CN106029976B

CN106029976B - Tablet and its manufacturing method

Info

Publication number: CN106029976B
Application number: CN201580010454.XA
Authority: CN
Inventors: 村原寿; 中井俊郎; 中井俊一郎; 土本贵大
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2014-02-27
Filing date: 2015-02-23
Publication date: 2018-08-31
Anticipated expiration: 2035-02-23
Also published as: EP3112530B1; TW201542635A; TWI711660B; KR20160127019A; KR102297654B1; EP3112530A4; US20200149216A1; US20160362832A1; JP6551227B2; WO2015129602A1; JPWO2015129602A1; EP3112530A1; CN106029976A

Abstract

The present invention relates to the manufacturing methods for the tablet that organic solvent is not used in manufacturing process, provide a kind of surface quality and the good tablet of feel and its manufacturing method.The tablet of the present invention is to assign the macromolecular elastomer with hydrophilic radical as tablet made of binder to the fibrous substrate formed by superfine fibre, in the section obtained by the through-thickness cutting of tablet, in the macromolecular elastomer observed in cutting section, relative to the area in the artificial leather section in field of view, independently and there are 50 μm²The possession ratio of the part of above area of section is 0.1% or more and 5.0% or less.The manufacturing method of the tablet of the present invention is following methods：In the fibrous substrate to being formed by superfine fibre assigns manufacturing method of the macromolecular elastomer with hydrophilic radical as tablet made of binder, the aqueous resin dispersion containing the macromolecular elastomer and thickener being dispersed in water is assigned to fibrous substrate, so that macromolecular elastomer is solidified in the hot water that temperature is 50~100 DEG C.

Description

Tablet and its manufacturing method

Technical field

The present invention relates to organic solvent, environmental-friendly tablet manufacturing method is not used in manufacturing process, especially It is related to surface quality and the good tablet of feel and its manufacturing method.

Background technology

Mainly have natural leather unexistent excellent by the tablet that the fibrous substrates such as non-woven fabrics and polyurethane are formed Feature has been widely used in the multiple uses such as artificial leather.Especially for the tablet for having used polyester fiber matter base material For, due to excellent in light-resistance, in the use on the way such as dress material, seat surface rapidoprint and automotive interior trim material Increase year by year.

As manufacture when tablet, the combination of the following processes of generally use：The organic solvent solution of polyurethane is set to contain After being dipped in fibrous substrate, obtained fibrous substrate is impregnated in the non-solvent i.e. water or aqueous solutions of organic solvent of polyurethane In, so that polyurethane wet type is solidified.In this case, as solvent, that is, organic solvent of polyurethane, N, N- dimethyl methyls can be used The miscible organic solvents such as amide.However, organic solvent is usually big to the harm of human body, environment, therefore, in manufacture tablet When, it is strongly required the method without using organic solvent.

As its specific solution, following methods are had studied：Using including that hydrophilic radical and will gather in the molecule Water dispersant type polyaminoester made of urethane is dispersed in water replaces the polyurethane of previous organic solvent class.

However, water dispersant type polyaminoester dispersion liquid obtained by water dispersant type polyaminoester will be made to disperse in a liquid is impregnated in fibre Tablet has that feel is easy to be hardened obtained from tieing up matter base material and polyurethane being made to solidify.

One of the main reasons for this is that the solidification mode of the two is different.That is, the solidification mode of organic solvent class polyurethane liquid It is the so-called wet type solidification mode that solvent displacement is carried out to the polyurethane molecular of dissolving in organic solvent with water and is solidified, If being observed in the form of polyurethane film, low density perforated membrane is formed.Therefore, it is impregnated in fibrous substrate by polyurethane And in the case of so that it is solidified, the bond area of fiber and polyurethane is reduced, and forms soft tablet.

On the other hand, the mainstream solidification mode of water dispersant type polyaminoester is following damp and hot solidification modes, that is, mainly by adding Heat destroys the hydration status of water dispersant type polyaminoester dispersion liquid, so that polyaminoester emulsion is aggregated with one another, is thus solidified, is obtained Polyurethane film structure become the high non-porous film of density.Therefore, fibrous substrate is bonding with polyurethane becomes close, securely The interlaced sections of fiber are held, so feel hard.

In order to improve the feel brought by the application water dispersant type polyaminoester, that is, in order to inhibit caused by polyurethane The holding to fiber interweaving point, it is proposed that make the polyurethane in fibrous substrate structure become porous structure technology.

Specifically, it is proposed that following methods：The water-dispersion type containing foaming agent is assigned to fibrous substrates such as non-woven fabrics Polyurethane liquid makes foaming agent foam by heating, and the structure of the polyurethane in fibrous substrate is made to become porous structure (referring to special Sharp document 1.).In the motion, by making water dispersant type polyaminoester be porous, to make the bond area of fiber and polyurethane subtract It is few, the hold of fiber interweaving point is weakened, can be obtained the tablet with excellent handle of soft-touch, but with imparted The case where solvent class polyurethane, is compared, and there are still the trend for lacking flexibility.

In addition, becoming the technology of porous structure as the structure of the polyurethane made in fibrous substrate, it is proposed that by right The water dispersant type polyaminoester dispersion liquid containing association thickener is assigned in fibrous substrate and carries out damp and hot solidification, to make water Disperseing type polyurethane becomes porous method (referring to patent document 2).In the motion, it is again by water dispersant type polyaminoester is made It is porous, to make the bond area of fiber and polyurethane reduce, the hold of fiber interweaving point is weakened, soft-touch can be obtained The tablet with excellent handle, but compared with the case where imparting organic solvent class polyurethane, there are still lack flexibility Trend.

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2011-214210 bulletins

Patent document 2：No. 4042016 bulletins of Japanese Patent No.

Invention content

Therefore, in view of the background of the above-mentioned prior art, it is an object of the present invention to by environmental-friendly manufacturing process, It provides with not a halfpenny the worse uniform sense compared with the artificial leather for applying organic solvent class polyurethane and with graceful surface The tablet and its manufacturing method of quality and good feel.

A kind of type polyurethane is dissipated to realize the more of polyurethane by applied moisture it is further an object that providing Pore structure, to have and apply the extremely similar crease recovery of artificial leather obtained from solvent polyurethane and softness The tablet and its manufacturing method of property.

Present invention the above subject to be solved, tablet of the invention are to being formed by superfine fibre and/or superfine fibre beam Fibrous substrate assign the macromolecular elastomer with hydrophilic radical as tablet made of binder (binder), It is characterized in that, obtained by the through-thickness cutting of the tablet in section, the high score observed in cutting section In elastic body, relative to the area in the artificial leather section in field of view, independently and there are 50 μm²Above area of section Partial possession ratio is 0.1% or more and 5.0% or less.

The preferred embodiment of tablet according to the present invention, the section obtained by the through-thickness cutting of the tablet In, 1% or more and the 35% or less of the periphery of superfine fibre and/or superfine fibre area of beam is covered by macromolecular elastomer envelope Lid.

The preferred embodiment of tablet according to the present invention, tablet as claimed in claim 1 or 2, which is characterized in that institute Stating macromolecular elastomer has via structure obtained by cross-linking agents.

Present invention the above subject to be solved, tablet of the invention are characterized in that, in the fibre to being formed by superfine fibre Matter base material is tieed up to assign in manufacturing method of the macromolecular elastomer with hydrophilic radical as tablet made of binder, it is right Fibrous substrate assigns the aqueous resin dispersion containing the macromolecular elastomer and thickener being dispersed in water, and is 50 in temperature Solidify the macromolecular elastomer in~100 DEG C of hot water.

Non newtonian is presented in the preferred embodiment of the manufacturing method of tablet according to the present invention, the aqueous resin dispersion Property.

The preferred embodiment of the manufacturing method of tablet according to the present invention, the thickener are nonionic class thickener.

Thixotropy is presented in the preferred embodiment of the manufacturing method of tablet according to the present invention, the aqueous resin dispersion.

The preferred embodiment of the manufacturing method of tablet according to the present invention, the thickener that the aqueous resin dispersion contains To thicken polysaccharide.

The preferred embodiment of the manufacturing method of tablet according to the present invention, the thickener are guar gum.

The preferred embodiment of the manufacturing method of tablet according to the present invention, the aqueous resin dispersion contain thermocoagulation Agent.

The preferred embodiment of the manufacturing method of tablet according to the present invention, the aqueous resin dispersion contain crosslinking agent.

In accordance with the invention it is possible to obtain following tablets by environmental-friendly manufacturing process, the tablet makes moisture The case where dissipating type polyurethane as porous structure, capable of reaching with to fibrous substrate imparting organic solvent class polyurethane extremely phase As crease recovery and flexibility, and contain and apply organic solvent class polyurethane artificial leather equal extent it is equal Even raising length feels excellent graceful surface quality and soft and crease recovery also excellent good hand with fiber densification Sense.

Description of the drawings

Fig. 1 is the attached drawing replacement SEM photograph in the artificial leather section obtained in the embodiment of the present invention 13.

Fig. 2 be the present invention comparative example 4 in the obtained attached drawing replacement SEM photograph in artificial leather section.

Fig. 3 is for illustrating 50 μm²The computational methods of the possession ratio of the aporate block of above macromolecular elastomer The attached drawing of summary is substituted with reference to SEM photograph.

Fig. 4 is the attached drawing replacement reference of the macromolecular elastomer envelope rate computational methods for illustrating superfine fibre section SEM photograph.

Specific implementation mode

[about tablet]

First, the tablet of the present invention is illustrated.

The tablet of the present invention is to assign being gathered by water-dispersion type to fibrous substrates such as the non-woven fabrics that is formed by superfine fibre The macromolecular elastomer that the resin that urethane etc. contains hydrophilic radical is formed is formed as binder.

As the fiber for constituting fibrous substrate, can enumerate by polyethylene terephthalate, poly terephthalic acid fourth The polyamide such as the polyester such as diol ester, polytrimethylene-terephthalate and polylactic acid, nylon 6, nylon66 fiber, acrylic compounds, poly- second Alkene, polypropylene and thermoplastic cellulose etc. can carry out the fiber that the thermoplastic resin of melt spinning is formed.Wherein, from intensity, ruler From the viewpoint of very little stability and light resistance, polyester fiber is preferably used.Alternatively, it is also possible to which the different fiber of raw material is mixed It closes and constitutes fibrous substrate.

Can be circular section as the cross sectional shape of superfine fibre, also can be used the polygons such as oval, flat and triangle, The cross sectional shape of the odd-shaped cross sections such as fan-shaped and cross.

The average single fiber diameter for constituting the superfine fibre of fibrous substrate is preferably 0.1~7 μm.By making average single fiber Dimension diameter is preferably 7 μm or less, more preferably 6 μm or less, further preferably 5 μm hereinafter, the softness for having excellent can be obtained The tablet of property, excellent pile quality.On the other hand, by making average single fiber diameter be preferably 0.1 μm or more, more preferably Be 0.3 μm or more, further preferably 0.7 μm or more, particularly preferably 1 μm or more, to dye after colour rendering, utilize sand The dispersibility and fibrillation easiness of bundle fiber when the processing of the piles such as the grinding of the progress such as paper are excellent.

As the form of the fibrous substrate formed by superfine fibre, woven fabric, knitted fabric and non-woven fabrics etc. can be used.Its In, the surface quality of tablet when due to progress surface nappy processing is good, thus it is preferable to use non-woven fabrics.

As non-woven fabrics, any one of staple fiber nonwoven fabric and nonwoven fabric of long fibers can be used, from feel, quality side Face considers, preferably uses staple fiber nonwoven fabric.

The fibre length of staple fiber in staple fiber nonwoven fabric is preferably 25mm or more and 90mm hereinafter, more preferably 35mm Above and 75mm or less.By making fibre length be 25mm or more, the tablet of excellent in wear resistance can be obtained by complexing. In addition, by make fibre length be 90mm hereinafter, the superior tablet of feel, quality can be obtained.

When the fibrous substrate formed by superfine fibre is non-woven fabrics, Preferable scheme is that：The non-woven fabrics has ultra-fine fibre Structure made of beam (fibre bundle) complexing of dimension.By making superfine fibre be complexed with the state of beam, the intensity of tablet improves.On Stating the non-woven fabrics of form can obtain in the following manner：Superfine fibre is shown fiber type in advance to complex with one another, is then made ultra-fine Fiber shows.

It, can be in the inside of the non-woven fabrics for the purpose of improving intensity when superfine fibre or its fibre bundle constitute non-woven fabrics It is inserted into woven fabric, knitted fabric.Constitute such woven fabric, the average single fiber diameter of fiber of knitted fabric is preferably 0.1~10 μ M or so.

It is the resin containing hydrophilic radical as the elastomeric polymer as binder in the tablet of the present invention, it can Enumerate the copolymerization of water-dispersion type organic siliconresin, dispersed acrylic resin and water dispersant type polyaminoester resin, these resins Object, wherein from the aspect of feel, preferably use water dispersant type polyaminoester.

The use of by number-average molecular weight is preferably preferably 500 or more 5000 macromolecular multi-components below as polyurethane Resin obtained from the reaction of alcohol, organic multiple isocyanate and chain extender.In addition, in order to improve water dispersant type polyaminoester dispersion liquid Stability, can and with hydrophilic radical the compound containing active hydrogen component.By the number for making macromolecule polyol Average molecular weight is 500 or more, more preferably 1500 or more, can prevent from feeling hard, in addition, by making the number-average molecular weight be 5000 or less, 4000 are more preferably hereinafter, being able to maintain that the intensity as the polyurethane as binder.

As the polyether alcohol in above-mentioned macromolecule polyol, it can enumerate and be incited somebody to action as initiator using polyalcohol, polyamines Ethylene oxide, propylene oxide, epoxy butane, styrene oxide (styrene oxide), tetrahydrofuran, epichlorohydrin and cyclohexene Equal monomers carry out polyalcohol obtained from addition polymerization, and with Bronsted acid, lewis acid and cationic catalyst etc. are to urge Above-mentioned monomer is carried out polyalcohol obtained from ring-opening polymerisation by agent.Specifically, polyethylene glycol can be enumerated, polypropylene glycol, gathered Butanediol etc. and the polyol for being composed them.

As polyester polyol, can enumerate polyester obtained from various low molecular weight polyols and polyacid condensation is more First alcohol, as by polyalcohol obtained from lactone ring opening polymerization etc..

As low molecular weight polyols, for example, can enumerate selected from ethylene glycol, 1,3-PD, 1,4-butanediol, 1,5- penta The straight-chain alkyl-subs glycol such as glycol, 1,6- hexylene glycols, 1,7- heptandiols, 1,8- ethohexadiols, 1,9- nonanediols, 1,10- decanediols, Neopentyl glycol, 3- methyl-1s, 5- pentanediols, 2,4- diethyl -1,5-PD, 2- methyl-1s, the branched alkylens such as 8- ethohexadiols Base glycol, 1 in aromatic diols such as the ester ring types such as Isosorbide-5-Nitrae-cyclohexanediol glycol and bis- (beta-hydroxy ethyoxyl) benzene of Isosorbide-5-Nitrae-etc. Kind or two or more.In addition, also can various epoxyalkane and bisphenol-A be carried out addition product obtained from addition is used as low molecular weight Polyalcohol.

In addition, as polyacid, for example, can enumerate selected from succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, pungent Diacid, azelaic acid, decanedioic acid, dodecanedioic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA) and hexahydro isophthalic diformazan It is one kind or two or more in acid etc..

As poly-lactone polyol, can enumerate using polyalcohol as initiator and by individual gamma-butyrolacton, gamma-valerolactone, And 6-caprolactone etc. or the mixture of more than two kinds in them etc. carry out poly-lactone polyol etc. obtained from ring-opening polymerisation.

As polycarbonate-based polyalcohol, can enumerate through the carbon such as polyalcohol and dialkyl carbonate, diaryl carbonate Compound obtained from the reaction of ester compound.

As the polyalcohol in the manufacture raw material of polycarbonate polyol, it may be used in the manufacture raw material of polyester polyol The polyalcohol enumerated.As dialkyl carbonate, dimethyl carbonate, diethyl carbonate etc. can be used, as diaryl carbonate, Dipheryl carbonate base ester etc. can be enumerated.

In the macromolecular elastomer containing hydrophilic radical used in the present invention, parent is assigned as to macromolecular elastomer The ingredient of aqueous group, for example, the active hydrogen component containing hydrophilic radical can be enumerated.As the activity containing hydrophilic radical Hydrogen ingredient can enumerate the change containing nonionic group and/or anionic group and/or cationic groups and reactive hydrogen Close object etc..As the compound with nonionic group and reactive hydrogen, the active hydrogen component comprising 2 or more or 2 can be enumerated A above isocyanate group and the polyoxyethylene glycol for being 250~9000 with molecular weight on side chain The trihydroxylic alcohols such as the compound of (polyoxyethylene glycol) group etc. and trimethylolpropane, tri hydroxy methyl butane Deng.

In addition, as the compound with anionic group and reactive hydrogen, 2,2- dihydromethyl propionic acids, 2,2- can be enumerated The compounds containing carboxyl such as dimethylolpropionic acid, 2,2- dihydroxymethyl valeric acids and their derivative, 1,3- phenylenediamines -4,6- Disulfonic acid, 3- (2,3- dihydroxy propoxyl group) -1- propane sulfonic acid etc. contain sulfonic compound and their derivative, Yi Jiyong Salt obtained from neutralizer neutralizes above compound.

In addition, as the compound containing cationic groups and reactive hydrogen, 3- dimethyl amino propanols, N- first can be enumerated Compound containing tertiary amino and their derivatives such as base diethanol amine, N- propyl diethanol amine.

The above-mentioned active hydrogen component containing hydrophilic radical can also be with the shape of salt obtained from being neutralized with neutralizer State uses.

For for the active hydrogen component containing hydrophilic radical in polyurethane molecular, from the machine of polyurethane resin From the viewpoint of tool intensity and dispersion stabilization, it is preferable to use 2,2- dihydromethyl propionic acids, 2,2- dimethylolpropionic acids and they Neutralization salt.

By importing especially hydroxyl, sulfonic group in the above-mentioned active hydrogen component containing hydrophilic radical in polyurethane And carboxyl etc., to which the hydrophily of polyurethane molecular can not only be improved, but also can be right by aftermentioned crosslinking agent Three-dimensional crosslinking structure is assigned in polyurethane molecular, to improve physical property, it is therefore preferable that suitably selecting above-mentioned containing hydrophilic radical Active hydrogen component and manufactured.

As chain extender, it may be used at the compound used in previous polyurethane manufacture, wherein preferable use is dividing In son with 2 or more active hydrogen atoms that can react with isocyanate group, molecular weight be 600 low molecule chemical combination below Object.Specifically, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6- hexylene glycols, 3- methyl-1s can be enumerated, 5- pentanediols, new penta The trihydroxylic alcohols such as glycols, trimethylolpropane, the tri hydroxy methyl butanes such as glycol, Isosorbide-5-Nitrae-cyclohexanediol, benzene dimethanol, hydrazine, second two Amine, isophorone diamine, piperazine, 4,4 '-methylene dianiline (MDA)s, toluenediamine, benzene dimethylamine, hexamethylene diamine, 4,4 '-two Amino alcohols such as three amine such as the Diamines such as cyclohexyl-methane diamines, diethylenetriamines, amino-ethyl alcohol and aminopropyl alcohol etc..

As organic multiple isocyanate, the aliphatic categories such as hexamethylene diisocyanate diisocyanate, different Buddhist can be enumerated That ketone diisocyanate (being also abbreviated as IPDI sometimes below), hydrogenation xylylene diisocyanate, dicyclohexyl methyl hydride two are different Alicyclic rings same clan diisocyanate, the xylylene diisocyanates such as cyanate (hereinafter, being abbreviated as hydrogenation MDI sometimes) are (hereinafter, have When be abbreviated as XDI), aromatic/aliphatics diisocyanate, the toluene di-isocyanate(TDI) such as two methylene diisocyanate of isophthalic, four methyl esters (being abbreviated as TDI sometimes below), 4,4 '-methyl diphenylene diisocyanates (being abbreviated as MDI sometimes below), tolidine two are different Two isocyanide of aromatic series such as cyanate (tolidine diisocyanate) and naphthalene diisocyanate (being abbreviated as NDI sometimes below) Acid esters etc..

By importing sulfonic group, carboxyl, hydroxyl or primary amino group or secondary amino group in the polyurethane that is used in the present invention, And polyurethane dispersing liquid is made to contain with these officials group with reactive crosslinking agent, to make resin become macromolecule after the reaction It measures resin and the crosslink density of resin is made to increase.Therefore, durability, against weather, heat resistance and moistening be can further improve When strength retention.

As crosslinking agent, may be used at intramolecular with 2 or more can be with the reactive base that has been directed into polyurethane The crosslinking agent for the reactive group that group is reacted.Specifically, water-soluble isocyanate compound, sealing end isocyanic acid can be enumerated The polyisocyanates such as ester compounds crosslinking agent, melamine class crosslinking agent, oxazoline classes crosslinking agent, the crosslinking of carbodiimide class The crosslinking agents such as agent, aziridine class crosslinking agent, epoxy crosslinking agent and hydrazine crosslinking agent.Crosslinking agent can be used alone a kind, also may be used It is used in combination of two or more.

Water-soluble isocyanate ester compound is the compound for having in the molecule 2 or more isocyanate group, can be enumerated The above-mentioned compound etc. containing organic multiple isocyanate.As commercially available product, Bayer Material Science (strain) can be enumerated Make " Bayhydur " (registered trademark) series, " Desmodur " (registered trademark) series etc..

Blocked isocyanate class compound is the compound for having in the molecule 2 or more blocked isocyanate bases.Sealing end Isocyanate group refers to utilizing the envelopes such as alcohols, amine, phenols, imines, thio-alcohol, pyrazoles, oximes, active methylene group class Agent is held, group obtained from above-mentioned organic polyisocyanate compound is blocked.As its commercially available product, the first industry can be enumerated " Elastron " (registered trademark) series of pharmacy (strain), " Duranate " (note of ASAHI KASEI CHEMICALS (strain) systems Volume trade mark) series and Mitsui Chemicals (strain) system " TAKENATE " (registered trademark) series etc..

As melamine series crosslinking agent, the change with 2 or more methylols, methoxyl group methylol in the molecule can be enumerated Close object.As commercially available product, " U-VAN " (registered trademark) series, Nihon Cytec (strain) systems of Mitsui Chemicals (strain) system can be enumerated " Cymel " (registered trademark) series and Sumitomo Chemical (strain) system " Sumimal " (registered trademark) series.

Zuo Wei oxazoline crosslinkers can be enumerated in the molecule with oxazolinyl (oxazolines skeleton Shang 2 Yi) change Close object.As commercially available product, Nippon Shokubai Co., Ltd's system " EPOCROS " (registered trademark) series etc. can be enumerated.It is sub- as carbon two Amine system crosslinking agent can enumerate the compound with 2 or more carbodiimides in the molecule.As its commercially available product, can enumerate Nisshinbo Industries, Inc. systems " Carbodilite " (registered trademark) series etc..

As epoxies crosslinking agent, the compound with 2 or more epoxy groups in the molecule can be enumerated.As commercially available product, Nagase ChemteX corporations " Denacol " (registered trademark) series, the diepoxy polycyclic of slope this pharmaceutical industries can be enumerated Oxygen class compound and DIC corporations " EPICRON " (registered trademark) series etc..

As aziridine class crosslinking agent, the compound with 2 or more aziridine bases in the molecule can be enumerated. As hydrazine crosslinking agent, hydrazine and the in the molecule compound with 2 or more diazanyls (hydrazine skeleton) can be enumerated.

In these compounds, as functional group possessed by polyurethane, preferably hydroxyl and/or carboxyl and/or sulfonic group, As crosslinking agent, preferably polyisocyanates crosslinking agent and carbodiimide compound.In addition, by and with carbodiimide chemical combination Object and polyisocyanates crosslinking agent can further improve the cross-linked structure of polyurethane resin, and can maintain flexibility Humidity resistance effect is improved under state.

For water dispersant type polyaminoester, due to usually containing hydrophilic radical in molecular structure, so with previous Organic solvent class polyurethane compare, it is high with the compatibility of hydrone, swelling, the molecule knot of polyurethane are easy under moist environment Structure is easy relaxation, therefore, there is the tendency for the high physical property that the when of being not easy to maintain dry obtains under moist environment.On the other hand, lead to It crosses using above-mentioned crosslinking agent, moisture-proof thermal effect can be improved, the tensile strength (tensile of sheet material when can be improved moistening strength).As a result, can inhibit the structure change of the polyurethane molecular caused by the water in dyeing process etc., can be maintained as For the morphological stability and polyurethane of tablet and the adhesion of fibrous substrate, therefore, it can be achieved that high physical property and with equal The quality of even sense.

Carbodiimide cross-linking agent due in a low temperature of 100 DEG C or less have excellent crosslinking reactivity, From the aspect of productivity it is preferable to use.In addition, for isocyanate compound and/or blocked isocyanate compounds, Other than mainly being reacted with hydroxyl, especially in 120 DEG C or more and 200 DEG C temperature below, excellent in high-temperature area It is selected as at 140 DEG C or more and 200 DEG C of temperature below, the urethane bond with the part hard segment (HS) for constituting polyurethane And/or the reactivity of urea bond also increases, and forms allophanic acid ester bond, biuret linkage, so as to assign more tough cross-linked structure, Keep the micro phase separation structure of polyurethane apparent.

From the viewpoint of flexibility and resilience, storage modulus of the polyurethane film in 20 DEG C of temperature in the present invention E ' is preferably 1~100MPa, more preferably 2~50MPa.In addition, loss modulus is preferably 0.1MPa~20MPa, more preferably 0.5MPa~12MPa.In addition, tan δ are preferably 0.01~0.4, more preferably 0.02~0.35.

Storage modulus E ' and tan δ in the present invention is the film (film) for the polyurethane for being 200 μm for film thickness, using storage Can modulus measurements device [DMA7100 { Hitachi High-Tech Science Corporation systems }], with the frequency of 12Hz The value measured.Tan δ are the numerical value indicated with E "/E ' (E " indicates loss modulus).

In addition, E ' indicates the elastic property of polyurethane resin, if the E ' is too small, tablet lacks crease recovery, if Excessive, then tablet is felt hard.

On the other hand, refer to poly- ammonia with the meaning of E "/E ' (E " i.e. loss modulus indicates adhesion properties) tan δ indicated The ratio of adhesion properties when on the basis of the elastic property of ester.If tan δ are too small, it is extensive to lack wrinkle for tablet in the same manner as E ' Renaturation, if excessive, tablet is felt hard.

The density of the tablet of the present invention is preferably 0.2~0.7g/cm³.Density is more preferably 0.2g/cm³More than, into one Step is preferably 0.25g/cm³More than.By making density be 0.2g/cm³More than, so as to make appearance become fine and close, show Advanced quality.On the other hand, by making the density of tablet be preferably 0.7g/cm³Below, it is more preferably 0.6g/cm³Hereinafter, It can prevent feeling hard for tablet.

The ratio for the polyurethane that the tablet of the present invention contains is preferably 10~80 mass %.By the ratio for making polyurethane For 10 mass % or more, more preferably 15 mass % or more, sheet strength is not only can get, but also falling off for fiber can be prevented. In addition, by making, the ratio of polyurethane is 80 mass % or less, more preferably 70 mass % are hereinafter, can prevent from feeling hard, energy Access good pile quality.

For the tablet of the present invention, the elastomeric polymers such as type polyurethane are dissipated by applied moisture, and make the water The aqueous dispersions and thickener and the liquid obtained from of dispersion type polyurethane etc. solidify in the hot water, water-dispersed to realize The porous structure of type polyurethane (elastomeric polymer) can obtain extremely similar to the artificial leather for applying solvent polyurethane , excellent crease recovery and flexibility.

That is, the tablet of the present invention is to assign tool to the fibrous substrate formed by superfine fibre and/or superfine fibre beam There is the macromolecular elastomer of hydrophilic radical as tablet made of binder, which is characterized in that on the edge of the tablet In section obtained by thickness direction cutting, in the macromolecular elastomer observed in cutting section, relative to field of view The area in interior artificial leather section independently and has 50 μm²The possession ratio of the part of above area of section is 0.1% or more And 5.0% or less.

In addition, preferred embodiment according to the present invention, the tablet is to being formed by superfine fibre and/or superfine fibre beam Fibrous substrate assign with hydrophilic radical macromolecular elastomer as tablet made of binder, feature exists In, in the section obtained by the through-thickness cutting of the tablet, the periphery of superfine fibre and/or superfine fibre area of beam 1% or more and 35% or less covered by macromolecular elastomer envelope.

[manufacturing method of tablet]

Then, the manufacturing method of the tablet of the present invention is illustrated.

Fibrous substrate used in the present invention, as described above, preferably using woven fabric, knitted fabric and non-woven fabrics Equal cloth and silks.The surface quality of tablet when wherein, due to progress surface nappy processing is good, and it is advantageous to use non-woven fabrics. In the fibrous substrate of the present invention, the suitably stacking such as these woven fabrics, knitted fabric and non-woven fabrics can be used in combination.

Non-woven fabrics used in the present invention, can be any one of staple fiber nonwoven fabric and nonwoven fabric of long fibers, But from the aspect of it can obtain the surface quality comprising uniform raising length, staple fiber nonwoven fabric is preferably used.

The fibre length of staple fiber in staple fiber nonwoven fabric is preferably 25mm~90mm, more preferably 35mm~75mm. By making fibre length be 25mm or more, the tablet of excellent in wear resistance can be obtained by complexing.In addition, by making fiber Length is 90mm hereinafter, the superior tablet of quality can be obtained.

As the fiber for constituting fibrous substrate, can be used by polyethylene terephthalate, poly terephthalic acid fourth The polyamide such as the polyester such as diol ester, polytrimethylene-terephthalate and polylactic acid, nylon 6 and nylon66 fiber, acrylic compounds, poly- second The fiber that the thermoplastic resin of the fusible spinning such as alkene, polypropylene and thermoplastic cellulose is formed.Wherein, steady from intensity, size From the viewpoint of qualitative and light resistance, polyester fiber is preferably used.Alternatively, it is also possible to the different fiber of raw material is mixed Constitute fibrous substrate.

The cross-sectional shape of the fiber used in the present invention can be circular section, and oval, flat and triangle etc. can also be used Polygon, sector and the odd-shaped cross sections such as cross.

The avarage fiber diameter for constituting the fiber of fibrous substrate is preferably 0.1~7 μm, more preferably 0.3~5 μm.It is logical Crossing makes the avarage fiber diameter of fiber for 7 μm hereinafter, the sense of touch of fibrous substrate becomes more soft.On the other hand, by making fibre The avarage fiber diameter of dimension is 0.1 μm or more, and the colour rendering after dyeing is better.

It,, can be inside it for the purpose of improving intensity in the case where fibrous substrate is non-woven fabrics in the present invention Woven fabric, knitted fabric are combined in non-woven fabrics.For the combination of non-woven fabrics and woven fabric, knitted fabric, may be used by Woven fabric, knitted fabric layer are laminated on non-woven fabrics, and woven fabric, knitted fabric any one of are inserted into non-woven fabrics etc. side Method.Wherein, from it can be expected that from the viewpoint of morphological stability raising and intensity raising, preferred embodiment is to use woven fabric.

As the single thread (warp thread and weft yarn) for constituting woven fabric, knitted fabric, can enumerate by polyester fiber, Fypro etc. The single thread that synthetic fibers are formed, from the aspect of dyeing firmness, preferably by with the ultra-fine fibre that finally constitutes the cloth and silks such as non-woven fabrics Dimension is the fibroplastic sliver of identical raw material.

As the form of such single thread, filament yarn (filament yarn), textile strand etc. can be enumerated, is preferably made With their strong twisted yarn.In addition, since textile strand can lead to falling off for surface villus, it is advantageous to use filament yarn.

When using strong twisted yarn, twisting count be preferably 1000T/m or more and 4000T/m hereinafter, more preferably 1500T/m or more and 3500T/m or less.If twisting count is less than 1000T/m, caused by needling treatment, the broken filament change of composition strong twisted yarn It is more, show the reduction of the physical characteristic of product, single fiber becomes more trend in the exposing of product surface.In addition, if twisting count is big In 4000T/m, although can then inhibit broken filament, the strong twisted yarn due to constituting woven fabric, knitted fabric becomes really up to the mark, because This shows the trend for the hardening for causing feel.

In addition, in the present invention, it is preferred mode to show fiber type using superfine fibre in fibrous substrate.By Show fiber type using superfine fibre in fibrous substrate, can steadily obtain the shape of the Shu Jinhang complexings of above-mentioned superfine fibre State.

In the case where fibrous substrate is non-woven fabrics, which there is the beam (fibre bundle) of superfine fibre to be complexed Made of structure be preferred mode.It is complexed with the state of beam by superfine fibre, is improved to the intensity of tablet.It is such The non-woven fabrics of form can obtain in the following manner：Superfine fibre is shown fiber type in advance to complex with one another, then makes ultra-fine fibre Dimension shows.

Show fiber type as superfine fibre, following fibers may be used：By the heat of 2 kinds of different ingredients of solvent solubility Sea component is dissolved using solvent etc. and is removed, island component is thus made to form ultra-fine fibre as sea component and island component by plastic resin The islands-in-sea bicomponent fibre of dimension；And the thermoplastic resin of 2 kinds of ingredients is alternately configured with radial or multilayer shape in fiber On section, each ingredient is removed and is divided, thus cuts the fine exfoliated composite fibre etc. at superfine fibre.

Wherein, for islands-in-sea bicomponent fibre, due to by removing sea component can between island component, it is i.e. ultra-fine Appropriate gap is assigned between fiber, so from the viewpoint of the flexibility, feel of tablet, it is also preferred that multiple using fabric of island-in-sea type Condensating fiber.

Islands-in-sea bicomponent fibre includes following fibers：Using fabric of island-in-sea type it is compound with nozzle, by this 2 kinds of sea component and island component The islands-in-sea bicomponent fibre that ingredient is mutually arranged and spins；Sea component and this 2 kinds of ingredients mixing of island component are spun In terms of the superfine fibre that uniform fiber number can be obtained and sufficiently long ultra-fine fibre can be obtained in mix spinning fiber of yarn etc. It ties up and also contributes to from the aspect of the intensity of tablet, it is preferable to use islands-in-sea bicomponent fibre.

As the sea component of islands-in-sea bicomponent fibre, can be used polyethylene, polypropylene, polystyrene, by M-phthalic acid Copolyester, polylactic acid and polyvinyl alcohol etc. obtained from the copolymerization such as sodium sulfonate, polyethylene glycol.Wherein, it is preferable to use not using Sodiosulfoisophthalic acid, polyethylene glycol etc. (are copolymerized and obtain by organic solvent, that is, decomposable, caustic digestion copolyester To), polylactic acid and the polyvinyl alcohol for dissolving in hot water.

For (ratio) ratio of the sea component of islands-in-sea bicomponent fibre and island component, island fiber is relative to fabric of island-in-sea type The mass ratio of composite fibre is preferably 0.2~0.9, and more preferably 0.3~0.8.By the mass ratio for making sea component and island component It is 0.2 or more, the removal rate of sea component can be reduced, productivity further increases.In addition, by making mass ratio for 0.9 hereinafter, can The fibrillation of island fiber is improved, and prevents the interflow of island component.The number on island can suitably be adjusted by the design of nozzle.

The major diameter that the superfine fibres such as islands-in-sea bicomponent fibre show the single fiber of fiber type is preferably 5~80 μm, more preferably It is 10~50 μm.If it is 5 μm that the major diameter of single fiber, which is less than, the intensity of fiber is weak, there is the single fiber in aftermentioned needling treatment etc. The fracture of dimension becomes more trend.In addition, if the major diameter of single fiber is more than 80 μm, cannot achieve in needling treatment etc. sometimes The complexing of effect.

About the method for the non-woven fabrics for obtaining fibrous substrate used in the present invention, can be used using at needle thorn Reason, spun lacing (water jet punching) processing make method, spun-bond process, meltblown and the copy paper method etc. that web is complexed.Its In, it is preferable to use following methods：After the form for forming superfine fibre beam as described above, at needling treatment, spun lacing The method of the processing such as reason.

In addition, for the non-woven fabrics as fibrous substrate is integrated with the stacking of woven fabric, knitted fabric, from fiber Complexing from the aspect of, it is preferable to use needling treatment, spun lacing processing etc..Wherein, needle thorn is not limited by sheet thickness, can be made Fiber is upwardly oriented in the Vertical Square of fibrous substrate, is considered from the viewpoint, it is preferable to use needling treatment.

The radical of the barb (barb) of the needle used in needling treatment is preferably 1~9.By making the radical of barb be 1 More than root, the complexing of fiber can be effectively performed.On the other hand, by making the radical of barb for 9 hereinafter, fiber can be inhibited Damage.If barb radical is more than 9, fibre damage aggravates, in addition, remaining needle tracking on fibrous substrate sometimes to lead Cause product appearance bad.

In addition, when non-woven fabrics is integrated with woven fabric, knitted fabric complexing, assigning the mode being complexed in advance to non-woven fabrics is Ideal mode, this is because can by needling treatment by non-woven fabrics and woven fabric, knitted fabric in the way of inseparable one The generation of fold is further prevented when body.As described above, when using the method being complexed in advance is assigned in advance using needling treatment, With 20/cm²Above needling density carries out being effective.It is preferred that with 100/cm²Above needling density assigns pre- network It closes, more preferably with 300/cm²~1300/cm²Needling density assign pre- complexing.

The reason is that the needling density being complexed in advance is less than 20/cm²When, due in the complexing with woven fabric, knitted fabric And the reason of needling treatment later, the width of non-woven fabrics remains the leeway to narrow, therefore, with the variation of width, sometimes Fold is generated on woven fabric, knitted fabric, to be unable to get smooth fibrous substrate.In addition, if the needle thorn being complexed in advance is close Degree is more than 1300/cm², then the complexing of usual non-woven fabrics itself excessively carries out, for only sufficiently formed with constitute woven fabric, The mobile leeway of the complexing of the fiber of knitted fabric is reduced, and therefore, is unfavorable for realizing non-woven fabrics and woven fabric, knitted fabric network securely Inseparable integral structure made of conjunction.

In the present invention, no matter there are inorganic fabric, knitted fabric, preferably needle is made to pierce when fiber is complexed using needling treatment Ranging from 300/the cm of density²~6000/cm², more preferably 1000/cm²~3000/cm²。

Woven fabric, needle can be laminated in complexing for non-woven fabrics and woven fabric, knitted fabric on the one or both sides of non-woven fabrics Fabric, or woven fabric, knitted fabric are clamped between more nonwoven fabric cloth, fiber is twined into network, shape each other using needling treatment later Filament forming material base material.

In addition, when carrying out spun lacing processing, preferred embodiment is to be carried out in the state that water is columnar flow.Specifically, excellent Choosing makes water be sprayed from the nozzle of 0.05~1.0mm of diameter with the pressure of 1~60MPa.

Needling treatment or spun lacing treated shown by superfine fibre the non-woven fabrics that fiber type is formed apparent density it is preferred For 0.13~0.45g/cm³, more preferably 0.15~0.30g/cm³.By making apparent density be 0.13g/cm³More than, it can obtain To the artificial leather with sufficient morphological stability and dimensional stability.On the other hand, by making apparent density be 0.45g/cm³ Hereinafter, being able to maintain that the sufficient space for assigning macromolecular elastomer.

The thickness of fibrous substrate be preferably 0.3mm or more and 6.0mm hereinafter, more preferably 1.0mm or more and 3.0mm with Under.If the thickness of fibrous substrate is less than 0.3mm, the morphological stability of tablet becomes insufficient sometimes.In addition, if thickness is big In 6.0mm, then have the tendency that needle, which frequently occurs, in needle thorn process breaks.

For what is obtained in the above manner shows the non-woven fabrics that fiber type is formed by superfine fibre, from densification Viewpoint considers, xeothermic or damp and hot or the two can be utilized to make its contraction, and then form high density.

When using islands-in-sea bicomponent fibre, the water-dispersed of water dispersant type polyaminoester can contained to fibrous substrate imparting Before type polyurethane dispersion liquid and/or after assigning, the de- sea processing for the sea component for removing the fiber is carried out.If water-dispersed assigning De- sea processing is carried out before type polyurethane dispersion liquid, then is easy to form the structure that polyurethane is directly sealed at superfine fibre, it can jail Admittedly hold superfine fibre, therefore, the wear resistance of tablet becomes good.

On the other hand, derived by assigning cellulose to superfine fibre before assigning water dispersant type polyaminoester dispersion liquid The inhibitor such as object, polyvinyl alcohol (being abbreviated as PVA sometimes below) then assign water dispersant type polyaminoester dispersion liquid, so as to The adaptation of superfine fibre and polyurethane resin is reduced, and then can realize soft feel.

Above-mentioned inhibitor can be assigned before or after the de- sea processing of the fiber of island structure.By in de- sea processing Inhibitor is assigned before, even if can if in the case where the weight per unit area of fiber reduces, the tensile strength of sheet material reduces Improve the form retentivity of fibrous substrate.Therefore, other than it can steadily process slim sheet material, additionally it is possible to improve de- The thickness conservation rate of fibrous substrate in extra large treatment process, thus can inhibit the densification of fibrous substrate.On the other hand, By assign above-mentioned inhibitor after de- sea processing, it can be achieved that fibrous substrate densification, it is therefore preferable that according to mesh The mode that suitably adjusts of progress.

As above-mentioned inhibitor, since the enhancing effect of fibrous substrate is good, is not easy to dissolve out in water, it is advantageous to make Use PVA.In PVA, from inhibitor capable of being made to be not easy to dissolve out when assigning water dispersant type polyaminoester dispersion liquid and can further pressed down Superfine fibre and polyurethane processed it is closely sealed from the viewpoint of, more preferably application is less readily soluble in the high saponification degree PVA of water.

The saponification degree of high saponification degree PVA is preferably 95% or more and 100% hereinafter, more preferably 98% or more and 100% Below.By making saponification degree be 95% or more, dissolution when can inhibit to assign water dispersant type polyaminoester dispersion liquid.

The degree of polymerization of PVA is preferably 500 or more and 3500 hereinafter, further preferably 500 or more and 2000 or less.Pass through It is 500 or more to make the degree of polymerization of PVA, the dissolution of high saponification degree PVA when can inhibit to assign polyurethane dispersing liquid.In addition, logical Crossing makes the degree of polymerization of PVA be 3500 hereinafter, the viscosity of high saponification degree PVA liquid will not become excessively high, can be steadily to cellulosic Base material assigns high saponification degree PVA.

Relative to the fibrous substrate remained in product, the imparting amount of PVA is preferably the 0.1 mass % of mass %~80, More preferably 5 mass % or more and 60 mass % or less.By assigning the high saponification degree PVA of 0.1 mass % or more, can be improved de- Morphological stability effect in extra large treatment process and the adaptation for inhibiting superfine fibre and polyurethane.In addition, by making high soap For 80 mass % hereinafter, to which the adaptation of superfine fibre and polyurethane will not be reduced excessively, the fiber of raising becomes change degree PVA It obtains uniformly, can be made into the uniform product of surface quality.

As the method for assigning above-mentioned inhibitor to fibrous substrate, examined from the viewpoint that can equably assign inhibitor Consider, it is preferable to use following methods：So that above-mentioned inhibitor is dissolved in the water, by it containing being dipped into fibrous substrate, it is dry to carry out heating It is dry.For drying temperature, the drying time needed if temperature is too low is long, if the excessively high inhibitor of temperature is thoroughly insoluble Change, removing can not be dissolved later.It is therefore preferable that being dried in 80 DEG C or more and 180 DEG C of temperature below, further preferably 110 DEG C or more and 160 DEG C or less.In addition, from the viewpoint of processability, drying time is preferably 1 minute or more and 30 minutes Below.

For the dissolving removing of inhibitor processing, preferably：The cellulosic base of the inhibitor will be imparted Material is immersed in steam and 60 DEG C or more and the hot water of 100 DEG C of temperature below of 100 DEG C or more of temperature, is utilized as needed Ironer etc. squeezes out liquid, thus dissolves inhibitor and removes.

De- sea processing can carry out in the following manner：Fibrous substrate comprising islands-in-sea bicomponent fibre is immersed in liquid In, squeeze out liquid.As the solvent for dissolving sea component, in the case where marine origin is divided into polyethylene, polypropylene and polystyrene, The organic solvents such as toluene, trichloro ethylene can be used, in the case where marine origin is divided into copolyester, polylactic acid, hydroxide can be used Hot water can be used in the case where marine origin is divided into polyvinyl alcohol in the alkaline solutions such as sodium water solution.

Then, the polyurethane that macromolecular elastomer is used as in the present invention is illustrated.

In the case where disperseing in an aqueous medium polyurethane in the form of particle, from the dispersion stabilization of polyurethane Viewpoint considers that the constituent as polyurethane is, it is preferable to use the above-mentioned active hydrogen component containing hydrophilic radical, uses neutralization Salt is preferred mode.

As for the compound with hydrophilic radical and reactive hydrogen neutralization salt neutralizer, can enumerate trimethylamine, Hydroxide such as triethylamine, the aminated compounds of triethanolamine, sodium hydroxide and potassium hydroxide etc..

For the addition time for the neutralizer of the active hydrogen component containing hydrophilic radical, it polymerize in polyurethane The additions such as before and after the dispersion step disperseed before and after process or in aqueous media, are not particularly limited, but exist from polyurethane From the viewpoint of stability in water-borne dispersions, it is situated between before the dispersion step preferably disperseed in aqueous media or in hydrotropism It is added in the dispersion step disperseed in matter.

From the viewpoint of the dispersion stabilization of polyurethane and water resistance, the active hydrogen component containing hydrophilic radical and/ Or the content for quality of its salt based on polyurethane is preferably 0.005~30 mass %, more preferably 0.01~15 mass %.

It is above-mentioned containing hydrophily in addition to using in the case where disperseing in an aqueous medium polyurethane in the form of particle Except the active hydrogen component of group, also can be used surfactant as polyurethane external emulsification agent and extremely by they In aqueous medium.

As such surfactant, nonionic surfactant, anion surfactant, cation form can be enumerated Face activating agent and amphoteric surfactant.Surfactant can be used alone, and can also be used in combination of two or more.

As nonionic surfactant, ethylene nonyl phenyl ether can be enumerated, polyoxyethylene dinonyl phenyl ether, gathered Polyol types such as the alkylene oxides such as ethylene oxide lauryl ether and polyoxyethylene stearyl base ether add-on type, glycerol monosterate etc..

As anion surfactant, sodium laurate, NaLS, Texapon Special, dodecane can be enumerated Carboxylates, sulfuric acid, sulfonate and the phosphate ester salts such as base benzene sulfonic acid sodium salt, higher alcohol di-phosphate ester sodium salt.

As cationic surfactant, quaternary ammonium salts such as VARISOFT TA100 etc. can be enumerated.As both sexes table Face activating agent can enumerate lauryl amino propionic acid methyl esters, Empigen and coco-nut oil fatty acid amidopropyl Dimethylaminoethyl acid glycine betaine etc..

The method system that the dispersion liquid of the polyurethane used in the present invention can apply previous manufacture polyurethane dispersing liquid It makes.For example, following methods can be enumerated：In the presence of emulsifier, above-mentioned polyisocyanates, polyalcohol, chain extension will be made in water The method that liquid polymer is emulsified obtained from agent and/or polyol reaction containing hydrophilic radical；Manufacture makes Obtained from above-mentioned polyisocyanates, polyalcohol and/or chain extender and/or polyol reaction containing hydrophilic radical, point Sub- end has the prepolymer of isocyanate group, is emulsified in water in the presence of by the prepolymer in emulsifier same When/or later, the method for completing lengthening reaction with chain extender；Make above-mentioned polyisocyanates, polyalcohol and/or chain extender and/ Or after the polyol reaction containing hydrophilic radical, without using emulsifier, and the method directly emulsified in water.In not shape It, can be in the absence of solvent at above-mentioned prepolymer directly into the case of in the case of polymerization and by prepolymer polymerization Implement, can also implement under conditions of there are methyl ethyl ketone, toluene and acetone and other organic solvent.

The water dispersant type polyaminoester dispersion liquid for the water dispersant type polyaminoester for containing above-mentioned synthesis is immersed in cellulosic base The medium mode of material, polyurethane is assigned to fibrous substrate, its solidification, solidification are then made by being thermally dried.

In the present invention, the water dispersant type polyaminoester dispersion of above-mentioned thickener is added to by being assigned to fibrous substrate Liquid, and so that water dispersant type polyaminoester is solidified in the hot water that temperature is preferably 50 DEG C~100 DEG C, more preferably 60 DEG C~97 DEG C, Thus enable that polyurethane becomes porous structure.

Dip time in the hot water be preferably 10 seconds or more and 5 minutes hereinafter, more preferably 30 seconds or more and 3 minutes with Under.By the way that dip time is arranged such, polyurethane can be made fully to solidify.

By using hot water coagulation to be used as the clotting method of polyurethane as described above, polyurethane is assigned per unit time Heat increases, and therefore, setting rate rises, uneven distribution situation of the water dispersant type polyaminoester dispersion liquid in fibrous substrate It reduces, therefore, fiber is bonding with polyurethane to be reduced, and feel becomes soft.

In addition, by water dispersant type polyaminoester dispersion liquid and with thickener, for being impregnated in the water of fibrous substrate For polyaminoester emulsion in distributed polyurethane dispersing liquid, due to the influence of the viscosity of the liquid, the Brownian movement quilt of lotion Inhibit.Therefore, the mutual frequency of exposure of lotion is reduced, and so as to reduce polyurethane block when solidification, and can realize softness Feel.In addition to this, dispersion liquid is not spread in the hot water, can inhibit polyurethane falling off when solidifying process, Ke Yishi Existing productivity also very excellent solidifying process.

By making in the hot water to coagulate the aqueous dispersions of water dispersant type polyaminoester etc. and thickener and the dispersion liquid obtained by Gu the envelope of water dispersant type polyaminoester (elastomeric polymer) becomes smaller, soft feel is formed.In addition, covering fibrous substrate Polyurethane envelope is reduced, and forms soft feel.

For the thickener added in water dispersant type polyaminoester dispersion liquid, nonionic class, anion can be applied The thickener of class, cationic and double ion class.Wherein, it is preferable to use nonionic class thickener.

As the type of thickener, can be selected from association thickener and Water Soluble Polymer Type thickener.As Association thickener can apply urethane-modified compound, acrylic modified compounds and their copolymer etc. The association thickener known.For example, Japanese Unexamined Patent Publication 2003-292937 bulletins, Japanese Unexamined Patent Publication No. 2001-254068 number can be enumerated Bulletin, No. No. 60-49022 bulletin of Japanese Unexamined Patent Application, Japanese Unexamined Patent Publication 2008-231421 bulletins, Japanese Unexamined Patent Publication 2002-069430 Carbamates association thickener, Japanese Unexamined Patent Application described in number bulletin and Japanese Unexamined Patent Publication 9-71766 bulletins etc. Carbamate monomer described in 62-292879 bulletins and Japanese Unexamined Patent Publication 10-121030 bulletins etc. and others third Association thickener etc. obtained by the copolymerization of alkene acrylic monomer.

As water-soluble high-molecular compound, can enumerate natural polymer, semi-synthetic high-molecular compound and Synthetic macromolecular compound etc..

As natural polymer, tamarind gum (tamarind gum), guar gum, locust bean gum can be enumerated The chemical combination of the nonionics such as (locust bean gum), bassora gum, starch, dextrin, gelatin, agar, casein and curdlan Object, xanthan gum, carrageenan, Arabic gum, pectin, collagen, sodium chondroitin sulfate, Sodium Hyaluronate, carboxymethyl form sediment The cationic compounds such as the anionic property compounds such as powder and starch phosphate, cationic starch and chitosan.

As semi-synthetic high-molecular compound, methylcellulose, ethyl cellulose, hydroxyethyl cellulose, second can be enumerated The nonionics such as ethylhydroxyethylcellulose, methylhydroxypropylcellulose, soluble starch and methyl starch compound, carboxymethyl are fine The anionic property compounds such as dimension element, carboxymethyl starch and alginate.

In addition, as synthetic macromolecular compound, can enumerate polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, The compounds of the nonionics such as polymethyl vinyl ether, polyethylene glycol and polyisopropyl acrylamide, carboxyl vinyl polymer, The anionic property compounds such as Sodium Polyacrylate and kayexalate, dimethyl aminoethyl (methyl) acrylate quaternary salt, The cationic compounds such as dimethyl diallyl ammonium chloride, poly- amidine, polyvinyl imidazol quinoline and polyethyleneimine.

In the present invention, as thickener, it is preferable to use being not easy to influence the non-of the stability of water dispersant type polyaminoester dispersion liquid Ionic thickener.

In addition, non-Newtonianism is preferably presented in the water dispersant type polyaminoester dispersion liquid for being added to thickener.If water-dispersion type is poly- Urethane dispersion liquid is for non-Newtonianism and with the property that viscosity reduces by applied force, then viscosity is by the applied forces such as stirring It reduces, therefore, it is possible to be impregnated in fibrous substrate with making above-mentioned homogeneous dispersion, in turn, after impregnation, viscosity passes through pre- It first stands and restores to original level, therefore, the above-mentioned dispersion liquid being impregnated in fibrous substrate becomes to be not easy from cellulosic Base material falls off.

In addition, thixotropy is preferably presented in the water dispersant type polyaminoester dispersion liquid for being added to thickener.If the poly- ammonia of water-dispersion type Ester dispersion liquid is thixotropy, then viscosity is reduced by applied forces such as stirrings, is impregnated in fibre with capable of making above-mentioned homogeneous dispersion It ties up in matter base material, in turn, by being stood in advance after applied force, viscosity recovery is impregnated in fibrous substrate to original level Interior above-mentioned dispersion liquid becomes to be not easy to fall off from fibrous substrate.

As thixotropic thickener is presented, can suitably be selected, it is preferable to use being added with few from above-mentioned thickener The natural polymer (polysaccharide) of big thickening effect is presented in dosage.It is further, excellent from water solubility as thickener It is different, with the compatibility of water dispersant type polyaminoester liquid is also excellent, from the viewpoint of thixotropy height at low concentrations, more preferably melon That glue.

The viscosity of aqueous resin dispersion containing thickener is preferably 200mPas~100000mPas, more preferably For 200mPas~10000mPas, further preferably 200mPas~5000mPas.By making above-mentioned aqueous tree The viscosity of fat dispersion liquid is 200mPas or more, can inhibit polyurethane falling off in hot water coagulation process, in addition, passing through Make viscosity be 100000mPas hereinafter, being impregnated in fibrous substrate while water dispersant type polyaminoester homogeneous dispersion can be made.

From the migration of polyurethane when polyurethane can be inhibited to solidify, polyurethane is made equably to be impregnated in fibrous substrate Viewpoint considers, assigns to the water dispersant type polyaminoester dispersion liquid of fibrous substrate and preferably comprises heat coagulant.

As heat coagulant, it is inorganic that sodium sulphate, magnesium sulfate, calcium sulfate, calcium chloride, magnesium chloride and calcium chloride etc. can be enumerated Ammonium salts such as salt, sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate and ammonium sulfate etc..By being used alone or being used in combination 2 kinds in them Additive amount is adjusted above and suitably, the setting temperature of water dispersant type polyaminoester is adjusted, then heats water dispersant type polyaminoester dispersion Liquid keeps its unstable, it is possible thereby to make its solidification.

From the viewpoint of the feel of the fiber product after storage stability and processing, above-mentioned water dispersant type polyaminoester point The heat freezing temperature of dispersion liquid is preferably 40~90 DEG C, more preferably 50~80 DEG C.

In polyurethane dispersing liquid, other than above-mentioned crosslinking agent, heat coagulant, following various additives can be also added Deng.

For example, pigment, antioxidant (Hinered phenols and the antioxidants such as sulphur class, Phosphorus), the ultraviolet lights such as carbon black can be contained The absorbent ultra-violet absorber etc. of triazines, benzophenone and benzoates (benzotriazole), hindered amines light are steady Determine the weathering stabilizers such as agent, waterproof softening agent (the fluothane base ester of the organo-silicon compound such as polysiloxanes, modified silicon oil and acrylic acid The waterproofs such as fluorine compounds such as Type of Collective object softening agent), wetting agent (wetting agents such as ethylene glycol, diethylene glycol, propylene glycol and glycerine), Antifoaming agent (octanol, sorbitan monooleate, dimethyl silicone polymer, Siloxane-Oxyalkylene Copolymers and the poly- silica of fluorine richness The antifoaming agent such as alkane), the filler (fillings such as the particles such as calcium carbonate, titanium oxide, silica, talcum, ceramics, resin and hollow pearl Agent), the fire retardant (resistance of halogen system, phosphorus system, antimony system, melamine series, guanidine system, dicyandiamidines system etc., polysiloxane series and inorganic system Fire agent), microballoon (example：Loose this grease system：" Matsumoto Microsphere " (registered trademark)), foaming agent is [for example, two is sub- Nitro pentamethylene tetramine (example：Three association chemical conversion system " Cellmic A " (registered trademark)), azodicarbonamide (example：The chemical conversion of three associations Make " Cellmic CAP " (registered trademark)), p, the double benzene sulfonyl hydrazide (examples of p '-oxygroups：Three association's chemical conversion " Cellmic S " (registrars Mark)), N, N '-dinitrosopentamethylene tetramine (examples：Yonghe County chemical conversion system " Cellular GX " (registered trademark)) etc. organics Foaming agent and sodium bicarbonate (example：Three association's chemical conversion systems " Cellmic 266 " (registered trademark)) etc. inorganics foaming agent etc.], 2,2 '- Bis- [2- methyl-N- (2- hydroxyethyls) the propionamide] (examples of azo：With Wako Pure Chemical Industries system " VA-086 "), viscosity modifier, increasing Mould agent (phthalic acid ester, adipate ester etc.) and releasing agent (wax class, metal soap and their mixing class releasing agent Deng) etc. additives.

It is impregnated in fibrous substrate and after being solidified by water dispersant type polyaminoester dispersion liquid, it is water-dispersed in order to promote The melting of type polyurethane lotion, improves humidity resistance at the molecular structure for optimizing polyurethane, carries out additional heating (curing (cure)) It is preferred mode.Can after water dispersant type polyaminoester dispersion liquid is impregnated in fibrous substrate, with make its solidify process it is continuous Ground is cured, alternatively, it is also possible to which water dispersant type polyaminoester dispersion liquid is being impregnated in fibrous substrate and is carrying out solidification processing Afterwards, implement to cure using other processes.

It is prolonged dry due to being needed when temperature is too low, and the thermal decomposition of polyurethane is promoted when the temperature is excessively high, therefore, For drying temperature, it is preferable over 80 DEG C or more and 200 DEG C temperature below and dries, more preferably 120 DEG C or more and 190 DEG C Hereinafter, further preferably 150 DEG C or more and 180 DEG C or less.

In addition, from the viewpoint of processability, drying time is preferably 1 minute or more and 60 minutes hereinafter, more preferably 1 Minute or more and 30 minutes or less.In the present invention, by making curing temperature be high temperature and being handled with the short time, it can improve The mobility of polyurethane molecular, comprising the hard segment portion (HS) mainly formed by carbamate groups and urea groups with mainly by more The cohesion that the portions HS are further increased in the molecular structure in portion soft chain segment (SS) that first alcohol is formed, makes the microphase-separated knot in the portions HS and SS Structure is apparent, and can also improve humidity resistance.

For the obtained tablet for imparting polyurethane is cut into two along sheet thickness direction after assigning polyurethane It partly or is divided into for several pieces mode, production efficiency is excellent, is preferred mode.

Before aftermentioned raising processing, silicone emulsion (silicone can be assigned to the tablet for imparting polyurethane The lubricants such as emulsion).In addition, from the side that grounds travel caused by the tablet caused by grinding is not easy to accumulate on sand paper Face considers that it is preferred mode to assign antistatic agent before raising processing.

In order to form pile on the surface of tablet, raising processing can be carried out.Raising processing can by using sand paper, roll Methods being ground such as roller grinding machine (roll sander) etc. are implemented.

If the thickness of tablet is excessively thin, the physical characteristics such as tensile strength, tearing strength of tablet die down, if blocked up Tablet is felt hard, and therefore, the thickness of tablet is preferably from about 0.1~5.0mm.

Tablet can be dyed.As colouring method, since rubbing effect can be assigned while dyeing tablet And keep tablet soft, it is advantageous to use liquid-flow dyeing machine.For dyeing temperature, polyurethane is bad sometimes if excessively high Change, conversely, dyestuff is insufficient for the dyeing of fiber if too low, therefore, can be set according to the type of fiber.Dyeing Temperature is preferably generally 80 DEG C or more and 150 DEG C hereinafter, more preferably 110 DEG C or more and 130 DEG C or less.

The dyestuff used is selected according to the type for the fiber for constituting fibrous substrate.For example, if it is polyesters fibre Dimension then uses disperse dyes, if it is polyamide fiber, then uses acid dyes, containing golden dyestuff, their group also can be used It closes.When being dyed to tablet with disperse dyes, reduction washing can be carried out after dyeing.

In addition, it is also preferred mode to use dyeing assistant in dyeing.By using dyeing assistant, dyeing can be improved Uniformity, reproducibility.In addition, while being dyed or after dyeing, it can implement to have used softening agents such as organosilicon, anti-quiet The dressing agent of electric agent, waterproofing agent, fire retardant, photostabilizer and antiseptic etc. is handled.

The tablet obtained by the present invention mainly can be used as artificial leather, for example, can suitably serve as：As furniture, chair And the skin material of the indoor seat of the vehicles such as wall material, automobile, electric car and aircraft, ceiling and upholstery etc. is with non- Vamp, the decoration of the shoes such as interior material, shirt, jacket, playshoes, sport footwear, Men's Shoes and the women's shoes of normal aesthetic look (trim), packet, waistband, wallet etc. and the dress material material for their part, cleaning wiping cloth, abrasive cloth and the CD curtains etc. such as Industrial material.

Embodiment

Hereinafter, using embodiment, the tablet and its manufacturing method of the present invention are illustrated in further detail, but this Invention is not limited to these examples.

[evaluation method]

(1) expulsion rate when solidification of polyurethane：

It measures the quality of fibrous substrate and water dispersant type polyaminoester dispersion liquid is impregnated in the matter after the fibrous substrate Amount, using the polyurethane solid state component amount for including in the two difference as polyurethane adhesion amount A.Then, make above-mentioned containing being soaked with moisture The fibrous substrate for dissipating type polyurethane dispersion liquid solidifies in hot water or steam, the quality after drying is measured, by itself and cellulosic The difference of base material is as polyurethane adhesion amount B.Polyurethane expulsion rate when solidifying is calculated by following formula, to measure obtained by 10 points As a result average value is evaluated.

Polyurethane expulsion rate (%)=polyurethane adhesion amount B/ polyurethane adhesion amounts A × 100.

(2) viscosimetric analysis of water dispersant type polyaminoester dispersion liquid：

Use rotational viscometer (B shape viscosimeters：Tokyo gauge manufactures institute), in the case where temperature is 25 DEG C of atmosphere with 0.5 turn/ The speed conditions of minute and 10 revs/min of speed conditions measure the viscosity of prepared water dispersant type polyaminoester dispersion liquid.

(3) exterior quality of tablet：

For the exterior quality of tablet, 20 masterpieces 10 each with the adult human male of health and adult female, total For estimator, visually and sensory evaluation, 5 grades of evaluations are carried out in the following manner, using most evaluations as exterior quality. About exterior quality, 4 grades~5 grades are considered as good.

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

4 grades：For the evaluation between 5 grades and 3 grades.

3 grades：There is slightly undesirable part in the dispersity of fiber, but there are the pile of fiber, and appearance is reluctantly good.

2 grades：For the evaluation between 3 grades and 1 grade.

1 grade：The dispersity of fiber is excessively poor on the whole, bad order.

(4) feel of tablet：

For the feel of tablet, using the adult human male of health and adult female, 10 each, total 20 as commenting Valence person carries out 3 grades of evaluations in the following manner using the sensory evaluation of sense of touch, the evaluation by most evaluations as feel.It closes In feel, ◎ is considered as good (caoutchouc elasticity is excellent).

◎：Compared with the artificial leather of the organic solvent class polyurethane for the weight per unit area for applying equal extent, more Softness, and crease recovery is excellent.

○：It is same compared with the artificial leather of the organic solvent class polyurethane for the weight per unit area for applying equal extent Deng pliability and crease recovery.

×：Sheet material is hard, the sense of touch of class paper sense.

(5)50μm²The computational methods (parameter A) of the possession ratio of above aporate block：

Using scanning electron microscope (SEM), seen on the length direction of artificial leather or width direction with 500 times of multiplying power Section is ground for 10 observed SEM images using US National health obtained by examining the through-thickness cutting of artificial leather Study carefully developed image analysis software ImageJ (versions：1.44p), it calculates 50 in the polyurethane section observed in cutting section μm²Field of view (4.3 × 10 of above block relative to SEM image region⁴μm²) in artificial leather section area for The average value of ratio, the numerical value for opening image by the meter 10 of calculating is evaluated.The schematic diagram of Fig. 3 expression parameter A computational methods.Figure 3 are the schematic diagram of the polyurethane block 1 of expression parameter A, and illustrate that polyurethane block 1 refers to the poly- ammonia observed in the section of artificial leather Ester section (not including the part that depths is more leaned on compared with section).

(6) computational methods (parameter B) of the macromolecular elastomer envelope rate in superfine fibre section：

Using scanning electron microscope (SEM), seen on the length direction of artificial leather or width direction with 500 times of multiplying power Section is ground for 10 observed SEM images using US National health obtained by examining the through-thickness cutting of artificial leather Study carefully developed image analysis software ImageJ (versions：1.44p), superfine fibre is vertically cut in the length direction with fiber It is observed in the state of beam, for the 5 superfine fibre beams observed, calculates in its outer perimeter and thickness is 1 μm or more The ratio of the part of resin coating contact.Amount to the high score bullet in 50 superfine fibre sections by 5 × 10 images of calculating The average value of property body envelope rate is evaluated.The schematic diagram of Fig. 4 expression parameter B computational methods.Fig. 4 be parameter B superfine fibre and/ Or the schematic diagram of the periphery 2 and the periphery 3 covered by macromolecular elastomer envelope of superfine fibre beam, and illustrate that bold portion is ultra-fine The periphery 2 of fibre bundle, dotted portion are the periphery 3 covered by macromolecular elastomer envelope.

[preparation of polyurethane liquid A]

[ASAHI KASEI CHEMICALS (strain) make " DURANOL " (registrar to the polycarbonate glycol for being 2,000 by Mn Mark) T5652] it is used as polyalcohol, MDI is used as isocyanates, 2,2- dihydromethyl propionic acids are used as intramolecular hydrophilic radical, After prepolymer being made in toluene solvant, addition water, the ethylene glycol as chain extender and ethylenediamine, gathering as external emulsification agent Ethylene oxide nonylplenyl ether after stirring, eliminates toluene by decompression, obtains water dispersant type polyaminoester dispersion liquid A.

[preparation of polyurethane liquid B]

[ASAHI KASEI CHEMICALS (strain) make " DURANOL " (registrar to the polycarbonate glycol for being 2,000 by Mn Mark) T6002] it is used as polyalcohol, IPDI is used as isocyanates, will there are the diatomic alcohol compounds and 2 of polyethylene glycol in side chain, 2- dihydromethyl propionic acids are used as intramolecular hydrophilic radical, after making prepolymer in acetone solvent, add water and as chain extension The ethylene glycol and ethylenediamine of agent after stirring, eliminate acetone by decompression, obtain water dispersant type polyaminoester dispersion liquid B.

[preparation of polyurethane liquid C]

[ASAHI KASEI CHEMICALS (strain) make " DURANOL " (registrar to the polycarbonate glycol for being 2,000 by Mn Mark) T5652] it is used as polyalcohol, IPDI is used as isocyanates, trimethylolpropane is used as intramolecular hydrophilic radical, After making prepolymer in methyl acetate, water, the ethylene glycol as chain extender and ethylenediamine are added, as external emulsification agent Ethylene nonyl phenyl ether, after stirring, by decompression eliminate demethyl ethyl ketone, obtain water dispersant type polyaminoester dispersion liquid C。

[embodiment 1]

As sea component, there is the polyethylene terephthalate of the 5-sodium sulfo isophthalate of 8 moles of % using copolymerization Ester, using polyethylene terephthalate, is divided into 20 mass %, island component is 80 mass %'s as island component with marine origin Recombination rate obtains the long filament (filament) of 16 islands island Shuo Wei/1, the islands-in-sea bicomponent fibre that avarage fiber diameter is 20 μm.It will Obtained islands-in-sea bicomponent fibre cuts into the fibre length of 51mm, and staple fiber (staple) is made, and passes through carding machine (card) And cross lapping machine (crosslapper) forms web, and non-woven fabrics is made using needling treatment.

The non-woven fabrics obtained in the above manner is impregnated 2 minutes in the hot water that temperature is 97 DEG C, makes its contraction, in 100 DEG C of temperature makes it dry 5 minutes.Then, polyurethane solid component concentration is being made to the 20% poly- ammonia of water-dispersion type Relative to the association thickener that polyurethane solid state component is 4 mass %, [SAN NOPCO (strain) make for addition in ester dispersion liquid A " Thickener 627N "] active ingredient, the magnesium sulfate relative to polyurethane solid state component for 1.2 mass % disperseed Liquid, in the non-woven fabrics that gained dispersion liquid is impregnated in, after being handled 1 minute in the hot water that temperature is 95 DEG C, in 100 DEG C Drying temperature makes its heated-air drying 15 minutes, and then, further obtained sheet material is added 20 points of heating by the temperature in 160 DEG C Clock.

It has obtained imparting moisture in such a way that polyurethane quality is 35 mass % relative to the island component quality of non-woven fabrics Dissipate the sheet material of type polyurethane.Falling off for polyurethane of the polyurethane in hot water coagulation is 0.1%, almost without falling off.

Then, the sheet material obtained in the above manner is immersed in 10g/L's that be heated to 95 DEG C of temperature, a concentration of In sodium hydrate aqueous solution, processing in 25 minutes, the de-sea sheet material of the sea component for the islands-in-sea bicomponent fibre that has been removed are carried out. A diameter of 4.2 μm of the average single fiber of the single fiber on obtained the de-sea sheet material surface.Then, using with annular belt knife The half of (endless band knife) cuts out machine, and the de-sea sheet material is cut into two halves along the direction vertical with thickness direction, utilizes 120 The sand paper of mesh and 240 mesh is ground the face for not carrying out half sanction side, implements raising processing.Then, it is contaminated using circular Color machine is dyed using disperse dyes and is carried out reduction washing, and it is 221g/m to obtain weight per unit area²Artificial leather. The exterior quality of the artificial leather arrived is good, and feel is also good, no class paper sense.Parameter A is 4.0%, and parameter B is 27.1%.

[embodiment 2]

In the above-mentioned water dispersant type polyaminoester dispersion liquid A that solid component concentration is adjusted to 20% addition relative to The active ingredient for the epoxies crosslinking agent [DIC (strain) make " CR-5L "] that polyurethane solid state component is 5 mass %, relative to poly- ammonia The active ingredient for the association thickener [SAN NOPCO (strain) make " Thickener 627N "] that ester solid state component is 4 mass %, And the magnesium sulfate relative to polyurethane solid state component for 1.2 mass % obtains dispersion liquid, and gained dispersion liquid is impregnated in and reality It applies in 1 identical non-woven fabrics of example, in addition to this, operates similarly with example 1, it is 223g/m to obtain weight per unit area²'s Artificial leather.Falling off for polyurethane of the water dispersant type polyaminoester in hot water coagulation is 0.1%, almost without falling off.Obtained people The exterior quality of fabricate-leather is good, and feel is also good, no class paper sense.Parameter A is 4.1%, and parameter B is 25.4%.

[embodiment 3]

As sea component, there is the polyethylene terephthalate of the 5-sodium sulfo isophthalate of 8 moles of % using copolymerization Ester, using polyethylene terephthalate, is divided into 20 mass %, island component is 80 mass %'s as island component with marine origin Composite quality ratio obtains the long filament of 16 islands island Shuo Wei/1, the islands-in-sea bicomponent fibre that avarage fiber diameter is 20 μm.By what is obtained Islands-in-sea bicomponent fibre cuts into the fibre length of 51mm, and staple fiber is made, and fiber is formed by carding machine and cross lapping machine Non-woven fabrics is made using needling treatment in net.

The non-woven fabrics obtained in the above manner is impregnated 5 minutes in the hot water that temperature is 97 DEG C, makes its contraction, in 100 DEG C of temperature makes it dry 10 minutes.Then, it is 99% by saponification degree to obtained non-woven fabrics imparting, the degree of polymerization 1400 PVA [Japan's synthesis chemical (strain) system " NM-14 "] be adjusted to it is water-soluble obtained from the aqueous solution that solid state component is 10 mass % Liquid is dried 10 minutes in 100 DEG C of temperature, is then heated in the addition of 150 DEG C of temperature implementation 20 minutes, obtain sheet material.It connects It, the sheet material obtained in the above manner is immersed in the sodium hydroxide of 100g/L that be heated to 50 DEG C of temperature, a concentration of In aqueous solution, processing in 20 minutes, the de-sea sheet material of the sea component for the islands-in-sea bicomponent fibre that has been removed are carried out.What is obtained is de- The avarage fiber diameter of the single fiber on the surface of extra large sheet material is 4.2 μm.Then, the moisture that will have been prepared similarly to Example 2 It dissipates type polyurethane dispersion liquid A to be impregnated in the de-sea sheet material, after handling 1 minute in the hot water that temperature is 95 DEG C, in 100 DEG C do Dry temperature makes its heated-air drying 15 minutes, obtained with polyurethane quality relative to non-woven fabrics island component quality be 35 mass % Mode impart the sheet material of water dispersant type polyaminoester.By the above-mentioned sheet material for imparting water dispersant type polyaminoester temperature be 98 DEG C Hot water in impregnate 10 minutes, remove the PVA that has assigned, then the temperature in 100 DEG C is dried 10 minutes.Then, further in Obtained sheet material is added heating 20 minutes by 160 DEG C of temperature.

Then, machine is cut out using half with annular belt knife, the de-sea sheet material is cut into two along the direction vertical with thickness direction Half, the face for not carrying out half sanction side is ground using the sand paper of 120 mesh and 240 mesh, carries out raising processing, then, is used Circular overflow dyeing machines are dyed using disperse dyes and are carried out reduction washing, and it is 230g/m to obtain weight per unit area²'s Artificial leather.Falling off for polyurethane of the water dispersant type polyaminoester in hot water coagulation is 0.2%, almost without falling off.Obtained people The exterior quality of fabricate-leather is good, and feel is also good, no class paper sense.Parameter A is 3.8%, and parameter B is 20.3%.

[embodiment 4]

Addition is relative to poly- in the above-mentioned water dispersant type polyaminoester dispersion liquid B that solid component concentration is adjusted to 20% The association thickener [SAN NOPCO (strain) make " Thickener 623N "] that urethane solid state component is 3 mass % it is effective at Divide and obtain dispersion liquid, gained dispersion liquid is impregnated in non-woven fabrics same as Example 1, it is in addition to this, same with embodiment 1 It operates to sample, it is 218g/m to obtain weight per unit area²Artificial leather.

Falling off for polyurethane of the water dispersant type polyaminoester in hot water coagulation is 0.1%, almost without falling off.Obtained people The exterior quality of fabricate-leather is good, and feel is also good, no class paper sense.Parameter A is 4.0%, and parameter B is 26.8%.

[embodiment 5]

Addition is relative to poly- in the above-mentioned water dispersant type polyaminoester dispersion liquid B that solid component concentration is adjusted to 20% [Bayer Material Science (strain) make " Desmodur " (note to the water-based isocyanate that urethane solid state component is 3 mass % Volume trade mark) N3900] and active ingredient, relative to polyurethane solid state component be 3 mass % carbodiimide class crosslinking agent The active ingredient of [Nisshinbo Chemical (strain) make " Carbodilite " (registered trademark) V-02-L2] and relative to poly- The association thickener [SAN NOPCO (strain) make " Thickener 623N "] that urethane solid state component is 3 mass % it is effective at Divide and obtain dispersion liquid, the dispersion liquid of gained is impregnated in non-woven fabrics same as Example 1, in addition to this, with embodiment 1 It similarly operates, it is 220g/m to obtain weight per unit area²Artificial leather.

Falling off for polyurethane of the water dispersant type polyaminoester in hot water coagulation is 0.2%, almost without falling off.Obtained people The exterior quality of fabricate-leather is good, and feel is also good, no class paper sense.Parameter A is 4.3%, and parameter B is 30.3%.

[embodiment 6]

Addition is relative to poly- in the above-mentioned water dispersant type polyaminoester dispersion liquid B that solid component concentration is adjusted to 20% [Bayer Material Science (strain) make " Desmodur " (note to the water-based isocyanate that urethane solid state component is 3 mass % Volume trade mark) N3900] and active ingredient, relative to polyurethane solid state component be 3 mass % carbodiimide class crosslinking agent The active ingredient of [Nisshinbo Chemical (strain) make " Carbodilite " (registered trademark) V-02-L2] and relative to poly- The association thickener [SAN NOPCO (strain) make " Thickener 623N "] that urethane solid state component is 3 mass % it is effective at Divide and obtain dispersion liquid, the dispersion liquid of gained is impregnated in non-woven fabrics same as Example 3, in addition to this, with embodiment 3 It similarly operates, it is 220g/m to obtain weight per unit area²Artificial leather.

Falling off for polyurethane of the water dispersant type polyaminoester in hot water coagulation is 0.2%, almost without falling off.Obtained people The exterior quality of fabricate-leather is good, and feel is also good, no class paper sense.Parameter A is 4.2%, and parameter B is 20.4%.

[embodiment 7]

Using the island-in-sea type composite fiber of embodiment 1, web, the fibre that will be obtained are formed by carding machine and cross lapping machine It is folded to tie up stratum reticulare, then, by the twist yarn of longitude and latitude be 84dtex-72 long filaments, to knit density be every 1 inch 96 × 76 (warp × latitude) Woven layer is laminated on the surface and the back side of above-mentioned laminated fabric net, then utilizes needling treatment, stacking non-woven fabrics is made, and with poly- Urethane quality relative to and the island component quality of non-woven fabrics assign water dispersant type polyaminoester as the mode of 28 mass %, also, Cut out machine using half with annular belt knife, the de-sea sheet material be cut into two halves along the direction vertical with thickness direction, using 120 mesh and The sand paper of 240 mesh is ground to having carried out the face that half cuts out side, carries out raising processing, in addition to this, similarly to Example 6 Ground operates, and it is 393g/m to obtain weight per unit area²Artificial leather.Polyurethane of the water dispersant type polyaminoester in hot water coagulation It is 0.2% to fall off, almost without falling off.The exterior quality of obtained artificial leather is good, and feel is also good, no class paper sense.Parameter A It is 3.6%, parameter B is 20.1%.

[embodiment 8]

In the above-mentioned water dispersant type polyaminoester dispersion liquid A that solid component concentration is adjusted to 20%, addition relative to [Bayer Material Science (strain) make " Desmodur to the water-based isocyanate that polyurethane solid state component is 3 mass % (registered trademark) " N3900] active ingredient, relative to polyurethane solid state component be 3 mass % carbodiimide class crosslinking agent The active ingredient of [Nisshinbo Chemical (strain) make " Carbodilite " (registered trademark) V-02-L2], relative to poly- ammonia The active ingredient of the guar gum [sun chemistry (strain) makes " Neosoft G "] for the thickening polysaccharide that ester solid state component is 2 mass %, And dispersion liquid is obtained relative to the magnesium sulfate that polyurethane solid state component is 1.2 mass %, gained dispersion liquid is impregnated in and is implemented In 3 identical non-woven fabrics of example, and handle 3 minutes in the hot water of 95 DEG C of temperature after polyurethane dispersing liquid impregnation, in addition to this, It operates similarly to Example 3, it is 221g/m to obtain weight per unit area²Artificial leather.

Falling off for polyurethane of the water dispersant type polyaminoester in hot water coagulation is 0.1%, almost without falling off.In addition, with The face that half sanction machine has been cut into two halves does not have the attachment of polyurethane uneven, and polyurethane is equably impregnated in fibrous substrate.It obtains Artificial leather exterior quality it is good, feel is also good, no class paper sense.Parameter A is 3.3%, and parameter B is 18.9%.

[embodiment 9]

Using the island-in-sea type composite fiber of embodiment 1, web, the fibre that will be obtained are formed by carding machine and cross lapping machine It is folded to tie up stratum reticulare, then, by the twist yarn of longitude and latitude be 84dtex-72 long filaments, to knit density be every 1 inch 96 × 76 (warp × latitude) Woven layer is laminated on the surface and the back side of above-mentioned laminated fabric net, then utilizes needling treatment, stacking non-woven fabrics is made, and with poly- Urethane quality relative to and the island component quality of non-woven fabrics assign water dispersant type polyaminoester as the mode of 28 mass %, also, Cut out machine using half with annular belt knife, the de-sea sheet material be cut into two halves along the direction vertical with thickness direction, using 120 mesh and The sand paper of 240 mesh is ground to having carried out the face that half cuts out side, carries out raising processing, in addition to this, similarly to Example 8 Ground operates, and it is 390g/m to obtain weight per unit area²Artificial leather.Polyurethane of the water dispersant type polyaminoester in hot water coagulation It is 0.1% to fall off, almost without falling off.There is no the attachment of polyurethane uneven in addition, being cut into the face of two halves with half sanction machine, poly- ammonia Ester is equably impregnated in fibrous substrate.The exterior quality of obtained artificial leather is good, and feel is also good, no class paper sense.Ginseng Number A is 2.9%, and parameter B is 19.2%.

[embodiment 10]

Not implementing the PVA that saponification degree is 99%, the degree of polymerization is 1400 to non-woven fabrics, [Japan's synthesis chemical (strain) makes " NM- 14 "] imparting and drying operate similarly to Example 9 in addition to this, and it is 388g/m to obtain weight per unit area²It is artificial Leather.Falling off for polyurethane of the water dispersant type polyaminoester in hot water coagulation is 0.1%, almost without falling off.In addition, cutting out machine with half The face for being cut into two halves does not have the attachment of polyurethane uneven, and polyurethane is equably impregnated in fibrous substrate.What is obtained is artificial The exterior quality of leather is good, and feel is also good, no class paper sense.Parameter A is 1.1%, and parameter B is 4.9%.

[embodiment 11]

In the above-mentioned water dispersant type polyaminoester dispersion liquid B that solid component concentration is adjusted to 20%, addition relative to [Bayer Material Science (strain) make " Desmodur " to the water-based isocyanate that polyurethane solid state component is 4 mass % (registered trademark) N3900] active ingredient, relative to polyurethane solid state component be 2.5 mass % thickening polysaccharide Guar The active ingredient of glue [sun chemistry (strain) system " Neosoft G "] and obtain dispersion liquid, gained dispersion liquid is impregnated in non-woven fabrics In, it in addition to this, operates similarly to Example 9, it is 388g/m to obtain weight per unit area²Artificial leather.

Falling off for polyurethane of the water dispersant type polyaminoester in hot water coagulation is 0.1%, almost without falling off.In addition, with The face that half sanction machine has been cut into two halves does not have the attachment of polyurethane uneven, and polyurethane is equably impregnated in fibrous substrate.It obtains Artificial leather exterior quality it is good, feel is also good, no class paper sense.Parameter A is 2.5%, and parameter B is 14.3%.

[embodiment 12]

In the above-mentioned water dispersant type polyaminoester dispersion liquid C that solid component concentration is adjusted to 20%, addition is opposite In the carbodiimide class crosslinking agent that polyurethane solid state component is 4 mass %, [Nisshinbo Chemical (strain) make " Carbodilite " (registered trademark) V-02-L2] active ingredient, relative to polyurethane solid state component be 2 mass % thickening The active ingredient of the guar gum [sun chemistry (strain) system " Neosoft G "] of polysaccharide and relative to polyurethane solid state component it is The magnesium sulfate of 3.0 mass % and obtain dispersion liquid, gained dispersion liquid is impregnated in non-woven fabrics, it is in addition to this, same with embodiment 9 It operates to sample, it is 386g/m to obtain weight per unit area²Artificial leather.

Falling off for polyurethane of the water dispersant type polyaminoester in hot water coagulation is 0.1%, almost without falling off.In addition, with The face that half sanction machine has been cut into two halves does not have the attachment of polyurethane uneven, and polyurethane is equably impregnated in fibrous substrate.It obtains Artificial leather exterior quality it is good, feel is also good, no class paper sense.Parameter A is 1.2%, and parameter B is 5.2%.

[embodiment 13]

Not implementing the PVA that saponification degree is 99%, the degree of polymerization is 1400 to non-woven fabrics, [Japan's synthesis chemical (strain) makes " NM- 14 "] imparting and drying operate similarly to Example 12 in addition to this, and it is 388g/m to obtain weight per unit area²People Fabricate-leather.Falling off for polyurethane of the water dispersant type polyaminoester in hot water coagulation is 0.1%, almost without falling off.In addition, being cut out with half The face that machine has been cut into two halves does not have the attachment of polyurethane uneven, and polyurethane is equably impregnated in fibrous substrate.Obtained people The exterior quality of fabricate-leather is good, and feel is also good, no class paper sense.Parameter A is 0.7%, and parameter B is 4.0%.

Fig. 1 shows the sections of the artificial leather obtained in embodiment 13.The polyurethane that is observed in the section of Fig. 1 and super The state of fine fibre beam is as follows：Polyurethane section few (caking of polyurethane is small), in addition, superfine fibre beam and polyurethane bonding Also few.

[comparative example 1]

In the above-mentioned water dispersant type polyaminoester dispersion liquid A that solid component concentration is adjusted to 20%, addition relative to Polyurethane solid state component obtains dispersion liquid for the magnesium sulfate of 1.2 mass %, gained dispersion liquid is impregnated in same as Example 1 Non-woven fabrics in, in addition to this, operate similarly with example 1, obtain weight per unit area be 223g/m²Artificial leather.Water It is 22.1% to disperse the falling off of polyurethane of the type polyurethane in hot water coagulation, and polyurethane has occurred for the attached of fibrous substrate Unevenness.

[comparative example 2]

The above-mentioned water dispersant type polyaminoester dispersion liquid B that solid component concentration is adjusted to 20% is impregnated in and embodiment It in 1 identical non-woven fabrics, in addition to this, operates similarly with example 1, it is 223g/m to obtain weight per unit area²It is artificial Leather.Falling off for polyurethane of the polyurethane in hot water coagulation is 15.1%, and attachment of the polyurethane for fibrous substrate has occurred It is uneven.

[comparative example 3]

The above-mentioned water dispersant type polyaminoester dispersion liquid B that solid component concentration is adjusted to 20% is impregnated in and embodiment In 1 identical non-woven fabrics, is handled after five minutes under 97 DEG C of temperature, the damp and hot atmosphere of humidity 100%, make it in 110 DEG C of temperature It dries 15 minutes, it is poly- to assign water-dispersion type in such a way that polyurethane quality is 35 mass % relative to the island component quality of non-woven fabrics Urethane resin operates similarly with example 1 in addition to this, and it is 223g/m to obtain weight per unit area²Artificial leather.Moisture It is 0.0% to dissipate falling off for polyurethane of the type polyurethane in hot water coagulation, but the class paper sense of the feel of obtained artificial leather is strong.Ginseng Number A is 7.9%, and parameter B is 42.2%.

[comparative example 4]

The above-mentioned water dispersant type polyaminoester dispersion liquid B that solid component concentration is adjusted to 20% is impregnated in and embodiment In 13 identical non-woven fabrics, handles after five minutes under 97 DEG C of temperature, the damp and hot atmosphere of humidity 100%, make in 110 DEG C of temperature It is dried 15 minutes, is assigned in such a way that polyurethane quality becomes 28 mass % relative to the island component quality of non-woven fabrics water-dispersed Type polyurethane resin operates similarly to Example 13 in addition to this, and it is 389g/m to obtain weight per unit area²Artificial leather. Falling off for polyurethane of the water dispersant type polyaminoester in hot water coagulation is 0.0%, but the class paper sense of the feel of obtained artificial leather By force.Parameter A is 8.1%, and parameter B is 43.1%.

Fig. 2 indicates the section of the artificial leather obtained in comparative example 4.The polyurethane that is observed in the section of Fig. 2 and ultra-fine The state of fibre bundle is as follows：Polyurethane section more (caking of polyurethane is big), in addition, the bonding of superfine fibre beam and polyurethane compared with It is more.

By the result of above-described embodiment 1~7 and comparative example 1~4 conclude it is shown in table 1,2.

[table 2]

【Table 2】

The numerical value of the parameter A of embodiment is compared with smaller for comparative example, and therefore, polyurethane block is small, and polyurethane equably divides It dissipates inside artificial leather, forms soft feel.In addition, the parameter B of embodiment is compared with also therefore smaller surpasses for comparative example The bonding of fine fibre beam and polyurethane is few, forms soft feel.

Reference sign

1：Polyurethane block

2：The periphery of superfine fibre beam

3：The periphery covered by macromolecular elastomer envelope

Claims

1. a kind of manufacturing method of tablet, which is characterized in that have in the fibrous substrate imparting to being formed by superfine fibre In manufacturing method of the macromolecular elastomer of hydrophilic radical as tablet made of binder, fibrous substrate imparting is contained There are the macromolecular elastomer being dispersed in water, the aqueous resin dispersion of heat coagulant and the thickening polysaccharide as thickener, Solidify the macromolecular elastomer in the hot water that temperature is 50~100 DEG C.

2. the manufacturing method of tablet as described in claim 1, which is characterized in that non newtonian is presented in aqueous resin dispersion Property.

3. the manufacturing method of tablet as claimed in claim 1 or 2, which is characterized in that thixotroping is presented in aqueous resin dispersion Property.

4. the manufacturing method of tablet as claimed in claim 1 or 2, which is characterized in that thickener is guar gum.

5. the manufacturing method of tablet as claimed in claim 3, which is characterized in that thickener is guar gum.

6. the manufacturing method of tablet as claimed in claim 1 or 2, which is characterized in that aqueous resin dispersion is containing crosslinking Agent.

7. the manufacturing method of the tablet as claimed in claim 3, which is characterized in that aqueous resin dispersion contains friendship Join agent.

8. the manufacturing method of the tablet as claimed in claim 4, which is characterized in that aqueous resin dispersion contains friendship Join agent.

9. the manufacturing method of the tablet as claimed in claim 5, which is characterized in that aqueous resin dispersion contains friendship Join agent.

10. the manufacturing method of tablet as claimed in claim 1 or 2, which is characterized in that macromolecular elastomer is water-dispersion type Polyurethane.

11. the manufacturing method of tablet as claimed in claim 3, which is characterized in that macromolecular elastomer is poly- for water-dispersion type Urethane.

12. the manufacturing method of tablet as claimed in claim 4, which is characterized in that macromolecular elastomer is poly- for water-dispersion type Urethane.

13. the manufacturing method of tablet as claimed in claim 5, which is characterized in that macromolecular elastomer is poly- for water-dispersion type Urethane.

14. the manufacturing method of tablet as claimed in claim 6, which is characterized in that macromolecular elastomer is poly- for water-dispersion type Urethane.

15. the manufacturing method of tablet as claimed in claim 7, which is characterized in that macromolecular elastomer is poly- for water-dispersion type Urethane.

16. the manufacturing method of tablet as claimed in claim 8, which is characterized in that macromolecular elastomer is poly- for water-dispersion type Urethane.

17. the manufacturing method of tablet as claimed in claim 9, which is characterized in that macromolecular elastomer is poly- for water-dispersion type Urethane.

18. the tablet that a kind of manufacturing method using described in any one of claim 1~17 obtains, is to by superfine fibre And/or macromolecular elastomer of the fibrous substrate imparting with hydrophilic radical that superfine fibre beam is formed is formed as binder Tablet, which is characterized in that in section, observed in cutting section obtained by the through-thickness cutting of the tablet The macromolecular elastomer in, it is independent that simultaneously there are 50 μm relative to the area in the artificial leather section in field of view²Above The possession ratio of the part of area of section is 0.1% or more and 5.0% or less.

19. tablet as claimed in claim 18, which is characterized in that the section obtained by the through-thickness cutting of tablet In, 1% or more and the 35% or less of the periphery of superfine fibre and/or superfine fibre area of beam is covered by macromolecular elastomer envelope Lid.

20. the tablet as described in claim 18 or 19, which is characterized in that macromolecular elastomer has via cross-linking agents Obtained by structure.