JP2020037241A - Skin material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a skin material having excellent molding processability and excellent wear resistance, which is less likely to generate pills even when the skin material is rubbed, has excellent pilling resistance, and is less likely to impair the appearance quality. To provide. SOLUTION: In the skin material of the present invention, the abundance of the binder on one main surface A side is larger than that on the other main surface B side in the base mat constituting the skin material, and the base mat has. A resin layer is provided on the entire surface of one of the main surfaces A, and the base mat further contains anti-pilling fibers. Further, in the skin material of the present invention, the abundance of the binder on one main surface A side in the base mat constituting the skin material is larger than that on the other main surface B side, and one of the base mats. A resin layer is provided on the entire surface of the main surface A, and the resin layer further contains 0.06 g / m2 or more of a resin containing silicone. [Selection diagram] None

Description

  The present invention relates to a skin material that can be used for vehicle interior materials such as ceiling materials, door trims, dash outers, pillar garnishes, partitions, and wallpaper. In particular, the present invention relates to a skin material, such as a door trim, a dash outer, and a pillar garnish, which can be suitably used as an interior material for a vehicle requiring high wear resistance.

  Conventionally, a nonwoven fabric has been used as a material constituting the skin material. Further, in order to prevent deterioration of the skin material due to friction, the skin material is required to have wear resistance.

  Therefore, the applicant of the present application impregnated the binder with the needle-punched surface as a wear-resistant skin material using a nonwoven fabric, and then applied a binder with less tack to the opposite surface of the needle-punched surface. An interior skin material impregnated (Patent Document 1) has been proposed.

  The skin material according to Patent Literature 1 has abrasion resistance because it is unlikely to cause fluffing due to friction, and is a moldable skin material. However, it is particularly suitable for vehicles such as door trims that require high wear resistance. Abrasion resistance was insufficient for use as a skin material for interior materials.

JP-A-62-257472

  Under such circumstances, the present applicant has excellent moldability, and furthermore, in order to provide a skin material having more excellent abrasion resistance, `` in a base mat in which constituent fibers are bonded to each other with a binder, The amount of the binder present on the one main surface A side is larger than that on the other main surface B side, and the base mat has a resin layer on the entire surface on the one main surface A. , A skin material. ", And a patent application (Japanese Patent Application No. 2017-171492) has already been filed.

  In this skin material, since the amount of the binder present on one main surface A side is larger than that on the other main surface B side in the base mat constituting the skin material, the constituent fibers on the main surface B side are mainly used. It is not strongly adhered by the binder than the constituent fibers on the surface A side, and is easy to move. Therefore, when the skin material is subjected to a molding process such as injection molding, the main surface B side with less binder easily follows the shape of the mold, and thus is excellent in moldability. In addition, since the constituent fibers on the main surface A side, which can be the surface in contact with the person of the skin material, are strongly adhered to the binder, the skin material has a main surface excellent in abrasion resistance such that fluffing due to friction hardly occurs. is there.

  Further, this skin material has a resin layer on the whole of one main surface A of the base mat constituting the skin material. Therefore, since the constituent fibers on the main surface A side of the skin material are protected by the resin layer, the skin material is more excellent in abrasion resistance such that fluffing due to friction hardly occurs.

  Therefore, this skin material is a skin material excellent in molding workability and further excellent in wear resistance.

  However, when the skin material is rubbed and fuzzing due to friction occurs on the surface of the skin material, the fluff may be gathered and a pill may be generated, resulting in poor pilling resistance. There was a problem that the external appearance quality was impaired. In particular, the generation of this pill was relatively soft, such as a human palm, and was likely to occur when the skin material was rubbed.

  The present invention has been made under such circumstances, and is a skin material having excellent moldability and more excellent abrasion resistance. Furthermore, even if the skin material is rubbed, pills are less likely to be generated. It is an object of the present invention to provide a skin material which is excellent in property and hardly impaired in appearance quality.

  The invention according to claim 1 of the present invention relates to a method according to claim 1, wherein in a base mat in which constituent fibers are bonded to each other with a binder, the amount of the binder present on one main surface A side is larger than that on the other main surface B side. And a base layer, wherein the base mat has a resin layer on the entire surface on the one main surface A, and the base mat further contains anti-pilling fibers. .

The invention according to claim 2 of the present invention relates to a method for producing a base mat in which constituent fibers are bonded to each other with a binder, wherein the amount of the binder present on one main surface A side is larger than that on the other main surface B side. And a resin layer is provided on the entire surface of the one main surface A of the base mat, and the resin layer contains a resin containing silicone in an amount of 0.06 g / m ² or more. The skin material.

  In the skin material according to claim 1 of the present invention, since the base mat constituting the skin material contains anti-pilling fibers, fuzzing due to friction occurs on the surface of the skin material, and when the fluff is collected, The constituent fibers of the mat are easily cut, and pills are not easily generated. Therefore, the skin material according to claim 1 of the present invention is a skin material that is excellent in pilling resistance and hardly impairs the appearance quality even when rubbed.

In the skin material according to claim 2 of the present invention, the resin layer constituting the skin material contains the resin containing silicone in an amount of 0.06 g / m ² or more, so that fluffing due to friction is less likely to occur. Therefore, the skin material according to claim 2 of the present invention is a skin material that has excellent pilling resistance and hardly impairs the appearance quality even when rubbed.

  The base mat constituting the skin material of the present invention refers to a sheet-like fibrous structure such as a woven fabric, a knitted fabric, or a nonwoven fabric, in which fibers are bonded to each other with a binder. In particular, when the base mat constituting the present invention is derived from a nonwoven fabric, the base mat is flexible and easily conforms to the shape of the mold, so that a skin material having excellent moldability can be provided, which is preferable.

  The constituent fibers of the base mat in the present invention are not particularly limited, but may be, for example, polyester fibers, nylon fibers, acrylic fibers, vinylon fibers, rayon fibers, and the like. Among them, it is preferable to include a polyester fiber excellent in heat resistance, light resistance, antifouling property and the like, and / or a rayon fiber excellent in flame retardancy. The constituent fiber may be a single fiber or a composite fiber containing two or more kinds of resins, such as a core-sheath type or a side-by-side type. For example, it is preferable to use a latently crimped fiber (such as a side-by-side type conjugate fiber), since the fiber develops crimp by heat and the structure of the base mat becomes denser by using the fiber in which the crimp is developed. . Further, the cross section of the constituent fibers may be circular, or may be an irregular shape such as an ellipse, a square, or a Y-shaped cross section. In addition, fibrillated fibers may be included.

  The skin material of the present invention can further include anti-pilling fibers in the constituent fibers of the base mat. If the base mat contains anti-pilling fibers, fluffing occurs due to friction on the skin material, and when the fluffs are gathered, the constituent fibers of the base mat are easily cut and pills are hardly generated. Therefore, it has excellent pilling resistance, and the appearance quality is not easily impaired even if the skin material is rubbed. The anti-pilling fiber refers to a fiber obtained by forming surface irregularities or voids in a normal fiber to reduce the strength. As a typical example of the anti-pilling fiber, for example, there is a fiber in which a polyester fiber is alkali-treated and partially hydrolyzed to form surface irregularities and reduce the strength.

While the single fiber strength of the anti-pilling fiber is lower, the above-described effects are more easily obtained, while if too low, the permeability of the manufacturing process is deteriorated, and molding such as resin seepage due to a decrease in the tensile strength of the skin material is reduced. 2-3 cN / dtex is preferable because there is a possibility that workability may be deteriorated.
In addition, the "single fiber strength" means that a constant-speed tension-type tensile tester is used in accordance with JIS L 1015: 2010, 8.7.1 (standard time test), a grip distance is 20 mm, and a pulling speed is 20 mm / min. Refers to the value below.

  The weight ratio of the anti-pilling fiber to the constituent fibers of the base mat is preferably 3% by weight or more, more preferably 5% by weight or more, and more preferably 10% by weight, since the above-mentioned effect is easily obtained when a large amount of the anti-pilling fiber is contained. The above is more preferred. On the other hand, if the weight ratio of the anti-pilling fiber to the constituent fibers of the base mat is too high, the tensile strength of the skin material is reduced, and the moldability may be deteriorated. % Or less, more preferably 30% by weight or less.

  In addition, if the anti-pilling fiber is included on one main surface A side of the base mat, which can be a surface of the skin material that comes into contact with a person, the hair ball is easily cut from the skin material, and the appearance quality of the skin material is not easily deteriorated. From the viewpoint of obtaining the effect, it is preferable that the anti-pilling fiber is contained on one main surface A side of the base mat. In the present invention, "the one main surface A side contains anti-pilling fibers" means that the surface of the one main surface A side is observed with a microscope or the like and the presence of the anti-pilling fibers can be observed. . The “main surface” refers to the widest surface of the base mat and the skin material.

  As will be described later, when thermocompression bonding is performed during the production of the base mat, the dry heat shrinkage is 4% or more as a constituent fiber of the base mat in order to improve abrasion resistance and to form a clear print. (Preferably 4.5 to 20%, more preferably 5 to 10%) polyester stretched short fiber. The “dry heat shrinkage rate” is in accordance with JIS L1015 (2010) 8.15 b) Dry heat dimensional change rate, except that the initial load is 1.3 mg and the temperature is left at 140 ° C. for 10 minutes. Refers to the value measured.

  The constituent fibers may be white or colored. When the constituent fibers are colored, the fibers themselves may be original fibers containing pigment and / or dye in the constituent resin, or may be fibers colored with pigment and / or dye. It is preferable to use original fibers since the fibers are less likely to be discolored by friction.

  Although the fiber length of the constituent fibers of the base mat in the present invention is appropriately adjusted, the fiber length of the constituent fibers is preferably from 38 to 114 mm, and is preferably from 38 to 76 mm, since the base mat has excellent moldability. More preferably, it is 38-52 mm. The “fiber length” refers to a value measured according to the JIS L1015 (2010) 8.4.1c) direct method (C method).

  In addition, the fineness of the constituent fibers of the base mat in the present invention is also appropriately adjusted. However, if the fibers are too thick, it becomes difficult to form a surface material having a smooth surface, and the surface material having an uneven surface is caught by friction. It tends to be fuzzy, and thus has poor abrasion resistance. On the other hand, if the fibers are too thin, pills are generated during the production of the base mat, and the productivity tends to deteriorate. Therefore, the fineness of the constituent fibers of the base mat is preferably 0.2 to 6 dtex, more preferably 0.8 to 4 dtex, and still more preferably 1 to 3 dtex.

  The skin material of the present invention may be a base mat constituted by a single fiber layer or a base mat constituted by laminating a plurality of fiber layers. In the base mat formed by laminating a plurality of fiber layers, fiber layers having the same fiber composition may be laminated, or fiber layers having different fiber compositions may be laminated.

  The base mat of the present invention is formed by bonding constituent fibers to each other with a binder. Examples of the aspect in which the constituent fibers are bonded to each other with a binder include, for example, a mode in which a binder is attached to an intersection of the constituent fibers, and a mode in which the binder bonds the constituent fibers to each other and a mode in which a binder exists between the fibers and is bonded And the like.

  The type of the binder used in the present invention is not particularly limited and may be appropriately adjusted, and examples thereof include a polyurethane resin, an acrylic resin, and a polyester resin. Among these, an acrylic resin (particularly, a self-crosslinking acrylic resin) is preferable because it is appropriately softened during molding, has excellent followability to a mold, and does not easily generate wrinkles or fine irregularities. Of the acrylic resins, a soft acrylic resin having a low glass transition temperature and being soft is preferable because it is easily stretched and has excellent moldability. On the other hand, if the glass transition temperature of the acrylic resin is too low, the adhesive strength of the binder is improved, but the rupture strength of the binder resin is inferior, so that the abrasion resistance is inferior. Therefore, the glass transition temperature is preferably −40 ° C. to 10 ° C., more preferably −20 ° C. to 5 ° C., and even more preferably −10 ° C. to 5 ° C. The “glass transition temperature” in the present invention refers to a temperature at an intersection of a tangent to a base line in a DTA curve measured by a differential thermal analyzer (DTA) and a tangent to a steep drop position of an endothermic region due to glass transition.

The base mat constituting the skin material of the present invention is characterized in that the amount of the binder present on one main surface A side is larger than that on the other main surface B side. In the present invention, “the amount of the binder present on the main surface A side (or the main surface B side)” means 20% of the thickness of the base mat from the main surface A (or the main surface B) with respect to the entire thickness of the base mat. It means the amount of binder present in the region up to the thickness. With this configuration, the main surface A side has excellent abrasion resistance such that fluffing due to friction is less likely to occur, and the constituent fibers on the main surface B side are more strongly adhered by the binder than the main surface A side. Because it is easy to move, a skin material having excellent moldability can be provided.
As a method for confirming the amount of the binder, for example, the binder contained in the base mat is colored with a dye such as Kayastain Q (manufactured by Nippon Kayaku Co., Ltd.), and the cross section in the thickness direction of the base mat is used. Can be confirmed by visual observation or observation with an optical microscope.

  The distribution mode of the amount of the binder contained in the base mat may be appropriately adjusted as long as the amount of the binder present on one main surface A side of the base mat is larger than that on the other main surface B side. However, when the amount of the binder present continuously decreases from the main surface A side to the main surface B side, the amount of the binder inside the base mat continuously changes, and the distribution of the amount of the binder is reduced. Since it is not concentrated on a very small portion of the base mat, it is preferable because the binder is hardly separated from the portion where the binder is concentrated and the other portion, and the abrasion resistance and the moldability are excellent.

When the amount of the binder contained in the base mat increases, the abrasion resistance tends to be more excellent. Therefore, the amount of the binder is preferably ² g / m ² or more, more preferably 10 g / m ² or more, and more preferably 15 g / m ² or more. Is more preferred. On the other hand, if the amount of the binder contained in the base mat is too large, the skin material tends to be hard and the moldability tends to deteriorate, so it is preferably 30 g / m ² or less, and more preferably 20 g / m ^2. It is more preferable that:

  The skin material of the present invention is excellent in abrasion resistance, for example, due to the configuration in which the resin layer is provided on the entire main surface A of the base mat on the main surface A side, the generation of fuzz due to friction is less likely to occur. Note that the “entire surface on one main surface A” of the present invention refers to the entirety of one main surface A of the base mat seen when the base mat is viewed from directly above the one main surface A of the base mat. Point.

  The resin layer of the present invention can be a layer composed of the following resin. Examples of the type of the resin include the same resins as the above-described binder resin. For example, a polyurethane resin, an acrylic resin, or a polyester resin can be given. Among these, it is preferable to use an acrylic resin (particularly, a self-crosslinking acrylic resin) which is appropriately softened at the time of molding, has excellent followability to the mold, and hardly generates wrinkles and fine irregularities. Of the acrylic resins, a soft acrylic resin having a low glass transition temperature and being soft is preferable because it is easily stretched and has excellent moldability. On the other hand, if the glass transition temperature of the acrylic resin is too low, the adhesive strength of the binder is improved, but the rupture strength of the binder resin is inferior, so that the abrasion resistance is inferior. Therefore, the glass transition temperature is preferably −40 ° C. to 10 ° C., more preferably −20 ° C. to 5 ° C., and even more preferably −10 ° C. to 5 ° C.

  Further, if the difference between the glass transition temperature of the resin contained in the binder and the resin contained in the resin layer is 10 ° C. or less, the difference in the elongation manner between the base mat portion and the resin layer portion in the skin material during molding processing. By making it difficult to come out, a delamination hardly occurs between the base mat and the resin layer, and a skin material having more excellent moldability can be provided, which is preferable. The difference between the glass transition temperature of the resin contained in the binder and the resin contained in the resin layer is preferably 5 ° C. or less, more preferably 3 ° C. or less, and most preferably the same temperature. The “resin layer” in the present invention refers to a layer that includes a region of only the resin and completely covers one main surface A of the base mat. Further, the region of only the resin is observed as a film-like layer when the cross section in the thickness direction of the skin material is observed. The resin layer may be composed of only a resin-only region, or may be composed of a region in which fibers and resin are mixed in addition to a region of only resin.

As the amount of the resin layer of the skin material increases, the wear resistance tends to be more excellent. Therefore, the amount of the resin layer is preferably 5 g / m ² or more, more preferably 10 g / m ² or more, and 15 g / m ² or more. Is more preferred. Also, if the amount of the resin layer is too large, the texture, feel, and moldability of the skin material tend to be impaired, so that the amount is preferably 20 g / m ² or less. In addition, as the thickness of the resin layer of the skin material increases, the abrasion resistance tends to be more excellent. Therefore, the thickness of the resin layer is preferably 0.001 mm or more, more preferably 0.002 mm or more, and 0.004 mm. The above is more preferred. If the thickness of the resin layer is too large, the texture, feel, and moldability of the skin material tend to be impaired, so that the thickness is preferably 0.02 mm or less. The thickness of the resin layer can be measured by observing the cross section in the thickness direction of the skin material with an electron microscope, and the arithmetic average value of the resin layer thickness at 10 randomly selected points is defined as the “resin layer” of the present invention. Thickness ”.

  The skin material of the present invention may be provided with a printed pattern so as to be more excellent in abrasion resistance and to be more excellent in design property of the skin material. The print is present on the main surface A side derived from the base mat, which has a relatively large amount of binder, since the pattern by the print becomes clear and the wear resistance of the skin material can be improved by the presence of the print. Is preferred. In addition, the printing is performed on the main surface of the base mat and the resin layer covers the print from above, or on the main surface of the skin material (the main surface where the resin layer is exposed). Surface), the print is applied on the main surface A of the base mat so that the print is not easily peeled off by friction, and a resin layer covers the print from above. Is preferred.

  Although the print pattern of the skin material of the present invention is not particularly limited, for example, as disclosed in Japanese Patent Application Laid-Open No. 2012-179985, a print pattern in which the color difference gradually changes, Utility Model Registration No. 3072493 The printed pattern may have a three-dimensional pattern as disclosed in Japanese Patent No. The print may be one type or two or more types.

  The configuration of the print applied to the skin material of the present invention is appropriately prepared, and the type thereof is the same as the binder resin described above, for example, a resin such as a polyurethane resin, an acrylic resin, or a polyester resin. You can do it. Further, the print may contain a pigment, and the color, type and amount of the pigment can be appropriately adjusted.

When the amount of the resin contained in the print increases, the skin material tends to be more excellent in abrasion resistance. Therefore, the amount of the resin contained in the print is preferably 3 g / m ² or more, more preferably 5 g / m ² or more. It is preferably 9 g / m ² or more, more preferably. If the amount of the resin contained in the print is too large, the clarity of the printed pattern and the moldability tend to be impaired, so that the amount is preferably 20 g / m ² or less.

  The binder, the resin layer, and the print can include a functional material in addition to the above-described resins. For example, since the skin material can be colored by containing the pigment, the design of the skin material is improved. In addition, by containing a water-repellent resin such as a resin containing silicone or a resin containing fluorine, the skin material is hardly stained, and the wear resistance can be improved. Further, by incorporating a flame retardant, an antibacterial agent, a deodorant, a VOC generation inhibitor, an inorganic compound such as an inorganic powder, etc., various functions can be imparted to the skin material.

The skin material of the present invention can contain a resin containing silicone in a resin layer of 0.06 g / m ² or more. When the resin layer contains a resin containing silicone in an amount of 0.06 g / m ² or more, the abrasion resistance of the skin material can be further improved, and fluff due to friction is less likely to occur on the skin material. Less likely to occur. Therefore, it has excellent pilling resistance, and the appearance quality is not easily impaired even when rubbed. In order to further exert the above-described effects, the resin containing silicone contained in the resin layer is more preferably 0.1 g / m ² or more, and even more preferably 0.15 g / m ² or more. On the other hand, even if the resin layer contains a resin containing silicone in an amount exceeding ² g / m ² , the wear resistance and the pilling resistance are not improved, and the touch feeling on the surface of the skin material becomes oily. Due to the tendency, the resin containing silicone contained in the resin layer is preferably ² g / m ² or less.

  This silicone is a polymer compound having a skeleton of a siloxane bond (Si-O-Si bond) in the main chain, and an organic group may be introduced into a side chain. For example, even a straight silicone having only a methyl group or a phenyl group introduced, or a modified silicone modified with an amino group, an amide group, a carboxyl group, a fluoroalkyl group, a polyether group, an epoxy group, an aralkyl group, etc. Can be used. The mode of the silicone is not particularly limited, and may be an oil type, a powder type, or an emulsion type. Among them, emulsion type silicone is preferable because it can be used in combination with a binder resin such as an acrylic resin. Examples of suitable emulsion types include dimethyl silicone, amino-modified silicone, epoxy-modified silicone, and hydrophilic polyether-modified silicone. In addition, a silicone resin in which silicone itself is cross-linked, or a silicone copolymer resin in which acrylic or the like is copolymerized with silicone may be used.

The basis weight and thickness of the skin material of the present invention are appropriately adjusted depending on the intended use, required strength, and the like, but if the basis weight of the skin material is too light, the moldability is deteriorated because the skin material may be broken during molding. and the basis weight is too great force is required for molding heavy, since the molding processability is deteriorated, and the basis weight is preferably from 140~260g / ^{m 2,} more preferably from 150 to 250 g / ^{m 2} , 160 to 250 g / m ² . Also, if the thickness of the skin material is too thin, the moldability becomes poor, and if it is too thick, it becomes difficult to handle, so the thickness is preferably 1-2 mm, and preferably 1.5-1.8 mm. More preferably, it is still more preferably 1.5 to 1.6 mm. The “thickness” of the skin material, the base mat, and the needle-punched nonwoven fabric described in the examples refers to the value of the length between two main surfaces under a load of 100 g / 5 cm ² , and was randomly selected. It means the arithmetic mean value of the thickness at 10 points.

  The 20% modulus of the skin material of the present invention is appropriately adjusted depending on the intended use. However, if the 20% modulus in the vertical direction, which tends to be higher than that in the horizontal direction due to the orientation of the fiber, is too high, the moldability deteriorates. Because of this tendency, the 20% modulus in the vertical direction is preferably 90 N / 3 cm width or less, more preferably 80 N / 3 cm width or less, and even more preferably 70 N / 3 cm width. If the 20% modulus is too low, the entanglement between the fibers is insufficient and the moldability and wear resistance deteriorate, so the lower limit of the 20% modulus in the vertical direction is 50 N / 3 cm. preferable. In addition, the 20% modulus ratio in the vertical direction and the horizontal direction is 3/2 to 3/1 in the vertical / horizontal direction, because the setting to the mold is easy during molding and the moldability is excellent. Is preferred. In the present invention, the “longitudinal direction” refers to a production direction (flow direction) during nonwoven fabric production, and the “lateral direction” refers to a method orthogonal to the vertical direction, that is, a width direction.

  Next, the manufacturing method of the skin material of the present invention will be illustrated and described.

  First, a fibrous structure such as a woven fabric, a knitted fabric, or a nonwoven fabric is manufactured using the above-described fibers. The method for producing the fiber structure is not particularly limited, but when the fiber structure is a woven or knitted fabric, it can be produced by weaving or knitting the above-mentioned fibers. When the fibrous structure is a non-woven fabric, for example, a dry method in which the fibers are entangled by providing the above-described fibers to a card device or an air laying device, a wet method in which the fibers are dispersed in a solvent and the fibers are formed into a sheet and entangled, Direct spinning method (using a melt blow method, a spun bond method, an electrostatic spinning method, a method of spinning by discharging a spinning solution and a gas flow in parallel (for example, a method disclosed in JP-A-2009-287138), A method of spinning and collecting the fiber], but it is preferable to have a certain amount of bulk so as to have excellent moldability, so that the fiber is entangled with a card device or an air-lay device. It is preferable to adopt a dry method for combining.

  When producing a skin material containing anti-pilling fibers in the constituent fibers of the base mat, for example, anti-pilling fibers and other constituent fibers may be mixed to form a fiber structure, or A fibrous structure can be manufactured by laminating one or more fiber layers containing anti-pilling fibers and one or more fiber layers not containing anti-pilling fibers and integrating them by, for example, entanglement, adhesion, fusion or the like. .

The fiber structure formed as described above is preferably entangled with a water stream or a needle so that it can be easily handled. In particular, it is preferable to entangle with the needle so as not to impair the thickness and consequently impair the moldability. Is not particularly limited needle entangling conditions are preferred, it is preferable to entangled with a needle density of 300 to 1000 present / cm ^2, more preferably entangled with 300-600 present / cm ^2.

  If necessary, after forming the fiber structure, thermocompression bonding may be performed before the constituent fibers are bonded to each other with the binder. This “thermocompression bonding” does not mean that the fibers are in a state of being fused or plasticized and deformed and bonded, but the gap between the fibers is reduced by heat and pressure, and the fibers are densely adhered to each other. It means that it is in a state of being done. In particular, when the fibrous structure contains the stretched polyester short fibers having a dry heat shrinkage of 4% or more as described above, when thermocompression bonding is performed, the fibers shrink slightly slightly and the surface becomes smooth. Since the fibers are less likely to be caught by friction and have excellent abrasion resistance, and a clear print can be formed at the time of printing, it is preferable to perform thermocompression bonding before the constituent fibers are bonded to each other with a binder.

  Such a polyester stretched fiber having a dry heat shrinkage of 4% or more can have a dry heat shrinkage of 4% or more by appropriately adjusting the temperature at the time of heat setting when producing the fiber. . Specifically, after the fiber is drawn, heat setting is performed at a temperature equal to or higher than the glass transition temperature of the polyester, that is, at a temperature equal to or higher than 70 ° C., so that the dry heat shrinkage can be increased to 4% or more.

  Next, after the binder resin liquid is applied from one main surface A side of the fibrous structure by a method such as foaming impregnation, coating, or spraying, and then dried, the constituent fibers of the fibrous structure are adhered to each other by the binder. Then, a base mat having a larger amount of binder on one main surface A side than on the other main surface B side is manufactured.

  A method of manufacturing a base mat in which the amount of the binder present on one main surface A side is larger than that on the other main surface B side is appropriately selected, but the foam weight from one main surface side of the fiber structure is 90 to 150 g / g. It can be manufactured by impregnating with L foamed binder liquid and passing the mixture through two rollers whose gap between rolls is adjusted. At this time, the side to which the binder is applied is the main surface A side. The “form weight” refers to the weight (g) of the foamed binder per liter of volume. When a foam liquid having a foam weight that is too light is used, the binder tends to hardly penetrate into the fiber structure, and when a foam liquid that has a foam weight that is too heavy is used, the binder permeates the entire fiber structure. There is a possibility that a base mat having a larger amount of binder on one main surface A side than on the other main surface B side cannot be manufactured. Therefore, the foam weight of the foamed binder liquid applied to the fiber structure is more preferably 100 to 130 g / L.

  After applying the binder to the fiber structure, the dispersion medium / solvent is removed from the binder liquid. The method for removing the dispersion medium / solvent is appropriately prepared. For example, the dispersion medium / solvent can be removed by heating with a dryer. The type of dryer is not particularly limited, but a can dryer or a dryer with tenter pins is preferable in order to suppress shrinkage due to drying.

Finally, a surface layer material is manufactured by applying a resin layer coating solution, which is a dispersion / solution of a resin constituting the resin layer, to the entire surface on the main surface A of the base mat to form a resin layer. When producing a skin material in which the resin layer contains a resin containing silicone in an amount of 0.06 g / m ² or more, a resin containing silicone can be added to the resin layer coating liquid. The method of applying the resin layer coating solution is not particularly limited, but, for example, a cylinder having a through hole on the entire surface is prepared, such as a cylindrical silk screen, and the resin layer coating solution is supplied through the through hole of the cylinder. The dispersion medium / solvent is removed from the applied resin layer coating solution applied on the main surface A. The method of removing the dispersion medium / solvent is appropriately prepared. For example, the dispersion medium / solvent can be removed by heating and drying the skin material with a floating dryer or a dryer with a tenter pin that does not contact the surface of the skin material.

  When printing is performed on the skin material, the printing process can be performed on the main surface of the base mat or on the surface of the resin layer. The arrangement of the prints is not particularly limited, but can be implemented by a conventionally known method. For example, it is possible to prepare a cylinder having an opening corresponding to a desired pattern, print a printing liquid through the cylinder, dry the printing liquid, and arrange the print. When two or more types of print resins are arranged, they can be arranged by repeating the above operation. Prints have a relatively large amount of binder, because the printed pattern becomes clearer and because the print covers a part of one main surface and makes the skin material excellent in abrasion resistance. It is preferably applied to the surface A side. Further, in order to make the print hard to be peeled off by friction, it is preferable that the print is applied on the main surface of the base mat and the print is covered with a resin layer from above.

  The skin material of the present invention can be used as a skin material for interior materials for vehicles and the like. Although there is no particular limitation on the molding method, for example, a molding method in which a skin material is put into a mold and pressure or heat is applied together with a urethane resin or a glass sheet, or a skin material is put in a mold, and a space between the skin material and the mold is formed. A method such as injection molding in which a resin is poured into the substrate and pressure or heat is applied thereto can be employed.

  Further, this skin material can be subjected to secondary processing such as laminating another knitted fabric, woven fabric, or nonwoven fabric on the skin material, or cutting out the skin material so that the skin material can be applied to various uses.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

(Preparation of needle punched nonwoven fabric A)
An original polyester fiber (fineness: 2.2 dtex, fiber length: 38 mm, single fiber strength: 4.1 cN / dtex, color: gray) was opened at 100 mass% using a card machine to form a fiber web. Next, a fiber web made of 100 mass% of anti-pilling fiber (fineness: 2.2 dtex, fiber length: 51 mm, single fiber strength: 2.5 cN / dtex, color: gray) separately from the fiber web was added to the fiber web. After the overlapping, needle punching treatment was performed at a needle density of 400 needles / cm ² from the surface opposite to the surface on which the fiber web made of the anti-pilling fiber was overlapped. Thereafter, the mixture was supplied between hot calender rolls having a temperature of 170 ° C. and a roll interval of 0.4 mm, and the needle-punched fiber web was thermocompressed to produce a needle-punched nonwoven fabric A (basis weight: 180 g / m ² , Thickness: 1.5 mm). The ratio of the anti-pilling fiber to the total weight of the needle-punched nonwoven fabric A was 25% by weight.

(Preparation of needle punched nonwoven fabric B)
Using 100 mass% of original polyester fiber (fineness: 2.2 dtex, fiber length: 38 mm, color: gray), the fiber web is formed by a carding machine, and the needle density is 400 needles / cm ² from one side. Punch processing was performed. Thereafter, the mixture was supplied between hot calender rolls at a temperature of 170 ° C. and a roll interval of 0.4 mm, and the needle-punched fiber web was thermocompressed to produce a needle-punched nonwoven fabric (basis weight: 180 g / m ² , thickness). Length: 1.5 mm).

(Preparation of binder liquid)
A binder dispersion liquid was prepared in the following ratio.
(1) Acrylic binder liquid (glass transition temperature: −5 ° C.): 15 parts by weight (2) Carboxymethyl cellulose-based thickener: 0.2 parts by weight (3) Surfactant: 0. 2 parts by weight (4) ammonia water 0.1 parts by weight (5) water 84.5 parts by weight The obtained dispersion was foamed to prepare a binder liquid. The foam weight of the binder liquid was 120 g / L.

(Preparation of printing liquid A)
A printing liquid A was prepared in the following ratio.
(1) Carboxyvinyl polymer thickener: 0.36 parts by weight (2) Dimethylsiloxane defoamer liquid: 0.5 parts by weight (3) Acrylic binder liquid (glass transition temperature: -40 ° C) ... 18 parts by weight (4) Acrylic thickener ... 0.28 parts by weight (5) Ammonia water ... 1 part by weight (6) Water ... 79.62 parts by weight (7) Black pigment: 0.24 parts by weight

(Preparation of printing liquid B)
A printing liquid B was prepared in the following ratio.
(1) Carboxyvinyl polymer thickener: 0.36 parts by weight (2) Dimethylsiloxane defoamer liquid: 0.5 parts by weight (3) Acrylic binder liquid (glass transition temperature: -40 ° C) ... 12.3 parts by weight (4) Acrylic thickener ... 0.28 parts by weight (5) Ammonia water ... 1 part by weight (6) Water ... 83.38 parts by weight ( 7) Black pigment: 0.18 parts by weight (8) Modified dimethylsiloxane resin dispersion: 2 parts by weight

(Preparation of resin layer coating solution A)
A resin layer coating liquid A was prepared in the following ratio. In addition, after adding materials other than aqueous ammonia and stirring sufficiently, aqueous ammonia is added dropwise with stirring and adjusted to a viscosity of 9000 to 11000 cp under the condition of a B-type viscometer at 20 rpm, so that the resin layer coating liquid A Was prepared.
(1) Carboxyvinyl polymer-based thickener: 0.36 parts by weight (2) Dimethylsiloxane-based defoamer liquid: 1.6 parts by weight (3) Acrylic binder liquid (glass transition temperature: -5 ° C) 7.5 parts by weight (4) Acrylic thickener 1 part by weight (5) Ammonia water 1 part by weight (6) Water 88.54 parts by weight

(Preparation of resin layer coating solution B)
A resin layer coating liquid B was prepared in the following ratio. In addition, after adding materials other than ammonia water and stirring sufficiently, ammonia water is dropped with stirring and adjusted to a viscosity of 9000 to 11000 cp under the condition of a B-type viscometer at 20 rpm, whereby the resin layer coating solution B Was prepared.
(1) Carboxyvinyl polymer-based thickener: 0.36 parts by weight (2) Dimethylsiloxane-based defoamer liquid: 1.6 parts by weight (3) Acrylic binder liquid (glass transition temperature: -5 C) 7.5 parts by weight (4) Acrylic thickener 1 part by weight (5) Ammonia water 1 part by weight (6) Water 88.04 parts by weight (7) Modified dimethyl siloxane resin dispersion: 0.5 parts by weight

(Example 1)
The binder liquid A is applied to the main surface of the needle-punched nonwoven fabric A on the side on which the fiber web composed of the anti-pilling fiber is superimposed and penetrated, and the needle-punched non-woven fabric is interposed between two rollers having an interval between rolls of 0.25 mm. The binder liquid A penetrated from the main surface A side to the B side through A. Thereafter, the base mat was dried with a can dryer at a temperature of 160 ° C. to prepare a base mat (basis weight: 185 g / m ² , thickness: 1.5 mm). Is the principal surface B side). The anti-pilling fiber was contained on the main surface A side of the base mat. The cross section of the base mat was stained with Kayastain Q (manufactured by Nippon Kayaku Co., Ltd.), and the amount of the binder was confirmed by an optical microscope. In addition, more binder exists on the main surface A side than on the main surface B side, and the amount of the binder decreases continuously from the main surface A side to the main surface B side.
Next, a printing liquid A is printed on the main surface A using a cylinder, and a first printing region (line width) extending linearly obliquely upward to the right at an angle of 30 ° from the width direction of the base mat. : 0.3 mm, line interval: 1 mm), print the printing liquid B by using another cylinder, and straightly diagonally downward to the right at an angle of -30 ° from the width direction of the base mat. An extended second print area (line width: 0.3 mm, line interval: 1 mm) was formed. Then, it was dried with a dryer at a temperature of 160 ° C. The coating amount of Print A was 4 g / m ² , and the coating amount of Print B was 5 g / m ² .
Subsequently, on the main surface A side of the base mat, the resin layer coating solution A was uniformly applied over the entire main surface A to form a resin layer. After applying the resin layer coating solution A, the solution was applied to a dryer at a temperature of 160 ° C. and dried to prepare a skin material.

(Example 2)
Using a needle-punched non-woven fabric B instead of the needle-punched non-woven fabric A, applying the foamed binder solution A to one main surface of the needle-punched non-woven fabric A, and allowing it to penetrate to prepare a base mat. A skin material was prepared in the same manner as in Example 1 except that the resin layer coating solution B was used instead of the solution A.

(Example 3)
A skin material was prepared in the same manner as in Example 1, except that the resin layer coating solution B was used instead of the resin layer coating solution A.

(Comparative Example 1)
A needle mat was prepared using a needle-punched non-woven fabric B instead of the needle-punched non-woven fabric A, except that the foamed binder solution A was applied to one main surface of the needle-punched non-woven fabric A, and was then allowed to penetrate to prepare a base mat. A skin material was prepared in the same manner as in Example 1.

  Table 1 shows the needle-punched nonwoven fabric of the skin material, the coating liquid of the resin layer, and the amount of silicone of the resin layer in Examples and Comparative Examples. Further, the skin materials of Examples and Comparative Examples were evaluated by the following methods.

(Evaluation of skin material)
(1) Measurement of 20% modulus strength (i) From the skin material or the base mat, three rectangular samples having a width of 30 mm and a length of 200 mm were sampled vertically and horizontally.
(Ii) After fixing the sample between the chucks (distance: 100 mm) of a tensile strength tester (manufactured by Orientec, Tensilon UTM-III-100), the sample was pulled at a pulling speed of 200 mm / min, and the distance between the chucks was 120 mm ( (20% elongation) was read.
(Iii) The stress was measured for each of the three samples, and the arithmetic average value was defined as the 20% modulus in the vertical and horizontal directions.

(2) Performance evaluation method and wear resistance evaluation method of skin material The skin material cut into 3 cm x 25 cm was fixed to a Gakushin type friction tester (RT-200, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) and resin A 1 kg load is applied to a friction element (2 cm × 2.5 cm) having a hook-and-loop fastener (male type, Kuraray Fastening Co., Ltd., A hook for sewing, 100% polyester) on the side having a layer, and a surface of the skin material is applied. The main surface of the skin material was rubbed by making 20 reciprocations (60 reciprocations / minute) of the area A of 3 cm × 10 cm.
Thereafter, the surface condition of a 3 cm × 5 cm area B excluding 2.5 cm at both ends of the long side of the area A of the rubbed skin material was observed, and abrasion resistance was evaluated according to the following criteria.
(Evaluation criteria for wear resistance)
5: No change 4: Fluffing can be partially confirmed, and the fluffing height is 0 mm or more and 5 mm or less. The color of the base mat can be checked visually.
3: Fluffing was confirmed as a whole, and the fluffing height was 0 mm or more and 5 mm or less. The color of the base mat can be checked visually.
2: Fluffing was confirmed as a whole, and the fluffing height was more than 5 mm and 10 mm or less. The color of the base mat can be checked visually.
1: Fluffing was confirmed as a whole, and the fluffing height exceeded 5 mm and was 10 mm or less. The color of the base mat cannot be visually confirmed due to fluff.

-Pilling resistance evaluation method A skin material cut into 3 cm x 25 cm was fixed to the same device as that used in the wear resistance evaluation, and EPDM rubber having a Shore C hardness of 40 was provided on the main surface having the resin layer. The main surface of the skin material was rubbed by applying a load of 1 kg to the friction element (2 cm × 2.5 cm) and making 90 reciprocations (60 reciprocations / minute) in a region A of 3 cm × 10 cm on the skin material or the base mat. .
Thereafter, the surface state of a 3 cm × 5 cm area B excluding 2.5 cm at both ends of the long side of the area A of the skin material after rubbing was observed, and pilling resistance was evaluated according to the following criteria.
(Evaluation criteria for pilling resistance)
5: No pills on the surface of the skin material or the base mat, or less than 1 pill with a long side of less than 1 mm per 1 cm ² .
4: 1 to less than 4 pills with a long side of less than 1 mm per cm ² .
3: 4 to less than 8 pills with a long side of less than 1 mm per cm ² .
2: The number of pills having a long side of less than 1 mm is 8 or more and less than 12 per cm ² .
1: There are 12 or more pills having a long side of less than 1 mm per 1 cm ² , or pills having a long side of 1 mm or more.
The reason for using EPDM rubber having a Shore C hardness of 40 in this evaluation method is to evaluate the pilling resistance when rubbing against a relatively soft object such as a human palm, which easily generates pills. This is because

Injection molding was performed using a fully automatic injection molding machine (UBE MAX MB450-IV-I13 1.6.5B, manufactured by Ube Industries, Ltd.).
After the skin material is fixed with a pin in a molding die (length: 19 cm, width: 31 cm) provided with a recess (length: 4 cm, width: 8 cm, depth: 1 cm) near the center of the mold, and then set , Set the mold spacing to 5mm, inject the polypropylene molten resin to the side of the skin material without the resin layer, then press for 30 seconds at a pressure of about 5 tons, carry out injection molding to create a molded product did. After cooling the molded product to room temperature, the surface state of the molded product on the side having the resin layer derived from the skin material was observed, and the moldability of the skin material was evaluated according to the following criteria.
(Evaluation criteria for moldability)
：: Molded product was not broken at all and molding processability was good. X: Molded product was broken and molding processability was poor.

Based on the above results, comprehensive evaluation was performed on the performance of the skin material.
(Criteria for comprehensive evaluation)
：: Abrasion resistance, pilling resistance and molding workability were all excellent X: Abrasion resistance, pilling resistance and molding workability were not excellent Table 2 shows the evaluation results.

  From the results of comparing the pilling resistance evaluations of Examples 1 and 3 in which the base mat contains anti-pilling fibers and Comparative Example 1 in which the base mat does not contain anti-pilling fibers, Examples 1 and 3 are better. Excellent pilling resistance. Therefore, in the base mat in which the constituent fibers are bonded to each other with the binder, the amount of the binder present on one main surface A side is larger than that on the other main surface B side, and A skin material having an anti-pilling fiber in a base mat in addition to a resin layer on the entire surface of the one main surface A is more excellent in pilling resistance than a skin material which is not so, and the skin material is rubbed. However, it was found that the appearance quality was hardly impaired.

In addition, Examples 2 and 3 in which the resin containing silicone is contained in the resin layer in an amount of 0.06 g / m ² or more and Comparative Example 1 in which the resin containing silicone is contained in the resin layer is less than 0.06 g / m ² . From the result of comparing the pilling resistance evaluations, Examples 2 and 3 were superior in pilling resistance. Therefore, in the base mat in which the constituent fibers are bonded to each other with the binder, the amount of the binder present on one main surface A side is larger than that on the other main surface B side, and A skin material having a resin layer on the entire surface of the one main surface A and containing 0.06 g / m ^{2 of} silicone in the resin layer is excellent in pilling resistance as compared with a skin material which is not so. It was found that even when the material was rubbed, the appearance quality was not easily impaired.

Further, in Example 1 in which the base mat contains anti-pilling fibers, or in Example 2 in which the resin layer contains 0.06 g / m ² or more of the resin containing silicone, the base mat contains anti-pilling fibers. From the result of comparison of the pilling resistance evaluation with that of Example 3 in which the resin containing silicone is contained in the resin layer in an amount of 0.06 g / m ² or more, the pilling resistance of Example 3 is higher. Was found to be excellent.

  The skin material of the present invention is, for example, ceiling materials, door trims, dash outers, interior materials for vehicles such as pillar garnishes, partitions, applications such as wallpaper, in particular, door trims, dash outers, pillar garnishes, etc., have high wear resistance. Or as an interior material for vehicles that require pilling resistance.

Claims (2)

In the base mat in which the constituent fibers are bonded to each other with a binder, the amount of the binder present on one main surface A side is larger than that on the other main surface B side,
And in the base mat, having a resin layer on the entire surface on the one main surface A,
A skin material, wherein the base mat contains anti-pilling fibers. In the base mat in which the constituent fibers are bonded to each other with a binder, the amount of the binder present on one main surface A side is larger than that on the other main surface B side,
And in the base mat, having a resin layer on the entire surface on the one main surface A,
The skin material further comprises a resin containing silicone in the resin layer in an amount of 0.06 g / m ² or more.