JPH0669741B2 - Sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a sheet-like material. More specifically, it relates to a novel sheet-like article having a collagen-containing coating layer.

[Conventional technology]

Heretofore, many proposals have been made regarding a sheet-like article having a coating layer containing a polymer as a main component on the surface of a base material mainly composed of fibers, for example, JP-B-46-14352 and JP-B-59-42109. .

However, such a sheet material has many defects such as inferior breathability, moisture permeability, and water absorbency, poor dyeability, appearance, and feeling, and a strong rubber feel and vinyl feel to the touch. It was never satisfactory for use as a clothing material.

These disadvantages are fatal that the properties of these synthetic polymers are directly expressed as the defects because the substance constituting the coating layer is composed of synthetic polymers such as polyurethane, polyvinyl chloride, and polyacryl. It was a thing.

Furthermore, such a conventional sheet-like material has been exclusively developed for use in clothing and materials, and an example applied to the medical field has not been known. This is understandable because a material having biocompatibility has not been used as a constituent material of a conventional sheet-like material.

On the other hand, collagen, which has excellent biocompatibility and dialysis ability, is known as a material suitable for a base material for artificial skin, a dialysis membrane, etc., but an ultrafine synthetic fiber of 0.5 denier or less as in the present invention. The structure integrated with the sheet-like fibrous base material mainly composed of the entangled body is not known.

[Problems to be solved by the invention]

The present invention provides a sheet-like material which is moist but does not have an unpleasant stickiness, has a smooth and seemingly contradictory touch property at the same time, and has excellent moisture permeability, water absorption, dyeability, and a soft texture. Further, it is an object of the present invention to provide a sheet-like product having a collagen-containing coating layer excellent in biocompatibility and dialysis as a medical material.

[Means for solving problems]

As a result of earnest studies for this purpose, the present invention has finally been reached.

That is, the present invention is a sheet-like article having a coating layer on the surface of a substrate mainly composed of an entangled body of ultrafine synthetic fibers having a denier of 0.5 or less, wherein the substance constituting the coating layer is at least collagen. It is a sheet material.

Collagen as referred to in the present invention is obtained by separating from connective tissue such as animal skin, bone, tendon, blood vessel, cornea, etc., and is a so-called insoluble collagen in the form of short fibers which are crosslinked between collagen molecules. Or atelocollagen obtained by treating the insoluble collagen with proteolytic enzymes such as pepsin or alkali to cleave and digest the telopeptides present at both ends of the collagen molecule and involved in crosslinking, or a mixture thereof. And so on.

In addition, when the sheet-like material in the present invention is used in the medical field such as artificial skin, -CO of collagen molecule is used.
OH group, ε-NH ₂ group, arginine, histidine, etc., at least a part of which is chemically modified, such as methylated or succinylated, has a better interaction with blood than non-chemically modified collagen, and is a living cell. It is more preferably used because it has a characteristic that it is easily compatible with it.

In addition, depending on the purpose, for example, gelatin in which the triple helix of collagen molecules is unwound and modified into a random coil can be used in the coating layer.

The collagen that constitutes the coating layer forms crosslinks between collagen molecules or between collagen molecules and other substances by irradiation with ultraviolet rays or γ rays, or by aldehydes, isocyanates, phenolic crosslinking agents, chromium, tannic acid, etc. Those obtained are more preferably used. It is more preferable when the coating layer is required to have heat resistance and chemical resistance, particularly high tensile strength.

As the coating layer, a mixture of the above-mentioned collagen and another high molecular weight polymer such as polyurethane, polyvinyl chloride, polyacryl, polyamide, polyester, polyamino acid and the like can also be used. The mixing ratio of these can be freely changed depending on the application.

On the other hand, the coating layer has at least one layer made of collagen, and further has a laminated structure of two or more layers with a layer of a high molecular polymer made of polyurethane, polyvinyl chloride, polyacryl, polyamide, polyester, polyamic acid, or the like. It is preferable that the compound (1) has excellent characteristics due to physical properties such as adhesiveness between the base material and the coating layer, flexibility of the coating layer, and tensile strength.

Further, the coating layer may be added with a pigment, a dye, a stabilizer, an antistatic agent, a smoothing agent or the like depending on the purpose.

The substrate referred to in the present invention is made of ultrafine synthetic fibers such as polyester fiber, polyamide fiber, polyacrylic fiber, etc., and is a fiber such as a non-woven fabric, knitted fabric or woven fabric obtained by needle punching, warder jet punching or the like. A sheet-like material is mainly used, and if necessary, various commonly known high molecular weight polymers such as polyurethane and polyacryl are added.

In the present invention, it is important that the substrate is mainly composed of an entangled body of ultrafine synthetic fibers having a denier of 0.5 denier or less, whereby the flexibility of the substrate is good and the smoothness of the surface is also good. Becomes thinner. Therefore, the sheet-like material has an extremely soft texture. Furthermore, ultrafine synthetic fibers are 0.
Substrates of 3 denier or less are more preferable.

Further, the substrate is mainly composed of an entangled body of ultrafine synthetic fibers of 0.2 denier or less, preferably 0.05 denier or less or a bundle thereof or a mixture thereof, and by setting the distance between the fiber entanglement points to be 200 microns or less, as described below, The surface of the material has a high degree of denseness, and as a result, the strength of the coating layer is excellent, and a sheet-like material in which cracking of the coating layer due to rubbing or the like is less likely to occur. Furthermore, the distance between fiber entanglement points
A more preferable effect can be obtained with a substrate having a thickness of 100 microns or less.

Here, the distance between the fiber entanglement points refers to the value obtained by the following method, and as one measure showing the denseness of the entanglement of fibers, the smaller the value is, the more dense the entanglement is. . FIG. 1 is an enlarged schematic view of the constituent fibers when the constituent fibers of the base material are observed from the surface side. The constituent fibers are f ₁ , f ₂ ,
f _3, ...... and then the fibers f _1, f ₂ of which any two intersect in the form of fibers f ₂ becomes below the other fiber which is on the point of confounding in a ₁ and a ₁ The point is traced and the point of intersection is defined as a ₂ (the confounding point of f ₂ and f ₃ ). Similarly a ₃ , a ₄ , a ₅ , ......
And Next, the horizontal straight line distance between the confounding points a ₁ a ₂ ,, a ₂ a ₃ ,, a ₃ a ₄ ,, a ₄ a ₅ ,, a ₅ a ₆ ,, a ₆ a ₇ ,, a ₇ a ₃ ,, a ₃ a ₈ , a ₈ a ₇ , a ₇ a
₉ , a ₉ a ₆ , ... are measured, and the average value of these many measured values is obtained and used as the distance between fiber entanglement points.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 A card having a denier of 3.8 mm and a 51 mm staple of sea-island type fiber having 8 island components in 1 filament at a ratio of 50 parts of polystyrene as a sea component and 50 parts of polyethylene terephthalate as an island component. A web is formed through a cross wrapper, and then needle punching is performed to entangle the sea-island type fibers, and the basis weight is 510 g / m ² , apparent density
A non-woven fabric of 0.18 g / cm ³ was obtained. Furthermore, this non-woven fabric is 97-100
After shrinking with hot water at ℃ and drying, the areal weight was 823 g / m ² and the apparent density was 0.33 g / cm ³ .

5% of polyvinyl alcohol (hereinafter PVA) on this non-woven fabric
The solution was impregnated with an aqueous solution, dried and then soaked in trichlorethylene, immersed and repeatedly squeezed to almost completely extract and remove sea components, and dried to evaporate and dry residual trichlorethylene. At this time, one island component was 0.28 denier.

Next, the desulfurized nonwoven fabric was impregnated with an 8% dimethylformamide (hereinafter referred to as DMF) solution of polyester-based polyurethane, water-immersed and solidified, PVA-free, DMF-free and dried. A 5% DMF solution of a mixture of 20 parts of insoluble collagen, 5 parts of atelocollagen, and 75 parts of polyamino acid-based polyurethane copolymer was applied to the surface of this non-woven fabric with a gravure coater, dried and then pressed through a heating embossing roll to give a leather-like appearance. I stamped a Jiho pattern. Then, dyeing was carried out at atmospheric pressure using a jet dyeing machine.

The obtained sheet-like material had a very nice touch and was extremely smooth. Moreover, it has excellent moisture permeability and water absorbency, and when measured by the moisture permeable cup method, 6300 g /
It showed a high moisture permeability of m ² · 24hr. Further, the dyeability of the coating layer was also excellent.

Example 2 20 parts of 2-ethylhexyl acrylate, 60 parts of a copolymer of 80 parts of styrene (hereinafter referred to as AS resin) as a binding component and 40 parts of nylon 6 as an ultrafine fiber component, 16 islands in one filament It has a component and the island component further contains a large number of ultrafine fiber components.
A web is formed through a card cross wrapper using staples of m, and then the polymer inter-array fibers are entangled by needle punching, and a basis weight of 398 g / m ² and an apparent density of 0.17 g / cm ³ are obtained. A non-woven fabric was obtained.

On both sides of this non-woven fabric, a hole with a hole diameter of 0.25 mm is processed between the centers of the holes.
Water with a pressure of 100 kg / cm ² was jetted and contacted at a high speed once each from nozzles arranged in a line at a pitch of 0.6 mm.

Next, to this nonwoven fabric, a solution prepared by adding a pigment to a 10% solution of polyurethane obtained by chain-extending a prepolymer of a mixed diol of polyethylene adipate and polybutylene adipate and P, P′-diphenylmethane diisocyanate with ethylene glycol was added. It was applied with a gravure coater and dried. A 0.5% dilute hydrochloric acid solution (PH3.2) of a mixture consisting of 30 parts of insoluble collagen and 70 parts of atelocollagen was applied onto the urethane layer with a gravure coater, and after drying, a 15w germicidal lamp was applied to the coating layer from a distance of 10 cm for 30 cm. Irradiate for a minute to cross-link collagen molecules, then soak in drichlorethylene, dip, repeat squeeze, and almost completely center AS resin and dry to evaporate and remove residual trichlorethylene, then at atmospheric pressure. It dye | stained using the jet dyeing machine. One ultrafine synthetic fiber component (nylon 6) that constitutes the non-woven fabric is 0.1
It was denier.

The obtained sheet-like material had a very nice touch and was extremely smooth. Moreover, it was also excellent in moisture permeability and water absorption. 6500 when measured by the moisture permeable cup method
It showed high moisture permeability of g / m ² · 24hr. In addition, it had a graceful appearance, was soft and had a feeling of unity.

The resistance to scratching of this product was also very excellent.

The coating layer of this sheet was extracted and removed with a solvent, and the distance between fiber entanglement points on the surface of the equipment was measured.

Example 3 The non-woven fabric after contacting with the high-pressure water jet prepared in Example 2 was nipped through a mangle while containing water, dried, and soaked in trichlorethylene, soaked and repeatedly squeezed AS
The resin was removed by extraction and dried. One ultrafine synthetic fiber component (nylon 6) constituting the nonwoven fabric was 0.1 denier.

A 1% dilute hydrochloric acid solution (PH2.9) of atelocollagen was applied to the surface of this nonwoven fabric with a gravure coater and dried. Next, this intermediate product was immersed in a 0.1% glutaraldehyde solution containing 0.02 M disodium hydrogen phosphate for 20 minutes, washed with water and dried.

The obtained sheet-like material had a moist and smooth feel, and had excellent moisture permeability and water absorbency. High moisture permeability of 6900 g / m ² · 24 hr was measured by the moisture permeable cup method. Further, when a surgical test was conducted on rabbits, the coating layer had excellent adhesion to the wound and had a good hemostatic effect.

The coating layer of this sheet-like material was extracted and removed with a solvent, and the distance between the fiber entanglement points on the surface of the substrate was measured.

Comparative Example 1 Using 20 parts of sea component polystyrene, 80 parts of island component polyethylene terephthalate, 4.5 denier with 4 islands / filament and 51 mm staple, a sheet-like material was obtained in the same manner as in Example 1. One final island component was approximately 1 denier.

The obtained product was slightly lacking in smoothness of the surface, the mixture of collagen and polyamino acid polyurethane copolymer was poor in riding, had unevenness in thickness, color unevenness was observed throughout, and the texture was hard. .

〔The invention's effect〕

The sheet material of the present invention exhibits the following effects.

(1) The coating layer has a very moist yet smooth hand feeling.

(2) Since it has a coating layer with excellent moisture permeability, it does not peel when used for clothing.

(3) Further, since it is a coating layer having excellent water absorbency, rapid sweating property is good.

(4) It has a glossy and elegant coating layer.

(5) It has a coating layer with very good dyeability and dye fastness.

(6) Furthermore, since collagen, which has excellent biocompatibility, is a component that constitutes the coating layer, it is also suitable for medical materials such as artificial skin.

(7) Further, it has excellent hemostatic properties and adhesiveness to the wound due to the function of the collagen coating layer.

(8) It can be applied as a cell culture substrate.

(9) Since it is composed of a collagen coating layer and a fibrous base material, it has excellent dialysis properties and toughness.

[Brief description of drawings]

FIG. 1 is an enlarged schematic view of constituent fibers when a base material mainly composed of fibers is observed from the surface side. f ₁ ...... f ₆ : Constituent fiber a ₁ ...... a ₉ : Entrance point

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location D06M 13/08

Claims (6)

[Claims] 1. A sheet-like article having a coating layer on the surface of a base material mainly composed of an entangled body of ultrafine synthetic fibers having a denier of 0.5 or less, wherein the substance constituting the coating layer is at least collagen. Sheet-like material to do. 2. The sheet-like product according to claim 1, wherein the collagen is insoluble collagen, atelocollagen or a mixture thereof. 3. The sheet material according to claim 1, wherein at least a part of the collagen molecule is crosslinked. 4. The sheet-like material according to claim 1, wherein the substance constituting the coating layer is mainly a mixture of collagen and another high molecular weight polymer. 5. The sheet-like article according to claim 1, wherein the coating layer has a laminated structure of two or more layers including at least a layer made of collagen and a layer mainly made of another polymer. . 6. The base material is mainly composed of an entangled body of ultrafine synthetic fibers having a denier of 0.2 denier or less or a bundle thereof or a mixture thereof, and the entangled body has a distance between fiber entanglement points of 200 microns or less. The sheet-like article according to item (1).