JPH04240264A - Fiber structure having shape-memory property - Google Patents

Abstract

PURPOSE:To obtain the subject structure having excellent washing fastness by using a shape-memory resin in combination with an isocyanate compound or treating a fiber structure with an organosilicon compound and applying a shape-memory resin layer to the fiber structure. CONSTITUTION:A fiber structure such as yarn, woven fabric or knit fabric of synthetic fiber, semi-synthetic fiber or natural fiber is immersed in a treating liquid containing a norbornene polymer as a shape-memory resin in combination with an isocyanate compound (e.g. tolylene diisocyanate) and dried and heat- treated to form 1g/m<2> of a resin layer or the fiber structure is immersed in an aqueous dispersion of an organic diene compound [e.g. n-beta-(aminoethyl)-gamma- aminopropyltrimethoxy-silane], dried, treated with the above shape-memory resin liquid and heat-treated to obtain a shape-memory fiber structure having excellent wash resistance and crease-recovery without deteriorating the tear strength and feeling of the original fiber structure. The process is especially suitable for the treatment of hemp cloth.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a fibrous structure with shape memory, and more particularly, a fibrous structure with shape memory that has excellent washing fastness and is easy to remove wrinkles, and retains arbitrary irregularities. The present invention relates to a fibrous structure having shape memory that is easy to store.

0002

2. Description of the Related Art Conventionally, attempts have been made to impart shape memory properties to fibers or fiber structures. For example, in Japanese Patent Application Laid-Open No. 62-62989, vegetable fibers such as silk and rayon are treated with natural proteins such as keratin and collagen to give them anti-wrinkle properties due to the shape memory effect. It is not industrially advantageous because it is not consistent in terms of supply, quality, and price. Furthermore, in Japanese Patent Application Laid-Open No. 63-35885, protein fibers such as wool are treated with a reducing agent such as ammonium thioglycolate, then treated with a natural protein such as collagen, and then treated with an oxidizing agent such as hydrogen peroxide. Although similar effects can be obtained, in addition to the same disadvantages as mentioned above, this method is not preferred in practice because it uses compounds that require careful handling, such as reducing agents and oxidizing agents.

On the other hand, in recent years, shape memory resins have been developed by applying polymer synthesis technology. For example, the special public service
In Publication No. 800, a polymer (norbornene polymer) was synthesized by ring-opening polymerization of various alkyl-substituted or alkoxy-substituted bicyclo(2,2,1) heptene-2, and attention was paid to the shape memory properties of this polymer. For example, Japanese Patent Application Laid-Open No. 59-53528 proposes application to joining materials for pipes of different diameters, fixing materials for construction, casts, etc.

Focusing on the properties of the shape memory resin, it has been proposed to apply and dry an organic solvent solution of norbornene-based polymer to the Nishijin-ori belt in order to eliminate the knot wrinkles in the Nishijin-ori belt (Nikkei). New Material, July 9, 1990 issue, p. 64, published by Nikkei BP), but when applied to general clothing, it is not practical because the adhesion of the shape memory resin to the base fiber is insufficient. The problem was that it did not have good washing fastness.

[0005]

[Problems to be Solved by the Invention] In view of the above points, the present inventors have conducted intensive research and have developed a novel fiber structure having excellent washing fastness, easy wrinkle removal, and shape memory properties. The object of the present invention is to provide a fiber structure having shape memory properties that allows easy retention of unevenness.

[0006]

[Means for Solving the Problems] The present invention involves using an isocyanate compound in combination with a layer made of shape memory resin on a fibrous structure, or treating the fibrous structure in advance with an organosilicon compound. Regarding the fiber structure that has shape memory properties with excellent washing fastness, more specifically, the shape memory resin does not fall off even after washing, and it can be washed repeatedly, and wrinkles caused by its use can be removed by ironing. It is a fiber structure that is durable and can be used repeatedly, and has shape memory properties that allow it to easily retain any irregularities.

[0007]

[Example] The fiber structure in the present invention can be in various forms such as yarn, knitted fabric, woven fabric, nonwoven fabric, and paper, but is not limited to these.

Materials for the fiber structure in the present invention include synthetic fibers such as polyester, nylon, polyacrylonitrile, polyurethane, polyvinyl chloride, polyethylene, and polypropylene, viscose rayon, cuprammonium rayon, diacetate rayon, and triacetate rayon. Semi-synthetic fibers such as silk, animal fibers such as wool, and vegetable fibers (cellulose fibers) such as cotton and hemp are used alone or in combination, but cellulose fibers are preferred. More preferably, hemp is used, but the material is not limited to these.

[0009] Isocyanate compounds in the present invention include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate,
Isocyanate compounds such as isophorone diisocyanate and trimethylolpropane tolylene diisocyanate adduct can be used alone or in combination, and if necessary, a catalyst may be used in combination to promote the reaction, but the invention is not limited to these.

Examples of the organosilicon compounds in the present invention include vinyltrichlorosilane, vinyltriethoxysilane, vinyltri(β-methoxyethoxy)silane,
γ- Glycidoxypropyltrimethoxysilane, γ-
Methacryloxypropyltrimethoxysilane, n-β
Organosilicon compounds such as (aminoethyl)γ-aminopropylmethyldimethoxysilane and n-β(aminoethyl)γ-aminopropyltrimethoxysilane can be used alone or in combination, and if necessary, a catalyst can be used to accelerate the reaction. They may be used in combination and are not limited to these.

[0011] In carrying out the present invention, commercially available liquefied shape memory resins can be used, such as norbornene-based polymers such as trade name: Norsolex-L (manufactured by Zeon Kasei Co., Ltd.). Yes, but not limited to these.

[0012] Next, in order to mix and dissolve the isocyanate compound into the liquefied shape memory resin, the isocyanate compound is mixed at a ratio of 15 to 45 parts by weight per 100 parts by weight of the solid content of the shape memory resin. Bye. If the amount of the isocyanate compound is less than 15 parts by weight, it is difficult to obtain the effects of the present invention, and if it exceeds 45 parts by weight, not only the effect cannot be increased but also the practical physical properties are undesirably deteriorated.

[0013] In order to apply the mixed solution of the liquefied shape memory resin and the isocyanate compound or the liquefied shape memory resin alone to the fiber structure, it is possible to apply the mixed solution of the liquefied shape memory resin and the isocyanate compound or the liquefied shape memory resin alone to the fiber structure using a known coating machine such as a knife coater or roll coater, or a spraying method. The amount of adhesion to the fiber structure is 0.15 to 10.5 g/m as the solid content of the shape memory resin.
2 is fine. If the amount of adhesion is less than 0.15 g/m2, the effect of the present invention cannot be obtained, and if it exceeds 10.5 g/m2, no increase in the effect can be obtained, which is not preferable.

[0014] When the fibrous structure is treated with an organosilicon compound in advance, 0.2% of the organosilicon compound
The fiber structure may be immersed in an aqueous dispersion of up to 20% by weight and then the excess liquid may be squeezed out using a mangle, or the treatment may be carried out using the above-mentioned coating machine, spray, etc., but is not limited thereto. The amount of the organosilicon compound attached to the fiber structure is 0.15 to 0.15 as the solid content of the organosilicon compound.
10.5 g/m2 or 0.15 g/m
If the amount is less than 2, the effect of the present invention cannot be obtained, and if the amount is less than 10.5 g/
If it exceeds m2, no increase in effect can be obtained, which is not preferable.

[0015] After the various solutions described above are applied to the fibrous structure, it is dried and, if necessary, heat-treated. For example, drying may be performed at 80 to 120°C for 1 to 10 minutes, and further heat treatment may be performed at 140 to 180°C for 1 to 4 minutes, but the method is not limited thereto.

[0016] The present invention will be explained in more detail below based on Examples, but the present invention is not limited thereto.

Examples 1 to 3 A liquefied shape memory resin (trade name: Nosolex-L (manufactured by Zeon Kasei Co., Ltd.) and an isocyanate-based compound were applied to linen fabric in an amount as shown in Table 1. To facilitate the determination of washing fastness, an oil-soluble dye (trade name: Spiron Red G.H. Conc Liquid) was added to the mixed solution with the trimethylolpropane tolylene diisocyanate adduct to 100 parts by weight of the mixed solution. A solution prepared by mixing and dissolving 1 part by weight of Hodogaya Chemical Industry Co., Ltd. was applied using a wire rod No. 22, dried at 80°C for 5 minutes, and then
A fibrous structure of the present invention was obtained by heat treatment at 0° C. for 2 minutes.

Examples 4 to 6 Linen fabrics were immersed in an aqueous dispersion of n-β (aminoethyl)γ-aminopropyltrimethoxysilane as an organosilicon compound so that the coating amount was as shown in Table 1. The excess liquid was squeezed out using a mangle, and after drying at 80°C for 5 minutes, heat treatment was further performed at 160°C for 2 minutes, and then 100 parts by weight of the liquefied shape memory resin was added to give the adhesion amount as shown in Table 1. On the other hand, a solution in which 1 part by weight of the same oil-soluble dye as above was mixed and dissolved was added to wire rod No. 22
After coating, dry at 80°C for 5 minutes, and then dry for 1
A fibrous structure of the present invention was obtained by heat treatment at 60° C. for 2 minutes.

Examples 7 to 9 Linen fabrics were immersed in an aqueous dispersion of n-β (aminoethyl)γ-aminopropyltrimethoxysilane as an organosilicon compound so that the amount of adhesion was as shown in Table 1. Excess liquid was squeezed out using a mangle, and after drying at 80°C for 5 minutes, heat treatment was further performed at 160°C for 2 minutes, and then the fiber structure of the present invention was obtained in the same manner as in Examples 1 to 3.

Comparative Example 1 A fibrous structure was obtained in the same manner as in Example 1 except that the isocyanate compound was not used in Example 1 so that the coating amount was as shown in Table 2.

Comparative Examples 2 to 3 As shown in Table 2, fiber structures were obtained in the same manner as in Examples 2 to 3, except that the amounts of adhesion were different in Examples 2 to 3.

Comparative Examples 4 and 5 As shown in Table 2, fiber structures were obtained in the same manner as in Examples 5 and 6, except that the amounts of adhesion were different in Examples 5 and 6.

Comparative Examples 6-7 As shown in Table 2, fibrous structures were obtained in the same manner as in Examples 8-9, except that the amounts of adhesion were different in Examples 8-9.

The fibrous structure obtained by the above method was evaluated by the method shown below. The results are shown in the lower columns of Tables 1 and 2.

[0025] Washing fastness: Pour 10 liters of water into a household washing machine and add commercially available detergent (product name: New Beads).
was added and dissolved at a concentration of 0.2%, and the fiber structure obtained in Example 1 was added thereto and heated at 20°C.
After washing for 5 minutes at 100°C, rinsing for 2 minutes with water at 20°C twice, and drying at 110°C for 5 minutes, the degree of adhesion of the shape memory resin was visually observed and evaluated on a 5-point scale. Subsequently, the same procedure was carried out for the fiber structures obtained in other Examples and Comparative Examples. The numbers in the table indicate the grade: 5 indicates good adhesion, the smaller the number, the worse the adhesion, and 1 indicates complete removal.

Wrinkle recovery property: After the washing fastness evaluation, the fibrous structure was ironed (at a temperature of 170°C), and it was observed whether the wrinkles could be removed, and a 4-level evaluation was performed. The symbols in the table are: ◎ indicates that wrinkles can be removed easily, ◯ indicates relatively easy, △ indicates slightly difficult, and × indicates that wrinkles cannot be removed.

[0027] Tear resistance: After the above-mentioned washing fastness evaluation, the fiber structure was evaluated on a 4-grade scale with respect to resistance when it was torn by hand. The symbols in the table indicate that ◎ is equivalent to a fibrous structure provided with a layer made only of shape memory resin, ○ is almost equivalent, △ is slightly easy to tear, and × is extremely easy to tear.

[0028] Hand: After the above-mentioned washing fastness evaluation, the fibrous structure was evaluated on a 4-grade scale for its softness when touched with the hand. The symbols in the table indicate that ◎ is equivalent to a fiber structure provided with a layer made only of shape memory resin, ○ is approximately equivalent, △ is slightly hard, and × is very hard.

As is clear from the evaluation results in the lower columns of Tables 1 and 2, the fiber structure obtained by the present invention does not lose its shape memory resin even after washing, and retains its wrinkle recovery properties. ,
It is a fibrous structure that has good tear resistance and shape memory that allows it to have any desired texture.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

Effects of the Invention As described above, the present invention requires that an isocyanate compound be used in combination with a layer made of shape memory resin on a fibrous structure, or that the fibrous structure be previously treated with an organosilicon compound. It is characterized by easy removal of wrinkles, excellent fastness to washing, easy retention of any irregularities, and shape memory properties that allow the texture to be adjusted as desired after a layer of shape memory resin is applied. It provides fiber structures such as yarn, knitted fabrics, woven fabrics, non-woven fabrics,
It can be widely applied to various forms of materials such as paper.

Claims (6)

[Claims] 1. A fibrous structure having shape memory properties and excellent washing fastness, comprising a fibrous structure provided with a layer made of a shape memory resin and an isocyanate compound. 2. The fibrous structure having shape memory properties according to claim 1, wherein the fibrous structure is previously treated with an organic silicon compound. 3. A fibrous structure having shape memory properties with excellent washing fastness, which is obtained by treating the fibrous structure in advance with an organic silicon compound and then providing a layer made of a shape memory resin thereon. 4. The fibrous structure having shape memory properties according to claim 1 or 3, wherein the shape memory resin is a norbornene polymer. 5. The fibrous structure having shape memory properties according to claim 1, 2 or 3, wherein the fibrous structure is made of cellulose fibers. 6. The fibrous structure having shape memory properties according to claim 5, wherein the cellulose fibers are fibers mainly composed of hemp.