JP4338950B2 - Sheet material and method for producing the same - Google Patents

Description

【００３７】
実施例１〜３と比較例１を比較すれば本発明の皮革様シートが非常に優れた柔軟性とオイル感を有することがわかる。また実施例１〜３と比較例２〜４を比較するならば、本発明の皮革シートがこれまでの柔軟化技術に比べ、著しく柔軟性、オイル感などの風合いに優れているにもかかわらず、オイルの移行が見られない、洗濯に対しても耐性を有するなどの点で優位にあることが分かる。しかも、本発明の皮革様シートは従来の類似技術で問題となっていた、オイルの移行が著しく改良されているため、基材中に大量にシリコーンゲルを含ませることが可能であり、充実感などについても優れたものを得ることが可能である。り、充実感などについても優れたものを得ることが可能である。
【００３８】
【発明の効果】
本発明によれば、繊維質基材からなるシート状物に関して、柔軟性に優れ、天然皮革の持つオイル調のしっとりとした触感を有し、さらにオイル等の油状物質の移行が少なく高級感に優れた皮革様シートを得ることができる。かかるシートは、手袋、衣類等にしたとき風合い・高級感に優れたものとなり有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a leather-like sheet having both natural leather-like flexibility and oil-like feel, little oil transfer, and excellent washing resistance.
[0002]
[Prior art]
There are leather-like sheets (so-called synthetic leather, artificial leather, etc.) that artificially reproduce the excellent characteristics of natural leather. However, the conventional ones are widely used because they have various advantages that natural leather does not have, such as various washable care, lightness, and uniformity. However, especially when compared with high-grade leather, the softness of the touch, the unique oil feeling, and the sense of fulfillment have not yet been fully reproduced. On the other hand, for softness, known softeners such as silicon emulsion and wax are known, and for oil feeling, JP-A-1-139877 also contains an oil-soluble surfactant. The method is public. However, these methods are not only inferior in softness, texture or oil feeling, etc., but also have the disadvantage of being unable to wash, which is an advantage of the leather-like sheet when such treatment is performed. .
[0003]
On the other hand, softening with a greasing agent treated with natural leather, such as fish oil or vegetable oil, gives the texture and feel close to those of natural leather, but this is not only a problem of washing but also a problem of oil migration. There is. As can be seen from the above, there has not yet been obtained a natural leather-like product that does not migrate oily substances such as oil, and is excellent in flexibility and oil feeling.
[0004]
[Problems to be solved by the invention]
The present invention relates to a sheet-like material composed of a fibrous base material, which has excellent flexibility, has a moist feel of oil-like nature of natural leather, and has a low migration of oily substances such as oil and its It is an object to provide a manufacturing method.
[0005]
[Means for Solving the Problems]
In order to achieve the above-mentioned problems, the present inventors have intensively studied to arrive at the present invention. That is, in the present invention, the needle depth measured using a 1/4 scale cone by a method defined in JIS K2220 is at least inside the fibrous base material (A), and is toluene. The silicone gel (B) crosslinked until the extraction amount of silicon atoms when extracted at 70 ° C. for 30 minutes is 20% or less with respect to the total amount of silicon atoms is 100 mass by mass of the fiber substrate (A). 0.1 to 200 parts by mass with respect to the part. Moreover, the sheet-like material whose fiber which comprises a fibrous base material (A) is an ultrafine fiber below 0.2 dtex is preferable. Furthermore, the fibrous base material (A) is preferably a sheet-like material comprising a fiber-entangled nonwoven fabric and an elastic polymer impregnated therein.
And it is a sport glove obtained using this sheet-like material.
Also, a liquid in which an organopolysiloxane (C) having at least one vinyl group in the molecule and an organopolysiloxane (D) having at least one hydrogen atom directly bonded to a silicon atom in the molecule is mixed in advance. , Impregnating the inside of the fibrous base material (A) in which the elastic polymer is impregnated into the ultrafine fiber cloth composed of the ultrafine fiber bundle of 0.2 dtex or less, and applying the 1/4 scale cone by the method specified in JIS K2220 Until the needle depth measured by using is in the range of 30 to 120, and the extraction amount of silicon atoms is 30% or less with respect to the total silicon atom amount when extracted at 70 ° C. for 30 minutes using toluene. This is a method for producing a sheet-like material that is crosslinked to form a silicone gel.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
[0007]
The fibrous base material (A) in the present invention is not particularly limited as long as it is a fiber fabric such as a knitted fabric or a non-woven fabric, but is preferably one in which an elastic polymer is impregnated. And it is preferable that it is a sheet | seat base material which has favorable thickness and texture as artificial leather. Of course, a woven fabric and a non-woven fabric may be overlapped and integrated. In particular, in the present invention, a three-dimensional entangled nonwoven fabric is preferable in order to achieve natural leather-like stretchability and texture.
[0008]
The fibers constituting the fiber fabric are not particularly limited, and synthetic fibers such as known cellulose fibers, acrylic fibers, polyester fibers, polyamide fibers, polyolefin fibers, polyvinyl alcohol fibers, natural fibers, Examples thereof include recycled fibers and semi-synthetic fibers, and these fibers may be used alone or in combination.
[0009]
In order to obtain good handling properties, and further, the softness, texture, and feel of natural leather, the fineness of the fibers constituting the fibrous base material (A) is preferably 0.2 dtex or less. Particularly, a so-called ultrafine fiber bundle in which several to several hundred ultrafine fibers having a single fineness of 0.2 decitex or less are converged and a total decitex is 0.5 to 20 decitex is preferable in terms of flexibility and napping properties. . Such an ultra-fine fiber bundle is obtained by mixing and melting two or more kinds of incompatible polymers, discharging them from a spinneret and stretching them, or by separately melting the polymers and spinning the melt into a spinneret. By discharging together and stretching, a so-called ultrafine fiber-forming fiber having a cross-section of the fiber having a sea-island structure or a multi-layer bonded structure is produced, and the sea component polymer is removed from the fiber or peeled off between the layers. Can be obtained. Examples of the island component polymer constituting this ultrafine fiber-forming fiber include polyamides such as nylon-6, nylon-610 and nylon-66, polyesters such as polyethylene terephthalate and polybutylene terephthalate, and sea component polymers. Examples thereof include polyethylene, polystyrene, copolymers having these repeating units as a part of structural units, and copolyesters.
[0010]
It is particularly preferable that the fibrous base material (A) of the present invention is further impregnated with an elastic polymer inside the fiber fabric from the viewpoint of texture, durability, flexibility and the like. As a method for obtaining such a fibrous base material (A), a fiber cloth is impregnated with an elastic polymer solution or dispersion, and the elastic polymer solution is wet coagulated with a non-solvent, or the dispersion is destroyed by heat. And a dry coagulation method and a method of adding an easily extractable component at the time of impregnation of the elastic polymer and extracting and removing the easily extractable component after the elastic polymer is solidified. From the viewpoint of texture and mechanical strength, a method of impregnating the elastic polymer solution into the three-dimensional entangled nonwoven fabric made of the ultrafine fiber-forming fibers and wet coagulating the elastic polymer is preferable.
[0011]
As the elastic polymer constituting the fibrous base material, a known elastic polymer can be used, but a polyurethane resin is preferably used from the viewpoint of obtaining a good texture. Preferred polyurethane resins include polyester diols obtained by reacting diols with dicarboxylic acids or ester-forming derivatives thereof, and block copolymerized diols of these with polyethers, polylactone diols, polycarbonate diols, polyether diols, and the like. Examples include so-called segmented polyurethanes obtained by using at least one polymer diol having a number average molecular weight of 500 to 5,000 selected from the above and reacting it with a diisocyanate compound and a low molecular weight extender. As the diol compound used for the synthesis of the polyester diol, it is preferable to use at least part of a compound having 6 to 10 carbon atoms in terms of durability or leather-like texture. Examples include 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and the like. Representative examples of dicarboxylic acids include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, and sebacic acid, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid.
[0012]
When the number average molecular weight of the polymer diol is less than 500, it is not preferable because it lacks flexibility and a natural leather-like texture cannot be obtained. When the number average molecular weight of the polymer diol exceeds 5,000, the urethane group concentration in the polyurethane is reduced, so that it is difficult to obtain an artificial leather balanced in flexibility, durability, heat resistance, and hydrolysis resistance.
Examples of the low molecular chain extender include low molecular weight compounds having two active hydrogen atoms such as ethylene glycol, propylene glycol, butanediol, hexanediol, ethylenediamine, and isophoronediamine. Examples of the diisocyanate compound include aromatic compounds such as diphenylmethane-4,4′-diisocyanate, tolylene diisocyanate, phenylene diisocyanate, and xylylene diisocyanate, aliphatic compounds represented by hexamethylene diisocyanate, and dicyclohexylmethane-4,4 ′. -An alicyclic type thing, such as diisocyanate and isophorone diisocyanate, is mentioned. If necessary, pigments, dyes, coagulation regulators, stabilizers and the like may be added, and two or more kinds of polymers may be used in combination.
[0013]
The mass ratio of the fibers constituting the fiber fabric of the fibrous base material (A) and the elastic polymer is preferably in the range of 30/70 to 80/20 because it gives a texture closer to that of natural leather. More preferably, it exists in the range of 40 / 60-55 / 45. If the fiber ratio is too low in the fibrous base material, a rubber-like texture is unfavorable, and if the fiber ratio is too high, it becomes paper-like and the desired natural leather-like texture cannot be obtained.
[0014]
When the fibrous base material (A) is composed of ultrafine fiber-forming fibers, the ultrafine fiber-forming fibers may be modified into ultrafine fiber bundles before impregnating the elastic polymer, After impregnation, the ultrafine fiber-forming fiber may be modified into an ultrafine fiber bundle. Preferably, when the ultrafine fiber-forming fiber is a sea-island structure fiber, the ultrafine fiber is impregnated after impregnating the elastic polymer, and natural leather-like flexibility can be easily obtained by using this method. The thickness of the base layer is preferably from 0.3 to 2.0 mm because a natural leather-like one is easily obtained.
[0015]
Further, the sheet-like material of the present invention is preferably subjected to napping on the surface as desired. Although there is no particular limitation on the method of causing napping to exist on the surface of the sheet-like material, it is preferable that the method of rubbing the surface with an abrasive such as sandpaper and digging the fiber out of the impregnated resin has a high-class feeling. It is preferable because the surface feeling can be obtained.
[0016]
Furthermore, in the present invention, the fibrous base material (A) is preferably subjected to a treatment usually performed on a leather-like sheet such as dyeing / embossing according to necessity and purpose. It is also preferable to provide a layer made of a resin such as polyurethane on the surface of the substrate. As a method of providing such a layer, a method of gravure / drying a resin solution or emulsion on the surface, a so-called dry surface forming method in which a film obtained by coating / drying the solution on a release paper is attached with an adhesive, a resin solution For example, a so-called wet surface forming method in which the substrate is dipped in a poor solvent such as water or a coat on a substrate and solidified in a sponge shape can be exemplified. It is preferable from the viewpoint of the effectiveness and stability of the treatment that these treatments, excluding embossing, are performed in advance before the silicone gel (B) is contained.
[0017]
In the present invention, the silicone gel (B) contained in the fibrous base material (A) refers to a three-dimensional cross-linked cured product having a low cross-linking density made of an organopolysiloxane. Such gels are known per se. For example, the production method is known from Japanese Patent Application Laid-Open Nos. 58-7252, 62-20557, 62-181357, and 5-70693. be able to. When such a silicone gel is contained, the fibrous base material (A) becomes extremely flexible, has an oil-like texture, is excellent in durability and light weight, and has deteriorated in performance even for washing. It is possible to obtain a sheet-like material that combines the advantages of high-quality natural leather and the advantages of artificial leather-like sheets. On the other hand, the conventional method of impregnating with silicone oil has a limitation that it cannot be sufficiently softened due to a limit in the oil absorption amount of the base material, in addition to problems such as contamination due to oil transfer and deterioration of texture due to washing. . Among such silicone gels, organopolysiloxane (C) having at least one vinyl group in the molecule, organopolysiloxane (D) having at least one hydrogen atom directly bonded to a silicon atom in the molecule, and optionally a catalyst A silicone gel obtained by blending, and being crosslinked and cured is most preferable in that it has a long pot life during production and is relatively unaffected by production conditions and stable in quality.
[0018]
The silicone gel (B) of the present invention has a needle depth of 10 to 10 measured using a 1/4 scale cone by a method defined in JIS K2220 in a single state not impregnated in the fibrous base material (A). It is preferably in the range of 200, more preferably in the range of 20 to 160, and particularly preferably in the range of 30 to 120. When the needle depth is less than 10, the texture when made into a sheet-like material is biased toward the harder, and the use application is limited. When it exceeds 200, there may be a transition of the silicone gel (B) during use. is there.
[0019]
The silicone gel (B) of the present invention uses 20 times the amount (mass) of toluene as the leather-like sheet, and the amount of silicon atoms extracted when extracted at 70 ° C. for 30 minutes is 50% or less of the total amount of silicon atoms. It is preferably 40% or less, more preferably 30% or less, and most preferably 20% or less. If it exceeds 50%, the oil content may be transferred depending on the ratio of the fibrous base material (A) to the silicone gel (B).
[0020]
The abundance of the silicone gel (B) in the present invention is between 0.1 and 200 parts by mass, preferably 1 to 150 parts by mass when the mass of the fibrous base material (A) is 100 parts by mass. 120 mass parts is more preferable, and 5-100 mass parts is the most preferable. If the amount is less than 0.1 parts by mass, both the softening effect and the oil touch texture are ineffective. On the other hand, if it exceeds 200 parts by mass, the tack becomes strongly sticky, which makes it an inappropriate material for a leather-like sheet.
[0021]
In the present invention, as a method for incorporating the silicone gel (B) into the base material (A), for example, the organopolysiloxane (C) having one or more vinyl groups in the molecule as a raw material is directly bonded to a silicon atom. A liquid in which an organopolysiloxane (D) having one or more hydrogen atoms in the molecule and a catalyst, if desired, is mixed in advance is prepared, impregnated into the fibrous base material (A), squeezed with a mangle or the like, and then crosslinked. -The method of making it harden | cure, the method of bridge | crosslinking and hardening after apply | coating and penetrating the adjusted liquid with a gravure coater etc. can be illustrated. In addition, during the operation, the prepared liquid is further diluted with a solvent such as toluene, soaked into the fibrous base material (A), dried to remove the diluted solvent, and then crosslinked and cured. The method is particularly recommended from the viewpoint that the permeability can be adjusted and the silicone gel (A) can be more uniformly distributed. In addition, as a method of crosslinking / curing, there are a method of performing a heat treatment if necessary, a method of leaving and aging at an arbitrary temperature, and the like.
[0022]
【Example】
The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. In the examples, “%” and “parts” are based on mass unless otherwise specified. The characteristic value measurement method and evaluation method are as follows.
[0023]
[Flexibility]
The inventors perform sensory evaluation with a test piece of 20 cm × 30 cm,
A: Very soft O: Soft Δ: Slightly soft X: Hard
[0024]
[Oil feeling]
The inventors perform sensory evaluation with a test piece of 20 cm × 30 cm,
A: There is a strong oil feeling B: There is a feeling of oil B: Some oil feeling is felt
[0025]
[Oil transferability]
Place the test piece between the filter papers and leave it for 24 hours to visually evaluate the transfer of oil components to the filter paper.
○: No transition is observed Δ: Transition portion is observed to some extent ×: The transition is observed on almost the entire surface.
[0026]
[Washing resistance]
Washing was performed under the conditions of No. A-1 described in JIS L0844, and the dried texture was dried by the evaluation method of [Flexibility].
[0027]
[Toluene extraction]
2 g of the sample was immersed in 40 g of toluene and extracted at 70 ° C. for 30 minutes while refluxing. The sample was taken out and dried, and toluene was also evaporated to dryness. Furthermore, elemental analysis was performed on the sample and the residue obtained by distillation, and the ratio of the extracted silicone was determined.
[0028]
Example 1
Nylon and polyethylene are mixed in a 50/50 quantity ratio with a chip, spun in an extruder, and sea-island fibers (nylon is an island component, polyethylene is a sea component) are spun, drawn, and cut to a length of 51 mm. Thus, a short fiber having a thickness of 4 dtex (hereinafter also referred to as decitex) was obtained. This short fiber was used as a web and entangled with a needle punch to obtain a three-dimensional entangled nonwoven fabric. After impregnating this nonwoven fabric with a dimethylformamide solution of polyurethane (polyester ether diol having an average molecular weight of 2000 comprising polymethylpentane adipate and polyethylene glycol, polyurethane comprising 4,4′-diphenylmethane diisocyanate and butanediol) and wet coagulating, The sea component of the fiber component was extracted to form an ultrafine fiber bundle and dyed black with a dye. Thus, a sheet having a basis weight of 270 g / m ² , a thickness of 0.8 mm, and a polyurethane / fiber ratio of 55/45 was obtained. The fineness of the nylon ultrafine fiber of the obtained sheet was 0.06 dtex. One side of the obtained sheet was buffed with sandpaper to give a raised surface composed of the nylon ultrafine fibers, and used as a substrate. This is called a fibrous base material (A).
[0029]
Shin-Etsu Silicone (TM) KE1052A and KE1052B manufactured by Shin-Etsu Chemical Co., Ltd. were stirred and mixed at a ratio of 50:50, and the fibrous base material (A) was immersed in this liquid, then taken out and squeezed with mangles, 140 ° C. × 30 minutes. Heating, cross-linking and curing, and further aging at room temperature for 1 week to obtain a sheet-like material containing a silicone gel in a fibrous base material. The amount of silicone gel present in this sheet was 80 parts by mass per 100 parts by mass of the substrate. The evaluation results of this sheet are shown in Table 1. Moreover, the liquid used for the impregnation was heated at 140 ° C. for 30 minutes, crosslinked and cured, and further aged at room temperature for 1 week to obtain a single gel. The needle penetration degree of this gel was 65 (JIS K2220, 1/4 cone, load 9.38 g).
[0030]
Example 2
Shin-Etsu Chemical Co., Ltd. Shin-Etsu Silicone (TM) KE1052A, KE1052B, and toluene were stirred and mixed at a ratio of 50: 50: 300, and the fibrous base material (A) was dipped in this liquid, taken out, and then squeezed with a mangle. C. for 30 minutes, dried and crosslinked and cured, and further aged at room temperature for 1 week to obtain a sheet-like material containing a silicone gel in the substrate. The amount of silicone gel present in this sheet was 15 parts by mass per 100 parts by mass of the base material. The evaluation results of this sheet are shown in Table 1.
[0031]
Example 3
Shin-Etsu Chemical Co., Ltd. Shin-Etsu Silicone (TM) KE1052A, KE1052B and toluene were stirred and mixed at a ratio of 50: 50: 600, and the fibrous base material (A) was immersed in this liquid, taken out, and then squeezed with a mangle. Heated at 30 ° C. for 30 minutes, dried and crosslinked and cured at room temperature for 1 week to obtain a leather-like sheet containing a silicone gel in the substrate. The amount of silicone gel present in this sheet was 4 parts by mass per 100 parts by mass of the base material. The evaluation results of this sheet are shown in Table 1.
[0032]
Comparative Example 1
Evaluation similar to Example 1 was performed about fibrous base material (A) itself. The evaluation results are shown in Table 1.
[0033]
Comparative Example 2
It was immersed in a stock solution of a commercially available silicone softener emulsion (Nikka Silicon (TM) AM-204, manufactured by Nikka Chemical Co., Ltd.), then taken out with a mangle and dried at 100 ° C. The amount of the silicone flexible material in this sheet was 3.5 parts by mass per 100 parts by mass of the base material. The evaluation results of this sheet are shown in Table 1.
[0034]
Comparative Example 3
A commercially available silicone softener emulsion (Nikka Silicon (TM) AM-204, manufactured by Nikka Chemical Co., Ltd.) was immersed in 10% water dilution, taken out and then dried at 100 ° C. with a mangle. The amount of the silicone flexible material in this sheet was 0.35 parts by mass per 100 parts by mass of the base material. The evaluation results of this sheet are shown in Table 1.
[0035]
Comparative Example 4
Commercially available sulfonated natural oil greasing agent for natural leather (immersed in Nippon Seika Co., Ltd. New Choline (TM) stock solution, taken out and dried with mangle at 100 ° C. Presence of greasing agent in this sheet The amount was 60 parts by mass per 100 parts by mass of the substrate, and the evaluation results of the sheet are shown in Table 1.
[0036]
[Table 1]

[0037]
Comparing Examples 1 to 3 and Comparative Example 1, it can be seen that the leather-like sheet of the present invention has very excellent flexibility and oily feeling. Further, if Examples 1 to 3 and Comparative Examples 2 to 4 are compared, the leather sheet of the present invention is remarkably superior in softness, oily feeling and the like as compared with conventional softening techniques. It can be seen that there is an advantage in that there is no oil transfer, and resistance to washing. In addition, the leather-like sheet of the present invention has been greatly improved in oil transfer, which has been a problem with conventional similar technologies, so it is possible to include a large amount of silicone gel in the base material, and a sense of fulfillment It is possible to obtain an excellent one. In addition, it is possible to obtain a superior sense of fulfillment.
[0038]
【The invention's effect】
According to the present invention, with respect to a sheet-like material comprising a fibrous base material, it has excellent flexibility, has a moist feel of oil-like nature of natural leather, and has a high-class feeling with little migration of oily substances such as oil. An excellent leather-like sheet can be obtained. Such a sheet is useful because it is excellent in texture and luxury when used in gloves, clothing and the like.

Claims (5)

At least inside the fibrous base material (A), the needle depth measured using a 1/4 scale cone by the method defined in JIS K2220 is in the range of 30 to 120, and toluene is used at 70 ° C. The silicone gel (B) crosslinked until the extraction amount of silicon atoms when extracted for 30 minutes is 20% or less with respect to the total silicon atom amount is 0 with respect to 100 parts by mass of the fibrous base material (A). .1 to 200 parts by mass of a sheet-like material. The sheet-like article according to claim 1, wherein the fiber constituting the fibrous base material (A) is an ultrafine fiber of 0.2 dtex or less. The sheet-like material according to claim 1 or 2, wherein the fibrous base material (A) comprises a fiber-entangled nonwoven fabric and an elastic polymer impregnated therein. A sports glove which consists of a sheet-like object given in any 1 paragraph of Claims 1-3. A liquid in which an organopolysiloxane (C) having at least one vinyl group in the molecule and an organopolysiloxane (D) having at least one hydrogen atom directly bonded to a silicon atom in the molecule is mixed in advance. Using a 1/4 scale cone by the method prescribed in JIS K2220, impregnating the inside of the fibrous base material (A) impregnated with the elastic polymer inside the ultrafine fiber fabric composed of the ultrafine fiber bundle of 2 dtex or less Crosslinking is carried out until the measured needle depth is in the range of 30 to 120, and the extraction amount of silicon atoms is 30% or less with respect to the total amount of silicon atoms when extracted at 70 ° C. for 30 minutes using toluene. To produce a sheet-like material that is converted into a silicone gel.