JPH023602A - Vermin-proofing microcapsule and vermin-proofing fiber - Google Patents

Abstract

PURPOSE:To provide a microcapsule composed of a vermin-proofing agent included in a wall membrane composed mainly of a formalin resin and to obtain a vermin-proofing fiber such as sheet, curtain or stockings having durable vermin-proofing effect by attaching the microcapsule with a binder. CONSTITUTION:A core substance compound with a vermin-proofing agent (e.g., 2-ethyl-1,3-hexanediol) is emulsified together with urea or melamine in water, an aqueous solution of formalin is added to the emulsion, the obtained mixture is heated at 70 deg.C under stirring to effect polycondensation reaction and the reaction product is filtered and dried to obtain a microcapsule containing a vermin-proofing agent. The size of the capsule can be controlled in the range of 2-300mum mainly by the power of agitation and the concentration of emulsifier. The content of the wall membrane is 3-50wt.%. The microcapsule is compounded with 1-2 times weight of a binder (e.g., silicone resin) and a vermin-proofing fiber containing 0.3-7.0% of the above components is produced by the immersion, padding, coating, etc., of the mixture. Vermin-proofing effect is developed by the gradual breakage of the capsule caused by friction.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides insect repellent-containing microcapsules and insect repellent fibers to which they are attached, more specifically, microcapsules containing an insect repellent are attached to fibers to improve durability. The invention relates to fibers that have a certain insect repellent effect.

(Prior Art) Various types of fibers having insect repellent effects have been developed and many have been on the market.

However, most of these products are simply sprayed with insect repellent on the finished product, or simply coated with a mixture of insect repellent, glue, or thermoplastic polymer on the surface.
When insect repellent comes into contact with water, it loses its insect repellent effectiveness.
In addition, they had poor washing resistance and the insect repellent completely fell off after 9.1 washes (for example, JP-A-61
-284210). Alternatively, insect repellent was added to the packaging bag during packaging.

Furthermore, Japanese Patent Application Laid-open No. 61-63716 discloses that the core has 4 incense sticks.
An aromatic core-sheath type composite fiber is used in which aromatic core-sheath type composite fibers are dispersed and combined and have a hollow core, but fragrances usually change in quality by volatilization at temperatures above 150°C, and there are a limited number of fragrances that can withstand melt spinning. There was a problem that

(Problems to be Solved by the Invention) However, it goes without saying that the fibers obtained as described above have poor insect repellent effect, and the insect repellent effect completely disappears after just one washing. As a result, it had extremely low commercial value. Furthermore, the insect repellent evaporates or disappears immediately upon contact with the outside air or water while being worn, and some even maintain their insect repellent effect for only a few hours after being worn. Furthermore, in cases where the smell of the insect repellent is transferred to clothing in a packaging bag, the product itself may be defective due to the strong odor of the insect repellent.

In view of the above-mentioned circumstances, the present inventors conducted repeated studies with the aim of imparting a durable insect repellent effect to fibers, and found that using microcapsules containing an insect repellent is suitable for insect repellent processing. We obtained the knowledge that

However, the present invention provides a long-lasting insect repellent effect by attaching microcapsules containing an insect repellent to fibers, and 1. ! This method focuses on the fact that the microcapsules are broken little by little by rubbing, or by intentionally rubbing them, which produces a dissipating effect. However, Japanese Patent Application Laid-open Nos. 49-19197 and 52-31
As disclosed in Japanese Patent Publication No. 200, fragrance-containing microcapsules and a binder may be simply attached to the mW product, or as disclosed in Japanese Patent Application Laid-open No. 106885/1985, they may be attached by a transfer printing method. It is not possible to provide a sufficiently durable i+. Furthermore, there was a problem in that the binder penetrated into the mW yarn, resulting in an extremely hard texture.

The present invention was made based on the above-mentioned knowledge, and 1@The present invention has been made based on the above-mentioned knowledge. The object of the present invention is to provide insect repellent-containing microcapsules with satisfactory effects and fibers to which the microcapsules are attached.

Means for Solving Problem C) That is, the insect repellent-containing microcapsules of the present invention are microcapsules that contain at least an insect repellent and have a size in the range of 2 to 300μ, and have a formalin-based wall membrane. It is characterized by having resin as its main component. In addition, the insect repellent fiber of the present invention is a fiber to which microcapsules containing an insect repellent are attached, and the microcapsules and the binder are provided in a ratio (weight ratio) of 2:1 to 1:5, and the adhesion of both microcapsules and binder is The amount is 0.3 to 7.0 of the fiber weight of the attached part.
%. Moreover, the insect repellent sheets of the present invention are sheets to which microcapsules containing an insect repellent are attached, and the microcapsules and the binder are 2=
It is characterized in that it is applied at a ratio (weight ratio) of 1 to 1:5, and that both of these layers account for 0.3 to 7.0% of the weight of the fabric in the attached area. Further, the insect repellent lace curtain of the present invention is a metal lace curtain to which microcapsules containing an insect repellent are attached, and the microcapsules and the binder are provided in a ratio (weight ratio) of 2:1 to 1:5,
And the adhesion amount of both of these is 0.3 to 7.0% of the fabric type (■)
It is characterized by occupying In addition, the insect repellent stockings of the present invention are futon kings in which insect repellent-containing microcapsules are uniformly adhered to almost the entire surface of the knitted fabric, and the ratio of microcapsules to binder is 2:1 to 1:5 (
It is characterized in that the adhesion amount of both of them accounts for 0.63% to 7.0% of the weight of the knitted fabric in a dry state.

The pest control agent used in the present invention includes 2-ethyl-1
, 3-hexanediol, indalone, dimethyl phthalate, or amide repellents such as N,N-diethyl-m-toluamide, N-butylacetanilide and propyl N,N-diethyl succinate, naphthalene, insecticidal ingredients of chrysanthemum pyrethrins, allethrin, fresrin,
Cineole, citronellal, which are components of eucalyptus oil,
Known examples include citronellol, geraniols, pipridone, limonene, and citral, and one or more of these can be used.

In order to effectively exhibit the insect repellent effect, known synergists may be mixed in as appropriate (e.g., propyl itum, piperonyl butoxide, chrysanthemate, etc.).Especially against mosquitoes, the insecticidal components of the above-mentioned pyrethrum, eucalyptus Oil component or N.

N-diethyl-m-1-lamide is effective.

The main component of the microcapsule wall membrane of the present invention is formalin-based resin (50ff&ffi% or more), preferably urea-formalin-based resin or melamine-formalin-based resin, and has excellent heat resistance, pressure resistance, and water resistance. ing. The size of microcapsules is usually in the range of 1 to 300μ, and when attached to fibers, the size of microcapsules is smaller than the diameter of a single fiber.
The content of the wall film is preferably from 3 to 50% by weight based on the weight of the microcapsules, and preferably from 5 to 25% by weight when attached to fibers.

The composition of the insect repellent-containing microcapsules used in the present invention is not particularly limited, as long as the insect repellent is exposed when broken by appropriate PJ rubbing (preferably releases the odor of the insect repellent). Microcapsules are preferred.

The above-mentioned microcapsules can be manufactured by a known method (for example, Industrial Technology Library 25.
Microcapsules, written by MciJI Kin.

Published by Nikkan Kogyo Shimbun, 1972, Special Publication 1972-772
No. 4 Public [). For example, products with formalin-based resin as a wall film are made by emulsifying a core material containing a small amount of pest control agent and urea or melamine in water (emulsifiers include sodium polystyrene sulfonate, sodium polyacrylate, polyvinyl alcohol, polyethylene). Glycol, etc., if necessary
Then, after adding an aqueous formalin solution, the temperature was raised to 70°C with stirring to carry out a polycondensation reaction. Next, the generated microcapsules were subjected to tIFy.
When dried, microcapsules containing the insect repellent of the present invention are obtained. The size of the wall film is controlled mainly by the strength of stirring and the concentration of the emulsifier, the content of the wall film is controlled mainly by the concentration of urea or melamine in the oil droplets, and the porosity of the wall film is controlled mainly by the concentration of formalin. (Use highly concentrated formalin to do this.)

The fibers used in the present invention may include yarns, IW materials, and non-woven fabrics, and may be natural fibers, recycled fibers, synthetic fibers, or blends, doublings, blends, etc. of these fibers, and water repellency of fabrics. In terms of processing, a larger basis weight is more advantageous; on the other hand, extremely small items such as stockings have disadvantages such as a hard texture and loss of transparency. Furthermore, from the viewpoint of binder adhesion, fibers having irregularities such as cotton, porous fibers having macrovoids, or fibers having affinity with the binder are advantageous.

Furthermore, the fibers used in the present invention are pre-treated with ta
It is preferable to perform water treatment, so that the binder and microcapsules mainly adhere to the surface of the cloth, so that the original texture of the fibers is not impaired. Known methods can be used for water repellent treatment, but! For applications that do not require aqueous treatment, a relatively small amount of treatment agent may be simply impregnated and then dried.

For example, there is a method of impregnating and drying an emulsion made by adding an emulsifier and a protective colloid to aluminum acetate and paraffin, and a method of impregnating and drying an emulsion with an emulsion of methylhydrodiene polysiloxane and a metal soap, followed by heat treatment.

The insect repellent fiber of the present invention can be used for sheets, stockings, socks, curtains, carpets, pajamas, sportswear, duvet covers, casual wear, etc.

The preferred processing method for this insect repellent fiber is to apply a treatment agent containing a mixture of fragranced microcapsules and a silicone resin binder to fabrics or clothing that have been previously treated to be water repellent by dipping, banding, coating, or printing. There is a way to do it.

The binder is not particularly limited as long as it is publicly known, but it is preferable to use one that forms a rubber-like film from the viewpoint of durability.In particular, a silicone resin binder has a coating effect and is suitable for bonding insect repellent-containing microcapsules to knitted fabrics. Among them, a silicone-based aqueous emulsion type, which has excellent dispersibility in water and can be easily diluted with water, is preferred, for example, a silicone-based aqueous emulsion type containing organopolysiloxane as a main component and emulsified with an emulsifier. This cures by removing water and forms a rubbery film having the characteristics of silicone rubber, and is 0.5 to 5 times more durable than rubber, preferably 1 to 2 times (weight ratio). Even if more than 5 times the amount is given, the adhesion rate of microcapsules hardly changes, and on the contrary, problems are caused in the soft texture of fibers and fabrics, which is not preferable. Further, the amount of both of these substances usually accounts for 0.3 to 7.0%, preferably 0.5 to 3.0%, of the fiber weight of the attached portion. That is, the microcapsules sufficiently adhere to the fibers by being provided with the silidine resin binder in the above ratio, but this is insufficient.
On the other hand, if the content is more than 7.0%, it affects the feel of the fiber, and there is also the problem that the odor of the insect repellent sometimes emitted becomes too strong, both of which are unsuitable. In other words, the above-mentioned adhesion amount satisfies all the requirements of a desirable insect repellent, such as having an odor-releasing effect, a suitable texture and flexibility, and the insect repellent effect having appropriate durability.

It is preferable to apply a silicone resin binder to a final product such as clothing that does not undergo a post-processing process, and the product may be immersed in a treatment liquid bath made of a silicone resin binder, and then dehydrated and dried in a manner that does not impair the texture.

Hereinafter, preferred embodiments of the present invention will be summarized and described.

(a) The microcapsule according to claim 11, wherein the pest control agent is an insecticidal component of pyrethrum such as pyrethrins or allethrin, a component of eucalyptus oil, or an amide repellent.

(in) Formalin-based resin is urea-formalin-based resin.

12. The microcapsule according to claim 11, which is a melamine-formalin resin.

(c) Claim full whose size is in the range of 5 to 15μ
Microcapsules as described.

12. The microcapsule according to claim 11, wherein the content of the wall film is 3 to 25% by weight based on the weight of the microcapsule.

(e) The fiber or textile product according to claims (2) to (5), wherein the binder forms a rubbery film.

(f) Claim (2) in which the binder is a silicone resin
) to (5) above.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 1 g of pyrethrin, an insecticidal component of pyrethrum, 10 g of propyl itum, 9 g of eucalyptus oil, 6 g of sodium polystyrene sulfonate, and 4 g of urea were added to 300 g of water, the pH was adjusted to 4.0, and the temperature was raised to 40 °C while stirring. 0 then 3 emulsified
Add 10g of 0% formalin water/8 solution, Labos 9 55
While stirring at -1O0Orp, the liquid temperature was raised from 40°C to 7Q''c in 15 minutes, and maintained at 70'C for 60 minutes to cause a polycondensation reaction.The generated fine particles were filtered through a glass filter into the mother liquor. Wash with water separated from
After air drying at Z, heat treatment was performed at 105° C. for 1 minute.

The obtained microcapsules had a size of 7 to 15 μm (average 10 μm), and a wall film content of 18%.

Example 2 The following four types of dyed woven and knitted fabrics and clothing were subjected to water-repellent treatment according to a standard method (18 water softener: mainly composed of methylhydrodiene polysiloxane). Furthermore, 10 g/l of the insect repellent-containing microcapsules of Example 1 were mixed with 30 g/7 of a silicone-based aqueous emulsion whose main component was epoxy-modified dimethylpolysiloxane resin! mixed with. Next, apply the emulsion so that the amount of microcapsules adhered to is 0.45% of the weight of the woven or knitted fabric or clothing material on which it is attached! [
After immersing the proboscis, etc., it was centrifugally dehydrated so that the pick-up rate was 100%, dried, and heated at 120 to 130°C for 1 minute. The woven or knitted fabrics or clothes to which the insect repellent-containing microcapsules were attached in this manner were dried according to a standard method and sent to a final setting process to become insect-proof woven or knitted fabrics or insect-proof clothes.

■ Cotton Ne40/2 single jersey (sports shirt fabric) ■ Ne45 (120x 35% polyester, 65% cotton)
76/inch) flat VA (sheet fabric)■ Raschel knit lace (lace curtain fabric) made of polyester 75 denier 24 filament and the inserted yarn is its 7 twisted yarns (lace curtain fabric) ■The surface thread is cotton N e 60/2 and ■The thread is nylon 3
Plain knit socks with 0 denier twin yarn.

Next, from the above woven and knitted fabric ■, a sports shirt, from ■, sheets,
After making lace curtains from (1), they were tested for washing durability and texture.

The washing resistance test was conducted according to the JIS L0217103 method, and was expressed as the number of times until the fragrance disappeared.

The insect repellent effect was evaluated by releasing 100 mosquitoes into a room and observing the behavior of the mosquitoes while wearing shirts or socks, sitting with sheets spread out, or hanging a lace curtain. No mosquito tried to approach any of the products of the present invention.

In addition, 10 people evaluated the texture on a 3-point scale, with a score of 0.1 for good, slightly inferior, and poor texture.
, -2, and the average score was taken as the evaluation score. Example 3 After knitting, dyeing, and fixing the following two types of stockings, the microcapsules containing the insect repellent of Example 1 and the silicone binder (4 Miyakoshi Silicone KM-20) were knitted, dyed, and fixed.
02T, manufactured by Shin-Etsu Chemical Co., Ltd.)), the toe and leg portions of the stockings are immersed in a treatment bath mixed with
was maintained within the range of 4 to 6 using a buffer (Ultra MT, manufactured by Mitejima Kagaku Kogyo tII).Next, a durable water-absorbing softener was added, followed by heat treatment at 50°C for 20 minutes.

The stockings thus obtained were sent to the next step of dehydration, drying, and final setting to become a product. The results are shown in Table 2.

Test item: ■Pantystokison leg part 15d/3f Kennel thread panty toe part 30d/8f Woolly thread ■Bantystokison leg part (20X13XL3DCY) X13d/3f Raw silk panty part (20x30POY) X30d/8f Woolly thread tow part 13 d/3 f raw silk x3Qd/8f'7-I
J-type x 70d/18r The results show that the insect repellent fiber according to the present invention has achieved the objective of our laboratory. That is, it will be clear that it has a durable insect repellent effect and a good texture.

(Effects of the Invention) The present invention achieves the following effects with the configuration described above.

First, since microcapsules containing an insect repellent are attached to the fibers, the capsules gradually break during wear or due to intentional friction, thereby exerting an insect repellent effect. Therefore, the effect is not dissipated all at once and disappears,
It has sufficient durability.

Furthermore, by adding a binder to the microcapsules in an appropriate ratio, the adhesive force and adhesion properties are significantly improved, and the desired amount of adhesion and durability of the insect repellent effect are achieved.

The processing method does not require complicated processing steps, and by applying a treatment agent containing a mixture of microcapsules and a binder in an appropriate ratio and performing heat treatment, insect repellent fibers and insect repellent clothing according to the present invention can be used. This is a method that can reliably produce.

Claims (5)

[Claims] (1) Contains at least a pest control agent and has a size of 2 or more
A microcapsule containing an insect repellent, which is a microcapsule with a size in the range of 300μ, and whose wall film is mainly composed of formalin resin. (2) Fibers to which microcapsules containing an insect repellent are attached, where the ratio of microcapsules to binder is 2:1 to
Insect repellent fibers are provided at a ratio (weight ratio) of 1:5, and the amount of both of them attached accounts for 0.3 to 7.0% of the fiber weight. (3) Sheets to which microcapsules containing an insect repellent are attached, where the ratio of microcapsules and binder is 2:1.
An insect repellent sheet in which the ratio (weight ratio) of the two is applied at a ratio of ~1:5, and the amount of both of these adhered accounts for 0.3 to 7.0% of the weight of the fabric. (4) A lace curtain to which microcapsules containing an insect repellent are attached, in which the microcapsules and the binder are provided at a ratio (weight ratio) of 2:1 to 1:5, and the amount of both attached is equal to the weight of the fabric. Insect-proof lace curtains account for 0.3 to 7.0% of the total. (5) Stockings in which insect repellent-containing microcapsules are uniformly adhered to substantially the entire surface of the knitted fabric, and the microcapsules and the binder are provided in a ratio (weight ratio) of 2:1 to 1:5; Insect-proof stockings in which the amount of both of these substances attached accounts for 0.3 to 7.0% of the weight of the knitted fabric in a dry state.