CN104838063A

CN104838063A - Sheet-shaped object and process for producing the sheet-shaped object

Info

Publication number: CN104838063A
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: 2015-08-12
Anticipated expiration: 2033-11-27
Also published as: KR102090355B1; EP2927368A4; JP6225917B2; WO2014084253A1; TWI580840B; EP2927368B1; JPWO2014084253A1; CN104838063B; EP2927368A1; TW201439398A; US20150315741A1; KR20150090122A

Abstract

The present invention provides a process for producing a sheet-shaped object which has a piled graceful appearance and a soft texture and which has even better wear resistance, the process being characterized in that the following steps (1) to (5) are conducted successively. (1) A step in which a polyvinyl alcohol having a degree of saponification of 98% or higher and a degree of polymerization of 800-3,500 is dissolved in water to obtain an aqueous polyvinyl alcohol solution in which the contents of methyl acetate, acetic acid, and methanol are 50 ppm or less each; (2) a step in which the polyvinyl alcohol is imparted to a fibrous base that comprises, as the main constituent component, fibers capable of forming ultrafine fibers, in an amount of 0.1-50 mass percent relative to the fibers of the fibrous base; (3) a step in which ultrafine fibers having an average single-fiber diameter of 0.3-7 [micro]m are formed from the fibrous base obtained in the step (2); (4) a step in which a water dispersion type polyurethane is imparted to the fibrous base obtained in the step (3); and (5) a step in which the polyvinyl alcohol is removed from the fibrous base obtained in the step (4).

Description

The manufacture method of tablet and this tablet

Technical field

The present invention relates to the manufacture method of tablet and this tablet, described tablet, by using water dispersant type polyaminoester as adhesive resin, reduce the use amount of the organic solvent in manufacturing process, with regard to eco-friendly tablet, good flexibility and first-class exterior quality can be realized simultaneously, and there is good mar proof.

Background technology

The tablet formed primarily of fibrous substrate and polyurethane has the feature of the unexistent excellence of natural leather, is widely used in a variety of applications where.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 annual all in increase.

When manufacturing above-mentioned tablet, the following operation of usual employing: after making the organic solvent solution of polyurethane be impregnated in fibrous substrate, the fibrous substrate obtained is immersed in the non-solvent of polyurethane and the mixed solution of water or organic solvent/water, polyurethane wet type is solidified.As solvent and the organic solvent of above-mentioned polyurethane, employ DMF and (be also expressed as below " DMF ".) etc. miscible organic solvents, such as, propose following method: nonwoven fabric impregnation polyvinyl alcohol (is also expressed as " PVA " below.) aqueous solution, obtain fiber tablet, this fiber tablet is immersed in polyurethane containing in immersion liquid, and then, after polyurethane wet type being solidified in the 45%DMF aqueous solution of 20 DEG C, with hot water removing DMF and the polyvinyl alcohol of 85 DEG C, thus manufacture tablet (see patent document 1).But, because organic solvent is usually high to the harmfulness of human body and environment, therefore, when manufacturing tablet, strong need not method with an organic solvent.

As the solution that it is concrete, such as, have studied the method using and the water dispersant type polyaminoester of they in water is replaced the polyurethane of existing organic solvent type.But, to fibrous substrate impregnation, impart water dispersant type polyaminoester and the tablet formed exists the hardening problem of feel.The main cause of this problem is, the fiber strength ground of polyurethane and fibrous substrate bonds.Be studied to solve the problem, propose following method: be suitable for existing organic solvent type polyurethane manufacturing process in the same manner as, in order to part suppresses the bonding of fiber and polyurethane, manufactures space between fiber and polyurethane, and give PVA to fibrous substrate in advance, then give polyurethane, then remove the method (see patent document 2) of PVA.

Here, because PVA is water-soluble, so when getting wet after giving PVA to fibrous substrate, PVA can dissolve and come off, therefore, in order to suppress the dissolving of PVA described above in the operation got wet and come off, in patent document 2, utilize at (i) in the impregnation operation of the fine operation of the fiber of alkaline aqueous solution and (ii) water dispersant type polyaminoester and have employed following methods.Namely, by add in alkaline aqueous solution borax inhibit at the former be, coming off in the fine operation of fiber, on the other hand, 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 the PVA of 500, inhibit PVA to coming off in water.But, about the effect of adding borax in the fine operation of fiber, due to when the fine of fiber, expend longer to the dip time in alkaline aqueous solution, even if so add borax in alkaline aqueous solution, PVA can not be suppressed completely to the dissolving in water.In addition, about the impregnation operation of water dispersant type polyaminoester, because the degree of polymerization of PVA is low, so it can not be suppressed completely to the dissolving in water, can not suppress to coming off in water dispersant type polyaminoester liquid, therefore PVA is dissolved in water dispersant type polyaminoester liquid, thus causes the tacky state that stably can not control polyurethane and fiber, there is the problem that the feel of tablet is hardening.

In addition, for the problem in each operation of above-mentioned (i) (ii), propose following method: giving saponification degree to nonwoven fabric sheet is the PVA of more than 90%, and carry out the heating of 150 ~ 195 DEG C, reduce PVA thus to the deliquescent method (see patent document 3) of water.Although by carrying out high-temperature heating, making the intermolecular hydrogen bonding of PVA strong, thus reducing the dissolubility to water, if but temperature is too high or heat time heating time is long, then PVA can be insoluble, the redissolution of Xiang Shuizhong becomes difficulty, therefore, there is the problem of the stabilisation difficulty of felicity condition.

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

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

Patent document 3: Japan Patent No. 4644971 publication

Summary of the invention

The manufacture method that the invention provides a kind of tablet and the tablet utilizing above-mentioned manufacture method to obtain, described manufacture method can reduce the use of the organic solvent in manufacturing process, environmentally friendly, described tablet can realize having the aesthetic look of pile and soft feel simultaneously, and has good mar proof.

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

Operation 1: make that saponification degree is more than 98%, the degree of polymerization be the polyvinyl alcohol dissolution of 800 ~ 3500 in water, obtain methyl acetate, acetic acid, methyl alcohol concentration be respectively the polyvinyl alcohol water solution of below 50ppm;

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

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

Operation 4: to impart this polyvinyl alcohol with superfine fibre be main composition composition fibrous substrate give water dispersant type polyaminoester;

Operation 5: be remove polyvinyl alcohol the fibrous substrate of main composition composition with superfine fibre from what impart this water dispersant type polyaminoester.

The preferred embodiment of the manufacture method of tablet of the present invention is: via obtain methyl acetate, acetic acid, methyl alcohol concentration be respectively the operation of the polyvinyl alcohol water solution of 0.1 ~ 50ppm.

According to the preferred embodiment of the manufacture method of tablet of the present invention, the operation manifesting superfine fibre carries out with alkaline aqueous solution the operation that processes.

The preferred embodiment of the manufacture method of tablet of the present invention is: comprise the operation of giving described polyvinyl alcohol, carrying out heating in 80 ~ 170 DEG C.

According to the preferred embodiment of the manufacture method of tablet of the present invention, described to manifest with superfine fibre the fibrous substrate that fiber type is main composition composition integrated with fabric and/or braided fabric complexing.

In addition, the density of the tablet obtained is preferably 0.2 ~ 0.7g/cm ³.

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

Detailed description of the invention

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

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

For the manufacture method of tablet of the present invention, it is important for carrying out operation 1 ~ 5 successively.To manifesting fibrous substrate that fiber type is main composition composition with superfine fibre, to give saponification degree be more than 98%, the degree of polymerization is after polyvinyl alcohol (being also the expressed as PVA) aqueous solution of 800 ~ 3500, carry out manifesting from superfine fibre the operation (de-extra large operation) that fiber type shows superfine fibre, then be that the fibrous substrate of main composition composition gives water dispersant type polyaminoester liquid with superfine fibre to what impart PVA, and then PVA is removed from this fibrous substrate, the large space deriving from PVA and sea component is produced thus between fiber and polyurethane, and because polyurethane portion ground directly holds superfine fibre, therefore, it is possible to present graceful outward appearance and soft feel, and the physical characteristic such as good mar proof.

In addition, when the PVA aqueous solution being imparted to fibrous substrate and carrying out heat drying, there is so-called transport phenomena (namely in the PVA in water, the top layer being attached to fibrous substrate is concentrated by the drive of the movement of water), become the top layer being attached to fibrous substrate in a large number, the state being attached to internal layer on a small quantity.By making PVA move, the water dispersant type polyaminoester given after making mainly is attached to the internal layer of fibrous substrate.Then, when PVA is removed, near the top layer of fibrous substrate being attached with a large amount of PVA, between fiber and polyurethane, produce large space, become graceful outward appearance (pile not bunchy and fibrillation equably) through the appearance of the tablet of napping operation.

On the other hand, if carry out the process of de-sea after removing PVA, then can generate by the space that causes of removing PVA with by both the spaces caused by the sea component in de-sea between polyurethane and superfine fibre, therefore, although the area that polyurethane directly holds superfine fibre tails off further, 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, that is, makes the PVA that saponification degree is more than 98%, the degree of polymerization is 800 ~ 3500 be dissolved in water, obtain methyl acetate, acetic acid, methyl alcohol concentration be respectively the operation of the PVA aqueous solution of below 50ppm.

Methyl acetate, acetic acid, methyl alcohol improve at the precursor synthesized from PVA and polyvinyl acetate the material generated in the process of saponification degree, in addition, is by not by material that the decomposition of the remaining polyvinyl acetate of abundant saponification also can generate.About methyl acetate, acetic acid, methyl alcohol, below 50ppm is respectively by making the concentration of the methyl acetate in the PVA aqueous solution, acetic acid, methyl alcohol, make easily to form PVA intermolecular hydrogen bonding when heat drying, PVA can be suppressed to the dissolubility in water (comprising warm water), acid, alkaline aqueous solution.In addition, because PVA intermolecular hydrogen bonding is easily formed, therefore heat drying temperature can be set as lower temperature (80 ~ 140 DEG C), thus the thermal decomposition of PVA can be suppressed.The concentration of the methyl acetate in the PVA aqueous solution, acetic acid, methyl alcohol is more preferably respectively 0.1 ~ 50ppm, by make methyl acetate, acetic acid, methyl alcohol respectively micro-exist, they and PVA molecule weaker hydrogen bonding, PVA intermolecular distance is diminished, and PVA intermolecular hydrogen bonding is easily formed.If the concentration of methyl acetate, acetic acid, methyl alcohol is too high separately, then can suppress the formation of PVA intermolecular hydrogen bonding on the contrary, therefore, preferred concentration is 0.3 ~ 40ppm, more preferably 5 ~ 40ppm.

It should be noted that, the concentration of the methyl acetate in the PVA aqueous solution, acetic acid, methyl alcohol analysis is carried out as follows.In 24mL heating tube, load PVA aqueous solution 1g, heat 1 hour at 90 DEG C.Gather 0.1mL with air hermetic entry needle (gas-tight syringe) from heating tube and gas occurs, import in GC/MS (directly linking the mass spectrograph of gas chromatograph) and analyze.

In order to reduce the concentration of methyl acetate in the PVA aqueous solution, acetic acid, methyl alcohol, methyl acetate when can be used in the heating of the PVA self before making the aqueous solution, acetic acid, the PVA that methyl alcohol growing amount is few, or in the preparation of the PVA aqueous solution, extend heat time heating time when heating up (it is for being dissolved in PVA in water).For the former, saponification degree is higher, and methyl acetate, acetic acid, methyl alcohol growing amount are fewer, therefore preferably uses the high saponification degree PVA of more than 98%.In addition, for the latter, if the temperature heated up is too low, then can not fully remove methyl acetate, acetic acid, methyl alcohol, therefore be preferably 80 ~ 100 DEG C, if heat time heating time is too short, then can not fully remove methyl acetate, acetic acid, methyl alcohol, therefore be preferably more than 1 hour.It should be noted that, also methyl acetate, acetic acid, methyl alcohol can be removed completely from the PVA aqueous solution.

In embodiments of the present invention, the saponification degree being imparted to the PVA of fibrous substrate is more than 98%, and the degree of polymerization is 800 ~ 3500.By making the saponification degree of PVA be more than 98%, when giving water dispersant type polyaminoester, PVA can be prevented to be dissolved in water dispersant type polyaminoester liquid.If PVA is dissolved in water dispersant type polyaminoester liquid; then not only can not obtain the effect on the surface of the superfine fibre being enough to protection structure pile; and when further the water dispersant type polyaminoester liquid being dissolved with PVA being imparted to fibrous substrate; PVA is absorbed into polyurethane inside; afterwards PVA removing is become difficulty; therefore stably can not control the tacky state of polyurethane and fiber, feel is hardening.

In addition, about PVA, according to the difference of the degree of polymerization, it changes the dissolubility of water, and the degree of polymerization of PVA is less, and when giving water dispersant type polyaminoester, PVA more dissolves in water dispersant type polyaminoester liquid.The degree of polymerization of PVA is higher, and the viscosity of the PVA aqueous solution is higher, and when to the fibrous substrate impregnation PVA aqueous solution, PVA can not infiltrate into fibrous substrate inside, and therefore, the degree of polymerization of PVA is preferably 1000 ~ 3000, is more preferably 1200 ~ 2500.

In the present invention, for PVA, viscosity during 20 DEG C of the 4 quality % aqueous solution is preferably 10 ~ 70mPas.By making the viscosity of PVA be above-mentioned scope, when carrying out drying, the migration structure of appropriateness can be obtained in fibrous substrate inside, obtain the harmony between the flexibility of tablet and the physical characteristic such as appearance, mar proof.By making above-mentioned viscosity be more than 10mPas, more preferably more than 15mPas, can suppress to form extreme migration structure.On the other hand, by making viscosity be below 70mPas, more preferably below 50mPas, further preferred below 40mPas, PVA can be made to be easy to containing being immersed in fibrous substrate.

In the present invention, the vitrification point (Tg) of PVA is preferably 70 ~ 100 DEG C.By making the vitrification point of PVA be more than 70 DEG C, more preferably more than 75 DEG C, softening in drying process can be prevented, obtain the DIMENSIONAL STABILITY of fibrous substrate, the deterioration of tablet appearance can be suppressed.In addition, by making vitrification point be less than 100 DEG C, more preferably less than 95 DEG C, can prevent becoming the treatability that causes really up to the mark by fibrous substrate and worsening.

In the present invention, the fusing point of PVA is preferably 200 ~ 250 DEG C.By making the fusing point of PVA be more than 200 DEG C, more preferably more than 210 DEG C, softening in drying process can be prevented, obtain the DIMENSIONAL STABILITY of fibrous substrate, the deterioration of tablet appearance can be suppressed.In addition, by making the fusing point of PVA be less than 250 DEG C, more preferably less than 240 DEG C, can prevent becoming the treatability that causes really up to the mark by fibrous substrate and worsening.

In the present invention, the tensile strength of the film of PVA is preferably 400 ~ 800kg/cm ².Be 400kg/cm by making the tensile strength of PVA film ²above, more preferably 450kg/cm ²above, change in size when processing can be suppressed, suppress the deterioration of tablet appearance.Be 800kg/cm by making the tensile strength of PVA film ²below, more preferably 750kg/cm ²below, the sheet material imparting PVA can not become really up to the mark, can suppress the generation of the wrinkling grade of warpage when processing.It should be noted that, here so-called tensile strength, is measure and the value obtained 100 μm of PVA thick films under the atmosphere of temperature 20 DEG C, humidity 65%.

[the 2nd operation]

Next, the 2nd operation is described, that is, gives the PVA aqueous solution to manifesting the fibrous substrate that fiber type is main composition composition with superfine fibre, give the operation of this PVA of 0.1 ~ 50 quality % thus relative to the fiber quality contained by fibrous substrate.

Superfine fibre is manifested fiber type as main constituent by fibrous substrate of the present invention.By using superfine fibre to manifest fiber type, via follow-up fiber fine operation by fiber fine, graceful appearance can be obtained.

In preferred embodiment of the present invention, the average single fiber diameter manifesting the superfine fibre that fiber type obtains via fiber fine operation from superfine fibre is 0.3 ~ 7 μm.Be less than 7 μm, more preferably less than 6 μm by making average single fiber diameter, preferably less than 5 μm further, the tablet of flexibility and pile excellent quality can be obtained.On the other hand, be more than 0.3 μm, more preferably more than 0.7 μm by making average single fiber diameter, preferably more than 1 μm further, the excellent dispersion of the bundle fiber during pile process such as the colour rendering after dyeing, the grinding utilizing sand paper etc., fibrillation easiness is also excellent.

Fiber type is manifested as above-mentioned superfine fibre, following fiber can be adopted: (a) using the thermoplastic resin of different for solvent solubility two kinds of compositions as sea component and island component, use solvent etc. to dissolve removing sea component, make island component be the islands-in-sea type fibre of superfine fibre thus; B the thermoplastic resin of two kinds of compositions is alternately configured on fibre section with radial or multilayer shape by (), peel off each composition of segmentation, cuts the exfoliated composite fibre etc. of fine one-tenth superfine fibre thus.Wherein, islands-in-sea type fibre by removing sea component, can between island component, namely give the space of appropriateness between superfine fibre, therefore, also can preferably use from the viewpoint of the flexibility of tablet, feel.

Described islands-in-sea type fibre comprises such as following fiber: use fabric of island-in-sea type compound nozzle, sea component and these two kinds of compositions of island component are arranged the islands-in-sea bicomponent fibre carrying out spinning mutually; Sea component and these two kinds of composition mixing of island component are carried out the blend spinning fiber etc. of spinning.From can obtain even fiber number superfine fibre aspect and sufficiently long superfine fibre can be obtained, the also useful aspect of the intensity of tablet is considered, preferably can 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 polyester such as polyethylene terephthalate, polybutylene terephthalate (PBT), polytrimethylene terephthalate and PLAs, the polyamide such as 6-nylon and 66-nylon, acrylic acid, polyethylene, the fiber that the thermoplastic resin of the melt-spinnable such as polypropylene and thermoplastic cellulose etc. are formed.Wherein, consider from intensity, DIMENSIONAL STABILITY and sunproof viewpoint, preferably use polyester fiber.In addition, consider from eco-friendly viewpoint, the fiber obtained from regeneration (recyle) raw material, the raw material that derives from plant is preferred.And then fibrous substrate also can be made up of different raw-material fibers mixture.

As the sea component of islands-in-sea type fibre, be not particularly limited, such as polyethylene can be used, polypropylene, polystyrene, the copolyester that the copolymerization such as sodiosulfoisophthalic acid, polyethylene glycol is obtained and PLA, PVA etc.Wherein, consider from eco-friendly viewpoint, preferably the PVA of the with an organic solvent i.e. copolyester that the copolymerization such as sodiosulfoisophthalic acid, polyethylene glycol is obtained of decomposable caustic digestion or PLA, hot water soluble.

The shape of cross section of fiber forming fibrous substrate is not particularly limited, and can be circular section, also can adopt the polygons such as ellipse, flat and triangle, the odd-shaped cross section such as fan-shaped and cross.

In the present invention, the average single fiber diameter forming the fiber of fibrous substrate is preferably 0.3 ~ 20 μm.Average single fiber diameter is thinner, more can obtain the tablet of flexibility and pile excellent quality, on the other hand, because average single fiber diameter is thicker, dispersiveness and the fibrillation easiness of the colour rendering after dyeing, bundle fiber when utilizing the pile process such as the grinding of sand paper etc. are more excellent, therefore average single fiber diameter is more preferably 0.7 ~ 15 μm, is particularly preferably 1 ~ 7 μm.

The form of fibrous substrate of the present invention can adopt fabric, braided fabric and nonwoven fabric etc.Wherein, because the appearance of tablet during surface nappy process is good, therefore preferably nonwoven fabric can be used.

Nonwoven fabric can be any one in staple fiber nonwoven fabric and nonwoven fabric of long fibers, but compared with staple fiber nonwoven fabric, the fiber of thickness direction of nonwoven fabric of long fibers when napping towards the tablet becoming pile is few, the densification sense step-down of pile, there is the tendency of surface appearance inferior, therefore preferably can use staple fiber nonwoven fabric.

The fiber of the staple fibre in above-mentioned staple fiber nonwoven fabric is long is preferably 25 ~ 90mm.By making fiber length be more than 25mm, the tablet of excellent in wear resistance can be obtained by complexing.In addition, being below 90mm by making fiber long, the tablet of feel and excellent quality can be obtained.Fiber is long is more preferably 30 ~ 80mm.

As the method for the fiber or fibre bundle complexing that make nonwoven fabric, acupuncture (needle punch) or water thorn (water jet punch) can be adopted.

In the present invention, when the fibrous substrate formed by superfine fibre is nonwoven fabric, preferred embodiment is: this nonwoven fabric has the structure of bundle (superfine fibre bundle) complexing of superfine fibre.By superfine fibre with the state complexing of bundle, the intensity of tablet improves.The nonwoven fabric of aforesaid way can obtain through following method: in advance superfine fibre is manifested fiber type and complex with one another, then make superfine fibre manifest.

When superfine fibre or its superfine fibre bundle form nonwoven fabric, for the object of intensity etc. improving its inside, can be integrated with fabric, braided fabric complexing.Such as, during for fabric, plain cloth, TWILL CLOTH and SATIN AND SATEEN CLOTH etc. can be enumerated, from the viewpoint of cost, preferably can use plain cloth.In addition, during for braided fabric, round braided fabric, tricot and La Sheer (Raschel) tricot etc. can be enumerated.The average single fiber diameter forming the fiber of described fabric and braided fabric is preferably 0.3 ~ 20 μm.

As preferred embodiment of the present invention, fabric and/or braided fabric are when manifesting the fibrous substrate inner complexation integration that fiber type is main composition composition with superfine fibre, by giving PVA, the area that the water dispersant type polyaminoester given afterwards directly holds fabric and/or braided fabric tails off, the limpen effect of tablet feel can be obtained, especially fabric and/or braided fabric by be not fiber that superfine fibre manifests fiber type form time, significant soft bating effect can be obtained.

To the imparting amount of the PVA of fibrous substrate, be 0.1 ~ 50 quality % for the fiber quality of fibrous substrate, be preferably 1 ~ 45 quality %.By making the imparting amount of PVA be more than 0.1 quality %, flexibility and the good tablet of feel can being obtained, by making the imparting amount of PVA be below 50 quality %, the tablet that the physical characteristics such as processability is good, mar proof are good can be obtained.

In the present invention, as the method for fibrous substrate being given to PVA, be not particularly limited, various method usually used in this field can be adopted, but from the viewpoint of giving equably, preferably make PVA be dissolved in water, containing to be immersed in fibrous substrate and to carry out the method for heat drying.About baking temperature, due to temperature too low time need longer drying time, when temperature is too high, PVA can be insoluble, can not dissolve removing afterwards, is therefore preferable over 80 ~ 140 DEG C and carries out drying, baking temperature more preferably 110 ~ 130 DEG C.Be generally 1 ~ 20 minute drying time, from the viewpoint of processability, be preferably 1 ~ 10 minute, be more preferably 1 ~ 5 minute.In addition, in order to PVA is insoluble further, heat treated can be carried out after the drying.The preferable temperature of heat treated is 80 ~ 170 DEG C.By heat treated, the heat deterioration of the insoluble and PVA of PVA is carried out simultaneously, and therefore preferred temperature is 80 ~ 140 DEG C.

[the 3rd operation]

Next, the 3rd operation is described, that is, shows from manifesting the fibrous substrate that fiber type is main composition composition with superfine fibre the operation that average single fiber diameter is the superfine fibre of 0.3 ~ 7 μm.

The fiber ultra fine (process of de-sea) that fiber type is the fibrous substrate of main composition composition is manifested, by being flooded in a solvent, extruding liquid to carry out by fibrous substrate with superfine fibre.Superfine fibre manifests fiber type when being islands-in-sea type fibre, as solvent, when marine origin is divided into polyethylene, polypropylene or polystyrene, the organic solvent such as toluene, trichloro-ethylene can be used, when marine origin is divided into copolyester or PLA, the alkaline aqueous solution of NaOH etc. can be used.In addition, when marine origin is divided into PVA, hot water can be used.Consider from the environment amenable viewpoint of operation, preferably carry out the process of de-sea with the alkaline aqueous solution of NaOH etc., hot water.

[the 4th operation]

Next, the 4th operation being described, that is, is that the fibrous substrate of main composition composition gives the operation of water dispersant type polyaminoester with superfine fibre to what impart PVA.

Above-mentioned water dispersant type polyaminoester is divided into: (I) uses the surfactant forcibly forced emulsification type polyurethane of decentralized stabilization in water; Even if (II) have in polyurethane molecular structure hydrophilic structure do not exist surfactant also can in water the self-emulsifying type polyurethane of decentralized stabilization, use any one in the present invention.

Give the method for water dispersant type polyaminoester as to fibrous substrate, be not particularly limited, fibrous substrate is coated in the impregnation of water dispersant type polyaminoester liquid, solidify after carry out the method for heat drying, owing to giving equably, so be preferred.

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

In addition, in order to improve storage stability and masking, the water dispersant type polyaminoester liquid used in the present invention can containing the water-miscible organic solvent being below 40 quality % for polyurethane liquid, but from the viewpoint of saving masking environment etc. from damage, preferably make the content of organic solvent be below 1 quality %.

In addition, as the water dispersant type polyaminoester liquid used in the present invention, preferably there is thermal coagulation.By using, there is heat coagulable water dispersant type polyaminoester liquid, on the thickness direction of fibrous substrate, polyurethane can be given equably.

In the present invention, so-called thermal coagulation, refers to when heating polyurethane liquid, and when reaching certain temperature (heat freezing temperature), the mobility of polyurethane liquid reduces thus the character of solidifying.When manufacturing with the tablet of polyurethane, after polyurethane liquid is imparted to fibrous substrate, being solidified by dry type, damp and hotly to solidify, wet type is solidified or their combination makes it solidify, and carries out drying, gives polyurethane thus to fibrous substrate.As the method making not show heat coagulable water dispersant type polyaminoester liquid and solidify, it is real in the industrial production that dry type is solidified, but in this situation, the transport phenomena that polyurethane concentrates on the top layer of fibrous substrate can occur, and the feel with the tablet of polyurethane has the tendency of sclerosis.In this situation, by preventing migration by the viscosity of thickener adjustment water dispersant type polyaminoester liquid.In addition, during for showing heat coagulable water dispersant type polyaminoester liquid, also can by adding thickener, carry out dry type and solidify and prevent migration.

The heat freezing temperature of water dispersant type polyaminoester liquid is preferably 40 ~ 90 DEG C.By making heat freezing temperature be more than 40 DEG C, the stability during storage of polyurethane liquid becomes good, the polyurethane when operating can be suppressed to be attached to machine first-class.In addition, by making heat freezing temperature be less than 90 DEG C, polyurethane can be suppressed to the transport phenomena on fibrous substrate top layer.

In a kind of mode of the present invention, in order to make heat freezing temperature described above, suitably can add heat coagulant.As heat coagulant, the inorganic salts such as such as sodium sulphate, magnesium sulfate, calcium sulfate and calcium chloride can be enumerated; The radical reaction initators etc. such as sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, azodiisobutyronitrile and benzoyl peroxide.

In preferred embodiment of the present invention, can by the impregnation of polyurethane liquid, to coat fibrous substrate first-class, solidified by dry type, damp and hotly to solidify, wet type is solidified or their combination makes polyurethane solidify.

Above-mentioned wet thermoset temperature is preferably more than the heat freezing temperature of polyurethane, is preferably 40 ~ 200 DEG C.By making wet thermoset temperature be more than 40 DEG C, more preferably more than 80 DEG C, the time till polyurethane solidifies can be shortened to, suppress transport phenomena further.On the other hand, by making wet thermoset temperature be less than 200 DEG C, more preferably less than 160 DEG C, the heat deterioration of polyurethane, PVA can be prevented.

The temperature that above-mentioned wet type is solidified is preferably more than the heat freezing temperature of polyurethane, is 40 ~ 100 DEG C.The temperature of solidifying by making the wet type in hot water is more than 40 DEG C, more preferably more than 80 DEG C, can shorten to the time till polyurethane solidifies, suppress transport phenomena further.

The temperature that above-mentioned dry type is solidified and baking temperature are preferably 80 ~ 140 DEG C.By making dry type setting temperature and baking temperature be more than 80 DEG C, more preferably more than 90 DEG C, productivity ratio is excellent.On the other hand, by making dry type setting temperature and baking temperature be less than 140 DEG C, more preferably less than 130 DEG C, the heat deterioration of polyurethane, PVA can be prevented.

In the present invention, heat treated can be carried out after making polyurethane solidify.By carrying out heat treated, the interface between polyurethane molecular is reduced, and becomes more strong polyurethane.In preferred mode, preferably after remove PVA from the sheet material imparting water dispersible polyurethane, carry out heat treated.The temperature of heat treated is preferably made to be 80 ~ 170 DEG C.

As the polyurethane used in the present invention, preferably by the polyurethane be obtained by reacting of polymer diatomic alcohol, organic diisocyanate and chain elongation agent.

As above-mentioned polymer diatomic alcohol, be not particularly limited, the dihydroxylic alcohols of such as polycarbonate-based, polyesters, polyethers, silicone based and fluorine class can be adopted, also can use the copolymer they combinations obtained.From the viewpoint of hydrolytic resistance, dihydroxylic alcohols that is polycarbonate-based and polyethers preferably can be used.In addition, from the viewpoint of light resistance and heat resistance, polycarbonate-based and polyesters can preferably be used.And then consider from hydrolytic resistance, balanced viewpoint between heat resistance and light resistance, more preferably the dihydroxylic alcohols of polycarbonate-based and polyesters, can particularly preferably use polycarbonate-based dihydroxylic alcohols.

Above-mentioned polycarbonate-based dihydroxylic alcohols manufactures by alkylene glycol and the ester exchange reaction of carbonic acid ester or the reaction etc. of phosgene or chloro-formate and alkylene glycol.

As above-mentioned alkylene glycol, be not particularly limited, the straight chain alkylen glycol such as such as ethylene glycol, propylene glycol, BDO, 1,5-PD, 1,6-hexylene glycol, 1,9-nonanediol, 1,10-decanediol can be enumerated; Neopentyl glycol, 3-methyl isophthalic acid, 5-pentanediol, 2,4-diethyl-1,5-PD, 2-methyl isophthalic acid, the side chain alkylene glycols such as 8-ethohexadiol; The aromatic diols such as cycloaliphatic diols, bisphenol-A such as Isosorbide-5-Nitrae-cyclohexanediol; Glycerol, trimethylolpropane and pentaerythrite etc.Can, for the polycarbonate-based dihydroxylic alcohols obtained by each independent alkylene glycol, also can be the copolymerization polycarbonate class dihydroxylic alcohols obtained by alkylene glycol of more than two kinds.

As above-mentioned polyesters dihydroxylic alcohols, can enumerate and make various low molecular weight polyols and polyacid condensation and the polyester-diol obtained.

As above-mentioned low molecular weight polyols, be not particularly limited, such as, can use and be selected from ethylene glycol, 1,2-propylene glycol, 1,3-PD, 1,3-BDO, 1,4-butanediol, 2,2-dimethyl-1,3-propylene glycol, 1,6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 1, one or more in 8-ethohexadiol, diethylene glycol (DEG), triethylene glycol, dipropylene glycol, 3 third glycol, cyclohexane-Isosorbide-5-Nitrae-glycol and cyclohexane-Isosorbide-5-Nitrae-dimethanol.In addition, the various alkylene oxide of addition in bisphenol-A can also be used and the addition product obtained.

In addition, as above-mentioned polyacid, be not particularly limited, one or two or more kinds that be such as selected from butanedioic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dodecanedioic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA) and six hydrogen M-phthalic acids can be enumerated.

As above-mentioned polyethers dihydroxylic alcohols, be not particularly limited, the copolymer glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol can enumerated and their combinations are obtained.

Number-average molecular weight for polymer diatomic alcohol of the present invention is preferably 500 ~ 4000.By making number-average molecular weight be more than 500, more preferably more than 1500, feel can be prevented hardening.In addition, by making number-average molecular weight be less than 4000, more preferably less than 3000, the intensity of polyurethane can be maintained as.

As above-mentioned organic diisocyanate, be not particularly limited, the fragrant same clan vulcabond such as aliphatic category vulcabond, methyl diphenylene diisocyanate and toluene di-isocyanate(TDI) such as such as hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, isophorone diisocyanate, xylylene diisocyanate can be enumerated, in addition, also above-mentioned organic diisocyanate can be combinationally used.Wherein, consider from sunproof viewpoint, can preferably use the aliphatic category vulcabond such as hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate and isophorone diisocyanate.

As above-mentioned chain elongation agent, be not particularly limited, the chain elongation agent of the di-alcohols such as chain elongation agent and ethylene glycol of the amine such as ethylenediamine and methylene dianiline can be used.In addition, the polyamines that polyisocyanates and water also can be used to react and obtain is as chain elongation agent.

For the object improving resistance to water, mar proof and hydrolytic resistance etc., also can according to be desirably in polyurethane and to use crosslinking agent.Crosslinking agent can be the external crosslinker added as the 3rd composition relative to polyurethane, in addition, also can be in polyurethane molecular structure, import the internal crosslinking agent becoming the reflecting point of cross-linked structure in advance.In the present invention, from the viewpoint of can comparatively be formed uniformly crosslinking points in polyurethane molecular structure, the minimizing of flexibility can be alleviated, preferably use internal crosslinking agent.

As above-mentioned crosslinking agent, the compound with isocyanate group, oxazolinyl, carbodiimide, epoxy radicals, melmac and silanol base etc. can be used.Wherein, due to crosslinked excessively carry out time, polyurethane can harden, and the feel of tablet also has hardening tendency, therefore from the viewpoint of reactive harmonious with flexibility, can preferably use the crosslinking agent with silanol base.

In addition, the polyurethane used in the present invention preferably has hydrophilic radical in molecular structure.By there is hydrophilic radical in molecular structure, the dispersion stabilization as water dispersant type polyaminoester can be improved.

As above-mentioned hydrophilic radical, the cationic such as such as quaternary ammonium salt can be adopted, the anionic species such as sulfonate, carboxylate, the nonionic classes such as polyethylene glycol, any hydrophilic radical in the combination of the combination of cationic and nonionic class and anionic species and nonionic class.Wherein, the hydrophilic radical of nonionic class (its worry not caused xanthochromia by light and caused disadvantage by neutralizer) can particularly preferably be used.

It should be noted that, during hydrophilic radical for anionic species, neutralizer becomes required, such as, when described neutralizer is the tertiary amine of ammonia, triethylamine, triethanolamine, triisopropanolamine, trimethylamine and dimethylethanolamine etc., due to heat when masking, drying, cause amine to produce volatilization, be released into outside system.Therefore, in order to suppress the deterioration of airborne release, operating environment, the device of the amine reclaiming volatilization must be introduced.In addition, also think when amine is not remained in end article and tablet by heating volatilization, be discharged in environment when the burning of goods etc.In contrast, during hydrophilic radical for nonionic class, owing to not using neutralizer, therefore do not need to introduce amine retracting device, do not have amine to remain in worry in tablet yet, therefore can preferably use.

In addition, when the neutralizer of above-mentioned anionic species hydrophilic radical is the hydroxide etc. of the alkali metal such as NaOH, potassium hydroxide and calcium hydroxide or alkaline-earth metal, alkalescence can be demonstrated when polyurethane portion gets wet, and when being the hydrophilic radical of nonionic class, owing to not using neutralizer, therefore do not need to worry to cause deterioration by the hydrolysis of polyurethane yet.

According to expectation, various additive can be contained for water dispersant type polyaminoester of the present invention, such as, the pigment such as carbon black, Phosphorus, halogen, the fire retardants such as silicone based and mineral-type, phenol, sulphur class and the antioxidant such as Phosphorus, benzotriazole, benzophenone, salicylate class, the ultra-violet absorbers such as cyanoacrylate and oxanilide class, hindered amines, the light stabilizers such as benzoates, the stabilizer against hydrolysis such as poly-carbodiimide, plasticizer, antistatic additive, surfactant, softener, waterproofing agent, solidify adjusting agent, viscosity modifier, dyestuff, preservative agent, antiseptic, deodorant, cellulose granules, the fillers such as microballoon, and silica, the inorganic particulates etc. such as titanium oxide.In addition, in order to make the space between fiber and polyurethane larger, can containing mineral-type, 2 such as sodium bicarbonates, the blowing agent of the organics such as 2 '-azo two [2-methyl-N-(2-hydroxyethyl) propionamide].

The ratio that contains of the polyurethane in the present invention for taking superfine fibre as the fibrous substrate of main composition composition is preferably 1 ~ 80 quality %.By making the ratio of polyurethane be more than 1 quality %, more preferably more than 5 quality %, can sheet strength be obtained, and coming off of fiber can be prevented.In addition, by making the compounding ratio of polyurethane be below 80 quality %, more preferably below 70 quality %, feel can be prevented hardening, obtaining good pile quality.

[the 5th operation]

Next, the 5th operation being described, that is, take superfine fibre as the operation removing PVA the fibrous substrate of main composition composition from what impart PVA and water dispersant type polyaminoester.

In preferred embodiment of the present invention, by removing PVA from the fibrous substrate after imparting polyurethane, obtain soft tablet.The method of removing PVA is not particularly limited, and such as, preferred embodiment is: be immersed in by sheet material in the hot water of 60 ~ 100 DEG C, shut out liquid as required with ironer etc., dissolves removing PVA thus.

In the manufacture method of tablet of the present invention, can at least comprise following operation: after giving water dispersant type polyaminoester to the fibrous substrate imparting PVA, through-thickness is cut into two halves.In the operation of giving PVA, due to migration, make PVA be attached to the top layer of fibrous substrate in a large number, the adhesion amount of PVA inner layer is few.Then, two halves are cut into by through-thickness after imparting water dispersant type polyaminoester, can obtain the tablet of following structure, described structure is: a small amount of attached water dispersion type polyurethane in the side that PVA adhesion amount is many, the structure of a large amount of attached water dispersion type polyurethane in the side that PVA adhesion amount is few.When the face (water dispersant type polyaminoester adheres to few face) adhered in a large number by PVA is as the pile face of tablet, owing to imparting PVA, large space is produced between polyurethane and the superfine fibre forming pile, the free degree is given to the fiber forming pile, the feel on surface becomes soft, can obtain good exterior quality and soft feel.Otherwise, when the face adhered on a small quantity by PVA (face that water dispersant type polyaminoester attachment is many) is as the pile face of tablet, although the fiber forming pile is strongly held by polyurethane, make length of pile shorter, but the good exterior quality with fine and close sense can be obtained, and then mar proof becomes good.And then, by comprising the operation being cut into two halves along sheet thickness direction, can enhance productivity.

In the present invention, napping process can be carried out at least one side of tablet, thus form pile on surface.The method forming pile is not particularly limited, and can adopt various method usually used in this field (utilizing the polishing etc. of sand paper etc.).When length of pile is too short, be difficult to obtain graceful outward appearance, time long, there is the tendency that balling-up easily occurs, therefore, length of pile is preferably 0.2 ~ 1mm.

In addition, in a kind of mode of the present invention, before napping process, can to the organosilicon etc. of tablet imparting as lubricant.By giving lubricant, utilize the napping of surface grinding to become easy realization, surface quality becomes very good, therefore preferably.In addition, also can give antistatic additive before napping process, by giving antistatic additive, not easily pile up on sand paper by grinding the grounds travel causing tablet to produce, therefore being preferred embodiment.

In a kind of mode of the present invention, tablet can dye.As colouring method, various method usually used in this field can be adopted, rub effect from the viewpoint of giving while dyeing to tablet, by tablet softnessization, preferably use the method for liquid-flow dyeing machine.

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

The dyestuff used in the present invention can be selected according to the kind of the fiber forming fibrous substrate, is not particularly limited, such as, if polyester fiber, then DISPERSE DYES can be used, if polyamide-based fiber, then can use ACID DYES or contain golden dyestuff, and then their combination can be used.When dyeing by DISPERSE DYES, reduction cleaning can be carried out after dyeing.

In addition, dyeing assistant is used also to be preferred embodiment when dyeing.By using dyeing assistant, the uniformity of dyeing, reappearance can be improved.In addition, bathe with dyeing or after dyeing, the dressing agent process using the softeners such as such as organosilicon, antistatic additive, waterproofing agent, fire retardant, photostabilizer and antiseptic etc. can be implemented together.

The density of the tablet of the present invention obtained by aforesaid operations is preferably 0.2 ~ 0.7g/cm ³.Be 0.2g/cm by making density ³above, more preferably 0.3g/cm ³above, appearance becomes fine and close, can show first-class quality.On the other hand, by making density be 0.7g/cm ³below, more preferably 0.6g/cm ³below, the feel of tablet can be prevented hardening.

[embodiment]

Next, illustrated in greater detail the manufacture method of tablet of the present invention by embodiment, but the present invention is not limited to these embodiments, in technical conceive of the present invention, those skilled in the art can carry out various deformation.

[evaluation method]

(1) organic solvent concentration of the PVA aqueous solution

PVA aqueous solution 1g is loaded, in 90 DEG C of heating 1 hour in 24mL heating tube.Gather 0.1mL with air hermetic entry needle from heating tube and gas occurs, import in GC/MS, carry out the concentration analysis of methyl acetate, acetic acid, methyl alcohol.It should be noted that, the detectability of GC/MS is lower than 0.1ppm.

(2) viscosity of the PVA aqueous solution

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

(3) tensile strength of PVA

10 quality %PVA aqueous dispersions being added polyethylene pallet (is longitudinally 5cm, is laterally 10cm, the degree of depth is 1cm) in, in 25 DEG C after air-dry 8 hours, serviceability temperature is the air drier heat treatment 2 hours of 120 DEG C, obtains the PVA dry type film of thick 100 μm.For this PVA dry type film, according to the A method recorded in JIS L1096 (2010) 8.14.1 (galley proof method (strip method)), use stretching test machine determination tensile strength.

(4) average single fiber diameter

Average single fiber diameter calculates as follows: scanning electron microscope (SEM) photo taking fibrous substrate or tablet surface with multiplying power 2000 times, and Stochastic choice 100 fibers measure single fiber diameter, calculating mean value.

When the fiber of formation fibrous substrate or tablet is odd-shaped cross section, calculate the periphery circular diameter of odd-shaped cross section as single fiber diameter.In addition, when circular cross-section and odd-shaped cross section mixing, the mixing of single fiber diameter visibly different cross section time etc., select to calculate to there is the corresponding hits of radical ratio to respective, amount to 100.But, be inserted with in fibrous substrate the fabric, the braided fabric that strengthen such, when measuring average single fiber diameter, the fabric of this enhancing, the fiber of braided fabric are not included in sample objects.

(5) stiffness of tablet

Based on the A method recorded in JIS L1096 (2010) 8.21.1 (45 ° of cantilever methods), make the test film being respectively 2cm × 15cm in machine and transverse direction, be positioned on the horizontal stand on the inclined-plane with 45 °, test film is slided, the position of other end when being read the central point of one end and the contact of incline plane of test film by scale.Stiffness is represented by the length (mm) of test film movement.Obtain the mean value of this movable length of 5 test films, as stiffness.

(6) appearance of tablet

For the appearance of tablet, using adult human male good for health status and each 10 of adult female (amounting to 20) as estimator, carry out 5 grades of evaluations as described below, using maximum evaluations as appearance by visual and sense evaluation.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 bad a little, but have fiber pile, outward appearance can be said to be good.

Evaluation between 2 grades: 3 grades and 1 grade.

1 grade: the non-constant of the dispersity of fiber 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 long 11mm along the direction vertical with the length direction of fiber, by neat for the fiber of 100 Gen Qie get bunchy, use and 97 these fibre bundles are configured as 6 heavy concentric circles (1, centers in the circle of diameter 110mm, in the circle of diameter 17mm 6, in the circle of diameter 37mm 13, in the circle of diameter 55mm 19, in the circle of diameter 74mm 26, in the circle of diameter 90mm 32, each circle in be at equal intervals) round-type brush (9700, nylon yarn), at load 8 pounds (about 3629g), rotary speed 65rpm, under the condition that number of revolutions is 50 times, make the surface abrasion of the circular sample (diameter 45mm) of tablet, measure the mass change of the sample before and after wearing and tearing, by the mean value of the mass change of 5 samples, i.e. abrasion decrement (mg) is considered as mar proof.

[embodiment 1]

(preparation of the PVA aqueous solution)

Be 99% by saponification degree, the degree of polymerization be 1400 PVA (Japanese synthetic chemistry Co., Ltd. NM-14) be added in the water of 25 DEG C, after being warming up to 90 DEG C, stir 2 hours while keep 90 DEG C, prepare the aqueous solution of solid state component 10 quality %, obtain the PVA aqueous solution.The methyl acetate contained in the PVA aqueous solution, acetic acid, methanol concentration are respectively 10.2ppm, 0.8ppm, 5.2ppm.

(fibrous substrate nonwoven fabric)

As sea component, copolymerization is used to have the polyethylene terephthalate of the 5-sodium sulfo isophthalate of 8mol%, as island component, use polyethylene terephthalate, with the recombination rate of sea component 45 quality %, island component 55 quality %, obtain the islands-in-sea bicomponent fibre of Dao Shuo 36 island/1 fiber, average single fiber diameter 17 μm.The islands-in-sea bicomponent fibre obtained is cut into the long 51mm of fiber as cut staple (staple), forms fiber web by carding machine and cross lapping machine, make nonwoven fabric by needling treatment.Be flood 2 minutes in the hot water of 98 DEG C in temperature by the nonwoven fabric obtained by aforesaid operations, make it shrink, at the temperature of 100 DEG C, drying 5 minutes, makes fibrous substrate nonwoven fabric.

(imparting of PVA)

Make in above-mentioned PVA aqueous solution impregnation to above-mentioned fibrous substrate nonwoven fabric, at the temperature of 140 DEG C, carry out heat drying 10 minutes, obtain the sheet material imparting PVA, wherein, relative to the fiber quality of fibrous substrate nonwoven fabric, the adhesion amount of PVA) be 30 quality %.

(fiber fine (de-sea))

The concentration sheet material of the above-mentioned PVA of imparting being immersed in the temperature being heated to 95 DEG C is in the sodium hydrate aqueous solution of 10g/ liter, processes 30 minutes, the de-extra large sheet material of the sea component of the islands-in-sea bicomponent fibre that has been removed.The average single fiber diameter of de-extra large sheet surface is 3 μm.

(preparation of polyurethane liquid)

For the solid state component of the polycarbonate-based self-emulsifying type polyurethane liquid (use polyhexamethylene carbonic acid ester as polyalcohol, use dicyclohexyl methyl hydride diisocyanate as isocyanates) of 100 parts by mass, add the ammonium persulfate as heat coagulant (APS) of 2 parts by mass, utilize water that entirety preparation is become solid state component 20 quality %, obtain water dispersant type polyaminoester liquid.Heat freezing temperature is 72 DEG C.

(imparting of polyurethane)

The impregnation of above-mentioned polycarbonate-based polyurethane liquid is made to impart in the de-extra large sheet material of PVA to above-mentioned, be after processing 5 minutes under the damp and hot atmosphere of 100 DEG C in temperature, heated-air drying 5 minutes at the temperature of baking temperature 120 DEG C, and then dry heat treatment is carried out 2 minutes at the temperature of 140 DEG C, obtain thus making sheet material that the adhesion amount of polyurethane (for the fiber quality of nonwoven fabric) is 30 quality %, that impart 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, the sheet material of the PVA given that has been removed.

(half cuts out napping dyeing reduction cleaning)

The sheet material through-thickness of the above-mentioned PVA of eliminating is cut into two halves, napping process is carried out by grinding double sanction face and contrary surface of using 240 objects annular sand paper (endless sandpaper), then liquid-flow dyeing machine (Circular) is used to utilize disperse dyeing, carry out reduction cleaning, obtain tablet.The appearance of the tablet obtained is good, and have soft feel, mar proof is also good.

[embodiment 2]

(preparation of the PVA aqueous solution)

Operate similarly to Example 1, obtain the PVA aqueous solution.

(fibrous substrate nonwoven fabric)

Operate similarly to Example 1, obtain fibrous substrate nonwoven fabric.

(imparting of PVA)

Use the PVA aqueous solution similarly to Example 1, regulate the mangle after impregnation thus the adhesion amount of change PVA, in addition, operate similarly to Example 1, sheet material that the adhesion amount (for the fiber quality of fibrous substrate nonwoven fabric) obtaining PVA is 20 quality %, that impart PVA.

(fiber fine (de-sea))

Operate similarly to Example 1, obtain de-extra large 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 the sheet material imparting polyurethane.

(removing of PVA)

Operate similarly to Example 1, be removed the sheet material of PVA.

(half cuts out napping dyeing reduction cleaning)

Operate similarly to Example 1, obtain tablet.The appearance of the tablet obtained is good, and have soft feel, mar proof is also good.

[embodiment 3]

(preparation of the PVA aqueous solution)

Operate similarly to Example 1, obtain the PVA aqueous solution.

(fibrous substrate nonwoven fabric)

As sea component, copolymerization is used to have the polyethylene terephthalate of the 5-sodium sulfo isophthalate of 8mol%, as island component, use polyethylene terephthalate, with the recombination rate of sea component 20 quality %, island component 80 quality %, obtain the islands-in-sea bicomponent fibre of Dao Shuo 16 island/1 fiber, average single fiber diameter 30 μm.The islands-in-sea bicomponent fibre obtained is cut into the long 51mm of fiber as cut staple, forms fiber web by carding machine and cross lapping machine, make nonwoven fabric by needling treatment.Be flood 2 minutes in the hot water of 98 DEG C in temperature by the nonwoven fabric obtained by aforesaid operations, make it shrink, at the temperature of 100 DEG C, drying 5 minutes, makes fibrous substrate nonwoven fabric.

(imparting of PVA)

Use the PVA aqueous solution similarly to Example 1, sheet material that the adhesion amount (for the fiber quality of fibrous substrate nonwoven fabric) obtaining PVA is 30 quality %, that impart PVA.

(fiber fine (de-sea))

Similarly to Example 1 above-mentioned fibrous substrate nonwoven fabric is processed, the de-extra large sheet material of the sea component of the islands-in-sea bicomponent fibre that has been removed.The average single fiber diameter of de-extra large sheet surface is 4.4 μm.

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

(removing of PVA)

Operate similarly to Example 1, be removed the sheet material of PVA.

(half cuts out napping dyeing reduction cleaning)

[embodiment 4]

(preparation of the PVA aqueous solution)

Be 99% by saponification degree, the degree of polymerization be 1100 PVA (Japanese synthetic chemistry Co., Ltd. NM-11) be added in the water of 25 DEG C, after being warming up to 90 DEG C, stir 2 hours while keep 90 DEG C, prepare the aqueous solution of solid state component 10 quality %, obtain the PVA aqueous solution.The methyl acetate contained in the PVA aqueous solution, acetic acid, methanol concentration are respectively 7.2ppm, 0.4ppm, 2.4ppm.

(fibrous substrate nonwoven fabric)

Use fibrous substrate nonwoven fabric similarly to Example 1.

(imparting of PVA)

Make in above-mentioned PVA aqueous solution impregnation to above-mentioned fibrous substrate nonwoven fabric, heat drying is carried out 10 minutes, sheet material that the adhesion amount (for the fiber quality of fibrous substrate nonwoven fabric) obtaining PVA is 30 quality %, that impart PVA at the temperature of 140 DEG C.

(fiber fine (de-sea))

Operate similarly to Example 1, obtain de-extra large sheet material from above-mentioned fibrous substrate nonwoven fabric.

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

(removing of PVA)

Operate similarly to Example 1, be removed the sheet material of PVA.

(half cuts out napping dyeing reduction cleaning)

[embodiment 5]

(preparation of the PVA aqueous solution)

Be 99% by saponification degree, the PVA of the degree of polymerization 2600 (Japanese synthetic chemistry Co., Ltd. NH-26) is added in the water of 25 DEG C, after being warming up to 90 DEG C, stir 2 hours while keep 90 DEG C, prepare the aqueous solution of solid state component 10 quality %, obtain the PVA aqueous solution.The methyl acetate contained in the PVA aqueous solution, acetic acid, methanol concentration are respectively 32.2ppm, 8.3ppm, 20.1ppm.

(fibrous substrate nonwoven fabric)

Use fibrous substrate nonwoven fabric similarly to Example 1.

(imparting of PVA)

Make in above-mentioned PVA aqueous solution impregnation to above-mentioned fibrous substrate nonwoven fabric, heat drying is carried out 10 minutes, sheet material that the adhesion amount (for the fiber quality of fibrous substrate nonwoven fabric) obtaining PVA is 10 quality %, that impart PVA at the temperature of 140 DEG C.

(fiber fine (de-sea))

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

(removing of PVA)

Operate similarly to Example 1, be removed the sheet material of PVA.

(half cuts out napping dyeing reduction cleaning)

[embodiment 6]

(preparation of the PVA aqueous solution)

Operate similarly to Example 1, obtain the PVA aqueous solution.

(fibrous substrate nonwoven fabric)

As sea component, copolymerization is used to have the polyethylene terephthalate of the 5-sodium sulfo isophthalate of 8mol%, as island component, use polyethylene terephthalate, with the recombination rate of sea component 20 quality %, island component 80 quality %, obtain the islands-in-sea bicomponent fibre of Dao Shuo 16 island/1 fiber, average single fiber diameter 30 μm.The islands-in-sea bicomponent fibre obtained is cut into the long 51mm of fiber as cut staple, fiber web is formed by carding machine and cross lapping machine, on the two sides of net, laminated 84dtex-72f, the twist employing polyethylene terephthalate (PET) is the plain cloth of the high twist yarn of 2000T/m, makes nonwoven fabric by needling treatment.Be flood 2 minutes in the hot water of 98 DEG C in temperature by the nonwoven fabric obtained by aforesaid operations, make it shrink, at the temperature of 100 DEG C, drying 5 minutes, makes fibrous substrate nonwoven fabric.

(imparting of PVA)

Make in above-mentioned PVA aqueous solution impregnation to above-mentioned fibrous substrate nonwoven fabric, heat drying is carried out 10 minutes, sheet material that the adhesion amount (for the fiber quality of fibrous substrate nonwoven fabric) obtaining PVA is 15 quality %, that impart PVA at the temperature of 140 DEG C.

(fiber fine (de-sea))

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

(removing of PVA)

Operate similarly to Example 1, be removed the sheet material of PVA.

(half cuts out napping dyeing reduction cleaning)

[embodiment 7]

(preparation of the PVA aqueous solution)

Operate similarly to Example 1, obtain the PVA aqueous solution.

(fibrous substrate nonwoven fabric)

Operate similarly to Example 1, obtain fibrous substrate nonwoven fabric.

(imparting of PVA)

Operate similarly to Example 1, sheet material that the adhesion amount (for the fiber quality of fibrous substrate nonwoven fabric) obtaining PVA is 30 quality %, that impart PVA.

(fiber fine (de-sea))

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

(preparation of polyurethane liquid)

For the solid state component of the polycarbonate-based self-emulsifying type polyurethane liquid (use polyhexamethylene carbonic acid ester as polyalcohol, use dicyclohexyl methyl hydride diisocyanate as isocyanates) of 100 parts by mass, add the thickener (SAN NOPCO Ltd. SN THICKENER 627N) of 5 parts by mass, utilize water that entirety preparation is become polyurethane solid state component 20 quality %, obtain water dispersant type polyaminoester liquid.

(imparting of polyurethane)

The impregnation of above-mentioned polyurethane liquid is made to impart in the de-extra large sheet material of PVA to above-mentioned, heated-air drying 30 minutes at the temperature of baking temperature 100 DEG C, obtains making sheet material that the adhesion amount of polyurethane (for the fiber quality of nonwoven fabric) is 30 quality %, that impart polyurethane thus.

(removing of PVA)

Operate similarly to Example 1, be removed the sheet material of PVA.

(half cuts out napping dyeing reduction cleaning)

[embodiment 8]

(preparation of the PVA aqueous solution)

Operate similarly to Example 5, obtain the PVA aqueous solution.

(fibrous substrate nonwoven fabric)

Use fibrous substrate nonwoven fabric similarly to Example 1.

(imparting of PVA)

(fiber fine (de-sea))

Operate similarly to Example 1, obtain de-extra large sheet material by above-mentioned fibrous substrate nonwoven fabric.

(preparation of polyurethane liquid)

(imparting of polyurethane)

The impregnation of above-mentioned polyurethane liquid is made to impart in the de-extra large sheet material of PVA to above-mentioned, in the warm water of 80 DEG C, make it solidify, in 100 DEG C of heated-air dryings 15 minutes, obtain thus making sheet material that the adhesion amount of polyurethane (for the fiber quality of nonwoven fabric) is 30 quality %, that impart polyurethane.

(removing of PVA)

Operate similarly to Example 1, be removed the sheet material of PVA.

(half cuts out napping dyeing reduction cleaning)

[comparative example 1]

(preparation of the PVA aqueous solution)

Operate similarly to Example 1, obtain the PVA aqueous solution.

(fibrous substrate nonwoven fabric)

Use fibrous substrate nonwoven fabric similarly to Example 1.

(fiber fine (de-sea))

The concentration fibrous substrate nonwoven fabric obtained by aforesaid operations being immersed in the temperature being heated to 95 DEG C is in the sodium hydrate aqueous solution of 10g/ liter, processes 10 minutes, the de-extra large sheet material of the sea component of the islands-in-sea bicomponent fibre that has been removed.The average single fiber diameter of de-extra large sheet surface is 3 μm.

(imparting of PVA)

The PVA aqueous solution obtained in impregnation embodiment 1 in above-mentioned de-extra large sheet material, carries out heat drying 10 minutes at the temperature of 140 DEG C, sheet material that the adhesion amount (for de-extra large sheet material) obtaining PVA is 30 quality %, that impart PVA.

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

The above-mentioned polycarbonate-based polyurethane liquid of impregnation in the de-extra large sheet material of PVA is imparted above-mentioned, be after processing 5 minutes under the damp and hot atmosphere of 100 DEG C in temperature, heated-air drying 5 minutes at the temperature of baking temperature 120 DEG C, and then dry heat treatment is carried out 2 minutes at the temperature of 140 DEG C, obtain thus making sheet material that the adhesion amount of polyurethane (for superfine fibre quality) is 30 quality %, that impart polyurethane.

(removing of PVA)

Operate similarly to Example 1, be removed the sheet material of PVA.

(half cuts out napping dyeing reduction cleaning)

Operate similarly to Example 1, obtain tablet.Although the tablet appearance obtained is good, have soft feel, abrasion decrement is many.

[comparative example 2]

(preparation of the PVA aqueous solution)

By saponification degree 87%, the degree of polymerization be 500 PVA (Japanese synthetic chemistry Co., Ltd. GL-05) be added in the water of 25 DEG C, after being warming up to 90 DEG C, stir 2 hours while keep 90 DEG C, prepare the aqueous solution of solid state component 10 quality %, obtain the PVA aqueous solution.The methyl acetate contained in the PVA aqueous solution, acetic acid, methanol concentration are respectively 70.1ppm, 40.1ppm, 100.3ppm.

(fibrous substrate nonwoven fabric)

Use fibrous substrate nonwoven fabric similarly to Example 1.

(imparting of PVA)

The above-mentioned PVA aqueous solution of impregnation in above-mentioned fibrous substrate nonwoven fabric, regulate the mangle after impregnation thus the adhesion amount of change PVA, in addition, operate similarly to Example 1, sheet material that the adhesion amount (for the fiber quality of fibrous substrate nonwoven fabric) obtaining PVA is 10 quality %, that impart PVA.

(fiber fine (de-sea))

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

(removing of PVA)

Operate similarly to Example 1, be removed the sheet material of PVA.

(half cuts out napping dyeing reduction cleaning)

Operate similarly to Example 1, obtain tablet.The tablet obtained does not become uniform imparting state, appearance bad (dispersity of fiber is poor, and pile is felt without densification), Boardy Feeling because a PVA part is dissolved in alkaline aqueous solution and water dispersant type polyaminoester liquid.

[comparative example 3]

(preparation of the PVA aqueous solution)

Be 99% by saponification degree, the degree of polymerization be 500 PVA (Japanese synthetic chemistry Co., Ltd. NL-05) be added in the water of 25 DEG C, after being warming up to 90 DEG C, stir 2 hours while keep 90 DEG C, prepare the aqueous solution of solid state component 10 quality %, obtain the PVA aqueous solution.The methyl acetate contained in the PVA aqueous solution, acetic acid, methanol concentration are respectively 6.1ppm, 0.4ppm, 1.1ppm.

(fibrous substrate nonwoven fabric)

Use fibrous substrate nonwoven fabric similarly to Example 1.

(imparting of PVA)

(fiber fine (de-sea))

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

(removing of PVA)

Operate similarly to Example 1, be removed the sheet material of PVA.

(half cuts out napping dyeing reduction cleaning)

[comparative example 4]

(preparation of the PVA aqueous solution)

Operate similarly to Example 1, obtain the PVA aqueous solution.

(fibrous substrate nonwoven fabric)

Use fibrous substrate nonwoven fabric similarly to Example 1.

(imparting of PVA)

Use the PVA aqueous solution similarly to Example 1, regulate the mangle after impregnation thus the adhesion amount of change PVA, in addition, operate similarly to Example 1, sheet material that the adhesion amount (for the fiber quality of fibrous substrate nonwoven fabric) obtaining PVA is 55 quality %, that impart PVA.

(fiber fine (de-sea))

(preparation of polyurethane liquid)

Use water dispersant type polyaminoester liquid similarly to Example 1.

(imparting of polyurethane)

(removing of PVA)

Operate similarly to Example 1, be removed the sheet material of PVA.

(half cuts out napping dyeing reduction cleaning)

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

[comparative example 5]

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

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

[table 1]

[table 2]

The tablet obtained in embodiment 1 ~ 8, equal appearance is good, and have soft feel, mar proof is also good.On the other hand, the mar proof of the tablet obtained in comparative example 1 and 4 is poor, and the appearance of the tablet obtained in comparative example 2 ~ 5 is all bad.In addition, the Boardy Feeling of the tablet obtained in comparative example 2,3,5.

Utilizability in industry

Can be used as suitably according to the tablet that the present invention obtains: the skin material as the seat in the vehicle chamber of furniture, chair and wall material, automobile, electric car and airborne vehicle etc., ceiling and upholstery etc. has the interior material of very graceful outward appearance, the vamp, decoration (trim) etc. of the footwear such as shirt, jacket, playshoes, sport footwear, Men's Shoes and women's shoes, the dress material material of bag, waistband, wallet etc. and the part for them, the industrial materials such as cleaning wiping cloth, abrasive cloth and CD curtain.

Claims

1. a manufacture method for tablet, is characterized in that, carries out following operation 1 ~ 5 successively,

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

Operation 4: to described impart polyvinyl alcohol with superfine fibre be main composition composition fibrous substrate give water dispersant type polyaminoester;

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

2. the manufacture method of tablet as claimed in claim 1, is characterized in that, the concentration of the methyl acetate of described polyvinyl alcohol water solution, acetic acid, methyl alcohol is respectively 0.1 ~ 50ppm.

3. the manufacture method of tablet as claimed in claim 1 or 2, it is characterized in that, the operation showing superfine fibre is the operation carrying out processing in alkaline aqueous solution.

4. the manufacture method of the tablet according to any one of claims 1 to 3, is characterized in that, comprises the operation of giving described polyvinyl alcohol, carrying out heating in 80 ~ 170 DEG C.

5. the manufacture method of the tablet according to any one of Claims 1 to 4, is characterized in that, described to manifest with superfine fibre the fibrous substrate that fiber type is main composition composition integrated with fabric and/or braided fabric complexing.

6. a tablet, is characterized in that, the density of the tablet obtained by the manufacture method of the tablet according to any one of Claims 1 to 5 is 0.2 ~ 0.7g/cm ³.