JP7220036B2 - Skin material - Google Patents

Description

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

Non-woven fabrics have been conventionally used as a material that constitutes 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 uses a non-woven fabric as a surface material having abrasion resistance. An impregnated interior covering material (Patent Document 1) was proposed.

The skin material according to Patent Document 1 has wear resistance because it is less prone to fluffing due to friction, and is a skin material that can be molded. The abrasion resistance was insufficient for use as a surface material for interior materials.

JP-A-62-257472

Under such circumstances, the applicant of the present invention has proposed a method to provide a surface material having excellent molding processability and further excellent abrasion resistance, and has proposed a method for "a base mat in which constituent fibers are bonded to each other with a binder. , the presence amount of the binder on one main surface A side is larger than that on the other main surface B side, and the entire surface of the one main surface A of the base mat has a resin layer. , skin material.” and has already filed a patent application (Japanese Patent Application No. 2017-171492).

In this skin material, since the amount of 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 the main ones. It is not strongly adhered by the binder to the constituent fibers on the face A side, and is easy to move. Therefore, when this skin material is subjected to a molding process such as injection molding, the main surface B side, which has less binder, easily follows the shape of the mold, and thus has excellent molding processability. 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 people, are strongly bonded to each other by the binder, the surface material has a main surface with excellent wear resistance, such as less fluffing due to friction. be.

Furthermore, this skin material has a resin layer on the entire surface of one main surface A of the base mat that constitutes the skin material. Therefore, since the constituent fibers on the main surface A side of the skin material are protected by the resin layer, the skin material is less likely to become fuzzy due to friction, and thus has excellent abrasion resistance.

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

However, when the skin material is rubbed and fuzz occurs due to friction on the surface of the skin material, the fluff may be gathered and pills may occur, resulting in poor pilling resistance. There was a problem that the appearance quality of the product was impaired. In particular, the occurrence of fluff is likely to occur when the surface material is rubbed with a relatively soft object such as the palm of a person.

The present invention has been made under such circumstances, and provides a skin material that is excellent in moldability and wear resistance, and is resistant to pilling even when the skin material is rubbed. To provide a skin material which is excellent in durability and whose appearance quality is hardly damaged.

The invention according to claim 1 of the present invention is characterized in that "in a base mat constructed by bonding constituent fibers together with a binder, the amount of the binder on one main surface A side is greater than that on the other main surface B side. and having a resin layer on the entire surface of the one main surface A of the base mat, and further comprising an anti-pilling fiber in the base mat. .

The invention according to claim 2 of the present invention is characterized in that "in a base mat constructed by bonding constituent fibers together with a binder, the amount of the binder on one main surface A side is greater than that on the other main surface B side. and having a resin layer over the entire surface of the one main surface A of the base mat, and further comprising 0.06 g/m ² or more of a resin containing silicone in the resin layer. It is a skin material that can be used.

In the skin material according to claim 1 of the present invention, since the base mat constituting the skin material contains anti-pilling fibers, fluffing occurs on the surface of the skin material due to friction, and when the fluff is collected, the base mat The constituent fibers of the mat are easy to break, and pilling is less likely to occur. Therefore, the skin material according to claim 1 of the present invention is a skin material that is excellent in pilling resistance and whose appearance quality is not easily impaired even if it is rubbed.

In the skin material according to claim 2 of the present invention, since the resin layer constituting the skin material contains 0.06 g/m ² or more of a resin containing silicone, the skin material is less prone to fluffing due to friction. Therefore, the skin material according to claim 2 of the present invention is a skin material that is excellent in pilling resistance and whose appearance quality is not easily impaired even if it is rubbed.

The base mat that constitutes the skin material of the present invention refers to a sheet-like fiber structure such as woven fabric, knitted fabric, or non-woven fabric, in which fibers are bonded together with a binder. In particular, when the base mat constituting the present invention is derived from non-woven fabric, it is flexible and easily conforms to the shape of a mold.

The constituent fibers of the base mat in the present invention are not particularly limited, but may be, for example, polyester fibers, nylon fibers, acrylic fibers, vinylon fibers, rayon fibers and the like. Among these, it is preferable to contain polyester fibers, which are excellent in heat resistance, light resistance, antifouling properties, etc., and/or rayon fibers, which are excellent in flame retardancy. The constituent fibers may be single fibers or composite fibers containing two or more types of resin, such as core-sheath type and side-by-side type. For example, it is preferable to use latently crimped fibers (side-by-side type composite fibers, etc.) because the fibers develop crimps by heat, and the use of crimped fibers makes the structure of the base mat dense. . Furthermore, the cross section of the constituent fibers may be circular, elliptical, square, Y-shaped, or other irregular shape. In addition, it may contain fibrillated fibers.

The skin material of the present invention can further contain anti-pilling fibers as constituent fibers of the base mat. When the anti-pilling fibers are contained in the base mat, fluffing occurs in the skin material due to friction, and when the fluff is collected, the constituent fibers of the base mat are likely to break, and pilling is less likely to occur. Therefore, it has excellent pilling resistance, and even if the surface material is rubbed, the appearance quality is not easily impaired. The anti-pilling fiber refers to a normal fiber that has been reduced in strength by forming surface irregularities and voids. A typical anti-pilling fiber is, for example, polyester fiber that is treated with alkali and partially hydrolyzed to form unevenness on the surface and reduce strength.

The lower the single fiber strength of the anti-pilling fiber, the easier it is to obtain the above effects. 2 to 3 cN/dtex is preferable because there is a possibility that workability may deteriorate.
In addition, "single fiber strength" is defined in accordance with JIS L 1015: 2010, 8.7.1 (standard time test), using a constant-speed tension type tensile tester, with a grip interval of 20 mm and a tensile speed of 20 mm / min. means the value below.

The weight ratio of the anti-pilling fibers to the constituent fibers of the base mat is preferably 3% by weight or more, more preferably 5% by weight or more, and more preferably 10% by weight, because the above-mentioned effects are easily obtained when the anti-pilling fibers are contained in a large amount. The above is more preferable. On the other hand, if the weight ratio of the anti-pilling fibers to the constituent fibers of the base mat is too high, the tensile strength of the skin material may decrease, and the molding processability may deteriorate. % or less is more preferable, and 30% by weight or less is even more preferable.

In addition, if anti-pilling fibers are included on one main surface A side of the base mat, which can be the surface of the skin material that comes in contact with people, pills are easily cut off from the skin material, and the appearance quality of the skin material is less likely to deteriorate. It is preferable that one main surface A side of the base mat contains the anti-pilling fiber, because the effect can be obtained. In the present invention, "one main surface A side contains anti-pilling fibers" means that the presence of anti-pilling fibers can be observed by observing the surface of one main surface A side with a microscope or the like. . Further, the "principal surface" refers to the widest surface of the base mat or skin material.

As will be described later, when thermocompression bonding is performed during the production of the base mat, the fibers constituting the base mat must have a dry heat shrinkage rate of 4% or more in order to improve abrasion resistance and to form a clear print. (preferably 4.5-20%, more preferably 5-10%) of polyester drawn short fibers. In addition, this "dry heat shrinkage rate" is in accordance with JIS L1015 (2010) 8.15b) dry heat dimensional change rate, except that the initial load is 1.3 mg and the condition is left at a temperature of 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 dyed fibers containing pigments and/or dyes in constituent resins, or may be fibers colored with pigments and/or dyes. It is preferable to use dope-dyed fibers because the colors of the fibers do not easily fade due to friction.

The fiber length of the constituent fibers of the base mat in the present invention is appropriately adjusted, but the fiber length of the constituent fibers is preferably 38 to 114 mm, more preferably 38 to 76 mm, in order to obtain a base mat with excellent moldability. More preferably, it is still more preferably 38 to 52 mm. This "fiber length" refers to a value measured according to JIS L1015 (2010) 8.4.1c) direct method (method C).

In addition, the fineness of the constituent fibers of the base mat in the present invention is also appropriately adjusted, but if the fibers are too thick, it becomes difficult to obtain a skin material with a smooth surface, and the skin material with an uneven surface is caught by friction. Because it is easy to wear, it tends to become fuzzy and have poor wear resistance. On the other hand, if the fibers are too thin, pilling occurs during the production of the base mat, and 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, 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 laminated fiber layers. The base mat configured by laminating a plurality of fiber layers may be formed by laminating fiber layers having the same fiber composition or laminating fiber layers having different fiber compositions.

The base mat of the present invention is constructed by bonding constituent fibers together with a binder. Examples of a mode in which the constituent fibers are bonded to each other by a binder include a mode in which the binder adheres to the intersections 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 bonds them together. etc.

The type of binder used in the present invention is not particularly limited and may be adjusted as appropriate. Examples include polyurethane-based resins, acrylic-based resins, and polyester-based resins. Among these, acrylic resins (especially self-crosslinking acrylic resins) are preferred because they are moderately softened during molding, have excellent conformability to molds, and are less prone to wrinkles and fine irregularities. Among acrylic resins, acrylic resins having a low glass transition temperature and being soft are preferable because they are easy to stretch and have 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 poor, resulting in poor abrasion resistance. 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 even more 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 line of the baseline in the DTA curve measured by a differential thermal analyzer (DTA) and the tangent line of the steep downward position of the endothermic region due to glass transition.

The base mat constituting the skin material of the present invention is characterized in that the amount of the binder on one main surface A side is larger than that on the other main surface B side. In the present invention, "amount of binder on main surface A side (or main surface B side)" refers to 20% of the thickness of the entire base mat from main surface A (or main surface B) of the base mat. It means the amount of binder present in the area up to the thickness. With this configuration, on the main surface A side, fluffing due to friction is less likely to occur, and the constituent fibers on the main surface B side are more strongly bonded by the binder than on the main surface A side. Since it is easy to move without being worn, it is possible to provide a skin material that is excellent in moldability.
As a method for confirming the amount of the binder, for example, the binder contained in the base mat is colored with a dye such as Kayastain Q (manufactured by Nippon Kayaku Co., Ltd.), and the cross section of the base mat in the thickness direction is measured. It can be confirmed by observing the distribution of the binder in by visual observation or an optical microscope.

The distribution of the amount of the binder contained in the base mat may be adjusted appropriately as long as the amount 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 a mode in which the amount of binder present decreases continuously from the main surface A side to the main surface B side, the amount of binder present inside the base mat changes continuously, and the distribution of the amount of binder present changes. Since the binder is not concentrated in a very small part of the base mat, it is difficult for the binder to separate from the part where the binder is concentrated and other parts, and the wear resistance and moldability are excellent, which is preferable.

As the amount ^of binder contained in the base mat increases, the wear resistance tends to ^be more excellent ^. is more preferred. ^On the other hand, if the amount of the binder contained in the base mat is too large, the surface material tends to be hard and the moldability tends to deteriorate ^. More preferably:

The skin material of the present invention has excellent abrasion resistance, such as less fluffing due to friction on the main surface A side, due to the structure having the resin layer on the entire surface of one main surface A of the base mat. In the present invention, "the entire surface on one main surface A" 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 one main surface A of the base mat. Point.

The resin layer of the present invention can be a layer composed of the following resins. As the type of resin, the same resins as the binder resin described above can be used. For example, polyurethane-based resins, acrylic-based resins, or polyester-based resins can be used. Among these, acrylic resins (in particular, self-crosslinking acrylic resins) are preferable because they are moderately softened during molding, have excellent conformability to molds, and are less prone to wrinkles and fine irregularities. Among acrylic resins, acrylic resins having a low glass transition temperature and being soft are preferable because they are easy to stretch and have 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 poor, resulting in poor abrasion resistance. 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 even more preferably -10°C or higher and 5°C or lower.

Further, if the difference in glass transition temperature between the resin contained in the binder and the resin contained in the resin layer is 10°C or less, there will be a difference in elongation between the base mat portion and the resin layer portion of the surface material during molding. By making it difficult to come out, delamination between the base mat and the resin layer is unlikely to occur, and it is possible to provide a skin material that is more excellent in moldability, which is preferable. The difference in glass transition temperature between the resin contained in the binder and the resin contained in the resin layer is preferably 5°C or less, more preferably 3°C or less, and most preferably the same temperature. In addition, the "resin layer" of the present invention refers to a layer that includes a resin-only region 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 surface material in the thickness direction. The resin layer may be composed only of a resin-only region, or may be composed of a resin-only region and a region in which fibers and resin are mixed.

As the amount of the resin layer of the skin material increases, the wear resistance tends to be more excellent, so the amount of the resin layer is preferably 5 g/m ² or more, more preferably 10 g/m ² or more, and 15 g/m ² or more. is more preferred. Also, if the amount of the resin layer is too large, it tends to impair the texture, tactile feel, and moldability of the surface material, so the amount is preferably 20 g/m ² or less. In addition, the thicker the resin layer of the skin material, the more excellent the wear resistance tends to be. The above is more preferable. Moreover, if the thickness of the resin layer is too thick, it tends to impair the texture, touch, and molding processability of the skin material, so the thickness is preferably 0.02 mm or less. The thickness of the resin layer can be measured by observing a cross section of the skin material in the thickness direction with an electron microscope, and the arithmetic average value of the thickness of the resin layer at 10 randomly selected points is the "resin layer thickness of

The skin material of the present invention may be provided with a printed pattern so as to have more excellent abrasion resistance and to have a superior design property of the skin material. The printed pattern is clear, and the presence of the print improves the wear resistance of the skin material. is preferred. In addition, as a mode of printing, there is a mode in which a print is applied on the main surface of the base mat and a resin layer covers the print from thereon, or a mode in which the print is covered on the main surface of the skin material (main surface where the resin layer is exposed). However, in order to prevent the print from peeling off due to friction, the main surface A of the base mat is printed, and a resin layer covers the print. A preferred embodiment is

The printed pattern of the skin material of the present invention is not particularly limited. It can be a printed pattern with a three-dimensional pattern, as disclosed in US Pat. The number of prints may be one, or two or more.

The structure of the print applied to the skin material of the present invention is appropriately prepared, and the type of print is composed of the same resin as the binder resin described above, such as a resin such as a polyurethane resin, an acrylic resin, or a polyester resin. can do The print may also contain pigments, and the color, type and amount of pigments can be adjusted as appropriate.

As the amount ^of resin contained in ^the print increases, the surface material tends to have more excellent abrasion resistance. Preferably, 9 g/m ² or more is more preferable. Also, if the amount of resin contained in the print is too large, there is a tendency to impair the clarity of the printed pattern and the moldability, so the amount is preferably 20 g/m ² or less.

The binder, resin layer, and print can contain functional materials in addition to the resins described above. For example, since the skin material can be colored by containing a pigment, the design of the skin material is improved. In addition, since the surface material contains a water-repellent resin such as a resin containing silicone or a resin containing fluorine, the surface material is not easily soiled, and abrasion resistance can be improved. Furthermore, various functions can be imparted to the skin material by incorporating inorganic compounds such as flame retardants, antibacterial agents, deodorants, VOC generation inhibitors, and inorganic powders.

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

This silicone is a high-molecular compound having a skeleton formed by siloxane bonds (Si--O--Si bonds) in its main chain, and organic groups may be introduced into its side chains. For example, even if it is a straight silicone in which only a methyl group or a phenyl group is introduced, it may be a modified silicone modified with an amino group, an amide group, a carboxyl group, a fluoroalkyl group, a polyether group, an epoxy group, an aralkyl group, etc. can be used. Moreover, the mode of the silicone is not particularly limited, and may be an oil type, a powder type, or an emulsion type. Among these, the emulsion type silicone is suitable because it can be used together with a binder resin such as an acrylic resin. Examples of suitable emulsion types include dimethylsilicone, amino-modified silicone, epoxy-modified silicone, and hydrophilic polyether-modified silicone. A silicone resin in which silicone itself is self-crosslinked, or a silicone copolymer resin in which acrylic or the like is copolymerized with silicone may be used.

The basis weight and thickness of the skin material of the present invention are appropriately adjusted according to the intended use, required strength, etc. However, if the basis weight of the skin material is too light, the surface material may be torn during molding, resulting in poor moldability. Also ^, if the basis weight is too heavy, a large external force is required for molding, and the molding processability deteriorates ^. , 160 to 250 g/m ² . In addition, if the thickness of the skin material is too thin, the moldability will be poor, and if it is too thick, it will be difficult to handle. More preferably, it is 1.5 to 1.6 mm. The "thickness" of the skin material, the base mat, and the needle-punched nonwoven fabric described in the Examples refers to the length between the two main surfaces under a load of 100 g/5 ^cm2 , and was randomly selected. Means the arithmetic mean value of the thickness at 10 points.

The 20% modulus of the skin material of the present invention is appropriately adjusted depending on the intended use. However, the 20% modulus in the vertical direction tends to be higher than that in the horizontal direction due to the orientation of the fibers. Therefore, the 20% modulus in the machine direction is preferably 90 N/3 cm width or less, more preferably 80 N/3 cm width or less, and even more preferably 70 N/3 cm width or less. In addition, if the 20% modulus is too low, the entanglement of the fibers will be insufficient, and the moldability and abrasion resistance will deteriorate. preferable. In addition, the 20% modulus ratio in the vertical direction and the horizontal direction is 3/2 to 3/1 in the vertical/horizontal direction because it is easy to set in a mold during molding and has excellent molding processability. is preferred. The "longitudinal direction" in the present invention refers to the production direction (machine direction) during the production of nonwoven fabrics, and the "lateral direction" refers to the direction perpendicular to the longitudinal direction, that is, the width direction.

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

First, using the fibers described above, a fiber structure such as a woven fabric, a knitted fabric, or a nonwoven fabric is produced. The method of manufacturing the fiber structure is not particularly limited, but when the fiber structure is a woven or knitted fabric, it can be manufactured by weaving or knitting the above fibers. When the fiber structure is a non-woven fabric, for example, a dry method in which the above-mentioned fibers are subjected to a carding device or an air laying device to entangle the fibers, a wet method in which the fibers are dispersed in a solvent and the papered fibers are entangled in a sheet form. Using a direct spinning method [melt blowing method, spunbond method, electrostatic spinning method, spinning method in which a spinning stock solution and a gas stream are discharged in parallel (for example, the method disclosed in Japanese Patent Laid-Open No. 2009-287138), A method of spinning fibers and collecting them], etc., but it is preferable to have a certain amount of bulk so that molding processability is excellent. It is preferred to employ a dry method of combining.

When manufacturing a skin material containing anti-pilling fibers as constituent fibers of the base mat, for example, the anti-pilling fibers and other constituent fibers can be mixed to form a fiber structure, or A fiber structure can be produced by stacking one or more fiber layers containing anti-pilling fibers and one or more fiber layers not containing anti-pilling fibers and integrating them by, for example, entangling, bonding, or fusing. .

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

It should be noted that, if necessary, after the formation of the fiber structure, the constituent fibers may be heat-pressed before being bonded together with a binder. The term “thermocompression bonding” does not mean that the fibers are melted or plasticized and deformed and adhered. It means that the In particular, when the fiber structure contains polyester stretched short fibers having a dry heat shrinkage of 4% or more as described above, when thermocompression bonding is performed, microscopically, it shrinks slightly and the surface becomes smooth. Since the fibers are less likely to be caught by friction, it has excellent abrasion resistance, and a clear print can be formed when printing.

Such polyester drawn fibers having a dry heat shrinkage of 4% or more can have a dry heat shrinkage of 4% or more, for example, by appropriately adjusting the temperature during heat setting when manufacturing the fiber. . Specifically, after drawing the fiber, the dry heat shrinkage can be made 4% or more by heat setting at a temperature of 70° C. or higher, which is the glass transition temperature of polyester or higher.

Next, a binder resin liquid 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 together with the binder. , to manufacture a base mat in which the amount of binder present on one principal surface A side is greater than that on the other principal surface B side.

A method for producing a base mat in which the amount of binder present on one main surface A side is larger than that on the other main surface B side is appropriately selected, but the foam weight from one main surface side of the fiber structure is 90 to 150 g/ It can be produced by impregnating the foamed binder liquid of L and passing it through two rollers with an adjusted inter-roll gap. At this time, the side to which the binder is applied is the main surface A side. The "foam weight" refers to the weight (g) of the foamed binder per liter of volume. If a foamed binder solution with a too light foam weight is used, the binder tends to be difficult to penetrate into the interior of the fiber structure. There is a possibility that a base mat in which the amount of binder present on one main surface A side is larger than that on the other main surface B side cannot be manufactured. Therefore, it is more preferable to adopt a foam weight of 100 to 130 g/L of the foamed binder liquid applied to the fiber structure.

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

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

When printing is applied to the surface material, printing can be performed on the main surface of the base mat or the surface of the resin layer. The layout of the prints is not particularly limited, but can be carried out by a conventionally known method. For example, a cylinder having openings corresponding to the desired pattern can be provided, the printing fluid can be printed through the cylinder, and the print can be laid down upon drying. Moreover, when arranging two or more kinds of print resins, they can be arranged by repeating the above operation. Because the printed pattern is clear, and because the print covers a portion of one of the main surfaces, making the surface material more abrasion resistant, the print has a relatively large amount of binder. It is preferable to apply to the surface A side. Furthermore, 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 to cover the print with a resin layer thereon.

The skin material of the present invention can be used as a skin material such as a vehicle interior material. The molding method is not particularly limited, but for example, a molding method in which the skin material is put into a mold and pressure and heat are applied together with urethane resin or a glass sheet, or a method in which the skin material is put in a mold and the space between the skin material and the mold is applied. A method such as injection molding, in which resin is poured into the mold and pressure and heat are applied, can be used.

In addition, this skin material can be subjected to 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 are described below, but the present invention is not limited to the following examples.

(Preparation of needle-punched nonwoven fabric A)
100 mass % of dope-dyed polyester fibers (fineness: 2.2 dtex, fiber length: 38 mm, single fiber strength: 4.1 cN/dtex, color: gray) were opened by a carding machine to form a fiber web. Next, a fiber web made of 100 mass% anti-pilling fiber (fineness: 2.2 dtex, fiber length: 51 mm, single fiber strength: 2.5 cN/dtex, color: gray) is added to the fiber web separately from the fiber web. After the stacking, needle punching was performed at a needle density of 400 needles/cm ² from the side opposite to the side on which the fiber web made of anti-pilling fibers was stacked. Thereafter, the fiber web was fed between hot calender rolls at a temperature of 170° C. and a roll interval of 0.4 mm, and the needle-punched fiber web was thermocompressed to produce a needle-punched nonwoven fabric A (basis weight: 180 g/m ² , thickness: 1.5 mm). The ratio of the anti-pilling fibers to the total weight of the needle-punched nonwoven fabric A was 25% by weight.

(Preparation of needle-punched nonwoven fabric B)
Using 100 mass% of dope-dyed polyester fiber (fineness: 2.2 dtex, fiber length: 38 mm, color: gray), after opening with a carding machine to form a fiber web, it is needled from one side at a needle density of 400 / cm ² Punch processing was performed. After that, the needle-punched nonwoven fabric was produced by supplying between hot calender rolls at a temperature of 170° C. and a roll interval of 0.4 mm and thermocompression bonding the needle-punched fiber web (basis weight: 180 g/m ² , thickness height: 1.5 mm).

(Preparation of binder solution)
A binder dispersion was prepared with the following proportions:
(1) Acrylic binder liquid (glass transition temperature: −5° C.): 15 parts by weight (2) Carboxymethyl cellulose thickener: 0.2 parts by weight (3) Surfactant: 0. 2 parts by weight (4) Ammonia water...0.1 parts by weight (5) Water...84.5 parts by weight The resulting dispersion was foamed to prepare a binder solution. The form weight of the binder liquid was 120 g/L.

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

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

(Preparation of resin layer coating solution A)
A resin layer coating liquid A was prepared by blending in the following proportions. In addition, after adding materials other than ammonia water and sufficiently stirring, ammonia water was added dropwise while stirring to adjust the viscosity to 9000 to 11000 cp under the condition of a Brookfield viscometer of 20 rpm, thereby obtaining the resin layer coating solution A. was prepared.
(1) Carboxyvinyl polymer thickener: 0.36 parts by weight (2) Dimethylsiloxane antifoaming agent liquid: 1.6 parts by weight (3) Acrylic binder liquid (glass transition temperature: -5 ° C.) 7.5 parts by weight (4) Acrylic thickener 1 part by weight (5) Ammonia water 1 part by weight (6) Water 88.54 parts by weight

(Preparation of resin layer coating solution B)
A resin layer coating liquid B was prepared by blending in the following proportions. In addition, after adding materials other than ammonia water and sufficiently stirring, ammonia water is added dropwise while stirring to adjust the viscosity to 9000 to 11000 cp under the conditions of 20 rpm of a Brookfield viscometer, thereby obtaining resin layer coating liquid B. was prepared.
(1) Carboxyvinyl polymer thickener: 0.36 parts by weight (2) Dimethylsiloxane antifoaming agent liquid: 1.6 parts by weight (3) Acrylic binder liquid (glass transition temperature: -5 ° C.) 7.5 parts by weight (4) Acrylic thickener 1 part by weight (5) Ammonia water 1 part by weight (6) Water 88.04 parts by weight (7) Modified dimethylsiloxane resin dispersion: 0.5 parts by weight

(Example 1)
The binder liquid A is applied to the main surface of the needle-punched nonwoven fabric A on which the fiber web composed of the anti-pilling fibers is superimposed and permeated, and the needle-punched nonwoven fabric is formed between two rollers with an inter-roll spacing of 0.25 mm. The binder liquid A was permeated through A from the main surface A side to the B side. Then, it was dried with a can dryer at a temperature of 160° C. to prepare a base mat (weight per unit area: 185 g/m ² , thickness: 1.5 mm) (the side on which the binder liquid was applied was the main surface A side, and the main surface A side was is the main surface B side). The main surface A side of the base mat contains anti-pilling fibers, and the cross section of the base mat is stained with Kayastain Q (manufactured by Nippon Kayaku Co., Ltd.), and the amount of binder present is confirmed with an optical microscope. , more binder was present on the main surface A side than on the main surface B side, and the amount of binder continuously decreased from the main surface A side toward the main surface B side.
Next, the printing liquid A is printed on the main surface A side using a cylinder, and the first printing area (line width : 0.3 mm, line spacing: 1 mm), printing liquid B is printed using another cylinder, and is linearly obliquely downward to the right at an angle of -30° from the width direction of the base mat. A second elongated printed area (line width: 0.3 mm, line spacing: 1 mm) was formed. After that, it was dried with a dryer at a temperature of 160°C. The coating weight of print A was 4 g/m ² and the coating weight of print B was 5 g/m ² .
Subsequently, the resin layer coating solution A was applied uniformly over the main surface A of the base mat to form a resin layer. After applying the resin layer coating liquid A, the skin material was prepared by applying it to a dryer at a temperature of 160° C. and drying it.

(Example 2)
A needle-punched nonwoven fabric B was used instead of the needle-punched nonwoven fabric A, and one main surface of the needle-punched nonwoven fabric A was coated with the foamed binder liquid A and permeated to prepare a base mat, and a resin layer was applied. A skin material was prepared in the same manner as in Example 1, except that the resin layer coating liquid B was used instead of the liquid A.

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

(Comparative example 1)
A needle-punched nonwoven fabric B was used instead of the needle-punched nonwoven fabric A, and the binder liquid A foamed was applied to one main surface of the needle-punched nonwoven fabric A and permeated to prepare a base mat. A skin material was prepared in the same manner as in Example 1.

Table 1 shows the needle-punched non-woven fabric, the coating solution for the resin layer, and the amount of silicone in the resin layer of the skin materials of Examples and Comparative Examples. 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) Rectangular samples of width 30 mm and length 200 mm were taken from the skin material or base mat, three each in the vertical and horizontal directions.
(ii) After fixing the sample between chucks (distance: 100 mm) of a tensile strength tester (manufactured by Orientec, Tensilon UTM-III-100), it is pulled at a tensile speed of 200 mm / min, and the distance between chucks is 120 mm ( 20% elongation) was read.
(iii) The stress was measured for each of the three samples, and the arithmetic average value was taken as the 20% modulus strength in the vertical and horizontal directions.

(2) Skin material performance evaluation method / abrasion resistance evaluation method Gakushin type friction tester (RT-200, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) A skin material cut into 3 cm × 25 cm was fixed, and the resin On the layer side, a 1 kg load is applied to a friction element (2 cm x 2.5 cm) with a hook-and-loop fastener (male type, Kuraray Fastening Co., Ltd., A hook for sewing, 100% polyester) on the skin material. 20 reciprocations (60 reciprocations/minute) in a region A of 3 cm x 10 cm were rubbed on the main surface of the skin material.
After that, the surface condition of a region B of 3 cm×5 cm excluding 2.5 cm on each long side of the region A of the skin material after rubbing was observed, and the abrasion resistance was evaluated according to the following criteria.
(Abrasion resistance evaluation criteria)
5: No change 4: Fluffing can be partially confirmed, and the height of fluffing 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 on the whole, and the height of fluffing 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 on the whole, and the height of fluffing is more than 5 mm and 10 mm or less. The color of the base mat can be visually confirmed.
1: Fluffing can be confirmed on the whole, and the height of fluffing is more than 5 mm and 10 mm or less. The color of the base mat cannot be visually confirmed due to fluffing.

・ Pilling resistance evaluation method A skin material cut into 3 cm × 25 cm was fixed in the same equipment as used in abrasion resistance evaluation, and EPDM rubber with a Shore C hardness of 40 was placed on the main surface of the side having a resin layer. A rubbing element (2 cm x 2.5 cm) was applied with a load of 1 kg, and a 3 cm x 10 cm area A on the skin material or base mat was rubbed by 90 reciprocations (60 reciprocations/minute) to rub the main surface of the skin material. .
After that, the surface condition of a 3 cm×5 cm area B excluding 2.5 cm on each long side of the area A of the skin material after rubbing was observed, and the pilling resistance was evaluated according to the following criteria.
(Pilling resistance evaluation criteria)
5: There is no pill on the surface of the skin material or base mat, or less than 1 pill with a long side of less than 1 mm per 1 cm ² .
4: 1 or more but less than 4 pills with a long side of less than 1 mm per 1 cm ² .
3: 4 or more but less than 8 pills with a long side of less than 1 mm per 1 cm ² .
2: 8 or more but less than 12 pills with a long side of less than 1 mm per 1 cm ² .
1: There are 12 or more pills with a long side of less than 1 mm per 1 cm ² or pills with a long side of 1 mm or more.
In this evaluation method, the reason for using EPDM rubber with a Shore C hardness of 40 is to evaluate pilling resistance when rubbed against a relatively soft object such as a human palm, which is prone to pilling. This is because

· Method for evaluating molding processability 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 the skin material is fixed with pins and set in a mold (length: 19 cm, width: 31 cm) with a depression (length: 4 cm, width: 8 cm, depth: 1 cm) near the center of the mold. , setting the mold interval to 5 mm, injecting molten polypropylene resin to the side of the skin material that does not have a resin layer, and then pressing for 30 seconds at a pressure of about 5 tons to perform injection molding to create a molded product. bottom. After cooling the molded article to room temperature, the surface state of the side of the molded article 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 broken at all, and the molding processability was good. ×: The molded product was broken, and the molding processability was poor.

Based on the above results, a comprehensive evaluation was made of the performance of the skin material.
(Criteria for Comprehensive Evaluation)
◯: excellent in wear resistance, pilling resistance and moldability ×: poor in wear resistance, pilling resistance and moldability Table 2 shows the evaluation results.

Examples 1 and 3, in which the base mat contains anti-pilling fibers, and Comparative Example 1, in which the base mat does not contain anti-pilling fibers, were compared in evaluation of pilling resistance. Excellent pilling resistance. From this, it can be seen that in the base mat in which constituent fibers are bonded to each other with 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 in the base mat , The skin material having a resin layer on the entire surface of the one main surface A and containing anti-pilling fibers in the base mat has excellent pilling resistance compared to other skin materials, and the skin material is rubbed. It was found that the appearance quality is not easily impaired even if the

Moreover, Examples 2 and 3, in which the resin layer contains 0.06 g/m ² or more of the resin containing silicone, and Comparative Example 1, in which the resin layer contains less than 0.06 g/m ² of the resin containing silicone. From the result of comparing the pilling resistance evaluation, Examples 2 and 3 were superior in pilling resistance. From this, it can be seen that in the base mat in which constituent fibers are bonded to each other with 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 in the base mat , The skin material having a resin layer over the entire surface of the one main surface A and containing 0.06 g/m ² of silicone in the resin layer has excellent pilling resistance compared to other skin materials. It was found that even if the material is rubbed, the appearance quality is not easily impaired.

In addition, Example 1 in which the base mat contains anti-pilling fibers, or Example 2 in which the resin layer contains 0.06 g/m ² or more of a resin containing silicone, and Example 2 in which the base mat contains anti-pilling fibers and the resin layer contains 0.06 g/m ² or more of a resin containing silicone. was found to be superior to

The skin material of the present invention is used, for example, for vehicle interior materials such as ceiling materials, door trims, dash outers, and pillar garnishes, partitions, wallpaper, and the like. It can be suitably used as a vehicle interior material that requires anti-pilling properties.

Claims (1)

In a base mat formed by bonding constituent fibers together with 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 having a resin layer over the entire surface of the one main surface A of the base mat,
Further, the base mat contains anti-pilling fibers,
The fiber length of the constituent fibers of the base mat containing anti-pilling fibers is 38 to 114 mm,
The single fiber strength of the anti-pilling fibers contained in the base mat is 2 to 3 cN / dtex,
The weight ratio of the anti-pilling fibers to the constituent fibers of the base mat is 3% by weight or more and 50% by weight or less,
A skin material characterized in that the fineness of constituent fibers of the base mat is 0.2 to 6 dtex .