JPH06123040A - Shape memorizing alloy sheet and burned shape memorizing alloy sheet - Google Patents

Abstract

PURPOSE:To obtain a shape memorizing allay sheet capable of manifesting specific characters of a shape memorizing alloy to the maximum and simultaneously having performance over that of the alloy and a burned shape memorizing alloy sheet. CONSTITUTION:This shape memorizing alloy sheet is a sheetlike formed product which is at least partially composed of a complex of a shape memorizing alloy member and organic or inorganic fiber. Furthermore, the burned shape memorizing allay sheet is a sheetlike formed product which is at least partially composed of a complex of a shape memorizing alloy (especially a Ti-Ni-based shape memorizing alloy) and a burned fluororesin member (e.g. polytetrafluoroethylene).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a shape memory alloy sheet produced by using a shape memory alloy member, and in particular, a shape memory alloy firing useful for applications such as orthopedic core materials for clothing, eyeglass frames, medical materials and the like. It is about the seat.

[0002]

2. Description of the Related Art Various shape memory alloys such as Ti-Ni alloys and Ti-Ni-X alloys (X is Fe, Cr, Co, V, etc.) are prominent accompanying the reverse transformation of martensitic transformation. It is known to exhibit various shape memory effects and superelasticity.

On the other hand, in terms of application, various types of shape-memory alloy wires have been proposed as shaping core materials for clothing such as shoulder pads, corsets, girdles, brassieres, and body suits.

For example, Japanese Examined Patent Publication No. 1-37481 (Japanese Patent Laid-Open No. 58-13706) discloses that a transformation temperature of a body for a shaping body including a shaping core material for shaping the body shape is There is shown a dressing for orthopedic body in which a shape memory alloy wire having a temperature lower than the body temperature is mounted as the orthopedic core material having a shape-memorized shape.

Japanese Utility Model Laid-Open No. 63-11519 discloses a substantially semi-circular shoulder pad in which a core material such as urethane foam or non-woven fabric is enclosed by an outer cover, and at the edge of the shoulder pad, under body temperature. A shoulder pad in which a wire made of a shape memory alloy stored in advance in a curved shape of the shoulder mouth is inserted is shown in FIG.

In Japanese Utility Model Laid-Open No. Sho 63-170423, a locking portion which is curved in conformity with a vertical chevron formed by a wire-like shape memory alloy from the chest direction toward the back of the shoulder is formed. A core is formed by continuously connecting a curved connecting portion that is formed so as to be inclined from the lower end of the locking portion toward the side of the neck of the shoulder, and the core material is memorized and the concentric material is shouldered. A shoulder pad incorporated into the pad body is shown.

In Japanese Utility Model Laid-Open No. 2-115518, a shape memory cotton made of a shape memory alloy fine wire having a heat recovery function, which has been heat treated in advance and shaped the outer shape of a shape body to be used, is packed in a bag to deform the shape. Even though, a shape memory cotton garment structure is shown in which the shape is restored to the shaper used by body temperature, warm air, or warm water. Specific examples of the structure include a pad, a hanger,
It is a mannequin.

[0008]

However, the conventional material for the dressing core material using the shape memory alloy wire is used because the shape memory alloy wire is arranged along the contour for the core material. The position of the shape memory alloy wire was sometimes deviated from the predetermined position of the core material during or during washing.

Under such circumstances, the present invention provides a shape memory alloy sheet, and further a shape memory alloy fired sheet, which maximizes the characteristics of the shape memory alloy and is provided with a performance exceeding it. It is intended to be provided.

[0010]

The shape memory alloy sheet of the present invention is a sheet-shaped molded article, at least a part of which is a composite of a linear shape memory alloy member and an organic or inorganic fiber. It is characterized by being configured.

The shape-memory alloy fired sheet of the present invention is a sheet-shaped molded article, at least a part of which is composed of a composite of a shape-memory alloy member and a fired fluororesin member. It is a feature.

The present invention will be described in detail below.

The shape memory alloy sheet of the present invention is a sheet-shaped molded article composed of a composite of a linear shape memory alloy member and organic or inorganic fibers. The sheet-shaped molded product refers to woven fabric, knitted fabric, non-woven fabric, sheet and the like. Organic or inorganic fibers include synthetic fibers, natural fibers, regenerated fibers,
Examples include semi-synthetic fibers, inorganic fibers, carbon fibers and the like.

Such a shape memory alloy sheet is obtained, for example, by weaving a shape memory alloy wire as a warp and an ordinary thread as a weft, so that the position of the shape memory alloy wire is not displaced. However, in this case, there may remain a problem that fraying easily occurs from the end of the woven fabric. In addition, since the other party's thread that constitutes the woven fabric may be weak in strength, have poor wash resistance, or may have reduced strength during ironing, the shape memory alloy wire may be used. There may be a problem that the sustainability of the shape deformation is insufficient.

Therefore, if higher performance is required, it is desirable to use a sheet-shaped molded article composed of a composite of a shape memory alloy member and a fired fluororesin member. In the following, such molded articles will be mainly described.

The sheet-shaped molded product includes a flat sheet body, a curved sheet body, a rolled sheet body, a thin and thick molded body, and the like.

As the shape memory alloy member, in addition to the Ni-Ti system and Cu-Zn-Al system which have already been put to practical use, Au-Cd system, In-Tl system, Cu-Ni-Al system are also available.
System, Pd-Ti system, Ni-Ti-Cu system, Cu-Zn-
Al-Ni system, Fe-Mn-Si system, Au-Mn-Zn
Members made of various shape memory alloys, such as those of Mn-Cu system, Mn-Cu system, and Cu-Al-Be system are used. The shape memory alloy member is preferably subjected to cold working, but may be subjected to shape memory treatment in advance.

The shape memory alloy member is often linear, but it may be a thin ribbon or plate.

As the fluororesin member before firing, a preformed product made of a fluororesin or a rolled unfired yarn obtained by stretching a rolled product is preferably used. Here, as the fluororesin, polytetrafluoroethylene,
Examples thereof include tetrafluoroethylene-hexafluoroethylene copolymer, ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, and polyvinylidene fluoride.

For the fluororesin member, 100 parts by weight of polytetrafluoroethylene fine particles are allowed to absorb about 18 to 22 parts by weight of an organic solvent such as naphtha and white oil, and then a preliminary shape such as a sheet, a round bar and a wire is prepared. It is particularly preferable to use a non-sintered yarn having a porosity obtained by performing stretching after forming a molded product, if necessary using a roll or the like, and then rolling (in the case of a sheet, before or after stretching). Slit narrowly to make a thread).

In addition to the above shape memory alloy member and fluororesin member, other metal member, other resin or fiber member can be used together. Of these, other fiber members include synthetic fibers (aromatic polyamide, polyether ether ketone, ultra high molecular weight polyethylene, polyester, polyamide, polyacrylonitrile, polyvinylidene chloride, polyvinyl chloride, polyvinyl alcohol, polyurethane, polyolefin, etc.), Recycled fiber (rayon, etc.),
Semi-synthetic fibers (acetylated cellulose, etc.), natural fibers (cotton, hemp, wool, etc.), inorganic fibers (glass fibers, metal fibers, ceramics fibers, etc.), carbon fibers, etc.
Particularly, heat resistant or high strength fiber is preferable.

In manufacturing the shape memory alloy fired sheet, a method is used in which the shape memory alloy member and the fluororesin member (and other members) are formed into a sheet in advance, and then heat treated at a high temperature.

The sheet is formed into a woven fabric, a knitted fabric or a non-woven fabric by using a shape memory alloy member and a fluororesin member (further, other member) having a shape capable of being woven or knitted into a fiber, and further, if necessary. A method of deforming, winding, laminating, etc. is preferably adopted, but a method of superposing a shape memory alloy member and a fluororesin member (in this case, a sheet shape is preferable) can also be adopted.

When knitting or weaving, the shape memory alloy member and the fluororesin member are aligned and provided for knitting or weaving.
It is desirable to knit in such a manner that these intersect.
When the fluororesin member contains a solvent, rolling can be performed prior to the next high temperature treatment.

After being formed into a sheet, it is heat-treated at a high temperature and the fluororesin member is fired. The shape memory alloy member is preferably subjected to shape memory processing at this time, but may be previously subjected to shape memory processing. The treatment temperature in this case is preferably set to a temperature equal to or higher than the melting point of the fluororesin and lower than the thermal decomposition temperature, but the treatment can be performed at the thermal decomposition temperature or higher for a very short time. When the shape memory alloy member is a Ti-Ni type shape memory alloy member and the fluororesin member is a polytetrafluoroethylene member, it is desirable to set the heat treatment temperature to 327 to 600 ° C.

By the above treatment, the target sheet-shaped molded product, that is, the shape-memory alloy fired sheet, at least a part of which is composed of a composite of the shape-memory alloy member and the fired fluororesin member, Is obtained.

The fired sheet thus obtained is used as a shaping core material for clothing (shoulder pad, corset, girdle, brassiere, body suit, etc.), eyeglass frame, bracelet, hanger, mannequin, medical material (catheter, etc.). ), Containers, springs, joints, antennas, consumer products,
It is useful for various purposes such as medical and industrial purposes.

[0028]

Next, the operation of the present invention will be described in the case of a shape-memory alloy fired sheet (a sheet-shaped molded article composed of a composite of a shape-memory alloy member and a fired fluororesin member).

When the shape memory alloy member and the fluororesin member (further other members) are formed into a sheet in advance and then heat-treated at a high temperature, the fluororesin member is sintered and becomes a transparent and strong fluororesin member. The shape memory alloy member and other members are wrapped. for that reason,
Even when the above-mentioned sheet is formed of a knitted or woven fabric, fraying from the end portion is prevented.

The shape memory alloy fired sheet containing the fired fluororesin member has extremely excellent properties such as heat resistance, chemical resistance, water resistance, non-adhesiveness, slipperiness, abrasion resistance, and electrical insulation. The properties of the obtained fired sheet are extremely favorable, and the product can sufficiently withstand severe use conditions.

In this shape memory alloy fired sheet, even if it is significantly deformed below the martensitic transformation temperature, if the temperature above the reverse transformation temperature is applied by body temperature, hot air from a dryer, hot water, steam, etc. The shape-memory effect of the memory alloy causes it to return to a predetermined shape. Further, in the case of a fired sheet having a reverse transformation temperature of room temperature or lower, even if it is significantly deformed, it spontaneously recovers its shape, that is, it returns to a predetermined shape by superelasticity.

[0032]

EXAMPLES The present invention will be further described with reference to examples. Hereinafter, “parts” means parts by weight.

Example 1 FIG. 1 is a perspective view showing an example of a shoulder pad manufactured by using the shape memory alloy fired sheet of the present invention.

Fine powder of commercially available polytetrafluoroethylene (a primary particle diameter of about 0.2 to 0.3 μm separated and granulated from a dispersion produced by emulsion polymerization of tetrafluoroethylene, a secondary particle diameter of about 300 to 60)
Absorb 20 parts of white oil into 100 parts of 0 μm polytetrafluoroethylene particles) to form a paste, and then extrude into a round bar or a sheet to prepare a preform.
Then, the preform was rolled with a roll before the solvent was volatilized to obtain a green tape having porosity. This raw tape was uniaxially stretched and then slit into a predetermined width to obtain a raw tape yarn as an example of the fluororesin member (F).

A cold-worked shape memory alloy member (M) having a diameter of 0.5 mm and made of a Ni—Ti alloy wire containing 50.5% of Ni and 49.5% of Ti based on the number of atoms was prepared.

The shape memory alloy member (M) and the fluororesin member (F) are alternately arranged as the warp, and the fluororesin member (F) is used as the weft, and a plain weave woven fabric is prepared by a conventional method. Was woven.

Next, the woven fabric was dried to volatilize and remove the white oil, and then placed in a furnace while sandwiched in a frame for manufacturing a shoulder pad and baked at about 400.degree. As a result, shape memory treatment, firing treatment and shaping were achieved all at once.

The shoulder pad material thus obtained was placed in the middle portion of the non-woven fabric, which was laminated in about 10 layers as the cushioning material (A), to prepare a shoulder pad. This shoulder pad could be flattened or deformed because the shape memory alloy member (M) loses its springiness at a temperature of less than 10 ° C, but it can be heated to room temperature or higher by means such as hot air or steam. When warmed, it returned to its shape along the curved surface of the shoulder. In addition, at room temperature and above, it exhibited superelasticity that spontaneously recovers shape upon deformation.

This shoulder pad material is free from fraying from the cut end, and is also extremely excellent in ironing resistance, washing resistance, abrasion resistance, sweat resistance and the like.

Example 2 FIG. 2 is a perspective view showing another example of the shape memory alloy fired sheet of the present invention.

Ni-Ti was applied between the rolled green tapes of Example 1.
Arrange the alloy wire, bend it into a predetermined shape and put it in the furnace,
It was baked at about 400 ° C. As a result, shape memory treatment, firing and shaping were achieved all at once, and the shape memory alloy fired sheet shown in FIG. 2 was obtained. This shape memory alloy fired sheet exhibited the same shape memory property as in Example 1.

Example 3 FIG. 3 is a perspective view showing still another example of the shape memory alloy fired sheet of the present invention.

Fluororesin member (F) of Example 1, Example 1
The shape memory alloy member (M) and the aromatic polyamide fiber yarn as an example of the yarn (S) other than these were alternately arranged as warp yarns. Fluororesin member (F) and thread same as above
(S) was aligned to make a weft. The warp and weft yarns were woven by the bag weaving method to obtain a tubular seamless woven fabric.

When this was fired at 390 to 400 ° C., a tough seamless tube product having shape memory characteristics was obtained as shown in FIG.

Example 4 The shape-memory alloy member (M) of Example 1 and various fluororesin members (F) were twisted together to form a yarn, and then a plain-woven fabric was manufactured by a conventional method. As the fluororesin, polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoroethylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETF)
E), polychlorotrifluoroethylene (PCTF
E) and polyvinylidene fluoride (PVDF) were used.

Then, this woven fabric is subjected to 200 ° C., 300 ° C.,
Heat treatment was performed at 400 ° C., 500 ° C., 600 ° C. and 700 ° C. for 15 minutes. The results are shown in Table 1. The meanings of A and B in Table 1 and the evaluation criteria are as follows. A: Resin firing degree x: Insufficient firing or decomposition and peeling completed Δ: Decomposition and peeling large ○: Sufficient firing B: Shape memory degree Δ: Poor characteristics but practical use ○: Good characteristics

[0047]

[Table 1] PTFE FEP ETFE PCTFE PVDF 200 ℃ A × ○ ○ ○ ○ B △ △ △ △ △ 300 ℃ A × ○ ○ ○ ○ B △ △ △ △ △ 400 ℃ A ○ ○ ○ △ ○ B ○ ○ ○ ○ ○ 500 ℃ A ○ △ △ × × B ○ ○ ○ ○ ○ 600 ° C A △ × × × × B △ △ △ △ △ 700 ° C A × × × × × B △ △ △ △ △

Fluorine resin member (F) above the melting point of each resin
Was completely integrated, and peeling of the resin was observed at temperatures near the temperature at which pyrolysis was completed. On the other hand, looking at the effect of shape memory,
At a temperature of 300 ° C. or lower, shape fixing was insufficient, but it retained shape memory characteristics.

Example 5 In Example 4, polytetrafluoroethylene was treated at a firing temperature of 500 ° C., 600 ° C. and 700 ° C. for 5 to 60 minutes. However, a baked product was obtained that could be used for a short time of 5 minutes. The results are shown in Table 2. The meanings of A and B in Table 2 and the evaluation criteria are the same as in Table 2.

[0050]

[Table 2] 5min 10min 20min 30min 60min 400 ℃ A × ○ ○ ○ ○ B ○ ○ ○ ○ ○ 500 ℃ A ○ ○ ○ ○ ○ B ○ ○ ○ ○ ○ 600 ℃ A ○ △ × × × B ○ △ △ △ △ 700 ℃ A × × × × × B △ △ △ △ △

Example 6 The Ti—Ni alloy wire used in Example 1 was previously subjected to a memory treatment at a temperature of 400 ° C., and then a raw tape of polychlorotrifluoroethylene (PCTFE) was sandwiched from both sides to form a non-woven fabric. 200, 300, 400, 500 ° C, 600
Heat treatment was performed at 15 ° C. and 700 ° C. for 15 minutes. The results are shown in Table 3. The meanings of A and B in Table 3 and the evaluation criteria are as follows. A: degree of baking of resin X: insufficient baking or completion of decomposition and peeling Δ: large amount of decomposition and peeling ○: sufficient for baking B: shape memory degree X: stored in shape during baking Δ: shape stored in advance is slightly destroyed ○: Good characteristics

[0052]

[Table 3] Baking temperature (℃) 200 300 400 500 600 700 Resin baking degree A ○ ○ △ × × × Shape memory degree B ○ △ × × × ×

From Table 3, it can be seen that if the firing is performed at less than 300 ° C., a fired sheet can be obtained satisfactorily even if the shape memory treatment and the firing treatment are separately performed. Further, it can be seen that if the shape that was previously remembered is lost at the time of firing and a new shape is given at the time of firing for some reason, the firing should be performed at 400 ° C. or higher.

[0054]

According to the shape memory alloy sheet of the present invention, the position of the shape memory alloy wire does not deviate from the predetermined position of the core material during use or washing even when it is used as a material for a dressing or shaping core material. Produce an effect. Further, the shape memory alloy fired sheet of the present invention, in addition to the above effects, does not cause fraying from the end, heat resistance, chemical resistance, non-adhesiveness, slipperiness, abrasion resistance, electrical insulation, etc. It has excellent effects such as extremely good properties.

Therefore, the characteristics possessed by the shape memory alloy are maximized, and the performance exceeding them is imparted.

[Brief description of drawings]

FIG. 1 is a perspective view showing an example of a shoulder pad manufactured by using the shape memory alloy fired sheet of the present invention.

FIG. 2 is a perspective view showing another example of the shape-memory alloy fired sheet of the present invention.

FIG. 3 is a perspective view showing still another example of the shape memory alloy fired sheet of the present invention.

[Explanation of symbols]

 (M) ... Shape memory alloy member, (F) ... Fluororesin member, (C) ... Other member, (A) ... Cushion material

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[Procedure amendment]

[Submission date] June 15, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

[0010]

Shape memory alloy sheet of the present invention In order to achieve the above object, according to a sheet-like molded article, at least in part, consists of a complex with shape memory alloy member and an organic or inorganic fibers It is characterized by that.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

[0013] Shape memory alloys of the present invention the sheet is a shape memory alloy member and an organic or sheet-like molded article composed of a composite of an inorganic fiber. The sheet-shaped molded product refers to woven fabric, knitted fabric, non-woven fabric, sheet and the like. Examples of organic or inorganic fibers include synthetic fibers, natural fibers, regenerated fibers, semi-synthetic fibers, inorganic fibers, carbon fibers and the like.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location A41D 27/26 B C22C 19/03 A D02G 3/02 G02C 5/00 (72) Inventor Tetsuya Uchiyama 404, 2-24 Shimizuguchi, Shirai-cho, Inba-gun, Chiba Prefecture

Claims (5)

[Claims] 1. A shape-memory alloy sheet, which is a sheet-shaped molded article, at least a part of which is composed of a composite of a linear shape-memory alloy member and organic or inorganic fibers. . 2. A sheet-shaped molded article, at least a part of which is composed of a composite of a shape-memory alloy member and a fired fluororesin member, and a shape-memory alloy fired sheet. . 3. The shape-memory alloy fired sheet according to claim 2, wherein a preformed product made of a fluororesin or a tape thread obtained by drawing a rolled product is used as the fluororesin member before firing. . 4. A product obtained by heat-treating under a condition not lower than the melting point of the fluororesin and not completing thermal decomposition.
The shape memory alloy fired sheet described. 5. A shape memory alloy member is a Ti—Ni type shape memory alloy member, a fluororesin member is a polytetrafluoroethylene member, and these members are obtained by heat treatment at a temperature of 327 to 600 ° C. The shape memory alloy fired sheet according to claim 2.