JP2000328465A - Leather-like seat for balls - Google Patents

Abstract

(57) [Summary] [Problem] To provide a leather sheet having sufficient mechanical strength and excellent in non-slip properties due to sweat absorption performance, particularly suitable for basketball and American football. A porous substrate layer comprising a fiber entangled body, a porous elastic body and a penetrating agent present in the space of the entangled body, and a porous surface layer formed on the surface thereof. Has a diameter of 5 to 100 μm, and most of them have 300 to 10,000 microholes communicating with the internal pore space.
A leather-like sheet for balls, wherein there are 00 / cm ² and a penetrating agent is present inside the microhole.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a leather-like sheet for a ball which has sufficient mechanical strength and is excellent in non-slip property due to its sweat-absorbing property, particularly for basketball, American football and rugby. The present invention relates to a leather-like sheet for balls suitable for volleyball, baseball, and the like.

[0002]

2. Description of the Related Art Many leather-like sheets have been proposed as substitutes for natural leather as materials for balls. Many non-slip properties are required for ball materials. As a method for obtaining a leather-like sheet having non-slip properties, for example, Japanese Patent Publication No. 7-30285 discloses polyurethane resin having a hydroxyl group in a molecule, molecular A method of coating a sheet surface with a coating composition containing a liquid rubber having a hydroxyl group therein, an inorganic or organic filler, and an isocyanate prepolymer is disclosed in
No. 97475 discloses a method of impregnating and solidifying a nonwoven fabric with a resin exhibiting rubber elasticity, and slicing at an intermediate layer. Further, Japanese Unexamined Patent Publication No. 63-152483 discloses a method in which gelatin is mixed into a rubber material and heated. After foam molding, a method has been proposed in which a part of the surface skin layer of the molded product is removed, and gelatin on the surface is removed with hot water to make the surface porous.

[0003]

However, the above resin,
In the method of coating the sheet surface with the filler and the coating composition, the coated surface absorbs the sweat generated in the hand to some extent, but when the absorption limit is exceeded, its performance cannot be exhibited, so that the Not suitable for continuous use. Further, the resin or the like that has absorbed sweat is plasticized and becomes different from the original touch, and is not suitable for continuous use. Further, in the method of impregnating and solidifying the nonwoven fabric with a resin exhibiting rubber elasticity and slicing it in the intermediate layer, the surface strength is low and it cannot withstand hard use such as basketball. Furthermore, the above method for producing a surface layer having a porous structure also lacks mechanical strength and is not suitable for use.

[0004] It is an object of the present invention to provide a leather-like sheet for a ball which prevents slippage due to moisture such as sweat or rainwater of American football, basketball, rugby ball and the like, has excellent handling properties, and has sufficient mechanical strength. Is to do.

[0005]

Means for Solving the Problems In order to achieve the above-mentioned object, the present inventors have studied and as a result, have sufficient mechanical strength to absorb moisture such as sweat and rainwater from the surface. Another object of the present invention is to provide a leather-like sheet for a ball which exhibits non-slip properties, has excellent handling properties, and has sufficient mechanical strength. That is, the present invention comprises a fiber entangled body, a porous base layer made of a porous elastic body and a penetrant present in the entangled body space, and a porous surface layer formed on the surface thereof. The surface has an average diameter of 5-
300 to 10,000 microholes of 100 μm /
cm ² are present, and in the interior of said microholes is leather-like sheet for balls, wherein the penetrant is present.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The base layer used in the present invention is one in which an elastic resin is impregnated inside a three-dimensional entangled nonwoven fabric, which is present in a porous state inside the nonwoven fabric, and leather. The sheet is not particularly limited as long as the sheet has a good thickness and texture.

The fibers constituting the non-woven fabric are not particularly limited, and known cellulose fibers, acrylic fibers, polyester fibers, polyamide fibers, etc. may be used alone or in combination. However, an ultrafine fiber of 0.3 denier or less, particularly 0.1 denier or less, capable of realizing a soft texture closer to natural leather is preferably used.
Such an ultrafine fiber is obtained from an ultrafine fiber-generating fiber, and the ultrafine fiber-generating fiber is obtained by compound spinning or mixing spinning of two or more types of thermoplastic polymers having no compatibility. It is obtained by extracting or removing at least one component of the polymer, or by separating and separating the polymer at the interface of the constituent polymers. The typical fiber form is a so-called sea-island type fiber, and an ultrafine fiber bundle can be obtained by extracting or decomposing and removing the sea component polymer.

[0008] Such an island component polymer of the fiber is a polymer which can be melt-spun and sufficiently exhibit fiber properties such as strength, has a higher melt viscosity than the sea component polymer under spinning conditions, and has a surface tension. Is preferable, for example, a polyamide-based polymer such as 6-nylon and 66-nylon, and a copolymer mainly containing the same,
Polyester-based polymers such as polyethylene terephthalate and polybutylene terephthalate, and copolymers mainly composed of these are preferably used. Also, as the sea component polymer, the melt viscosity is lower than the island component polymer, the solubility and decomposability with the island component are different, and the solubility in the solvent or decomposer used for dissolving and removing the sea component is large. ,
Polymers having low compatibility with island components are preferred. For example, polyethylene, modified polyethylene, polypropylene, polystyrene, modified polystyrene, modified polyester and the like are suitably used.

[0009] The ultrafine fiber-generating fiber that suitably generates ultrafine fibers having a fineness of 0.3 denier or less, that is, the preferable sea-island volume ratio of sea-island fiber is sea / island = 30/70 to 70/30
Range. If the content of the sea component is less than 30%, the components that are dissolved or decomposed and removed with a solvent or a decomposer are too small to exhibit sufficient flexibility, and if the sea component exceeds 70%,
Absolute amount of fiber consisting of island components after dissolution or decomposition removal is small, and sufficient physical properties as a leather-like sheet cannot be secured,
Further, the fact that there are many components to be dissolved or decomposed and removed is also inappropriate from the viewpoint of productivity.

[0010] The three-dimensional entangled nonwoven fabric constituting the present invention is obtained by stretching the above-mentioned fiber, crimping it, and cutting it to a length of several cm.
Disintegrated with a card, forming a web through a webber, laminating the obtained fiber web to a desired weight and thickness, and then by a conventionally known entanglement method such as a needle punch method or a high-speed water entanglement method can get.

[0011] The nonwoven fabric thus obtained is then impregnated with a solution or dispersion of an elastic polymer and solidified into a sponge. As the polymer elastic body, an elastic resin conventionally used in the production of a leather-like sheet is preferably used. That is, polyurethane-based resins, polyester-based elastomers, rubber-based resins, polyvinyl chloride resins, polyacrylic acid-based resins, polyamino acid-based resins, silicon-based resins, copolymers thereof, and mixtures thereof are suitable. These resins are impregnated into the nonwoven fabric as an aqueous emulsion or an organic solvent solution, and then coagulated into a sponge by wet coagulation or the like. By making the impregnated polymer elastic body porous (sponge-like), physical properties and texture similar to natural leather can be obtained,
It is also excellent in non-slip properties.

Typical examples of the elastic polymer impregnated in the fiber entangled nonwoven fabric include, for example, an average molecular weight of 500 to 3,000.
0, polyester diol, polyether diol, polyester ether diol, polylactone diol,
At least one kind of polymer diol selected from polycarbonate and the like; and tolylene diisocyanate
G, xylylene diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate
G, 4,4'-dicyclohexylmethane diisocyanate
At least one organic diisocyanate selected from aromatic, alicyclic, and aliphatic organic diisocyanates such as isophorone diisocyanate and hexamethylene diisocyanate; Polyurethane obtained by reacting at least one type of chain extender selected from low molecular compounds having at least two active hydrogen atoms such as diol, diamine, hydroxyamine, hydrazine and hydrazide in a predetermined molar ratio is used. No. Polyurethane can be used as a polymer composition obtained by adding a polymer such as synthetic rubber, polyester elastomer, or polyvinyl chloride, if necessary.

When the above-mentioned ultrafine fiber-generating fiber is used as the fiber, it may be in the stage of the fibrous base material impregnated and coagulated with the polymer elastic solution or dispersion, or in the stage of the nonwoven fabric before the impregnation and coagulation. By treating with a solvent or a decomposing agent of one component of the ultrafine fiber-generating fiber, preferably a sea component polymer, to dissolve or decompose the component to obtain 0.3.
Generates ultrafine fibers of denier or less. When the microfiber-generating fiber is formed from a plurality of polymers that can be peeled between polymers, the fiber is chemically or physically treated to be peeled at the interface of the polymer constituting the fiber. An ultrafine method can also be used.
Thus, a leather-like substrate composed of ultrafine fibers and a polymer elastic body is obtained.

The thickness of the leather-like substrate can be arbitrarily selected according to the intended use, and is not particularly limited, but is preferably 0.6 mm to 3 mm. The weight ratio between the microfiber and the polymer elastic material is 35/65 to 65/35 by weight.
Is preferred. If the ratio is out of this range, the balance between the fiber and the elastic polymer is deteriorated, and it becomes impossible to obtain a sense of fulfillment and flexibility as a product.

As a method of forming a porous surface layer on the surface of the base layer, an elastic polymer resin solution is applied on one side of the base with a certain clearance, and the applied elastic polymer resin is dissolved in a poor solvent. It is preferable to make the elastic polymer resin layer porous by coagulation, but the elastic polymer resin solution impregnated in the nonwoven fabric and the elastic polymer resin solution applied to the surface may be coagulated simultaneously.

As the elastic polymer resin forming the porous surface layer, polyurethane is preferably used because of its elasticity, softness, abrasion resistance, and ease of forming the porous layer. As the polyurethane, at least one selected from polyesterdiol having an average molecular weight of 500 to 3,000, polyetherdiol, polyesteretherdiol, polylactonediol, polycarbonatenetdiol, and the like. One kind of polymer diol and tolylene diisocyanate,
Xylylene diisocyanate, phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4
'-Dicyclohexylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate
And at least one organic diisocyanate selected from aromatic, alicyclic and aliphatic organic diisocyanates such as diols, and the activity of diols, diamines, hydroxyamines, hydrazines and hydrazides. Those obtained by reacting at least one type of chain extender selected from low molecular compounds having at least two hydrogen atoms at a predetermined molar ratio are used. In terms of hydrolysis resistance and elasticity,
Those using a polyether-based polymer diol represented by polytetramethylene glycol are preferably used.

Additives such as a colorant, a light stabilizer and a dispersant are added to the elastic polymer resin solution to be applied according to the purpose. Further, in order to control the shape of the porous material, a coagulation controlling agent is selected as necessary, and is added alone or in combination of several kinds.

After applying the elastic polymer solution on the substrate layer,
Coagulates in a poor polyurethane solvent to form a porous layer. As the poor solvent, water is preferably used, but water may be mixed with a good solvent of an elastic polymer resin such as dimethylformamide for the purpose of controlling the porous shape.

The method of forming microholes contributing to water absorption in the porous surface layer of the present invention is characterized in that the elastic polymer for forming the porous surface layer is formed on the surface of the porous surface layer obtained by the above method. A good solvent is applied in the form of dots using a gravure roll or the like, and is left for a while before drying to dissolve the resin on the outermost surface of a part of the porous surface layer.

The size (diameter) and number of micro holes are
It can be controlled by the type of solvent, the amount of adhesion, the area of adhesion, the number of adhesion points, and the standing time. That is, the larger the ratio of the good solvent in the solvent, the larger the amount of adhesion, the larger the adhesion area, and the longer the leaving time, the larger holes are formed. The number of microholes increases as the number of solvent attachment points increases. The microholes need to have a hole diameter in the range of 5 to 100 μm, and the number of holes needs to be in the range of 300 to 10,000 / cm ² . If the pore size is less than 5 μm or the number of pores is less than 300 / cm ² , sufficient moisture cannot be absorbed, and the pore size is less than 100 μm.
A film having a size of μm or a number of holes exceeding 10,000 / cm ² is not preferable because the holes are too large or too large to be visually recognized to impair the appearance and to deteriorate the surface properties. In particular, the presence of microholes having a pore diameter of more than 100 μm impairs the appearance. Therefore, in the present invention, it is preferable that substantially no microholes having a diameter of more than 100 μm exist.

As a method for adhering the solvent, coating with a screen, spraying with a spray, etc. are possible, but coating with a gravure roll is preferred because the process itself, the amount of adhesion, and the standing time are easy to control. Used. As described above, by using the method of applying the solvent to the surface, most of the microholes formed on the surface communicate with the pores present inside the porous surface layer, and further, the pores and spaces in the base layer are formed. It will also communicate with. The diameter and the number of the microholes are measured by a method of taking 10 photographs of the surface with an electron microscope, measuring the diameter and the number of the microholes in a range of 500 μm square, and taking an arithmetic mean.

In the present invention, a penetrant is applied to the surface layer and the base layer in order to promote the absorption of water from the surface layer. Physically, it absorbs the moisture attached to the surface from the micro holes in the surface porous layer, but by applying a penetrant to the porous layer and the base layer, the absorption of moisture from the surface is promoted, Further, the movement from the surface porous layer to the base layer is promoted, and the entire leather-like sheet can absorb moisture. This makes it possible to prevent the surface of the ball from slipping due to moisture such as sweat for a long continuous time.

Examples of the penetrant used in the present invention include polyoxyalkylene ethers, alkylsulfosuccinates, alkylphosphates, acid ester salts,
Common penetrants such as quaternary ammonium-based and modified silicone-based are used. Among them, penetrants such as polyoxyethylene alkyl ethers and alkylsulfosuccinates are preferable, and the molecular weight is preferably 300 or more so that they are not easily washed away with water. The amount of the penetrant to be present is preferably 1 to 10 g / m ² . Considering that the penetrant is applied to both the surface porous layer and the base layer, the method of impregnating the leather-like sheet into the aqueous penetrant solution is optimal.

The leather-like sheet for a ball according to the present invention has an initial tactile sensation, by quickly absorbing moisture such as sweat coming out of a hand during use by the action of microholes on the surface and a penetrant contained therein. It has the function of maintaining non-slip properties, and is particularly suitable for basketball, American football, rugby, volleyball, and baseball.

[0025]

EXAMPLES Next, the present invention will be described specifically with reference to Examples.
The present invention is not limited to these examples. In the examples, parts and percentages relate to weight unless otherwise specified.

Example 1 A sea-island mixed spun fiber in which the island component was 6-nylon and the sea component was a high-flow low density polyethylene (sea component / island component ratio = 50/50) was melt spun. The obtained fiber was drawn, crimped, and cut to obtain a staple having a 3.5 denier and a cut length of 51 mm. The staples were passed through a card and were laminated into a web by a cross wrapper method. Next, a needle was punched with a needle having a barb at one place at a needle penetration density of 980 P / cm ² to obtain a nonwoven fabric having a basis weight of 450 g / m ² . After heating and drying this non-woven fabric and pressing to smooth the surface, 16%
Impregnated with a dimethylformamide (abbreviated as DMF) solution of a polyether-based polyurethane, coagulated with an aqueous DMF solution, washed with hot water, and extracted and removed from the polyethylene in the fiber with hot toluene. A substrate for artificial leather made of polyurethane was obtained.

The surface of the artificial leather substrate is made of polytetramethyl
Polyuret made of polyol mainly composed of len ether
400 g / m of a 20% DMF solution of tan²Apply, underwater
To form a porous surface layer. Table of this porous surface layer
Apply DMF to the surface with a 150 mesh gravure roll
After leaving it for 3 minutes, it was dried to form micro holes.
In addition, ether-based polyurethane ink containing tea pigment
And embossed for basketball embossing.
Next, polyoxyethylene octyl having an average molecular weight of 400
Impregnated with 1% aqueous solution of ether type penetrant at liquid content of 60%
Gave. 4 g / m²Met. The obtained leather-like
The sheet has an average pore diameter of 40 μm on the surface and about 1600 holes.
/ Cm ²Micro-holes, many of which
Was in communication with the hole. Miku with pore size over 100μm
I could hardly find Lohol. This leather-like sheet
Can exhibit non-slip properties due to good sweat absorption performance
The leather-like sheet was suitable for basketball. This
Make a basketball using the leather-like sheet of
Used in basketball games under high humidity and humidity conditions.
After use for a long time, the slip property does not change.
won.

Example 2 In Example 1, after forming the porous surface layer, DM was added to the surface.
F was applied with a 120 mesh gravure roll, left for 3 minutes, and dried to form micro holes. Further, it was colored with an ether-based polyurethane ink containing a tea pigment, and the embossed basketball was performed. Then, a 1% aqueous solution of a polyoxyethylene octyl ether type penetrant having an average molecular weight of 400 was impregnated with a liquid content of 60%. The adhesion amount was 4.2 g / m ² . The leather-like sheet obtained is
The surface has an average pore diameter of 50 μm and the number of pores is about 1,000 / cm ²
And microholes having a pore diameter exceeding 100 μm were hardly found. Most of the microholes on the surface were connected to the internal pores. This leather-like sheet was a leather-like sheet suitable for basketball, which can exhibit non-slip properties due to good sweat absorption performance.

Comparative Example 1 In Example 1, after the porous surface layer was formed, DM was added to the surface.
F with a 55 mesh gravure roll and release for 5 minutes
After placing, it was dried to form micro holes. In addition, tea
Color with ether-based polyurethane ink containing pigment
Skeet ball embossing was performed. The obtained leather-like
The sheet has an average pore diameter of 140 μm on the surface and about 800 holes
/ Cm ²Microholes for good sweat absorption performance
It was possible, but the micro hole was clearly visible with the naked eye.
It was of low value.

Comparative Example 2 In Example 1, after the porous surface layer was formed, DM was added to the surface.
F was coated with a 140 mesh gravure roll, left for 2 minutes, and dried to form micro holes. Furthermore, it is colored with ether-based polyurethane ink containing tea pigment,
Basketball embossing was performed. The obtained leather-like sheet has an average pore diameter of 50 μm on the surface and a number of pores of about 1200.
Although it has microholes per piece / cm ² , it does not exhibit sufficient sweat-absorbing performance because it does not contain a penetrant, and basketballs made of this leather-like sheet do not have sufficient non-slip properties. Was.

Comparative Example 3 In Example 1, after forming the porous surface layer, DM was added to the surface.
F was applied with a 200 mesh gravure roll, left for 1 minute, and dried to form micro holes. Furthermore, it is colored with ether-based polyurethane ink containing tea pigment,
Basketball embossing was performed. Since the obtained leather-like sheet has only microholes having an average pore diameter of 10 μm and the number of holes of about 100 / cm ² on its surface, it cannot exhibit a sufficient sweat-absorbing performance. It did not have a good non-slip property.

Claims (1)

[Claims] 1. A porous substrate layer comprising a fiber entangled body, a porous elastic body and a penetrant present in a space of the entangled body, and a porous surface layer formed on the surface thereof, and the surface of the porous surface layer Has 300 to 10,000 microholes / cm ² having an average diameter of 5 to 100 μm, and a penetrating agent is present inside the microholes. Sheet.