JP2021194889A - Skin material - Google Patents

Abstract

To provide a skin material which prevents keratin contained in hands from being attached to a skin material even when being rubbed by the hands, can sufficiently remove the keratin attached to the skin material when rubbing the skin material, and is excellent in contamination resistance and appearance quality.SOLUTION: In a skin material, a silicone resin amount in a resin layer constituting the skin material is more than 2.0 g/m2 and 7.2 g/m2 or less, accordingly keratin contained in hands is prevented from being attached to the resin layer of the skin material even when being rubbed by the hands, the keratin attached to the skin material can be sufficiently removed when rubbing the skin material, and appearance quality is excellent.SELECTED DRAWING: None

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.

The applicant of the present application has stated that, as a skin material having excellent wear resistance, "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 the other main surface. The base mat has a resin layer on the entire surface of one of the main surfaces A in the base mat, and the resin layer contains 0.06 g / m ² or more of a resin containing silicone. The skin material is characterized by the above. ”(Patent Document 1). In addition, Patent Document 1 discloses that the resin containing silicone contained in the resin layer ^{is preferably 2 g / m 2 or less.}

Japanese Unexamined Patent Publication No. 2020-037421 (Claim 2, [0041], etc.)

In the base mat in which the constituent fibers are bonded to each other by a binder, the amount of the binder on one main surface A side is larger than that on the other main surface B side, and the skin material is one main surface. It was a skin material with excellent wear resistance because it had a resin layer containing silicone resin on the entire surface of A. When the skin material is rubbed by hand, the keratin contained in the hand adheres to the skin material, and even if you try to scrape off the adhered keratin, it is difficult to remove the keratin attached to the skin material. It was easily soiled and inferior in appearance quality.

The present invention has been made under such circumstances, and even if it is rubbed by hand, the keratin contained in the hand does not easily adhere to the epidermis material, and when the epidermis material is rubbed, the keratin attached to the epidermis material can be sufficiently removed. The purpose is to provide a skin material having excellent stain resistance and appearance quality.

The invention according to claim 1 states that "in a base mat in which constituent fibers are bonded to each other by 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. In addition, the base mat has a resin layer on the entire surface of one of the main surfaces A, and the amount of silicone resin in the resin layer is ^{more than 2.0 g / m 2} and 7.2 g / m ² or less. Skin material. "

The invention according to claim 2 is "the skin material according to claim 1, wherein the proportion of the silicone resin in the resin layer is 19.1 to 3.3 mass%."

The skin material according to claim 1 of the present invention is rubbed by hand because the amount of silicone resin in the resin layer constituting the skin material is ^{more than 2.0 g / m 2} and 7.2 g / m ^{2 or less.} However, it was found that the keratin contained in the hands does not easily adhere to the resin layer of the epidermis material, and that the keratin attached to the resin layer of the epidermis material can be sufficiently removed by rubbing the epidermis material, and that the epidermis material having excellent appearance quality can be provided. rice field. This is because the resin layer constituting the skin material contains a large amount of silicone resin, so that the coefficient of friction on the surface of the resin layer of the skin material is low, and the amount of silicone resin contained in the resin layer constituting the skin material is high. It is considered that the resin layer is less likely to become sticky if the amount is not too large.

In the epidermis material according to claim 2 of the present invention, since the ratio of the silicone resin in the resin layer constituting the epidermis material is 19.1 to 3.3 mass%, the keratin contained in the hand is the epidermis even if it is rubbed by hand. It is difficult to adhere to the resin layer of the material, and when the skin material is rubbed, the keratin adhering to the resin layer of the skin material can be sufficiently removed, and the skin material having excellent appearance quality can be provided. This is because the ratio of the silicone resin is 19.1 mass% or more, the friction coefficient of the surface of the resin layer of the skin material is low, and the ratio of the silicone resin is 33.3 mass% or less, so that the resin layer is sticky. It is thought that this is because it is unlikely to occur.

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.

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 color of the fiber is not easily discolored by rubbing, it is preferable to use the dyed fiber.

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 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 L 1015 (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 even more preferably 1 to 3 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.

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 bonded to each other by the binder include a mode in which the binder adheres to the intersection of the constituent fibers and the binder bonds the constituent fibers to each other, 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, an acrylic resin (particularly, a self-crosslinking acrylic resin) is preferable because it is moderately softened at the time of molding, has excellent followability to the mold, and is less likely to cause wrinkles and fine irregularities. Among the 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 of 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 the binder contained in the base mat is too large, the skin material becomes hard and tends to moldability is deteriorated, preferably at 30 g / m ² or less, 20 g / m ² 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 a silicone resin described later and the following resin. Examples of the type of resin other than the silicone resin include resins similar to 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 the 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 of the acrylic resin 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 completely covers one main surface A of the base mat. Further, the "resin layer" 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 configured to include a region infiltrating the fiber layer and a mixture of fibers and resin in addition to the resin-only region. The resin layer may be a single layer or a layer composed of two or more layers. When the resin layer is composed of two or more layers, the resin composition may be the same or different resin compositions.

In the skin material of the present invention, the amount of silicone resin in the resin layer is more than ^{2.0 g / m 2.} As a result, the wear resistance of the skin material is excellent, and even if the skin material is rubbed by hand, the keratin contained in the hand does not easily adhere to the skin material, and when the skin material is rubbed, the keratin attached to the skin material is sufficiently removed. We have found that it is possible to provide a skin material with excellent appearance quality. It is considered that this is because the friction coefficient of the surface of the skin material becomes low because the skin material contains a large amount of silicone resin. Since the above-described effect is further exerted, the silicone resin amount in the resin layer is more preferably 2.3 g / ^{m 2} or more, 2.5 g / ^{m 2} or more is more preferable. On the other hand, if the amount of the silicone resin in the resin layer is too large, the silicone resin has poor compatibility with other resins, and the bonds of the constituent resins of the resin layer are weakened, which may result in a decrease in wear resistance. In addition, since the silicone resin causes stickiness in the resin layer and may make it difficult to remove the keratin adhering to the skin material, the silicone resin contained in the resin layer is 7.2 g / m ² or less, which is 6. It is more preferably 0 g / m ^{2 or less.}

This silicone resin is a polymer compound having a skeleton with a siloxane bond (Si—O—Si bond) in the main chain, and an organic group may be introduced in the side chain. For example, it may be 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 or the like. Can be used. Further, the embodiment of the silicone is not particularly limited, and may be an oil type, a powder type, or an emulsion type. Among these, emulsion type silicone is suitable because it can be used in combination with a binder resin such as an acrylic resin. Examples of this suitable emulsion type include dimethyl silicone, amino-modified silicone, epoxy-modified silicone, hydrophilic polyether-modified silicone and the like. It should be noted that the silicone resin itself may be a self-crosslinking silicone resin, or a silicone copolymer resin obtained by copolymerizing acrylic or the like with silicone.

In addition, when the ratio of silicone resin in the resin layer is high, even if the skin material is rubbed by hand, the keratin contained in the hand does not easily adhere to the resin layer of the skin material, and when the skin material is rubbed, the resin layer of the skin material is hard to adhere. On the other hand, if the ratio is too high, the resin layer may become sticky and it may be difficult to remove the keratin attached to the skin material. Since the strength of the resin layer may be inferior, 19.1 to 3.3 mass% is preferable, 19.1 to 30.0 mass% is more preferable, and 19.1 to 25.0 mass% is further preferable.

As the amount of the resin layer in the skin material tends to be more excellent in wear resistance, the amount of the resin layer ^{is preferably 5.0 g / m 2} or more, more preferably 10.0 g / m ² or more, and 15 More preferably, it is 0.0 g / m ^{2 or more.} 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 ^{20.0 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 0.005 mm or more, more preferably 0.008 mm or more, and more preferably 0.010 mm. The above is more preferable. Further, if the thickness of the resin layer is too thick, the texture, tactile sensation, and molding processability of the skin material tend to be impaired, so that the thickness is preferably 0.020 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 of 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. preferable. Further, 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 3.0 g / m 2} or more, preferably 5.0 g / m. ² or more is more preferable, and 9.0 g / m ² or more is further 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 molding processability tend to be impaired, so that the amount is preferably ^{20 g / m 2 or less.}

The binder, resin layer, and print can contain functional materials in addition to the above resins. 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 molding processability. and the basis weight is too great force is required for forming heavy, since the moldability is deteriorated and a basis weight is preferably from 140~260g / ^{m 2,} more preferably from 150 to 250 g / ^{m 2} , 160-250 g / m ² , more preferably. 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 1.0 to 2.0 mm, preferably 1.2 to 1.9 mm. It is more preferably 1.4 to 1.8 mm, and even more preferably 1.4 to 1.8 mm. Incidentally, the skin material and the base mat of the present invention, "thickness" of the needle-punched nonwoven fabric according to Example refers to the value of the length between the two main surfaces of at 100 g / 5 cm ² load, randomly chosen 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 vertical 20% modulus is preferably 145 N / 5 cm width or less, more preferably 130 N / 5 cm width or less, and even more preferably 120 N / 5 cm width or less. If the 20% modulus is too low, the fibers are not sufficiently entangled with each other, and the molding processability and wear resistance are deteriorated. Therefore, the lower limit of the 20% modulus in the vertical direction is 80 N / 5 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, the 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 the fiber and collecting it], but it is preferable that it has a certain amount of bulk so that it has excellent molding processability. 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. 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.

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, it is a dispersion liquid / solution of the resin constituting the resin layer on the entire surface on the main surface A of the base mat, and the resin layer coating liquid containing the silicone resin is applied to increase the amount of the silicone resin to more than ^{2.0 g / m 2.} A skin material is manufactured by forming a resin layer containing the resin. 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 mold 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. Then, the fibers were 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: 195 g / m ² , thickness). 1. 1.7 mm).
(Preparation of binder liquid)
A binder dispersion was prepared in the following proportions.
(1) Acrylic binder (glass transition temperature: -5 ° C) ... 9 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 ... 90.5 parts by weight The obtained dispersion was whipped to prepare a binder liquid. The foam weight of the binder liquid was 120 g / L.
(Preparation of printing liquid A)
The printing liquid A was prepared by blending in the following ratios.
(1) Carboxymethyl cellulose-based thickener: 0.36 parts by weight (2) Defoaming agent: 0.4 parts by weight (3) Acrylic binder (glass transition temperature: 5 ° C.): 10 parts by weight Part (4) Acrylic thickener ... 0.28 parts by weight (5) Ammonia water ... 1 part by weight (6) Water ... 87.72 parts by weight (7) Black pigment ... 0. 24 parts by weight (preparation of printing liquid B)
The printing liquid B was prepared by blending in the following ratios.
(1) Carboxymethyl cellulose-based thickener ... 0.36 parts by weight (2) Defoaming agent ... 0.4 parts by weight (3) Acrylic binder (glass transition temperature: -5 ° C) ... 18 Parts by weight (4) Acrylic thickener ... 0.28 parts by weight (5) Ammonia water ... 1 part by weight (6) Water ... 79.78 parts by weight (7) Black pigment ... 0 .18 parts by weight (preparation of resin layer coating liquid A)
A resin layer coating liquid A was prepared, which was blended in the following proportions.
(1) Carboxymethyl cellulose-based thickener ... 0.36 parts by weight (2) Defoaming agent ... 0.4 parts by weight (3) Acrylic binder (glass transition temperature: -5 ° C) ... 21 Parts by weight (4) Acrylic thickener: 1 part by weight (5) Ammonia water: 1 part by weight (6) Water: 76.24 parts by weight (preparation of resin layer coating liquid B)
A resin layer coating liquid B was prepared, which was blended in the following proportions.
(1) Carboxymethyl cellulose-based thickener ... 0.36 parts by weight (2) Defoaming agent ... 0.4 parts by weight (3) Acrylic binder (glass transition temperature: -5 ° C) ... 21 Parts by weight (4) Acrylic thickener: 1 part by weight (5) Ammonia water: 1 part by weight (6) Water: 71.24 parts by weight (7) Silicone resin: 5 parts by weight (Preparation of resin layer coating liquid C)
A resin layer coating liquid C blended in the following proportions was prepared.
(1) Carboxymethyl cellulose-based thickener ... 0.36 parts by weight (2) Defoaming agent ... 0.4 parts by weight (3) Acrylic binder (glass transition temperature: -5 ° C) ... 21 Parts by weight (4) Acrylic thickener: 1 part by weight (5) Ammonia water: 1 part by weight (6) Water: 69.24 parts by weight (7) Silicone resin: 7 parts by weight (Preparation of resin layer coating liquid D)
A resin layer coating liquid D was prepared, which was blended in the following proportions.
(1) Carboxymethyl cellulose-based thickener ... 0.36 parts by weight (2) Defoaming agent ... 0.4 parts by weight (3) Acrylic binder (glass transition temperature: -5 ° C) ... 21 Parts by weight (4) Acrylic thickener: 1 part by weight (5) Ammonia water: 1 part by weight (6) Water: 66.24 parts by weight (7) Silicone resin: 10 parts by weight (Preparation of resin layer coating liquid E)
A resin layer coating liquid E was prepared, which was blended in the following proportions.
(1) Carboxymethyl cellulose-based thickener ... 0.36 parts by weight (2) Defoaming agent ... 0.4 parts by weight (3) Acrylic binder (glass transition temperature: -5 ° C) ... 21 By weight (4) Acrylic thickener: 1 part by weight (5) Ammonia water: 1 part by weight (6) Water: 61.24 parts by weight (7) Silicone resin: 15 parts by weight (Preparation of resin layer coating liquid F)
A resin layer coating liquid F containing the following proportions was prepared.
(1) Carboxymethyl cellulose-based thickener ... 0.36 parts by weight (2) Defoamer ... 0.4 parts by weight (3) Acrylic binder (glass transition temperature: -5 ° C) ... 21 By weight (4) Acrylic thickener: 1 part by weight (5) Ammonia water: 1 part by weight (6) Water: 56.24 parts by weight (7) Silicone resin: 20 parts by weight

(Comparative Example 1)
The foamed binder liquid A was applied to the needle punched non-woven fabric, and the binder liquid A was permeated from the main surface A side to the B side by passing the needle punched non-woven fabric between two rollers having a roll spacing of 0.3 mm while infiltrating. .. Then, it was dried with a can dryer at a temperature of 160 ° C., and a base mat (weight: 200 g / m ² , thickness: 1.7 mm) was prepared. (The side to which the binder liquid is applied is the main surface A side, and the opposite surface of the main surface A side 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 decorate the main surface A side of the base mat, the printing liquid A is printed on the main surface A side using a cylinder, and the printing liquid A is printed diagonally upward to the right at an angle of 30 ° from the width direction of the base mat. A first print area (line width: 0.3 mm, line spacing: 1 mm) extending linearly toward is formed, and the printing liquid B is printed using another cylinder, and the angle from the width direction of the base mat is obtained. A second print area (line width: 0.3 mm, line spacing: 1 mm) extending linearly in the downward direction diagonally to the right was formed at −30 °. Then, it was dried by a dryer having a temperature of 160 ° C. The print amount of print A was 3.0 g / m ² , and the print amount of print B was 6.0 g / m ² .
Subsequently, in order to form a resin layer on the main surface A side of the base mat, the resin layer coating liquid A was uniformly applied to the entire surface of the main surface A. After applying the resin layer coating liquid A, the skin material (weight: 220.0 g / m ² , thickness: 1.6 mm, resin layer coating liquid) is applied by subjecting it to a dryer device having a temperature of 160 ° C. and drying it. Amount: 11.0 g / m ² , resin layer thickness: 0.009 mm) was prepared.

(Comparative Example 2)
^{Skin material (weight: 221.9 g / m 2} , thickness: 1.6 mm, resin) in the same manner as in Comparative Example 1 except that the resin layer coating liquid B was used instead of the resin layer coating liquid A. The coating amount of the layer coating liquid ^{: 12.9 g / m 2} , the thickness of the resin layer: 0.010 mm) was prepared.

(Example 1)
^{Skin material (weight: 222.6 g / m 2} , thickness: 1.6 mm, resin) in the same manner as in Comparative Example 1 except that the resin layer coating liquid C was used instead of the resin layer coating liquid A. The coating amount of the layer coating liquid: 13.6 g / m ² , the thickness of the resin layer: 0.011 mm) was prepared.

(Example 2)
^{Skin material (weight: 223.7 g / m 2} , thickness: 1.6 mm, resin) in the same manner as in Comparative Example 1 except that the resin layer coating liquid D was used instead of the resin layer coating liquid A. The coating amount of the layer coating liquid ^{: 14.7 g / m 2} , the thickness of the resin layer: 0.012 mm) was prepared.

(Example 3)
^{Skin material (weight: 225.5 g / m 2} , thickness: 1.6 mm, resin) in the same manner as in Comparative Example 1 except that the resin layer coating liquid E was used instead of the resin layer coating liquid A. The coating amount of the layer coating liquid: 16.5 g / m ² , the thickness of the resin layer: 0.014 mm) was prepared.

(Comparative Example 3)
^{Skin material (weight: 227.3 g / m 2} , thickness: 1.6 mm, resin) in the same manner as in Comparative Example 1 except that the resin layer coating liquid F was used instead of the resin layer coating liquid A. The coating amount of the layer coating liquid ^{: 18.3 g / m 2} , the thickness of the resin layer: 0.017 mm) was prepared.

The following table shows the resin layer coating liquid of the resin layer of the skin material of the examples and comparative examples, the amount of silicone resin in the resin layer (resin layer silicone resin amount), and the ratio of silicone resin in the resin layer (resin layer silicone resin ratio). Shown in 1.

In addition, 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, three rectangular samples having a width of 30 mm and a length of 200 mm were collected in the vertical and horizontal directions.
(Ii) The sample is fixed between chucks (distance: 100 mm) of a tensile strength tester (Tensilon UTM-III-100 manufactured by Orientec) 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 and wear resistance evaluation method of the skin material The skin material is fixed to the Gakushin type friction tester (RT-200, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.), and on the side having the resin layer, A load of 1 kg is applied to a friction element (20 mm x 25 mm) with a hook-and-loop fastener (male type, Clarefasning Co., Ltd., A hook for sewing, 100% polyester) to cover a 20 mm x 100 mm area A on the skin material. The main surface of the skin material was rubbed by making 20 reciprocations (60 reciprocations / minute).
Then, the surface condition of the 20 mm × 50 mm region B excluding 25 mm at both ends of the long side of the skin material region A 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. 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. The color of the base mat cannot be visually confirmed due to fluffing.

・ Stain resistance evaluation method A chalk with a width of 2 mm, which is obtained by fixing the skin material to a Gakushin type friction tester (RT-200, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) and cutting it to the side of the skin material having the resin layer. By contacting the width part of the chalk (personal mark chalk, Echizenya Tasaki Co., Ltd., yellow) and applying a load of 200 g to make one reciprocation (60 reciprocations / minute) of a straight line 100 mm on the epidermis material, the epidermis material The main surface was rubbed with chaco chalk and a line with a width of 2 mm was drawn.
After that, using a horsehair dust brush, the tip of the brush touches the skin material lightly, and the skin material is rubbed 50 times from one direction perpendicular to the line with the chaco choke. The chaco-chalk powder adhering to the surface was removed, and the state of the chaco-chalk powder in the portion rubbed with the horsehair dust brush of the skin material was evaluated according to the following evaluation criteria.
(Evaluation criteria for stain resistance)
5: Chalk chalk powder is completely removed from the skin material.
4: Chaco-chalk powder remains on the skin material, but the lines due to the chaco-chalk cannot be visually identified at the rubbed part.
3: The chaco-chalk powder remains on the skin material, and the lines due to the chaco-chalk bleed at the rubbed part, but it is not clear, but it can be visually identified. 2: The chaco-chalk powder remains on the skin material, and the rubbed part The line due to chaco chalk is not bleeding and is clear, but the color of the line is light.
1: Chalk chalk powder remains on the skin material, and the color of the line due to the chaco chalk is not lightened at all at the rubbed part.

-Molding processability 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 molding processability)
◯: 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.

Based on the above results, a comprehensive evaluation was made on the performance of the skin material.
(Criteria for comprehensive evaluation)
〇: Abrasion resistance, stain resistance, and molding processability were all excellent. ×: Abrasion resistance, stain resistance, and molding processability were not excellent. Table 2 shows the evaluation results.

The amount of silicone resin in the resin layer is ^{more than 2.0 g / m 2} and 7.2 g / m ² or less, and the amount of silicone resin in the resin layer is 2.0 g / m ^2. From the results of the stain resistance evaluation of the skin materials of Comparative Examples 1 and 2 and the skin material of ^{Comparative Example 3 in which the amount of silicone resin in the resin layer is more than 7.2 g / m 2, the results of Examples 1 to 2 are as follows.} It was found that the skin material is easier to remove even if it gets dirty, has excellent stain resistance, and has excellent appearance quality. Further, from the results of the wear resistance evaluation of the skin material of Comparative Example 3 in which the amount of silicone resin in the resin layer is ^{more than 7.2 g / m 2,} and the results of the wear resistance evaluation of Examples, if the amount of silicone resin in the resin layer is too large, the wear resistance is high. It was found that the sex was reduced. It is considered that this is because the silicone resin weakened the bond between the constituent resins of the resin layer. Further, in the skin materials of Examples 1 to 3 having excellent wear resistance and stain resistance, the ratio of the silicone resin in the resin layer was 19.1 to 3.3 mass%.

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. In addition, it can be suitably used as an interior material for vehicles in a portion where keratin is likely to adhere to the surface because it often comes into contact with the hand.

Claims (2)

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.
In addition, the base mat has a resin layer on the entire surface of one of the main surfaces A.
Further, the skin material in which the amount of silicone resin in the resin layer is ^{more than 2.0 g / m 2} and 7.2 g / m ^{2 or less.} The skin material according to claim 1, wherein the ratio of the silicone resin in the resin layer is 19.1 to 3.3 mass%.