TWI711660B - Sheet and its manufacturing method - Google Patents

Abstract

The present invention relates to a method for manufacturing a sheet material that does not use organic solvents in the manufacturing step, and provides a uniform feeling that is not inferior to artificial leather using organic solvent-based polyurethane. It is a sheet with good surface quality and tactility and its manufacturing method.

The sheet-like article of the present invention is a sheet-like article in which a polymer elastomer having a hydrophilic group is applied as a binding agent to a fibrous base material containing ultrafine fibers and/or ultrafine fiber bundles. On the cross-section cut in the thickness direction of the object, among the aforementioned polymer elastomers observed in the cut plane, the occupancy rate of the independent part having a cross-sectional area of 50μm ² or more is relative to the artificial Leather with a cross-sectional area of 0.1% to 5.0%.

The manufacturing method of the sheet-like article of the present invention is a method for manufacturing a sheet-like article in which a polymer elastomer having a hydrophilic group is applied as a binder to a fibrous base material containing ultrafine fibers and/or ultrafine fiber bundles. It is a method in which an aqueous resin dispersion containing a polymer elastomer dispersed in water and a tackifier is applied to a fibrous substrate, and the polymer elastomer is coagulated in hot water at a temperature of 50-100°C.

Description

Sheet and its manufacturing method

The present invention relates to a method of manufacturing a sheet with environmental considerations that does not use an organic solvent in the manufacturing step, and particularly to a sheet with good surface quality and good touch, and a manufacturing method thereof.

The sheet-like material mainly composed of a fibrous base material such as non-woven fabric and polyurethane has good characteristics not found in natural leather, but is widely used in various applications such as artificial leather. In particular, since the sheet-like article using a polyester-based fibrous base material has good light resistance, its use in clothing, seat covers, and automotive interior materials is expanding year by year.

When manufacturing such a sheet, generally speaking, after impregnating the fibrous substrate with an organic solvent solution of polyurethane, the obtained fibrous substrate is immersed in the non-polyurethane. A combination of the steps of wet solidification of the polyurethane in water or an aqueous organic solvent solution. In this case, as for the organic solvent of the polyurethane solvent, a water-miscible organic solvent such as N,N-dimethylformamide is used. However, because organic solvents are generally highly harmful to the human body and the environment, there is a strong desire not to use organic solvents in the production of sheet materials.

As a specific solution, there is research and use to make hydrophilic The water-dispersible polyurethane in which the sexual group is contained in the molecule and the polyurethane is dispersed in water replaces the conventional method of organic solvent-based polyurethane.

However, the fibrous base material is impregnated with a water-dispersible polyurethane dispersion in which a water-dispersible polyurethane is dispersed in a liquid and solidifies a sheet of polyurethane, which is called The problem that the touch is easy to harden.

As one of the main reasons, there is a difference between the solidification methods of the two. That is, the coagulation method of the organic solvent-based polyurethane liquid is the so-called wet coagulation method in which the polyurethane molecules dissolved in the organic solvent are replaced with water as a solvent to coagulate. Viewed from the formate film, a porous film with low density is formed. Therefore, when the polyurethane is impregnated in the fibrous base material and coagulated, the area where the fiber and the polyurethane are bonded is also reduced, and it becomes a soft sheet.

In addition, the water-dispersed polyurethane system collapses the hydration state of the water-dispersed polyurethane dispersion mainly by heating, and coagulates by coagulating the polyurethane emulsions. The so-called moist heat coagulation method is the mainstream, and the obtained polyurethane film structure is a non-porous film with high density. Therefore, the adhesion between the fibrous base material and the polyurethane becomes tight, and the interwoven part of the fiber is firmly clamped, so the touch becomes hard.

In order to improve the tactile feel caused by the use of the water-dispersed polyurethane, that is, to inhibit the clamping of fiber interweaving points caused by the polyurethane, it has been proposed to make the polyurethane in the fibrous substrate The structure of formate is a technology of porous structure.

Specifically, it has been proposed to apply a water-dispersed polyurethane liquid containing a foaming agent to a fibrous substrate such as non-woven fabric, and to foam the foaming agent by heating to make the fibrous substrate A method in which the polyurethane structure becomes a porous structure (refer to Patent Document 1). Although this proposal can make the water-dispersible polyurethane porous, the bonding area between the fiber and the polyurethane is reduced, and the clamping force of the fiber interlacing point is weakened, so as to obtain a soft touch. A sheet-like article having a good touch, but compared with the case where an organic solvent-based polyurethane is provided, it still tends to lack flexibility.

In addition, as a technique for making the polyurethane structure in the fibrous substrate into a porous structure, it has been proposed to provide the fibrous substrate with a water-dispersed polyurethane containing a bonding type thickener. A method of making the water-dispersed polyurethane porous by coagulating the ester dispersion liquid under moist heat (see Patent Document 2). Although this proposal can also make the water-dispersible polyurethane porous, the bonding area between the fiber and the polyurethane is reduced, and the clamping force of the fiber interlacing point is weakened, so as to obtain a soft touch. Although it is a sheet-like article with a good touch, it still tends to lack flexibility compared with the case where an organic solvent-based polyurethane is provided.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2011-214210 A

[Patent Document 2] Japanese Patent No. 4042016

Therefore, the object of the present invention is in view of the background of the above-mentioned prior art, and is to provide a sheet-like material and a manufacturing method thereof with environmentally-conscious manufacturing steps, and the sheet-like material has an organic solvent-based polyamine group Compared with the artificial leather of formate, it is not inferior to the uniformity, has a beautiful surface quality and a good touch.

Furthermore, the object of the present invention is to provide a sheet-like article and a manufacturing method thereof, and the sheet-like article is formed by using water-dispersed polyurethane to complete the porous structure of the polyurethane, and It has wrinkle recovery and flexibility similar to artificial leather using solvent-based polyurethane.

The present invention has accomplished the above-mentioned problems. The sheet-like article of the present invention is a sheet-like article obtained by imparting a polymer elastomer having a hydrophilic group as an adhesive to a fibrous base material containing ultrafine fibers and/or ultrafine fiber bundles. , Characterized in that: in the section of the aforementioned sheet material cut in the thickness direction, the occupancy rate of the part of the aforementioned polymer elastomer observed in the cut plane independently and having a cross-sectional area of 50μm ² or more is relative A sheet with a cross-sectional area of the artificial leather in the observation field of 0.1% or more and 5.0% or less.

According to the preferred aspect of the sheet-like article of the present invention, on the cross-section cut in the thickness direction of the aforementioned sheet-like article, 1% to 35% of the periphery of the section of the ultrafine fiber and/or ultrafine fiber bundle is covered by The polymer elastomer is covered by the membrane.

According to a preferred aspect of the sheet-like article of the present invention, it is the sheet-like article as described in claim 1 or 2, which is characterized in that the aforementioned polymer elastic system has a structure crosslinked by a crosslinking agent.

The present invention has accomplished the above-mentioned problems, and the method for producing a sheet-like article of the present invention is characterized by applying a polymer elastomer having a hydrophilic group as a binding agent to a fibrous substrate containing ultrafine fibers. In the manufacturing method, an aqueous resin dispersion containing a polymer elastomer dispersed in water and a tackifier is applied to the fibrous substrate, and the polymer elastomer is coagulated in hot water at a temperature of 50 to 100°C. The manufacturing method of the object.

According to a preferred aspect of the method for manufacturing a sheet-like article of the present invention, the aforementioned aqueous resin dispersion system exhibits non-Newtonian fluidity.

According to a preferred aspect of the method of manufacturing a sheet-like article of the present invention, the aforementioned thickener is a nonionic thickener.

According to a preferred aspect of the method for producing a sheet-like article of the present invention, the aforementioned aqueous resin dispersion system exhibits thixotropy.

According to a preferred aspect of the method of manufacturing a sheet-like article of the present invention, the thickener contained in the aforementioned aqueous resin dispersion is a thickening polysaccharide.

According to a preferred aspect of the method for manufacturing a sheet of the present invention, the aforementioned thickening agent is Guar gum.

According to a preferred aspect of the method of manufacturing a sheet-like article of the present invention, the aforementioned aqueous resin dispersion contains a heat-sensitive coagulant.

According to a preferred aspect of the method for producing a sheet-like article of the present invention, the aforementioned aqueous resin dispersion contains a crosslinking agent.

According to the present invention, it is possible to structure water-dispersed polyurethane into a porous structure by considering the manufacturing steps of the environment, and achieve To achieve the wrinkle recovery and flexibility similar to those in the case of imparting organic solvent-based polyurethane to the fibrous substrate, it is further possible to obtain a sheet-like material that contains and uses organic solvent-based polyurethane. The artificial leather has a fairly uniform raised length, and has a beautiful surface quality with excellent fiber density and a good touch of softness and excellent wrinkle recovery.

1‧‧‧Polyurethane block

2‧‧‧The periphery of the ultra-fine fiber bundle

3‧‧‧The periphery covered by the polymer elastomer film

[Figure 1] Figure 1 is a graphical representation of a cross-section of the artificial leather obtained in Example 13 of the present invention instead of an SEM photograph.

[Fig. 2] Fig. 2 is an illustration of a cross-section of the artificial leather obtained in Comparative Example 4 of the present invention instead of a SEM photograph.

[Fig. 3] Fig. 3 is a diagram for explaining the outline of the calculation method of the non-porous block occupancy rate of the polymer elastomer of 50μm ² or more, instead of the reference SEM photograph.

[Fig. 4] Fig. 4 is an illustration for explaining the calculation method of the polymer elastomer coating ratio of the ultrafine fiber cross section instead of the reference SEM photograph.

[About flakes]

First, the sheet of the present invention will be explained.

The sheet-like article of the present invention contains a polymer elastomer containing a hydrophilic group-containing resin such as water-dispersed polyurethane as a binder and is applied to a fibrous base material such as a nonwoven fabric containing ultrafine fibers.

Examples of fibers constituting the fibrous base material include polyester and nylon-6 containing polyethylene terephthalate, polybutylene terephthalate, trimethylene terephthalate, and polylactic acid. Or polyamide such as nylon-66 Thermoplastic resin fibers such as amine, acrylic, polyethylene, polypropylene, and thermoplastic cellulose that can be melt-spun. Among them, from the standpoint of strength, dimensional stability, and light resistance, polyester fiber is preferred. In addition, the fibrous base material can also be formed by mixing fibers of different materials.

Although the cross-sectional shape of the ultrafine fiber may be a circular cross-section, it is also possible to adopt a cross-sectional shape with a different cross-section such as an ellipse, a flat shape, and a triangular shape, a fan shape, and a cross shape.

The average single fiber diameter of the ultrafine fibers constituting the fibrous base material is preferably 0.1~7μm. The average single fiber diameter is preferably 7 μm or less, more preferably 6 μm or less, and more preferably 5 μm or less, thereby obtaining a sheet-like article with good flexibility and vertical hair quality. In addition, the average single fiber diameter is preferably 0.1 μm or more, preferably 0.3 μm or more, more preferably 0.7 μm or more, particularly preferably 1 μm or more, and the color development after dyeing or grinding by sandpaper etc. The bundle fiber dispersibility and ease of finishing are good during the iso-raising process.

Regarding the form of the fibrous base material containing ultrafine fibers, textiles, knitwear, non-woven fabrics, etc. can be used. Among them, in view of the good surface quality of the sheet during surface raising treatment, it is better to use non-woven fabric.

Regarding the non-woven fabric, although either short-fiber non-woven fabric and long-fiber non-woven fabric can be used, it is preferable to use short-fiber non-woven fabric from the viewpoint of touch and taste.

The fiber length of the short fiber in the short fiber non-woven fabric is preferably 25 mm or more and 90 mm or less, preferably 35 mm or more and 75 mm or less. It can be obtained by winding the fiber length to 25mm or more Sheets with good abrasion resistance. In addition, by making the fiber length 90 mm or less, a sheet-like article with better tactile quality can be obtained.

When the fibrous base material containing ultrafine fibers is a non-woven fabric, it is preferable that the non-woven fabric has a structure in which ultra-fine fiber bundles (fiber bundles) are entangled. Because the ultra-fine fibers are wound in bundles, the strength of the sheet will increase. Such a non-woven fabric can be obtained by entwining ultra-fine fiber phenotype fibers with each other in advance to express ultra-fine fibers.

When the ultrafine fibers or the fiber bundles constitute a non-woven fabric, for the purpose of increasing the strength inside the non-woven fabric, textiles or knitwear can be inserted. The average single fiber diameter of the fibers constituting such textiles and knitted products is preferably about 0.1 to 10 μm.

In the sheet-like article of the present invention, as for the resin containing the hydrophilic group used as the elastic polymer of the binder, water-dispersed silicone resins, water-dispersed acrylic resins, and water-dispersed amines can be mentioned. Carbamate resins and these copolymers, but among them, it is preferable to use water-dispersed polyurethane from the viewpoint of touch.

As for the polyurethane, it is preferable to be able to use a resin obtained by the reaction of a polymer polyol having a number average molecular weight of 500 or more and 5000 or less, an organic polyisocyanate, and a chain extender. In order to improve the stability of the water-dispersed polyurethane dispersion, a compound containing an active hydrogen component having a hydrophilic group is used in combination. By making the number average molecular weight of the polymer polyol to be 500 or more, preferably 1500 or more, it can prevent the touch from becoming hard, and by making the number average molecular weight to be 5000 or less, preferably 4000 or less, it can be maintained as become The strength of the polyurethane of the adhesive.

As for the polyether polyol among the aforementioned polymer polyols, polyols and polyamines can be used as initiators to add. Polyols polymerized with monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran, chlorocyclopropane, and cyclohexene, as well as proton acid, Lewis acid and cationic catalyst, etc. As a catalyst, a polyol obtained by ring-opening polymerization of the aforementioned monomers. Specifically, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., and copolymerized polyols combining these can be cited.

Examples of polyester-based polyols include polyester polyols obtained by condensing various low-molecular-weight polyols and polybasic acids, or polyols obtained by ring-opening polymerization of lactones.

For low molecular weight polyols, examples can be selected from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7- Straight-chain alkylene glycols such as heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1, Branched alkylene glycols such as 5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,4-cyclohexane One or two or more of alicyclic diols such as diols and aromatic divalent alcohols such as 1,4-bis(β-hydroxyethoxy)benzene. In addition, adducts obtained by adding various alkylene oxides to bisphenol A can also be used as low molecular weight polyols.

Moreover, as for the polybasic acid, it can be selected from succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecane One or more of carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydroisophthalic acid.

In terms of polylactone polyols, polyols can be cited as Initiating agent, and ring-opening polymerization of γ-butyrolactone, γ-valerolactone, and ε-caprolactone alone or a mixture of two or more kinds of polylactone polyols, etc.

Examples of polycarbonate-based polyols include compounds obtained by the reaction of polyols with carbonate compounds such as dialkyl carbonates and diaryl carbonates.

As for the polyol as the raw material for the production of polycarbonate polyol, the polyols exemplified as the raw material for the production of polyester polyol can be used. As dialkyl carbonate, dimethyl carbonate, diethyl carbonate, etc. can be used, and as diaryl carbonate, diphenyl carbonate and the like can be mentioned.

In the polymer elastomer having a hydrophilic group used in the present invention, as a component for making the polymer elastomer contain a hydrophilic group, an active hydrogen component containing a hydrophilic group can be exemplified. Examples of the active hydrogen component containing a hydrophilic group include compounds containing a nonionic group and/or an anionic group and/or a cationic group and active hydrogen. As for the compound having a nonionic group and active hydrogen, a compound containing two or more active hydrogen components or two or more isocyanate groups and having a polyoxyethylene glycol group with a molecular weight of 250 to 9000 in the side chain, etc., And triols such as trimethylolpropane or trimethylolbutane.

In addition, as for compounds having an anionic group and active hydrogen, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, and 2,2-dimethylolvaleric acid can be mentioned. Other carboxyl-containing compounds and their derivatives, or 1,3-phenylenediamine-4,6-disulfonic acid, 3-(2,3-dihydroxypropoxy)-1-propanesulfonic acid, etc. The sulfonic acid group-containing compounds and their derivatives, as well as the salts of these compounds neutralized by neutralizing agents.

Also, for compounds containing cationic groups and active hydrogen In other words, compounds containing tertiary amino groups such as 3-dimethylaminopropanol, N-methyldiethanolamine, and N-propyldiethanolamine, and derivatives thereof can be cited.

The aforementioned active hydrogen component containing a hydrophilic group can be used even in the form of a salt neutralized with a neutralizing agent.

The hydrophilic group-containing active hydrogen component used in the polyurethane molecule, from the viewpoint of the mechanical strength and dispersion stability of the polyurethane resin, uses 2,2-dimethylol Propionic acid, 2,2-dimethylolbutyric acid and these neutralized salts are preferred.

By introducing the aforementioned active hydrogen components containing hydrophilic groups, especially hydroxyl groups, sulfonic acid groups, and carboxyl groups into polyurethane, not only can the hydrophilicity of the polyurethane molecules be improved, but also by A crosslinking agent described later is used in combination to impart a three-dimensional crosslinked structure in the polyurethane molecule to improve physical properties. Therefore, it is preferable to appropriately select and use the aforementioned hydrophilic group-containing active hydrogen component for production.

、4,4’-亞甲二苯胺、甲苯二胺、二甲苯二胺、己二胺、4,4’-二環己基甲烷二胺等的二胺類、或二伸乙三胺等的三胺類、或胺基乙醇及胺基丙醇的等胺基醇等。 As for the chain extender, it is possible to use conventional compounds used in the manufacture of polyurethanes, among which low molecular weights with two or more active hydrogen atoms capable of reacting with isocyanate groups in the molecule are used. Molecular compounds are preferred. Specifically, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,4 -Diols such as cyclohexanediol and benzenedimethanol, or triols such as trimethylolpropane and trimethylolbutane, or hydrazine, ethylenediamine, isophoronediamine, piperazine

, 4,4'-methylene dianiline, toluene diamine, xylene diamine, hexamethylene diamine, 4,4'-dicyclohexyl methane diamine and other diamines, or diethylene triamine and other three Amines, or amino alcohols such as amino ethanol and amino propanol.

As for organic polyisocyanates, aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate (hereinafter referred to as IPDI), hydrogenated xylylene diisocyanate, and dicyclohexyl methane can be cited Alicyclic diisocyanate such as diisocyanate (hereinafter referred to as hydrogenated MDI), or aromatic/aliphatic such as xylylene diisocyanate (hereinafter referred to as XDI) or tetramethyl metaxylylene diisocyanate Group diisocyanate, or toluene diisocyanate (hereinafter referred to as TDI), 4,4'-diphenylmethane diisocyanate (hereinafter referred to as MDI), toluidine diisocyanate, and naphthalene diisocyanate (hereinafter referred to as NDI), etc. The aromatic diisocyanate and so on.

It is possible to introduce a sulfonic acid group, a carboxyl group, a hydroxyl group or a primary or secondary amine group into the polyurethane used in the present invention, and the crosslinking agent reactive with these functional groups can be contained in the polyamine In the carbamic acid ester dispersion liquid, after the reaction, the resin has a high molecular weight and the crosslink density of the resin increases. Therefore, durability, weather resistance, heat resistance, and strength maintenance rate when wet can be further improved.

唑啉系交聯劑、碳二醯亞胺系交聯劑、氮丙啶系交聯劑、環氧交聯劑及肼系交聯劑等的交聯劑。交聯劑係可單獨使用1種，亦能夠併用2種以上。 As the crosslinking agent, a crosslinking agent having two or more reactive groups capable of reacting with the reactive group introduced into the polyurethane can be used in the molecule. Specifically, polyisocyanate-based crosslinking agents such as water-soluble isocyanate compounds or blocked isocyanate compounds, melamine-based crosslinking agents,

Crosslinking agents such as oxazoline crosslinkers, carbodiimide crosslinkers, aziridine crosslinkers, epoxy crosslinkers, and hydrazine crosslinkers. A crosslinking agent system may be used individually by 1 type, and may use 2 or more types together.

Water-soluble isocyanate compounds are those having two or more isocyanate groups in the molecule, such as the aforementioned organic polyisocyanate Ester compounds, etc. As for the commercially available products, the "Bayhydur" (registered trademark) series manufactured by Bayer MaterialScience Co., Ltd., the "Desmodur" (registered trademark) series, and the like can be cited.

The blocked isocyanate compound is a compound having two or more blocked isocyanate groups in the molecule. Blocked isocyanate group means that the aforementioned organic polyisocyanate compound is blocked by alcohols, amines, phenols, imines, or thiols, or pyrazoles, oximes, or active methylenes, etc. Agent and block the thing. The commercially available products include the "ELASTRON" (registered trademark) series of Daiichi Industrial Pharmaceutical Co., Ltd., the "Duranate" (registered trademark) series manufactured by Asahi Kasei Chemical Co., Ltd., and Mitsui Chemicals Co., Ltd. "TAKENATE" (registered trademark) series and so on.

Examples of the melamine-based crosslinking agent include compounds having two or more methylol groups or methoxymethylol groups in the molecule. Commercially available products include the "U-VAN" (registered trademark) series manufactured by Mitsui Chemicals Co., Ltd., the "Cymel" (registered trademark) series manufactured by Nihon Cytec Co., Ltd., and Sumitomo "Sumimal" (registered trademark) series manufactured by Chemical Corporation.

唑啉系交聯劑而言，能夠舉出分子內具有2個以上

唑啉基(

唑啉骨架)的化合物。就市售品而言，能夠舉出日本觸媒股份有限公司製”Epocros”(註冊商標)系列等。就碳二醯亞胺系交聯劑而言，能夠舉出分子內具有2個以上碳二醯亞胺基的化合物。就其市售品而言，能夠舉出日清紡織股份有限公司製”Carbodilite”(註冊商標)系列等。 on

For the oxazoline-based crosslinking agent, there are two or more in the molecule

Oxazoline (

Oxazoline skeleton). As for commercially available products, the "Epocros" (registered trademark) series manufactured by Nippon Shokubai Co., Ltd. can be cited. As the carbodiimide-based crosslinking agent, a compound having two or more carbodiimide groups in the molecule can be mentioned. As for the commercially available products, the "Carbodilite" (registered trademark) series manufactured by Nissin Boshoku Co., Ltd. can be cited.

Examples of epoxy-based crosslinking agents include compounds having two or more epoxy groups in the molecule. As for the commercially available products, the "Denacol" (registered trademark) series manufactured by Nagase Chemical Technology Co., Ltd. and the diepoxy of Sakamoto Pharmaceutical Industry Co., Ltd. can be cited. Polyepoxy compounds, and "EPICRON" (registered trademark) series made by DIC.

Examples of the aziridine-based crosslinking agent include compounds having two or more aziridin groups in the molecule. Examples of the hydrazine-based crosslinking agent include hydrazine and compounds having two or more hydrazine groups (hydrazine skeleton) in the molecule.

Among them, the functional group with polyurethane is preferably a hydroxyl group and/or a carboxyl group and/or a sulfonic acid group, and a crosslinking agent is preferably a polyisocyanate-based crosslinking agent and carbon Diimide compound. In addition, by using a carbodiimide compound and a polyisocyanate-based crosslinking agent in combination, the crosslinked structure of the polyurethane resin can be further improved, and the effect of moisture and heat resistance can be improved while maintaining flexibility.

Since water-dispersed polyurethane generally contains hydrophilic groups in its molecular structure, compared to conventional organic solvent-based polyurethanes, it has high affinity for water molecules and is easy to swell in a humid environment. It is easy to relax the molecular structure of polyurethane, and therefore it tends to be difficult to maintain the high physical properties obtained when dry in a humid environment. On the other hand, by using the aforementioned crosslinking agent, the effect of heat and humidity resistance can be improved, and the tensile strength of the sheet when wet can be improved. As a result, since the structural change of the polyurethane molecules caused by water in the dyeing step can be suppressed, the morphological stability of the sheet and the stability of the polyurethane and the fibrous base material can be maintained. Adhesiveness, so it can achieve high physical properties and uniform quality.

Since the carbodiimide crosslinking agent has good crosslinking reactivity even at a low temperature of 100°C or less, it is preferably used from the viewpoint of productivity. In addition, the isocyanate compound and/or the blocked isocyanate compound mainly reacts with the hydroxyl group, and is in the high temperature range, particularly at a temperature of 120°C to 200°C, preferably at a temperature of 140°C to 200°C. The reactivity of the urethane bond and/or urea bond of the hard segment (HS) part of the urethane will increase, and can form allophanate bond and diurea bond, and give it stronger The cross-linked structure of the polyurethane makes the micro-phase separation structure of polyurethane clear.

From the viewpoint of flexibility and resilience, the storage elastic coefficient E'of the polyurethane film in the present invention at a temperature of 20°C is preferably 1-100 MPa, preferably 2-50 MPa. In addition, the coefficient of loss elasticity is preferably 0.1 MPa to 20 MPa, and more preferably 0.5 MPa to 12 MPa. In addition, tanδ is preferably 0.01 to 0.4, preferably 0.02 to 0.35.

The storage elastic coefficient E'and tanδ of the present invention are directed to a polyurethane film (film) with a film thickness of 200 μm, using a storage elastic coefficient measuring device [DMA7100 {manufactured by Hitachi High-Tech Co., Ltd.}] at 12 Hz The value measured by the frequency. tanδ is a value expressed by E"/E' (E" represents the loss elasticity coefficient).

In addition, E'represents the elastic properties of the polyurethane resin. If this E'is too small, the wrinkle recovery of the sheet will become poor, and if it is too large, the feel of the sheet will become hard.

On the other hand, the tanδ represented by E"/E' (E" is the loss of elastic coefficient and expresses the viscosity properties) means the ratio of the viscosity properties based on the elastic properties of polyurethane . If tanδ is too small, Like E', the wrinkle recovery property of the sheet-like material becomes insufficient, and if it is too large, the feel of the sheet-like material becomes hard.

The density of the flakes of the present invention is preferably 0.2 to 0.7 g/cm ³ . The density is preferably 0.2 g/cm ³ or more, more preferably 0.25 g/cm ³ or more. By increasing the density to 0.2g/cm ³ or more, the surface appearance will become denser and show high-grade quality. On the other hand, by making the density of the sheet-like article to be 0.7 g/cm ³ or less, preferably 0.6 g/cm ³ or less, it is possible to prevent the sheet-like article from becoming hard to the touch.

The ratio of the polyurethane contained in the sheet of the present invention is preferably 10 to 80% by mass. By making the ratio of the polyurethane to 10% by mass or more, preferably 15% by mass or more, it is possible to prevent fiber shedding while obtaining sheet strength. In addition, by making the ratio of the polyurethane to be 80% by mass or less, preferably 70% by mass or less, it is possible to prevent the touch from becoming hard and to obtain a good lint quality.

The sheet-like material of the present invention can be prepared by using elastic polymers such as water-dispersed polyurethane, and using a tackifier in combination with the water-dispersed polyurethane and other water-dispersed liquids It solidifies in hot water to achieve the porous structure of water-dispersed polyurethane (elastic polymer), and obtains excellent wrinkle recovery and softness similar to artificial leather using solvent-based polyurethane Sex.

That is, the sheet of the present invention is a sheet in which a polymer elastomer having a hydrophilic group is applied as a binder to a fibrous substrate containing ultrafine fibers and/or ultrafine fiber bundles, and is characterized by In the cross section of the sheet-like article cut in the thickness direction, the occupancy rate of the above-mentioned polymer elastic body observed in the cut plane independently and having a cross-sectional area of 50μm ² or more is relative to the artificial Leather with a cross-sectional area of 0.1% to 5.0%.

Furthermore, according to a preferred aspect, a polymer elastomer having a hydrophilic group as a binder is applied to a fibrous substrate containing ultrafine fibers and/or ultrafine fiber bundles. It is characterized in that 1% or more and 35% or less of the periphery of the cross section of the ultrafine fibers and/or ultrafine fiber bundles are covered by a polymer elastomer film on the cross section cut in the thickness direction of the sheet.

[Method of manufacturing flakes]

Next, the method of manufacturing the sheet of the present invention will be explained.

As for the fibrous substrate used in the present invention, as described above, cloth materials such as textiles, knitwear, and non-woven fabrics can be preferably used. Among them, in view of the good surface quality of the sheet during surface raising treatment, a non-woven fabric can be preferably used. In the fibrous base material of the present invention, these textiles, knitwear, and non-woven fabrics can be appropriately laminated and used in combination.

The non-woven fabric used in the present invention may be either short-fiber non-woven fabric or long-fiber non-woven fabric. However, it is preferable to use short-fiber non-woven fabric at the point that a surface grade including uniform raised length can be obtained.

The staple fiber length of the staple fiber non-woven fabric is preferably 25mm~90mm, preferably 35mm~75mm. By making the fiber length 25 mm or more, it is possible to obtain a sheet-like article having good abrasion resistance due to entanglement. It is also possible to obtain a good-quality sheet by making the fiber length 90 mm or less.

As far as the fibers constituting the fibrous base material are concerned, the package can be used Polyester containing polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polylactic acid, polyamides such as 6-nylon and 66-nylon, Melt-spinning thermoplastic resin fibers such as acrylic, polyethylene, polypropylene, and thermoplastic cellulose. Among them, from the standpoint of strength, dimensional stability, and light resistance, polyester fiber is preferred. In addition, the fibrous base material can also be formed by mixing fibers of different materials.

The cross-sectional shape of the fiber used in the present invention may be a circular cross-section, but it can be elliptical, flat, triangular, or other polygonal shapes, fan-shaped, and cross-shaped, and other special-shaped cross-sections.

The average fiber diameter of the fibers constituting the fibrous substrate is preferably 0.1 to 7 μm, preferably 0.3 to 5 μm. By making the average fiber diameter of the fibers 7 μm or less, the feel of the fibrous base material becomes softer. In addition, by making the average fiber diameter of the fibers 0.1 μm or more, the color development after dyeing becomes better.

In the present invention, when the fibrous base material is a non-woven fabric, it is possible to combine textiles and knitwear in the non-woven fabric for the purpose of enhancing the strength and the like inside. The combination of the non-woven fabric and the textile or knitwear can be any of laminating the textile or knitwear on the non-woven fabric, or inserting the textile or knitwear into the non-woven fabric. Among them, from the viewpoint of expectation of improvement in form stability and strength, it is preferable to use textiles.

As far as the single yarns (warp and weft) constituting textiles and knitwear are concerned, single yarns containing synthetic fibers such as polyester fibers or polyamide fibers can be cited. It is preferable that the ultra-fine fibers constituting the non-woven fabrics are yarns of fibers of the same material.

As for the form of such single yarns, filament yarns, machine-spun yarns, etc. can be cited, but it is preferable to use such strongly twisted yarns. Also, since machine spinning can cause surface fluff to fall off, it is better to use filament yarn.

When a strong twisted yarn is used, the twist number is preferably from 1000 T/m to 4000 T/m, preferably from 1500 T/m to 3500 T/m. If the number of twists is less than 1000T/m, the single fiber that constitutes the strong twisted yarn due to the needle rolling treatment will increase, and the physical properties of the product will be reduced or the single fiber will be exposed to the surface of the product. In addition, if the number of twists is more than 4000 T/m, single fiber breakage can be suppressed, but since the strongly twisted yarns constituting textiles or knitwear become too hard, they tend to harden to the touch.

Furthermore, in the present invention, it is preferable to use ultrafine fiber phenotype fibers for the fibrous substrate. It is possible to stabilize the entangled form of the aforementioned ultrafine fiber bundles by using ultrafine fiber phenotype fibers as the fibrous base material.

When the fibrous base material is a non-woven fabric, a structure in which the non-woven fabric has a bundle of very fine fibers (fiber bundles) entangled is a preferable aspect. The strength of the sheet will increase by winding the ultra-fine fibers in a bundle. Such a non-woven fabric can be obtained by pre-winding the ultra-fine fiber phenotype fibers with each other to express the ultra-fine fiber.

For ultra-fine fiber phenotype fibers, two-component thermoplastic resins with different solvent solubility can be used as the sea (continuous phase) component and the island (dispersed phase) component, and the sea component can be dissolved and removed by using a solvent, etc. The island component becomes the sea-island type composite fiber of ultra-fine fibers, and the two-component thermoplastic resin is arranged in a radial or multi-layer shape in the cross section of the fiber, and the fibers are split into ultra-fine fibers by peeling and dividing each component. Release composite fiber, etc.

Among them, the island-in-the-sea composite fiber can provide moderate voids between the island components, that is, between the ultrafine fibers by removing the sea component, so it can be better from the viewpoint of the flexibility and touch of the sheet. use.

Sea-island composite fibers include sea-island composite fibers that are spun by staggering the two components of the sea and island components using a sea-island composite mold, or mixed spun fibers that are spun by mixing the two components of the sea and island components. However, in terms of obtaining ultra-fine fibers of uniform fineness, and in terms of obtaining ultra-fine fibers of sufficient length and also contributing to the strength of the sheet, it is better to use sea-island composite fibers.

For the sea component of the island-in-the-sea composite fiber, polyethylene, polypropylene, polystyrene, copolymerized polyester such as sodium sulfoisophthalic acid or polyethylene glycol, polylactic acid and polyvinyl alcohol can be used. . Among them, the use of copolymerized polyesters such as alkali-decomposable sodium sulfoisophthalic acid or polyethylene glycol that can be decomposed without using organic solvents, or polylactic acid and hot-water-soluble polyvinyl alcohol Better.

The (proportion) ratio of the sea component to the island component of the sea-island composite fiber is preferably 0.2 to 0.9, preferably 0.3 to 0.8, relative to the mass ratio of the island fiber of the sea-island composite fiber. By making the mass ratio of the sea component and the island component 0.2 or more, the removal rate of the sea component can be reduced, and the productivity can be further improved. Furthermore, by making the mass ratio 0.9 or less, it is possible to prevent the improvement of the openability of the island fibers and the convergence of the island components. The number of islands can be adjusted appropriately by mold design.

Superfine fiber phenotype fiber such as sea-island composite fiber The long diameter of the single fiber is preferably 5 to 80 μm, preferably 10 to 50 μm. If the long diameter of the single fiber is less than 5 μm, the strength of the fiber is weakened, and single fiber breakage tends to increase in the needle rolling process described later. In addition, if the long diameter of the single fiber is larger than 80 μm, it may not be effectively entangled during the needle rolling process.

As for the method of obtaining the non-woven fabric as the fibrous base material used in the present invention, the method of entanglement of the fiber web by needle rolling treatment or water jet stamping treatment, spun bonding method, fusion bonding method, papermaking method, etc. . Among them, in addition to forming the ultrafine fiber bundles as described above, it is preferable to use a method that undergoes a needle rolling process or a water jet press process.

In addition, for the laminated integration of the non-woven fabric used as the fibrous base material and the textile or knitwear, from the viewpoint of the winding property of the fiber, it is preferable to use a needle pressing process or a water jet press process. Among them, from the viewpoint of being able to orient the fibers in the vertical direction of the fibrous base material without being restricted by the thickness of the sheet, it is preferable to use a needle rolling process.

The number of barbs used in the needle-rolling process is preferably 1-9. By increasing the number of barbs to one or more, efficient fiber winding can be performed. On the other hand, by making the number of barbs 9 or less, fiber damage can be suppressed. If the number of barbs is more than 9, fiber damage will increase, and stitches may remain on the fibrous base material and the appearance of the product may become poor.

In addition, when the non-woven fabric is integrated with the textile knitwear, the preparation of the non-woven fabric is provided in order to prevent the generation of wrinkles when the non-woven fabric and the textile or knitwear are combined and integrated by the needle rolling process. State. In this way, when the method of preliminarily applying preliminary winding by the needle rolling treatment is adopted, it is effective that the needle rolling density is 20 threads/cm ² or more. It is preferable to give the preliminary winding with a needle rolling density of 100 pieces/cm ² or more, and it is more preferable to give the preliminary winding with a needle rolling density of 300 pieces/cm ² to 1300 pieces/cm ² .

Because the pre-wrapped needle density is less than 20 counts/cm ² , the width of the non-woven fabric will be narrowed due to the needle-rolling process during and after winding with textiles or knitwear, so there will be The width changes, because textiles or knitwear produce wrinkles and it becomes impossible to obtain a smooth fibrous substrate. In addition, if the needle density of the preliminary winding is more than 1300 counts/cm ² , the winding of the non-woven fabric itself will generally be too excessive, so that only enough space for the winding of the fibers constituting the textile or knitwear is reduced. Therefore, it becomes disadvantageous to realize the integrated structure of the non-woven fabric and the textile or knitwear firmly entangled.

In the present invention, regardless of the presence or absence of textiles or knitwear, when the fiber is wound by needle rolling, it is better to make the needle rolling density in the range of 300 threads/cm ² to 6000 threads/cm ² , and the preferred aspect is In order to become 1000 pieces/cm ² ~3000 pieces/cm ² .

The entanglement of non-woven fabrics and textiles or knitted products is the ability to laminate textiles or knitted products on one or both sides of the non-woven fabric, or sandwich the textile or knitted products between multiple non-woven fabrics, and the fibers are entangled with each other by needle rolling. Become a fibrous substrate.

In addition, when performing waterjet press processing, it is preferable that the water system proceed in a columnar flow state. Specifically, it is better to spray water from a nozzle with a diameter of 0.05 to 1.0 mm at a pressure of 1 to 60 MPa.

The apparent density of the non-woven fabric containing ultrafine fiber-producing fibers after needle-rolling treatment or water jet stamping treatment is preferably 0.13-0.45 g/cm ³ , preferably 0.15-0.30 g/cm ³ . By making the apparent density 0.13 g/cm ³ or more, artificial leather with sufficient form stability and dimensional stability can be obtained. On the other hand, by making the apparent density 0.45 g/cm ³ or less, it is possible to maintain a sufficient space for imparting the polymer elastomer.

The thickness of the fibrous base material is preferably 0.3 mm or more and 6.0 mm or less, preferably 1.0 mm or more and 3.0 mm or less. If the thickness of the fibrous base material is less than 0.3 mm, the morphological stability of the sheet-like material may become insufficient. In addition, if the thickness is greater than 6.0 mm, needle breakage tends to occur in the needle rolling step.

From the viewpoint of densification, the nonwoven fabric containing the ultrafine fiber-generating fibers obtained in this manner can shrink by dry heat, moist heat, or both, and further increase the density.

The sea-removing treatment (de-continuous phase treatment) used to remove the sea component of the sea-island composite fiber when the sea-island type composite fiber is used is a water-dispersible type containing water-dispersible polyurethane on a fibrous base material. It is performed before or/and after the polyurethane dispersion liquid is imparted. If the sea-removing treatment is performed before the water-dispersed polyurethane dispersion is provided, it is easy to form a structure in which the polyurethane is directly attached to the ultrafine fibers, and the ultrafine fibers can be firmly clamped, so the sheet The wear resistance is good.

, On the other hand, it is possible to impart ultrafine fibers and cellulose derivatives before imparting a water-dispersible polyurethane dispersion. Or polyvinyl alcohol (hereinafter abbreviated as PVA) and other inhibitors, and then give a water-dispersible polyurethane dispersion to reduce the adhesion between the ultrafine fibers and the polyurethane resin, which can also achieve better Soft touch.

The aforementioned inhibitors can be applied before or after the sea-island structure fiber is removed from the sea. By adding inhibitors before the sea removal treatment, even when the average fiber mass per unit area decreases and the tensile strength of the sheet material decreases, the form maintaining power of the fibrous base material can be improved. Therefore, in addition to being able to be processed stably even in a sheet, the thickness retention rate of the fibrous substrate in the desalination step can be increased, and the increase in density of the fibrous substrate can be suppressed. On the other hand, since it is possible to achieve high density of the fibrous base material by applying the aforementioned inhibitor after the sea removal treatment, it is preferable to adjust it appropriately according to the purpose.

As for the aforementioned inhibitors, since the reinforcing effect from the fibrous base material is high and it is difficult to dissolve in water, it is preferable to use PVA. In PVA, from the viewpoint of making it difficult for the inhibitor to be eluted during the application of a water-dispersed polyurethane dispersion, and further suppressing the adhesion of ultrafine fibers to the polyurethane, it is more PVA with high saponification degree, which is poorly water-soluble, is a better aspect.

The degree of saponification of the high saponification degree PVA system is preferably 95% or more and 100% or less, preferably 98% or more and 100% or less. By making the degree of saponification 95% or more, it is possible to suppress elution during the application of the water-dispersed polyurethane dispersion.

The degree of polymerization of PVA is preferably 500 or more and 3500 or less, more preferably 500 or more and 2000 or less. By making the degree of polymerization of PVA 500 or more, the high saponification degree of polyurethane dispersion can be suppressed The dissolution of PVA. In addition, by making the degree of polymerization of PVA 3500 or less, the viscosity of the high saponification degree PVA solution does not become too high, and the high saponification degree PVA can be stably imparted to the fibrous substrate.

The amount of PVA is preferably 0.1% to 80% by mass relative to the fibrous substrate remaining in the product, and the amount of PVA is preferably from 5 to 60% by mass. By providing PVA with a high degree of saponification of 0.1% by mass or more, it is possible to suppress the effect of shape stability in the desalination step and the adhesion between ultrafine fibers and polyurethane. In addition, by providing PVA with a high degree of saponification of 80% by mass or less, the adhesion between ultrafine fibers and polyurethane will not be too low, and the fluffed fibers will become uniform and the finished surface will be uniform. Products.

Regarding the method of imparting the inhibitor to the fibrous substrate, from the viewpoint of uniformly imparting the inhibitor, it is preferable to use a method of dissolving the inhibitor in water and impregnating the fibrous substrate with heating and drying. If the drying temperature is too low, the drying time will take a long time. If the temperature is too high, the inhibitor will be completely insoluble, and it will become insoluble afterwards. Therefore, drying is preferably performed at a temperature of 80°C or higher and 180°C or lower, and more preferably 110°C or higher and 160°C or lower. In addition, the drying time is preferably 1 minute or more and 30 minutes or less from the viewpoint of workability.

The dissolution and removal treatment of the inhibitor is carried out by immersing the fibrous substrate to which the inhibitor has been given in steam at a temperature of 100°C or higher and hot water at a temperature of 60°C or higher and 100°C or lower, and performed by rolls as necessary. It is preferable to dissolve and remove by extrusion.

The sea removal treatment system can The dimensional fibrous base material is immersed in the liquid and squeezed to proceed. Regarding the solvent to dissolve the sea component, when the sea component is polyethylene, polypropylene, or polystyrene, organic solvents such as toluene or trichloroethylene can be used. When the sea component is copolymerized polyester and polylactic acid, it can An alkaline solution such as an aqueous sodium hydroxide solution is used, and hot water can be used when the sea component is polyvinyl alcohol.

Next, the polyurethane used as the polymer elastomer in the present invention will be explained.

When the polyurethane is dispersed as particles in an aqueous medium, from the viewpoint of the dispersion stability of the polyurethane, the aforementioned hydrophilic group-containing component is used as a constituent of the polyurethane. The active hydrogen component is better, and it is better to use neutralized salt.

The neutralizing agent used in the neutralization salt of the compound having a hydrophilic group and active hydrogen includes trimethylamine, triethylamine, triethanolamine amine compounds, sodium hydroxide, and potassium hydroxide. Hydroxide etc.

The addition period of the neutralizer used for the active hydrogen component containing the hydrophilic group is not specifically specified before and after the polyurethane polymerization step, or before and after the dispersion step for the aqueous medium. From the viewpoint of stability in the aqueous dispersion, it is preferable to add it before the dispersion step for the aqueous medium or during the dispersion step for the aqueous medium.

The content of the active hydrogen component and/or its salt containing the hydrophilic group based on the quality of the polyurethane. From the viewpoint of the dispersion stability and water resistance of the polyurethane, 0.005~30 Quality% is better , Preferably 0.01-15 mass%.

When polyurethane is used as particles to be dispersed in an aqueous medium, in addition to using the aforementioned active hydrogen component containing a hydrophilic group, a surfactant can be used as an external emulsifier of the polyurethane to make the polyamine group The formate is dispersed in an aqueous medium.

Examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. The surfactant system may be used alone or in combination of two or more kinds.

Non-ionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene dinonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc. Addition molding of alkylene oxide or polyol type such as glycerol monostearate.

The anionic surfactants include sodium dodecyl sulfate, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl benzenesulfonate, higher alcohol phosphate diester sodium salt, etc. The carboxylate, sulfate, sulfonate, and phosphate salts.

Cationic surfactants include quaternary ammonium salts such as dioctadecyldimethylammonium chloride. As the amphoteric surfactant, methyl lauryl amino propionate, dodecyl dimethyl betaine, coconut oil fatty acid amide propyl dimethyl amino betaine, and the like can be mentioned.

The polyurethane dispersion system used in the present invention can use a conventional method for producing polyurethane dispersions. Examples can include the aforementioned polyisocyanate, polyol, chain extender and/or hydrophilic A method in which a liquid polymer in which a polyalcohol is reacted with a hydrophilic group is placed in water in the presence of an emulsifier; or a method for making the aforementioned polyisocyanate, polyol and/or chain extender and/or a polyol containing a hydrophilic group are reacted A method of emulsifying the prepolymer in water in the presence of an emulsifier with an isocyanate group at the end of the molecule, and/or after the emulsification of the prepolymer with a chain extender to terminate the elongation reaction; or making the aforementioned polyisocyanate, poly A method in which alcohol and/or chain extender and/or hydrophilic group-containing polyol are reacted, and then emulsified directly in water without using an emulsifier. The case of polymerizing without forming the aforementioned prepolymer and the case of polymerizing the prepolymer can be carried out without a solvent, and can also be carried out in an organic solvent such as methyl ethyl ketone, toluene, and acetone.

The water-dispersed polyurethane dispersion containing the synthesized water-dispersed polyurethane is immersed in a fibrous base material or the like, and the fibrous base material is given polyurethane, and then The heating is dried, thereby solidifying and curing.

In the present invention, it is possible to provide a water-dispersible polyurethane dispersion with the aforementioned tackifier added to the fibrous substrate, and the temperature is preferably 50°C to 100°C, preferably 60°C The water-dispersed polyurethane is solidified in hot water at a temperature of ~97°C, and the porous structure of the polyurethane is achieved.

The immersion time in hot water is preferably 10 seconds or more and 5 minutes or less, and more preferably 30 seconds or more and 3 minutes or less. By setting the immersion time to this, the polyurethane can be sufficiently solidified.

Because the coagulation method of polyurethane is hot water coagulation in this way, the average time it takes for polyurethane is hot As the amount increases, because the coagulation speed is accelerated, and the deviation of the water-dispersed polyurethane dispersion on the fibrous substrate becomes less, the adhesion between the fiber and the polyurethane will be less and the touch will be soft化.

Furthermore, by using a tackifier in the water-dispersible polyurethane dispersion, the fiber base material is impregnated in the water-dispersible polyurethane dispersion. Due to the influence of the viscosity of the acid ester emulsion, the Brownian motion of the emulsion will be inhibited. Therefore, the number of times of contact of the emulsions with each other is reduced, the polyurethane block during coagulation can be reduced, and a soft touch can be achieved. In addition, the dispersion does not diffuse in hot water, and can inhibit the peeling of the polyurethane during the solidification step, and can achieve a solidification process with extremely good productivity.

By coagulating in hot water a dispersion liquid containing a thickener in an aqueous dispersion such as water-dispersed polyurethane, the coating of the water-dispersed polyurethane (elastic polymer) will change Small and become soft to the touch. In addition, the polyurethane film covering the fibrous base material is reduced, and it becomes soft to the touch.

As the thickener added to the water-dispersed polyurethane dispersion, nonionic, anionic, cationic, and diionic thickeners can be used. Among them, it is better to use non-ionic tackifiers.

As far as the type of tackifier is concerned, it can be selected from a combination tackifier and a water-soluble polymer tackifier. As the bonding type thickener, well-known bonding type thickening agents, such as a urethane modified compound, an acrylic modified compound, and these copolymerization compounds, can be used. Examples include Japanese Patent Application Publication No. 2003-292937, Japanese Patent Application Publication No. 2001-254068, Japanese Patent Application Publication No. 60-49022, Japanese Patent Application Publication 2008-231421, Japanese Patent Laid-Open No. 2002-069430, and Japanese Patent Laid-Open No. 9-71766, etc., the urethane-based bonding type tackifier; or Japanese Patent Laid-Open No. 62-292879 Bonded tackifiers obtained by copolymerizing urethane monomers and other acrylic monomers described in the gazette and JP-A-10-121030, etc.

The water-soluble polymer compounds include natural polymer compounds, semi-synthetic polymer compounds, synthetic polymer compounds, and the like.

As for natural polymer compounds, nonionic compounds such as tamarind gum, guar gum, locust bean gum, astragalus gum, starch, dextrin, gelatin, agarose, casein, and Cattleya polysaccharide can be cited; or Anionic compounds such as xanthan gum, carrageenan, gum arabic, pectin, collagen, sodium chondroitin sulfate, sodium hyaluronate, carboxymethyl starch and starch phosphate; or cationic starch and polyglucosamine Compound.

For semi-synthetic polymer compounds, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, soluble starch, and methyl starch can be mentioned. Other nonionic compounds, or anionic compounds such as carboxymethyl cellulose, carboxymethyl starch, and alginate.

In addition, for synthetic polymer compounds, nonionics such as polyvinyl alcohol, polypropylene amide, polyvinyl hydropyrrolidone, polymethyl vinyl ether, polyethylene glycol, and polyisopropyl acrylamide can be mentioned. Compounds; or anionic compounds such as vinyl carboxylate polymers, sodium polyacrylate and sodium polystyrene sulfonate; or dimethylaminoethyl (meth)acrylate grade 4 Cationic compounds such as salt, dimethyl diallyl ammonium chloride, polyamidine, polyvinylimidazoline, and polyethyleneimine.

In the present invention, as for the tackifier, it is preferable to use a nonionic tackifier that is unlikely to affect the stability of the water-dispersible polyurethane dispersion.

In addition, it is preferable that the water-dispersible polyurethane dispersion system to which a thickener is added shows non-Newtonian fluidity. As long as the water-dispersible polyurethane dispersion is non-Newtonian fluid, the viscosity will decrease by applying force, and the viscosity will decrease by applying force such as stirring, so it can make The aforementioned dispersion liquid is evenly impregnated in the fibrous base material. Furthermore, since it is restored to its original viscosity by standing still after impregnation, the aforementioned dispersion liquid system impregnated in the fibrous base material becomes difficult to remove from the fibrous base material. The substrate comes off.

Moreover, it is preferable that the water-dispersible polyurethane dispersion system to which a thickener is added shows thixotropy. As long as the water-dispersed polyurethane dispersion is thixotropic, the viscosity can be lowered by applying force such as stirring, and the aforementioned dispersion can be uniformly impregnated in the fibrous substrate. Furthermore, due to the After the force is applied, it will return to its original viscosity by standing still, so the aforementioned dispersion liquid impregnated in the fibrous substrate becomes less likely to fall off from the fibrous substrate.

As for the thickener exhibiting thixotropy, it can be suitably selected from the aforementioned thickeners, but it is better to use natural polymer compounds (polysaccharides) that are expected to have a large thickening effect with a small amount of addition. As far as the thickener is concerned, it is more preferable in terms of its compatibility with water-dispersed polyurethane liquids with good water solubility and high thixotropy at low concentrations. It is guar gum.

The viscosity of the aqueous resin dispersion containing the tackifier is 200mPa. s~100000mPa. s is better, preferably 200mPa. s~10000mPa. s, more preferably 200mPa. s~5000mPa. s. It is possible to make the viscosity of the aforementioned aqueous resin dispersion 200 mPa. s or more, while suppressing the peeling of the polyurethane in the hot water solidification step, and the viscosity can be 100,000mPa. s or less, and the water-dispersed polyurethane dispersion is uniformly impregnated in the fibrous base material.

The water-dispersed polyurethane dispersion applied to the fibrous substrate can inhibit the emulsification of the polyurethane during the coagulation of the polyurethane and make the polyurethane uniformly impregnated From the viewpoint of the fibrous base material, it is preferable to include a heat-sensitive coagulant.

The heat-sensitive coagulant includes inorganic salts such as sodium sulfate, magnesium sulfate, calcium sulfate, calcium chloride, magnesium chloride, and calcium chloride, or sodium persulfate, potassium persulfate, ammonium persulfate, and ammonium sulfate. The ammonium salt and so on. After adjusting the appropriate addition amount to adjust the solidification temperature of the water-dispersed polyurethane by using these alone or in combination of two or more, the water-dispersible polyurethane dispersion can be heated It becomes unstable and solidifies.

The heat-sensitive coagulation temperature of the aforementioned water-dispersible polyurethane dispersion is preferably 40 to 90°C, more preferably 50 to 80°C from the viewpoint of storage stability and the touch of the processed fiber product.

In addition to the aforementioned crosslinking agent and heat-sensitive coagulant, the following various additives can be further added to the polyurethane dispersion.

系、二苯基酮系及苯甲酸酯系的紫外線吸收劑等)、受阻胺系光安定劑等的耐候安定劑、柔軟撥水劑(聚矽氧烷、改質矽油等的聚矽氧化合物及丙烯酸的氯烷基酯系聚合物等的氟化合物等的柔軟撥水劑)、濕潤劑(乙二醇、二乙二醇、丙二醇及丙三醇等的濕潤劑)、消泡劑(辛醇、山梨糖醇單油酸酯、聚二甲基矽氧烷、聚醚改質聚矽氧及氟改質聚矽氧等的消泡劑)、填充劑(碳酸鈣、氧化鈦、矽石、滑石、陶瓷、樹脂等的微粒子及空心微珠等的填充劑)、阻燃劑(鹵素系、磷系、銻系、三聚氰胺系、胍系、胍脲系等、聚矽氧系及無機系的阻燃劑)、微氣球(例如：松本油脂製：”松本微球(Matsumoto Microsphere)”(註冊商標))、發泡劑[例如二亞硝基五亞甲基四胺(例：三協化成製”Cellmic A”(註冊商標))、偶氮二甲醯胺(例如：三協化成製”Cellmic CAP”(註冊商標))、p,p’-氧雙苯磺醯肼(例如：三協化成製”Cellmic S”(註冊商標))、N,N’-二亞硝基五亞甲基四胺(例如：永和化成製”Cellular GX”(註冊商標))等的有機系發泡劑及碳酸氫鈉(例如：三協化成製”Cellmic 266”(註冊商標))等的無機系發泡劑等]、2,2’-偶氮雙[2-甲基-N-(2-羥乙基)丙醯胺](例如：和光純藥工業製”VA-086”)、黏度調整劑、可塑劑(酞酸酯、己二酸酯等)、及離型劑(石蠟系、金屬皂系及該等的混合系離型劑等)等的添加劑。 It can be made to contain pigments such as carbon black, antioxidants (hindered phenol-based, sulfur-based, and phosphorus-based antioxidants), ultraviolet absorbers (benzotriazole-based, three

Type, benzophenone type and benzoate type UV absorbers, etc.), hindered amine-based light stabilizers and other weathering stabilizers, soft water repellents (polysiloxanes such as polysiloxanes, modified silicone oils, etc.) Compounds and soft water repellents such as fluorine compounds such as chloroalkyl ester polymers of acrylic acid), humectants (wetting agents such as ethylene glycol, diethylene glycol, propylene glycol, and glycerol), defoamers ( Octanol, sorbitol monooleate, polydimethylsiloxane, polyether modified polysiloxane and fluorine modified polysiloxane, etc. defoamers), fillers (calcium carbonate, titanium oxide, silicon Fillers such as fine particles of stone, talc, ceramics, and resins and hollow beads), flame retardants (halogen, phosphorus, antimony, melamine, guanidine, guanurea, etc., silicone and inorganic Series flame retardants), micro balloons (for example: "Matsumoto Microsphere" (registered trademark) manufactured by Matsumoto Oils and Fats), foaming agents (for example, dinitrosopentamethylenetetramine (for example: three "Cellmic A" (registered trademark) manufactured by Xiehuacheng, azobismethamide (for example: "Cellmic CAP" (registered trademark) manufactured by Sankyo Chemicals), p,p'-oxydiphenylsulfonamide (for example: Sankyo Chemicals "Cellmic S" (registered trademark)), N,N'-dinitrosopentamethylenetetramine (for example: "Cellular GX" (registered trademark) of Yonghe Chemicals, etc.) Agent and sodium bicarbonate (for example: "Cellmic 266" (registered trademark) manufactured by Sankyo Kasei), etc.], 2,2'-azobis[2-methyl-N-(2- (Hydroxyethyl) acrylamide] (e.g. "VA-086" manufactured by Wako Pure Chemical Industries, Ltd.), viscosity modifiers, plasticizers (phthalates, adipates, etc.), and release agents (paraffin-based, metal Soap-based and these mixed-based release agents, etc.) additives.

After the water-dispersed polyurethane dispersion is impregnated into the fibrous base material and coagulated, in order to promote the fusion of the water-dispersed polyurethane emulsion and maximize the molecular structure of the polyurethane To improve the moisture and heat resistance, it is better to perform additional heating (curing). The curing system can impregnate the water-dispersed polyurethane dispersion in the fibrous base material, and then proceed with the coagulation step. Moreover, it can also impregnate the water-dispersed polyurethane dispersion in After the fibrous base material is coagulated, it is implemented in other steps.

If the drying temperature is too low, the drying time will take a long time. If the temperature is too high, the thermal decomposition of polyurethane will be promoted. Therefore, it is better to dry at a temperature above 80℃ and below 200℃. It is 120°C or more and 190°C or less, more preferably 150°C or more and 180°C or less.

Furthermore, the drying time is preferably 1 minute or more and 60 minutes or less from the viewpoint of workability, and more preferably 1 minute or more and 30 minutes or less. In the present invention, it is possible to increase the fluidity of polyurethane molecules by setting the curing temperature to a high temperature and processing in a short time. In the molecular structure of the hard segment (HS) part and the soft segment (SS) part mainly formed by polyol, the condensation of the HS part is improved and the microphase separation structure of the HS and SS parts is clarified, and can Improve heat and humidity resistance.

After the polyurethane is imparted, the obtained polyurethane-enriched sheet is cut into half or divided into several pieces in the thickness direction of the sheet, and the production efficiency is good, which is a preferred state kind.

Before the raising treatment described later, a lubricant such as a silicone emulsion can be applied to the sheet-like article to which polyurethane has been applied. again The antistatic agent is provided before the fluffing treatment because the abrasive powder generated from the flakes due to the grinding is not easy to accumulate on the sandpaper, which is a preferred aspect.

In order to form vertical hairs on the surface of the sheet, it is possible to perform a raising treatment. The raising treatment system can be implemented by a method of grinding using sandpaper, a roller sander, etc.

If the thickness of the sheet is too thin, the tensile strength or tear strength of the sheet will be weakened, and if it is too thick, the feel of the sheet will become hard, so the thickness is about 0.1~5.0mm Better.

The sheet can be dyed. As far as the dyeing method is concerned, it is better to use a liquid flow dyeing machine in view of the fact that it can impart a twisting effect while dyeing the sheet to soften the sheet. If the dyeing temperature is too high, polyurethane may deteriorate. On the contrary, if the dyeing temperature is too low, the coloring of the fiber by the dye becomes insufficient, so it can be set according to the type of fiber. The dyeing temperature is usually 80°C or more and 150°C or less, preferably 110°C or more and 130°C or less.

The dye used is selected according to the type of fiber constituting the fibrous substrate. For example, if it is a polyester fiber, a disperse dye can be used, if it is a polyamide fiber, an acid dye or a metal complex dye can be used, and these combinations can be used further. When the sheet is dyed with disperse dyes, it can be reduced and washed after dyeing.

In addition, it is also preferable to use a dyeing auxiliary when dyeing. The uniformity or reproducibility of dyeing can be improved by using dyeing auxiliary agents. In addition, it is possible to perform finishing treatment using softeners such as silicone, antistatic agents, water repellents, flame retardants, light fasting agents, and antibacterial agents after dyeing or bathing.

The sheet obtained by the present invention is mainly used as artificial leather, and can be preferably used as, for example, as furniture, chairs and wall materials, or seats, ceilings and ceilings in vehicles such as automobiles, electric trains, and airplanes. Surface leather for interior decoration and other interior materials with a very beautiful appearance, shirts, jackets, casual shoes, sports shoes, uppers of men's and women's shoes, decorations, etc., leather bags, belts, wallets, etc., and used in Some of these are industrial materials such as clothing materials, wiping cloths, polishing cloths and CD curtains.

[Example]

The following examples are used to illustrate the sheet of the present invention and the manufacturing method thereof in more detail, but the present invention is not limited only by these examples.

[evaluation method]

(1) The fall-off rate of polyurethane during solidification:

Measure the mass of the fibrous base material and the mass after impregnating the water-dispersed polyurethane dispersion in the fibrous base material, and regard the solid content of the polyurethane contained in the difference as the poly Amount of carbamate adhesion. Subsequently, the fibrous substrate impregnated with the water-dispersible polyurethane dispersion is solidified with hot water and/or steam, and the mass after drying is measured, and the difference with the fibrous substrate is regarded as the poly The amount of urethane adhesion B. The polyurethane shedding rate during coagulation was calculated by the following formula and evaluated by the average of the results of the 10-point measurement.

. Polyurethane shedding rate (%)=Polyurethane adhesion amount B/Polyurethane adhesion amount×100.

(2) Determination of the viscosity of water-dispersed polyurethane dispersion:

Using a rotary viscometer (B-type viscometer: Tokyo Keiki Mfg. Co., Ltd.) in a gas environment at a temperature of 25°C, the prepared water-dispersed polymer was measured at a rotation speed condition of 0.5 revolutions/min and a revolution speed condition of 10 revolutions/min. The viscosity of the urethane dispersion.

(3) Appearance grade of flakes:

The appearance grade of the sheet-like article was evaluated by visual and sensory evaluations with 10 healthy adult males and 20 adult females as evaluators in 5 stages as follows, and the most evaluation was used as the appearance grade. The appearance grade is 4~5 as good.

Grade 5: It has uniform fiber vertical hairs, fiber dispersion state is good and appearance is good.

Level 4: Assessment between Level 5 and Level 3.

Grade 3: Although the dispersion state of the fibers has a slightly poor part, there are fiber vertical hairs and the appearance is still good.

Level 2: Assessment between Level 3 and Level 1.

Grade 1: The dispersion state of the whole fiber is extremely poor, and the appearance is not good.

(4) The touch of the sheet:

The tactile sensation of the sheet was evaluated by 10 healthy adult males and 20 adult females each as evaluators. The sensory evaluation of tactile sensation was performed in three stages as follows, and the most evaluation was used as the evaluation of tactile sensation. . The tactile feel is good (good rubber elasticity).

◎: The artificial leather using organic solvent-based polyurethane is softer than the average weight per unit area and has good wrinkle recovery.

○: The average unit area mass of the same degree uses organic Solvent-based polyurethane artificial leather has the same flexibility and wrinkle recovery properties.

×: The sheet is hard and feels like paper.

(5) Calculation method of the occupancy rate of non-porous blocks above 50μm ² (parameter A):

10 SEM images of cross-sections cut in the thickness direction of the artificial leather observed in the length or width direction of the artificial leather with a scanning electron microscope (SEM) at 500 times magnification, developed by the National Institute of Health The image analysis software ImageJ (version: 1.44p) calculates the area of 50μm ² or more in the polyurethane cross section observed on the cutting surface relative to the observation field of the SEM image range (4.3×10 ⁴ μm ² ) The ratio of the cross-sectional area of the artificial leather in the area is evaluated by the average of the calculated values of a total of 10 images. Figure 3 shows a schematic diagram of the calculation method of parameter A. Figure 3 is a schematic diagram showing the polyurethane block 1 of parameter A, which illustrates that the polyurethane block 1 is a polyurethane cross section (not Including the figure after the section).

(6) The calculation method of the film rate of the polymer elastomer of the ultra-fine fiber section (parameter B):

10 SEM images of cross-sections cut in the thickness direction of the artificial leather observed in the length or width direction of the artificial leather with a scanning electron microscope (SEM) at 500 times magnification, developed by the National Institute of Health The image analysis software ImageJ (version: 1.44p) of the image analysis software for the 5 ultra-fine fiber bundles observed in the state where the ultra-fine fiber bundles are cut vertically in the fiber length direction is calculated to be between the outer length and the thickness of 1μm or more The ratio of the connected parts of the resin film. Based on the calculated 5×10 images A total of 50 ultra-fine fiber cross sections are evaluated by the average value of the polymer elastomer coating rate. Figure 4 shows a schematic diagram of the calculation method of parameter B. Figure 4 is a schematic diagram showing the periphery 2 of the ultrafine fiber and/or ultrafine fiber bundle and the periphery 3 covered by the polymer elastomer film of parameter B. The solid line part is the periphery 2 of the ultrafine fiber bundle, the dotted line Part of it is a picture of the periphery 3 covered by a polymer elastomer film.

[Preparation of Polyurethane Liquid A]

Polycarbonate diol with Mn of 2,000 ["Duranol" (registered trademark) T5652" manufactured by Asahi Kasei Chemical Co., Ltd.] is used for polyol, MDI is used for isocyanate, and 2,2-dimethylolpropionic acid is used as intramolecular hydrophilic After making a prepolymer in toluene solvent, adding ethylene glycol and ethylenediamine as chain extenders, polyoxyethylene nonylphenyl ether and water as external emulsifiers and stirring, The toluene was removed under pressure to obtain a water-dispersed polyurethane dispersion A.

[Preparation of Polyurethane Liquid B]

Polycarbonate diol with Mn of 2,000 ["Duranol" (registered trademark) T6002" manufactured by Asahi Kasei Chemical Co., Ltd.] is used for polyol, IPDI is used for isocyanate, diol compound with polyethylene glycol on the side chain is used, and 2, 2-Dimethylolpropionic acid is used as an intramolecular hydrophilic group. After making a prepolymer in an acetone solvent, adding ethylene glycol and ethylenediamine as chain extenders and stirring, the acetone is removed by reducing pressure. A water-dispersed polyurethane dispersion liquid B was obtained.

[Preparation of Polyurethane Liquid C]

The polyol uses polycarbonate diol with Mn of 2,000 ["Duranol" (registered trademark) T5652" manufactured by Asahi Kasei Chemical Co., Ltd.], isocyanic acid The ester uses IPDI and trimethylolpropane as the intramolecular hydrophilic group. After prepolymer is made in methyl ethyl ketone solvent, ethylene glycol and ethylene diamine are added as chain extenders and polyoxyethylene After nonyl propyl ether was used as an external emulsifier and stirred, methyl ethyl ketone was removed by pressure reduction to obtain a water-dispersed polyurethane dispersion D.

[Example 1]

Polyethylene terephthalate copolymerized with 8 mol% sodium 5-sulfoisophthalate is used as the sea component, polyethylene terephthalate is used as the island component, and the sea component is 20% by mass. The composition is a composite ratio of 80% by mass, and a sea-island composite fiber with 16 islands per fiber filament and an average fiber diameter of 20 μm is obtained. The obtained sea-island composite fiber was cut into a fiber length of 51 mm and fixed, and a fiber web was formed by a carding machine and a cross-winding machine, and a non-woven fabric was made by needle rolling.

The non-woven fabric obtained in this way was immersed in hot water at a temperature of 97°C for 2 minutes to shrink, and dried at a temperature of 100°C for 5 minutes. Next, a water-dispersible polyurethane dispersion A prepared with a polyurethane solid content concentration of 20% is added with a binding type of 44% by mass relative to the polyurethane solid content. The active ingredient of the thickener [Sunnopco Co., Ltd. "Thickener 627N"], a dispersion of 1.2% by mass of magnesium sulfate based on the solid content of polyurethane is impregnated in the obtained non-woven fabric, and the temperature is 95°C After being treated in hot water for 1 minute, the drying temperature was 100°C hot air drying for 15 minutes, and then the obtained sheet was further heated at 160°C for 20 minutes.

In such a way that the mass of the polyurethane is 35% by mass relative to the mass of the island component of the non-woven fabric, the water-dispersible poly Urethane sheet. The peeling off of polyurethane during hot water solidification of polyurethane is 0.1% and almost no.

Subsequently, the thus-obtained sheet was immersed in a sodium hydroxide aqueous solution with a concentration of 10 g/L heated to a temperature of 95° C. for treatment for 25 minutes to obtain a sea-removed sheet from which the sea component of the island-in-the-sea composite fiber was removed. The average unidimensional diameter of the single fibers on the surface of the obtained seamed sheet was 4.2 μm. Then, using a half-cutting machine with a jointless belt knife, cut the seamed sheet into half vertically in the thickness direction, and polish the un-half-cut side with 120 mesh and 240 mesh sandpaper for raising treatment. Then use a circulating dyeing machine to dye with disperse dyes and perform reduction washing to obtain artificial leather with an average area mass of 221 g/m ² . The obtained artificial leather has good appearance and taste, and the touch is not as good as that of paper. Parameter A is 4.0%, and parameter B is 27.1%.

[Example 2]

In addition to adding 5% by mass of epoxy to polyurethane solid content to the water-dispersed polyurethane dispersion A with a prepared polyurethane solid content concentration of 20% It is the active ingredient of the crosslinking agent [DIC Co., Ltd. "CR-5L"], and 4% by mass relative to the solid content of polyurethane. The binding type thickener [Sunnopco Co., Ltd. "Thickener 627N" ] The active ingredient and the dispersion of 1.2% by mass with respect to the polyurethane solid content of magnesium sulfate were impregnated with the same non-woven fabric as in Example 1, and the average area mass was 223 g/m in the same manner as in Example 1. ^2. Artificial leather. The peeling off of the polyurethane during hot water coagulation of water-dispersed polyurethane is almost 0.1%. The obtained artificial leather has good appearance and taste, and the touch is not as good as that of paper. Parameter A is 4.1%, and parameter B is 25.4%.

[Example 3]

Polyethylene terephthalate copolymerized with 8 mol% sodium 5-sulfoisophthalate is used as the sea component, polyethylene terephthalate is used as the island component, and the sea component is 20% by mass. With a composite mass ratio of 80% by mass, a sea-island composite fiber with 16 islands per fiber filament and an average fiber diameter of 20 μm was obtained. The obtained sea-island composite fiber was cut into a fiber length of 51 mm and fixed, and a fiber web was formed by a carding machine and a cross-winding machine, and a non-woven fabric was obtained by needle rolling.

The nonwoven fabric thus obtained was immersed in hot water at a temperature of 97°C for 5 minutes to shrink, and dried at a temperature of 100°C for 10 minutes. Next, to the obtained non-woven fabric, a PVA with a saponification degree of 99% and a degree of polymerization of 1400 [manufactured by Nippon Synthetic Chemical Co., Ltd. "NM-14"] was adjusted to an aqueous solution with a solid content of 10% by mass. After drying for 10 minutes at a temperature, additional heating was performed at a temperature of 150°C for 20 minutes to obtain a sheet. Subsequently, the thus-obtained sheet was immersed in a sodium hydroxide aqueous solution with a concentration of 100 g/L heated to a temperature of 50° C. and processed for 20 minutes to obtain a sea-removing sheet from which the sea component of the sea-island composite fiber had been removed. The average unidimensional diameter of the single fibers on the surface of the obtained seamed sheet was 4.2 μm. Then, the water-dispersible polyurethane dispersion A adjusted in the same manner as in Example 2 was impregnated into the sea-removing sheet, treated in hot water at a temperature of 95°C for 1 minute, and dried with hot air at a drying temperature of 100°C In 15 minutes, the water-dispersible polyurethane-imparted sheet was obtained so that the mass of the polyurethane was 35% by mass relative to the mass of the island component of the nonwoven fabric. Impregnate the aforementioned sheet that has been given water-dispersible polyurethane In hot water at 98°C for 10 minutes, the applied PVA is removed and then dried at 100°C for 10 minutes. Then, the obtained sheet was further heated at a temperature of 160°C for 20 minutes.

Then use a half-cutting machine with a jointless belt knife to cut the sea-going sheet into half vertically in the thickness direction. Grind the un-half-cut side with 120 mesh and 240 mesh sandpaper for raising treatment, and then use a circulating dyeing machine. It is dyed with disperse dyes and subjected to reduction washing to obtain artificial leather with an average area mass of 230 g/m ² . The peeling off of the polyurethane during hot water coagulation of water-dispersed polyurethane is 0.2% and almost no. The obtained artificial leather has good appearance and taste, and the touch is not as good as that of paper. Parameter A is 3.8%, and parameter B is 20.3%.

[Example 4]

In addition to the water-dispersed polyurethane dispersion B with a prepared polyurethane solid content of 20%, a combination of 3% by mass relative to the polyurethane solid content is added. The dispersion liquid of the active ingredient of the tackifier [Sunnopco Co., Ltd. "Thickener 623N"] was impregnated with the same nonwoven fabric as in Example 1, and in the same manner as in Example 1, an artificial leather with an average area mass of 218 g/m ² was obtained.

The peeling off of the polyurethane during hot water coagulation of water-dispersed polyurethane is 0.1% and almost no. The obtained artificial leather has good appearance and taste, and the touch is not as good as that of paper. Parameter A is 4.0%, and parameter B is 26.8%.

[Example 5]

In addition to adding 3% by mass of aqueous isocyanate relative to the solid content of polyurethane to water-dispersible polyurethane dispersion B with a prepared polyurethane solid content of 20% [Bayer MaterialScience Co., Ltd. ""Desmodur" (registered trademark) N3900"]] active ingredient, a carbodiimide-based crosslinking agent with 3% by mass relative to the solid content of polyurethane [Nisshinbo The active ingredient of "Carbodilite" (registered trademark) V-02-L2" manufactured by Chemical Co., Ltd.] and a binding type tackifier with 3% by mass relative to the solid content of polyurethane [Sunnopco Co., Ltd. The dispersion of the active ingredient made "Thickener 623N"] was impregnated with the same non-woven fabric as in Example 1, and in the same manner as in Example 1, an artificial leather with a mass per unit area of 220 g/m ² was obtained.

The peeling off of the polyurethane during hot water coagulation of water-dispersed polyurethane is 0.2% and almost no. The obtained artificial leather has good appearance and taste, and the touch is not as good as that of paper. Parameter A is 4.3%, and parameter B is 30.3%.

[Example 6]

In addition to adding 3% by mass of aqueous isocyanate relative to the solid content of polyurethane to water-dispersible polyurethane dispersion B with a prepared polyurethane solid content of 20% [Bayer MaterialScience Co., Ltd. ""Desmodur" (registered trademark) N3900"]] active ingredient, a carbodiimide-based crosslinking agent with 3% by mass relative to the solid content of polyurethane [Nisshinbo The active ingredient of "Carbodilite" (registered trademark) V-02-L2" manufactured by Chemical Co., Ltd.] and a binding type tackifier with 3% by mass relative to the solid content of polyurethane [Sunnopco Co., Ltd. The dispersion liquid of the active ingredient made "Thickener 623N"] was impregnated with the same non-woven fabric as in Example 3, and in the same manner as in Example 3, an artificial leather with a mass per unit area of 220 g/m ² was obtained.

The peeling off of the polyurethane during hot water coagulation of water-dispersed polyurethane is 0.2% and almost no. The obtained artificial leather has good appearance and taste, and the touch is not as good as that of paper. Parameter A is 4.2%, and parameter B is 20.4%.

[Example 7]

The sea-island composite fiber of Example 1 was used to form a fiber web by a carding machine and a cross-winding machine. After the obtained fiber web was laminated, twisted yarns and warp and weft yarns were combined to form 84 dtex-72 long fibers, and the weaving density was averaged 1 After the 96×76 (warp×weft) textile is laminated on the front and back of the aforementioned laminated fiber web, the laminated non-woven fabric is formed by needle rolling, and the mass of the polyurethane is 28 mass relative to the mass of the non-woven island. % Method to give water-dispersed polyurethane, and use a half-cutting machine with a jointless ribbon knife to cut the sea-going sheet into half vertically in the thickness direction, and use 120 mesh and 240 mesh sandpaper on the side that is not half-cut Polishing and raising treatment were carried out in the same manner as in Example 6 except that the artificial leather having a mass per unit area of 393 g/m ² was obtained. When water-dispersed polyurethane hot water solidifies, the peeling off of polyurethane is 0.2% and almost no. The obtained artificial leather has good appearance and taste, and the touch is not as good as that of paper. Parameter A is 3.6%, and parameter B is 20.1%.

[Example 8]

In addition to adding 3% by mass of aqueous isocyanate relative to the solid content of polyurethane to the water-dispersible polyurethane dispersion A with a prepared polyurethane solid content of 20% [Bayer MaterialScience Co., Ltd. ""Desmodur" (registered trademark) N3900"]] active ingredient, a carbodiimide-based crosslinking agent with 3% by mass relative to the solid content of polyurethane [Nisshinbo The active ingredient of "Carbodilite" (registered trademark) V-02-L2" manufactured by Chemical Co., Ltd. is a guar gum [sun The active ingredient of "Neo Soft G" manufactured by Chemical Co., Ltd. and a dispersion of 1.2% by mass of magnesium sulfate based on the solid content of polyurethane were immersed in the same non-woven fabric as in Example 3, and impregnated with polyamine After the carbamate dispersion liquid was treated in hot water at a temperature of 95°C for 3 minutes, an artificial leather with a mass per unit area of 221 g/m ² was obtained in the same manner as in Example 3.

When the water-dispersed polyurethane hot water solidifies, the peeling of the polyurethane is 0.1% and almost no. The obtained artificial leather has good appearance and taste, and the touch is not as good as that of paper. Parameter A is 3.3%, and parameter B is 18.9%.

[Example 9]

The sea-island composite fiber of Example 1 was used to form a fiber web by a carding machine and a cross-winding machine. After the obtained fiber web was laminated, twisted yarns and warp and weft yarns were combined to form 84 dtex-72 long fibers, and the weaving density was averaged 1 After the 96×76 (warp×weft) textile is laminated on the front and back of the aforementioned laminated fiber web, the laminated non-woven fabric is formed by needle rolling, and the mass of the polyurethane is 28 mass relative to the mass of the non-woven island. % Method to give water-dispersed polyurethane, and use a half-cutting machine with a jointless ribbon knife to cut the sea-going sheet into half vertically in the thickness direction, and use 120 mesh and 240 mesh sandpaper on the side that is not half-cut Except for polishing and raising treatment, it was performed in the same manner as in Example 8 to obtain an artificial leather having a mass per unit area of 390 g/m ² . When the water-dispersed polyurethane hot water solidifies, the peeling of the polyurethane is 0.1% and almost no. The obtained artificial leather has good appearance and taste, and the touch is not as good as that of paper. Parameter A is 2.9%, and parameter B is 19.2%.

[Example 10]

Except that the non-woven fabric has a saponification degree of 99% and a degree of polymerization of 1400 PVA [manufactured by Nippon Synthetic Chemical Co., Ltd. "NM-14"] and drying are not performed, the same procedure as in Example 9 is carried out to obtain a mass per unit area of 388 g/m ^2. Artificial leather. When the water-dispersed polyurethane hot water solidifies, the peeling of the polyurethane is 0.1% and almost no. In addition, half of the sides are cut with a half-cutting machine, and there is no unevenness in the application of polyurethane, and the polyurethane is uniformly impregnated in the fibrous base material. The obtained artificial leather has good appearance and taste, and the touch is not as good as that of paper. Parameter A is 1.1%, and parameter B is 9.4%.

[Example 11]

In addition to adding 4% by mass of aqueous isocyanate relative to the solid content of polyurethane to the water-dispersible polyurethane dispersion B with a prepared polyurethane solid content of 20%. [Bayer MaterialScience Co., Ltd. ""Desmodur" (registered trademark) N3900"]] active ingredient and 2.5% by mass relative to the solid content of polyurethane guar gum [ The dispersion liquid of the active ingredient of "Neo Soft G" manufactured by Sun Chemical Co., Ltd. was impregnated with the same nonwoven fabric as in Example 3, and the same procedure as in Example 9 was carried out to obtain artificial leather with a mass per unit area of 388 g/m ² .

When the water-dispersed polyurethane hot water solidifies, the peeling of the polyurethane is 0.1% and almost no. In addition, the side cut into half with a half-cutting machine has no uneven polyurethane imparting and polyurethane It is evenly impregnated in the fibrous base material. The obtained artificial leather has good appearance and taste, and the touch is not as good as that of paper. Parameter A is 2.5%, and parameter B is 14.3%.

[Example 12]

In addition to the water-dispersed polyurethane dispersion C with a prepared polyurethane solid content of 20%, 4% by mass of carbon dioxide relative to the solid content of polyurethane is added. The effective ingredient of the imide-based crosslinking agent ["Carbodilite" (registered trademark) V-02-L2" manufactured by Nisshinbo Chemical Co., Ltd.], which increases the viscosity of 2% by mass relative to the solid content of polyurethane The active ingredient of polysaccharide guar gum ["Neo Soft G" manufactured by Taiyo Chemical Co., Ltd.] and a dispersion of 3.0% by mass of magnesium sulfate based on the solid content of polyurethane are impregnated outside the non-woven fabric, In the same manner as in Example 9, an artificial leather having a mass per unit area of 386 g/m ² was obtained.

When the water-dispersed polyurethane hot water solidifies, the peeling of the polyurethane is 0.1% and almost no. In addition, the side cut in half by a half-cutting machine has no unevenness in the application of polyurethane, and the polyurethane is uniformly impregnated in the fibrous base material. The obtained artificial leather has good appearance and taste, and the touch is not as good as that of paper. Parameter A is 1.2%, and parameter B is 5.2%.

[Example 13]

Except that the non-woven fabric has a saponification degree of 99% and a degree of polymerization of 1400 PVA [manufactured by Nippon Synthetic Chemical Co., Ltd. "NM-14"] and drying are not performed, the same procedure as in Example 12 is carried out to obtain a mass per unit area of 388 g /m ² . When the water-dispersed polyurethane hot water solidifies, the peeling of the polyurethane is 0.1% and almost no. In addition, half of the sides are cut with a half-cutting machine, and there is no unevenness in the application of polyurethane, and the polyurethane is uniformly impregnated in the fibrous base material. The obtained artificial leather has good appearance and taste, and the touch is not as good as that of paper. Parameter A is 0.7%, and parameter B is 4.0%.

Figure 1 shows a cross section of the artificial leather obtained in Example 13. The state of polyurethane and ultra-fine fiber bundles observed in the cross section of Figure 1 shows that the cross-section of polyurethane is small (polyurethane blocks are small), and the ultra-fine fiber bundles and Polyurethane has little adhesion.

[Comparative Example 1]

Except that the prepared water-dispersible polyurethane dispersion A with a polyurethane solid content concentration of 20% is added with 1.2% by mass of magnesium sulfate relative to the polyurethane solid content. The dispersion was impregnated with the same non-woven fabric as in Example 1, and the same procedure as in Example 1 was carried out to obtain an artificial leather with a mass per unit area of 223 g/m ² . When the water-dispersed polyurethane was coagulated in hot water, the peeling of the polyurethane was 22.1%, and the adhesion of the polyurethane to the fibrous substrate was uneven.

[Comparative Example 2]

Except that the water-dispersible polyurethane dispersion B whose solid content concentration has been adjusted to 20% was impregnated in the same nonwoven fabric as in Example 1, the same procedure as in Example 1 was carried out to obtain a mass per unit area of 223 g/m ^2. Artificial leather. When the water-dispersed polyurethane hot water solidifies, the peeling of the polyurethane is 15.1%, and the adhesion of the polyurethane to the fibrous substrate is uneven.

[Comparative Example 3]

The aforementioned water-dispersible polyurethane dispersion B whose solid content has been adjusted to 20% was impregnated into the same non-woven fabric as in Example 1, and treated for 5 minutes in a humid and hot environment with a temperature of 97°C and a humidity of 100% , Dried at a temperature of 110°C for 15 minutes to give the water-dispersed polyurethane resin a content of 35% by mass relative to the mass of the non-woven island components. Other than that, the same as in Example 1 The artificial leather with a mass per unit area of 223 g/m ² was obtained. Although the peeling of the polyurethane during hot water coagulation of water-dispersed polyurethane is 0.0%, the artificial leather obtained has a strong feel like paper. Parameter A is 7.9%, and parameter B is 42.2%.

[Comparative Example 4]

The aforementioned water-dispersible polyurethane dispersion B whose solid content has been adjusted to 20% was impregnated into the same non-woven fabric as in Example 13, and treated for 5 minutes in a humid environment with a temperature of 97°C and a humidity of 100% , Dried at a temperature of 110°C for 15 minutes to give the water-dispersed polyurethane resin 28% by mass relative to the mass of the non-woven island component. Other than that, the same as in Example 13 The artificial leather with a mass per unit area of 389 g/m ² was obtained. Although the peeling off of the polyurethane during hot water solidification of water-dispersed polyurethane is 0.0%, the artificial leather obtained has a strong feel like paper. Parameter A is 8.1%, and parameter B is 43.1%.

Figure 2 shows a cross section of the artificial leather obtained in Comparative Example 4. The state of polyurethane and ultra-fine fiber bundles observed in the cross section of Figure 2 is that the cross-section of polyurethane is large (the block of polyurethane is large), and the ultra-fine fiber bundles and A state where there are many polyurethanes.

The results of the foregoing Examples 1 to 7 and Comparative Examples 1 to 4 are collectively shown in Tables 1 and 2.

In the example, the value of parameter A is smaller than that of the comparative example, so the polyurethane block is small, and the polyurethane is uniformly dispersed It forms a soft touch inside the artificial leather. In addition, since the parameter B of the example is smaller than that of the comparative example, the adhesion between the ultrafine fiber bundle and the polyurethane is less, and a soft touch is formed.

[Industrial availability]

Claims (11)

A sheet-like article in which a polymer elastomer with a hydrophilic group is used as an adhesive and is applied to a fibrous base material containing ultrafine fibers and/or ultrafine fiber bundles, and is characterized in that: On the cross-section cut in the thickness direction of the sheet, the occupancy rate of the part of the polymer elastomer observed in the cut plane independently and having a cross-sectional area of 50 μm ² or more is relative to that in the observation field. The artificial leather composed of the sheet has a cross-sectional area of 0.1% to 5.0%, and 1% to 35% of the outer periphery of the section of the ultrafine fiber and/or ultrafine fiber bundle is covered by a polymer elastomer film. The sheet of claim 1, wherein the polymer elastic system has a structure crosslinked by a crosslinking agent. A method for manufacturing a sheet according to claim 1 or 2, which is a method for manufacturing a sheet in which a polymer elastomer having a hydrophilic group is applied as an adhesive to a fibrous base material containing ultrafine fibers It is characterized in that: the fibrous base material is given an aqueous resin dispersion containing a polymer elastomer dispersed in water and a tackifier, and the polymer elastomer is coagulated in hot water at a temperature of 50-100°C. The method for producing a sheet-like article according to claim 3, wherein the aqueous resin dispersion system exhibits non-Newtonian fluidity. The method for manufacturing a sheet-like article according to claim 3 or 4, wherein the thickener is a nonionic thickener. The method for producing a sheet-like article according to claim 3 or 4, wherein the aqueous resin dispersion system exhibits thixotropy. The method for manufacturing a sheet-like article according to claim 3 or 4, wherein the thickening agent is a thickening polysaccharide. As claimed in claim 3 or 4, the method of manufacturing a sheet, wherein the thickening agent is guar gum. The method for producing a sheet-like article according to claim 3 or 4, wherein the aqueous resin dispersion contains a heat-sensitive coagulant. The method for producing a sheet-like article according to claim 3 or 4, wherein the aqueous resin dispersion contains a crosslinking agent. According to claim 3 or 4, the method for producing a sheet-like article, wherein the polymer elastomer is a water-dispersed polyurethane.

Images