JPH0711081B2 - Sunscreen stockings and method of manufacturing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a stocking having an ultraviolet ray shielding effect, that is, a sunscreen effect, and a manufacturing method thereof.

(Prior Art) Various kinds of clothing have been conventionally devised to protect themselves from the sun's rays, and are widely available in the market. However, many of these are merely based on the original shielding effect of the cloth, and little consideration or improvement for positively increasing the shielding effect has been made. There are products such as parasols and masks as a means to avoid strong direct sunlight, but this also uses the shielding effect of the fabric as it is and does not actively absorb ultraviolet rays and increase the shielding effect. .

Stockings In particular, pantyhose worn by women has a very thin knitted fabric, and under strong direct sunlight, most of the ultraviolet rays that cause sunburn are transmitted, and in the case of pigmentation of the skin due to sunlight or significant cases Even the occurrence of the erythema phenomenon is seen. Therefore, in order to prevent the sunburn of the legs, the only conventional method is to wear thick slacks or a long skirt or apply cosmetics such as cream containing an ultraviolet absorber.

(Problems to be Solved by the Invention) However, thickening the knitted fabric of the socks in order to prevent the transmission of ultraviolet rays not only increases the weight, but is not suitable for the intended summer wear and impairs the appearance of the stockings. Causes practical problems.

On the other hand, it is conceivable to apply a drug such as an ultraviolet absorber to the stocking, but if it is simply applied to the stocking as it is, a problem occurs in washing durability and the product itself becomes defective.

In view of the above-mentioned circumstances, the inventors of the present invention have obtained the following knowledge, which is an effect that has been earnestly studied for the purpose of imparting a durable ultraviolet ray transmission preventing effect to stockings.
That is, the use of microcapsules containing an ultraviolet absorber together with a binder, the emulsification of an ultraviolet absorber together with a resin, and the combination of the above-mentioned are suitable for imparting the ultraviolet transmission preventing effect of stockings. Is.

The background to this knowledge is the following facts peculiar to stockings. In other words, in the case of stockings, considering the durability of the product itself, it is more effective in preventing UV light transmission for a certain period of time, that is, the number of times of washing for that durability period, than that of pursuing wash resistance of 20 or 30 times. It can be judged that something that can last for several times has high commercial value. For example, taking the application of microcapsules as an example, various manufacturing methods have been developed for microcapsules, and a representative one is Japanese Patent Publication No.
The method described in Japanese Patent Publication No. 7724 is cited, and various application of microcapsules to fibers has been proposed in Japanese Patent Laid-Open No. 19197/1974. However, stockings are made of extremely high-density knitted fabric, and the knitting raw yarn is a filament centering on nylon with little surface friction, so it is very difficult to attach microcapsules and Even if complicated processing is performed only for the purpose of increasing the amount, the texture tends to be deteriorated, and such a material is unsuitable as stockings. That is, considering the commercial value of stockings,
The one to which the ultraviolet absorber is added with a certain degree of washing durability without impairing the texture is suitable.

The present invention has been made based on the above judgment, and a stocking that can satisfy the balance bath with an ultraviolet ray transmission preventing effect, that is, a sunscreen effect, without impairing the soft feeling stretchability of the stocking itself. And a method for manufacturing the same.

(Means for Solving the Problem) A stocking according to the present invention is a stocking in which microcapsules containing an ultraviolet absorber are attached to substantially the entire surface of a knitted fabric, and the microcapsules and the binder are 2: 1.
A sunscreen stocking, which is given in a ratio (weight ratio) of ~ 1 to 5, and the amount of both of these is 1 to 15% of the total weight of the stocking in a dry state. The stocking is put into a treatment bath in which the encapsulating microcapsules and the binder are mixed at a ratio (weight ratio) of 2: 1 to 1: 5, and the hydrogen ion concentration of the treatment bath is adjusted to a range of 4 to 5 with a buffer. It is obtained by maintaining the setting and performing a heat treatment at 20 to 60 ° C.

Stockings that use the UV absorber as it is without being microencapsulated are made by emulsifying the UV absorber and resin.
Put stockings into the treatment bath mixed at a ratio of 2: 1 to 1: 5 (weight ratio), and maintain the treatment bath at a weak acidity,
It is obtained by performing a dipping treatment at 100 ° C.

In general, ultraviolet rays have a wavelength shorter than visible light, which is 200 to 400 μm.
It is well known that this is an electromagnetic wave, but the physical and biological actions differ depending on the wavelength region, and short wavelength ultraviolet rays (UV-C: 200-290nm), medium wavelength ultraviolet rays (UV-B: 290-320).
nm) and long-wavelength ultraviolet light (320 to 400 nm). Of these, most of UV-C is absorbed in the atmosphere and does not reach the ground. Therefore, it is UV-A and UV-B having a wavelength of 290 nm or more that adversely affect the human body. Especially UV-B
It causes erythema and pigmentation due to acute inflammation and is extremely harmful, and its effect on the human body is said to reach 1000 times that of UV-A.

Therefore, the ultraviolet absorber to be used must be one that is effective in at least UV-B of these wavelengths and is safe and does not cause allergy to the human body, that is, human skin. In addition, it is preferable to use one that has little yellowing because it is applied to stockings.

As such an ultraviolet absorber, for example, a p-aminobenzoic acid derivative, an anthranilic acid derivative, a salicylic acid derivative, a cinnamic acid derivative, a benzophenone derivative or the like, or a mixture thereof can be preferably used.

Hereinafter, the invention of each claim will be described in detail.

The microcapsules in the stockings according to claims 1 and 2 are such that the wall material is made of an organic synthetic resin such as urea formalin resin, acrylic resin or urethane resin, and has a particle diameter of 2 to 50.
The thickness is preferably 5 to 20 μm, and the wall thickness is 0.2 to 30 μm, preferably 0.5 to 6 μm.

The composition of the microcapsules is not particularly limited, but low formalin microcapsules are preferable.
Various manufacturing methods have been developed for microcapsules, and the representative one is as follows.
The method described in Japanese Patent No. 724 can be mentioned.

In the stockings of claims 1 and 2, the resin used as a binder serves as an adhesive between the microcapsules and the knitted fabric, and particularly has excellent dispersibility in water and can be easily diluted with water. It is preferable to use a silicone-based aqueous emulsion compound such as an organopolysiloxane which is a main component and is emulsified with an emulsifier. This type of emulsion cures when water is removed and forms a rubber-like film that has the characteristics of silicone rubber.
A durable adhesive effect is obtained. And this binder is 0.5 to 5 times that of microcapsules, preferably 1 to
It is given twice as much (weight ratio) and exhibits a sufficient adhesive effect. When it is less than 0.5 times, the binder effect is extremely poor, while when it is added more than 5 times, the binder effect is hardly changed, and conversely, the texture is deteriorated, which is not preferable.

In addition, the amount of these two attached is 1 to 15 of the stocking weight.
%, Preferably 2-10% is suitable. If the adhered amount of both of these is less than the above 1%, the ultraviolet ray transmission preventing effect and the durability are both insufficient, while if it exceeds 15%, the texture of the stocking deteriorates. That is, it is the above-mentioned adhesion amount that satisfies all the requirements of having a preferable ultraviolet ray transmission preventing effect and feeling and flexibility and having an excellent ultraviolet ray transmission preventing effect having appropriate durability.

Next, a method for manufacturing the stocking of claim 2 will be described.

In this manufacturing method, it is preferable that the treatment for adhering the microcapsules containing the ultraviolet absorber is carried out during the softening treatment after the stockings are dyed, because an excellent treatment effect can be efficiently obtained.

First of all, 2: 1 ~
It is added at a ratio of 1: 5 (weight ratio) and treated in the same bath as the softener. The drug is sufficiently dissolved or dispersed in water, diluted, and then added to the processor. Then, when these are sufficiently uniform, the pH adjuster is added. As long as the pH adjusting agent can set and maintain the pH of the treatment bath within the range of 4 to 6,
It is not particularly limited. That is, when the treatment bath is an acidic bath, the binder is stabilized and the reaction is promoted, so that the binding force is strengthened and the exhaustion property is improved. If the pH is less than 4, the chemicals are aggregated, which is not preferable. Therefore, it is necessary to set the pH of the treatment bath to 4 to 6.

Put stockings in this treatment bath and heat to 20-60 ° C. When the temperature is higher than 60 ° C, the dispersibility of the drug becomes poor, and it is particularly preferable to set the temperature to 20-40 ° C.
A processing time of about 15 to 30 minutes is sufficient. The stockings treated in this manner are dehydrated, dried and processed in the finishing setting process to become finished products.

Next, a description will be given of a stocking in which the ultraviolet absorbent according to claim 3 is used as it is without being microencapsulated.

Regarding the stocking of claim 3, among the above-mentioned ultraviolet absorbers, a benzophenone derivative is particularly preferable, and specific examples thereof include 2-ethylhexyl-p-dimethylaminobenzoate and ethylhexyl-p-methoxycymenate.

Various resins can be used, but a silicone-based aqueous emulsion compound which has excellent dispersibility in water and can be easily diluted with water, for example, one containing organopolysiloxane as a main component is preferable. When these are emulsified, they are cured by removal of water to form a rubber-like film having the characteristics of silicone rubber, and a durable adhesive cure is obtained.

In the method for manufacturing stockings according to claim 3, it is preferable that the treatment for applying the ultraviolet absorber is performed during the softening treatment after the stockings are dyed, because an excellent treatment effect can be efficiently obtained.

First, the ultraviolet absorber is emulsified with an emulsifier or the like. As the emulsifier, polyoxyethylene alkylphenyl ether and / or sodium dioctylsulfosuccinate are suitable.

Next, the emulsifier and the resin are added in a ratio (weight ratio) of 2: 1 to 1: 5 to treat the same bath with the softening agent. The drug is sufficiently dissolved or dispersed in water, diluted, and then added to the processor. Then, when these are sufficiently uniform, the pH adjuster is added. The pH adjusting agent is not particularly limited as long as it can maintain the treatment bath in a weakly acidic range, preferably pH in the range of 4 to 6. That is, when the treatment bath is an acidic bath, the binder is stabilized and the reaction is promoted, so that the binding force is strengthened and the exhaustion property is improved. If the pH is in a strong acid range, for example, less than 4, the drug is aggregated, which is not preferable.

Put stockings in this treatment bath and treat at a temperature of 20-100 ° C. When the temperature is higher than 100 ° C, the dispersibility of the drug becomes poor. A processing time of about 15 to 30 minutes is sufficient. The stockings treated in this way are dehydrated, dried and processed in the finishing setting process to become finished products.

The durability of the ultraviolet absorber is further improved by using a porous resin such as acrylic or urethane or cyclodextrin in the treatment bath in an amount of about 0.1 to 3% by weight. Further, it is also possible to use the above-mentioned microcapsule containing the ultraviolet absorbent in the present invention.

The stockings referred to in the present invention collectively refer to all stockings such as over-knee stockings with a leg length above the knee, through-length stockings up to the base of the thigh, and pantyhose in which the panty portion and the stocking portion are integrated. Is. In view of the purpose of sunscreen and the time of wearing it, it is preferable to use thin summer stockings.

Further, as the materials to be used, polyamides such as 6 nylon and 66 nylon which are commonly used for stockings, those in which spandex, silk and the like are mixed, and various materials such as polyester such as polybutylene terephthalate can be used.
Further, a so-called semi-dal yarn containing about 2 to 5% by weight of titanium oxide has an ultraviolet shielding effect, so that the effect is further increased when used in the present invention.

It is also possible to add the ultraviolet absorber by using the manufacturing methods of claims 2 and 3 together.

(Example) The following two types of stockings were knitted and subjected to ultraviolet absorber application processing.

Pantyhose leg part 15d / 3f Kennel thread Panty / toe part 30d / 8f Woolly thread Pantyhose (support type) Leg part (20 × 13 × 13DCY) × 13d / 3f raw thread Panty part (20 × 30POY) × 30d / 3f Woolly Thread toe 13d / 3f raw thread × 30d / 8f Woolly thread × 70d / 18f Woolly thread Washing durability was measured according to JIS L217 103 method and indicated by the number of times until the ultraviolet ray transmission preventing effect disappeared.

The effect of preventing ultraviolet ray transmission was measured by the following two methods, and the UV inhibition rate was calculated.

Method A UV irradiator: Toshiba UV irradiator with 20W SE-30 (UV-B)
The one equipped with 24 lamps was used.

Irradiation method: Two UV accumulators AB were installed 70 cm below the lamp, and the test sample was attached to the sensor part of A.
Irradiation was performed until the integrated amount of ultraviolet rays of B reached 5 j / cm ² (35 minutes). The test sample of A was removed, an untreated product was attached in the same manner, and the integrated amount was measured.

Method B Using a Hitachi 557 type wavelength spectrophotometer, the UV transmittance (290 to 320 nm) of the stockings to which the ultraviolet absorber was added and the untreated stockings were measured, and the UV suppression rate was calculated by the ratio of the transmittance.

Example 1 A stocking was knitted, and after the dyeing and fixing processes were completed, the stocking was dipped in a flexible bath having the following composition to be processed.

Softener Binder: Water-based silicone binder Shin-Etsu Silicone KM2002T (manufactured by Shin-Etsu Chemical Co., Ltd.) pH adjuster: Ultra MT (manufactured by Mijimajima Chemical Co., Ltd.) Softener: Water-absorbing softener 2% owf Sansofuna Tough A (Sanyo Kasei Co., Ltd.) Kogyo Co., Ltd.) Microcapsules: Urea-formalin resin as wall material, 2-ethylhexy-p dimethylaminobenzoate as ultraviolet absorber (20% by weight of capsule) Average particle size 10 μ The results are shown in Table 1.

Example 2 A stocking was knitted, and after the dyeing and fixing treatment was completed, the stocking was immersed in a flexible bath having the following composition for treatment.

Soft bath Water-absorbing softener Sun Softener Tough A (manufactured by Sanyo Kasei Co., Ltd.) 20% owf Water-based silicone resin KM2002T (manufactured by Shin-Etsu Chemical Co., Ltd.) pH adjuster Ultra MT (manufactured by Mijimajima Chemical Co., Ltd.) UV absorber Is a mixture of 2-ethylhexyl-p-dimethylamino-benzoate or ethylhexyl-p-methoxycinnamate with 25% owf of emulsifier polyoxyethylene alkylphenyl ether and sodium dioctylsulfosuccinate emulsified. Using.

The treatment was carried out by the dipping method at 40 ° C. for 20 minutes.

The results are shown in Table 2.

(Effect of the Invention) In the present invention, the effect of preventing the sunburn by the ultraviolet absorber lasts for the useful life of the stocking. Moreover, the thing using a microcapsule is very suitable also from the viewpoint of safety to the skin because the ultraviolet absorber is enclosed in the microcapsule.

Further, the present manufacturing method does not require complicated processing steps and is a method capable of stably manufacturing stockings having an ultraviolet ray preventing effect.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location D06M 15/643 23/12 7199-3B (72) Inventor Fukumoto Kiyo, 365 Senri, Sennan City, Osaka Prefecture ―21 (72) Inventor Rikuo Sotomaru 1-2-54 Fujisawadai, Tomitabayashi City, Osaka Prefecture (72) Mika Yokote 1-7-13 Sumiyoshibashi Town, Sakai City, Osaka Prefecture Examiner Koichi Monzen (56) References 63-75178 (JP, A) JP-A 63-12765 (JP, A) JP-B 44-8980 (JP, B1) JP-B 55-1367 (JP, B2)

Claims (3)

[Claims] 1. A stocking in which microcapsules containing an ultraviolet absorber are attached to substantially the entire surface of a knitted fabric, wherein the microcapsules and the binder are provided in a ratio (weight ratio) of 2: 1 to 1: 5, And the sunscreen stockings, in which the amount of these two adhered together accounts for 1 to 15% of the total weight of the dry stockings. 2. A stocking is placed in a treatment bath in which microcapsules containing an ultraviolet absorber and a binder are mixed at a ratio (weight ratio) of 2: 1 to 1: 5, and the hydrogen ion concentration of the treatment bath is used as a buffer. 2. The method for producing sunscreen stockings according to claim 1, wherein the heat treatment is performed at 20 to 60 [deg.] C. while setting and maintaining the temperature within the range of 4 to 5. 3. An emulsified ultraviolet absorber and a resin are 2: 1.
Add stockings to the treatment bath mixed at a ratio of 1: 5 (weight ratio) to maintain the treatment bath at a weak acidity, and
A method for producing a sunscreen stocking, which comprises performing a dipping treatment at 0 ° C.