JP7089866B2 - Sheet-like material having an opening and its manufacturing method - Google Patents

Description

An embodiment of the present invention relates to a sheet-like material having an opening and a method for producing the same. More specifically, one embodiment relates to a sheet-like material having an opening and a method for manufacturing the same, which can obtain sufficient wear resistance even when used for vehicle interior materials.

Conventionally, since the surface of synthetic leather and natural leather is covered with a resin layer, it gets stuffy due to sweating when seated for a long time, especially when used for vehicle interior materials, especially for seating surfaces. There is a problem that stickiness occurs.

In general, an attempt is made to solve this problem by forming an opening in leather by drilling (for example, Patent Document 1) and improving the moisture permeability of leather to solve stuffiness and stickiness. .. In synthetic leather and natural leather used for vehicle interior materials, the moisture permeability required to solve stuffiness and stickiness is considered to be 2000 g / m ² · h. However, synthetic leather and natural leather that satisfy this problem do not have sufficient wear resistance for use as vehicle interior materials, and there is a problem that stuffiness and stickiness cannot be eliminated and strength cannot be achieved at the same time. In addition, there is also a problem that burrs are generated around the opening due to the drilling process and the surface feel is poor.

In order to solve such a problem, in Patent Documents 2 and 3, a continuous porous polyurethane layer is formed on one side of a fibrous substrate, an open hole is formed on the surface, and then the closed hole is not completely closed. Disclosed is a silver-like artificial leather having improved surface smoothness, antifouling property, and abrasion resistance by covering the hole wall of the open hole with a finished polyurethane film, and a method for manufacturing the same. However, the manufacturing methods disclosed in Patent Documents 2 and 3 have a problem that a process load is applied because the drilling process and the formation of the finished polyurethane film are performed separately. Further, the formation of the finished polyurethane film covering the hole wall of the open hole is controlled by adjusting the viscosity of the polyurethane mixture and adjusting the coating amount by using a gravure roll, and there is a problem that the reproducibility is poor.

Japanese Unexamined Patent Publication No. 11-209800 Japanese Unexamined Patent Publication No. 8-0417886 Japanese Patent No. 3117996

An object of the present invention is to provide a sheet-like material having an opening, for example, a sheet-like material having sufficient wear resistance for use as a vehicle interior material, and a method for producing the same.

The sheet-like material according to the embodiment of the present invention includes a fibrous base material and an inner layer and an outermost layer made of a polyurethane resin laminated on one side of the fibrous base material, and has a plurality of openings on the surface. It is a sheet-like material. The outermost layer is non-porous. The thermal melting temperature of the outermost layer is higher than the softening temperature of the inner layer. The opening includes an opening peripheral edge in which the outermost layer is inclined toward the center of the opening.

Further, the method for producing a sheet-like material according to an embodiment of the present invention is a sheet-like material including a fibrous base material and an inner layer and an outermost layer made of a polyurethane resin laminated on one side of the fibrous base material. , A method for manufacturing a sheet-like material having openings, which forms a plurality of openings by needle embossing. The outermost layer is non-porous, the heat melting temperature of the outermost layer is higher than the needle embossing temperature, and the needle embossing temperature is higher than the softening temperature of the inner layer.

According to the present embodiment, it is possible to provide a sheet-like material having an opening, for example, a sheet-like material having sufficient wear resistance for use as a vehicle interior material, and a method for manufacturing the same.

It is sectional drawing of the sheet-like thing which concerns on one Embodiment. It is sectional drawing of the sheet-like thing which concerns on other embodiment.

The sheet-like material according to the present embodiment is a sheet-like material in which a polyurethane resin layer composed of two layers, an outermost layer and an inner layer, is laminated on one side of a fibrous base material, and has a plurality of openings on the surface.

FIG. 1 is a model showing the cross-sectional structure of the sheet-shaped object 1 according to the embodiment. In the sheet-like material 1, an inner layer 3 and an outermost layer 4 are provided on the surface of the fibrous base material 2, and a plurality of surfaces (front surface) 11 of the sheet-like material 1 for improving air permeability are provided. An opening 5 is provided. The opening 5 is provided so as to penetrate the inner layer 3 and the outermost layer 4.

FIG. 2 schematically shows the cross-sectional structure of the sheet-shaped object 1A according to another embodiment. In the sheet-like material 1A, the inner layer 3 is composed of a skin layer 31 and an adhesive layer 32, and the skin layer 31 and the outermost layer 4 are laminated on the fibrous base material 2 via the adhesive layer 32 in this order. Further, in this example, the opening 5 is provided so as to penetrate the outermost layer 4 and the inner layer 3 such as the skin layer 31 and the adhesive layer 32.

In the present embodiment, as the fibrous base material, for example, fabrics such as woven fabrics, knitted fabrics, and non-woven fabrics, and natural leather (including floor leather) can be used. Further, the cloth is coated or impregnated with a known solvent-free, solvent-based or water-based polymer compound, for example, a liquid containing a polyurethane resin or a copolymer thereof as a main component, and solidified by dry coagulation or wet coagulation. Can be used. In the cloth, the material of the fiber is not particularly limited, and examples thereof include natural fiber, regenerated fiber, semi-synthetic fiber, synthetic fiber and the like, and two or more kinds of these may be combined. Among them, synthetic fibers are preferable from the viewpoint of strength, and polyester fibers are more preferable.

Further, the fibrous substrate may be colored with a dye or a pigment. The dyes and pigments used for coloring are not particularly limited.

The sheet-like material according to the present embodiment has an inner layer made of a polyurethane resin as a first resin layer and an outermost layer made of a non-porous polyurethane resin as a second resin layer on the surface of the above-mentioned fibrous base material. Are laminated.

The inner layer is a layer made of a polyurethane resin formed on a fibrous base material, and is not limited to a one-layer structure, and may be two layers or three or more layers. For example, when a polyurethane adhesive is used to provide the inner layer, the adhesive layer formed by the adhesive also constitutes a part of the inner layer. More specifically, as shown in FIG. 1, the inner layer 3 as the epidermis layer may be directly laminated on the fibrous base material 2, but as shown in FIG. 2, the epidermis layer 31 is fibrous via the adhesive layer 32. It may be laminated on the base material 2. Through the adhesive layer, it is possible to suppress excessive penetration of the polyurethane resin constituting the inner layer into the fibrous base material, which may occur when the polyurethane resin is directly laminated. Therefore, it is possible to prevent the tactile sensation and texture from being impaired.

The polyurethane resin constituting the inner layer is not particularly limited, and examples thereof include a polyether polyurethane resin, a polyester polyurethane resin, and a polycarbonate polyurethane resin. These can be used alone or in combination of two or more. Of these, a polycarbonate polyurethane resin is preferable from the viewpoint of abrasion resistance and light fastness. The form of the polyurethane resin can be used regardless of solvent-free, hot-melt, solvent-based, water-based, etc., and further regardless of whether it is a one-component type or a two-component curable type, depending on the specific application. It can be selected as appropriate.

If necessary, the polyurethane resin constituting the inner layer may contain known additives such as a urethanization catalyst, a silane coupling agent, a filler, a thixo-imparting agent, a tackifier, a wax, a heat stabilizer, and a light-resistant stabilizer. , Fluorescent whitening agent, foaming agent, thermoplastic resin, thermosetting resin, dye, pigment, flame retardant, conductivity imparting agent, antistatic agent, moisture permeability improver, water repellent, oil repellent, hollow foam, Crystal water-containing compounds, water-absorbing agents, moisture-absorbing agents, deodorants, foam stabilizers, defoaming agents, antifungal agents, preservatives, algae-proofing agents, pigment dispersants, inert gases, blocking inhibitors, hydrolysis inhibitors , A matting agent, a tactile sensation improver, a slip improver, a cross-linking agent, a thickener, a leveling agent and the like can be used alone or in combination of two or more.

When the adhesive layer is provided as a part of the inner layer, the same resin as the polyurethane resin used for the inner layer can be used as the adhesive. Further, the composition of the polyurethane may be the same or different between the skin layer and the adhesive layer, for example.

The softening temperature of the inner layer is preferably 140 to 200 ° C, more preferably 150 to 170 ° C. When the softening temperature of the inner layer is 140 ° C. or higher, a sheet-like material having excellent heat resistance is obtained. Since the softening temperature of the inner layer is 200 ° C. or lower, the needle embossing workability is excellent. When a plurality of resin layers are provided as the inner layer, the softening temperature of the inner layer means all the softening temperatures of the plurality of resin layers.

The softening temperature of the inner layer can be obtained by the following method. That is, only the inner layer is produced as a single film having a thickness equivalent to the thickness of the inner layer in a sheet-like material. The obtained film is cut into 7 mm squares and softened by thermomechanical analysis of JIS K-7196 "thermoplastic plastic film and sheet" by a thermomechanical analyzer (EXSTAR TMA-SS6100, manufactured by Hitachi High-Tech Science Co., Ltd.). According to the "temperature test method", the displacement start temperature of the probe is measured by using the needle penetration method (load: 0.1 N, needle diameter: φ1 mm, heating rate: 5 ° C./min). The softening temperature can be obtained by producing 10 films, measuring the displacement start temperature of each, and calculating the average value of these. When the inner layer is composed of a plurality of resin layers, a film is prepared for each resin layer and the softening temperature is measured.

The thickness of the inner layer is not particularly limited, and may be, for example, 5 to 400 μm, 20 to 250 μm, or 100 to 200 μm. When the thickness of the inner layer is 5 μm or more, it becomes easy to form a uniform resin layer, and the inner layer is not partially missing, so that the wear resistance can be improved. When the thickness of the inner layer is 400 μm or less, it is possible to prevent the texture from becoming coarse and hard. When the inner layer is composed of a plurality of resin layers, the thickness of the inner layer is the sum of the thicknesses of the plurality of resin layers. For example, when the adhesive layer is provided, the value including the thickness of the adhesive layer is defined as the thickness of the inner layer.

The thickness of the inner layer can be obtained by the following method. That is, the vertical cross section of the sheet-like object is observed with a microscope (Digital HF Microscope VH-8000 manufactured by KEYENCE CORPORATION) magnified 100 times, and the thickness of the inner layer is measured. The thickness of the inner layer is measured at any five points and calculated by calculating the average value of these points.

The inner layer is preferably porous. Since it is porous, the needle embossing workability can be improved. The method for making the inner layer porous is not particularly limited, and a known method can be used. For example, physical foaming by mechanical stirring, chemical foaming by adding a foaming agent, or pore formation by adding hollow fine particles can be mentioned. Alternatively, pore formation by a wet coating of a polyurethane resin, pore formation by a moisture curing reaction of a polyurethane resin, and the like can be mentioned. When the inner layer is composed of a plurality of resin layers, it is preferable that all the resin layers are porous.

The sheet-like material according to the present embodiment is obtained by laminating an outermost layer made of a non-porous polyurethane resin as a second resin layer on the surface of an inner layer laminated on one surface of a fibrous base material. be. As shown in FIGS. 1 and 2, the outermost layer 4 is a resin layer forming the surface 11 of the sheet-like material 1, 1A, which imparts designability to the sheet-like material, and has abrasion resistance, heat resistance, and durability. It is formed on the surface of the inner layer for the purpose of improving the properties. Therefore, the outermost layer is a non-porous layer.

The polyurethane resin used for forming the outermost layer is not particularly limited, and examples thereof include a polyether polyurethane resin, a polyester polyurethane resin, a polycarbonate polyurethane resin, and the like, and these may be used alone or in combination of 2. It can be used in combination of more than one species. Of these, a polycarbonate polyurethane resin is preferable from the viewpoint of abrasion resistance and light fastness. Further, the form of the polyurethane resin can be used regardless of solvent-free, hot-melt, solvent-based, water-based, and further, one-component type or two-component curing type, and can be used as appropriate according to a specific application. You can choose.

If necessary, the outermost layer of the polyurethane resin is provided with a urethanization catalyst, a silane coupling agent, a filler, a thixo-imparting agent, and tack-imparting within a range that does not interfere with the effects of the present embodiment and does not impair the physical properties of the polyurethane resin. Agents, waxes, heat stabilizers, light stabilizers, fluorescent whitening agents, thermoplastic resins, thermosetting resins, dyes, pigments, flame retardants, conductivity-imparting agents, antistatic agents, moisture permeability improvers, water repellents , Oil repellent, crystalline water-containing compound, water absorbent, hygroscopic agent, deodorant, foam stabilizer, antifoaming agent, antifungal agent, preservative, algae-proofing agent, pigment dispersant, blocking inhibitor, hydrolysis inhibitor , A matting agent, a tactile sensation improver, a slip improver, a cross-linking agent, a thickener, a leveling agent and the like can be used alone or in combination of two or more.

The thermal melting temperature of the outermost layer is preferably 180 to 240 ° C, more preferably 200 to 220 ° C. When the heat melting temperature is 180 ° C. or higher, it is possible to prevent the outermost layer from melting during needle embossing and causing burrs in the openings. When the heat melting temperature is 240 ° C. or lower, it is possible to prevent the texture from becoming coarse and hard.

Further, the thermal melting temperature of the outermost layer is higher than the softening temperature of the inner layer described above. The heat melting temperature of the outermost layer is preferably 10 to 100 ° C. higher than the softening temperature of the inner layer, and more preferably 15 to 50 ° C. As a result, during the needle embossing process, the outermost layer is pushed into the opening formed by softening the inner layer without melting, and the outermost layer at the peripheral edge of the opening is inclined toward the center of the opening. Therefore, burrs do not occur in the openings, and therefore, a sheet-like material having an openings having good wear resistance and surface tactile sensation can be obtained.

The heat melting temperature of the outermost layer can be obtained by the following method. That is, only the outermost layer is produced as a single film having a thickness equivalent to the thickness of the outermost layer in a sheet-like material. The obtained resin layer film is cut into 7 mm squares, and this is cut by a differential scanning calorimeter (EXSTAR DSC6200, manufactured by Hitachi High-Tech Science Co., Ltd.) according to JIS K-7121 "Method for measuring transition temperature of plastic", and the heating rate is 10. The melting peak when the temperature is raised at ° C./min is measured. The thermal melting temperature can be obtained by producing 10 films, measuring the temperature of each melting peak, and calculating the average value of these.

The outermost layer is usually thinner than the inner layer. The thickness of the outermost layer (thickness of the outermost layer at the non-opening meat) is not particularly limited, and may be, for example, 3 to 50 μm, 5 to 40 μm, or 10 to 40 μm. When the thickness of the outermost layer is 3 μm or more, a uniform resin layer can be formed, and since the outermost layer is not partially missing, it is possible to prevent the wear resistance from being impaired. When the thickness of the outermost layer is 50 μm or less, it is possible to prevent the texture from becoming coarse and hard.

The thickness of the outermost layer can be obtained by the following method. That is, the vertical cross section of the sheet-like object is observed with a microscope (Digital HF Microscope VH-8000 manufactured by KEYENCE CORPORATION) magnified 100 times, and the thickness of the outermost layer is measured. The thickness of the outermost layer is measured at any five points and calculated by calculating the average value of these points.

Next, a method for manufacturing a sheet-like material according to the present embodiment will be described. The manufacturing method is a method of forming a plurality of openings by needle embossing on a sheet-like material obtained by laminating a polyurethane resin layer composed of at least two layers, an outermost layer and an inner layer, on one surface of a fibrous base material. This is a method in which the outermost layer is non-porous and the relationship of thermal melting temperature of the outermost layer> needle embossing temperature> softening temperature of the inner layer is satisfied.

By satisfying the relationship of thermal melting temperature of the outermost layer> needle embossing temperature> softening temperature of the inner layer, when the opening is formed by the needle embossing, the outermost layer becomes the opening without melting by the needle embossing. Be pushed in. As a result, the outermost layer at the peripheral edge of the opening is inclined toward the center of the opening. As a result, burrs do not occur in the opening, so that a sheet-like material having good wear resistance and surface tactile sensation can be obtained even though the opening is provided. Further, since such an opening can be formed only by the needle embossing process, the process load is reduced.

The manufacturing method according to one embodiment is
(1) A step of applying a resin solution for the outermost layer on a releasable substrate to form an outermost layer made of a polyurethane resin.
(2) A step of applying a resin solution for an inner layer on the outermost layer to form an inner layer made of a polyurethane resin.
(3) Step of bonding the inner layer and the fibrous base material,
(4) The step of peeling off the releasable substrate, and
(5) Step of forming an opening by needle embossing,
Is included.

First, a resin solution for the outermost layer is applied onto a releasable base material to form an outermost layer made of a polyurethane resin.

The releasable base material is not particularly limited, and may be a base material having releasability with respect to the polyurethane resin or a base material subjected to a releasable treatment, for example, a releasable paper or a releasable base material. A treated cloth, a water-repellent treated cloth, an olefin sheet or film made of polyethylene resin, polypropylene resin, or the like, a fluororesin sheet or film, a plastic film with a release paper, or the like can be used. The releasable base material may have an uneven pattern, and by using such a releasable base material, designability can be imparted to the surface of the sheet-like material.

As a method for applying the resin liquid for the outermost layer on the releasable substrate, various conventionally known methods can be adopted and are not particularly limited. For example, a method using a device such as a reverse roll coater, a spray coater, a roll coater, a gravure coater, a kiss roll coater, a knife coater, and a comma coater can be mentioned. Above all, coating with a reverse roll coater, a knife coater, or a comma coater is preferable in that a uniform thin film layer can be formed.

The coating thickness of the outermost layer resin liquid may be appropriately set according to the thickness of the outermost layer, and is not particularly limited, and may be, for example, 15 to 250 μm or 25 to 200 μm. By setting the coating thickness of the resin liquid for the outermost layer in this range, the outermost layer having the above-mentioned thickness of, for example, 3 to 50 μm can be formed.

After applying the outermost layer to the releasable substrate, heat treatment is performed if necessary. In the heat treatment, the solvent in the outermost layer resin liquid is evaporated to dry the resin, and when a cross-linking agent which causes a cross-linking reaction by the heat treatment is used or when a two-component curable resin is used, the reaction is carried out. It is done to promote and form a film with sufficient strength.

The heat treatment temperature is not particularly limited and may be appropriately set depending on the additives used, for example, 50 to 150 ° C. or 60 to 120 ° C. When the heat treatment temperature is 50 ° C. or higher, it is possible to prevent the heat treatment from taking a long time and increasing the process load, or by insufficient cross-linking of the resin and resulting in poor wear resistance. When the heat treatment temperature is 150 ° C. or lower, it is possible to prevent the texture of the sheet-like material from becoming coarse and hard. Further, the heat treatment time is not particularly limited, and may be, for example, 2 to 20 minutes or 2 to 10 minutes. When the heat treatment time is 2 minutes or more, it is possible to prevent insufficient cross-linking of the resin. When the heat treatment time is 20 minutes or less, it is possible to prevent the processing speed from becoming slow.

Next, the resin liquid for the inner layer is applied on the outermost layer to form an inner layer made of polyurethane resin.

As a method for applying the resin liquid for the inner layer on the outermost layer, various conventionally known methods can be adopted and are not particularly limited. For example, a method using a device such as a reverse roll coater, a spray coater, a roll coater, a gravure coater, a kiss roll coater, a knife coater, and a comma coater can be mentioned. Above all, coating with a reverse roll coater, a knife coater, or a comma coater is preferable in that a uniform thin film layer can be formed.

The coating thickness of the resin liquid for the inner layer may be appropriately set according to the thickness of the inner layer, and is not particularly limited, and may be, for example, 20 to 250 μm or 100 to 200 μm. By setting the coating thickness of the resin liquid for the inner layer in this range, the inner layer having the above-mentioned thickness of, for example, 5 to 400 μm can be formed.

After applying the resin solution for the inner layer to the releasable substrate, heat treatment is performed if necessary. In the heat treatment, the solvent in the resin liquid for the inner layer is evaporated to dry the resin, and the reaction is promoted when a cross-linking agent which causes a cross-linking reaction by the heat treatment is used or when a two-component curable resin is used. However, it is performed to form a film having sufficient strength.

The heat treatment temperature is not particularly limited and may be appropriately set depending on the additive used, for example, 50 to 150 ° C. or 60 to 130 ° C. When the heat treatment temperature is 50 ° C. or higher, it is possible to prevent the heat treatment from taking a long time and insufficient cross-linking of the resin. When the heat treatment temperature is 150 ° C. or lower, it is possible to prevent the texture of the sheet-like material from becoming coarse and hard. Further, the heat treatment time is not particularly limited, and may be, for example, 2 to 20 minutes or 2 to 10 minutes. When the heat treatment time is 2 minutes or more, it is possible to prevent insufficient cross-linking of the resin. When the heat treatment time is 20 minutes or less, it is possible to prevent the processing speed from becoming slow.

Next, the inner layer and the fibrous base material are bonded together. At the time of bonding, as described above, it may be laminated via an adhesive layer or directly. When the adhesive layer is provided, for example, an adhesive may be applied on the epidermis layer constituting a part of the inner layer and then bonded to the fibrous base material.

As a method for applying the adhesive, various conventionally known methods can be adopted, and the method is not particularly limited. For example, a method using a device such as a reverse roll coater, a spray coater, a roll coater, a gravure coater, a kiss roll coater, a knife coater, and a comma coater can be mentioned.

Then, the releasable substrate is peeled off from the outermost layer. By peeling off the releasable substrate, a laminate of the outermost layer, the inner layer, and the fibrous substrate (hereinafter, also simply referred to as a laminate) can be obtained.

When a plurality of resin layers other than the adhesive layer are formed as the inner layer, the surface of the first resin layer is formed on the outermost layer as the inner layer and before the adhesive is applied. A method of further coating and forming a polyurethane resin composition can be adopted. As for the method of coating and the heat treatment after coating, the same method as the above-mentioned method for forming the inner layer can be adopted.

The method for manufacturing the laminate of the outermost layer, the inner layer, and the fibrous base material can adopt the same manufacturing method as the conventionally known polyurethane synthetic leather, and is not limited to the above method. .. Conventionally known methods for producing polyurethane synthetic leather include, for example, (1) applying a resin solution for an inner layer on a releasable base material to form an inner layer, and (2) bonding the inner layer and the fibrous base material. , (3) The releasable base material is peeled off, and (4) the outermost layer resin liquid is applied onto the inner layer to form the outermost layer.

Finally, the laminated body is subjected to needle embossing. In the present embodiment, the needle embossing is performed from the surface side of the outermost layer. That is, the heated needle embossing mold is pressed against the laminate from the surface side of the outermost layer. As a result, a plurality of openings are formed on the surface of the laminated body, that is, the sheet-like material. The needle embossing device is a needle embossing device including a roll having a plurality of needles and a roll having a flat surface, an embossing device including a pair of embossing rolls manufactured so that uneven patterns of each other overlap each other at facing portions, or also. A known needle embossing device such as an embossing device provided with an embossing plate instead of an embossing roll can be used without limitation.

The needle embossing temperature (that is, corresponding to the heat treatment temperature of the laminated body at the time of heating and pressing, hereinafter also referred to as the needle embossing type heating temperature) is set higher than the softening temperature of the inner layer. The difference between the heating temperature of the needle embossing type and the softening temperature of the inner layer is preferably 50 ° C. or lower, more preferably 40 ° C. or lower. This difference may be, for example, 10 ° C. or higher. When the heating temperature of the needle embossing type is higher than the softening temperature of the inner layer, the opening can be easily formed by the needle embossing process.

Further, the needle embossing temperature is set lower than the heat melting temperature of the outermost layer. The difference between the heat melting temperature of the outermost layer and the heating temperature of the needle embossing type is preferably 10 ° C. or higher, more preferably 20 ° C. or higher. This difference may be, for example, 50 ° C. or lower, or 30 ° C. or lower. When the heating temperature of the needle embossing type is lower than the heat melting temperature of the outermost layer, the inner wall of the opening peripheral edge of the opening is covered with the outermost layer made of a non-porous polyurethane resin, which is obtained. The wear resistance and surface tactile sensation of the sheet-like material can be improved.

The time for pressing the heated needle embossing mold against the laminated body may be appropriately set according to the shape of the needle embossing mold. In the case of the embossing device provided with the roll-shaped embossing type, the pressing time (machining speed) may be, for example, 0.5 to 20 m / min or 1 to 10 m / min. Further, in the case of the embossing device provided with the flat plate-shaped embossing type, the pressing time may be, for example, 30 to 120 seconds or 50 to 90 seconds. When the pressing time is not less than the lower limit value (the processing speed is not more than the upper limit value), the opening can be easily formed by needle embossing. When the pressing time is not more than the upper limit value (the processing speed is not more than the lower limit value), it is possible to prevent burrs from forming in the opening and impairing the surface tactile sensation or making the texture rough and hard.

The clearance between the needle embossing type and the receiving roll (receiving plate) should be managed by subtracting 1 to 1.5 times the thickness of the polyurethane resin layer (sum of the thicknesses of the inner layer and the outermost layer) from the laminated body. Is preferable. By controlling the clearance within this range, it is possible to prevent the opening from being formed only in the polyurethane resin layer and impairing the strength of the obtained sheet-like material.

It should be noted that various conditions such as the pressure at the time of pressing and the introduction tension of the laminated body may be appropriately set so as to obtain a desired opening. Here, the introduction tension is the tension when the laminated body is introduced to the embossing device.

Thus, the sheet-like material according to the present embodiment is obtained.

The sheet-like material according to the present embodiment has a plurality of openings on the surface. The opening is formed by the above-mentioned needle embossing process. As shown in FIGS. 1 and 2, the opening 5 is provided so as to penetrate the outermost layer 4 and the inner layer 3 (in the example of FIG. 2, the skin layer 31 and the adhesive layer 32) from the surface of the outermost layer 4. The opening is preferably provided so as to penetrate at least the outermost layer and the inner layer, and may be formed so as to penetrate from the surface of the outermost layer to the back surface of the fibrous base material, but from the viewpoint of wear resistance. It is preferable not to penetrate the back surface of the fibrous base material, and more preferably, it penetrates only the resin layer composed of the outermost layer and the inner layer and does not reach the fibrous base material.

As shown in FIGS. 1 and 2, the opening 5 is formed to have an opening peripheral edge 51 formed so that the outermost layer 4 is inclined toward the center of the opening. As a result, the wear resistance and surface tactile sensation of the obtained sheet-like material become good. Specifically, as shown in FIG. 1, the opening 5 includes a penetrating portion 52 penetrating the outermost layer 4 and an opening peripheral edge portion 51 around the opening portion 5, and the outermost layer 4 faces the opening center at the opening peripheral edge portion. It is inclined downward in a tapered shape. That is, the opening peripheral edge portion 51 includes a tapered portion in which the outermost layer 4 is inclined in a tapered shape. In this example, the inner layer 3 is covered with the outermost layer 4 at the opening 5, and the inner layer 3 is not exposed as the inner wall of the opening 5.

Similarly, in the example shown in FIG. 2, the opening 5 has a tapered opening peripheral edge 51 in which the outermost layer 4 is inclined downward toward the center of the opening around the penetrating portion 52 penetrating the outermost layer 4. Have. In the example of FIG. 2, the opening 5 is further provided so as to penetrate the adhesive layer 32, and the skin layer 31 is covered with the outermost layer 4, but the adhesive layer 32 is covered with the outermost layer 4. It is not exposed and is exposed as an inner wall at the bottom of the opening 5.

The opening angle of the opening peripheral portion is preferably 45 to 60 degrees, more preferably 50 to 55 degrees. Here, the opening angle of the opening peripheral edge portion is, as shown in FIGS. 1 and 2, the taper angle θ of the opening peripheral edge portion 51 having a tapered shape. When the opening angle of the opening peripheral portion is 45 degrees or more, the wear resistance and the surface tactile sensation are good, and when the opening angle is 60 degrees or less, the designability is good.

The opening angle of the opening peripheral portion can be obtained as follows. That is, the vertical cross section of the sheet-like object is observed with a microscope (Digital HF Microscope VH-8000, manufactured by KEYENCE CORPORATION) at a magnification of 100 times, and the opening angle of the opening peripheral portion is measured. The opening angle is obtained by measuring at any five points and calculating the average value of these points.

The shape of the opening is not particularly limited, and can be selected from geometric patterns such as circles, triangles, and squares in consideration of design. From the viewpoint of strength, a circular shape is preferable. The size of the opening is preferably 0.001 to 0.197 mm ² (corresponding to an average pore diameter of 50 to 500 μm when the opening is circular), and more preferably 0.002 to 0.008 mm ² (opening). When the portion is circular, it corresponds to an average pore diameter of 55 to 100 μm). When the size of the opening is 0.001 mm ² or more, the moisture permeability of the sheet-like material can be increased, and the effect of suppressing stuffiness and stickiness when sitting for a long time can be enhanced. When the size of the opening is 0.197 mm ² or less, it is possible to suppress a decrease in the strength and wear resistance of the sheet-like material. If the shape of the opening is other than a perfect circle, the major axis of the opening is the hole diameter.

Here, as shown in FIGS. 1 and 2, the size of the opening is the area of the opening 5 on the surface 11 of the sheet-like objects 1 and 1A, and when the shape of the opening is circular, the reference numeral D is used. It is an area calculated as a hole diameter.

The aperture ratio, which is the ratio of the openings on the surface of the sheet-like material, is preferably 0.2% or more, more preferably 0.2 to 10%, still more preferably 0.4 to 5%. .. When the opening ratio is 0.2% or more, sufficient moisture permeability can be obtained as a vehicle interior material. On the other hand, when the aperture ratio is 10% or less, it is excellent in terms of strength and wear resistance. Here, the aperture ratio is the ratio of the total area of the plurality of openings existing in the surface to the total area of the surface including the openings when the surface of the sheet-like object is viewed in a plane.

Further, the distribution state of the openings (average density, that is, the number of openings in the unit area of the surface of the sheet-like material) is preferably 500,000 to 999,500 pieces / m ² , and more preferably 600,000 to 900,000 pieces / m ² . Is. When the average density is 500,000 pieces / m ² or more, the moisture permeability of the sheet-like material can be increased, and the effect of suppressing stuffiness and stickiness when sitting for a long time can be enhanced. When the average density is 999,500 pieces / m ² or less, it is possible to suppress a decrease in the strength and wear resistance of the sheet-like material.

The sheet-like material having such an opening preferably has a moisture permeability of 2000 g / m ² · h or more. The water permeability is more preferably 2500 g / m ² · h or more.

With the above-mentioned configuration, according to the present embodiment, the opening is provided so that the moisture permeability is 2000 g / m ² · h or more, but the wear resistance is sufficient for use as a vehicle interior material. It is possible to provide a sheet-like material having the above.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. The "part" in the embodiment shall be based on mass. Moreover, the evaluation of the obtained sheet-like material was performed according to the following method.

[Humidity permeability]
Measured according to JIS L1099 A-1 method. If the measured value is 2000 g / m ² · h or more, it can be said that the moisture permeability is sufficient for a sheet-like material, and the larger the value, the higher the moisture permeability.

[Abrasion resistance]
One test piece having a width of 70 mm and a length of 300 mm was collected from each of the vertical and horizontal directions, and a urethane foam having a width of 70 mm, a length of 300 mm and a thickness of 10 mm was attached to the back surface. With a wire having a diameter of 4.5 mm installed in the center of the lower surface of the urethane foam, it is fixed to a flat surface wear tester T-TYPE (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) and cotton cloth (JIS L3102: cotton sail cloth No. 6). A wear test was performed by applying a load of 19.6 N to the friction element so that the friction element covered with the friction element reciprocates on the wire in parallel with the wire. The friction element was reciprocally worn 3000 times at a speed of 60 reciprocations / minute between 140 mm on the surface of the test piece. The test piece was judged according to the following criteria. △ The above is a pass.
(criterion)
○: No cracks or tears in the resin layer △: Cracks occurred in the resin layer ×: Cracks occurred in the resin layer

[Surface touch]
Sensory evaluation was performed by the tactile sensation by the panelists, and the judgment was made according to the following criteria. △ The above is a pass.
(criterion)
◯: Smooth tactile sensation on the entire surface Δ: Tactile sensation slightly lacking in smoothness at the opening (slightly feel the presence of burrs)
X: Tactile sensation lacking smoothness at the opening (feeling the presence of burrs)

[Heat-resistant]
One test piece having a width of 100 mm and a length of 100 mm was collected. The test piece was placed in a wide-mouthed reagent bottle (250 mL bottle with a stopper, made of hard glass) along the side surface of the reagent bottle, and allowed to stand in a dryer adjusted to 110 ° C. for 400 hours for heat treatment. After the heat treatment, the reagent bottle was taken out from the dryer and cooled to room temperature, and then the reagent piece was taken out from the reagent bottle. The test piece was judged according to the following criteria. △ The above is a pass.
(criterion)
○: No change △: Slightly grained flow is seen ×: Clearly grained flow is seen

[Example 1]
Formulation 1 (resin composition for outermost layer)
100 parts of polycarbonate polyurethane resin (Chrisbon NY-328, manufactured by Dainippon Ink and Chemicals Co., Ltd.)
Dimethylformamide (DMF) 40 parts Carbon black pigment 15 parts (DIALAC BLACK L-1770S, manufactured by Dainippon Ink and Chemicals Co., Ltd.)
Crosslinking agent 2 parts (Bernock DN950, manufactured by Dainippon Ink and Chemicals Co., Ltd.)
Preparation method
A carbon black pigment and a cross-linking agent were added to a polycarbonate polyurethane resin, and the mixture was stirred and dispersed. Next, dimethylformamide was added to adjust the viscosity to 2000 mPa · s (B-type viscometer, rotor: No. 3, 10 rpm, 23 ° C.) to prepare a resin composition for the outermost layer.

Formulation 2 (resin composition for inner layer)
100 parts of urethane polyol prepolymer of Production Example 1 5 parts of urethane curing agent (4,4'-diphenylmethane diisocyanate)
Carbon black pigment 2 parts (Polyton Black, manufactured by Dainippon Ink and Chemicals Co., Ltd.)
Amine-based urethanization catalyst 1 part (TOYOCAT-DT, manufactured by TOSOH Co., Ltd.)
The equivalent ratio (isocyanate group of urethane curing agent / hydroxyl group of urethane polyol prepolymer of Production Example 1) was 1.2.
Preparation method
A carbon black pigment and an amine-based urethanization catalyst were added to the urethane polyol prepolymer of Production Example 1 heated and melted at 60 ° C., and the mixture was stirred and dispersed. Then, a urethane curing agent heated and melted at 40 ° C. was added and stirred to prepare a resin composition for an inner layer. Immediately after the preparation, it was subjected to a coating operation.

[Production Example 1] Urethane Polyol Prepolymer In a 1 L 4-necked flask heated at 60 ° C., 80 parts of a polyester polyol (Kurare polyol P2010, manufactured by Kurare Co., Ltd.) having a number average molecular weight of 2000 and a polycarbonate polyol having a number average molecular weight of 2000 are placed. After adding 50 parts of (Kurare polyol C2090, manufactured by Kurare Co., Ltd.) and 10 parts of a polyether polyol (PTMG1000, manufactured by Sanyo Kasei Kogyo Co., Ltd.) having a number average molecular weight of 1000 and stirring, 4,4'-diphenylmethane diisocyanate (MDI). ) Was added and stirred at 80 ° C. until the isocyanate group disappeared to obtain a urethane polyol prepolymer. At this time, the equivalent ratio (sum of hydroxyl groups of each polyol / isocyanate group of MDI) was 1.25. The softening temperature of the obtained urethane polyol prepolymer was 40 ° C., and the number average molecular weight was 17,000.

The resin composition for the outermost layer prepared according to the above-mentioned formulation 1 is put on a release paper (R-51, manufactured by Lintec Corporation) having a textured uneven pattern in a sheet shape so as to have a thickness of 200 μm with a comma coater. And heat-treated at 100 ° C. for 2 minutes in a dryer to form the outermost layer. The thickness of the outermost layer was 40 μm, and the thermal melting temperature was 204 ° C.

The resin composition for the inner layer prepared according to the above-mentioned formulation 2 is applied to the outermost layer surface formed on the release paper in the form of a sheet with a comma coater so as to have a thickness of 140 μm, and the temperature is 120 ° C. in a dryer. After heat treatment for 2 minutes, the resin composition for the inner layer was attached to a polyester tricot cloth while having a viscous state, and compacted with a mangle under a load of 5 kg / m ² to a temperature of 23 ° C. and a relative humidity of 65. After aging treatment for 1 day in an atmosphere of%, the release paper was peeled off to obtain a laminate of the outermost layer, the inner layer, and the fibrous base material. The thickness of the inner layer was 150 μm, and the softening temperature was 176 ° C.

The obtained laminate was subjected to a needle embossing device (electrically heated test embossing / calendar machine, manufactured by Yuri Roll Co., Ltd.) at a processing temperature of 190 ° C., a processing speed of 5 m / min, and a clearance of 0.8 mm. Needle embossing was performed from the outer layer side to obtain a sheet-like product of Example 1. The obtained sheet-like material had a thickness of about 1 mm, the outermost layer was a non-porous layer, and the inner layer was a porous layer. Further, a plurality of openings by needle embossing are provided on the surface so as to penetrate the outermost layer and the inner layer, and each opening has an opening peripheral edge portion in which the outermost layer is inclined so as to drop toward the center of the opening. Met. The size of the opening is 0.008 mm ² (hole diameter is 100 μm), the opening angle of the peripheral edge of the opening is 50 degrees, the distribution state (average density) of the openings is 900,000 pieces / m ² , and the aperture ratio is 0.79%. Met. Moreover, when the moisture permeability, wear resistance, surface touch and heat resistance of the sheet-like material were evaluated, the moisture permeability was 3000 g / m ² · h, the wear resistance was evaluated as ○, the surface touch was evaluated as ○, and the heat resistance. The evaluation of was ○.

[Example 2]
A sheet-like product was obtained in the same manner as in Example 1 except that the equivalent ratio of Formulation 2 was 1.05.

[Example 3]
A sheet-like product was obtained in the same manner as in Example 1 except that the equivalent ratio of Formulation 2 was set to 1.1.

[Example 4]
A sheet-like product was obtained in the same manner as in Example 1 except that the equivalent ratio of Formulation 2 was 1.25.

[Example 5]
A sheet-like product was obtained in the same manner as in Example 1 except that the cross-linking agent of Formulation 1 was 5 parts, the equivalent ratio of Formulation 2 was 1.3, and the needle embossing temperature was 220 ° C.

[Example 6]
A sheet-like product was obtained in the same manner as in Example 1 except that the cross-linking agent of Formulation 1 was 6 parts, the equivalent ratio of Formulation 2 was 1.4, and the needle embossing temperature was 240 ° C.

[Example 7]
A sheet-like product was obtained in the same manner as in Example 1 except that the equivalent ratio of Formulation 2 was 1.07.

[Example 8]
A sheet-like product was obtained in the same manner as in Example 1 except that the equivalent ratio of Formulation 2 was set to 1.21.

[Example 9]
A sheet-like product was obtained in the same manner as in Example 1 except that the equivalent ratio of Formulation 2 was 1.28.

[Comparative Example 1]
A sheet-like product was obtained in the same manner as in Example 1 except that the equivalent ratio of Formulation 2 was 1.35, the thickness of the inner layer was 170 μm, and the needle embossing temperature was 240 ° C.

[Comparative Example 2]
A sheet-like material was obtained in the same manner as in Example 1 except that the cross-linking agent of Formulation 1 was 0 parts, the equivalent ratio of Formulation 2 was 1.3, the thickness of the inner layer was 170 μm, and the needle embossing temperature was 240 ° C. rice field.

[Comparative Example 3]
A sheet-like material was obtained in the same manner as in Example 1 except that the resin composition for the outermost layer was foamed 1.2 times by mechanical foaming.

As shown in Table 1, in Examples 1 to 9, although the moisture permeability is high, burrs are not generated in the openings, the surface feel is excellent, and the durability is sufficient for use as a vehicle interior material. It was wearable. In Example 6, it was necessary to set the processing temperature high, and the processability was inferior.

On the other hand, in Comparative Example 1, the heat melting temperature of the outermost layer and the softening temperature of the inner layer are the same, and the needle embossing temperature is set higher than this in order to soften the inner layer, so that the outermost layer melts and burrs are formed. It occurred and was inferior in surface tactile sensation and wear resistance. The same was true for Comparative Example 2. In Comparative Example 3, since the outermost layer was a porous layer, the wear resistance and the surface feel were inferior.

Although some embodiments have been described above, these embodiments are presented as examples and are not intended to limit the scope of the invention. These embodiments can be implemented in various other embodiments, and various omissions, replacements, and changes can be made without departing from the gist of the invention. These embodiments and variations thereof are included in the scope of the invention described in the claims and the equivalent scope thereof, as are included in the scope and gist of the invention.

The sheet-like material according to the present embodiment is, for example, a building such as a vehicle interior material such as an automobile seat, a ceiling material, a dashboard, a door lining material, and an automobile interior material such as a handle, and a wall material. It can be used for various purposes such as interior materials, interior materials such as sofas and chairs, clothing, bags, and shoes.

1,1A ... sheet-like material, 11 ... surface, 2 ... fibrous base material, 3 ... inner layer, 31 ... epidermis layer, 32 ... adhesive layer, 4 ... outermost layer, 5 ... opening, 51 ... opening peripheral edge, 52 … Penetration

Claims (3)

A sheet-like material comprising a fibrous base material and an inner layer and an outermost layer made of a polyurethane resin laminated on one side of the fibrous base material.
The surface of the sheet-like object, which is the surface of the outermost layer, has a plurality of openings, and the openings are provided so as to penetrate at least the outermost layer and the inner layer.
The outermost layer is non-porous, the heat melting temperature of the outermost layer measured according to JIS K-7121 is 180 to 250 ° C., the load is 0.1 N, the needle diameter is 1 mm, and the temperature rise rate is increased according to JIS K-7196. The softening temperature of the inner layer measured by the needle penetration method of 5 ° C./min is 110 to 220 ° C., the thermal melting temperature of the outermost layer is 10 to 100 ° C. higher than the softening temperature of the inner layer, and
The opening includes an opening peripheral portion in which the outermost layer is inclined toward the center of the opening, the opening angle of the opening peripheral portion is 45 to 60 degrees, and the size of the opening is 0.001. A sheet-like material having a size of ~ 0.197 mm ² . The sheet-like material according to claim 1 , wherein the opening ratio, which is the ratio of the openings on the surface of the sheet-like material, is 0.2% or more. A sheet-like material comprising a fibrous base material and an inner layer and an outermost layer made of a polyurethane resin laminated on one side of the fibrous base material is subjected to needle embossing to form the sheet-like material which is the surface of the outermost layer. A method for manufacturing a sheet-like material having openings, which forms a plurality of openings on the surface .
The opening is provided so as to penetrate at least the outermost layer and the inner layer.
The outermost layer is non-porous, the thermal melting temperature of the outermost layer measured according to JIS K-7121 is 180 to 250 ° C., the load is 0.1 N, the needle diameter is 1 mm, and the temperature rise rate is increased according to JIS K-7196. The softening temperature of the inner layer measured by the needle penetration method of 5 ° C./min is 110 to 220 ° C., the thermal melting temperature of the outermost layer is 10 to 100 ° C. higher than the softening temperature of the inner layer, and the outermost layer has a softening temperature of 10 to 100 ° C. A method for producing a sheet-like material, wherein the heat melting temperature is higher than the needle embossing temperature, and the needle embossing temperature is higher than the softening temperature of the inner layer.

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