JP7021884B2 - Epidermis material - Google Patents

Description

The present invention relates to a skin material that can be used for a ceiling material, a door trim, a dash outer, a vehicle interior material such as a pillar garnish, a partition, a wallpaper, and the like. In particular, the present invention relates to a skin material that can be suitably used as an interior material for a vehicle that requires high wear resistance, such as a door trim, a dash outer, and a pillar garnish.

Conventionally, a non-woven 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 impregnates the surface subjected to the needle punching with a binder as a wear-resistant skin material using a non-woven fabric, and then applies a binder with less tack to the opposite surface of the surface subjected to the needle punching. We have proposed an interior skin material (Patent Document 1) that is impregnated.

The skin material according to Patent Document 1 is a skin material that has wear resistance and can be molded because fluffing due to friction is unlikely to occur, but it is used for vehicles such as door trims that require particularly high wear resistance. The wear resistance was insufficient for use as a skin material for interior materials.

Japanese Unexamined Patent Publication No. 62-257472

The present invention has been made under such circumstances, and an object of the present invention is to provide a skin material having excellent molding processability and further excellent wear resistance.

In the present invention, "in a base mat composed of constituent fibers bonded to each other by a binder, the abundance of the binder on one main surface A side is larger than that on the other main surface B side, and the abundance of binder is present. Is a mode in which is continuously reduced from the main surface A side to the main surface B side, and a pattern is applied by printing on one of the main surfaces A in the base mat, and the thickness is 0.001 mm or more from above. A skin material, characterized in that a resin layer of the above covers the print . "

In the skin material of the present invention, since 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, the constituent fibers on the main surface B side are used. Is not more strongly bonded by the binder than the constituent fibers on the main surface A side, and is easy to move. Therefore, the skin material of the present invention is excellent in moldability because the main surface B side with few binders easily follows the shape of the mold when subjected to molding processing such as injection molding. In addition, since the constituent fibers on the main surface A side, which can be the surface of the skin material that comes into contact with humans, are strongly adhered to each other by the binder, the skin material has a main surface with excellent wear resistance, such as less fluffing due to friction. be.

Further, the skin material of the present invention has a resin layer on the entire surface of one of the main surfaces 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, fluffing due to friction is less likely to occur, and the skin material is more excellent in wear resistance.

Therefore, the skin material of the present invention is excellent in molding processability and further excellent in wear resistance.

The base mat constituting the skin material of the present invention refers to a sheet-like fiber structure such as a woven fabric, a knitted fabric, or a non-woven 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 non-woven fabric, it is preferable because it is a base mat that is flexible and easily follows the shape of the mold, so that it is possible to provide a skin material having excellent molding processability.

The constituent fibers of the base mat in the present invention are not particularly limited, and may be, for example, polyester fibers, nylon fibers, acrylic fibers, vinylon fibers, rayon fibers, and the like. Among these, it is preferable to contain polyester fiber having excellent heat resistance, light resistance, stain resistance and / or rayon fiber having excellent flame retardancy. Further, 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 and a side-by-side type. For example, it is preferable to use latent crimped fibers (side-by-side type composite fibers, etc.) because the fibers develop crimping due to heat, and the structure of the base mat becomes denser by using the crimped fibers. .. Further, the cross section of the constituent fibers may be circular, or may be irregular such as an ellipse, a quadrangle, or a Y-shaped cross section. In addition, it may contain fibrillated fibers.

As will be described later, when thermocompression bonding is performed during the manufacture of the base mat, the dry heat shrinkage rate is 4% or more as a constituent fiber of the base mat in order to improve wear resistance and to form a clear print. It preferably contains (preferably 4.5 to 20%, more preferably 5 to 10%) polyester stretched staples. This "dry heat shrinkage rate" is based on JIS L1015 (2010) 8.15b) dry heat dimensional change rate, except that the initial load is 1.3 mg and the temperature is 140 ° C. for 10 minutes. It means the value measured by.

The constituent fibers may be white or colored. When the constituent fibers are colored, the fibers themselves may be uncoated fibers containing a pigment and / or a dye in the constituent resin, or may be fibers colored with a pigment and / or a dye. Since the fibers are not easily discolored by rubbing, it is preferable to use the dyed fibers.

Although the fiber lengths of the constituent fibers of the base mat in the present invention are appropriately adjusted, the fiber lengths of the constituent fibers are preferably 38 to 114 mm, preferably 38 to 76 mm, because the base mat has excellent moldability. It is more preferably 38 to 52 mm, and even more preferably 38 to 52 mm. This "fiber length" refers to a value measured according to JIS L1015 (2010) 8.4.1c) direct method (C method).

Further, the fineness of the constituent fibers of the base mat in the present invention is appropriately adjusted, but if the fibers are too thick, it becomes difficult to use a skin material having a smooth surface, and the skin material having a rough surface is caught by friction. Since it is easy to fluff, wear resistance tends to deteriorate. On the other hand, if the fibers are too fine, 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 further preferably 1 to 2 dtex.

The skin material of the present invention may be a base mat composed of a single fiber layer, or may be a base mat composed of a plurality of fiber layers laminated. In the base mat composed 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. Of these, a base mat composed of a single fiber layer is preferable because it can provide a skin material having excellent moldability without delamination during molding.

The base mat of the present invention is composed of constituent fibers bonded to each other by a binder. Examples of the mode in which the constituent fibers are adhered to each other by the binder include a mode in which the binder adheres to the intersection of the constituent fibers and the binder adheres to the constituent fibers, and a mode in which the binder exists between the fibers and adheres to each other. And so on.

The type of binder used in the present invention is not particularly limited and may be adjusted as appropriate, and examples thereof include polyurethane-based resin, acrylic-based resin, and polyester-based resin. Among these, acrylic resins (particularly, self-crosslinking acrylic resins) are preferable because they are moderately softened during molding, have excellent followability to the mold, and are less likely to cause wrinkles and fine irregularities. Among acrylic resins, a soft acrylic resin having a low glass transition temperature is suitable because it is easy to stretch 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 breaking strength of the binder resin is inferior, so that the wear resistance is inferior. Therefore, the glass transition temperature is preferably −40 ° C. or higher and 10 ° C. or lower, more preferably −20 ° C. or higher and 5 ° C. or lower, and further preferably −10 ° C. or higher and 5 ° C. or lower. The "glass transition temperature" in the present invention refers to the temperature at the intersection of the tangent of the baseline in the DTA curve measured by a differential thermal analyzer (DTA) and the tangent of the steep descent position of the endothermic region due to the glass transition.

The base mat constituting the skin material of the present invention is characterized in that the abundance of the binder on one main surface A side is larger than that on the other main surface B side. In the present invention, the "absence of binder on the main surface A side (or main surface B side)" is 20% from the main surface A (or main surface B) of the base mat with respect to the total thickness of the base mat. It means the abundance of binder in the area up to the thickness. With this configuration, fluffing due to friction is less likely to occur on the main surface A side, and the wear resistance is excellent, and the constituent fibers on the main surface B side are more strongly adhered by the binder than on the main surface A side. Since it is easy to move, it is possible to provide a skin material having excellent molding processability.
As a method for confirming the abundance 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. It can be confirmed by visually observing the distribution of the binder in the above and by observing it with an optical microscope.

The distribution mode of the abundance of the binder contained in the base mat may be adjusted as appropriate as long as the abundance of the binder on one main surface A side of the base mat is larger than that on the other main surface B side. However, in the embodiment in which the abundance of the binder continuously decreases from the main surface A side to the main surface B side, the abundance of the binder inside the base mat continuously changes, and the distribution of the abundance of the binder changes. Since it is not concentrated on a small part of the base mat, peeling between the portion where the binder is concentrated and the other portion is unlikely to occur, and it is preferable because it is excellent in wear resistance and molding processability.

As the amount of binder contained in the base mat tends to be better, the amount of binder is preferably 2 g / m ² or more, more preferably 10 g / m ² or more, and 15 g / m ² or more. Is more preferable. On the other hand, if the amount of binder contained in the base mat is too large, the skin material tends to become hard and the molding processability tends to deteriorate. Therefore, it is preferably 30 g / m ² or less, and 20 g / m ² or less. The following is more preferable.

The skin material of the present invention has an excellent wear resistance such that fluffing due to friction is less likely to occur on the main surface A side due to the structure having the resin layer on the entire surface A on one main surface A of the base mat. The "whole surface on one main surface A" of the present invention refers to the entire one main surface A of the base mat that can be seen when the base mat is viewed from directly above the one main surface A of the base mat. Point to.

The resin layer of the present invention can be a layer composed of the following resins. Examples of the type of resin include the same resins as the above-mentioned binder resin. For example, polyurethane-based resin, acrylic-based resin, or polyester-based resin can be mentioned. Among these, an acrylic resin (particularly, a self-crosslinking acrylic resin) that is moderately softened at the time of molding, has excellent followability to the mold, and is less likely to generate wrinkles and fine irregularities is preferable. Among acrylic resins, a soft acrylic resin having a low glass transition temperature is suitable because it is easy to stretch 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 breaking strength of the binder resin is inferior, so that the wear resistance is inferior. Therefore, the glass transition temperature is preferably −40 ° C. or higher and 10 ° C. or lower, more preferably −20 ° C. or higher and 5 ° C. or lower, and further preferably −10 ° C. or higher and 5 ° C. or lower.

Further, when 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, there is a difference in the elongation of the base mat portion and the resin layer portion of the skin material during the molding process. It is preferable that the skin material is less likely to come out, so that delamination is less likely to occur between the base mat and the resin layer, and a skin material having more excellent molding processability can be provided. The difference in glass transition temperature between the resin contained in the binder and the resin contained in the resin layer is more preferably 5 ° C. or lower, further preferably 3 ° C. or lower, and most preferably the same temperature. The "resin layer" of the present invention refers to a layer that includes a region of only resin and completely covers one main surface A of the base mat. Further, the resin-only region is observed as a film-like layer when observing the cross section of the skin material in the thickness direction. The resin layer may be composed of only a resin-only region, or may be composed of a resin-only region and a region in which fibers and resins are mixed.

As the amount of the resin layer of the skin material tends to be more excellent in wear resistance, 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 preferable. Further, if the amount of the resin layer is too large, the texture, texture and moldability of the skin material tend to be impaired, so that the amount is preferably 20 g / m ² or less. Further, the thicker the resin layer of the skin material, the more excellent the wear resistance tends to be. Therefore, the thickness of the resin layer is preferably 0.001 mm or more, more preferably 0.002 mm or more, and more preferably 0.004 mm. The above is more preferable. Further, if the thickness of the resin layer is too thick, the texture, texture, 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 of the skin material in the thickness direction with an electron microscope, and the arithmetic mean value of the thickness of the resin layer at 10 randomly selected points is the "resin layer" of the present invention. Thickness ".

The skin material of the present invention may be patterned by printing so as to have better wear resistance and better design 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, because the pattern produced by the print becomes clear and the wear resistance of the skin material can be improved by the presence of the print. Is preferable. In addition, as a mode of printing, a print is applied on the main surface of the base mat and a resin layer covers the print from above, or a main surface of the skin material (the resin layer is exposed). The print can be applied on the surface), but the print is applied on the main surface A of the base mat so that the print does not easily come off due to friction, and the resin layer covers the print from above. Is preferable.

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

The composition of the print to be applied to the skin material of the present invention is appropriately prepared, and the type thereof is composed of the same resin as the above-mentioned binder resin, for example, a resin such as a polyurethane resin, an acrylic resin, or a polyester resin. Can be done. Further, the print may contain a pigment, and the color, type and amount of the pigment can be appropriately adjusted.

As the amount of resin contained in the print increases, the skin material tends to have better wear resistance. Therefore, the amount of resin contained in the print is preferably 3 g / m ² or more, and more preferably 5 g / m ² or more. It is preferable, 9 g / m ² or more is more preferable. Further, if the amount of the resin contained in the print is too large, the sharpness of the pattern by the print and the moldability tend to be impaired, so that the amount is preferably 20 g / m ² or less.

Binders, resin layers and prints can contain functional materials in addition to the resins described above. For example, by containing a pigment, the skin material can be colored, so that the design of the skin material is improved. Further, by containing a water-repellent resin such as a resin containing silicone or a resin containing fluorine, the skin material is less likely to be soiled and the wear resistance can be improved. Further, by incorporating an inorganic compound such as a flame retardant, an antibacterial agent, a deodorant, a VOC generation inhibitor, and an inorganic powder, various functions can be imparted to the skin material.

The basis weight and thickness of the skin material of the present invention are appropriately adjusted depending on the intended use, required strength, etc. However, if the basis weight of the skin material is too light, the skin material may be torn during molding, resulting in deterioration of moldability. Further, if the basis weight is too heavy, a large external force is required for molding and the molding processability deteriorates. Therefore, the basis weight is preferably 140 to 260 g / m ² and more preferably 150 to 250 g / m ² . , 160-250 g / m ² is more preferable. Further, if the thickness of the skin material is too thin, the molding processability deteriorates, and if it is too thick, it becomes difficult to handle. Therefore, the thickness is preferably 1 to 2 mm, preferably 1.5 to 1.8 mm. It is more preferably 1.5 to 1.6 mm, and even 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 in the present invention refers to the value of the length between the ^two main surfaces under a load of 100 g / 5 cm, 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, but the value tends to be higher than that in the horizontal direction due to the orientation of the fibers. If the 20% modulus in the vertical direction is too high, the molding processability deteriorates. Since there is a 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 further preferably 70 N / 3 cm width or less. If the 20% modulus is too low, the fibers are not sufficiently entangled with each other, and the moldability and wear resistance are deteriorated. Therefore, the lower limit of the 20% modulus in the vertical direction is 50 N / 3 cm. preferable. Further, the 20% modulus ratio in the vertical direction and the horizontal direction is 3/2 to 3/1 in the vertical / horizontal direction because it is easy to set in the mold during molding and is excellent in molding processability. Is preferable. The "vertical direction" in the present invention means the production direction (flow direction) at the time of producing the nonwoven fabric, and the "horizontal direction" means a method orthogonal to the vertical direction, that is, a width direction.

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

First, a fiber structure such as a woven fabric, a knitted fabric, or a non-woven fabric is manufactured using the above-mentioned fibers. The method for producing the fiber structure is not particularly limited, but when the fiber structure is a woven fabric or a knitted fabric, it can be produced by weaving or knitting the above-mentioned fibers. When the fiber structure is a non-woven fabric, for example, a dry method in which the above-mentioned fibers are used in a card device, an air array device, or the like to entangle the fibers, or a wet method in which the fibers are dispersed in a solvent and the fibers are entangled in a sheet shape. Direct spinning method [melt blow method, spunbond method, electrostatic spinning method, method of discharging a spinning stock solution and a gas flow in parallel to spin (for example, the method disclosed in JP-A-2009-287138), etc. It can be manufactured by spinning fibers and collecting them], but it is preferable that they have a certain amount of bulk so that they can be easily molded. It is preferable to adopt the dry method of matching.

The fibrous structure formed as described above is preferably entangled with a stream of water or a needle for ease of handling. In particular, it is preferable to entangle with a needle so as not to impair the thickness and, as a result, the moldability. The suitable needle entanglement conditions are not particularly limited, but entanglement is preferably performed at a needle density of 300 to 1000 needles / cm ² , and entanglement is more preferably performed at a needle density of 300 to 600 needles / cm ² .

If necessary, thermocompression bonding may be performed after the fiber structure is formed and before the constituent fibers are bonded to each other by a binder. Note that this "thermocompression bonding" does not mean that the fibers are in a state of being melted or plastically deformed and adhered, but the gaps between the fibers become smaller due to heat and pressure, and the fibers adhere to each other at high density. It means that it is in a state of being. In particular, when the fiber structure contains polyester stretched short fibers having a dry heat shrinkage rate of 4% or more as described above, when thermocompression bonding is performed, the fibers are slightly shrunk and the surface becomes smooth. Since the fibers are less likely to be caught by friction, the fibers are excellent in wear resistance, and a clear print can be formed when printing is performed. Therefore, it is preferable to thermocompression-bond the constituent fibers before bonding them with a binder.

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

Next, a binder resin solution is applied from one main surface A side of the fiber structure by a method such as foaming impregnation, coating, or spraying, and then dried to bond the constituent fibers of the fiber structure to each other by a binder. , Manufacture a base mat in which the abundance of the binder on one main surface A side is larger than that on the other main surface B side.

A method for producing a base mat in which the abundance of binder on one main surface A side is larger than that on the other main surface B side is appropriately selected, but the foam weight is 90 to 150 g / g from one main surface side of the fiber structure. It can be manufactured by impregnating with the foamed binder liquid of L and passing it through two rollers having an adjusted spacing between rolls. At this time, the side to which the binder is applied becomes the main surface A side. The "foam weight" refers to the weight (g) of the foamed binder per 1 L of volume. If a foamed binder liquid with too light foam weight is used, the binder tends to be difficult to penetrate into the fiber structure, and if a foamed binder liquid with too heavy foam weight is used, the binder permeates the entire inside of the fiber structure. It tends to be easy, and 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, it is more preferable to use a foam weight of 100 to 130 g / L for the foaming binder liquid to be applied to the fiber structure.

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, but 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 a tenter pin is preferable in order to suppress shrinkage due to drying.

Finally, the skin material is manufactured by applying a resin layer coating liquid, which is a dispersion liquid / solution of the resin constituting the resin layer, on the entire surface of the main surface A of the base mat to form the resin layer. The method for applying the resin layer coating liquid is not particularly limited, but a cylinder having a through hole on the entire surface is prepared, for example, a tubular silk screen, and the resin layer coating liquid is applied through the through hole of this cylinder. It is applied on the main surface A, and the dispersion medium / solvent is removed from the applied resin layer coating 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 floating dryer or a dryer with a tenter pin that does not come into contact with the surface of the skin material to dry the skin material.

When printing is applied to the skin material, the printing process can be performed on the main surface of the base mat or the surface of the resin layer. The arrangement of the prints is not particularly limited, but can be carried out by a conventionally known method. For example, a cylinder having an opening corresponding to a desired pattern can be prepared, a printing liquid can be printed through this cylinder, and the printing liquid can be dried and placed. Further, when two or more types of print resins are arranged, they can be arranged by repeating the above operation. The print has a relatively large amount of binder because the pattern of the print becomes clear and the print covers a part of one of the main surfaces to improve the wear resistance of the skin material. It is preferable to apply it on the surface A side. Further, in order to prevent the print from peeling off due to friction, it is preferable to apply the print on the main surface of the base mat and cover the print with a resin layer from above.

The skin material of the present invention can be used as a skin material for vehicle interior materials and the like. The molding method is not particularly limited, but for example, a molding method in which a skin material is molded and pressure or heat is applied together with a urethane resin or a glass sheet, or a molding method in which the skin material is molded and between the skin material and the mold is used. It is possible to take a method such as injection molding in which resin is poured into the water and pressure or heat is applied.

Further, the skin material can be used for secondary processing such as laminating other knitted fabrics, woven fabrics, or non-woven fabrics 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 punch non-woven fabric)
Using 100 mass% of raw polyester fiber (fineness: 2.2 dtex, fiber length: 38 mm, color: gray), the fiber is opened by a card machine to form a fiber web, and then a needle with a needle density of 400 lines / cm ² from one side. Punch processing was performed. After that, it was supplied between thermal calender rolls having a temperature of 170 ° C. and a roll interval of 0.4 mm, and the fiber web subjected to needle punching was thermocompression bonded to produce a needle punched non-woven fabric (weight: 140 g / m ² , thickness). S: 1.2 mm).

(Preparation of binder liquid A)
A binder dispersion was prepared in the following proportions.
(1) Acrylic binder [Boncoat (registered trademark) E-240N, manufactured by DIC Co., Ltd., glass transition temperature: -5 ° C] ... 15 parts by weight (2) Thickener [Cerogen (registered trademark) WS-C , Dai-ichi Kogyo Seiyaku Co., Ltd.] ・ ・ ・ 0.2 parts by weight (3) Surfactant [Neogen (registered trademark) S-20D, Dai-ichi Kogyo Seiyaku Co., Ltd.] ・ ・ ・ 0.2 weight Part (4) Ammonia water ... 0.1 part by weight (5) Water ... 84.5 parts by weight The obtained dispersion was whipped to prepare a binder liquid A. The foam weight of the binder liquid A was 120 g / L.

(Preparation of binder liquid B)
A binder dispersion was prepared in the following proportions.
(1) Acrylic binder [Boncoat (registered trademark) E-240N, manufactured by DIC Co., Ltd., glass transition temperature: -5 ° C] ... 8 parts by weight (2) Thickener [Cerogen (registered trademark) WS-C , Dai-ichi Kogyo Seiyaku Co., Ltd.] ・ ・ ・ 0.2 parts by weight (3) Surfactant [Neogen (registered trademark) S-20D, Dai-ichi Kogyo Seiyaku Co., Ltd.] ・ ・ ・ 0.2 weight Part (4) Ammonia water ... 0.1 part by weight (5) Water ... 91.5 parts by weight The obtained dispersion was whipped to prepare a binder liquid B. The foam weight of the binder liquid B was 200 g / L.

(Preparation of printing liquid A)
The printing liquid A was prepared by blending in the following ratios.
(1) Thickener [Carbopol (registered trademark) 940, manufactured by Japan Lubrizol Co., Ltd.] ... 0.36 parts by weight (2) Antifoaming agent [Shin-Etsu Silicone KM-73, Shin-Etsu Chemical Co., Ltd. Manufactured by] ... 0.5 parts by weight (3) Acrylic binder [Boncoat (registered trademark) AB-886, manufactured by DIC Co., Ltd., glass transition temperature: -40 ° C] ... 18 parts by weight (4) Thickening Agent [Nicazole (registered trademark) VT-253, manufactured by Nippon Carbide Industries, Ltd.] ・ ・ ・ 0.28 parts by weight (5) Ammonia water ・ ・ ・ 1 part by weight (6) Water ・ ・ ・ 79.62 parts by weight (7) Black pigment [RWBLACK RC (V), manufactured by DIC Co., Ltd.] ... 0.24 parts by weight

(Preparation of printing liquid B)
The printing liquid B was prepared by blending in the following ratios.
(1) Thickener [Carbopol (registered trademark) 940, manufactured by Japan Lubrizol Co., Ltd.] ... 0.36 parts by weight (2) Antifoaming agent [Shinetsu Silicone KM-73, Shin-Etsu Chemical Industry Co., Ltd. Manufactured by] ... 0.5 parts by weight (3) Acrylic binder [Boncoat (registered trademark) AB-886, manufactured by DIC Co., Ltd., glass transition temperature: -40 ° C] ... 12.3 parts by weight (4) Thickener [Nicazole (registered trademark) VT-253, manufactured by Nippon Carbide Industries Co., Ltd.] ・ ・ ・ 0.28 parts by weight (5) Ammonia water ・ ・ ・ 1 part by weight (6) Water ・ ・ ・ 83.38 Parts by weight (7) Black pigment [RWBLACK RC (V), manufactured by DIC Co., Ltd.] ... 0.18 parts by weight (8) Silicone resin [YMR-7212, manufactured by GE Toshiba Silicone Co., Ltd.]・ ・ ・ 2 parts by weight

(Preparation of resin layer coating liquid)
A resin layer coating liquid was prepared in the following proportions. After adding a material other than ammonia water and stirring sufficiently, ammonia water is dropped while stirring to adjust the viscosity to 9000 to 11000 cp under the condition of B-type viscometer 20 rpm to prepare the resin layer coating liquid. Prepared.

(1) Thickener [Carbopol (registered trademark) 940, manufactured by Japan Lubrizol Co., Ltd.] ... 0.36 parts by weight (2) Antifoaming agent [Shin-Etsu Silicone KM-73, Shin-Etsu Chemical Co., Ltd. Manufactured by] ... 1.6 parts by weight (3) Acrylic binder [Boncoat (registered trademark) E-240N, manufactured by DIC Co., Ltd., glass transition temperature: -5 ° C] ... 7.5 parts by weight (4) Thickener [Nikazol (registered trademark) VT-253, manufactured by Nippon Carbide Industries Co., Ltd.] ・ ・ ・ 1 part by weight (5) Ammonia water ・ ・ ・ 1 part by weight (6) Water ・ ・ ・ 88.54 parts by weight

(Example 1)
The foamed binder liquid A is applied to the needle punched non-woven fabric and permeated, and the binder liquid A is permeated from the main surface A side to the B side through the needle punched non-woven fabric between two rollers having a roll spacing of 0.3 mm. rice field. Then, it was dried with a can dryer at a temperature of 160 ° C. to prepare a base mat (weight: 155 g / m ² , thickness: 1.2 mm) (the side to which the binder solution was applied was the main surface A side, and the main surface A side). The opposite side of is the main surface B side). When the cross section of the base mat was dyed with Kayastain Q (manufactured by Nippon Kayaku Co., Ltd.) and the abundance of binder was confirmed with an optical microscope, more binder was found on the main surface A side than on the main surface B side. It was present, and the amount of binder was continuously reduced from the main surface A side to the main surface B side.
Subsequently, in order to form a resin layer on the main surface A side of the base mat, the resin layer coating liquid was uniformly applied to the entire surface of the main surface A. After applying the resin layer coating liquid, the skin material was prepared by subjecting it to a dryer device having a temperature of 160 ° C. and drying it.

(Example 2)
A base mat is prepared in the same manner as in Example 1, and the printing liquid A is printed on the main surface A side using a cylinder, and the printing liquid A is linearly oriented diagonally upward to the right at an angle of 30 ° from the width direction of the base mat. Form the first print area (line width: 0.3 mm, line spacing: 1 mm) extending to, print the print liquid B using another cylinder, and right at an angle of -30 ° from the width direction of the base mat. A second print area (line width: 0.3 mm, line spacing: 1 mm) extending linearly in the diagonally downward direction was formed. Then, it was dried by a dryer having a temperature of 160 ° C.
Subsequently, as in Example 1, the resin layer coating liquid was uniformly applied to the entire surface of the main surface A on the main surface A side of the base mat on which the print is present. After applying the resin layer coating liquid, the skin material was prepared by subjecting it to a dryer device having a temperature of 160 ° C. and drying it.

(Example 3)
A needle punched nonwoven fabric was produced in the same manner as in Example 1 except that the basis weight was different. (Metsuke: 180 g / m ² , thickness: 1.5 mm). After that, the foamed binder liquid A is applied to the needle punched nonwoven fabric, permeated, and the binder liquid A is directed from the main surface A side to the B side by passing the needle punched nonwoven fabric between two rollers having a roll spacing of 0.25 mm. Infiltrated. Then, it was dried with a can dryer having a temperature of 160 ° C. to produce a base mat (weight: 185 g / m ² , thickness: 1.5 mm).
Next, the skin material was prepared by the same method as in Example 2 except that the coating amount of print A was 4 g / m ² and the coating amount of print B was 5 g / m ² .

(Comparative Example 1)
A base mat having no resin layer was prepared in the same manner as in Example 1 except that the resin layer coating liquid was not applied.

(Comparative Example 2)
No resin layer coating liquid was applied, binder liquid A was applied and permeated, and then a needle punched non-woven fabric was passed between two rollers with a roll spacing of 10 mm, and the coating amount of binder liquid A was 50 g / m ² . A base mat (weight: 190 g / m ² , thickness: 1.4 mm) having no resin layer was prepared in the same manner as in Example 1. When the cross section of the base mat was dyed with Kayastain Q (manufactured by Nippon Kayaku Co., Ltd.) and the abundance of binder was confirmed with an optical microscope, more binder was found on the main surface A side than on the main surface B side. It was present, and the amount of binder was continuously reduced from the main surface A side to the main surface B side.

(Comparative Example 3)
Using the same method as in Example 2 except that the resin layer coating liquid was not applied, the resin layer did not exist on the main surface A of the base mat, and instead, it was printed on the main surface A of the base mat. A base mat containing a print was prepared in the same manner as the skin material having the resin layer partially but not entirely.

(Comparative Example 4)
A skin material was prepared in the same manner as in Example 1 except that the resin layer coating liquid was uniformly applied to the entire surface from the main surface B side of the base mat using a cylinder. When the cross section of the base mat was dyed with Kayastain Q (manufactured by Nippon Kayaku Co., Ltd.) and the abundance of binder was confirmed with an optical microscope, more binder was found on the main surface A side than on the main surface B side. It was present, and the amount of binder was continuously reduced from the main surface A side to the main surface B side.

(Comparative Example 5)
The foamed binder liquid B was applied to the needle punched nonwoven fabric, and the binder was allowed to permeate the entire nonwoven fabric. Then, it was dried with a can dryer at a temperature of 160 ° C. to prepare a base mat (similar to Example 1, the side to which the binder solution was applied was the main surface A side, and the opposite surface of the main surface A side was the main surface B side. do). When the cross section of the base mat was dyed with kayastain and the abundance of the binder was confirmed with an optical microscope, the abundance of the binder on the main surface A side and the main surface B side was the same.
Subsequently, in the same manner as in Example 1, the resin layer coating liquid was applied from the main surface A side and dried to prepare a skin material.

Table 1 shows the non-woven texture of the skin material or base mat of Examples and Comparative Examples, the amount of binder, the amount of print, the amount of resin of the resin layer, the texture of the skin material or base mat, and the thickness of the skin material or base mat. Table 2 shows the position of the resin layer, the thickness of the resin layer, and the distribution of the binder. In addition, the skin materials or base mats of Examples and Comparative Examples were evaluated by the following methods.

(Evaluation of skin material or base mat)
(1) Measurement of 20% modulus strength (i) Three rectangular samples having a width of 30 mm and a length of 200 mm were collected from the skin material or the base mat in the vertical and horizontal directions.
(Ii) The sample is fixed between chucks (distance: 100 mm) of a tensile strength tester (Tencilon UTM-III-100 manufactured by Orientech) and then pulled at a tensile speed of 200 mm / min, and the distance between chucks is 120 mm (distance). The stress value at the time of 20% elongation) was read.
(Iii) The stress was measured for each of the three samples, and the arithmetic mean value was taken as the 20% modulus intensity in the vertical and horizontal directions.

(2) Performance evaluation method / wear resistance evaluation method for skin material or base mat Fix the skin material or base mat to the Gakushin type friction tester (RT-200, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) and use the skin. In the case of a material, it is on the side having a resin layer (Examples 1 to 3, Comparative Example 5 is on the main surface A side, and Comparative Example 4 is on the main surface B side), and in the case of a base mat, it is on the main surface A side or the side having a print. , 20 reciprocations (60 reciprocations / reciprocation) on the skin material by applying a load of 1 kg to a friction element (20 mm x 25 mm) with a hook-and-loop fastener (male type, Kuraray Fastening Co., Ltd., A hook for sewing, 100% polyester). The main surface of the skin material or the base mat was rubbed by letting it (minutes).
Then, the surface condition of the skin material or the base mat after rubbing was observed, and the wear resistance was evaluated according to the following criteria.
(Evaluation criteria for wear resistance)
5: No change 4: Partial fluffing can be confirmed, and the fluffing height is 0 mm or more and 5 mm or less. The color of the base mat can be visually confirmed.
3: Fluffing can be confirmed as a whole, and the fluffing height is 0 mm or more and 5 mm or less. The color of the base mat can be visually confirmed.
2: Fluffing can be confirmed as a whole, and the fluffing height exceeds 5 mm and is 10 mm or less. The color of the base mat can be visually confirmed.
1: Fluffing can be confirmed as a whole, and the fluffing height exceeds 5 mm and is 10 mm or less. The color of the base mat cannot be visually confirmed due to fluffing.
The following molding processability evaluation was performed only for those satisfying 3 or more in the above-mentioned wear resistance evaluation criteria. Among the examples and comparative examples, the skin materials of Examples 1 to 3 and Comparative Example 5 satisfied the evaluation criteria of wear resistance.

-Moldability evaluation method Injection molding was performed using a fully automatic injection molding machine (UBE MAX MB450-IV-I13 1.6.5B, manufactured by Ube Machinery Co., Ltd.).
After fixing the skin material with a pin and setting it in a molding mold (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. , Set the mold spacing to 5 mm and inject polypropylene molten resin (polyolefin resin manufactured by Sumitomo Chemical Co., Ltd., product number: AZ864E4 white) to the side of the skin material that does not have a resin layer, and then inject 30 at a pressure of about 5 tons. Pressing was performed for a second, injection molding was performed, and a molded product was prepared. After cooling the molded product to room temperature, the surface condition 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)
◯: The molded product was not torn at all and the molding processability was good. ×: The molded product was torn and the molding processability was poor.-: Because the evaluation criteria for wear resistance did not meet 3 or more. , Moldability was not evaluated

Based on the above results, a comprehensive evaluation was made on the performance of the skin material.
(Criteria for comprehensive evaluation)
◯: Excellent in both wear resistance and moldability ×: Not excellent in both wear resistance and moldability

The evaluation results are shown in Table 3.

※比較例１～３は、それぞれベースマットの目付・ベースマットの厚さのことを指す。

* Comparative Examples 1 to 3 refer to the basis weight of the base mat and the thickness of the base mat, respectively.

From the above results, the skin material of the example was excellent in both wear resistance and moldability, while the skin material of the comparative example was not excellent in both wear resistance and mold workability.

From the results of comparing the wear resistance evaluations of Example 1 having a resin layer on the entire surface of one of the main surfaces A of the base mat and Comparative Examples 1 and 2 having no resin layer, Example 1 is more wear resistant. It was excellent in sex. Further, from the results of comparing the wear resistance evaluations of Example 2 having a print and having a resin layer on the entire surface A on one main surface A of the base mat and Comparative Example 3 having a print but not having a resin layer. , Example 2 was superior in wear resistance. Further, a comparison between Example 1 having a resin layer on the entire surface of one main surface A of the base mat and a print having a print of the same aspect as that having a resin layer on a part of the main surface A of one of the base mats. From the results of comparing the wear resistance evaluations of Example 3, Example 1 was superior in wear resistance. From these facts, it was found that the skin material having a resin layer on the entire surface A on one main surface A of the base mat has excellent wear resistance.

Then, it was carried out from the result of comparing the wear resistance evaluation of Example 1 having a resin layer on the main surface side having a large amount of binder and Comparative Example 4 having a resin layer on the main surface side having a small amount of binder. Example 1 was superior in wear resistance. From this, it was found that the skin material having a resin layer on the main surface side in which the abundance of the binder is large in the base mat is excellent in wear resistance.

Further, in the first embodiment in which the abundance of the binder on one main surface A side is larger than that on the other main surface B side, and on the one main surface A side and the other main surface B side, the abundance amount of the binder is large. From the results of comparing the moldability evaluations of the same Comparative Example 5, Example 1 was superior in moldability. From this, it was found that the skin material in the base mat, in which the abundance of the binder on one main surface A side is larger than that on the other main surface B side, is excellent in molding processability.

From the above, it was found that the skin material having the constitution of the present invention is a skin material having excellent molding processability and further excellent wear resistance.

The skin material of the present invention is used for, for example, ceiling materials, door trims, dash outers, vehicle interior materials such as pillar garnishes, partitions, wallpaper, etc., and in particular, high wear resistance such as door trims, dash outers, pillar garnishes, etc. Can be suitably used as an interior material for vehicles, which is required to be used.

Claims (1)

In the base mat in which the constituent fibers are bonded to each other by a binder, the abundance of the binder on one main surface A side is larger than that on the other main surface B side, and the abundance of the binder is on the main surface A side. It is a mode in which it continuously decreases from the main surface B side to the main surface B side.
Further, the skin material is characterized in that a pattern by printing is applied on one of the main surfaces A of the base mat, and a resin layer having a thickness of 0.001 mm or more covers the print from above.