CN104838063B

CN104838063B - Tablet and the manufacture method of this tablet

Info

Publication number: CN104838063B
Application number: CN201380062155.1A
Authority: CN
Inventors: 小出现; 西村诚; 土本贵大
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2012-11-30
Filing date: 2013-11-27
Publication date: 2016-09-28
Anticipated expiration: 2033-11-27
Also published as: WO2014084253A1; JP6225917B2; US20150315741A1; CN104838063A; KR20150090122A; TW201439398A; KR102090355B1; JPWO2014084253A1; TWI580840B; EP2927368A4; EP2927368A1; EP2927368B1

Abstract

The present invention provides the aesthetic look and soft feel that the manufacture method of a kind of tablet, described tablet be capable of having pile, and has better mar proof.The manufacture method of the tablet of the present invention is characterised by, carries out following operation 1～5 successively.Operation (1): the polyvinyl alcohol that to make saponification degree be more than 98%, the degree of polymerization is 800～3500 is dissolved in water, obtains methyl acetate, acetic acid, methanol are respectively the polyvinyl alcohol water solution of below 50ppm；Operation (2): be this polyvinyl alcohol of 0.1～50 mass % for manifesting the fibrous substrate that fiber type is main composition composition with superfine fibre and giving relative to the fiber quality of this fibrous substrate；Operation (3): the fibrous substrate obtained from above-mentioned operation (2) shows the superfine fibre of average single fiber a diameter of 0.3～7 μm；Operation (4): give water dispersant type polyaminoester to the fibrous substrate obtained in above-mentioned operation (3)；Operation (5): remove polyvinyl alcohol in the fibrous substrate obtained from above-mentioned operation (4).

Description

Tablet and the manufacture method of this tablet

Technical field

The present invention relates to the manufacture method of tablet and this tablet, described tablet, by using the poly-ammonia of water-dispersion type Ester is as adhesive resin, and the usage amount of the organic solvent in minimizing manufacturing process, for eco-friendly tablet, it is possible to Realize good flexibility and first-class exterior quality simultaneously, and there is good mar proof.

Background technology

The main tablet formed by fibrous substrate and polyurethane has the feature of the unexistent excellence of natural leather, quilt It is widely used in various uses.It is emphasized that for using the leather-like sheet material of polyester fiber matter base material, Due to excellent in light-resistance, so the use in dress material, seat surface rapidoprint and automotive interior trim material applications etc. is every Year is all increasing.

When manufacturing above-mentioned tablet, generally use following operation: make the organic solvent solution of polyurethane be impregnated in fiber After matter base material, the fibrous substrate obtained is immersed in the non-solvent i.e. water of polyurethane or the mixed solution of organic solvent/water, Polyurethane wet type is made to solidify.As the solvent i.e. organic solvent of above-mentioned polyurethane, employ DMF (the most also It is expressed as " DMF ".) etc. miscible organic solvents, such as, it is proposed that following method: make non-woven fabrics impregnation polyvinyl alcohol (following It also is indicated as " PVA ".) aqueous solution, obtain fiber tablet, this fiber tablet is immersed in polyurethane and contains in immersion, and then, After making the solidification of polyurethane wet type in the 45%DMF aqueous solution of 20 DEG C, remove DMF and polyvinyl alcohol with the hot water of 85 DEG C, thus Manufacture tablet (seeing patent documentation 1).But, generally high to the harmfulness of human body and environment due to organic solvent, therefore, When manufacturing tablet, the method strongly needing not use organic solvent.

As the solution that it is concrete, such as, have studied and use they water dispersant type polyaminoester in water The method replacing the polyurethane of existing organic solvent type.But, to fibrous substrate impregnation, impart water dispersant type polyaminoester And there is the problem that feel is hardening in the tablet formed.The main cause of this problem is, polyurethane and the fiber of fibrous substrate Strongly bond.Studied to solve the problems referred to above, it is proposed that following method: with applicable existing organic solvent type The manufacturing process of polyurethane similarly, in order to part suppresses fiber and the bonding of polyurethane, manufactures between fiber and polyurethane Space, and give PVA to fibrous substrate in advance, then giving polyurethane, the method then removing PVA (sees patent documentation 2)。

Here, owing to PVA is water solublity, during so getting wet after giving PVA to fibrous substrate, PVA can dissolve de- Fall, therefore, in order to suppress the PVA described above dissolving in the operation got wet and come off, in patent documentation 2, utilize at (i) The impregnation operation of the super-refinement operation of the fiber of alkaline aqueous solution and (ii) water dispersant type polyaminoester have employed following methods. That is, by alkaline aqueous solution, add Borax inhibit at the former be, coming off in the super-refinement operation of fiber, the opposing party Face, for the latter be, the impregnation operation of water dispersant type polyaminoester, by using saponification degree to be 98% and the degree of polymerization is 500 PVA, it is suppressed that PVA coming off in water.But, about adding the effect of Borax in the super-refinement operation of fiber, due to During the super-refinement of fiber, the dip time in alkaline aqueous solution expends longer, even if so adding boron in alkaline aqueous solution Sand, can not completely inhibit PVA dissolving in water.Additionally, about the impregnation operation of water dispersant type polyaminoester, due to PVA's The degree of polymerization is low, so its dissolving in water can not be completely inhibited, it is impossible to suppression coming off in water dispersant type polyaminoester liquid, because of This PVA is dissolved in water dispersant type polyaminoester liquid, thus causes the tacky state that can not stably control polyurethane and fiber, deposits In the problem that the feel of tablet is hardening.

Additionally, for the problem in above-mentioned (i) (ii) each operation, it is proposed that following method: give soap to nonwoven fabric sheet Change degree is the PVA of more than 90%, and carries out the heating of 150～195 DEG C, thus reduces PVA and (sees the deliquescent method of water Patent documentation 3).Although by carrying out high-temperature heating, the intermolecular hydrogen bonding making PVA is strong, thus reduces the dissolubility to water, But if temperature is too high or heat time heating time is long, then PVA can be insoluble, and the redissolution of Xiang Shuizhong becomes difficulty, accordingly, there exist suitably The problem of the stabilisation difficulty of condition.

Patent documentation 1: Japanese Unexamined Patent Publication 2002-30579 publication

Patent documentation 2: Japanese Unexamined Patent Publication 2003-096676 publication

Patent documentation 3: No. 4644971 publications of Japanese Patent No.

Summary of the invention

Manufacture method that the present invention provides a kind of tablet and the tablet utilizing above-mentioned manufacture method to obtain, described system The method of making can reduce the use of the organic solvent in manufacturing process, environmentally friendly, and described tablet can realize tool simultaneously There are the aesthetic look of pile and soft feel, and there is good mar proof.

That is, the manufacture method of the tablet of the present invention is characterised by, carries out following operation 1～5 successively,

Operation 1: the polyvinyl alcohol that to make saponification degree be more than 98%, the degree of polymerization is 800～3500 is dissolved in water, and obtains second Acid methyl ester, acetic acid, the concentration of methanol are respectively the polyvinyl alcohol water solution of below 50ppm；

Operation 2: give this polyvinyl alcohol to manifesting, with superfine fibre, the fibrous substrate that fiber type is main composition composition Aqueous solution, gives this polyvinyl alcohol of 0.1～50 mass % thus relative to the fiber quality contained by fibrous substrate；

Operation 3: show average single fiber from manifesting, with superfine fibre, the fibrous substrate that fiber type is main composition composition Tie up the superfine fibre of a diameter of 0.3～7 μm；

Operation 4: to the fibrous substrate imparting water being main composition composition with superfine fibre imparting this polyvinyl alcohol Decentralized polyurethane；

Operation 5: from the fibrous substrate being main composition composition with superfine fibre imparting this water dispersant type polyaminoester Middle removing polyvinyl alcohol.

The optimal way of the manufacture method of the tablet of the present invention is: via the concentration obtaining methyl acetate, acetic acid, methanol It is respectively the operation of the polyvinyl alcohol water solution of 0.1～50ppm.

The optimal way of the manufacture method of the tablet according to the present invention, the operation manifesting superfine fibre is water-soluble by alkalescence Liquid carries out the operation processed.

The optimal way of the manufacture method of the tablet of the present invention is: include giving described polyvinyl alcohol, in 80～170 DEG C Carry out the operation heated.

The optimal way of the manufacture method of the tablet according to the present invention, described to manifest fiber type with superfine fibre be main The fibrous substrate of constituent is integrated with fabric and/or fabric complexation.

Additionally, the density of obtained tablet is preferably 0.2～0.7g/cm³。

According to the present invention, although being eco-friendly manufacturing process, it is also possible to the outward appearance of accomplished grace and softness Feel (this can not realize in the past simultaneously) and there is the tablet of better mar proof.

Detailed description of the invention

The manufacture method of the tablet of the present invention is characterised by, carries out following operation 1～5 successively,

Operation 2: give above-mentioned polyethylene to manifesting, with superfine fibre, the fibrous substrate that fiber type is main composition composition Alcohol-water solution, gives the above-mentioned polyvinyl alcohol of 0.1～50 mass % thus relative to the fiber quality contained by fibrous substrate；

For the manufacture method of the tablet of the present invention, it is important for carrying out operation 1～5 successively.To with ultra-fine fibre Dimension manifest fibrous substrate that fiber type is main composition composition give saponification degree be more than 98%, the degree of polymerization be 800～3500 Polyvinyl alcohol (also being indicated as PVA) aqueous solution after, carry out manifesting fiber type from superfine fibre and show the operation of superfine fibre (de-sea operation), then to the fibrous substrate imparting water-dispersion type being main composition composition with superfine fibre imparting PVA Polyurethane liquid, and then from this fibrous substrate, remove PVA, thus produce between fiber and polyurethane and derive from PVA and sea The big space of composition, and due to polyurethane portion ground directly hold superfine fibre, therefore, it is possible to present grace outward appearance and The physical characteristics such as soft feel and good mar proof.

During additionally, PVA aqueous solution is given to fibrous substrate and is thermally dried, the PVA in water occurs so-called Transport phenomena (that is, is concentrated the top layer being attached to fibrous substrate) by the drive of movement of water, becomes and is attached to fiber in a large number The top layer of matter base material, it is attached to the state of internal layer on a small quantity.By making PVA migrate so that the water dispersant type polyaminoester given afterwards Mainly it is attached to the internal layer of fibrous substrate.Then, when PVA is removed, on the top layer of the fibrous substrate being attached with a large amount of PVA Near, between fiber and polyurethane, producing big space, the appearance through the tablet of napping operation becomes graceful Outward appearance (pile not bunchy and equably fibrillation).

On the other hand, process if carrying out de-sea after removing PVA, then can generate between polyurethane and superfine fibre by removing Go to space that PVA causes and by both the spaces caused by the sea component in de-sea, therefore, although polyurethane directly holds super The area of fine fibre tails off further, and the feel of tablet becomes soft, but the physical characteristics such as mar proof exist deterioration tendency.

[the 1st operation]

First, the 1st operation is described, i.e. the PVA that to make saponification degree be more than 98%, the degree of polymerization is 800～3500 is dissolved in water In, obtain methyl acetate, acetic acid, the concentration of methanol are respectively the operation of PVA aqueous solution of below 50ppm.

Methyl acetate, acetic acid, methanol are during the i.e. polyvinyl acetate of the precursor synthesized from PVA improves saponification degree The material generated, additionally, be the material by also not generated by the decomposition of the remaining polyvinyl acetate of abundant saponification.About Methyl acetate, acetic acid, methanol, by make methyl acetate in PVA aqueous solution, acetic acid, the concentration of methanol be respectively 50ppm with Under so that it is readily formed PVA intermolecular hydrogen bonding when heat drying, it is possible to suppression PVA is to water (including warm water), sour, alkaline Dissolubility in aqueous solution.Additionally, due to PVA intermolecular hydrogen bonding is easily formed, therefore heat drying temperature can be set as Relatively low temperature (80～140 DEG C) such that it is able to the thermal decomposition of suppression PVA.Methyl acetate in PVA aqueous solution, acetic acid, methanol Concentration more preferably be respectively 0.1～50ppm, by existing with making methyl acetate, acetic acid, methanol trace respectively, they and PVA Molecule weaker hydrogen bonding so that PVA intermolecular distance diminishes, PVA intermolecular hydrogen bonding is easily formed.If methyl acetate, acetic acid, The concentration of methanol is the most too high, can suppress the formation of PVA intermolecular hydrogen bonding the most on the contrary, therefore, preferred concentration be 0.3～ 40ppm, more preferably 5～40ppm.

It should be noted that the concentration of methyl acetate in PVA aqueous solution, acetic acid, methanol is analysis is carried out as follows.To 24mL Add loading PVA aqueous solution 1g in heat pipe, heat 1 hour at 90 DEG C.With air hermetic entry needle (gas-tight syringe) from Add heat pipe and gather 0.1mL generation gas, import in GC/MS (directly linking the mass spectrograph of gas chromatograph) and be analyzed.

In order to reduce methyl acetate in PVA aqueous solution, acetic acid, the concentration of methanol, before being usable in making aqueous solution The methyl acetate during heating of PVA self, acetic acid, PVA that methanol growing amount is few, or in the preparation of PVA aqueous solution, extend Heat time heating time during intensification (it is for being dissolved in water PVA).For the former, saponification degree is the highest, methyl acetate, second Acid, methanol growing amount the fewest, the high saponification degree PVA of more than 98% is therefore preferably used.Additionally, for the latter, if heating up Temperature too low, then can not fully remove methyl acetate, acetic acid, methanol, the most preferably 80～100 DEG C, if mistake heat time heating time Short, then can not fully remove methyl acetate, acetic acid, methanol, the most preferably more than 1 hour.It should be noted that can also be by Methyl acetate, acetic acid, methanol remove completely from PVA aqueous solution.

In embodiments of the present invention, the saponification degree giving the PVA to fibrous substrate is more than 98%, and the degree of polymerization It is 800～3500.By making the saponification degree of PVA be more than 98%, when giving water dispersant type polyaminoester, it is possible to prevent PVA molten Solution is in water dispersant type polyaminoester liquid.If PVA is dissolved in water dispersant type polyaminoester liquid, the most not only can not obtain and be enough to protect structure Become the effect on the surface of the superfine fibre of pile, and further the water dispersant type polyaminoester liquid being dissolved with PVA is being given extremely During fibrous substrate, PVA is absorbed into inside polyurethane, is removed by PVA afterwards and becomes difficulty, therefore can not stably control to gather Urethane and the tacky state of fiber, feel is hardening.

Additionally, about PVA, according to the difference of the degree of polymerization, the dissolubility of water is changed by it, and the degree of polymerization of PVA is the least, is composing When giving water dispersant type polyaminoester, PVA gets over and dissolves in water dispersant type polyaminoester liquid.The degree of polymerization of PVA is the highest, PVA aqueous solution Viscosity is the highest, and when to fibrous substrate impregnation PVA aqueous solution, PVA is impermeable to fibrous substrate, therefore, and PVA's The degree of polymerization is preferably 1000～3000, more preferably 1200～2500.

In the present invention, for PVA, viscosity during 20 DEG C of 4 mass % aqueous solutions is preferably 10～70mPa s.Logical Crossing and making the viscosity of PVA is above-mentioned scope, when being dried, it is possible to obtains the migration structure of appropriateness inside fibrous substrate, obtains Obtain the harmony between flexibility and the physical characteristic such as appearance, mar proof of tablet.By making above-mentioned viscosity be More than 10mPa s, more preferably more than 15mPa s, it is possible to suppression forms extreme migration structure.On the other hand, glue by making Degree is below 70mPa s, more preferably below 50mPa s, further preferred below 40mPa s, it is possible to make PVA be prone to impregnation In fibrous substrate.

In the present invention, the vitrification point (Tg) of PVA is preferably 70～100 DEG C.It is 70 by the vitrification point making PVA More than DEG C, more preferably more than 75 DEG C, it is possible to prevent the softening in drying process, it is thus achieved that the dimensional stability of fibrous substrate, energy Enough suppress the deterioration of tablet appearance.Additionally, be less than 100 DEG C, more preferably less than 95 DEG C by making vitrification point, energy Enough preventing being become really up to the mark by fibrous substrate causes treatability to deteriorate.

In the present invention, the fusing point of PVA is preferably 200～250 DEG C.By to make the fusing point of PVA be more than 200 DEG C, more preferably More than 210 DEG C, it is possible to prevent the softening in drying process, it is thus achieved that the dimensional stability of fibrous substrate, it is possible to suppression tablet The deterioration of appearance.Additionally, be less than 250 DEG C, more preferably less than 240 DEG C by making the fusing point of PVA, it is possible to prevent by fiber Matter base material becomes really up to the mark and causes treatability to deteriorate.

In the present invention, the tensile strength of the film of PVA is preferably 400～800kg/cm².By making the tensile strength of PVA film For 400kg/cm²Above, more preferably 450kg/cm²Above, it is possible to change in size when suppression processes, outside suppression tablet surface The deterioration seen.It is 800kg/cm by the tensile strength making PVA film²Below, more preferably 750kg/cm²Hereinafter, impart PVA's Sheet material will not become really up to the mark, it is possible to the generation of the wrinkling grade of warpage when suppression processes.It should be noted that the most so-called tension Intensity, be temperature 20 DEG C, humidity 65% atmosphere under the film of 100 μ m-thick of PVA is measured and the value that obtains.

[the 2nd operation]

It follows that explanation the 2nd operation, i.e. manifest, to superfine fibre, the cellulosic base that fiber type is main composition composition Material gives PVA aqueous solution, gives this PVA of 0.1～50 mass % thus relative to the fiber quality contained by fibrous substrate Operation.

Superfine fibre is manifested fiber type as main constituent by the fibrous substrate of the present invention.Ultra-fine by using Fiber manifests fiber type, can be via follow-up fiber super-refinement operation by fiber super-refinement, it is possible to obtain outside graceful surface See.

In the optimal way of the present invention, from superfine fibre manifest that fiber type obtains via fiber super-refinement operation ultra-fine Average single fiber a diameter of 0.3～7 μm of fiber.By making below below a diameter of 7 μm of average single fiber, more preferably 6 μm, entering Below one step preferably 5 μm, it is possible to obtain flexibility and the tablet of pile excellent quality.On the other hand, by making average single fiber Tie up more than more than more than a diameter of 0.3 μm, more preferably 0.7 μm, further preferred 1 μm, color rendering properties after dyeing, utilize sand paper etc. The excellent dispersion of the pile such as grinding bundle fiber when processing, fibrillation easiness is the most excellent.

Manifest fiber type as above-mentioned superfine fibre, following fiber can be used: (a) is by different for solvent solubility two kinds The thermoplastic resin of composition, as sea component and island component, uses solvent etc. to dissolve and removes sea component, and it is super for thus making island component The islands-in-sea type fibre of fine fibre；B the thermoplastic resin of two kinds of compositions is alternately arranged in fiber with radial or many stratiforms by () On cross section, peel off and split each composition, thus cut the exfoliated composite fibre etc. of fine one-tenth superfine fibre.Wherein, islands-in-sea type fibre leads to Cross removing sea component, can between island component, i.e. give the space of appropriateness between superfine fibre, therefore, soft from tablet Can also be preferably used from the viewpoint of soft, feel.

Described islands-in-sea type fibre includes the most following fiber: use the compound nozzle of fabric of island-in-sea type, by sea component and island component The mutually arranged islands-in-sea bicomponent fibre carrying out spinning of both compositions；Sea component and island component both compositions are mixed and carries out The blend spinning fiber etc. of spinning.From can obtain uniform fiber number superfine fibre in terms of and can obtain sufficiently long ultra-fine Fiber, to the intensity of tablet the most useful from the standpoint of, preferably use islands-in-sea bicomponent fibre.

As the island component of islands-in-sea type fibre, be not particularly limited, can use such as by polyethylene terephthalate, The polyester such as polybutylene terephthalate (PBT), PTT and polylactic acid, the polyamides such as 6-nylon and 66-nylon Amine, acrylic acid, polyethylene, the fiber that the thermoplastic resin of the melt-spinnable such as polypropylene and thermoplastic cellulose etc. is formed.Its In, from the viewpoint of intensity, dimensional stability and light resistance, polyester fiber is preferably used.Additionally, from eco-friendly viewpoint Considering, from regeneration (recyle) raw material, to derive from the fiber that the raw material of plant obtains be preferred.And then, fibrous substrate is also Can be made up of different raw-material fiber mixing.

As the sea component of islands-in-sea type fibre, it is not particularly limited, can use such as polyethylene, polypropylene, polystyrene, The copolyester that the copolymerization such as sodiosulfoisophthalic acid, Polyethylene Glycol is obtained and polylactic acid, PVA etc..Wherein, from environment friend From the viewpoint of Hao, the most do not use the most decomposable caustic digestion of organic solvent by sodiosulfoisophthalic acid, poly-second two The copolymerization such as alcohol and the copolyester that obtains or polylactic acid, the PVA of hot water soluble.

The shape of cross section of the fiber constituting fibrous substrate is not particularly limited, and can be circular section, it would however also be possible to employ The polygons such as oval, flat and triangle, the odd-shaped cross section such as fan-shaped and cross.

In the present invention, the average single fiber diameter of the fiber constituting fibrous substrate is preferably 0.3～20 μm.Average single fiber Dimension diameter is the thinnest, more can obtain flexibility and the tablet of pile excellent quality, on the other hand, due to average single fiber diameter The thickest, color rendering properties after dyeing, the dispersibility of bundle fiber when utilizing the pile such as grinding of sand paper etc. to process and fibrillation are easy Property is the most excellent, and therefore average single fiber diameter is more preferably 0.7～15 μm, particularly preferably 1～7 μm.

The form of the fibrous substrate of the present invention can use fabric, fabric and non-woven fabrics etc..Wherein, rise due to surface The appearance of tablet when floss processes is good, the most preferably uses non-woven fabrics.

Non-woven fabrics can be any one in staple fiber nonwoven fabric and nonwoven fabric of long fibers, but with staple fiber nonwoven fabric phase Ratio, nonwoven fabric of long fibers is few towards the fiber of the thickness direction of the tablet becoming pile when napping, and the fine and close sense of pile becomes Low, there is the tendency of surface appearance inferior, the most preferably use staple fiber nonwoven fabric.

The fiber length of the chopped fiber in above-mentioned staple fiber nonwoven fabric is preferably 25～90mm.By make a length of 25mm of fiber with On, the tablet of excellent in wear resistance can be obtained by complexation.Additionally, by making a length of below the 90mm of fiber, it is possible to obtain Feel and the tablet of excellent quality.Fiber length is more preferably 30～80mm.

As making fiber or the method for fibre bundle complexation of non-woven fabrics, acupuncture (needle punch) or spun lacing can be used (water jet punch)。

In the present invention, superfine fibre when the fibrous substrate formed is non-woven fabrics, optimal way is: this non-woven fabrics has The structure of bundle (superfine fibre bundle) complexation of superfine fibre.By superfine fibre with the state complexation of bundle, tablet strong Degree improves.The non-woven fabrics of aforesaid way can obtain through following method: in advance superfine fibre is manifested fiber type and complexes with one another, then Superfine fibre is made to manifest.

In the case of superfine fibre or its superfine fibre bundle constitute non-woven fabrics, for the mesh improving its internal intensity etc. , can be integrated with fabric, fabric complexation.Such as, during for fabric, plain cloth, twills and crowfoot satin can be enumerated Things etc., from the standpoint of cost, preferably use plain cloth.During additionally, be fabric, round fabric, Trico can be enumerated WARP-KNITTING and La Sheer (Raschel) WARP-KNITTING etc..The average single fiber of the fiber constituting described fabric and fabric is straight Footpath is preferably 0.3～20 μm.

Fiber type is being manifested as main composition with superfine fibre as the optimal way of the present invention, fabric and/or fabric During the fibrous substrate inner complexation integration of composition, by giving PVA, the water dispersant type polyaminoester given afterwards directly holds The area of fabric and/or fabric tails off, and can obtain the effect that tablet feel becomes soft, especially in fabric and/or volume Fabric by be not superfine fibre manifest the fiber of fiber type constitute time, available significant soft bating effect.

Imparting amount to the PVA of fibrous substrate, is 0.1～50 matter for the fiber quality of fibrous substrate Amount %, preferably 1～45 mass %.Being more than 0.1 mass % by the imparting amount making PVA, available flexibility and feel are good The physics such as good tablet, is below 50 mass % by the imparting amount making PVA, available good, the mar proof of processability are special The tablet that property is good.

In the present invention, as the method giving PVA to fibrous substrate, it is not particularly limited, can use in this area Normally used various method, but from the viewpoint of can giving equably, preferably make PVA be dissolved in water, containing being immersed in fibre The method tieed up in matter base material and be thermally dried.About baking temperature, owing to needing longer drying time when temperature is too low, When temperature is too high, PVA can be insoluble, can not dissolve removing afterwards, is therefore preferable over 80～140 DEG C and is dried, and baking temperature enters One step is preferably 110～130 DEG C.It is usually drying time 1～20 minute, from the viewpoint of processability, preferably 1～10 point Clock, more preferably 1～5 minute.Additionally, in order to PVA is the most insoluble, heat treated can be carried out after the drying.Heating The preferable temperature processed is 80～170 DEG C.By heat treated, the heat deterioration of the insoluble and PVA of PVA is carried out, therefore simultaneously Preferred temperature is 80～140 DEG C.

[the 3rd operation]

It follows that explanation the 3rd operation, i.e. manifest, from superfine fibre, the cellulosic base that fiber type is main composition composition Material shows the operation of the superfine fibre of average single fiber a diameter of 0.3～7 μm.

Fiber ultra fine (the de-Hai Chu that fiber type is the fibrous substrate of main composition composition is manifested with superfine fibre Reason), can carry out by fibrous substrate impregnates in a solvent, extrudes liquid.It is fabric of island-in-sea type that superfine fibre manifests fiber type In the case of fiber, as solvent, when marine origin is divided into polyethylene, polypropylene or polystyrene, toluene, trichloro ethylene can be used Deng organic solvent, when marine origin is divided into copolyester or polylactic acid, the alkaline aqueous solution of sodium hydroxide etc. can be used.Additionally, it is extra large When composition is PVA, hot water can be used.Consider from the environment amenable viewpoint of operation, preferably water-soluble by the alkalescence of sodium hydroxide etc. Liquid, hot water carry out de-sea and process.

[the 4th operation]

It follows that explanation the 4th operation, i.e. to the cellulosic base being main composition composition with superfine fibre imparting PVA Material gives the operation of water dispersant type polyaminoester.

Above-mentioned water dispersant type polyaminoester is divided into: (I) uses surfactant forcibly decentralized stabilization in water Forced emulsification type polyurethane；(II) there is in polyurethane molecular structure hydrophilic structure, even if there be no surfactant Also can in water the self-emulsifying type polyurethane of decentralized stabilization, the present invention uses any one.

As the method giving water dispersant type polyaminoester to fibrous substrate, it is not particularly limited, by poly-for water-dispersion type ammonia The method that the impregnation of ester liquid is thermally dried after coating fibrous substrate, solidification, owing to giving equably, so being Preferably.

The concentration (content of the polyurethane for water dispersant type polyaminoester liquid) of water dispersant type polyaminoester liquid, from water From the viewpoint of the storage stability of decentralized polyurethane liquid, preferably 10～50 mass %, more preferably 15～40 mass %.

Additionally, in order to improve storage stability and masking, the water dispersant type polyaminoester liquid used in the present invention can contain Having for polyurethane liquid is the water-miscible organic solvent of below 40 mass %, but examines in terms of saving masking environment etc. from damage Considering, the content preferably making organic solvent is below 1 mass %.

Additionally, as the water dispersant type polyaminoester liquid used in the present invention, preferably there is thermal coagulation.Had by use Heat coagulable water dispersant type polyaminoester liquid, can give polyurethane on the thickness direction of fibrous substrate equably.

In the present invention, so-called thermal coagulation, when referring to polyurethane liquid is heated, reaching certain temperature (thermocoagulation Temperature) time polyurethane liquid mobility reduce thus the character that solidifies.When manufacturing the tablet with polyurethane, by polyurethane Liquid gives to fibrous substrate, and by dry type solidification, damp and hot solidification, wet type solidifies or combinations thereof makes it solidify, and carries out It is dried, thus gives polyurethane to fibrous substrate.As making not show what heat coagulable water dispersant type polyaminoester liquid solidified Method, dry type solidification is real in the industrial production, but in the case of being somebody's turn to do, it may occur that polyurethane concentrates on the table of fibrous substrate The transport phenomena of layer, has the tendency of hardening with the feel of the tablet of polyurethane.In the case of Gai, can be by adjusting with thickening agent The viscosity of water dispersant type polyaminoester liquid prevents from migrating.During additionally, be to show heat coagulable water dispersant type polyaminoester liquid, it is possible to With by add thickening agent, carry out dry type solidification prevent migrate.

The heat freezing temperature of water dispersant type polyaminoester liquid is preferably 40～90 DEG C.By make heat freezing temperature be 40 DEG C with On, the stability during storage of polyurethane liquid becomes good, it is possible to suppress the polyurethane when operation to be attached to machine first-class.This Outward, it it is less than 90 DEG C by making heat freezing temperature, it is possible to the suppression polyurethane transport phenomena to fibrous substrate top layer.

In a kind of mode of the present invention, in order to make heat freezing temperature as set forth above, it is possible to be properly added heat coagulant.Make For heat coagulant, the inorganic salts such as such as sodium sulfate, magnesium sulfate, calcium sulfate and calcium chloride can be enumerated；Sodium peroxydisulfate, potassium peroxydisulfate, The radical reaction initiators etc. such as Ammonium persulfate., azodiisobutyronitrile and benzoyl peroxide.

In a preferred embodiment of the present invention, can be impregnated with by polyurethane liquid, to coat fibrous substrate first-class, passes through dry type Solidification, damp and hot solidification, wet type solidification or combinations thereof make polyurethane solidify.

Above-mentioned wet thermoset temperature is preferably more than the heat freezing temperature of polyurethane, preferably 40～200 DEG C.By making Wet thermoset temperature is more than 40 DEG C, more preferably more than 80 DEG C, it is possible to shorten to the time till polyurethane solidification, further Suppression transport phenomena.On the other hand, it it is less than 200 DEG C, more preferably less than 160 DEG C by making wet thermoset temperature, it is possible to anti- Only polyurethane, the heat deterioration of PVA.

The temperature of above-mentioned wet type solidification is preferably more than the heat freezing temperature of polyurethane, is 40～100 DEG C.By making hot water In wet type solidification temperature be more than 40 DEG C, more preferably more than 80 DEG C, it is possible to shorten to polyurethane solidify till time, enter One step suppression transport phenomena.

Temperature and the baking temperature of the solidification of above-mentioned dry type are preferably 80～140 DEG C.By making dry type solidification temperature and being dried Temperature is more than 80 DEG C, more preferably more than 90 DEG C, and productivity ratio is excellent.On the other hand, by making dry type solidification temperature and being dried temperature Degree is less than 140 DEG C, more preferably less than 130 DEG C, it is possible to prevent the heat deterioration of polyurethane, PVA.

In the present invention, heat treated can be carried out after making polyurethane solidification.By carrying out heat treated, polyurethane molecular Between interface reduce, become more strong polyurethane.In preferred mode, preferably from imparting water dispersible polyurethane Heat treated is carried out after sheet material removes PVA.The temperature preferably making heat treated is 80～170 DEG C.

As the polyurethane used in the present invention, preferably by polymer diatomic alcohol, organic diisocyanate and chain elongation The polyurethane that the reaction of agent obtains.

As above-mentioned polymer diatomic alcohol, it is not particularly limited, the most polycarbonate-based, polyesters, polyethers can be used Class, silicone and the dihydroxylic alcohols of fluorine class, it is possible to use copolymer obtained by they are combined.Examine from the viewpoint of hydrolytic resistance Consider, preferably use the polycarbonate-based and dihydroxylic alcohols of polyethers.Additionally, from the viewpoint of light resistance and thermostability, can be excellent Choosing uses polycarbonate-based and polyesters.And then, examine from the balanced viewpoint between hydrolytic resistance, thermostability and light resistance Consider, the most polycarbonate-based and dihydroxylic alcohols of polyesters, can particularly preferably use polycarbonate-based dihydroxylic alcohols.

Above-mentioned polycarbonate-based dihydroxylic alcohols can be by alkylene glycol and the ester exchange reaction of carbonic ester or phosgene or chlorine Formic acid esters manufactures with the reaction etc. of alkylene glycol.

As above-mentioned alkylene glycol, be not particularly limited, can enumerate such as ethylene glycol, propylene glycol, BDO, 1,5- The straight chain alkylen glycol such as pentanediol, 1,6-HD, 1,9-nonanediol, 1,10-decanediol；Neopentyl glycol, 3-methyl isophthalic acid, 5-penta Glycol, 2,4-diethyl-1,5-pentanediol, 2-methyl isophthalic acid, the side chain alkylene glycol such as 8-ethohexadiol；The alicyclic rings such as 1,4-cyclohexanediol The aromatic diols such as race's dihydroxylic alcohols, bisphenol-A；Glycerol, trimethylolpropane and tetramethylolmethane etc..Can be independent by each The polycarbonate-based dihydroxylic alcohols that obtains of alkylene glycol, it is also possible to the poly-carbonic acid of copolymerization for being obtained by alkylene glycol of more than two kinds Esters dihydroxylic alcohols.

As above-mentioned polyesters dihydroxylic alcohols, can enumerate make various low molecular weight polyols and polyprotic acid condensation and obtain poly- Esterdiol.

As above-mentioned low molecular weight polyols, be not particularly limited, such as can use selected from ethylene glycol, 1,2-PD, 1,3-propylene glycol, 1,3 butylene glycol, 1,4-butanediol, 2,2-dimethyl-1,3-propylene glycol, 1,6-HD, 3-methyl isophthalic acid, 5- Pentanediol, 1,8-ethohexadiol, diethylene glycol, 2,2'-ethylenedioxybis(ethanol)., dipropylene glycol, 3 third glycol, hexamethylene-1,4-glycol and hexamethylene-1, One or more in 4-dimethanol.Additionally, be used as addition product obtained by the various alkylene oxide of addition in bisphenol-A.

Additionally, as above-mentioned polyprotic acid, be not particularly limited, can enumerate be selected from succinic acid, maleic acid, adipic acid, 1,3-propanedicarboxylic acid, 1,5-pentanedicarboxylic acid., suberic acid, Azelaic Acid, decanedioic acid, dodecanedioic acid, phthalic acid, M-phthalic acid, terephthaldehyde One or two or more kinds in acid and hexahydro M-phthalic acid.

As above-mentioned polyethers dihydroxylic alcohols, it is not particularly limited, such as Polyethylene Glycol, polypropylene glycol, polybutadiene can be enumerated Alcohol and the copolymer glycols that they combinations are obtained.

Number-average molecular weight for the polymer diatomic alcohol of the present invention is preferably 500～4000.By making number-average molecular weight It is more than 500, more preferably more than 1500, it is possible to prevent feel hardening.Additionally, by make number-average molecular weight be less than 4000, more Preferably less than 3000, it is possible to be maintained as the intensity of polyurethane.

As above-mentioned organic diisocyanate, it is not particularly limited, such as hexamethylene diisocyanate, bicyclo-can be enumerated The aliphatic category diisocyanate such as hexyl methane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, The fragrant same clan such as methyl diphenylene diisocyanate and toluene di-isocyanate(TDI) diisocyanate, in addition it is also possible to be applied in combination Above-mentioned organic diisocyanate.Wherein, from the viewpoint of light resistance, preferably use hexamethylene diisocyanate, bicyclo- The aliphatic category diisocyanate such as hexyl methane diisocyanate and isophorone diisocyanate.

As above-mentioned chain elongation agent, it is not particularly limited, the chain of the amine such as ethylenediamine and methylene dianiline can be used to prolong The chain elongation agent of the di-alcoholss such as long agent and ethylene glycol.Additionally, be used as making polyisocyanates react with water and obtain many Amine is as chain elongation agent.

For the purpose improving resistance to water, mar proof and hydrolytic resistance etc., it is also possible to according to being expected in polyurethane also Use cross-linking agent.Cross-linking agent can be the external crosslinker added as the 3rd composition relative to polyurethane, in addition it is also possible to be pre- In polyurethane molecular structure, first import the internal crosslinking agent of the reflecting point becoming cross-linked structure.In the present invention, from gathering From the standpoint of relatively evenly forming crosslinking points in urethane molecular structure, the minimizing of flexibility can being alleviated, inside is preferably used Cross-linking agent.

As above-mentioned cross-linking agent, can use and there is NCO, oxazoline base, carbodiimide, epoxy radicals, melamine The compound of polyimide resin and silanol base etc..Wherein, when excessively carrying out due to crosslinking, polyurethane can harden, and the feel of tablet is also There is hardening tendency, therefore from the standpoint of the reactive harmony with flexibility, preferably use the crosslinking with silanol base Agent.

Additionally, the polyurethane used in the present invention preferably has hydrophilic radical in molecular structure.By tying at molecule There is hydrophilic radical, it is possible to increase as the dispersion stabilization of water dispersant type polyaminoester in structure.

As above-mentioned hydrophilic radical, the cationic such as such as quaternary ammonium salt, the anion such as sulfonate, carboxylate can be used In class, the combination of nonionic class, cationic and the nonionic classes such as Polyethylene Glycol and the combination of anionic species and nonionic class Arbitrarily hydrophilic radical.Wherein, can particularly preferably use nonionic class hydrophilic radical (its not by light cause xanthochromia and by Nertralizer causes the worry of disadvantage).

During it should be noted that be the hydrophilic radical of anionic species, nertralizer becomes required, such as, and described nertralizer During for the tertiary amine of ammonia, triethylamine, triethanolamine, triisopropanolamine, trimethylamine and dimethylethanolamine etc., due to masking, it is dried Time heat, cause amine to produce volatilization, discharge to outside system.Therefore, in order to suppress the deterioration of airborne release, working environment, must The device of the amine reclaiming volatilization must be introduced.Additionally, be additionally considered that and do not volatilized by heating when amine and remain in end article i.e. lamellar Time in thing, it is discharged in environment when the burning of goods etc..In contrast, during for the hydrophilic radical of nonionic class, due to Do not use nertralizer, therefore need not introduce amine retracting device, do not have amine to remain in the worry in tablet yet, therefore preferably make With.

Additionally, the nertralizer of above-mentioned anionic species hydrophilic radical is the alkali such as sodium hydroxide, potassium hydroxide and calcium hydroxide During the hydroxide etc. of metal or alkaline-earth metal, will reveal whether alkalescence when polyurethane portion gets wet, and be the parent of nonionic class During aqueous group, owing to not using nertralizer, therefore also without worrying to be caused deterioration by the hydrolysis of polyurethane.

According to expectation, the water dispersant type polyaminoester for the present invention can contain various additives, such as, the face such as white carbon black The fire retardant such as material, Phosphorus, halogen, silicone and mineral-type, phenol, sulfur class and antioxidant, the benzotriazole such as Phosphorus UV absorbent, hindered amines, the benzene such as class, benzophenone, salicylic acid esters, cyanoacrylate and oxanilide class The stabilizer against hydrolysis such as light stabilizer, poly-carbodiimide, plasticizer, antistatic additive, surfactant, the softnesses such as formate ester Agent, waterproofing agent, solidification regulator, viscosity modifier, dyestuff, preservative, antibacterial, deodorizer, cellulose granules, microsphere etc. are filled out Fill agent and the inorganic particulate such as silicon dioxide, titanium oxide etc..Additionally, in order to make the space between fiber and polyurethane bigger, permissible Foaming containing organics such as the mineral-type such as sodium bicarbonate, 2,2 '-azos double [2-methyl-N-(2-hydroxyethyl) propionic acid amide .] Agent.

In the present invention, polyurethane for superfine fibre for the fibrous substrate of main composition composition contains Ratio is preferably 1～80 mass %.By making the ratio of polyurethane be more than more than 1 mass %, more preferably 5 mass %, it is possible to Obtain sheet strength, and be prevented from coming off of fiber.Additionally, by the compounding ratio making polyurethane be 80 mass % with Under, below more preferably 70 mass %, it is possible to prevent feel hardening, it is thus achieved that good pile quality.

[the 5th operation]

It follows that explanation the 5th operation, i.e. be main structure from impart PVA and water dispersant type polyaminoester with superfine fibre Become the operation removing PVA in the fibrous substrate of composition.

In a preferred embodiment of the present invention, by the fibrous substrate after giving polyurethane removes PVA, softness is obtained Tablet.The method removing PVA is not particularly limited, for example, it is preferable to mode is: sheet material is immersed in the heat of 60～100 DEG C In water, shut out liquid with ironer etc. as required, thus dissolve and remove PVA.

In the manufacture method of the tablet of the present invention, can at least include following operation: to the cellulosic base imparting PVA After material gives water dispersant type polyaminoester, through-thickness is cut into two halves.In the operation giving PVA, owing to migrating so that PVA is attached to the top layer of fibrous substrate in a large number, and the adhesion amount of PVA inner layer is few.Then, by giving water dispersant type polyaminoester Rear through-thickness is cut into two halves, and the tablet of available following structure, described structure is: the side many at PVA adhesion amount is few Amount attached water dispersion type polyurethane, in the structure of a large amount of attached water in the side that PVA adhesion amount is few dispersion type polyurethane.PVA is big When the face (water dispersant type polyaminoester attachment few face) of amount attachment is as the pile face of tablet, owing to imparting PVA, poly- Produce big space between urethane and the superfine fibre constituting pile, give degree of freedom, the hands on surface to the fiber constituting pile Sense becomes soft, can obtain good exterior quality and soft feel.Otherwise, (water-dispersion type gathers in the face adhered on a small quantity by PVA The face that urethane attachment is many) as the pile face of tablet time, although the fiber constituting pile is strongly held by polyurethane so that Length of pile is shorter, but can obtain the good exterior quality with fine and close sense, and then mar proof becomes good.And then, logical Cross the operation including being cut into two halves along sheet thickness direction, it is possible to increase production efficiency.

In the present invention, at least one side of tablet can be carried out napping process, thus form pile on surface.Form floss The method of head is not particularly limited, and can use various method usually used in this field (utilizing the polishing etc. of sand paper etc.).Floss When head length is too short, it is difficult to obtaining graceful outward appearance, time long, there is the tendency being susceptible to balling-up, therefore, length of pile is excellent Elect 0.2～1mm as.

Additionally, in a kind of mode of the present invention, before napping processes, tablet can be given and having as lubricant Machine silicon etc..By giving lubricant, utilizing the napping of surface grinding to become easily and realize, surface quality becomes very good, therefore Preferably.In addition it is also possible to give antistatic additive before napping processes, by giving antistatic additive, grinding cause lamellar produce Raw grounds travel is difficult on sand paper pile up, therefore is optimal way.

In a kind of mode of the present invention, tablet can dye.As colouring method, can use in this area Normally used various method, rubs effect, by tablet softness from giving while dyeing tablet From the standpoint of, the method that liquid-flow dyeing machine is preferably used.

Dyeing temperature is different also according to the difference of kinds of fibers, but preferably 80～150 DEG C.By making dyeing temperature be More than 80 DEG C, more preferably more than 110 DEG C, it is possible to fiber is dyeed by efficiency well.On the other hand, by making dyeing temperature It it is less than 150 DEG C, more preferably less than 130 DEG C, it is possible to prevent the deterioration of polyurethane.

The dyestuff used in the present invention can select according to the kind of the fiber constituting fibrous substrate, limits the most especially Fixed, such as, if polyester fiber, then can use disperse dyes, if polyamide-based fiber, then can use acid stain or contain Gold dyestuff, and then combinations thereof can be used.When dyeing with disperse dyes, reduction cleaning can be carried out after dyeing.

Additionally, using dyeing assistant when dyeing is also optimal way.By using dyeing assistant, it is possible to increase dyeing Uniformity, repeatability.Additionally, with dyeing with bath or after dyeing, it is possible to implement use softening agent, the antistatic such as such as organosilicon The dressing agent of agent, waterproofing agent, fire retardant, photostabilizer and antibacterial etc. processes.

The density of the tablet of the present invention obtained by aforesaid operations is preferably 0.2～0.7g/cm³.By making density For 0.2g/cm³Above, more preferably 0.3g/cm³Above, appearance becomes fine and close, it is possible to show first-class quality.The opposing party Face, by making density be 0.7g/cm³Below, more preferably 0.6g/cm³Below, it is possible to the feel preventing tablet is hardening.

[embodiment]

It follows that illustrated in greater detail the manufacture method of the tablet of the present invention by embodiment, but the present invention does not limit Due to these embodiments, in the technology of the present invention is conceived, those skilled in the art can carry out various deformation.

[evaluation methodology]

(1) organic solvent concentration of PVA aqueous solution

Add loading PVA aqueous solution 1g in heat pipe to 24mL, heat 1 hour in 90 DEG C.With air hermetic entry needle from adding heat pipe Gather 0.1mL and gas occurs, import in GC/MS, carry out the concentration analysis of methyl acetate, acetic acid, methanol.It should be noted that GC/ The detection limit of MS is less than 0.1ppm.

(2) viscosity of PVA aqueous solution

Utilize the rotating cylinder viscometer method described in 3.11.1 of JIS K6726 (1994) polyvinyl alcohol test method, measure 4 Viscosity during 20 DEG C of quality %PVA aqueous solution.

(3) tensile strength of PVA

10 mass %PVA aqueous dispersions are added polyethylene pallet (be longitudinally 5cm, be laterally 10cm, the degree of depth is 1cm) In, after air-drying 8 hours in 25 DEG C, the air drier heat treatment using temperature to be 120 DEG C 2 hours, obtain the PVA of thick 100 μm Dry film.For this PVA dry film, according to the A method (galley proof method (strip described in JIS L1096 (2010) 8.14.1 Method)), stretching test machine determination tensile strength is used.

(4) average single fiber diameter

Average single fiber diameter calculates as follows: with multiplying power 2000 times shooting fibrous substrate or the sweep type on tablet surface Ultramicroscope (SEM) photo, randomly chooses 100 fibers, measures single fiber diameter, calculates meansigma methods.

When the fiber of composition fibrous substrate or tablet is odd-shaped cross section, calculate the periphery circular diameter conduct of odd-shaped cross section Single fiber diameter.Additionally, time when circular cross-section and odd-shaped cross section mix, the mixing of single fiber diameter visibly different cross section etc., Selection calculate with the respective corresponding hits of radical ratio that exists, 100 altogether.But, insert in fibrous substrate In the case of having the fabric of enhancing, fabric such, when measuring average single fiber diameter, the fabric of this enhancing, braiding The fiber of thing is not included in sample objects.

(5) stiffness of tablet

Based on the A method (45 ° of cantilever methods) described in JIS L1096 (2010) 8.21.1, make and divide in machine and transverse direction Not Wei the test film of 2cm × 15cm, be positioned on the horizontal stand on the inclined-plane with 45 °, make test film slide, read by scale The position of the other end when central point of one end of test film and contact of incline plane.Length (mm) table that stiffness is moved by test film Show.Obtain the meansigma methods of this movable length of 5 test films, as stiffness.

(6) appearance of tablet

For the appearance of tablet, by each to adult human male good for health status and adult female 10 (altogether 20 Name) as estimator, by visually and 5 grades of evaluations being discussed below of sense evaluation, using most evaluations as outside surface See.Appearance is considered as good at 3 grades～5 grades.

5 grades: there is uniform fiber pile, the dispersity of fiber is good, and outward appearance is good.

Evaluation between 4 grades: 5 grades and 3 grades.

3 grades: there is the part that the dispersity of fiber is the most bad, but have fiber pile, outward appearance can be said to be good.

Evaluation between 2 grades: 3 grades and 1 grade.

1 grade: the dispersity of fiber is excessively poor on the whole, or fiber pile is long, and outward appearance is bad.

(7) the mar proof evaluation of tablet

The nylon fiber of the diameter 0.4mm formed by nylon 6 is cut into length along the direction vertical with the length direction of fiber 11mm, by the neat bunchy of fiber of 100 Gen Qie get, uses and 97 these fibre bundles is configured as in the circle of diameter 110mm 6 weights Concentric circles (1, center, diameter 17mm circle in 6,13,19, diameter in the circle of diameter 55mm in the circle of diameter 37mm In the circle of 74mm 26, in the circle of diameter 90mm 32, be at equal intervals in each circle) round-type brush (nylon yarn 9700 Root), under conditions of load 8 pounds (about 3629g), rotary speed 65rpm, number of revolutions 50 times, make the circular sample of tablet The surface abrasion of (diameter 45mm), measures the mass change of sample before and after abrasion, average by the mass change of 5 samples Value, i.e. abrasion decrement (mg) are considered as mar proof.

[embodiment 1]

(preparation of PVA aqueous solution)

By saponification degree be 99%, the degree of polymerization be that PVA (the Japan synthesis KCC NM-14) interpolation of 1400 is to 25 DEG C water in, after being warming up to 90 DEG C, stir 2 hours and keep 90 DEG C, prepare the aqueous solution of solid state component 10 mass %, Obtain PVA aqueous solution.The methyl acetate that contains in PVA aqueous solution, acetic acid, methanol concentration be respectively 10.2ppm, 0.8ppm, 5.2ppm。

(fibrous substrate non-woven fabrics)

As sea component, use copolymerization has the polyethylene terephthalate of the 5-sodium sulfo isophthalate of 8mol% Ester, as island component, uses polyethylene terephthalate, with sea component 45 mass %, island component 55 mass % compound Ratio, obtains Dao Shuo 36 island/1 fiber, the islands-in-sea bicomponent fibre of average single fiber diameter 17 μm.The fabric of island-in-sea type obtained is combined Fiber is cut into the long 51mm of fiber as cut staple (staple), forms fleece by carding machine and cross lapping machine, passes through Needling treatment makes non-woven fabrics.The non-woven fabrics obtained by aforesaid operations is impregnated 2 minutes in the hot water that temperature is 98 DEG C, makes It shrinks, and is dried 5 minutes, makes fibrous substrate non-woven fabrics at a temperature of 100 DEG C.

(imparting of PVA)

Make, in above-mentioned PVA aqueous solution impregnation extremely above-mentioned fibrous substrate non-woven fabrics, to heat at a temperature of 140 DEG C It is dried 10 minutes, obtains imparting the sheet material of PVA, wherein, relative to the fiber quality of fibrous substrate non-woven fabrics, PVA's For adhesion amount) it is 30 mass %.

(fiber super-refinement (de-sea))

The concentration that the sheet material of the above-mentioned PVA of imparting is immersed in the temperature being heated to 95 DEG C is the sodium hydroxide water that 10g/ rises In solution, process 30 minutes, the de-sea sheet material of the sea component of the islands-in-sea bicomponent fibre that has been removed.Putting down of de-sea sheet surface All single fiber diameters are 3 μm.

(preparation of polyurethane liquid)

(polyhexamethylene carbonic ester conduct is used relative to the polycarbonate-based self-emulsifying type polyurethane liquid of 100 mass parts Polyhydric alcohol, use dicyclohexyl methyl hydride diisocyanate as isocyanates) solid state component for, add the work of 2 mass parts For the Ammonium persulfate. (APS) of heat coagulant, utilize water that entirety preparation is become solid state component 20 mass %, obtain water-dispersion type and gather Urethane liquid.Heat freezing temperature is 72 DEG C.

(imparting of polyurethane)

Make in the most above-mentioned de-sea sheet material imparting PVA of above-mentioned polycarbonate-based polyurethane liquid impregnation, be 100 DEG C in temperature Damp and hot atmosphere under process after 5 minutes, hot air drying 5 minutes at a temperature of baking temperature 120 DEG C, and then in the temperature of 140 DEG C Carrying out dry heat treatment under degree 2 minutes, the adhesion amount (for the fiber quality of non-woven fabrics) thus obtaining making polyurethane is 30 mass %, the sheet material that imparts polyurethane.

(removing of PVA)

The above-mentioned sheet material imparting polyurethane is immersed in the water being heated to 95 DEG C, processes 10 minutes, be removed The sheet material of the PVA given.

(half cuts out napping dyeing reduction cleaning)

The sheet material through-thickness of the above-mentioned PVA of eliminating is cut into two halves, by using the annular sand paper of 240 mesh Double sanction face of the grinding of (endless sandpaper) and contrary surface carry out napping process, then use liquid-flow dyeing machine (Circular) utilize disperse dyeing, carry out reduction cleaning, obtain tablet.The appearance of the tablet obtained is good Good, there is the feel of softness, mar proof is the best.

[embodiment 2]

(preparation of PVA aqueous solution)

Operate similarly to Example 1, obtain PVA aqueous solution.

(fibrous substrate non-woven fabrics)

Operate similarly to Example 1, obtain fibrous substrate non-woven fabrics.

(imparting of PVA)

Use PVA aqueous solution similarly to Example 1, regulate the mangle after impregnation thus change the adhesion amount of PVA, except this In addition, operate similarly to Example 1, obtain PVA adhesion amount (relative to fibrous substrate non-woven fabrics fiber quality and Speech) be 20 mass %, the sheet material that imparts PVA.

(fiber super-refinement (de-sea))

Operate similarly to Example 1, obtain de-sea sheet material.

(preparation of polyurethane liquid)

Operate similarly to Example 1, obtain water dispersant type polyaminoester liquid.

(imparting of polyurethane)

Operate similarly to Example 1, obtain imparting the sheet material of polyurethane.

(removing of PVA)

Operate similarly to Example 1, the sheet material of the PVA that has been removed.

(half cuts out napping dyeing reduction cleaning)

Operate similarly to Example 1, obtain tablet.The appearance of the tablet obtained is good, has softness Feel, mar proof is the best.

[embodiment 3]

(preparation of PVA aqueous solution)

Operate similarly to Example 1, obtain PVA aqueous solution.

(fibrous substrate non-woven fabrics)

As sea component, use copolymerization has the polyethylene terephthalate of the 5-sodium sulfo isophthalate of 8mol% Ester, as island component, uses polyethylene terephthalate, with sea component 20 mass %, island component 80 mass % compound Ratio, obtains Dao Shuo 16 island/1 fiber, the islands-in-sea bicomponent fibre of average single fiber diameter 30 μm.The fabric of island-in-sea type obtained is combined Fiber is cut into the long 51mm of fiber as cut staple, forms fleece by carding machine and cross lapping machine, passes through needling treatment Make non-woven fabrics.The non-woven fabrics obtained by aforesaid operations is impregnated 2 minutes in the hot water that temperature is 98 DEG C so that it is shrink, It is dried 5 minutes at a temperature of 100 DEG C, makes fibrous substrate non-woven fabrics.

(imparting of PVA)

Use PVA aqueous solution similarly to Example 1, obtain the adhesion amount of PVA (relative to fibrous substrate non-woven fabrics Fiber quality for) be 30 mass %, the sheet material that imparts PVA.

(fiber super-refinement (de-sea))

Processing above-mentioned fibrous substrate non-woven fabrics similarly to Example 1, the fabric of island-in-sea type that has been removed is combined The de-sea sheet material of the sea component of fiber.A diameter of 4.4 μm of average single fiber of de-sea sheet surface.

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

(removing of PVA)

(half cuts out napping dyeing reduction cleaning)

[embodiment 4]

(preparation of PVA aqueous solution)

By saponification degree be 99%, the degree of polymerization be that PVA (the Japan synthesis KCC NM-11) interpolation of 1100 is to 25 DEG C water in, after being warming up to 90 DEG C, stir 2 hours and keep 90 DEG C, prepare the aqueous solution of solid state component 10 mass %, Obtain PVA aqueous solution.The methyl acetate that contains in PVA aqueous solution, acetic acid, methanol concentration be respectively 7.2ppm, 0.4ppm, 2.4ppm。

(fibrous substrate non-woven fabrics)

Use fibrous substrate non-woven fabrics similarly to Example 1.

(imparting of PVA)

Make, in above-mentioned PVA aqueous solution impregnation extremely above-mentioned fibrous substrate non-woven fabrics, to heat at a temperature of 140 DEG C Being dried 10 minutes, the adhesion amount (for the fiber quality of fibrous substrate non-woven fabrics) obtaining PVA is 30 mass % , the sheet material imparting PVA.

(fiber super-refinement (de-sea))

Operate similarly to Example 1, obtain de-sea sheet material from above-mentioned fibrous substrate non-woven fabrics.

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

(removing of PVA)

(half cuts out napping dyeing reduction cleaning)

[embodiment 5]

(preparation of PVA aqueous solution)

By saponification degree be 99%, the PVA of the degree of polymerization 2600 (Japan synthesis KCC NH-26) interpolation is to 25 DEG C Water in, after being warming up to 90 DEG C, stir 2 hours and keep 90 DEG C, prepare the aqueous solution of solid state component 10 mass %, To PVA aqueous solution.The methyl acetate that contains in PVA aqueous solution, acetic acid, methanol concentration be respectively 32.2ppm, 8.3ppm, 20.1ppm。

(fibrous substrate non-woven fabrics)

Use fibrous substrate non-woven fabrics similarly to Example 1.

(imparting of PVA)

Make, in above-mentioned PVA aqueous solution impregnation extremely above-mentioned fibrous substrate non-woven fabrics, to heat at a temperature of 140 DEG C Being dried 10 minutes, the adhesion amount (for the fiber quality of fibrous substrate non-woven fabrics) obtaining PVA is 10 mass % , the sheet material imparting PVA.

(fiber super-refinement (de-sea))

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

(removing of PVA)

(half cuts out napping dyeing reduction cleaning)

[embodiment 6]

(preparation of PVA aqueous solution)

Operate similarly to Example 1, obtain PVA aqueous solution.

(fibrous substrate non-woven fabrics)

As sea component, use copolymerization has the polyethylene terephthalate of the 5-sodium sulfo isophthalate of 8mol% Ester, as island component, uses polyethylene terephthalate, with sea component 20 mass %, island component 80 mass % compound Ratio, obtains Dao Shuo 16 island/1 fiber, the islands-in-sea bicomponent fibre of average single fiber diameter 30 μm.The fabric of island-in-sea type obtained is combined Fiber is cut into the long 51mm of fiber as cut staple, forms fleece by carding machine and cross lapping machine, at two surface layers of net The plain weave of high twist yarn that conjunction employs the 84dtex-72f of polyethylene terephthalate (PET), the twist is 2000T/m is knitted Thing, makes non-woven fabrics by needling treatment.The non-woven fabrics obtained by aforesaid operations is impregnated 2 in the hot water that temperature is 98 DEG C Minute so that it is shrink, be dried 5 minutes at a temperature of 100 DEG C, make fibrous substrate non-woven fabrics.

(imparting of PVA)

Make, in above-mentioned PVA aqueous solution impregnation extremely above-mentioned fibrous substrate non-woven fabrics, to heat at a temperature of 140 DEG C Being dried 10 minutes, the adhesion amount (for the fiber quality of fibrous substrate non-woven fabrics) obtaining PVA is 15 mass % , the sheet material imparting PVA.

(fiber super-refinement (de-sea))

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

(removing of PVA)

(half cuts out napping dyeing reduction cleaning)

[embodiment 7]

(preparation of PVA aqueous solution)

Operate similarly to Example 1, obtain PVA aqueous solution.

(fibrous substrate non-woven fabrics)

Operate similarly to Example 1, obtain fibrous substrate non-woven fabrics.

(imparting of PVA)

Operate similarly to Example 1, obtain the adhesion amount (cellulosic relative to fibrous substrate non-woven fabrics of PVA For amount) be 30 mass %, the sheet material that imparts PVA.

(fiber super-refinement (de-sea))

Operate similarly to Example 1, obtain de-sea sheet material.

(preparation of polyurethane liquid)

(polyhexamethylene carbonic ester conduct is used relative to the polycarbonate-based self-emulsifying type polyurethane liquid of 100 mass parts Polyhydric alcohol, use dicyclohexyl methyl hydride diisocyanate as isocyanates) solid state component for, add the increasing of 5 mass parts Thick dose (SAN NOPCO Ltd. SN THICKENER 627N), utilizes water that entirety preparation is become polyurethane solid state component 20 Quality %, obtains water dispersant type polyaminoester liquid.

(imparting of polyurethane)

Make in the most above-mentioned de-sea sheet material imparting PVA of above-mentioned polyurethane liquid impregnation, at a temperature of baking temperature 100 DEG C Hot air drying 30 minutes, the adhesion amount (for the fiber quality of non-woven fabrics) thus obtaining making polyurethane is 30 mass % , the sheet material imparting polyurethane.

(removing of PVA)

(half cuts out napping dyeing reduction cleaning)

[embodiment 8]

(preparation of PVA aqueous solution)

Operate similarly to Example 5, obtain PVA aqueous solution.

(fibrous substrate non-woven fabrics)

Use fibrous substrate non-woven fabrics similarly to Example 1.

(imparting of PVA)

(fiber super-refinement (de-sea))

Operate similarly to Example 1, above-mentioned fibrous substrate non-woven fabrics obtain de-sea sheet material.

(preparation of polyurethane liquid)

(imparting of polyurethane)

Make, in the most above-mentioned de-sea sheet material imparting PVA of above-mentioned polyurethane liquid impregnation, to make it solidify in the warm water of 80 DEG C, In 100 DEG C of hot air dryings 15 minutes, the adhesion amount (for the fiber quality of non-woven fabrics) thus obtaining making polyurethane was 30 mass %, the sheet material that imparts polyurethane.

(removing of PVA)

(half cuts out napping dyeing reduction cleaning)

[comparative example 1]

(preparation of PVA aqueous solution)

Operate similarly to Example 1, obtain PVA aqueous solution.

(fibrous substrate non-woven fabrics)

Use fibrous substrate non-woven fabrics similarly to Example 1.

(fiber super-refinement (de-sea))

By the concentration that the fibrous substrate non-woven fabrics obtained by aforesaid operations is immersed in the temperature being heated to 95 DEG C it is In the sodium hydrate aqueous solution that 10g/ rises, process 10 minutes, the de-sea sheet of the sea component of the islands-in-sea bicomponent fibre that has been removed Material.A diameter of 3 μm of average single fiber of de-sea sheet surface.

(imparting of PVA)

It is impregnated with in embodiment 1, in the sheet material of above-mentioned de-sea, the PVA aqueous solution obtained, heats at a temperature of 140 DEG C It is dried 10 minutes, sheet material that the adhesion amount (for the sheet material of de-sea) obtaining PVA is 30 mass %, that impart PVA.

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

In the de-sea sheet material of the above-mentioned PVA of imparting, it is impregnated with above-mentioned polycarbonate-based polyurethane liquid, is 100 DEG C in temperature After processing 5 minutes under damp and hot atmosphere, hot air drying 5 minutes at a temperature of baking temperature 120 DEG C, and then in the temperature of 140 DEG C Under carry out dry heat treatment 2 minutes, the adhesion amount (for superfine fibre quality) thus obtaining making polyurethane is 30 matter Sheet material that measure %, that impart polyurethane.

(removing of PVA)

(half cuts out napping dyeing reduction cleaning)

Operate similarly to Example 1, obtain tablet.Although the tablet appearance obtained is good, there is softness Feel, but abrasion decrement is many.

[comparative example 2]

(preparation of PVA aqueous solution)

It is that PVA (the Japan synthesis KCC GL-05) interpolation of 500 is to 25 DEG C by saponification degree 87%, the degree of polymerization Water in, after being warming up to 90 DEG C, stir 2 hours and keep 90 DEG C, prepare the aqueous solution of solid state component 10 mass %, To PVA aqueous solution.The methyl acetate that contains in PVA aqueous solution, acetic acid, methanol concentration be respectively 70.1ppm, 40.1ppm, 100.3ppm。

(fibrous substrate non-woven fabrics)

Use fibrous substrate non-woven fabrics similarly to Example 1.

(imparting of PVA)

In above-mentioned fibrous substrate non-woven fabrics, it is impregnated with above-mentioned PVA aqueous solution, regulates the mangle after impregnation thus change The adhesion amount of PVA, in addition, operates similarly to Example 1, obtains the adhesion amount of PVA (relative to fibrous substrate nothing For spinning the fiber quality of cloth) be 10 mass %, the sheet material that imparts PVA.

(fiber super-refinement (de-sea))

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

(removing of PVA)

(half cuts out napping dyeing reduction cleaning)

Operate similarly to Example 1, obtain tablet.The tablet obtained is dissolved in alkaline water due to a PVA part Solution and water dispersant type polyaminoester liquid do not become uniform imparting state, the bad (dispersity of fiber of appearance Difference, pile is without densification sense), Boardy Feeling.

[comparative example 3]

(preparation of PVA aqueous solution)

By saponification degree be 99%, the degree of polymerization be that PVA (the Japan synthesis KCC NL-05) interpolation of 500 is to 25 DEG C water in, after being warming up to 90 DEG C, stir 2 hours and keep 90 DEG C, prepare the aqueous solution of solid state component 10 mass %, Obtain PVA aqueous solution.The methyl acetate that contains in PVA aqueous solution, acetic acid, methanol concentration be respectively 6.1ppm, 0.4ppm, 1.1ppm。

(fibrous substrate non-woven fabrics)

Use fibrous substrate non-woven fabrics similarly to Example 1.

(imparting of PVA)

(fiber super-refinement (de-sea))

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

(removing of PVA)

(half cuts out napping dyeing reduction cleaning)

[comparative example 4]

(preparation of PVA aqueous solution)

Operate similarly to Example 1, obtain PVA aqueous solution.

(fibrous substrate non-woven fabrics)

Use fibrous substrate non-woven fabrics similarly to Example 1.

(imparting of PVA)

Use PVA aqueous solution similarly to Example 1, regulate the mangle after impregnation thus change the adhesion amount of PVA, except this In addition, operate similarly to Example 1, obtain PVA adhesion amount (relative to fibrous substrate non-woven fabrics fiber quality and Speech) be 55 mass %, the sheet material that imparts PVA.

(fiber super-refinement (de-sea))

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

(removing of PVA)

(half cuts out napping dyeing reduction cleaning)

Operate similarly to Example 1, obtain tablet.Although the tablet obtained is soft, but due to PVA mistake Many, so polyurethane is insufficient to the holding of fiber, appearance becomes bad (pile is long), and mar proof is poor.

[comparative example 5]

Do not carry out the preparation of PVA aqueous solution, the imparting of PVA and removing, in addition, operate similarly to Example 1, To tablet.The feel of the tablet obtained is hardening.Additionally, appearance bad (not having pile).

The evaluation result of each embodiment and the experimental condition of comparative example and tablet is shown in Tables 1 and 2.

[table 1]

[table 2]

The tablet obtained in embodiment 1～8, equal appearance is good, has the feel of softness, and mar proof is the best Good.On the other hand, the mar proof of the tablet obtained in comparative example 1 and 4 is poor, the table of the tablet obtained in comparative example 2～5 Face outward appearance is the most bad.Additionally, the Boardy Feeling of the tablet obtained in comparative example 2,3,5.

Industrial applicability

Can suitably serve as according to the tablet that the present invention obtains: as furniture, chair and wall material, automobile, electricity The skin material of seat, ceiling and upholstery etc. in the vehicle chamber of car and airborne vehicle etc. has the interior of the most graceful outward appearance Portion's ornament materials, the vamp of the footwear such as shirt, jacket, playshoes, sport shoes, Men's Shoes and women's shoes, decoration (trim) etc., bag, belt, Wallet etc. and for industrial materials such as their the dress material material of a part, cleaning wiping cloth, abrasive cloth and CD curtains.

Claims

1. the manufacture method of a tablet, it is characterised in that carry out following operation 1～5 successively,

Operation 1: the polyvinyl alcohol that to make saponification degree be more than 98%, the degree of polymerization is 800～3500 is dissolved in water, and obtains acetic acid first Ester, acetic acid, the concentration of methanol are respectively the polyvinyl alcohol water solution of below 50ppm；

Operation 2: give described polyvinyl alcohol water to manifesting, with superfine fibre, the fibrous substrate that fiber type is main composition composition Solution, gives the described polyvinyl alcohol of 0.1～50 mass % thus relative to the fiber quality contained by fibrous substrate；

Operation 3: to show average single fiber straight from manifesting, with superfine fibre, the fibrous substrate that fiber type is main composition composition Footpath is the superfine fibre of 0.3～7 μm；

Operation 4: to the described fibrous substrate imparting moisture being main composition composition with superfine fibre imparting polyvinyl alcohol Dissipate type polyurethane；

Operation 5: from described impart water dispersant type polyaminoester with superfine fibre for the fibrous substrate of main composition composition Remove polyvinyl alcohol.

2. the manufacture method of tablet as claimed in claim 1, it is characterised in that the acetic acid first of described polyvinyl alcohol water solution Ester, acetic acid, the concentration of methanol are respectively 0.1～50ppm.

3. the manufacture method of tablet as claimed in claim 1 or 2, it is characterised in that the operation showing superfine fibre is The operation processed is carried out in alkaline aqueous solution.

4. the manufacture method of tablet as claimed in claim 1 or 2, it is characterised in that include giving described polyvinyl alcohol, in 80～170 DEG C carry out the operation heated.

5. the manufacture method of tablet as claimed in claim 1 or 2, it is characterised in that described to manifest type with superfine fibre fine Dimension is integrated with fabric and/or fabric complexation for the fibrous substrate of main composition composition.

6. a tablet, it is characterised in that obtained by the manufacture method of the tablet according to any one of Claims 1 to 5 To the density of tablet be 0.2～0.7g/cm³。