JP5739238B2 - Method for producing leather-like sheet - Google Patents

Description

  The present invention relates to a method for producing a leather-like sheet material, and more particularly to a method for producing a leather-like sheet material obtained using a polymer elastic emulsion.

  Artificial leather is hard to stretch when worn compared to natural leather, requires no care, has uniform physical properties depending on the part, is water resistant, and does not deform during storage, such as shoes, clothing, vehicles, etc. It is widely used as a substitute for natural leather or as a new material in various fields of sports and sports fields. And higher quality and texture are required.

  Further, as a conventional method for producing artificial leather, a wet coagulation method using an organic solvent solution of a polymer elastic body is generally used. However, organic solvents are flammable, and organic solvents particularly suitable for wet coagulation methods are often difficult to handle, and their replacement is being promoted. One of them is a method of impregnating and solidifying a polymer elastic body emulsion in which a polymer elastic body component is dispersed in water on a fibrous base material.

  However, when water-based polymer elastic emulsions are used in this way, they tend to be inferior in terms of fullness and soft texture with a soft texture compared to conventional wet coagulation methods using organic solvents. There was a problem that it did not reach a certain level.

  For example, in a process in which a fibrous base material is impregnated with a polymer elastic emulsion and heated and dried, the polymer elastic body tends to have a bonded structure in which fibers in the fibrous base material are strongly restrained. Unlike the solvent-based wet coagulation process, there is no liquid around the fiber during coagulation, so that it was very difficult to control. For this reason, the flexibility of the sheet-like material has inevitably been lost and tends to have a hard texture.

  Therefore, in order not to impair the flexibility, an attempt was made to reduce the amount of adhesion of the polymer elastic body to the fiber, but this time the fibrous base material becomes paper-like, and it becomes easier to crease Problem has occurred. In addition, when strong elongation deformation is given to the obtained leather-like sheet material, for example, in the process of making shoes, unevenness due to density spots of the fibrous base material appears on the sheet-like material as it is, and the leather-like sheet shape There has been a problem that the texture is lowered such as that which does not exist in natural leather, such as unnatural unevenness in objects or floating wrinkles when bent inward.

On the other hand, a method of increasing the amount of adhering polymer elastic body, relaxing density spots in the fibrous base material with the polymer elastic body, and improving unnatural unevenness and floating wrinkles has been considered. However, in this case, there is a problem that the flexibility of the obtained leather-like sheet is lowered and the texture becomes hard.
In other words, when a water-based polymer elastic body is used, it is difficult to improve the quality, and it is extremely difficult to obtain a high-quality feeling similar to that of natural leather.

  Therefore, in Patent Document 1, after applying a mixture of dimethylpolysiloxane and methylhydropolyene polysiloxane, which are soft water repellents, to a fiber, a polymer elastic emulsion solution having specific physical properties is applied and dried. A method is disclosed. However, since the fibrous base material has water repellency, it is difficult to impregnate the water-based polymer elastic emulsion, and even if impregnated, the network structure of the polymer elastic body is hindered by the water repellency of each fiber surface. Therefore, there is a problem that unnatural unevenness caused by the fibrous base material is easily emphasized.

  In Patent Document 2, a mixture of dimethylpolysiloxane and amino-modified silicone is used as a water-repellent silicone oil, and a fibrous material is treated with a silicone treatment-containing liquid containing a silicone resin. A method for producing a leather-like sheet material impregnated and solidified is disclosed. However, this method has a problem that the solid adhesion amount of the silicone to the fiber is as high as 10% by weight, and although the regreasing effect having a heavy feeling with low resilience is obtained, the flexibility cannot be obtained as expected. .

JP 2000-303371 A JP 2004-324012 A

  An object of the present invention is to obtain a high-quality leather-like sheet-like material that is flexible but does not generate unnatural unevenness and floating wrinkles when bent.

In the method for producing a leather-like sheet of the present invention, a treatment liquid containing a silicone compound is applied to a fibrous base material, dried, impregnated with a polymer elastic body solution, and solidified. In the production method, the silicone compound has a hydrophilic side chain, and the hydrophilic side chain of the silicone compound includes at least one of a polyether side chain, a polyether acetate side chain, and a polyglycerin side chain. And the elastic polymer solution is an aqueous emulsion.

Furthermore, the treatment liquid containing the silicone compound is an aqueous treatment liquid, the silicone compound in the treatment liquid is in a dispersed state, and the solid content concentration of the silicone compound in the treatment liquid is 0.2 to 5% by weight. and a call is preferred.

  ADVANTAGE OF THE INVENTION According to this invention, the high quality leather-like sheet-like thing which does not generate | occur | produce an unnatural unevenness | corrugation and a floating wrinkle when it bends is provided, although it is flexible.

  The method for producing a leather-like sheet according to the present invention is a method for producing a leather-like sheet in which a fibrous base material is immersed in a treatment liquid containing a silicone compound, dried, impregnated with a polymer elastic body solution, and solidified. In this invention, it is essential that the silicone compound has a hydrophilic side chain and the polymer elastic body solution is an aqueous emulsion.

  Here, the fibrous base material used in the present invention is a variety of fibrous bases such as non-woven fabrics and synthetic fabrics, woven and knitted fabrics, etc., which are conventionally used in the production of leather-like sheets. Material can be used. Among them, in the present invention, as the fibrous base material, a fibrous base material made of only a nonwoven fabric is more preferably used, and in particular, an entangled nonwoven fabric is preferably used.

  As the fiber constituting the fibrous base material, one of conventionally known synthetic resins capable of forming fibers, such as polyester, polyamide, polyacryl, and polyolefin, or synthetic fibers composed of two or more resins can be used. Furthermore, synthetic fibers such as polyester fibers, polyamide fibers, acrylic fibers, polyolefin fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers and polyvinyl alcohol fibers; semi-synthetic fibers; cotton, wool, hemp, etc. A natural fiber etc. can be mentioned. Among these, it is particularly preferable to use a polyester, polyamide, or polyester / polyamide. Examples of the polyester used as the fiber include polyethylene terephthalate, polybutylene terephthalate, and polypropylene terephthalate. Examples of the polyamide include nylon-6, nylon-66, and nylon-12. Among these, polyethylene terephthalate, nylon-6, and the like are preferable from the viewpoint of process stability and cost.

  The thickness of the fibers constituting the fibrous base material is not particularly limited, and can be selected according to the use of the obtained leather-like sheet, but generally the single fiber fineness is 0.01 to 10 dtex. Preferably there is.

  The fibrous base material used in the present invention is most preferably an entangled nonwoven fabric because of its high texture. As a method for forming such an entangled nonwoven fabric, conventionally known methods such as carding from short fibers, a method by entanglement treatment, a method of forming a long fiber directly into a sheet, and a method by entanglement treatment can be employed.

More specifically, as a fiber entanglement method used when producing a fibrous base material, a laminated wave is produced with a random weber or a cross wrapper, and needle punching or hydroentanglement is used to produce 3 Dimensionally entangled nonwoven fabric can be obtained. However, in high-pressure columnar water flow entanglement, when the basis weight increases, the water flow does not sufficiently permeate in the thickness direction and the entanglement tends to be insufficient. Therefore, a mechanical entanglement method such as a needle punch is more preferable.
The thickness of the fibrous base material can be arbitrarily selected depending on the intended use of the leather-like sheet-like material to be obtained, but in general, it is about 0.3 to 3.0 mm from the point of feeling. Preferably, it is about 0.8 to 2.5 mm.

Furthermore, in order to obtain a leather-like sheet having a soft texture, moderate waist feeling and resilience, a fibrous material formed using at least a part of a shrinkable polyethylene terephthalate fiber as a fibrous base material A substrate is preferred. In this case, after the fibers are entangled, the fibers are contracted to obtain a fibrous base material to be used for processing. When a part of the fibers is contracted in this way, the apparent density is 0.20 to 0.4 g. A non-woven fabric of / cm ³ is preferable.

  Further, it is also preferable to use a non-woven fabric made of ultrafine fibers using a split split fiber made of different types of polymer elastic bodies such as polyester and nylon. Furthermore, it is also preferable to use a long fiber entangled nonwoven fabric with high production efficiency. The spun peelable split composite fiber is preferably peeled and splitted after entanglement for the purpose of production efficiency and quality assurance. When using ultrafine fibers composed of such exfoliated split fibers, compared to the case of using an extraction type sea-island ultrafine fiber, the abundance ratio of ultrafine fibers in the base material can be finally increased. The texture can be improved.

  In the production method of the present invention, the fibrous base material as described above is subjected to a pretreatment by applying a treatment liquid containing a silicone compound and drying, and the silicone compound at this time has a hydrophilic side chain. It needs to be a thing. Furthermore, the hydrophilic side chain of the silicone compound is preferably composed of one or more of a polyether side chain, a polyether / acryl side chain, and a polyglycerin side chain. In addition, it is preferable that polyoxyethylene (PEG) or polyoxypropylene (PPG) is added to the hydrophilic side chain, and it is possible to increase hydrophilicity by adding PEG in particular. More specifically, the silicone compound is preferably polyether-modified silicone, polyether-acetate-modified silicone, or polyglycerin-modified silicone, and is dispersed or dissolved in a solvent in the state of resin or oil. It is preferable. If the silicone compound is not hydrophilic but water-repellent, the impregnation of the polymer elastic body solution, which is a water-based emulsion, becomes nonuniform and a small amount, and the effects of the present invention cannot be exhibited.

  Moreover, it is preferable that the processing liquid containing the silicone compound used in the present invention is an aqueous processing liquid. By using an aqueous processing solution in which the solvent is water, it is possible to eliminate the use of an organic solvent in the production process as in the subsequent impregnation and solidification processes. Further, the silicone compound in the treatment liquid is preferably in a dispersed state, and since it is not dissolved, it can be prevented from falling off in a later step, and more effective treatment can be performed. However, it is preferable that it is stably dispersed during the treatment process. The solid content concentration of the silicone compound in the treatment liquid is preferably 0.2 to 5% by weight. If it is 0.2% or less, sufficient effects tend to be difficult to obtain, and if it is 5% or more, the tackiness of the treating agent tends to impair the tactile sensation of the leather-like sheet as the final product.

  The silicone compound used in the present invention is usually modified with a hydrophilic component as described above, but the HLB value which is the hydrophilic / lipophilic balance is preferably 4 or more, and more preferably in the range of 5-9. Preferably there is. The viscosity is preferably 200 mPa · s or more, more preferably 300 to 30000 mPa · s. Moreover, when using water as a solvent, it is preferable that a cloud point is low, and it is 25 degreeC or less which is normal temperature, Comprising: It does not melt | dissolve at normal temperature, and it is preferable that it is a dispersed state. Due to such physical properties, it tends to be difficult to fall off while uniformly adhering to the fiber.

  In the present invention, a treatment liquid containing the silicone compound as described above is applied to the fibrous base material and dried. By applying the silicone compound having a hydrophilic side chain, The fibers in the fiber material substrate become non-bonded, and a very soft leather-like sheet is formed.

  As a specific treatment method, for example, a fibrous base material is immersed in a silicone-containing treatment solution prepared by diluting with a solvent such as water, and the amount of adhesion is controlled by squeezing with a nip roll, and then dried. Can be obtained by: The adhesion amount before drying (pickup amount of the treatment liquid) is preferably in the range of 60 to 150% by weight. If the amount of adhesion is too small or too large, the adhesion state tends to be non-uniform.

  As a drying method, a conventionally known method can be used, and a hot air drying method or a heating roll method is generally used, but hot air drying is more preferable from the viewpoint of migration. The drying temperature is preferably 110 to 140 ° C., and the drying time is preferably 3 to 15 minutes. The adhesion amount of the processing agent solids after drying is preferably 0.2 to 5% by weight. By drying the treatment liquid in this manner, the silicone compound adheres firmly to the fibers, and it is possible to bring about an interaction with the polymer elastic body solution to be impregnated later.

  The adhesion strength of the silicone compound to the fibrous base material can be evaluated as a residual rate by measuring the elution amount of the silicone compound from the fibrous base material after the drying treatment into water. That is, the amount of the silicone compound adhered to the fibrous base material after drying was divided by the residual amount of the silicone compound after the fibrous base material was washed with water at 25 ° C. for 3 minutes and squeezed and dried. Become. When the silicone compound is easily dissolved in water, the silicone compound having a hydrophilic side chain is dropped at the time of impregnation with the polymer elastic body emulsion solution. The joining effect tends to be reduced. The residual rate is preferably 20% or more, and more preferably 40% or more.

  In the production method of the present invention, as described above, a treatment liquid containing a silicone compound is applied to a fibrous base material and dried, and then impregnated with a polymer elastic body solution and solidified to produce a leather-like sheet. The polymer elastic body solution used in the present invention needs to be an aqueous emulsion.

  Any polymer-based water-based emulsion may be used as long as it exhibits elastomeric properties after removal of water, and examples thereof include polymer elastic emulsions such as polyurethane emulsion, NBR emulsion, SBR emulsion, and acrylic emulsion. Among these, polyurethane emulsions are preferable from the viewpoints of flexibility, strength, weather resistance, and the like. These polymer elastic emulsions may be used alone or in combination.

  Moreover, in this invention, it is preferable that this polymer elastic body emulsion has heat-sensitive gelling property. The heat-sensitive gelling emulsion is an emulsion that loses fluidity when heated and becomes a gel. By adopting heat-sensitive gelation, migration during drying can be suppressed at a higher level. As such a heat-sensitive gelling polymer elastic body emulsion, an emulsion containing a polymer elastic body having a heat-sensitive gelling property by itself, or a heat-sensitive gelling agent is added to the polymer elastic body emulsion. Any of the emulsions that are heat-sensitive gelling can be used.

  When the polymer elastic body emulsion has a heat-sensitive coagulation temperature, a range of 40 ° C. or more and 90 ° C. or less is preferable. Here, the heat-sensitive coagulation temperature of the elastic polymer emulsion refers to 50 g of an emulsion resin solution containing various additives in a 100 ml glass beaker and the contents are stirred with a thermometer while the beaker is heated to 95 ° C. The temperature at which the contents gradually lose their fluidity and solidify when heated gradually with water. If the heat-sensitive coagulation temperature is too low, the stability of the resin itself is poor, and in particular, it tends to generate agglomerates or gel during storage in the summer. It is not sharp, and it is difficult for the resin to be uniformly filled in the fiber, and it tends to cause some migration.

  In addition, the polymer elastic body solution used in the present invention may be added to a known additive, for example, a heat-sensitive gelling agent, an antioxidant, a UV absorber, a penetrating agent or the like, a thickener, if necessary. 1 or 2 of stabilizers such as antifungal agents, water-soluble polymer compounds such as polyvinyl alcohol and carboxymethylcellulose, dyes, inorganic or organic pigments, fillers, coagulation regulators, hydrolysis inhibitors, and crosslinking agents It may contain seeds or more.

  In the production method of the present invention, the method for impregnating the fibrous base material with the water-based emulsion of the polymer elastic body is not particularly limited as long as it is a commonly performed method. Examples thereof include a coating method and a spray method. In particular, in order to uniformly impregnate, a method of immersing a fibrous base material in an emulsion of a polymer elastic body is preferably employed. Furthermore, it is preferable to adjust the impregnation amount of the polymer elastic body emulsion to an appropriate amount using a press roll or a doctor knife after impregnating the fibrous base material with the polymer elastic body emulsion.

  Next, the emulsion of the polymer elastic body impregnated in the fibrous base material is solidified. As the coagulation treatment, heat treatment is generally used, and heat-sensitive coagulation in a high-temperature and high-humidity atmosphere is particularly preferably employed because a leather-like sheet-like material having a softer texture can be obtained. In the case of heat-sensitive coagulation treatment, the treatment temperature is preferably equal to or higher than the heat-sensitive coagulation temperature of the polymer elastomer emulsion, and is preferably 50 ° C. or higher and 180 ° C. or lower. However, for more stable production, heat treatment is performed. More preferably, the gelation temperature is 10 ° C. or higher. Further, the relative humidity is preferably 80% or more, and further, the closer to 100%, the more preferable the drying from the surface is suppressed. The treatment time is usually preferably 1 minute to 10 minutes. Further, as a treatment after the coagulation, it is preferable to wash the composite sheet made of the fiber and the polymer elastic body obtained by the coagulation method with hot water. By extracting and removing the water-soluble component with hot water, it becomes possible to obtain a leather-like sheet-like material that is more stable in quality.

The obtained leather-like sheet is preferably subjected to heat drying or air drying in order to remove moisture contained in the leather-like sheet. As a specific treatment method, for example, any drying method such as hot air heating, infrared heating, and cylinder heating is possible. In general, hot air heating is preferred particularly from the viewpoint of balance between cost and quality. The drying temperature is preferably 80 ° C. or higher and 180 ° C. or lower.
As a ratio of the polymer elastic body to the fiber in the obtained leather-like sheet material, the polymer elastic body / fiber (hereinafter referred to as R / F) is preferably in the range of 20/100 to 70/100. . In addition, the density of the leather-like sheet material that becomes the impregnated substrate layer is preferably 0.2 to 0.4 g / cm ³ .

  Furthermore, it is also preferable to provide a layer made of a polymer elastic body on the surface of the obtained leather-like sheet material to form a leather-like sheet material (artificial leather) with a silver tone. In particular, this polymer elastic body layer forms a polymer elastic body layer as the outermost surface on a release paper, and an adhesive layer made of a polymer elastic body is provided thereon, and a leather-like sheet material serving as a substrate. It is preferable that the laminate method is used. As the polymer elastic body to be used, the same polymer elastic body used for impregnation of the fibrous base material can be used, and it should be an aqueous polymer elastic body, particularly an aqueous polyurethane polymer. Is preferred.

  The leather-like sheet-like material obtained by such a production method of the present invention has a natural leather-like flexibility and is inferior to artificial leather obtained by a conventional wet coagulation method. . This is considered to be because in the leather-like sheet-like material obtained in the present invention, the fibers in the fiber material substrate and the polymer elastic body such as polyurethane resin are not joined. Incidentally, this can be confirmed, for example, by photographing the cross section with an electron microscope. In the leather-like sheet-like material obtained in the present invention, the binding force is reduced because the polymer elastic body is not bonded to the fiber even though the fiber and the polymer elastic body are present at a high density. A decrease in flexibility is prevented, and a high texture is obtained.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples. In the examples and comparative examples, “parts” and “%” are based on weight unless otherwise specified. Moreover, each measured value in an Example was measured with the following method.

(1) Thickness Measured with a spring type dial gauge (load: 1.18 N / cm ² ).
(2) Weight A test piece cut to 10 cm × 10 cm was measured with a precision balance.
(3) Impregnation of impregnating solution The penetrability of the impregnating solution was evaluated as being easy to permeate and difficult to permeate in the order of Δ and ×.
(4) Flexibility The flexibility of the obtained artificial leather was determined by human sense. ◎ is the most flexible evaluation, and the evaluation becomes harder in the order of ○, Δ, ×.
(5) Residual rate of silicone compound First, the weight of the fibrous base material (nonwoven fabric) used was measured (a). Next, it was impregnated with a 5% concentration treatment solution (5 times the concentration of the treatment solution containing the silicone compound used in each Example and Comparative Example), squeezed with mangles, dried at 140 ° C. for 10 minutes, and the weight was measured. Measured (b). Then, it was further washed with water at 25 ° C. for 3 minutes, squeezed and dried at 140 ° C. for 10 minutes, and then the weight was measured (c).
The residual ratio of each material to water treatment was calculated by the following formula.
Residual rate (%) = (c−a) ÷ (b−a) × 100

[Example 1]
After mixing 50 parts of polyester shrink fiber and 50 parts of non-shrink polyethylene terephthalate short fiber with 0.8 dtex and cut length of 38 mm, a web was made through a card machine, and then a needle equipped with a needle having one barb Punching was performed in a locker room at a driving density of 1500 pieces / cm ² , and the fibers were entangled to obtain a web having a basis weight of 180 g / m ² . The web was immersed in warm water at 70 ° C. for 2 minutes to shrink so that the area shrinkage was 35%, and then dried at 110 ° C. to have a basis weight of 277 g / m ² , a thickness of 1.0 mm, and an apparent density of 0.1. A fibrous base material (nonwoven fabric) of 277 g / cm ³ was obtained.
Subsequently, polyether acetate-modified silicone having hydrophilic side chains on the obtained fibrous base material (SH-28 manufactured by Toray Dow Corning Co., Ltd., kinematic viscosity 300 mm ² / s <25 ° C., cloud point 25 ° C. or lower) A 1% aqueous dispersion was applied and the wet pick-up was adjusted to 100% with a mangle and then dried with a hot air dryer at 120 ° C. for 10 minutes. The adhesion amount of the silicone compound to the fiber was 1%. In addition, although this silicone compound containing process liquid was cloudy, it was disperse | distributing uniformly and was excellent also in stability. The residual rate was high, and a uniform quality nonwoven fabric could be obtained.

On the other hand, as a polymer elastic body solution, a heat-sensitive coagulation-type water-based polyurethane emulsion (Dainippon Ink Science & Technology Co., Ltd., Hydran WL602, heat-sensitive coagulation temperature 60 ° C.) has a solid content of 15%. An impregnation treatment liquid having a solid content of 1% was prepared from Kogyo Co., Ltd., Assister T2).
When the fibrous base material to which the silicone compound obtained previously was impregnated was impregnated with this impregnation treatment liquid, it was impregnated uniformly. Then, the excess dispersion liquid on the surface was scraped off and coagulated in a heat-sensitive coagulation box in which the atmospheric temperature was controlled to 95 ° C. and the relative humidity was controlled to 99%. Then, it was immersed in water and cooled, then squeezed with a mangle roll, and dried for 10 minutes with a hot air dryer at 120 ° C. to obtain a leather-like sheet (impregnated substrate). The ratio R / F between the polymer elastic body and the fibers of the obtained leather-like sheet was 30%.

Next, on a release paper (Rintech Co., Ltd., R53), a polyurethane 33% aqueous dispersion (Dainippon Ink Chemical Co., Ltd., Hydran WLS202) 100 parts thickener (Dainippon Ink Chemical Co., Ltd.) , Hydran Assister T1), and 5 parts of a coloring agent (Dailac Black HS9560, manufactured by Dainippon Ink & Chemicals, Inc.) were added with stirring to adjust the viscosity to 8000 mPa · s at a weight of 90 g / m ² . It was coated and dried at 70 ° C. for 2 minutes and at 110 ° C. for 2 minutes to form a polyurethane colored film. Furthermore, 100 parts of a water-dispersible polyurethane adhesive (Dainippon Ink Chemical Co., Ltd., Hydran A441, 45% concentration) on the surface thereof and a colorant (Dailac Black HS9560, manufactured by Dainippon Ink & Chemicals, Inc.) 5 Part and a thickener (manufactured by Dainippon Ink Chemical Co., Ltd., Hydran Assist T1) were mixed with a preparation liquid having a viscosity adjusted to 5000 mPa · s and coated at a basis weight of 150 g / m ² . Next, after drying at a temperature of 90 ° C. for 2 minutes, the impregnated substrates were superposed and passed through a roll with a gap of 0.6 mm on the surface of a heated cylinder at a temperature of 110 ° C. and pressure bonded. Then, after leaving for 2 days in an atmosphere at a temperature of 60 ° C., the release paper was peeled off to obtain an artificial leather with silver tone.
The results are shown in Table 1.

[Example 2]
Instead of the polyether acetate-modified silicone of Example 1, a polyether-modified silicone oil having a high HLB value of 14 (FZ-2104 manufactured by Toray Dow Corning Co., Ltd., viscosity 1000 mPa · s <35 ° C.> (converted dynamic viscosity 970 mm ² / A leather-like sheet (base material) and a silver-tone artificial leather were obtained in the same manner as in Example 1 except that s)) was used. In addition, although the silicone compound containing process liquid was high in viscosity here, it was disperse | distributed uniformly and was excellent also in stability. The residual rate was high, and a uniform quality nonwoven fabric could be obtained.
The results are also shown in Table 1.

[Example 3]
Instead of the polyether acetate-modified silicone of Example 1, a polyether-modified silicone oil having an HLB value of 4.5 (manufactured by Shin-Etsu Chemical Co., Ltd. KF-6016, PEG-9 methyl ether dimethicone, kinematic viscosity 150 mm ² / <25 ° C.> ) Was used in the same manner as in Example 1 to obtain a leather-like sheet (base material) and a silver-tone artificial leather. The silicone compound-containing treatment solution had a slight difficulty in stability, but the residual ratio was high.
The results are also shown in Table 1.

[Example 4]
Instead of the polyether acetate modified silicone of Example 1, polyglycerin modified silicone oil (KF-6104 manufactured by Shin-Etsu Chemical Co., Ltd., polyglyceryl-3 polydimethylsiloxyethyl dimethicone, viscosity 4000 mPa · s <25 ° C.> (converted kinematic viscosity 4000 mm) ² / s)) was used in the same manner as in Example 1 to obtain a leather-like sheet (base material) and silver-like artificial leather. The silicone compound-containing treatment solution had a slight difficulty in stability, but the residual ratio was high.
The results are also shown in Table 1.

[Example 5]
Instead of the polyether acetate-modified silicone of Example 1, a polyether-modified silicone oil having an HLB value of 7.0 (manufactured by Shin-Etsu Chemical Co., Ltd. KF-6012, PEG / PPG-20 / 22 butyl ether dimethicone, kinematic viscosity 1600 mm ² / < 25 ° C., cloud point 35 ° C.) was used in the same manner as in Example 1 to obtain a leather-like sheet (base material) and a silver-tone artificial leather.
The results are also shown in Table 1.

[Example 6]
Instead of the polyether acetate-modified silicone of Example 1, a polyether-modified silicone oil having an HLB value of 14.5 (KF-6043, PEG-10 dimethicone manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity 400 mm ² / <25 ° C.>, cloudiness A leather-like sheet (base material) and a silver-tone artificial leather were obtained in the same manner as in Example 1 except that the point 71 ° C) was used. This silicone compound-containing treatment liquid had high solubility in water and excellent solution stability, but it tended to have a large amount of elution into water and a low residual rate.
The results are also shown in Table 1.

[Comparative Example 1]
A leather-like sheet (base material) and silver-tone artificial leather were obtained in the same manner as in Example 1 except that the treatment with the silicone compound of Example 1 was not performed.
The results are shown in Table 2.

[Comparative Example 2]
In the same manner as in Example 1 except that a water-repellent amino-modified silicone (NX-1 manufactured by Matsumoto Yushi Co., Ltd.) was used instead of the hydrophilic polyether-acetate-modified silicone of Example 1, a leather-like sheet-like material was used. A product (base material) and a silver-finished artificial leather were obtained.
The results are also shown in Table 2.

[Comparative Example 3]
In the same manner as in Example 1 except that water-repellent dimethyl silicone (IE-7046T manufactured by Toray Dow Corning Co., Ltd.) was used instead of the hydrophilic polyether acetate-modified silicone of Example 1, a leather-like sheet-like material was used. A product (base material) and a silver-finished artificial leather were obtained.
The results are also shown in Table 2.

[Comparative Example 4]
A leather-like sheet (base material) was prepared in the same manner as in Example 1 except that a PEG ester having a HLB value of 10 (Marvelin DS100 manufactured by Matsumoto Yushi Co., Ltd.) was used instead of the polyether acetate-modified silicone of Example 1. ) And silver-finished artificial leather.
The results are also shown in Table 2.

[Example 7]
Instead of the fibrous base material (nonwoven fabric) made of polyester fibers having the normal fineness of Example 1, a fibrous base material (long fiber nonwoven fabric) made of a peelable split type composite fiber made of polyester fiber / polyamide fiber was used.
That is, a cross section of a 16-part multilayer laminate type in which polyethylene terephthalate copolymerized with isophthalic acid having shrinkage properties is used as the first component, and the second component is nylon-6 containing 2% by weight of polyethylene glycol having a molecular weight of 19000. A split split type composite fiber having a parent yarn fineness of 3.0 dtex having a diameter of 5 was spun. The spun long fibers are used as they are as a web, and an oil agent is applied thereto. After eight sheets are overlapped with a cross layer, they are entangled with a needle punch having a penetrate number of 1400 / cm ² , and have a basis weight of 250 g / m ² , thickness. A 1.22 mm long non-split non-woven fabric was obtained. Next, after immersing in warm water at 50 ° C., and performing a split splitting process with a striking-type splitting machine, the non-woven fabric after split processing is immersed in a 75 ° C. hot water tank for 60 seconds, and the first component polyethylene terephthalate fiber is The entire area was shrunk by 45% and dried to obtain a long fiber nonwoven fabric. The long fiber nonwoven fabric (fibrous substrate) had a thickness of 1.25 mm, an apparent density of 0.34 g / cm ³ , and a basis weight of 420 g / m ² .
Except that this non-woven fabric was used as a fibrous base material, a treatment with hydrophilic polyether acetate-modified silicone was performed in the same manner as in Example 1 to obtain a leather-like sheet (base material) and silver-tone artificial leather. However, it was very soft.

[Comparative Example 5]
The same long fiber nonwoven fabric as in Example 7 was used, and a sheet-like material (base material) and a silver-coated sheet were obtained in the same manner as in Example 7 except that the treatment with the silicone compound of Example 7 was not performed. It was very hard and was not a leather-like sheet.

Claims (4)

A method for producing a leather-like sheet material in which a treatment liquid containing a silicone compound is applied to a fibrous base material, dried, impregnated with a polymer elastic body solution, and solidified, wherein the silicone compound is a hydrophilic side chain The hydrophilic side chain of the silicone compound is composed of one or more of a polyether side chain, a polyether acetate side chain, and a polyglycerin side chain, and the polymer elastic body solution is an aqueous emulsion. A method for producing a leather-like sheet, characterized by   The process for producing a leather-like sheet according to claim 1, wherein the treatment liquid containing a silicone compound is an aqueous treatment liquid.   The method for producing a leather-like sheet according to claim 1 or 2, wherein the silicone compound in the treatment liquid is in a dispersed state.   The method for producing a leather-like sheet according to any one of claims 1 to 3, wherein the concentration of the solid content of the silicone compound in the treatment liquid is 0.5 to 5% by weight.