JPH0713321B2 - Aromatic stocking and manufacturing method thereof - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a stocking having an aroma, and more specifically, a perfume-encapsulating microcapsule is attached to a knitted fabric of the stocking, and when the wall film of the microcapsule is worn. The present invention relates to a scented stocking in which fragrance is released by breaking it by friction or the like, and a method for manufacturing the scented stocking.

[Prior Art] Conventionally, various developments have been made for fragranced fiber products, and they have been widely marketed. However, many of these are simply sprayed with a fragrance substance such as perfume or the like on the surface of the final product at the time of finishing, or only a fragrance substance is applied to the surface, and once the fragrance evaporates, the fragrance is released. It completely disappeared, and had almost no washing resistance.

Therefore, for the purpose of maintaining the fragrance imparted to the fiber or the like for a long period of time, a processing method therefor is disclosed in JP-B-53-47440.
JP-A-54-112283 and the like.

In such a situation, if the scent can be imparted to the stockings, it is possible to eliminate the sweat odor when wearing the stockings, which not only makes the wearer feel refreshed but also improves the surrounding environment. It has been thought that it may be possible to do so, and there have been some attempts to impart an aroma to stockings. In the past, this was like spraying a perfume at the time of finishing, or encapsulating an aromatic paper in a packaging bag at the time of packaging, or using the core paper as an aromatic paper to transfer the scent to stockings. .

[Problems to be Solved by the Invention]

However, it goes without saying that the fragrance stockings obtained as described above have poor durability, and the fragrance is completely lost after only one wash,
It had a very low commercial value. Further, some of them even evaporate the fragrance immediately upon contact with the outside air and can maintain the fragrance for only a few hours. Also, in a packaging bag that transfers the scent of aromatic paper to stockings, the strength of the fragrance given to the stockings changes depending on the elapsed time after bag sealing,
As a result, this may not be a pleasant scent, but rather may give an unpleasant feeling.

In addition, Japanese Utility Model Publication No. 38-9451 discloses a permanent aroma-dissipating woman in which a layer such as a pattern formed by heat-pressing a resin composition containing a heat-resistant fragrance is integrally bonded to the knitting structure of the opening of a sock. Socks have been proposed. However, although this sock has the advantage that it has aroma and is permanent, it has the problem that the texture of the knitted fabric to which the above layers are bonded becomes hard. That is, since a paste-like composition in which a fragrance is mixed with a thermoplastic resin and a pigment is printed on a transfer paper and dried and cured, a layer of a pattern or the like is integrally bonded to a knitting structure. On the other hand, although the effect of reinforcing the knitting structure of the bonded portion is obtained, the texture of the bonded portion is unavoidably hardened. Therefore, with such a method, although it is possible to partially impart the fragrance to the opening portion of the sock, it is impossible to impart the fragrance to almost the entire surface of the stocking body while maintaining the soft texture. there were.

Therefore, the inventors of the present invention have conducted extensive studies for the purpose of imparting a durable fragrance to almost the entire surface of the stocking, and as a result, it has been found that the fragrance is applied to the knitted fabric in a closed system in which microcapsules are enclosed. We obtained the finding that it is suitable for the aroma processing. Then, the microcapsules were destroyed by the stress applied to the knitted fabric due to friction during wearing and the like, and the microcapsules were converted into an open system, and an attempt was made to obtain a product that diffuses an aroma.

Various manufacturing methods have been developed for such microcapsules, and a typical method is the method described in JP-B-37-7724. Also, application of microcapsules to fibers has been proposed in JP-A-49-19197.

In the present invention, however, a persistent fragrance can be obtained by fixing the perfume-containing microcapsules to almost the entire surface of the stockings, that is, the wall film of the microcapsules is gradually broken by friction during wearing and continues. It focuses on the effective divergence effect.

However, since the stocking is made of an extremely high-density knitted fabric, and the knitting raw yarn is a filament yarn centered on nylon with little surface friction, it is very difficult to fix the microcapsules. . That is, it is relatively easy to hook and fix the microcapsules on the porous chemical fiber or the like, but it is difficult to fix the microcapsules to the stocking using nylon filament or the like as the knitting raw yarn. And even if complicated processing is performed only for firmly fixing the microcapsules, the texture and transparency of the knitted fabric will be deteriorated only by the fragrance becoming tight.
As a result, no scented stockings were obtained.

That is, in the fragrance stockings, considering the durability of the product itself, the texture is softer than the one that pursues the fragrance's wash resistance 20 to 30 times, and the original transparency is not impaired and it is subtle. It is ideal that such aroma can be continuously emitted for a certain period of time, and it is not possible to obtain such an ideal aroma stocking by simply diverting the technique proposed in the past as described above. I couldn't.

The present invention has been made in view of the circumstances as described above, the soft texture of the stocking itself, without impairing the elasticity and transparency, aroma stockings that can continuously emit a preferred scent and its manufacturing method. It is intended to be provided.

[Means for Solving the Problems]

In order to achieve the above object, the fragrance stocking of the present invention has the following configuration. That is, the perfume-encapsulating microcapsules in which the perfume is completely encapsulated by the wall film are substantially uniformly adhered to the knitted fabric forming the stocking by the urethane binder in a state where the following (A) and (B) are satisfied. It is an aromatic stocking that is characterized by being.

(A) The weight ratio a: b of the perfume-encapsulating microcapsules (a) and the urethane-based binder (b) is 5: 1 to 1: 5.

(B) The adhesion amount (a + b) of the perfume-encapsulating microcapsules (a) and the urethane-based binder (b) is 1.0 to 8.0% by weight of the total weight of the fragrance stocking.

Then, as a method for producing this fragrance stocking, the stocking is put into a treatment bath in which a fragrance-encapsulating microcapsule in which a fragrance is completely encapsulated by a wall film and a urethane binder are mixed in a state satisfying the following (C), and the treatment is carried out. There is a method in which the hydrogen ion concentration of the bath is set and maintained in the range of 4 to 6 with a buffer and heat treatment is performed at 20 to 80 ° C.

(C) The weight ratio a: b of the perfume-encapsulating microcapsules (a) and the urethane-based binder (b) is 5: 1 to 1: 5.

[Action]

That is, the inventors of the present invention, due to the slight friction between the skin and the skin, the microcapsules are partly sequentially broken and a suitable fragrance is continuously released, and the knitted fabric is stretched even when the knitted fabric is stretched. A series of studies were conducted for the purpose of obtaining a fragrance stocking that does not fall out of the fabric and does not impair the texture of the knitted fabric, transparency and wearing feeling. And, in the course of the research, it is optimal to use a urethane-based binder as a binder for fixing the perfume-containing microcapsules to the knitted fabric, that is, if a urethane-based binder is used, the elasticity of urethane acts, Excessive slipperiness is imparted to the knitted fabric to prevent slipping when worn, and the heel feels slippery when the shoe is worn, causing the shoe to come off easily. It has been found that it is possible to fix the microcapsules to the knitted fabric while preventing the above-mentioned (which often occurs when a silicon-based material is used). As a result of further research, by limiting the weight ratio of the urethane binder and the perfume-containing microcapsules and the amount of the two adhering to each other within a specific range, the stocking texture, transparency and wearing comfort can be appropriately adjusted. They have found that it can be used as an aroma stocking that emits aroma.

However, the present inventors have confirmed that when the microcapsules encapsulating a fragrance and the urethane-based binder are fixed substantially uniformly on the entire surface of the knitted fabric of the stocking, not only the knees and the base of the crotch, which have large friction, but also the calf. Even in the thighs and thighs, the wall film of the microcapsules is sequentially destroyed by the movement of the muscles in those parts, the friction given when sitting with legs crossed, and the strain stress given when the knitted fabric expands and contracts. Ascertaining that the fragrance is gradually released for each part and the persistence of the fragrance is increased, further, in the method for producing the fragrance stocking, the pH of the treatment bath in which the perfume-containing microcapsules and the urethane-based binder are mixed is used.
By using an acidic bath within the range of 4 to 6, the binding force between the microcapsules / binders and the adsorptivity between the microcapsules / binders / knitted fabrics are improved, and a suitable adhesion amount is obtained under a stable reaction. We have found that

〔Example〕

 Next, the present invention will be specifically described.

The stockings referred to in the present invention collectively refer to all stockings such as over-knee stockings with leg lengths above the knees, full-length stockings up to the base of the thigh, and pantyhose in which the panty portion and the stocking portion are integrated. The material may be synthetic fiber such as nylon fiber or polyester fiber, or natural fiber such as cotton fiber, and the knitting structure is not particularly limited.

Further, the perfume-encapsulating microcapsules that are adhered substantially uniformly to the substantially entire surface of the knitted fabric of the stocking are those in which the perfume is completely encapsulated by the wall film, and the wall film is destroyed by friction or physical force. This will release the fragrance. The composition and the like are not limited, but those whose main component (50% by weight or more) of the wall film is formalin resin, preferably urea-formalin resin, melamine-formalin resin are heat resistance, pressure resistance and It is excellent in water resistance and suitable, and low formalin microcapsules are particularly preferable.

The size of the perfume-encapsulating microcapsules is usually in the range of 2 to 300 µ, and when fixed to the stocking, it is preferably in the range of 5 to 20 µ. Further, the content of the wall film is usually within the range of 3 to 50% by weight based on the weight of the microcapsules, and when it is fixed to the stocking, it is preferably within the range of 5 to 25% by weight.

The above-mentioned perfume-encapsulating microcapsules can be produced by a known method (industrial technology library 25, microcapsules, published by Nikkan Kogyo Shimbun, written by Asashi Kondo, Showa 45, Japanese Patent Publication No. 37-7724, etc.). ). For example, a formalin-based resin as a wall film is obtained by emulsifying at least a core substance containing a fragrance and urea or melamine in water (emulsifiers include sodium polystyrene sulfonate, sodium polyacrylate, polyvinyl alcohol, polyethylene glycol, etc. , Adjust pH if necessary, water temperature is 40 ℃),
After adding a formalin aqueous solution, the temperature is raised to 70 ° C. with stirring to carry out a polycondensation reaction. Then, the generated microcapsules are filtered and dried to obtain microcapsules in which the perfume is enclosed in the wall membrane.

Further, the urethane-based binder used in the present invention is
It serves as an adhesive between the perfume-encapsulating microcapsules and the knitted fabric, and is preferably an emulsion type which has excellent dispersibility in water and can be easily diluted with water.
This forms a film by evaporation of water, and has a durable adhesive effect.

As the urethane-based binder, various known ones may be used, but among them, a reactive polyurethane water dispersion is preferable, and a reinforced emulsion polyurethane water dispersion is particularly preferable because it is excellent in hot water resistance and wet heat resistance. is there. Since this is a hydrophobic urethane elastomer skeleton, the film is excellent in water resistance, hot water resistance, and moist heat resistance, and has a crosslinked structure, which is excellent in solvent resistance and elastic recovery rate.

Then, the weight ratio a: b of the microcapsule (a) containing the fragrance and the urethane binder (b) needs to be set to 5: 1 to 1: 5. Within this range, the microcapsule containing the fragrance is contained. Can be fixed to the knitted fabric with sufficient strength. That is, when the amount of the urethane-based binder in the perfume-containing microcapsules is out of the above range and is small, the microcapsules are not sufficiently fixed,
Not only is the fragrance released by the obtained fragrance stocking insufficient, but also the wash resistance is poor and the fragrance disappears after only one wash. On the other hand, if the amount of urethane binder exceeds the above range, the texture of the stocking fabric will become stiff and the texture will become stiff, and the stitches will become more clogged and stretchable and transparent. The feeling is also impaired and the wearer feels uncomfortable.

Then, the adhered amount (a + b) of the fragrance-encapsulating microcapsules (a) and the urethane-based binder (b) is required to be 1.0 to 8.0% by weight of the total weight of the obtained fragrance stocking. That is, since the fragrance-encapsulated microcapsules are sufficiently adhered to the knitted fabric by the urethane binder being provided in the above proportion (A), the fragrance should be less than 1.0% by weight. Is too weak and its durability becomes insufficient. On the other hand, when it is more than 8.0% by weight, the texture and stretchability of the knitted fabric are deteriorated as described above, and the scent emitted at one time becomes too tight, which causes discomfort. Will be given. That is, in order to obtain a product which has the effect of continuously releasing a proper fragrance and has a soft texture, elasticity and transparency as a stocking, the adhesion of the above (B) is required. It is necessary to adjust the amount, and it is preferable to set it in the range of 2.0 to 7.0% by weight.

Next, a method for manufacturing the above fragrance stocking will be described.

In this manufacturing method, the process of fixing the microcapsules containing the perfume to the knitted fabric is preferably performed at the time of the softening process after the stocking is dyed and subjected to the fixing process, which efficiently exhibits excellent processing effects and is preferable. .

First, a fragrance-encapsulated microcapsule and a urethane-based binder are put into a processing machine at a ratio (weight ratio) of 5: 1 to 1: 5 to form a processing bath which is the same as the softening agent. At this time, each chemical is added after being sufficiently dissolved and diluted with water. Then, when these are sufficiently uniform, a buffer is added. This buffering agent is for adjusting the hydrogen ion concentration of the treatment bath and setting and maintaining it at an optimum pH. For example, various agents such as those exhibiting excellent pH buffering ability with condensed phosphate as the main component. However, there is no particular limitation as long as the pH of the treatment bath can be set and maintained within the range of 4 to 6 depending on the nature and the amount added. That is, since the treatment is stabilized and the reaction is promoted by making the treatment bath an acidic bath, the binding force between the microcapsule / binder and the microcapsule / binder / knitted fabric is strengthened and the adsorption property is improved. Will be significantly improved. Therefore, the pH of the treatment bath is set to less than 6, but when the pH becomes too low to be less than 4, microcapsules, binders, softening agents, etc. condense to form a complex.
This is not suitable because it causes uneven adhesion. Therefore, the pH of the treatment bath is set within the range of 4 to 6 by the buffer, and the particularly suitable pH of 4.5 to 5.5 is set as the target value.

Then add stockings to the treatment bath and
Perform heat treatment at ~ 80 ° C. That is, this processing temperature is 20
If it is less than ℃, even if the treatment time is extended, a satisfactory treatment effect cannot be obtained. On the other hand, if it is higher than 80 ℃, it is not preferable for each chemical and stocking, and quality problems occur. Therefore, the temperature is set within the above range. In particular, it is preferable to set the softening treatment temperature to 40 to 60 ° C. Regarding the time of this treatment, there is a relation with the temperature, but if it is made longer, an excellent treatment effect is not obtained.
30 minutes is enough.

Then, the stocking of the treating agent obtained as described above is sent to the next step of dehydration, drying and finishing setting step to be a finished product.

Specific example After knitting and dyeing and fixing the following 2 specifications of stocking, 8 kinds of fragrance stockings in which the ratio of the microcapsules encapsulating the fragrance and the binder are made different by the above-mentioned binder are prepared by the above manufacturing method. After manufacturing, each was evaluated for wash resistance, aroma and texture.

Test product; Pantyhose leg part: 15d / 3f Kennel thread Panty / toe part: 30d / 8f Woolly thread Pantyhose leg part: (20 × 13 × 13DCY) × 13d / 3f Raw silk panty part: (20 × 30POY) × 30d / 8f Woolly thread Toe part: 13d / 3f raw thread × 30d / 8f Woolly thread × 70d / 8f Woolly thread Binder; Superflex E-2000 2% owf [Daiichi Kogyo Seiyaku Co., Ltd.] Buffering agent; Ultra MT [Minjima Chemical Kogyo Co., Ltd.] The washing resistance test was performed according to JIS L0217 103 method, and was represented by the number of times of washing until the aroma disappeared. In addition, the fragrance was evaluated by 10 people in each of 5 grades (0 is given to those that emit the optimum fragrance, +1, +2 is too strong above and below, and -1 and -2 is too weak. ) Was performed and the average score was used as the evaluation score. Also, regarding the texture, the same 10 people checked only the ones that they felt were particularly inferior and expressed by the number of checks.

The results are shown in the table below.

Looking at this result, the fragrance stockings according to the present invention,
It becomes clear that it is an ideal scented stocking that maintains its soft texture as a stocking and continuously emits a durable and good scent.

〔The invention's effect〕

The present invention has the following effects due to the configuration described above.

First, since the perfume-encapsulating microcapsules, in which the perfume is completely enclosed by the wall film, are adhered almost uniformly to almost the entire surface of the knitted fabric of the stocking, the microscopic stress caused by friction during fiber wear or expansion and contraction of fibers causes The wall film of the capsule is sequentially broken to emit a suitable scent. Therefore, the fragrance does not diffuse and disappear at once, and is continuously released according to the movement of each part of the body.

In addition, a urethane binder is used in a specific ratio to the microcapsule containing the fragrance, and the elastic adhesive action of the urethane binder ensures that the microcapsule containing the fragrance is firmly attached to the knitting ground. It does not fall off, and the fragrance is effectively released by the destruction of the wall film of the microcapsule due to friction during wearing. It also has excellent wash resistance,
The fragrance will not disappear even after repeated washing several times.

Furthermore, in the present invention, since the urethane binder is used and the knitted fabric is not imparted with excessive slipperiness, the inner surface of the shoe loses its adhesion to the heel when the shoe is worn, and the shoe is likely to come off. There is no problem of deterioration of wearing feeling.

Moreover, the present invention impairs the properties required for stockings, that is, the soft texture, elasticity and transparency, by setting the mutual use ratio and the adhesion amount of the perfume-containing microcapsules and the urethane binder within the specific ranges. It provides an ideal fragrance stocking that can continuously emit a durable fragrance.

Claims (3)

[Claims] 1. A perfume-encapsulating microcapsule in which a perfume is completely encapsulated by a wall film over substantially the entire surface of a knitted fabric that constitutes a stocking, and is formed by a urethane-based binder in a state where the following (A) and (B) are satisfied. Aromatic stockings characterized by being fixed uniformly. (A) The weight ratio a: b of the perfume-encapsulating microcapsules (a) and the urethane-based binder (b) is 5: 1 to 1: 5. (B) The adhesion amount (a + b) of the perfume-encapsulating microcapsules (a) and the urethane-based binder (b) is 1.0 to 8.0% by weight of the total weight of the fragrance stocking. 2. A fragrance stocking in which the urethane binder according to claim 1 is a forced emulsion type polyurethane water dispersion. 3. A stocking is put into a treatment bath in which a perfume-containing microcapsule in which a perfume is completely enclosed by a wall film and a urethane-based binder are mixed in a state satisfying the following (C), and a stocking is added to adjust the hydrogen ion concentration of the treatment bath. 4 to 6 with buffer
The method for producing a fragrance stocking, which comprises performing heat treatment at 20 to 80 ° C. while maintaining the setting within the range. (C) The weight ratio a: b of the perfume-encapsulating microcapsules (a) and the urethane-based binder (b) is 5: 1 to 1: 5.