JP2006291418A - Oil-touch leathery sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oil-touch leathery sheet having soft and solid feeling inherent in natural leather, and enabling its oil touch to be controlled without causing rough feeling while keeping oily substance migration little. <P>SOLUTION: The oil-touch leathery sheet is characterized by that the non-plush fiber bundles(B) of a fibrous base material surfaced mainly with (A) resin coating film and (B) the non-plush fiber bundles is coated with (C) a gel-like material comprising an oily substance 50-10,000 mPa in viscosity at 30°C and a holder thereof. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an oil-like leather-like sheet having flexibility and surface touch like an oil-like natural leather and having appropriate air permeability.

  The material that imitates natural leather has a velvety type that is raised for a relatively long time and covered with rough napping, and a nubuck type that is raised for a relatively short time and covered with dense napping, and on the surface. There is a type with silver that does not have napping or a type with silver at first glance, but when viewed microscopically, there is a short napping, and it is roughly divided into `` silvered tone '' such as a type with semi-silver that has a touch close to the nubuck type Above all, the leather-like sheets on the market account for the largest proportion of silvery tones due to the influence of natural leather distribution.

  Various proposals have already been made as methods for producing a silvered leather-like sheet. For example, the “wet surface forming method” in which an elastic resin solution is applied to the surface of a fibrous base material selected from woven and knitted fabrics, nonwoven fabrics, and those containing an elastic resin, and wet coagulated, or on a release paper “Dry surface making method” in which an elastic resin film is made and bonded to the surface of the fibrous base material via an adhesive has been industrialized, and many of these methods have been produced by combining these methods alone or in combination. Silver-finished leather-like sheet products are on the market.

  In order to reproduce the soft and rich texture of oil-like natural leather on these silver-finished leather-like sheets, treatment with various additives has been conventionally performed. However, a thing close to natural leather has not yet been obtained. For example, when softening is performed using a greasing agent treated with natural leather, such as fish oil or vegetable oil, a texture close to that of natural leather can be obtained, but the transition to the surface of oil or oil is noticeable. Moreover, if it sews on clothes etc. and wears and wash | cleans with a detergent etc., a greasing agent will drop | omit and a prickly feeling will arise and the previous texture cannot be maintained. Accordingly, there has been a demand for a texture close to natural leather that does not migrate oily substances such as fats and oils and is excellent in flexibility and fulfillment.

  On the other hand, a method of using a softening agent such as a silicon emulsion treatment or a wax treatment as a softening agent has been proposed in order to make artificial leather a texture in which the natural leather has a sense of fulfillment and flexibility (see Patent Document 1). .) However, when folded, the oil movement inside the leather will change the lightness of the color, producing natural spots, but the appearance of an oil-up tone can be reproduced, but the softness and rich texture of natural leather can be fully produced. I couldn't. In addition, the present inventors have proposed a method of applying an oily substance and its holding body to the surface of a fibrous base material having napping on the surface (see Patent Document 2). However, this method is an improvement of the touch oil feeling of the napped surface, and basically a composition comprising an oily substance and a holding body is attached to the napped portion of the surface to form a nubuck type leather-like sheet. The silver-tone appearance as in the present invention cannot be obtained.

  Therefore, in order to solve such a problem, the present inventors have an oily substance having a viscosity of 50 to 10,000 mPa · s at 30 ° C. and a gel-like substance composed of a holder thereof at least inside the fibrous base material. The fiber base material characterized by this is proposed (see Patent Document 3). The fibrous base material obtained here has a feature that the oily substance is hardly transferred and the oily feeling is maintained even by washing with water. However, when a leather-like sheet with a silver finish was created by wet surface preparation and dry surface preparation using the fiber equipment obtained here, the oil-like feel that was soft and close to natural leather could be reproduced. There is a problem that oil blades are generated from the gel-like material applied to the surface of the silver-finished leather-like sheet, and an oil-finished leather-like sheet-like material that is flexible and excellent in oil-like touch has not been obtained.

JP-A-6-264371 (2nd page, 2nd column, lines 36-49) JP 2001-131880 A (2nd page, 2nd column, 5th line-26th line) JP 2004-44068 A (page 3, lines 26-44)

  Currently, there is a demand for an oil-finished leather-like sheet that has a soft and solid texture and oil-like texture of natural leather and that does not cause the texture to harden with very little transfer of oily substances. Yes.

In order to achieve the above-mentioned problems, the present inventors have intensively studied and have found the following oil-finished leather-like sheet. That is, the present invention
(1) The non-raised fiber bundle (B) of the fibrous base material having a surface mainly composed of the resin coating (A) and the non-raised fiber bundle (B) has a viscosity at 30 ° C. of 50 to 10,000 mPa · s. The oil-like leather-like sheet is characterized in that the oily substance and a gel-like material (C) comprising the support are adhered. Also,
(2) The non-raised fiber bundle (B) is an oil-finished leather-like sheet according to (1) in which 10 or more ultrafine fibers of 0.5 decitex or less converge.
(3) The oil-coated leather-like sheet according to (1) or (2), wherein the resin coating (A) and the non-raised fiber bundle (B) satisfy the following formula:
50 <Sa <95
5 <Sb <50
(However, Sa: Area ratio (%) the resin film (A) existing on the surface occupies the entire surface of the oil-like leather-like sheet) Sb: Non-napped fiber bundle (B) exposed on the surface is oil-like Ratio of area to the entire leather-like sheet surface (%))
(4) The oil-coated leather-like sheet according to any one of (1) to (3), wherein the resin coating (A) is made of polyurethane.
(5) The oil-toned leather-like sheet according to any one of (1) to (4), wherein a space communicating with the inside of the fibrous base material is formed around the non-napped fiber bundle (B) exposed on the surface,
(6) The oil-finished leather-like sheet according to any one of (1) to (5), wherein micropores (D) satisfying the following formula are present on the surface.
10 <Rd <100
5 <Nd <100
1 <Sd <35
(However, Rd: Radius (μm) Nd: Number of micropores (D) per unit area (pieces / mm ² ) Sd: Area ratio (%) that micropore (D) occupies with oil-finished leather-like sheet surface

  The oil-like leather-like sheet of the present invention has a soft texture like natural leather and a touch feeling peculiar to oil-like natural leather. It is suitable for all kinds of artificial leather and is particularly useful for application to sports gloves because of its excellent touch and fit to the skin.

  Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the following descriptions.

  First, the fibrous base material used in the present invention is not particularly limited, and a known fibrous base material can be used. For example, a woven fabric, a non-woven fabric, a woven fabric, or those impregnated with a polymer elastic body can be used.

  In particular, it is preferable to use a fibrous base material obtained by impregnating an ultrafine fiber entangled non-woven fabric made of fibers having a single fiber diameter of 0.5 dtex or less with a polymer elastic body in terms of natural leather-like flexibility. More preferably, it is in the range of 0.3 to 0.0001 dtex. If the thickness exceeds 0.5 decitex, the texture of the leather-like sheet is hardened and a rough feel is not preferable. On the other hand, if it is less than 0.0001 dtex, the breaking strength of the fiber is lowered, so that the peel strength and breaking strength of the leather-like sheet are lowered.

  As a method for producing the ultrafine fiber, a known method can be used, and it is not particularly limited, but two or more kinds of polymers that are not compatible in the molten state and have different solubility or decomposability are used. After obtaining ultrafine fiber-generating fibers by the mixed spinning method, the sea-island structure fiber manufacturing method by the sea-island type composite spinning method, the split-type composite fiber manufacturing method by the composite spinning method, etc., and a part (for example, sea component) Representative examples include a method of extracting or decomposing and removing ultrafine fibers to make ultrafine fibers, or a method of peeling the interface between different polymers of split-type composite fibers to make ultrafine fibers. In addition to these methods, it is also possible to use a method such as a so-called melt-blowing method in which fibers are blown away with a high-speed gas immediately after the fiber-forming polymer is discharged from the melt spinning nozzle. However, from the viewpoint of fiber thickness management and the quality stability of the ultrafine fiber, a method via the ultrafine fiber generating fiber is preferable.

  The number of ultrafine fibers present in one bundle of ultrafine fibers is preferably in the range of 10 to 5000, and particularly preferably in the range of 10 to 1000. When the number of single fibers in the fiber bundle is less than 10, it is not preferable because the texture of the final product tends to be hard, and when the number is 5000 or more, it is possible to stably obtain ultrafine fiber generating fibers. Is not preferable because it is difficult.

  The resin constituting the ultrafine fiber of the present invention is not particularly limited, but includes polyethylene terephthalate, polypropylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and copolymer polyesters mainly composed of these. Aromatic polyesters, polyamides such as nylon 6, nylon 66, and nylon 610, and polyolefins such as polyethylene and polypropylene. Of these, the above aromatic polyesters and polyamides are preferred because natural leather-like artificial leather can be obtained and dyeing properties are excellent. These resins are also added with known stabilizers such as pigments such as carbon black, colorants such as dyes, UV inhibitors, etc. as long as the stability during spinning is not impaired. Also good.

  Examples of the resin component extracted or decomposed and removed from the ultrafine fiber generating fiber include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, polystyrene, and styrene-acrylic monomer copolymer. Examples thereof include at least one polymer selected from polymers such as polymers, styrene-ethylene copolymers, and copolyesters. Of these, polyethylene, polystyrene, or a copolymer mainly composed of these are preferable from the viewpoint of easy extraction.

  Next, a known method is used as a method of forming the entangled nonwoven fabric composed of the ultrafine fibers or the ultrafine fiber-generating fibers and the fibrous base material impregnated with the polymer elastic body therein. For example, a step of manufacturing an entangled nonwoven fabric composed of ultrafine fiber-generating fibers, a step of impregnating the entangled nonwoven fabric with a polymer elastic body solution and solidifying, and a step of modifying ultrafine fiber-generating fibers into ultrafine fibers are sequentially performed. Can be achieved. Of course, the step of modifying into ultrafine fibers and the step of impregnating and solidifying the polymer elastic body solution may be reversed.

As a method for producing an entangled nonwoven fabric using an ultrafine fiber generating fiber, the ultrafine fiber generating fiber is subjected to processing such as spinning, drawing, heat setting, crimping, cutting, etc. by a conventionally known method. Examples thereof include a method of producing staples, defibrating such staples with a card, forming a random web or a cross-wrap web with Webber, and laminating the obtained web as necessary to obtain a desired weight. The weight of the web at this time is appropriately selected according to the intended final application field, and is generally preferably in the range of 100 to 3000 g / m ² . For the purpose of cost reduction, etc., an entangled non-woven fabric of about twice the required mass is impregnated and solidified with a polymer elastic body solution, and then divided in the thickness direction with a band knife or the like to efficiently reduce the weight. Two fibrous substrates can be produced at a time.

Following web lamination, an entangled nonwoven fabric is formed by performing an entanglement process using a known method such as a needle punching method or a high-pressure water jet method. In the case of needle punching method varies the shape and the web of the thickness of the used needle, generally the entangled nonwoven fabric structure to set the condition of the range punching density of 200 to 2500 punches / cm ² This is preferable because the density and physical properties of the nonwoven fabric as a leather-like sheet are easily balanced. However, if the punching density is excessively increased, the non-rabbed fiber bundles essential for the present invention are extremely reduced. Therefore, it is necessary to appropriately set conditions so as to obtain a desired state.

  Prior to the impregnation treatment of the polymer elastic body, the entangled nonwoven fabric may be subjected to a surface smoothing treatment by a known method such as hot pressing, if necessary. If the fibers that make up the entangled nonwoven fabric are sea-island structure fibers, for example, with polyethylene as the sea component and polyester or polyamide as the island component, the sea component polyethylene is fused by hot pressing to bond the fibers together. By doing so, an entangled nonwoven fabric with extremely excellent surface smoothness can be obtained. In addition, when the fiber constituting the entangled nonwoven fabric is not a sea-island structure fiber that can be dissolved and removed by dissolving one component, the impregnated polymer elastic body is fixed to the fiber and the texture becomes harder. In order to prevent this, it is preferable that the fiber surface is covered with a temporarily filling material such as polyvinyl alcohol prior to the impregnation treatment of the polymer elastic body, and the temporary filling material is removed after applying the polymer elastic body. Also in the case of sea-island structure fibers that can be made into ultrafine fibers by dissolving or removing one component to dissolve and remove, the above-mentioned temporary filling substance is applied at the stage of the entangled nonwoven fabric to cover the surface of the multicomponent fibers. By removing the temporary filling material after applying the elastic body, a more flexible sheet can be obtained. Thus, it is preferable to generate ultrafine fibers from ultrafine fiber-generating fibers represented by sea-island structure fibers and the like. That is, the fiber constituting the fibrous base material is an ultrafine fiber bundle, and the gel substance (C) composed of the oily substance of the present invention and its holding body is easily contained selectively in the ultrafine fiber bundle. The leather-like soft texture and richness will be excellent.

  Next, as the resin to be impregnated into the entangled nonwoven fabric, a known polymer elastic body such as natural rubber, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, polyurethane elastomer, other synthetic rubber, or a mixture thereof should be used. Is possible. Of these, polyurethane resins are preferably used from the viewpoint of excellent texture. Preferred polyurethane resins include, as soft segments, polyester diols, polylactone diols, polycarbonate diols, polyether diols, and polyether ester diols obtained by reacting diols with dicarboxylic acids or ester-forming derivatives thereof. And so-called segmented polyurethane obtained by reacting a diisocyanate compound with a low molecular chain extender using at least one polymer diol having a number average molecular weight of 500 to 5,000 selected from the group consisting of It is done.

  The diol compound used for the synthesis of the polymer diol constituting the soft segment is preferably an aliphatic compound having 6 to 10 carbon atoms in terms of durability or leather-like texture. For example, 3-methyl-1,5 -Pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and the like. Representative examples of the dicarboxylic acid include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid.

  When the number average molecular weight of the polymer diol is less than 500, it is not preferable because it lacks flexibility and a natural leather-like texture cannot be obtained. On the other hand, when the number average molecular weight of the polymer diol exceeds 5,000, the urethane group concentration decreases, so that it is difficult to obtain a leather-like sheet balanced in flexibility, durability, heat resistance, and hydrolysis resistance. Examples of the diisocyanate compound include aromatic, aliphatic, and alicyclic compounds such as 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and hexamethylene diisocyanate. A diisocyanate compound is mentioned.

  Examples of the low molecular chain extender include 2 active hydrogen atoms having a molecular weight of 300 or less such as ethylene glycol, propylene glycol, butanediol, hexanediol, N-methyldiethanolamine, ethylenediamine, diaminodiphenylmethane, diaminodicyclohexylmethane, and isophoronediamine. The low molecular compound which has one is mentioned.

  The polyurethane synthesis method may be a one-shot method or a prepolymer method.

  If necessary, the polyurethane may be added with a coagulation regulator, a stabilizer and the like, and other polymers may be used in combination as long as the object of the present invention is not impaired. Further, a colorant such as carbon black or a dye may be added.

  The method of adding polyurethane to the entangled nonwoven fabric is not particularly limited, but from the viewpoint of the balance of the texture, a polyurethane solution diluted with a good polyurethane solvent such as dimethylformamide is used for the entangled nonwoven fabric, or an aqueous dispersion of polyurethane. A method of directly impregnating and, if necessary, squeezing with a mangle or a method of impregnating a polyurethane solution or an aqueous dispersion of polyurethane with a coater is preferred. The polyurethane is impregnated into the entangled nonwoven fabric by wet coagulation or dry coagulation of the impregnated polyurethane liquid, and the wet coagulation method is particularly preferred because a natural leather-like texture and feel can be obtained. And, from the viewpoint of a soft texture like natural leather, the mass ratio between the fibers constituting the fibrous base material and polyurethane is preferably in the range of 30/70 to 90/10, more preferably 35/65 to 80 /. Within the range of 20. If the fiber ratio is too lower than this range, the leather-like sheet will have a rubber-like texture, and if the fiber ratio is too high, it will have a paper-like texture, so that the desired natural leather-like texture cannot be obtained.

  In order to develop a silver-tone appearance that is the object of the present invention, it is effective to form a porous film on the entangled nonwoven fabric and expose the fibers constituting the entangled nonwoven fabric through the holes on the surface. is there. In order to form this porous film, various methods such as bonding the porous film to the obtained substrate can be selected and are not particularly limited, but the polyurethane resin solution impregnated with the entangled nonwoven fabric is not limited. Is most preferable from the viewpoint of simplification of the process by allowing the polyurethane resin solution to coagulate by wet coagulation. For example, after impregnating a polyurethane resin into an entangled nonwoven fabric, the excess polyurethane solution remaining on the nonwoven fabric surface is scraped off with a mangle roller or a coater knife to control the surface state of the fibrous base material after coagulation However, a polyurethane resin coating layer having an appropriate thickness can be formed by controlling the pressure applied by the mangle roller or the clearance of the knife coater. When a resin film layer is applied by this method, the thickness of the polyurethane resin film formed on the entangled nonwoven fabric is as follows, in order to give the surface strength at the level of silvering without damaging the flexibility of natural leather. The squeezing pressure or the clearance of the knife coater is preferably controlled so that the average thickness after solidification is 7 μm to 80 μm, preferably 10 μm to 50 μm. When the thickness of the polyurethane film after coagulation is 7 μm or less, the flexibility is good, but it is difficult to obtain the surface strength of the final product. When the thickness exceeds 80 μm, the surface strength of the final product tends to be sufficiently obtained. However, it is inflexible and less exposed to the surface of the non-napped fiber bundle, so the gel-like substance cannot be retained on the surface, making it difficult to obtain an oil-like touch and appearance, and durability in the retained state. This is not preferable because the properties are poor. The thickness of the polyurethane resin film corresponds to the average of the top 10 points of the fibers constituting the upper part of the fibrous base material except for the fibers exposed on the surface, arbitrarily selecting an electron microscopic cross-sectional photograph of the leather-like sheet. A point is drawn parallel to the surface of the leather-like sheet, and the distance from the line to the surface is measured.

  When sea-island structured fibers are used, after entangled nonwoven fabric with polyurethane, the island components of polyurethane and ultrafine fiber generating fibers are non-solvent and the sea components of ultrafine fiber generating fibers Is treated with a solvent or a liquid that acts as a decomposing agent to transform ultrafine fiber-generating fibers into ultrafine fiber bundles, thereby forming a fibrous base material precursor comprising ultrafine fiber entangled nonwoven fabric and polyurethane. Of course, prior to impregnation with polyurethane, a fiber base material can be formed by using a method of transforming ultrafine fiber-generating fibers into ultrafine fiber bundles. In the case where a peelable split type composite fiber is used, it is possible to peel it at the interface of the fiber constituent polymer by treating with a liquid that promotes peeling to form an ultrafine fiber bundle.

  The obtained fibrous base material can be used in a desired color. As a coloring method, a known dyeing method for dyeing a woven fabric or a non-woven fabric can be used, and it is not particularly limited. The dye used may be a known dye. For example, if the resin of the raised portion of the fibrous base material is polyester, it is a disperse dye, if it is polyamide, it is an acid dye, sulfur dye, vat dye, and if it is acrylic, it is a cation. A dye or the like may be used. The dyeing machine may be a known dyeing machine such as a circular, wins, dash line, washer dyeing machine, Tyco dyeing machine or continuous dyeing machine, and is not particularly limited.

The coloring method is not limited to dyeing with a dye, and it is also possible to disperse the pigment in an arbitrary resin and apply it to the surface of the fibrous base material. It is also possible to combine dyeing with a dye and coloring by pigment application. The resin for dispersing the pigment is not particularly limited, but polyurethane is most preferable from the viewpoint of adhesion to the polyurethane coating layer present on the surface of the fibrous base material. The method for applying is not particularly limited, and a known method such as gravure printing can be used. The adhesion amount of the resin solution in which the pigment to be applied is dispersed is not particularly limited, but is preferably 50 g / m ² or less as the resin solid content. An adhesion amount of 50 g / m ² or more is not preferable because a coating of a colored layer is formed on the surface and the number of fiber bundles exposed on the surface that suppresses oil bleed in the final product decreases.

  When the surface of the fibrous base material thus obtained is observed, a coating made of a polymer elastic body (hereinafter, the coating existing on the surface of the fibrous base material is referred to as a resin coating (A)) and a resin coating (A). Open pores (hereinafter referred to as “small holes (E)”) and non-napped fiber bundles (hereinafter referred to as “napped” existing on the surface of this fibrous base material) The fiber bundle in a state along the surface (the fiber is lying on the surface) is defined as a non-napped fiber bundle (B)), and the inside of the fibrous base material from the small hole (E) A space communicating with is formed. The non-raised fiber bundle (B) here is a fiber bundle that has not been subjected to open fiber raising treatment such as buffing treatment using sandpaper, or that has not been substantially raised even if raising treatment is performed. That is, it refers to a fiber bundle in which the fiber bundle is present while lying along the surface direction of the fibrous base material.

  The final oil-finished leather-like sheet has an “oil-like surface feel”, “surface strength”, “oil-like durability”, or “breathability”. It varies depending on the area ratio of the fiber bundle (B). And it is often determined by the area ratio of the resin coating (A) on the surface of the oil-like leather-like sheet and the non-napped fiber bundle (B) on the surface.

  When the area ratio of the resin coating (A) occupying the surface of the fibrous base material is small and when the area ratio of the non-napped fiber bundle (B) is large, the surface strength of the oil-finished leather-like sheet as the final product is It tends to decline. In addition, when the area ratio of the resin coating (A) is large and the area ratio of the non-hair-like fiber bundle (B) is small, the non-hair-like fiber bundle (B) that is the holding body of the gel-like object (C) The ratio decreases, and the endurance of the oil-like leather-like sheet, which is the final product, is poor, and the air permeability of the final product is lowered. Therefore, the area ratio that the resin coating (A) occupies with respect to the surface of the fibrous base material is greater than 50% and less than 95%, and the non-rafted fiber bundle (B) with respect to the surface of the fibrous base material The area ratio occupied is preferably greater than 5% and less than 50%. However, the area ratio with respect to the surface of the fibrous base material is an electron micrograph obtained by photographing any five locations on the surface of the fibrous base material, and the resin coating (A) and the non-napped fiber bundle (B) Is the average of the values calculated by the cut-out mass method.

  Of all the small holes (E) present in the resin coating (A), it is preferable that 70% or more of the small holes (E) include a non-napped fiber bundle (B) in the hole. As a result, the non-napped fiber bundle (B) existing in the vicinity of the surface layer of the fibrous base material is exposed on the surface of the fibrous base material. When the proportion of small holes (E) containing non-napped fiber bundles (B) in the holes is less than 70% with respect to all the small holes (E) existing in the resin coating (A) When the gel-like product (C) is applied in the post-process, the number of non-napped fiber bundles (B) serving as a holder for the gel-like product (C) is reduced. It is not preferable because it is difficult to obtain a feeling and its durability is poor.

The hole diameter and the number of holes of the small holes (E) existing on the surface of the fibrous base material depend on the mass ratio of the above-mentioned fiber / polymer elastic body and the film thickness of the resin coating (A) at the time of manufacturing the fibrous base material. The ratio of the fiber / polymer elastic body and the film thickness of the resin coating (A) are preferably controlled within the aforementioned ranges. When the hole diameter of the opening of the small hole (E) is small and when the number of openings of the small hole is small, the small hole disappears when the gel-like material (C) is applied in the subsequent process, and the air permeability is reduced. Degradation is likely to occur. When the hole diameter of the small hole (E) is too large and when the number of openings of the small hole is too large, the surface wear strength is lowered, which is not preferable. Therefore, the hole diameter of the small hole (E) is in the range of about 10 μm or more and 200 μm or less, and the number of holes is preferably about 5 / mm ² or more and 100 / mm ² or less. However, the hole diameter of the small hole (E) represents the radius when the shape of the opening of the small hole (E) is a circle having the same area, and the number of holes of the small hole (E) is the fibrous base. The average value measured from the electron micrograph of arbitrary 5 places on the surface of a material is represented.

  Next, the gel substance (C) comprising the oily substance and the support constituting the present invention will be described. First, the holding body is a high-molecular substance exhibiting elastomeric properties at room temperature, that is, when it is a sheet having a thickness of 0.5 mm, the elongation is 100% or more at room temperature and easily deforms when an external force is applied. It is a polymer material that immediately recovers to its original form. Furthermore, when the powder of the polymer substance is immersed in an oily substance used in combination with it and left at room temperature for 24 hours and then naturally filtered, the increase in the mass of the powder becomes 200% or more by absorbing the oily substance. It is. Among these, vinyl aromatic elastomers are preferably used from the viewpoint of oil retention.

  Next, the present invention will be described with respect to a vinyl aromatic elastomer which is a preferred example of the holder. The vinyl aromatic elastomer is a block copolymer having a polymer block A made of a vinyl aromatic compound and a polymer block B having a glass transition point of 0 ° C. or lower.

  There are no particular restrictions on the number of polymer blocks A and polymer blocks B in the block copolymer. Here, when the polymer block A is simply denoted as A and the polymer block B is simply denoted as B, the structures of suitable block copolymers are: AB, (AB) n, (AB) n-A , (BA) n-B (wherein n represents an integer of 1 to 10 in these structural formulas), (AB) m X (X represents a residue of an m-valent coupling agent, m Represents an integer of 2 to 15). Among these, a triblock copolymer represented by A-B-A is particularly preferable from the viewpoint of retaining oily substances. In the block copolymer, the content of the vinyl aromatic compound is preferably 5 to 75% by mass from the viewpoint of retention of the oily substance, and more preferably 10 to 65% by mass.

  Examples of the vinyl aromatic compound constituting the polymer block A in the block copolymer include styrene, α-methylstyrene, o-, m-, or p-methylstyrene, 1,3-dimethylstyrene, vinylnaphthalene, And vinyl anthracene. Among these, styrene or α-methylstyrene is preferable from the viewpoint of flexibility. A vinyl aromatic compound may be used independently and may use 2 or more types together.

  Further, the polymer constituting the polymer block B in the block copolymer is not particularly limited as long as it has a glass transition point of 0 ° C. or lower, but from the viewpoint of flexibility, a polymer of conjugated diene or hydrogenation thereof. The product is particularly preferred. Examples of such conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Among these, isoprene, 1,3-butadiene or a mixture thereof is preferable in terms of flexibility and prevention of migration of oily substances to the surface. Conjugated dienes may be used alone or in combination of two or more. In particular, SBS (triblock copolymer consisting of styrene polymer block-butadiene polymer block-styrene polymer block), SEBS (tripolymer block consisting of styrene polymer block-ethylene-butadiene copolymer block-styrene polymer block) are generally used. Block copolymer), SEPS (triblock copolymer consisting of styrene polymer block-ethylene / propylene copolymer block-styrene polymer block), SIS (styrene polymer block-isoprene polymer block-styrene polymer) Resins such as block triblock copolymer), SEEPS (styrene polymer block-ethylene / ethylene / propylene copolymer block-triblock copolymer block composed of styrene polymer block), etc. Base It can be used as a suitable block copolymer in terms of texture.

  The number average molecular weight of the block copolymer is not particularly limited, but is preferably 50,000 to 500,000, more preferably 100,000 to 400,000. If it is less than 50,000, the retention of the oily substance is lowered, and if it exceeds 500,000, the flexibility tends to be lowered.

  Such a block copolymer is already known, and as its production method, for example, the following known anionic polymerization method can be used. That is, a vinyl aromatic compound and a conjugated diene are polymerized in an inert organic solvent such as n-hexane or cyclohexane using an alkyllithium compound as an initiator to form a block copolymer. At this time, a coupling agent such as dichloromethane, carbon tetrachloride, or tetrachlorosilane may be used as desired.

  When the block copolymer is a hydrogenated product of the block copolymer, a hydrogenated block copolymer is obtained by hydrogenation in the presence of a hydrogenation catalyst in an inert organic solvent according to a known method. Can do.

  In the present invention, a hydrogenated block copolymer that is the above block copolymer or a hydrogenated product thereof is used as the holder, but a hydrogenated block copolymer is more preferable from the viewpoint of heat resistance and weather resistance. More preferably, 70% or more of the carbon-carbon double bonds derived from the conjugated diene in the block copolymer before hydrogenation are hydrogenated. The content of the carbon-carbon double bond in the polymer block B in the hydrogenated block copolymer can be determined by iodine value measurement, infrared spectrophotometer, nuclear magnetic resonance method or the like. In addition to the above two types of blocks, other monomers may be copolymerized in block form or randomly within a range not impairing the present invention. The styrene elastomer may contain a styrene-containing rubber such as SBR (styrene butadiene rubber) in addition to the block copolymer as described above.

  Furthermore, with respect to the resin constituting the support used in the present invention, a functional group such as a carboxyl group, a hydroxyl group, an acid anhydride group, an amino group, or an epoxy group is present in the molecular chain or at the molecular end unless the purpose of the present invention is impaired. It may contain a group.

  The oily substance to be blended in such a holding body needs to be a liquid substance having a viscosity of 50 to 10,000 mPa · s at 30 ° C., and is a substance that is substantially incompatible with water at room temperature and phase-separates. Used. When the viscosity is less than 50 mPa · s, the oily substance migrates after being applied to the substrate. On the other hand, if it exceeds 10000 mPa · s, it is not suitable because it does not mix with the holding body and has a thin oily feeling and lacks flexibility.

  Specific examples of the types of oily substances include paraffinic or naphthenic process oil, white oil, mineral oil, ethylene and α-olefin oligomers, paraffin wax, liquid paraffin, silicone oil, vegetable oil, aromatic oil, and the like. These are used alone or in combination. Among these, paraffinic process oil is preferable in that it is similar to the oily feeling of natural leather.

  Next, a method for blending the obtained support and the oily substance will be described. The method of emulsifying and blending the support and the oily physical properties is not particularly limited. For example, in the case of preparing an emulsion, the following methods can be mentioned. (Method 1) A method in which a mixed solution composed of a support, an oily substance and a hydrocarbon solvent is poured into water in which an emulsifier is dissolved, and mixed and emulsified under a high shear force. (Method 2) The support, an oily substance and carbonization A method of mixing an emulsifier with a mixed solution composed of a hydrogen-based solvent, then adding water, stirring and phase inversion, and emulsifying under a high shearing force as necessary. (Method 3) Retainer, oily substance and A method in which a mixed solution composed of a hydrocarbon solvent, an emulsifier, and water are added all at once, followed by stirring and phase inversion, and emulsification under a high shear force as necessary.

  The hydrocarbon solvent used in the present invention is not particularly limited, and specifically, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, trimethylcyclohexane, Methyl ethyl cyclohexane, decalin, aromatic solvent for carbon C8 fraction, solvent obtained by nuclear hydrogenation of aromatic solvent for carbon C8 fraction, aromatic solvent for carbon C9 fraction, aromatic for carbon C9 fraction Examples are hydrocarbon solvents having a carbon number of 10 or less, such as a solvent obtained by nuclear hydrogenation of a solvent, a solvent obtained by nuclear hydrogenation of an aromatic solvent having a carbon number of C10, and a mixture thereof. Of these, toluene and xylene are preferable because of their low price and excellent solubility. Further, from the viewpoint of protection of the natural environment, safety of the work environment, and safety for the human body, non-aromatic solvents such as methylcyclohexane and ethylcyclohexane are preferable. The said solvent can also be used individually by 1 type or in combination of 2 or more types.

  Among these, the method of phase inversion emulsification in (Method 2) and (Method 3) (hereinafter referred to as “phase inversion emulsification method”) provides an emulsion dispersion in which the particle size of the thermoplastic elastomer is below a certain level. preferable. For the mixed emulsification and phase inversion emulsification, a known emulsification apparatus commonly used in the field such as a homomixer, homogenizer, free mix, nanomizer, cavitron, line mixer, universal stirrer, bottom ribbon blade type stirrer or the like can be used. it can. Moreover, when manufacturing continuously, the method of producing efficiently with a line mixer is preferable. On the other hand, when manufacturing with a batch type, the method of producing easily with the manufacturing apparatus equipped with the condenser and the bottom ribbon blade type | formula stirring apparatus. Is preferred.

  The temperature at the time of emulsification is not particularly limited, and is usually about 10 ° C to 200 ° C, preferably about 20 to 150 ° C, and more preferably about 25 to 100 ° C.

  The emulsified dispersion containing the hydrocarbon solvent thus obtained can be removed from the hydrocarbon solvent by, for example, azeotroping with water under conditions of 80 to 100 ° C. and normal pressure to 300 kPa. it can.

  Depending on the type of emulsifier used, when removing the organic solvent, it takes a long time to remove the solvent because of foaming. It is recommended to add. The antifoaming agent / antifoaming agent is not particularly limited, and examples thereof include amide type, silica / silicone type, silicone type, and wax type antifoaming agents / antifoaming agents. Specific examples of the antifoaming agent / antifoaming agent include SN deformer 477, SN deformer 475-L, SN deformer 5013, SN deformer 5016 (manufactured by San Nopco Co., Ltd.). The addition amount is about 0.01 to 0.5% by mass, preferably about 0.02 to 0.3% by mass, based on the mass of the emulsified dispersion.

  Furthermore, the thermoplastic elastomer aqueous emulsion dispersion of the present invention prepared to have a desired solid content concentration by distilling or adding water as required can be obtained. The solid content concentration is usually about 10 to 90%, preferably about 20 to 60%.

  The styrene thermoplastic elastomer emulsion (median diameter) thus obtained is usually in the range of 0.05 to 50 μm, preferably about 0.1 to 30 μm. If it is less than 0.05 μm, the viscosity is high and handling becomes difficult, and if it exceeds 50 μm, mechanical stability (stability against stirring force during stirring and pumping) and stationary stability tend to decrease.

  In the present invention, the mass ratio between the support and the oily substance is preferably “(mass of oily substance) / (mass of support) = 1-20”. When this mass ratio is less than 1, the mixture of the oily substance and the support is usually solid, so that when applied to the surface of the fibrous base material, a soft texture is hardly expressed, and more than 20 In some cases, the formulation is normally in liquid form, and oily substances tend to migrate when applied to the surface of the fibrous base material. More preferably, the range is “(mass of oily substance) / (mass of holding body) = 3 to 12”. In this range, the mixture of the oily substance and the support is usually a gel.

  In the present invention, the type and molecular weight of the support, the type of oily substance and the mass ratio when two or more oily substances are used in combination, the ratio of the support and oily substance, and the surface of the fibrous base material By changing the applied amount, it is possible to reproduce the desired flexibility and fullness of natural leather.

  By giving the fibrous base material the oily substance having a viscosity of 50 to 10000 mPa · s obtained at 30 ° C. and a carrier (C) thus obtained to the fibrous base material, the texture and oily feeling of natural leather are obtained. An oil-like leather-like sheet can be obtained. Examples of the method for imparting the gel-like material (C) include a method in which a solution in which the gel-like material (C) is dissolved in a good solvent is prepared and applied or impregnated on the fibrous base material, and the solvent is removed and fixed. However, the adoption of the method of making the gel (C) into an aqueous dispersion is not only excellent in terms of environmental considerations, but also has little influence on each component constituting the fibrous base material, so it is combined It has a high degree of freedom, and is also excellent in terms of quality, such as being as flexible as natural leather and easy to finish with a rich texture. As a method of applying the gel-like material (C) to the surface of the fibrous base material, various conventionally known coating methods such as gravure coating method, direct coating method, reverse roll coating method, spray coating method, dipping method, Conventionally known various impregnation methods such as a dip nip method and a lip coating method are exemplified, and among them, a gravure coating method is preferably used. The stage to be applied to the surface of the fibrous base material is not particularly limited. However, when using a fibrous base material that is subjected to a coloring process until the final product is obtained, it is more oily in the coloring process to be processed after coloring. Since there is no detachment | desorption of a component, it is preferable at the point which is easy to manage a process.

  In order to control the oily feeling on the surface and to control the texture as a leather-like sheet, not only the required gel-like material (C) is applied to obtain a feeling of oil on the fibrous base material, but also a gel-like material. Of course, it is also possible to apply (C) to a portion other than the surface of the fibrous base material. There are no particular restrictions on the application method, and any of the above impregnation methods and coating methods may be used at any stage before or after application to the surface.

  In addition, the ratio of the fibrous base material of the present invention to the total amount of the gel-like material (C) applied as described above is in the range of 5 to 80% by mass with respect to the fibrous base material as well as the oil feeling. From the viewpoint of natural leather-like flexibility and texture, 10 to 50% by mass is more preferable. If the amount is less than 5% by mass, naturally the oil feeling intended in the invention tends to be insufficient and tends to have a hard texture. On the other hand, if it exceeds 80% by mass, the surface is strongly sticky even if the gelled material does not fall off. This is not preferable.

  The gel-like material (C) applied to the fibrous base material penetrates not only into the surface of the non-napped fiber bundle on the surface and the inner fibers and fiber bundles but also into the fiber bundle during the drying process. In this state, it is dried and solidified.

  Then, if necessary, the fibrous base material can be hot-pressed to obtain an oil-finished leather-like sheet. It is possible to increase the oil strength and further enhance the surface strength because the film is formed by the holder contained in the gel-like material (C) present on the surface by hot pressing. As a method of hot pressing, a known technique such as an embossing method in which a heated metal roll is heated and pressed on the surface of the fibrous base material can be used. It is also possible to obtain a sheet in which various patterns are embossed by performing desired engraving on the surface of the embossing roll and hot pressing. The heating temperature is determined by the type of holding body selected when synthesizing the gel-like material, but is generally preferably about 130 to 200 ° C. If it is 130 ° C. or lower, it is not preferable because it is difficult to form a film in which the holding body is melted.

  When the surface of the obtained oil-finished leather-like sheet was observed, a gel-like material thermally adhered to the space around the non-napped fiber bundle (B) found on the surface of the fibrous base material was present, and the resin coating ( A silver-tone surface is formed continuously with A). On the surface of the oil-finished leather-like sheet, the pores (E) that existed on the surface of the fibrous base material remain partly narrow, but the resulting sheet exhibits air permeability (hereinafter referred to as this). Micropores remaining on the surface of the oil-like leather-like sheet are defined as micropores (D)). In the pores of the micropores (D) in which the small pores (E) existing on the surface of the fibrous base material are narrowed by the application of the gel-like material (C), the small pores before the gel-like material (C) is applied. Non-raised fiber bundle (B) present in the vicinity of the surface layer of the oil-finished leather-like sheet in a state where the gel (C) is attached to the non-raised fiber bundle (B) present in the pore of the hole (E) Is exposed on the surface of the oil-like leather-like sheet.

  In order for the oil-finished leather-like sheet, which is the final product, to have a high commercial value, it is preferable to have “silver surface feeling”, “surface strength”, and “oil bleed resistance”. The “feel of oil” of the resulting leather-finished leather-like sheet is that the area ratio of the resin film (A) (hereinafter, the area ratio of the resin film (A) is referred to as Sa) and the gel-like material (C) are not adhered. Depending on the area ratio of the napped fiber bundle (B) (hereinafter, the area ratio of the non-napped fiber bundle (B) is referred to as Sb), the sum of both, especially the ratio of the non-napped fiber bundle (B) is large. The oil on the surface becomes stronger. The “surface strength” of the oil-like leather-like sheet obtained increases as Sa increases, but on the other hand, it decreases when Sb increases too much, and the surface condition of a silver surface with an oily feeling disappears easily due to wear. Appears to have a nubuck-like appearance. The “durability of oil feeling” of the obtained oil-finished leather-like sheet increases as Sb increases, but decreases as Sa increases, so that oil can be easily detached during use. Therefore, it is preferable that the following formula is satisfied with respect to the ratio of Sa and Sb. However, the area ratio is calculated by cutting out the area ratio of the resin coating (A) and the non-nap fiber bundle (B) using an electron micrograph obtained by photographing any five locations on the oil-finished leather-like sheet surface. The average of the values obtained.

50 <Sa <95
5 <Sb <50
(However, Sa: Area ratio (%) the resin film (A) existing on the surface occupies the entire surface of the oil-like leather-like sheet) Sb: Non-napped fiber bundle (B) exposed on the surface is oil-like Ratio of area to the entire leather-like sheet surface (%))

  Further, the “breathability” of the obtained oil-finished leather-like sheet depends on the area ratio of the micropores (D) existing on the surface (hereinafter, the area ratio of the micropores (D) is referred to as Sd). The larger it is, the greater the air permeability. The inventors of the present invention have excellent “silver surface feeling”, “surface strength”, and “durability of oil feeling” by making the above-mentioned formulas compatible, and furthermore, the resin coating (A) and the non-raised fiber bundle. As a result of intensive studies on the shape and number of micropores (D) which are surface regions other than (B), the hole diameter Rd of the micropores (D), the number Nd of micropores (D), and the area of the micropores (D) It has been found that, when the ratio Sd satisfies the following formula, “breathability” can be secured in addition to “oil feeling”, “surface strength”, and “durability of oil feeling”. That is, by controlling the state of the micropores (D) existing on the surface of the fibrous base material as described above, the state of the micropores (D) remaining on the surface of the oil-finished leather-like sheet as the final product is as follows. Satisfies formula 3. In addition, the radius of the micropore (D) described here and the number of holes per unit area mean an average value of values observed from electron micrographs of five randomly selected surfaces. The hole diameter means a radius when the shape of the opening of the microhole is a circle having the same area. The area ratio of the micropores (D) refers to the area ratio of the micropores (D) by using an electron micrograph taken of any five locations on the surface of the fibrous base material or oil-finished leather-like sheet. The average of values calculated by the method.

10 <Rd <100
5 <Nd <100
1 <Sd <35
(However, Rd: Radius (μm) Nd: Number of micropores (D) per unit area (pieces / mm ² ) Sd: Area ratio (%) that micropore (D) occupies with oil-finished leather-like sheet surface

  Next, the present invention will be described with specific examples, but the present invention is not limited to these examples. And the part in an Example is related with mass, unless there is a notice.

Each physical property was calculated | required as follows.
(I) Fiber Diameter of Ultrafine Fiber A fiber cross section was photographed with an electron microscope, and the fiber diameter of 50 ultrafine fibers arbitrarily selected from the photograph was measured using a caliper and calculated from the average value.
(Ii) Breathability Measured according to JIS L1096 (Breath rate measurement method B).
(Iii) Method for evaluating the durability of oil or gel-like materials Judging whether the oil or gel-like materials adhere to the hand by grasping or rubbing the product with the hand, the evaluation results are good: ○ Slightly good: Δ, poor: x.
(Iv) Texture, appearance, oil feeling The inventors determined by visual and tactile sensations on the surface of the leather-like sheet. The evaluation results were expressed as good: ◯, slightly good: Δ, and poor: x.
(V) Viscosity of aqueous emulsion dispersion The viscosity was measured using a BL type viscometer manufactured by Toki Sangyo Co., Ltd.
(Vi) Emulsion particle size (median diameter)
Measurement was performed using a laser scattering / diffraction particle size distribution analyzer LA-910 manufactured by Horiba, Ltd.
(Vii) Non-volatile content of aqueous emulsion dispersion (%)
The aqueous emulsified dispersion was taken in a petri dish, dried at 105 ° C. for 2 hours, the solid content mass was determined, and the solid content concentration (%) was determined from the following formula.
Solid content concentration (%) = [mass after evaporative drying (g) / sampled amount (g)] × 100

Example of production of fibrous base material Nylon-6 and polyethylene are mixed at a mass ratio of 50:50 in the form of chips and melt-spun by an extruder, and polyethylene is a sea component and nylon-6 is an island component. Sea island structure fiber is spun, drawn, crimped and cut to produce 4 dtex, 51 mm long staples, cross-wrapped with webber and needle punched at 700 punch / cm ² using a needle punching machine. A composite nonwoven fabric was obtained. This non-woven fabric was impregnated with a dimethylformamide (hereinafter sometimes abbreviated as DMF) solution of a polyurethane resin having a poly-3methylpentane adipate diol having an average molecular weight of 2000 and polyethylene glycol as a polymer diol for a soft segment. After removing about 30 μm of clearance on the surface of the entangled nonwoven fabric and scraping off the remaining DMF solution of polyurethane resin using a knife and coagulating it in water, the polyethylene which is the sea component of the fiber is made of perchlorethylene. Extraction was performed to obtain a sheet base material having a basis weight of 450 g / m ² , a thickness of 1.3 mm, and a polyurethane resin to fiber ratio of 40/60. The fineness of the nylon ultrafine fibers of the obtained sheet base material was 0.006 dtex on average.
The obtained sheet base material was sliced with a band knife to a thickness of 0.5 mm, and a polyurethane white pigment (trade name: M6094, manufactured by Dainichi Seika Co., Ltd.) was solidified on the surface using a gravure printing machine. A fibrous base material was obtained by applying 20 g / m ^{2 in} terms of conversion. An electron micrograph of the obtained fibrous base material is shown in FIG. On the surface of the obtained fibrous base material, 45 small holes with a pore diameter of 20 to 150 μm were present / 45 ² . It was confirmed that 95% or more of these small holes had non-napped fiber bundles exposed on the surface in the holes. In addition, the area ratio of the resin film made of polyurethane was 84%, and the area ratio of the non-raised fiber bundle was 13%.

Example of gel-like product synthesis In an emulsification vessel equipped with a homomixer (trade name “TK Homomixer Mark II” manufactured by Tokushu Kika Kogyo Co., Ltd.), 1119 g of water and dodecylbenzenesulfonic acid triethanolamine salt (Matsumoto Yushi Seiyaku ( Co., Ltd., trade name “Haimar 2”) 71 g was added, and the temperature was raised to 90 ° C. Next, 75 g of vinyl aromatic elastomer (trade name “Septon 4055” manufactured by Kuraray Co., Ltd.) and 600 g of paraffinic process oil (trade name “Diana Process Oil PW-90” manufactured by Idemitsu Kosan Co., Ltd.) are added to 750 g of toluene. The dissolved solution was added and pre-emulsified by stirring and mixing at 90 ° C. for 5 minutes at a blade speed of 8 m / s of a homomixer. Subsequently, this preliminary emulsion was treated with a homogenizer (manufactured by Gaulin, trade name “LAB40-10RBFI type”) at 90 ° C. and 40 MPa, and then cooled to obtain 2561 g of a toluene-containing emulsion dispersion. 1.0 g of the obtained toluene-containing emulsified dispersion and antifoaming agent (manufactured by San Nopco, trade name “SN Deformer 5013”) are put into a 5 L four-necked flask equipped with a condenser, a decanter and a dropping funnel. Under pressure, the temperature was raised while stirring the propeller, and toluene was distilled off while replenishing the same amount of water as the azeotropic water. When the toluene content in the emulsified dispersion became 500 ppm by gas chromatography, heating was stopped and the mixture was cooled to room temperature to obtain an aqueous emulsified dispersion having a nonvolatile content of 40% and a median diameter of 1.1 μm.

Oil-like leather-like sheet production example The aqueous emulsion dispersion obtained in the gel-like material synthesis example was diluted with water so that the non-volatile content was 30%, and the surface obtained in the fibrous base material production example was The fibrous base material colored in white was impregnated with mangle, and the squeezing rate was set to 70%, followed by drying with a dryer at 60 ° C. An aqueous emulsified dispersion having a non-volatile content of 40% is further applied to the surface of this sheet with a gravure printing machine so that the amount of adhesion is 20 g / m ² , and then the surface is heated at 150 ° C. using an embossing machine. By performing the treatment, an oil-like leather-like sheet 1 was obtained. The obtained oil-like leather-like sheet 1 had an oil-like appearance with a slimy luster and a moist feel like natural leather. There was no oil bleed. When the obtained oil-like leather-like sheet 1 was observed with a scanning electron microscope, the area ratio due to the resin coating was 87%, the area ratio due to the non-nap fiber bundle was 10%, and the surface covered with the polyurethane coating There were about 15 small holes / mm ² with a pore diameter of 10 to 50 μm, and it was confirmed that the non-napped ultrafine fiber bundle covered with the gel-like material was exposed on the surface inside the small holes. . The gel-like material applied to the surface almost disappeared due to the heat treatment, and it was observed that the film was thinned. The obtained sheet has moderate air permeability due to the presence of small holes, and when it was sewn as a golf glove and subjected to a test shot of 500 shots for 10 monitors, there was little stuffiness after wearing. It was evaluated that the silver-colored appearance remained. The physical properties and surface electron micrographs of the obtained oil-finished leather-like sheet 1 are shown in Table 1 and FIG.

Comparative Example 1
The aqueous emulsion dispersion obtained in the gel-like synthesis example is diluted with water so that the non-volatile concentration is 30%, and the surface obtained in the fibrous base material production example is colored white. The substrate was impregnated with mangle, and the squeezing rate was 70%, followed by drying with a dryer at 60 ° C. Next, a polyurethane solution of 100 parts of polyether-based polyurethane (trade name: Resamine ME8115 manufactured by Dainichi Seika Co., Ltd.), 30 parts of methyl ethyl ketone, and 30 parts of DMF as a skin layer on a release paper with a texture (Lintec TP R-8) is wet. 100 g / m ^{2 was} applied and heated at 100 ° C. for 5 minutes to obtain a skin layer having a thickness of 30 μm. On top of that, 100 parts of polyether-based polyurethane (trade name: Resamine UD8310 modified by Dainichi Seika), 60 parts of DMF, 10 parts of cross-linking agent (trade name: NE cross-linking agent, manufactured by Dainichi Seika), cross-linking accelerator (manufactured by Daiichi Seika (Product name: 102 accelerator) 8 parts of polyurethane solution was wet coated at 100 g / m ² , heated at 70 ° C. for 1 minute, and bonded to the surface of the sheet substrate impregnated and dried with the gel material. This was aged at 60 ° C. for 48 hours, and the release paper was peeled off from the sheet substrate. Then, an aqueous emulsion dispersion having a non-volatile content of 40% was further applied to the surface of the sheet substrate with a gravure printing machine at 20 g / m. After coating so that the amount of adhesion was ^2, an oil-like leather-like sheet 2 was obtained by subjecting the surface of the sheet substrate to a heat treatment at 150 ° C. using an embossing machine. The oil-like leather-like sheet 2 thus obtained had an oil-like appearance with a slimy luster and a moist feel like natural leather, but the surface oil was hard and the surface oil The feeling itself was somewhat insufficient, and when the surface was lightly rubbed several times with a finger, the gel-like substance was detached and adhered to the finger. When the obtained oil-like leather-like sheet 2 was observed with a scanning electron microscope, the polyurethane on the surface was formed into a film, and no small pores and non-napped fiber bundles were found on the surface. The gel-like material applied to the surface almost disappeared due to the heat treatment, and it was observed that the film was thinned. The obtained sheet was completely non-breathable and was sewn as a golf glove and tested 500 shots on 10 monitors. As a result, although the change in appearance was small, the oil feeling itself was insufficient as described above. The wearing feeling was also hard, the feeling of stuffiness during wearing was strong, and the product value was low. Table 1 shows the physical properties of the obtained oil-finished leather-like sheet 2.

Comparative Example 2
An oil-like leather-like sheet 3 was obtained in the same manner as in Example 1 except that the surface of the fibrous base material was used after raising the surface with sandpaper. The resulting oil-like leather-like sheet 3 had a moist feel like natural leather and a glossy silver-like appearance, and there was no oil bleed. The feeling disappeared and the appearance was nubuck. When the obtained oil-like leather-like sheet 3 was observed with a scanning electron microscope, it was confirmed that the ultrafine fiber napping existing on the surface was stuck by the gel-like material. I couldn't see it. It was observed that the gel-like material applied to the surface almost disappeared due to the heat treatment. The obtained sheet was moderately breathable and sewed as a golf glove and subjected to a test shot of 500 shots for 10 monitors, but there was little stuffiness after wearing, but immediately after the test. The oil-like appearance gradually disappeared and changed to a nubuck-like appearance. Table 1 shows the physical properties of the oil-like leather-like sheet 3 obtained.

  The oil-like leather-like sheet of the present invention has a soft texture equivalent to natural leather and an oil-like touch feeling, which is suitable for any artificial leather such as shoes, clothing and gloves. In particular, it is useful for application to sports gloves because of its excellent touch and fit to the skin.

It is a surface photograph (drawing substitute photograph) which shows the surface form of the fibrous base material of this invention. It is a surface photograph (drawing substitute photograph) which shows the surface form of the oil-finished leather-like sheet | seat of this invention.

Claims (6)

  An oily substance having a viscosity of 50 to 10000 mPa · s at 30 ° C. on the non-raised fiber bundle (B) of the fibrous base material having a surface mainly composed of the resin coating (A) and the non-raised fiber bundle (B) And an oil-finished leather-like sheet, to which a gel-like material (C) comprising the support is attached. 2. The oil-like leather-like sheet according to claim 1, wherein the non-rafted fiber bundle (B) is a bundle of 10 or more ultrafine fibers of 0.5 dtex or less. The oil-finished leather-like sheet according to claim 1 or 2, wherein the resin coating (A) and the non-raised fiber bundle (B) satisfy the following formula.
50 <Sa <95
5 <Sb <50
(However, Sa: Area ratio (%) the resin film (A) existing on the surface occupies the entire surface of the oil-like leather-like sheet) Sb: Non-napped fiber bundle (B) exposed on the surface is oil-like Ratio of area to the entire leather-like sheet surface (%))   The oil-finished leather-like sheet according to any one of claims 1 to 3, wherein the resin coating (A) is made of polyurethane.   The oil-finished leather-like sheet according to any one of claims 1 to 4, wherein a space communicating with the inside of the fibrous base material is formed around the non-napped fiber bundle (B) exposed on the surface. The oil-finished leather-like sheet according to any one of claims 1 to 5, wherein micropores (D) satisfying the following formula are present on the surface.
10 <Rd <100
5 <Nd <100
1 <Sd <35
(However, Rd: Radius (μm) Nd: Number of micropores (D) per unit area (pieces / mm ² ) Sd: Area ratio (%) that micropore (D) occupies with oil-finished leather-like sheet surface

Images