velocity fluid stream handles and improve the method (for example, patent documentation 4,5) of complexing.This method is useful as the method for the efficient that interweaves that improves the processing of high-velocity fluid stream.But, according to present inventors' viewpoint, think and only make up acupuncture and the processing of high-velocity fluid stream, be difficult to obtain keeping satisfied rerum natura and grade etc., and can reduce the nonwoven fabric of the quantity delivered degree of polyurethane.
In addition, disclose and used and above-mentioned different additive method, carry out acupuncture by the polyester fiber of use low modulus and the polyester fiber of heat-shrinkable, then carry out heat treated and hot-pressing processing, do not flood polyurethane even make, also can obtain having the Leathery sheet matrix material (for example, patent documentation 6) of abundant performance.But, according to present inventors' viewpoint, think when the nonwoven fabric that will obtain like this dyes with for example liquid-flow dyeing machine etc., because kneading action etc. and often breaking.
Patent documentation 1:WO01/30729 communique
Patent documentation 2: the spy opens flat 2001-348457 communique
Patent documentation 3: the spy opens clear 52-12902 communique
Patent documentation 4: special fair 1-18178 communique
Patent documentation 5: the spy opens flat 5-78986 communique
Patent documentation 6: special fair 7-62301 communique
Summary of the invention
The invention provides a kind of particularly as Leathery sheet with matrix material micro staple fiber nonwoven fabric useful, that have abundant intensity and manufacture method thereof.In addition, and then provide a kind of Leathery sheet and manufacture method thereof, even this Leathery sheet does not contain the macromolecular elastomer of polyurethane etc. in fact, also can have sufficient grade, feel, rerum natura, and have good usability, yellowing resistance etc. again.
In order to solve above-mentioned problem, the present invention has following formation.That is, micro staple fiber nonwoven fabric of the present invention is characterized in that, contains the filament fiber number and be 0.0001～0.5 dtex, the fibre length staple fibre smaller or equal to 10cm, and it is 100～550g/m that order is paid (weight per unit area)
2, the fiber apparent density is 0.280～0.700g/cm
3, tensile strength is more than or equal to 70N/cm, tearing brute force is 3～50N.
In addition, the manufacture method of micro staple fiber nonwoven fabric of the present invention, it is characterized in that, use can produce the composite short fiber of 1～10 dtex of the superfine fibre of 0.0001～0.5 dtex, make the composite short fiber nonwoven fabric with needle point method, then under the pressure of 10MPa at least, carry out high-velocity fluid stream and handle.
And then a form of Leathery sheet of the present invention is characterized in that, is made of nonwoven fabric, and is made of the fibrous material of non-elastic polymer in fact.
In addition, other forms of Leathery sheet of the present invention is characterized in that, comprise that fibre number be that 0.0001～0.5 dtex, fibre length pay smaller or equal to 10cm, order is 100～550g/m
2, the fiber apparent density is 0.230～0.700g/cm
3The micro staple fiber nonwoven fabric that is colored formation, tearing brute force is 3～50N, and satisfies following formula,
Tensile strength (N/cm) 〉=0.45 * order is paid (g/m
2)-40.
A form of the manufacture method of Leathery sheet of the present invention, it is characterized in that, micro staple fiber nonwoven fabric is dyeed, it is 0.0001～0.5 dtex, the fibre length staple fibre smaller or equal to 10cm that described micro staple fiber nonwoven fabric contains the filament fiber number, and it is 100～550g/m that order is paid
2, the fiber apparent density is 0.280～0.700g/cm
3, tensile strength is more than or equal to 70N/cm, tearing brute force is 3～50N.
In addition, other forms of the manufacture method of Leathery sheet of the present invention, it is characterized in that, after utilizing needle point method to make the composite short fiber complexing of the superfine fibre that can produce 0.0001～0.5 dtex, form superfine fibre and make micro staple fiber nonwoven fabric, then under the pressure of 10MPa at least, carry out high-velocity fluid and handle and make its complexing once more, dye then.
According to the present invention, can provide a kind of micro staple fiber nonwoven fabric base fabric, that the intensity rerum natura is good that particularly is applicable to Leathery sheet.In addition, can provide amount of paying that can significantly reduce polyurethane or the high-grade Leathery sheet that does not use polyurethane fully.
And then, according to the present invention, can obtain can be used in the good Leathery sheet of solid sense of footwear, furniture, dress material etc.
The specific embodiment
Micro staple fiber nonwoven fabric of the present invention is that the fiber of 0.0001～0.5 dtex forms for containing the filament fiber number.The filament fiber number is preferably 0.001～0.3 dtex, more preferably 0.005～0.15 dtex.When less than 0.0001 dtex, not preferred because intensity reduces.In addition, when surpassing 0.5 dtex, the feel hardening, and complexing takes place become insufficient, the problem of surperficial grade reduction etc., therefore not preferred.In addition, in the scope of not damaging effect of the present invention, also can contain the fiber of the fiber number that surpasses above-mentioned scope.
Manufacture method to the so-called superfine fibre of filament fiber number in above-mentioned scope is not particularly limited, and the method for directly superfine fibre being carried out spinning is for example arranged; Spinning then makes it produce the method for superfine fibre as the fiber that can produce superfine fibre (superfine fibre generation fiber type) of the fiber of common fiber number.And, as using superfine fibre to produce the method for fiber type, for example can make with following method, that is, the spinning islands-in-sea bicomponent fibre, remove the method for sea component then; The spinning Splittable conjugate fiber, cut apart the method etc. of super-refinement then.Wherein, in the present invention, from can stably obtaining the angle of superfine fibre easily, preferably make with islands-in-sea bicomponent fibre or Splittable conjugate fiber, and then when making Leathery sheet, from obtaining easily and can more preferably making with the angle of superfine fibre dyeing of the same race, that constitute by similar polymers with islands-in-sea bicomponent fibre.
Said islands-in-sea bicomponent fibre among the present invention, be meant and carry out compound in any stage composition more than 2 kinds or 2 kinds, the mixed fiber that forms the island state, as the method that obtains this fiber, be not particularly limited, can list, for example (1) 2 kind or more than 2 kinds the polymer of composition admix with the fragment state, the method of spinning, (2) carry out the polymer of composition more than 2 kinds or 2 kinds mixing in advance, carry out the method for spinning behind the fragmentation, (3) 2 of molten condition kinds or the polymer of composition mixes with silent oscillation milling device etc. in the assembly of spinning machine more than 2 kinds method, (4) special public clear 44-18369 communique, the spy opens method made from spinning head of clear 54-116417 communique etc. etc.Can both make well with any method in the present invention, but the aspect of the easiness of selecting from polymer considers, preferably adopt the method for above-mentioned (4).
In the method for these (4), to islands-in-sea bicomponent fibre with remove sea component and the section configuration of the island fiber that obtains is not particularly limited, specifiable have, for example round, polygon, Y, H, X, W, C, π shape etc.In addition, the number of the type of polymer used also is not particularly limited, if but consider stability of spinning process, dyeability, then be preferably 2～3 kinds of compositions, especially preferably 2 kinds of compositions by a kind of sea component, a kind of island component constitute.In addition, the composition ratio of this moment in the weight ratio of island fiber with respect to islands-in-sea bicomponent fibre, is preferably 0.30～0.99, and more preferably 0.40～0.97, more preferably 0.50～0.80.When being lower than 0.30, the rate of removing of sea component uprises, and therefore considers from the cost aspect, and is not preferred.In addition,, then be easy to generate the interflow between the island component if surpass 0.99, from the angle of stability of spinning process, not preferred.
In addition, there is no particular limitation to the polymer that uses, for example as island component, can use polyester, polyamide, polypropylene, polyethylene etc. according to suitable purposes, from the angle of dyeability, intensity, is preferably polyester, polyamide.
As spendable polyester among the present invention, so long as by dicarboxylic acids or its ester formation property derivative and glycol or the synthetic polymer of its ester formation property derivative, the material that can be used as the composite fibre use gets final product, and is not particularly limited.Specifically, specifiable have, for example, polyethylene terephthalate, poly terephthalic acid 1,3-propylidene ester, poly terephthalic acid 1,4-butylidene ester, poly terephthalic acid cyclohexylidene dimethylene ester, poly-2,6-naphthalenedicarboxylic acid second diester, poly-1, two (2-chlorophenoxy) ethane-4 of 2-, 4 '-dioctyl phthalate second diester etc.The present invention, the wherein preferred polyester copolymer that uses the most widely used polyethylene terephthalate or mainly contain the Polyethyleneglycol Terephthalate unit.
As the polyamide that can use in the present invention, specifiable have, for example the polymer of the amide containing key of nylon 6, nylon 66, NYLON610, nylon 12 etc.
The polymer that uses as the sea component of islands-in-sea bicomponent fibre, so long as with the polymer phase ratio that constitutes island component, the polymer with chemical property of higher dissolubility, decomposability gets final product, and is not particularly limited.According to the difference of the selection of the polymer that constitutes island component, also for example can use the polyolefin of polyethylene or polystyrene etc.; The polyester that 5-sulfoisophthalic acid sodium, polyethylene glycol, neopelex, bisphenol-A compound, M-phthalic acid, adipic acid, dodecanedioic acid, hexahydrobenzoid acid etc. are copolymerized into etc.Consider from the aspect of stability of spinning process, preferred polystyrene, never with an organic solvent, the aspect that can remove easily considers preferably have sulfonic copolyester.As this copolymerization ratio, consider from processing speed, stable aspect, be preferably greater than and equal 5 moles of %, consider from the aspect of the easiness of polymerization, spinning, stretching, preferably smaller or equal to 20 moles of %.In the present invention, as preferred combination, be island component use polyester or polyamide or its both, marine origin is divided into polystyrene or has sulfonic copolyester.
In these polymer, can in polymer, add inorganic particulates such as Titanium particles in order to improve disguise, in addition, also can add lubricant, pigment, heat stabilizer, ultra-violet absorber, conductive agent, heat-storing material, antiseptic etc. according to various purposes.
In addition, be not particularly limited for the method that obtains islands-in-sea bicomponent fibre, for example can be for, the use spinning head shown in the method for above-mentioned (4), pull out undrawn yarn after, utilize damp and hot or xeothermic or both carry out 1～3 section stretching its.
As the kind of the nonwoven fabric among the present invention,, must be staple fiber nonwoven fabric from grade, angle that feel is good.For this reason, above-mentioned fiber is necessary to be cut into suitable length, considers the feel of productivity ratio, resulting product, makes it smaller or equal to 10cm.Be preferably smaller or equal to 7cm.In the limit of not damaging effect of the present invention, also can contain fibre length greater than 10cm's.In addition, its lower limit is not particularly limited, can sets according to the manufacture method of nonwoven fabric is suitable, if less than 0.1cm, then existing comes off becomes the trend that the characteristic of many, intensity, abrasion performance etc. reduces, so is preferably greater than and equals 0.1cm.And,, preferably make these staple fibres carry out complexing from the angle of solid sense, intensity.In addition, consider the rerum natura, product grade of the intensity etc. of the Leathery sheet that obtains thus etc., the fibre length of preferred each staple fibre of micro staple fiber nonwoven fabric of the present invention is inhomogenous.That is, in the scope of the fibre length of 0.1～10cm, the preferred mixing exists staple fibre and long fiber.Specifiable have, for example 0.1～1cm, be preferably 0.1～0.5cm staple fibre with 1～10cm, be preferably 2～7cm long fiber and mix the nonwoven fabric that exists.In such nonwoven fabric, for example the short fiber of fibre length helps raising, the densification of surperficial grade, and the fiber that fibre length is long helps to obtain high rerum natura etc.
Method to the mixed with fibers that makes different fibre lengths like this is not particularly limited, specifiable have, use the different islands-in-sea bicomponent fibre of island fibre length method, will have the method that the staple fibre of various fibre lengths mixes, the method that after forming nonwoven fabric, changes fibre length etc.In the present invention, from the viewpoint of the nonwoven fabric that obtains different fibre lengths especially easily, and can set out the preferred method that after forming nonwoven fabric, changes fibre length that adopts in the angle that each stage forms the fibre length that is suitable for 2 kinds of complexing methods of aftermentioned.For example, utilize along tearing into 2 or the method more than it (tearing processing) on the thickness direction perpendicular to nonwoven fabric, can produce easily before tearing processing is single fibre length, and tearing after the processing is the nonwoven fabric of various fibre lengths.Here what is called is torn processing, is meant the processing of the segmentation process that is similar to general natural leather, and the cutting mill of filtering etc. that for example utilizes the field, chamber to make institute's (strain) carries out.
In addition, when using Splittable conjugate fiber, can be mainly in spinning head compound composition more than 2 kinds or 2 kinds, carry out according to the manufacture method of above-mentioned islands-in-sea bicomponent fibre.
As the method for making micro staple fiber nonwoven fabric of the present invention, what preferably adopt is the method that combination needle point method and high-velocity fluid stream are handled, and when carrying out acupuncture, the formation fibre length is the nonwoven fabric of 1～10cm, preferred 3～7cm, then be processed into 2 or more than it by tearing on perpendicular to thickness direction, form staple fibre, handle, can easily obtain the micro staple fiber nonwoven fabric that rerum natura is good, have fine and close surface sense by carrying out high-velocity fluid stream.
As the method for staple fibre being carried out nonwoven fabricization, can adopt and use carding machine, intersect winder (crosswrapper), blue many net making machines (rando-webber) obtains fibroreticulate dry process or utilizes the damp process of copying paper method etc., in the present invention, preferably can make up the dry process that needle point method and high-velocity fluid stream is handled these 2 kinds of complexing methods easily.When complexing is handled, for the stretching that makes its appropriateness or stop and stretch,, also can make itself and other fabric, braided fabric, nonwoven fabric integrated perhaps for the rerum natura of the intensity that improves resulting nonwoven fabric etc.
In addition, to pay be 100～550g/m to the order of micro staple fiber nonwoven fabric of the present invention
2Order is paid and is preferably 120～450g/m
2, 140～350g/m more preferably
2When less than 100g/m
2The time, when nonwoven fabric tectosome just, rerum natura reduces, and when fabric and/or braided fabric were carried out lamination, the become outward appearance and the grade of seeing fabric and/or braided fabric easily of surface reduces, and be therefore not preferred.In addition, when surpassing 550g/m
2The time, abrasion performance has the trend of reduction, and is therefore not preferred.In addition, the fiber apparent density is 0.280～0.700g/cm
3The fiber apparent density is preferably 0.300～0.600g/cm
3, 0.330～0.500g/cm more preferably
3When being lower than 0.280g/cm
3The time, when dyeing, break or balling-up etc., be difficult to obtain full intensity, abrasion performance.When surpassing 0.700g/cm
3The time, form the feel of similar paper, not preferred.
In addition, the fiber apparent density is, measures order according to JIS L 10968.4.2 (1999) and pays, and then measures its thickness, then with the mean value of the fiber apparent density that obtains as the fiber apparent density.In addition, when measuring thickness, use and carve disc thickness and measure meter (the rugged making of (strain) tail is made, trade name " ピ one コ Star Network H "),, use its mean value 10 points of sample determination.Said fiber apparent density is meant the apparent density of fibrous material among the present invention.Therefore, for example under the situation that contains the nonwoven fabric tectosome that is soaked with fibrous material resin in addition, the apparent density of the fibrous material of this resin is removed in expression.
In addition, micro staple fiber nonwoven fabric of the present invention, the tensile strength of any direction of warp-wise and broadwise is all more than or equal to 70N/cm.The tensile strength of any direction that is preferably warp-wise and broadwise is all more than or equal to 80N/cm.When the tensile strength of any direction of warp-wise or broadwise was lower than 70N/cm, for example when making Leathery sheet, the operation trafficability characteristic variation in ensuing senior manufacturing procedure had and breaks or the trend of change in size etc., so not preferred.In addition, when making Leathery sheet, also existed for the problem that obtains sufficient rerum natura and must supply with a large amount of polyurethane.In addition, the upper limit is not particularly limited, but is generally smaller or equal to 200N/cm.According to JIS L10968.12.1 (1999), take the sample of wide 5cm, long 20cm, be spaced apart 10cm, use constant speed elongation type extensiometer with extracting, make its elongation with 10cm/ minute draw speed, try to achieve tensile strength.According to the value that obtains, with the wide load of every 1cm as tensile strength (unit: N/cm).In order to obtain such intensity, the intensity of used fiber is preferably more than and equals the 2cN/ dtex.
And then micro staple fiber nonwoven fabric of the present invention all is 3～50N at the tearing brute force of any direction of warp-wise and broadwise.The tearing brute force that is preferably any direction of warp-wise and broadwise all is 5～30N.When the tearing brute force of any direction of warp-wise and broadwise all was lower than 3N, the technology trafficability characteristic reduced, and is difficult to steady production.On the contrary, when the tearing brute force of any direction of warp-wise and broadwise all surpasses 50N, the trend of excessive softnessization is arranged generally, be difficult to obtain the balance with feel, therefore not preferred.In addition, measure tearing brute force according to JIS L 10968.15.1 (1999) D method (pendulum method).
In order to obtain such tearing brute force, can realize that generally when carrying out densification, intensity has the trend of reduction by the fiber apparent density is adjusted in the proper range.
Micro staple fiber nonwoven fabric of the present invention, for the distortion that prevents the sheet in the back operation of further carrying out according to purposes, break, 10% modulus that is preferably warp-wise is more than or equal to 8N/cm, more preferably 10N/cm.In addition, the upper limit is not particularly limited, but when surpassing 50N/cm, feel hardening, operability reduce, and be therefore not preferred.When making,, can improve the value of 10% modulus by fully carrying out acupuncture processing, the processing of high-velocity fluid stream with above-mentioned manufacture method.In addition, also can make its increase by making fabric and/or braided fabric etc. carry out lamination.
In addition, these worthwhile right meetings are owing to implementing the dyeing processing or rubbing to handle and reduce, but the stage of the micro staple fiber nonwoven fabric before carrying out these processing, by making these values within the scope of the invention, can easily obtain the Leathery sheet of better technology trafficability characteristic and good grade.
In addition, 10% modulus is similarly carried out with the assay method of tensile strength, and the intensity during with 10% elongation is worth as it.
The micro staple fiber nonwoven fabric of the present invention that obtains like this, even when only constituting by fibrous material, by firm complexing,, so has good technology trafficability characteristic even make and under the kneading action that for example liquid-flow dyeing machine is strong like that, also to be difficult to break etc.Therefore, micro staple fiber nonwoven fabric of the present invention can be suitable as Leathery sheet and uses with base fabric.For example, if use micro staple fiber nonwoven fabric of the present invention,, also can obtain the Leathery sheet of solid sense even do not use or the macromolecular elastomer of a small amount of use polyurethane compared with the past etc.For example, be preferably macromolecular elastomer, can produce the Leathery sheet of solid sense smaller or equal to 10% weight by paying with respect to fibrous material.In addition, especially, even the elastomeric structure of pbz polymer not in fact also can obtain having good hand feeling, the rerum natura of solid sense, the Leathery sheet of grade.Therefore, according to the feel of purpose or rerum natura etc., can suitably pay macromolecular elastomer.
In addition, micro staple fiber nonwoven fabric of the present invention has very high rerum natura and fine and close structure, therefore except Leathery sheet, also is applicable to abrasive cloth, filter cloth, wiping cloth (rags), heat-barrier material, sound-absorbing material etc.
Below, an example of the manufacture method of micro staple fiber nonwoven fabric of the present invention is described.
Be used to obtain the method for optimizing of micro staple fiber nonwoven fabric of the present invention, be by using 1～10 dtex can produce superfine fibre composite fibre, utilize needle point method to make the composite short fiber nonwoven fabric, then carry out the processing of high-velocity fluid stream under at least more than or equal to the pressure of 10MPa, for example water stream carries out water thorn (water jet punch) processing.Handle by making up this needle point method and high-velocity fluid stream, can carry out the complexing of height.
This composite short fiber nonwoven fabric is preferably handled by acupuncture, makes the fiber apparent density be preferably 0.120～0.300g/cm
3, 0.150～0.250g/cm more preferably
3When being lower than 0.120g/cm
3The time, complexing is insufficient, is difficult to the rerum natura that obtains requiring.In addition, the upper limit is not particularly limited, when surpassing 0.300g/cm
3The time, produce the problem of the fractureing of pin, residual pin hole etc., therefore not preferred.
In addition, when carrying out acupuncture, the filament fiber number of composite fibre is preferably 1～10 dtex, more preferably 2～8 dtexs, more preferably 2～6 dtexs.When the filament fiber number is lower than 1 dtex or surpasses 10 dtexs, utilize the complexing of acupuncture to become insufficient, be difficult to obtain the good micro staple fiber nonwoven fabric of rerum natura.
Acupuncture among the present invention, being preferably not is the effect of only playing for the temporary joint that obtains the technology trafficability characteristic, but makes the abundant complexing of fiber.Therefore filling density is preferably greater than and equals 100/cm
2, more preferably greater than equaling 500/cm
2, further be preferably greater than and equal 1000/cm
2
The composite short fiber nonwoven fabric that obtains like this, preferably by xeothermic or damp and hot or these two shrink, and then carry out densification.
Then, preferably after carrying out ultra fine or with ultra fine simultaneously, or reach simultaneously thereafter with ultra fine, carry out high-velocity fluid stream and handle, carry out the complexing between the superfine fibre.Handle the double as ultra fine though can make high-velocity fluid stream, but angle from the complexing between the further promotion superfine fibre, preferably after the ultra fine major part is finished at least, also carry out high-velocity fluid stream and handle, further preferably after carrying out ultra fine, carry out high-velocity fluid stream and handle.
Method as ultra fine is not particularly limited, and specifiable have, for example, and the method for the method of machinery, chemistry etc.Method as so-called machinery has the method for carrying out super-refinement by the stimulation of paying physics, and in addition the method for paying impact of for example above-mentioned needle point method or water acupuncture manipulation etc., can list the method for pressurizeing, the method for carrying out ultrasonic Treatment etc. between roller.In addition, the method as so-called chemistry for example can list, to constituting at least 1 composition of composite fibre, by medicament make that it expands, decomposes, the method for the variation of dissolving etc.Particularly using the superfine fibre that is formed by the labile sea component of alkali to produce fiber type makes the composite short fiber nonwoven fabric, follows the method for handling, carrying out super-refinement with the aqueous solution of neutrality～alkalescence, do not use solvent, thereby consider from the operating environment aspect, it is preferred, is one of optimal way of the present invention.The aqueous solution of neutrality～alkalescence described here is meant that pH is 6～14 the aqueous solution, and the medicament that uses etc. is not particularly limited.For example as the aqueous solution that contains organic or inorganic salts, as long as show the pH of above-mentioned scope, can list the alkali earth metal salt of the alkali metal salt of NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate, sodium bicarbonate etc., calcium hydroxide, magnesium hydroxide etc. etc.In addition, the amine of all right in case of necessity also usefulness triethanolamine, diethanol amine, monoethanolamine etc., reduction promoter, carrier etc.Wherein, from the angle of the easiness of price, processing etc., preferred NaOH.More preferably, after the aqueous solution processing to the above-mentioned neutrality～alkalescence of sheet enforcement, neutralize as required, wash and remove residual chemicals, analyte etc., carry out drying then.
Carry out the method that ultra fine and high-velocity fluid stream is handled simultaneously as these, for example can list, use contains the composite fibre of water miscible sea component, sting the method for removing with complexing by water, use the different composite fibre of composition more than 2 kinds or 2 kinds of alkali decomposition rate, after by alkali treatment liquid easy-soluble component being carried out resolution process, finally remove the method handled with complexing etc. by the water thorn.
Handle as high-velocity fluid stream, from the angle of operating environment, preferably use current the water thorn handle.At this moment, water preferably carries out with the state of columnar flow.Be to obtain columnar flow, normally obtain by gushing out with the pressure of 1～60MPa by the nozzle of diameter 0.06～1.0mm.In order to obtain effective complexing and surface of good grade, this processing is preferably, and the diameter of nozzle is 0.06～0.15mm, and at interval smaller or equal to 5mm, more preferably diameter is 0.06～0.12mm, at interval smaller or equal to 1mm.When repeatedly handling, these nozzle specifications there is no need to adopt all identical conditions, for example can and use the nozzle of large aperture and small-bore, preferably at least once use the nozzle of above-mentioned formation.Particularly when diameter surpassed 0.15mm, the complexing between the superfine fibre reduced, the surface easy balling-up that becomes, and surface smoothing also reduces, and therefore not preferred.Therefore, the little person in preferred nozzle aperture, but when less than 0.06mm,, filter so water must be carried out height because spray nozzle clogging takes place easily, make cost become big, therefore not preferred.In addition, in order on thickness direction, to realize interweaving uniformly and/or to improve the flatness of nonwoven surface, preferably carry out repeatedly repeated treatments.In addition, this water flow pressure is paid suitably according to the order of nonwoven fabric to be processed and is selected, and is preferably order and pays highly more, uses high pressure more.And then, in order to make height complexing between the superfine fibre, preferably under pressure, handle at least 1 time, more preferably greater than equaling 15MPa more than or equal to 10MPa.In addition, the upper limit is not particularly limited, but pressure is big more, cost is high more, in addition, if pay for low order, then nonwoven fabric become inhomogeneous, sometimes also because fine hair takes place in the cut-out of fiber, so preferably smaller or equal to 40MPa, be more preferably less than and equal 30MPa.By such processing, for example the time for the superfine fibre that obtains by composite fibre, in general, the superfine fibre bundle that boundling forms between the fiber mainly is that complexing forms, in the present invention, can obtain between the superfine fibre micro staple fiber nonwoven fabric that the height complexing forms to the degree of the complexing that does not observe the superfine fibre bundle substantially, in addition, also can improve the surface characteristic of abrasion performance etc. thus.In addition, before carrying out the processing of water thorn, can carry out water retting and handle.In order further to improve the grade on surface, can adopt: shower nozzle and nonwoven fabric are relatively moved, and after interweaving, the insertion wire netting waits the method for carrying out aqueous dispersion processing etc. between nonwoven fabric and nozzle.Be preferably in addition, carrying out before high-velocity fluid stream handles, on direction, tear and be processed into 2 or more than it perpendicular to thickness.Like this, make preferably that complexing reaches more than or equal to 8N/cm until 10% modulus of warp-wise between the micro staple fiber, more preferably reach more than or equal to 10N/cm.
In addition, after carrying out the processing of high-velocity fluid stream, if and then under 100～250 ℃ temperature, thickness is compressed to 0.1～0.8 times with calender, then can further increase the fiber apparent density, in addition, when superfine fibre nonwoven cloth of the present invention was made into Leathery sheet, from improving abrasion performance, obtaining the angle of fine and close feel, this was preferred.When compression was lower than 0.1 times, feel was too hard, and is not preferred.In addition, also can surpass 0.8 times, still, compression effects diminishes, and handles owing to for example dyeing to wait to make caliper recovery.And then, less than 100 ℃ the time, to handle, compression effects also diminishes, and is not preferred.In addition when when the temperature that is higher than 250 ℃ is handled, because there is the trend that makes the feel hardening owing to the fusion adhesion, so not preferred.In addition, if before high-velocity fluid stream is handled, compress, then because the complexing that utilizes high-velocity fluid stream to handle becomes to be difficult to carry out, so not preferred.
The present invention is conceived to utilize the fiber of the easy complexing of acupuncture to handle the difference of the fiber of easy complexing with utilizing high-velocity fluid stream, found particularly by utilizing technology as described above to make, can obtain the invention of good micro staple fiber nonwoven fabric of the present invention easily.That is, be the invention that utilizes following trend: there is excellent trend in the complexing that the fiber of 1～10 dtex is undertaken by acupuncture for thick state the time, handle the complexing of carrying out by high-velocity fluid stream when the ultra-fine zone of 0.0001～0.5 dtex exists excellent trend.For these fibre numbers are matched with the complexing method, preferred use fiber number be 1～10 dtex superfine fibre generation type composite fibre, carry out abundant complexing by acupuncture, then after the ultra fine of the superfine fibre that is used to obtain 0.0001～0.5 dtex or reaching simultaneously thereafter simultaneously or with ultra fine, carry out high-velocity fluid stream and handle with ultra fine.
Below, Leathery sheet of the present invention is described.
A form of Leathery sheet of the present invention is, constituted and is the Leathery sheet that is made of the fibrous material of non-elastic polymer in fact by nonwoven fabric.Here said Leathery sheet, be meant the goods of excellent appearance with the such imitative chamois leather of natural leather, nubuck, lambskin etc., especially, the present invention is preferably, aspect the outward appearance of transferring in the napping of the imitative chamois leather of what is called, nubuck, have the goods of smooth sense of touch and good luster effect.In general, the Leathery sheet that is called as synthetic leather, dermatine, be that macromolecular elastomer and fibrous material by polyurethane etc. constitutes, but a form of Leathery sheet of the present invention, do not contain in fact polyurethane etc. macromolecular elastomer, the fibrous material by non-elastic polymer constitutes in fact.Here the fiber of said non-elastic polymer is meant the polymer the rubber-like elasticity fiber with excellent of polyurethanes fiber except polyether ester fibrid or so-called Spandex (spandex) etc. etc.Specifically, can list the fiber that constitutes by polyester, polyamide, polypropylene, polyethylene etc.Be preferably the polymer that constitutes aforesaid micro staple fiber nonwoven fabric.By constituting by the fibrous material of non-elastic polymer in fact, can realize not having the rubber sense and have abundant feel.In addition, and then can realize the various effects of easy recycle, high-color rendering, high-light-fastness, yellowing resistance etc.Particularly in order to carry out the chemical cycle utilization, fibrous material preferably is made of polyethylene terephthalate or nylon 6.In addition, a form of Leathery sheet of the present invention, most preferably be the macromolecular elastomer of the polyurethanes fiber that do not contain polyether ester fibrid or Spandex etc. fully etc., but in the scope that does not depart from effect of the present invention, also can contain macromolecular elastomer.In addition, also can contain the functional medicine that for example dyestuff, softener, feel adjustment agent, balling-up prevent agent, antiseptic, deodorant, waterproofing agent, photostabilizer, weatherability agent etc.
A form of Leathery sheet of the present invention is to be made of nonwoven fabric at least, can obtain the such feel of leather thus.In addition, if contain the goods of nonwoven fabric, then can be the goods that contain the braided fabric that has carried out lamination etc., but if goods that are made of braided fabric only then be difficult to obtain good hand feeling.
In addition, as Leathery sheet, can transfer for grain, napping accent etc. any, but when only constituting, especially,, therefore be preferably and make the one side napping at least because, can obtain more surface of good grade especially forming the napping timing by fibrous material.For obtain that grain transfers surperficial the time, different with the article of the resin bed of existing formation polyurethane etc., preferably form the fibrolaminar method of VHD on the surface.In addition, Leathery sheet of the present invention is made of fibrous material in fact, but different with simple nonwoven fabric, and it is the goods that have with the similar surperficial grade of general natural leather, dermatine.
Such Leathery sheet is that the superfine fibre of 0.0001～0.5 dtex constitutes by the filament fiber number especially preferably, more preferably 0.005～0.15 dtex, further preferred 0.005～0.1 dtex.
Method as the Leathery sheet that obtains to be made of such fibrous material is not particularly limited, and for example can use above-mentioned superfine fibre nonwoven cloth of the present invention to make.When being lower than 0.0001 dtex, intensity decreases, colour rendering reduce, and be therefore not preferred.When surpassing 0.5 dtex, feel hardening, surperficial grade also descend, and be therefore not preferred.In addition, in the scope of not damaging effect of the present invention, also can contain the fiber of the filament fiber number that surpasses above-mentioned scope.
And such Leathery sheet preferably dyes.
Then, other forms of Leathery sheet of the present invention is characterized in that, contain the filament fiber number and be that 0.0001～0.5 dtex, fibre length pay smaller or equal to 10cm, order is 100～550g/m
2, the fiber apparent density is 0.230～0.700g/cm
3Be colored and the micro staple fiber nonwoven fabric that forms, tearing brute force is 3～50N, and satisfies following formula,
Tensile strength (N/cm) 〉=0.45 * order is paid (g/m
2)-40.
The filament fiber number is 0.0001～0.5 dtex, is preferably 0.001～0.3 dtex, more preferably 0.005～0.15 dtex, more preferably 0.005～0.1 dtex.When being lower than 0.0001 dtex, intensity decreases, therefore not preferred.In addition, when surpassing 0.5 dtex, degradation problem under the surperficial grade in addition, also takes place in the feel hardening, and is therefore not preferred.In addition, in the scope of not damaging effect of the present invention, also can contain the fiber of the fiber number that surpasses above-mentioned scope.
In addition, from grade, angle that feel is good, Leathery sheet of the present invention contains staple fiber nonwoven fabric, and its fibre length is smaller or equal to 10cm.Fibre length is preferably smaller or equal to 7cm.In the limit of not damaging effect of the present invention, also can contain the nonwoven fabric of fibre length greater than 10cm.In addition, lower limit is not particularly limited, can suits according to the manufacture method of nonwoven fabric to set, but when less than 0.1cm, coming off becomes many, in addition, have the trend of the characteristic reduction of intensity or abrasion etc., thus not preferred.In addition, under the situation of considering the rerum natura of intensity etc., grade etc., the inhomogeneous person of optimum fiber length.That is, in the scope of the fibre length of 0.1～10cm, the preferred mixing exists staple fibre and long fiber.Can example for example illustrate, 0.1～1cm, the staple fibre and the 1～10cm that are preferably 0.1～0.5cm, the long fiber that is preferably 2～7cm mix the nonwoven fabric that exists.Here, for example staple fibre has the effect that improves surperficial grade, densification etc., and in addition, long fiber has the effect that obtains high rerum natura etc.
It is 100～550g/m that the order of Leathery sheet is paid
2, be preferably 120～450g/m
2, 140～350g/m more preferably
2When less than 100g/m
2The time, rerum natura reduces, and when fabric and/or braided fabric carry out lamination, becomes and sees the outward appearance of fabric and/or braided fabric on the surface easily, and grade reduces, and is therefore not preferred.In addition, when greater than 550g/m
2The time, the trend that has abrasion performance to reduce, therefore not preferred.In addition, the fiber apparent density of this Leathery sheet is 0.230～0.700g/cm
3The fiber apparent density is preferably 0.280～0.650g/cm
3, 0.300～0.600g/cm more preferably
3When less than 0.230g/cm
3The time, particularly abrasion performance reduces, and is therefore not preferred.In addition, when greater than 0.700g/cm
3The time, the feel hardening, therefore not preferred.
All in the scope of 3～50N, the tearing brute force of any direction of warp-wise and broadwise all is preferably 5～30N, more preferably 10～25N to the tearing brute force of the warp-wise of Leathery sheet of the present invention and any direction of broadwise.When less than 3N, except easy breakage, the technology trafficability characteristic also reduces, and very difficult steady production becomes.In addition, when greater than 50N, generally have excessive softnessization trend, be difficult to obtain and feel between balance, therefore not preferred.In order to obtain such tearing brute force, can realize that in general, if carry out densification, then intensity has the trend of reduction by the fiber apparent density is adjusted in the optimum range.In addition, also can wait and to carry out softnessization and improve tearing brute force by rubbing processing.
The tensile strength of any direction of warp-wise and broadwise all must satisfy following formula,
Tensile strength (N/cm) 〉=0.45 * order is paid (g/m
2)-40.
When tensile strength is in the scope that does not satisfy this formula, for the elastomeric Leathery sheet of pbz polymer not in fact, problems such as breakage may take place particularly, therefore not preferred.In addition, the upper limit is not particularly limited, is generally smaller or equal to 250N/cm.
In addition, the tensile strength that also is preferably any direction of warp-wise and broadwise all satisfies following formula,
Tensile strength (N/cm) 〉=0.5 * order is paid (g/m
2)-40.
And then more preferably the tensile strength of any direction of warp-wise and broadwise all satisfies following formula,
Tensile strength (N/cm) 〉=0.6 * order is paid (g/m
2)-40.
Leathery sheet of the present invention does not contain the macromolecular elastomer of polyurethane etc., is the goods that are made of fibrous material in fact, except the feel with solid sense, also has good recycle etc., and is therefore preferred.In addition similarly, for fibrous material, also be preferably and do not contain the fiber that the elastomeric polymer by so-called Spandex etc. constitutes, and be the fiber that constitutes by non-elastic polymer.
In addition, Leathery sheet of the present invention can be any of grain accent, napping accent etc., but owing to for the napping timing can obtain better surperficial grade, therefore preferably makes the one side napping at least.
And then, from the good angle of abrasion performance, preferably make in the fibrous material that constitutes Leathery sheet to contain particulate.Especially, more preferably form the structure of complexing between the superfine fibre of fibrous material, have particulate, can obtain the effect of very big raising abrasion performance by making it.
Here said atomic material is not particularly limited as long as insoluble in water, and the organic substance of the inorganic substances of silica, titanium oxide, aluminium, mica etc., melmac etc. can example for example be shown.In addition, atomic average grain diameter is preferably 0.001～30 μ m, more preferably 0.01～20 μ m, more preferably 0.05～10 μ m.When being lower than 0.001 μ m, be difficult to the effect that obtains expecting, in addition, when surpassing 30 μ m, owing to washing resistance is descended from fibre shedding.In addition, use the assay method that is fit to of reply material, size, for example BET method, laser method, Ku Leertefa measure average grain diameter.
These particulates can suit to adjust its use amount in the scope that can bring into play effect of the present invention, but be preferably 0.01～10 weight %, more preferably 0.02～5 weight %, more preferably 0.05～1 weight %.So long as, then can significantly bring into play the effect that improves abrasion performance more than or equal to 0.01 weight %, exist its amount to increase more, its effect has the trend that becomes big more.But, when surpassing 10 weight %, the feel hardening, not preferred.In addition, in order to prevent the atomic durability that comes off, improves, the preferred merging used a spot of resin.
In addition, in order to obtain soft hand feeling and smooth surface touch, Leathery sheet of the present invention preferably contains softener.Be not particularly limited as softener, can suitably be chosen in the general softener that uses in the fabric according to the kind of fiber.For example can from dyeing handbook the 23rd edition (sale room Co., Ltd. look dyes society, distribution on August 31st, 2002), suitably select material with the title record of feel processing agent, soft finishing agent.Wherein,, be preferably polysiloxane-based emulsion, more preferably carried out amino modified or epoxide modified polysiloxane-based emulsion from the good angle of the effect of flexibility.Therefore preferably when containing these softeners, abrasion performance has the trend of reduction, on the basis of obtaining as the feel of target and the balance between the abrasion performance, suitably adjusts the amount and the above-mentioned atomic amount of this softener.Therefore, its amount is not particularly limited, but, then can not brings into play effect,, the adhesion sense is arranged then, so preferred in the scope of 0.01～10 weight % if too much because if very few.
Any form of Leathery sheet of the present invention, in the abrasion performance test of measuring with load (12kPa) according to JIS L 1096 (1999) 8.17.5E methods (Martindale's method) furniture, the wear loss of carrying out 20000 test cloth after the abrasion is smaller or equal to 20mg, be preferably smaller or equal to 15mg, more preferably smaller or equal to 10mg, and the balling-up that is preferably existence is smaller or equal to 5, more preferably smaller or equal to 3, more preferably smaller or equal to 1.When wear loss during, the trend that exists fine hair on clothes, to adhere in actual the use, therefore not preferred greater than 20mg.In addition, lower limit is not particularly limited, so long as leather-shaped sheets of the present invention, also just can obtains not have substantially the goods of wear loss.In addition, for the balling-up that is produced, if greater than 5, the appearance change when then using causes grade to reduce, and is therefore not preferred.
In order to obtain such abrasion performance, the fiber apparent density is a particular importance, and the densification degree is high more good more.In addition,, then can improve abrasion performance greatly, on the contrary,, then find the tendency of its reduction if use softener etc. in a large number if supply with particulate.Therefore, on the basis of having obtained with the balance of feel, must set these conditions.
Any form of Leathery sheet of the present invention, from the angle of dyeability, intensity, all preferred micro staple fiber is polyester and/or polyamide.
And then, any form of Leathery sheet of the present invention, from the angle of texture, intensity, grade, all preferred fibre-bearing length is the micro staple fiber of 1～10cm, and is complexing between the micro staple fiber.
Manufacture method to Leathery sheet of the present invention is not particularly limited, and the angle of the target properties that is easy to get is calmly set out, and preferably makes by aforesaid micro staple fiber nonwoven fabric of the present invention is dyeed.By using aforesaid micro staple fiber nonwoven fabric of the present invention, can satisfy the various features of Leathery sheet of the present invention.
In addition, other modes of the manufacture method of Leathery sheet of the present invention are, after the composite short fiber that makes the superfine fibre that can produce 0.0001～0.5 dtex carries out complexing by acupuncture, produce superfine fibre and form micro staple fiber nonwoven fabric, then under the pressure of 10MPa at least, carry out high-velocity fluid and handle and make complexing once more, dye subsequently.The manufacture method of their concrete method and micro staple fiber nonwoven fabric of the present invention is carried out equally, then dyes.
When making Leathery sheet of the present invention, when supplying with the macromolecular elastomer of polyurethane etc., after making micro staple fiber nonwoven fabric, be immersed in the macromolecular elastomer.As this macromolecular elastomer, can select to use the macromolecular elastomer of the various feels that can obtain suitable purpose, rerum natura, grade, for example can list polyurethane, acrylic acid, styrene-butadiene etc.Wherein, from the angle of flexibility, intensity, grade etc., preferably use polyurethane.Manufacture method as polyurethane is not particularly limited, and can promptly, make macromolecule polyol, vulcabond, cahin extension agent carry out appropriate reaction and make with present known method.In addition, can be solvent system, also can be aqueous dispersion, from the angle of operating environment, the preferred water disperse system.
But,, be preferably in fact not the pbz polymer elastomer, mainly constitute by fibrous material from clearer and more definite, of the present invention Leathery sheet of the feature of micro staple fiber nonwoven fabric of the present invention and present more excellent angle.And then, even for fibrous material, also preferably constitute by the fiber of non-elastic polymer in fact.
The method that this micro staple fiber nonwoven fabric is dyeed is not particularly limited, as employed dyeing machine, except liquid-flow dyeing machine, can also be any of thermosol dyeing machine, high pressure dye gigging dyeing machine etc., but, preferably use liquid-flow dyeing machine to dye from the good angle of feel of the Leathery sheet that obtained.
In addition, for the Leathery sheet that mainly constitutes,, after dyeing, can adopt 0.1～0.8 times the method that is compressed in order to obtain the surface that half grain is transferred by fibrous material.Thus, the surface forms half grain and transfers, and also can improve abrasion performance in addition.This compresses processing, can be before dyeing, and also can be after dyeing.
And then, in the time will obtaining the Leathery sheet that imitative chamois leather is transferred, nubuck is transferred, preferably carry out napping and handle with sand paper or brush etc.This napping is handled and can perhaps be carried out before dyeing and after the dyeing before or after dyeing.In addition, in order to improve abrasion performance, preferably carrying out carrying out the method that napping is handled after above-mentioned compression is handled.
In the manufacture method of Leathery sheet of the present invention,, preferably include particulate is supplied to operation in the fibrous material in order to improve abrasion performance.By particulate is supplied in the fibrous material, also can obtain to give the effect of the feel of dry sensation and harsh feeling etc.As supplying with this atomic method, be not particularly limited the method for except padding method, can suitably select to use the method for liquid-flow dyeing machine, dye gigging dyeing machine, spraying with sprayer etc.
In addition, in order to obtain soft hand feeling and smooth surface touch, also preferably include softener is paid operation in the fibrous material.The method of paying softener is not had special provision yet, except padding method, also can use, the method for spraying etc. with the method for liquid-flow dyeing machine or dye gigging dyeing machine, with sprayer.From the angle of manufacturing cost, preferably pay simultaneously with particulate.
In addition, preferably after dyeing, pay particulate, softener.If before dyeing, pay, then have to cause the situation that effect reduces because of coming off of when dyeing or produce the stain situation, therefore not preferred.In addition, be furnished with the trend that is difficult to napping, therefore under the situation of carrying out napping, preferably after napping, pay particulate because contain atomic nonwoven.
Embodiment
Below, by embodiment the present invention is described in further detail.In addition, the physics value among the embodiment is measured with following described method.
(1) order pay, the fiber apparent density
Order is paid with the method for JIS L 10968.4.2 (1999) and is measured.In addition, measure meter (the rugged making of (strain) tail is made, trade name " ピ one コ Star Network H ") and measure thickness,, obtain the fiber apparent density by calculating from the value that order is paid with carving disc thickness.
(2) tensile strength, 10% modulus
According to JIS L 1096 8.12.1 (1999), take the sample of wide 5cm, long 20cm, with extracting be spaced apart 10cm, with constant speed elongation type extensiometer, to make its elongation in draw speed 10cm/ minute.It is wide that the value that obtains is scaled every 1cm, as tensile strength.Intensity during in addition, with warp-stretch 10% is as the value of 10% modulus.
(3) tearing brute force
Measure according to JIS L 1096 8.15.1 (1999) D method (pendulum method).
(4) Martindale's abrasion test
In the abrasion performance test of measuring with the standard of load (12kPa) according to JIS L 1096 (1999) 8.17.5.E methods (Martindale's method) furniture, the weight decrement of carrying out 20000 test cloth after the abrasion is estimated, and gone out the number of balling-up according to the outward appearance number.
Embodiment 1
Using the filament fiber number that is made of 55 parts polyethylene terephthalate by 45 parts polystyrene, as island component as sea component is 3 dtexs, 36 islands, the fibre length fabric of island-in-sea type composite short fiber as 51mm, makes fiber web by the carding machine or the winder that intersects.Then by the acupuncture of 1 barb type, with 1500/cm
2Filling density handle, obtaining the fiber apparent density is 0.210g/cm
3The composite short fiber nonwoven fabric.Then, be immersed in and heat to the aqueous solution that about 95 ℃ degree of polymerization is 500, saponification degree is 88% polyvinyl alcohol (PVA1) 12%, make and convert, reach 25% with respect to nonwoven fabric weight, adhesion amount with solid constituent, when in PVA, flooding, carry out 2 minutes shrink process, carry out drying at 100 ℃ and remove moisture.The sheet that obtains is handled till removing polystyrene fully with about 30 ℃ trichloro-ethylene, obtained the superfine fibre that the filament fiber number is about 0.046 dtex.Then, the standard type of using the field, chamber to make institute's (strain) system cutting mill of filtering, tear on perpendicular to thickness direction be treated to 2 after, utilize the water of aperture 0.1mm, the shower nozzle formation of 0.6mm at interval to sting, with 1m/ minute processing speed positive and negative is all handled under 10MPa and 20MPa, when removing PVA1, carried out complexing.
The micro staple fiber nonwoven fabric that obtains like this is that PVA1 comes off fully, between the superfine fibre complexing the sheet of densification.The evaluation result of its rerum natura is as shown in table 1.
Embodiment 2
Before carrying out the processing of high-velocity fluid stream, till removing PVA1 fully, in addition, handle similarly to Example 1 with 95 ℃ hot water treatment PVA1.The micro staple fiber nonwoven fabric that obtains so similarly to Example 1, be between the superfine fibre complexing the sheet of densification.The evaluation result of its rerum natura is as shown in table 1.
Embodiment 3
Using by 20 parts of polystyrene as sea component, 80 parts of filament fiber numbers that constitute as the polyethylene terephthalate of island component is 5 dtexs, 25 islands, the fibre length islands-in-sea bicomponent fibre (fiber number of island component is about 0.16 dtex) as 51mm, in addition, handle similarly to Example 1, obtained micro staple fiber nonwoven fabric.The micro staple fiber nonwoven fabric that obtains like this be between the superfine fibre complexing the sheet of densification.The evaluation result of its rerum natura is as shown in table 1.
Embodiment 4
As island component, replace polyethylene terephthalate and use nylon 6, in addition, operation has similarly to Example 1 obtained micro staple fiber nonwoven fabric.The micro staple fiber nonwoven fabric that obtains like this be between the superfine fibre complexing the sheet of densification.The evaluation result of its rerum natura is as shown in table 1.
Comparative example 1
Using by 45 parts of polystyrene as sea component, 55 parts of filament fiber numbers that constitute as the polyethylene terephthalate of island component is 3 dtexs, 36 islands, the fibre length islands-in-sea bicomponent fibre as 51mm, makes fiber web by the carding machine or the winder that intersects.Then, by the acupuncture of 1 barb type, with 1500/cm
2Filling density handle, having obtained the fiber apparent density is 0.210g/cm
3The composite short fiber nonwoven fabric.Then, utilize aperture 0.1mm, the water thorn that forms of the shower nozzle of 0.6mm at interval, with 1m/ minute processing speed to the two sides all under 10MPa, 20MPa, handle, complexing.Then, be immersed in and heat to 12% the aqueous solution of about 95 ℃ PVA1, make and convert, reach 25% with respect to nonwoven fabric weight, adhesion amount with solid constituent, dipping in PVA simultaneously, carry out 2 minutes shrink process, carry out drying, remove moisture at 100 ℃.The sheet that obtains is handled till removing polystyrene fully with about 30 ℃ trichloro-ethylene, then removes PVA1, obtains the superfine fibre that the filament fiber number is about 0.046 dtex.
The micro staple fiber nonwoven fabric that obtains like this is the structure that superfine fibre Shu Weizhu complexing becomes, compares with embodiment 1～4, and be the goods of the form retentivity difference of easy deformation.The evaluation result of its rerum natura is as shown in table 1.
Comparative example 2
With the degree of polymerization be 500, saponification degree is 98% the PVA2 PVA1 that replaces embodiment 1, carry out 5 minutes dry heat at 150 ℃ handles, in addition, handle similarly to Example 1.Because carrying out after high-velocity fluid stream handles, PVA2 is residual approximately 90% with respect to adhesion amount, removes so further extract with 90 ℃ of hot water.The micro staple fiber nonwoven fabric that obtains is the structure that superfine fibre Shu Weizhu complexing becomes, compares with embodiment 1～4, and be the goods of the form retentivity difference of easy deformation.The evaluation result of its rerum natura is as shown in table 1.
Comparative example 3
In embodiment 1, condition as the water thorn, use aperture 0.25mm, the shower nozzle of 2.5mm at interval, and when shower nozzle is shaken with amplitude 7mm, 5Hz on perpendicular to the direction of sheet, positive and negative is all respectively handled under the pressure of 9MPa 2 times with 1m/ minute speed.The micro staple fiber nonwoven fabric that obtains is to mix the complexing have superfine fibre bundle and superfine fibre, compares with comparative example 1, comparative example 2, and the goods that the form retentivity is good, but than the goods that differ from embodiment 1～4.The evaluation result of its rerum natura is as shown in table 1.
Embodiment 5
Use the micro staple fiber nonwoven fabric that obtains among the embodiment 1, be immersed in the polyaminoester emulsion (solar corona chemistry (strain) system " エ バ Off ア ノ one Le APC-55 "), make and give 5% solid constituent, 150 ℃ of heat treatments 10 minutes.Then, utilize liquid-flow dyeing machine, with Sumikaron BlueS-BBL200 (firmly change ケ system テ Star Network ス (strain) system), with the concentration of 20%owf, after 45 minutes, carry out napping with sand paper and handle, obtain the Leathery sheet of flock suede formula 120 ℃ of dyeing.The rerum natura of the goods that obtain is as shown in table 2, though the amount of polyurethane seldom, has obtained very strong rerum natura.
Embodiment 6
Use the micro staple fiber nonwoven fabric that obtains among the embodiment 1, then, with liquid-flow dyeing machine, similarly to Example 5 dye after, by suppressing, thickness is compressed to 0.52 times at 150 ℃, the calendering of heating with 5m/ minute processing speed.Then, carry out napping with sand paper and handle, obtained Leathery sheet.The feel of the goods that obtain has solid sense very much, and is as shown in table 2 in addition, and rerum natura is also very excellent.
Embodiment 7
Except the use amount that changes fiber, similarly to Example 1, make and pay 139g/m by order
2, fiber apparent density 0.317g/cm
3Superfine fibre between the micro staple fiber nonwoven fabric that forms of complexing, then, handle similarly to Example 6, obtained Leathery sheet.The goods that obtain are very thin, soft and have the feel of solid sense, and as shown in table 2 in addition, rerum natura is also very excellent.
Embodiment 8
Except changing use amount, similarly to Example 1, make and pay 495g/m by order
2, fiber apparent density 0.326g/cm
3Superfine fibre between the micro staple fiber nonwoven fabric that forms of complexing, then, handle similarly to Example 6 and obtaining Leathery sheet.The goods that obtain are very thick, have the feel of solid sense especially, and as shown in table 2 in addition, rerum natura is also very excellent.
Embodiment 9
Except the use amount that changes fiber, further do not tear the processing, similarly to Example 1, obtained paying 181g/m by order
2, fiber apparent density 0.322g/cm
3Superfine fibre between the micro staple fiber nonwoven fabric that forms of complexing.Then handle similarly to Example 6, obtained Leathery sheet.The goods that obtain, as shown in table 2, particularly have the good rerum natura of high abrasion resistance and tearing brute force etc., still, surperficial grade is compared low slightly with embodiment 7.
Embodiment 10
Use the micro staple fiber nonwoven fabric that obtains among the embodiment 1, carry out napping with sand paper and handle, dye with liquid-flow dyeing machine.Then, with solid weight meter, supply with the particulate (コ ロ イ ダ Le シ リ カ " ス ノ one テ Star Network ス 20L " Nissan Chemical Ind Ltd's system, average grain diameter 0.04～0.05 μ m:BET method) of 0.1 weight %.The Leathery sheet that obtains is the good goods of flexibility and abrasion performance.The result of gained is as shown in table 2.
Comparative example 4
Use the micro staple fiber nonwoven fabric that obtains in the comparative example 1, be immersed in the polyaminoester emulsion (solar corona chemistry (strain) system " エ バ Off ア ノ one Le APC-55 "), make the solid constituent of supplying with reach 5%, then 150 ℃ of heat treatments 10 minutes.Then, utilize liquid-flow dyeing machine, dye similarly to Example 6, the result is damaged in dyeing, can not obtain Leathery sheet.
Comparative example 5
Use the micro staple fiber nonwoven fabric that obtains in the comparative example 2, utilize liquid-flow dyeing machine, dye similarly to Example 6, the result is damaged in dyeing, can not obtain Leathery sheet.
Comparative example 6
As polymer diol, 50: 50 mixture of the polyhexamethylene carbonate glycol of use molecular weight 2000 and the polytrimethylene ether glycol of molecular weight 2000, as vulcabond, use 4,4-diphenyl methane diamines isocyanates is as cahin extension agent, make spent glycol, obtaining polyurethane, be diluted to solid constituent with DMF by well-established law is 12 weight %, and then the ultra-violet absorber for the benzophenone of additive that adds that 1.5 weight % do is modulated polyurethane impregnated liquid.Then, pay except order and be 150g/m
2Outside, handle equally with comparative example 1, resulting micro staple fiber nonwoven fabric is immersed in this polyurethane impregnated liquid, regulate the quantity delivered of maceration extract with squeezing roller, make the solid constituent of polyurethane reach 60%, in the DMF aqueous solution, polyurethane is solidified then with respect to fibre weight.Then, remove DMF, carry out drying at 100 ℃ then with 85 ℃ hot water.After then dyeing similarly to Example 6, carry out napping with sand paper and handle, obtain Leathery sheet.The rubber sense of the article that obtain is strong, not with the similar solid sense of natural leather.The rerum natura of gained Leathery sheet is as shown in table 2.
Comparative example 7
The micro staple fiber nonwoven fabric that obtains in the comparative example 1 is not dyeed, handle, obtain the tablet of white and carry out napping with sand paper.The goods that obtain have basic and the same rerum natura of micro staple fiber nonwoven fabric, but can not obtain outward appearance like the leather, and abrasion performance is also poor.Its result is as shown in table 2.
Comparative example 8
Use the superfine fibre nonwoven cloth that obtains in the comparative example 3, handle similarly to Example 7, obtain tablet.The goods that obtain are not damaged because of dyeing, stretch or to tear the rerum natura that waits good, but the surface produce balling-up, and surperficial product potential difference can not obtain outward appearance like the leather, and abrasion performance is also poor in addition.The result of this rerum natura is as shown in table 2.
The industry utilizability
According to the present invention, even in fact not the pbz polymer elastomer, mainly consisted of by fibrous material The non-woven fabric structure body, also can obtain sufficient rerum natura and grade as Leathery sheet. Because Leathery sheet of the present invention has the excellent feature such as cyclicity, easy-care properties, yellowing resistance, institute Certainly can be used for dress material, furniture, automotive seat, groceries, polishing cloth, cloth for wiping or dusting, film etc. Purposes wherein is preferred for having used cyclicity or characteristic feel, particularly car seat or clothing In the material. In addition, napping formula Leathery sheet of the present invention, because its superfine fibre is difficult to bunchy, The fiber compactness on surface, open fibre, excellent in uniform, so as the magnetic to recording disc etc. The polishing cloth that recording medium thing matrix material carries out polishing is useful, is one of preferred purposes.
Claims (20)
1. a micro staple fiber nonwoven fabric is characterized in that, contains filament fiber number 0.0001～0.5 dtex, the fibre length staple fibre smaller or equal to 10cm, complexing between the staple fibre, and it is 100～550g/m that order is paid
2, the fiber apparent density is 0.280～0.700g/cm
3, tensile strength is more than or equal to 70N/cm, tearing brute force is 3～50N, and does not use macromolecular elastomer.
2. micro staple fiber nonwoven fabric as claimed in claim 1 is characterized in that this staple fibre is more than or equal to 1cm.
3. micro staple fiber nonwoven fabric as claimed in claim 1 is characterized in that, 10% modulus of warp-wise is more than or equal to 8N/cm.
4. micro staple fiber nonwoven fabric as claimed in claim 1 is characterized in that, this staple fibre is made of polyester fiber and/or polyamide-based fiber.
5. the manufacture method of a micro staple fiber nonwoven fabric, it is characterized in that, use can produce the fabric of island-in-sea type composite short fiber of 1～10 dtex of the superfine fibre of 0.0001～0.5 dtex, make the composite short fiber nonwoven fabric with needle point method, remove sea component and make it generate superfine fibre, then using at least, the pressure of 10MPa carries out the processing of high-velocity fluid stream.
6. the manufacture method of micro staple fiber nonwoven fabric as claimed in claim 5 is characterized in that, in this needle point method, by filling density more than or equal to 500/cm
2Acupuncture, make the fiber apparent density of composite short fiber nonwoven fabric become 0.120～0.300g/cm
3
7. the manufacture method of micro staple fiber nonwoven fabric as claimed in claim 5 is characterized in that, uses the nozzle of the diameter with 0.06～0.15mm to carry out the high-velocity fluid processing.
8. the manufacture method of micro staple fiber nonwoven fabric as claimed in claim 5 is characterized in that, carries out being processed into more than 2 or 2 along tearing perpendicular to thickness direction before this high-velocity fluid stream handles.
9. the manufacture method of micro staple fiber nonwoven fabric as claimed in claim 5 is characterized in that, after implementing this high-velocity fluid stream processing, the thickness compression is handled to 0.1～0.8 times.
10. a Leathery sheet is characterized in that, contains filament fiber number 0.0001～0.5 dtex, fibre length is paid smaller or equal to 10cm, order is 100～550g/m
2, the fiber apparent density is 0.230～0.700g/cm
3Be colored the micro staple fiber nonwoven fabric that forms, complexing between this micro staple fiber, and do not use macromolecular elastomer, tearing brute force is 3～50N, and satisfies following formula,
Tensile strength (N/cm) 〉=0.45 * order is paid (g/m
2)-40.
11. Leathery sheet as claimed in claim 10 is characterized in that, this fibrous material is made of the fiber of non-elastic polymer.
12. Leathery sheet as claimed in claim 10 is characterized in that, one side is formed by napping at least.
13. want 10 described Leathery sheets, it is characterized in that in the abrasion test of Martindale's method, the wear loss when carrying out 20000 abrasion is smaller or equal to 20mg, and the number of balling-up is smaller or equal to 5 as right.
14. Leathery sheet as claimed in claim 10, this micro staple fiber are polyester and/or polyamide.
15. Leathery sheet as claimed in claim 10 is characterized in that, contains the micro staple fiber that fibre length is 1～10cm.
16. Leathery sheet as claimed in claim 10 is characterized in that, contains particulate in this fibrous material.
17. Leathery sheet as claimed in claim 16 is characterized in that, this atomic particle diameter is 0.001～30 μ m.
18. the manufacture method of a Leathery sheet, it is characterized in that, after the fabric of island-in-sea type composite short fiber of 1～10 dtex that makes the superfine fibre that can produce 0.0001～0.5 dtex carries out complexing by acupuncture, removing sea component makes its generation superfine fibre make micro staple fiber nonwoven fabric, then carrying out high-velocity fluid under the pressure of 10MPa at least handles, make its complexing once more, dye subsequently, obtain the not elastomeric leather-like sheet material of pbz polymer thus.
19. the manufacture method of Leathery sheet as claimed in claim 18 is characterized in that, uses the nozzle of the diameter with 0.06～0.15mm to carry out the high-velocity fluid processing.
20. the manufacture method of Leathery sheet as claimed in claim 18 is characterized in that, dyes with liquid-flow dyeing machine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003198962 | 2003-07-18 | ||
| JP198962/2003 | 2003-07-18 | ||
| JP417656/2003 | 2003-12-16 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102093777A Division CN101701425B (en) | 2003-07-18 | 2004-07-07 | Leather-like article in sheet form, and method for their production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1823188A CN1823188A (en) | 2006-08-23 |
| CN100572638C true CN100572638C (en) | 2009-12-23 |
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| CNB2004800206579A Expired - Fee Related CN100572638C (en) | 2003-07-18 | 2004-07-07 | Micro staple fiber nonwoven fabric and Leathery sheet and manufacture method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3208368B1 (en) * | 2013-02-26 | 2021-04-28 | Mitsubishi Chemical Corporation | Fibrous bundle |
| US9739009B2 (en) * | 2013-09-13 | 2017-08-22 | Toray Industries, Inc. | Sheet-shaped object and process for producing same |
| JP7148502B2 (en) * | 2017-05-01 | 2022-10-05 | 株式会社クラレ | Artificial leather base material and grain-finished artificial leather |
| CN109112723A (en) * | 2018-10-16 | 2019-01-01 | 中原工学院 | A kind of elastomer spunlace non-woven face-cloth base fabric and preparation method |
| CN112921498A (en) * | 2019-12-06 | 2021-06-08 | 财团法人纺织产业综合研究所 | Method for making non-woven fabric |
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