JPH03234877A - Mothproof textile and its production - Google Patents

Abstract

PURPOSE:To obtain the subject textile excellent in washing durability and moth- proofing effect by forming a perforated low-temperature reactive resin coating film containing a sublimative moth-proofing agent having a specified boiling point on the textile surface. CONSTITUTION:A treatment liquid containing an emulsion composed of a sublimative moth-proofing agent (preferable example: N,N'-diethyl-m-tolamide and/or isobornyl thiocyanoacetic acid, etc.) having >=200 deg.C boiling point, a low temperature reactive resin, a foaming agent, a tackifier, etc., dispersed in an organic solvent is applied to a textile such as a woven fabric or a non-woven fabric. Heat treatment is carried out after drying, thus obtaining the objective mothproof textile having a perforated resin coating film, excellent in washing resistance and dry-cleaning resistance and having a high safety and excellent moth-proofing effect.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a fiber structure having an insect repellent effect.

(Prior Art) Conventional methods of insect repellent processing of fibers include coating or spraying insect repellents on natural or synthetic fibers, or impregnating the fibers with a compound solution (Japanese Patent Laid-Open No. 6M-25903, etc.). ). In addition, in Japanese Patent Application Laid-Open No. 61284/210,
Japanese Patent Laid-Open No. 59-27801 describes a curtain made of a synthetic resin containing an insect repellent formed into a sheet shape, in which the insect repellent is added to rubber and applied to the back side of the carpet.

(Problem to be solved by the invention) However, simply apply or spray insect repellent.

Impregnated insect repellents have the disadvantage that their effectiveness is not sustainable and that the attached insect repellent easily falls off after washing or the like. In addition, insect repellent substances are generally sensitive to high temperatures, and when fixed using ordinary resins as in the prior art described above, the insect repellent effect is lost or the effective ingredients evaporate. For this reason, at present, a fiber structure that has both an insect repellent effect and washing durability has not yet been completed.

An object of the present invention is to provide a fiber structure that is durable against washing and has an excellent insect repellent effect.

(Means for Solving the Problems) The present invention provides (11) an insect repellent fiber structure having on its surface a perforated resin film containing a sublimable insect repellent.

(2) A treatment liquid containing an emulsion of a sublimable insect repellent with a boiling point of 200°C or higher, a low-temperature reactive resin, and an organic solvent is applied to the fiber structure, and then heat-treated at a temperature of 150°C or lower. A method for manufacturing an insect-repellent fiber structure.

It is.

The sublimation insect repellent referred to in the present invention is one that has a large sublimation pressure at room temperature and exhibits a remarkable insect repellent effect due to its gas. Such sublimation insect repellents include naphthalene, camphor, p-dichlorobenzene, N,N-diethyl-m-)ylamidoisobornyl thiocyanoacetic acid,
1.2 benzene dicarboxylic acid diethyl ester, etc., but N,N-diethyl-m-toluamide and/or isobornyl thiocyanoacetic acid are preferred from the viewpoint of effectiveness as a pest repellent, type of aroma, and relationship with the manufacturing method described later. , especially mixtures of both in approximately equal amounts, and insect repellent substances 1
In 00g, 81g of 1,2 benzenedicarboxylic acid diethyl ester, 5g of piveronyl butoxide,
One containing 5 g of octyldodecyl myristate and 9 g of an emulsifier is particularly preferred because of its high insect repellent effect.

Next, the resin film referred to in the present invention is acrylic, urethane,
It is made by crosslinking a high molecular weight polymer such as silicone, and has many small pores at least on the surface. In this porous resin film, the sublimable insect repellent is almost uniformly dispersed over the entire surface, and its content is 0.01 to 10% by weight (solid content) at the initial stage of sublimation (at the time of manufacture). (relative to the weight of the fibrous structure) is preferred. The fiber structure is
There is no particular limitation as long as the porous resin film can be provided on the surface, and various materials such as woven fabrics and non-woven fabrics can be used. In addition, various methods such as coating, impregnation, and lamination can be used to join the porous resin film and the fiber structure, but it is preferable to integrate the resin film by coating in terms of texture.

Next, the method of the present invention will be described.

As a sublimation insect repellent, the active ingredient transpires and
It is necessary to have a boiling point of 200°C or higher to avoid deterioration.

As such substances, those mentioned above can be used, and in particular, for drugs and insect repellents containing approximately the same amount of N,N-diethyl-m-toluamide and isobornyl thiocyanoacetic acid as well as dispersants and emulsifiers. 1.2 81% by weight of Henzendicarboxylic acid diethyl ester, 5% by weight of piperonyl butoxide, 5% by weight of octyldodecyl myristate.
Preference is given to medicaments containing 9% by weight and emulsifier.

Examples of low-temperature-reactive resins include emulsions of low-temperature-reactive blocked isocyanate prepolymers and emulsions of low-temperature-reactive organopolysiloxane prepolymers. Sodium sulfite,
Acetylacetone, ethyl acetoacetate, diethyl malonate, etc., react with isocyanate groups to temporarily create stable compounds, which are then thermally dissociated by heat treatment.7.
It is a compound containing at least one blocked isocyanate group in the molecule to regenerate isocyanate groups, and is obtained by polymerizing an acrylic or methacrylic compound and a silicon-modified, fluorine-modified, etc., modified acrylic or methacrylic compound.Propolymer emulsion and These are emulsions of polyurethane prepolymers consisting of diisocyanates and polyols, emulsions of natural polyesters such as starch and cellulose, and emulsions of natural proteins.

In addition, the emulsion of a low-temperature-reactive organoborisioxane prebolimer refers to 100 parts by weight of an organopolysiloxane and its derivatives having at least two hydroxyl groups bonded to a silicon atom in one molecule and an aminofunctional silane or its derivatives. 0.1 to 10 parts by weight of a reaction product of a hydrolyzate and an acid anhydride and 1 colloidal silico
0.01 to 10 parts by weight of a uniform dispersion of ~50 parts by weight based on the polysiloxane, an anionic emulsifier of 0.3 to 20 parts by weight based on the polysiloxane, and water based on the polysiloxane. It is an aqueous emulsion of silicone containing 0.3 to 20 parts by weight.

As the emulsion of the organic solvent, it is preferable to use a hydrocarbon such as kerosene, various halogenated hydrocarbons, etc. that are immiscible with water. Kerosene is particularly preferred from the viewpoint of ease of handling and the state of the pores formed. It may be added together with an emulsifier to form an emulsion.

An emulsion of such a sublimable insect repellent, a low-temperature reactive resin, and an organic solvent is mixed to form a treatment liquid, and in one example, the solid content is 0.00% based on the weight of the fibrous structure. 2 to 15.0% by weight of the low temperature reactive resin is reduced to a viscosity of 50% by a thickener containing kerosene, water and an emulsifier.
Prepare a processing solution by adjusting the centivoise to 00 to 20,000 centivoise.

Examples of the thickener include Ryudai W Reducer Conc 450 (trademark) manufactured by Dainippon Ink Co., Ltd., and the amount used is 40 to 70% by weight in solution concentration.

This is applied to the fiber structure by a coating method. Or, further add a foaming agent and the above thickener to reduce the viscosity to 50.
It is adjusted to 00 to 20,000 centipoise and applied to the fiber structure by a foam processing method.

Examples of devices used in the coating process include a knife coater, an air doctor coater, a blade coater, a reverse roll coater, a gravure coater, and a kiss coater. The amount of coating liquid applied varies depending on the material used for the fiber structure, the purpose, etc., but is generally 10 to 80 g.
/m", preferably 20 to 70 g/m2.

Suitable blowing agents used in foam processing include ethyleneoxide adducts of mixed CII-C15 linear secondary alcohols having about 10 to 50 ethyleneoxide units in the molecule, preferably about 12 to 20 ethyleneoxide units, carbon Ethylenoxide adducts of several 10 to 16 linear primary alcohols, 5 to about 50 ethyleneoxides, preferably F to 20 ethyleneoxides of alkylphenols having 8 to 12 carbon atoms
fatty acid alkanolamides such as coconut fatty acid monoethanolamide, disodium N
-Octadecyl sulfosuccinate.

Tetrasodium N-(1,2-dicarboxyethyl)
-N-octadecyl sulfosuccinate, cyamyl ester of sodium sulfosuccinate, dioctyl ester of sodium sulfosuccinate.

In addition to nonionic and anionic surfactants such as sulfosuccinate ester salts, such as dioctyl ester of sodium sulfosuccinate, distearylpyridinium chloride, N-coco-aminopropionic acid (
N-tallow or N-lauryl derivatives) or the sodium salt, stearyldimethylhensylammonium chloride.

Cationic or amphoteric surfactants such as betaine can also be used.

These foaming agents are added in an amount of 0.05 to 0.05 to the weight of the fiber structure.
5% by weight, preferably 0.1-3% by weight is used.

For foaming textile structures, there are generally known methods 2 machines, such as the FFT foam applicator from Gaston Calanti, the skeg from Stokl.

Foam processing machines such as Toshin Kogyo Co., Ltd.'s Universal Quarter, Custar Co., Ltd.'s Custar Applicator, Fapcon's Fabcon FFT System, and Toshin Kogyo Co., Ltd.'s rotary screen, kiss coater, gravure coater, textile printing machine, etc. may be used. . The amount of foaming liquid applied varies depending on the material used for the fiber structure, the basis weight, etc., but is generally 10 to 80 g/m2.

In addition to this, we also adjust the texture of the fiber structure as necessary.
Epoxy-modified silicone oil emulsion, for example, Disoc Silicone Softener A- manufactured by Dainippon Ink Co., Ltd.
900 (trademark), an amino-modified silicone oil emulsion, for example, Dick Silicone Softener 200 (trademark) manufactured by Dainippon Ink Co., Ltd., are further added in an amount of 0.2 to 0.8% by weight as a solid content based on the weight of the fiber structure. It's okay.

As mentioned above, after applying the treatment liquid, the temperature is 100-130℃.
After drying at a temperature of 80~150℃, preferably 100~
By performing a heat treatment at 130° C. for 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes, a resin film having 0 to a large number of small pores is fixed to the fibrous structure.

(Example) Regarding the insect repellent effect (1) in the example, feed (6 cm in diameter) was spread on the bottom of a glass petri dish with an inner diameter of 6 cm, and about 200 test insects were placed on it together with a breeding medium (150 mg as the medium).
), and the mortality rate over time was determined under conditions of 25° C. and 75% RH. To determine whether the animals were alive or dead, stimulation was applied using a microneedle under a stereoscopic microscope, and those that did not respond were classified as dead or alive. In addition, the test insects include Dermatophaga, -(Dermatophago
idesfarinae), and Ebios (
A mixture of equal amounts of yeast) and insect rearing feed was used.

(2) The above-mentioned test was conducted on the washed products after washing them 5 times and 10 times according to the JIS-L-0217-103 method.

(3) For dry cleaning products, JT 5-L0
The above test for dry cleaning 3 concave edges was conducted using the 217-401 method.

(4) Air permeability was measured according to JIS-L-], ]096-A.

Example 1 A desizing, scouring, bleaching, mercerizing, and dyed 100% cotton, 40-count satin fabric with a basis weight of 130 g/m'' was coated with the following treatment solution using a commonly known method.・Thiocyanoacetic acid CC+3H+q
NO□5) 20% by weight (boiling point 212℃, melting point 204"C
), 20% by weight of diethyl toluamide (CI2H17ON) (boiling point 166°C) and 50 g/ff of something consisting of some dispersant/emulsifier and water, blocked isocyanate manufactured by Dai-Kogyo Seiyaku Co., Ltd. as a low temperature reactive resin. Emulsion, Elastron M-207650 g/n and Catalyst 325 g/l manufactured by Dai-Kogyo Seiyaku Co., Ltd. Amine-modified silicone oil emulsion manufactured by Dainippon Ink Co., Ltd., Disoku Silicone Softener 200 (trademark, containing 40% solids) 10 g /i Epoxy-modified silicone oil emulsion manufactured by Dainippon Ink Co., Ltd., Daisoku Silicone Softner 900 (trademark, solid content 40%) 1
0 g/l, Ryudai W manufactured by Dainippon Ink Co., Ltd. and Reducer Conc 450 as thickeners containing kerosene.
(Trademark) 400g/! , and the remainder is water, and the viscosity is 7.
000 centipoise processing solution. 50g of the treatment liquid
/m2 After applying to satin fabric, dry at 100°C,
Heat treatment was performed at 30° C. for 3 minutes to obtain an insect repellent satin fabric to which 0.75% by weight of insect repellent, 0.15% by weight of amino-modified silicone oil, and 0.15% by weight of epoxy-modified silicone oil were applied to the fiber structure. Ta.

Table 1 shows the insect repellent effects of the resulting processed fabrics, the fabrics after 10 washes, and the fabrics after 10 dry cleanings, and the air permeability of the processed fabrics.

Furthermore, when the insect-repellent satin material was used as a side material for a feather comforter, no filler material was ejected and a suitable fragrance was obtained.

Example 2 Using the same satin fabric and insect repellent as in Example 1, 50 g/β of isobornyl thiocyanoacetic acid was added as an insect repellent.
Organopolysiloxane prepolymer emulsion KM20 manufactured by Shin-Etsu Chemical Co., Ltd. as a low-temperature reactive resin
02L-1 at 50g/β, amino-modified silicone oil emulsion manufactured by Dainippon Ink Co., Ltd., Disoku Silicone Softener 200 (trademark, containing 40% solids) Log/
p, epoxy-modified silicone oil emulsion manufactured by Dainippon Ink Co., Ltd., Disoku Silicone Softener 900 (
Ryudai W manufactured by Dainippon Ink Co., Ltd. as a thickener containing kerosene (Trademark, solid content 40%) 10g/β,
Reducer Conc 450 (trademark) 400g/β and Meihomer F218 from Meisei Kasei Co., Ltd. as a foaming agent
A mixture of Log/p and the balance of water was applied to a foaming machine to produce foam with a foaming ratio of 20 times and a viscosity of 8,000 centibois, and then a foam of 70 g/m" was produced using a rotary stalin manufactured by Toshin Kogyo Co., Ltd. was applied to a 100% cotton satin fabric.This was dried at 100°C and heat-treated at 150°C for 3 minutes to obtain an insect-proof satin fabric34.The obtained fabric after processing and the fabric after washing 10 times , and the insect repellent effect of the fabric after 10 times of dry cleaning.
Table 1 shows the air permeability of the processed fabric.

Comparative Example 1 Regarding the same 100% cotton sateen fabric used in Example 1, the insect repellent effect of the untreated fabric, the fabric after 10 washes, and the fabric after 10 dry cleanings, and the air permeability of the processed fabric were evaluated as follows: It is shown in Table and Table 2.

Comparative Example 2 50% of Elastron M-2076, a blocked isocyanate emulsion manufactured by Dai-Kogyo Seiyaku, was applied as a low-temperature reactive resin to the same 100% cotton satin fabric used in Example 1.
g/IL and Catalyst 32 manufactured by Dai-Kogyo Seiyaku Co., Ltd. at 5 g/IL, amine-modified silicone oil emulsion manufactured by Dainippon Ink & Chemicals Co., Ltd., Dick Silicone Softener 200 (trademark, solid content 40%)
Contains) Log/l Epoxy-modified silicone oil emulsion manufactured by Dainippon Ink & Chemicals Co., Ltd., Dick Silicone Softener 900 (trademark, solid content 40%) 10g
/I2, Ryudai W manufactured by Dainippon Ink Co., Ltd., Reducer Conc 450 as a thickener containing kerosene
(Trademark) 400g/β, Meisei Kasei Co., Ltd.'s Mehomer F218 10g/β as a foaming agent, and the balance water was applied to a foaming machine, with a foaming ratio of 20 times and a viscosity of 8.
000 centibois foam was made, and using a rotary screen manufactured by Toshin Kogyo Co., Ltd., 70 g'/m'' of foam was applied to a 100% cotton satin fabric. This was dried at 100°C and then heated at 150°C. The insect-proof satin fabric was obtained by heat treatment for 3 minutes.The obtained fabric after processing, the fabric after washing 10 times,
Table 1 shows the insect repellent effect of the fabric after 10 dry cleanings and the air permeability of the processed fabric.

Example 3 An insect-proof satin fabric was obtained by carrying out the same treatment as in Example 1, except that 20% by weight of isobornyl thiocyanoacetic acid, some dispersants/emulsifiers, and water were used as the insect-proof substance.

Comparative Example 3 In Example 1, ordinary urethane emulsion resin (Bondic 1 manufactured by Dainippon Ink) was used instead of the low temperature reactive resin.
61ONS) 90g/l, dried at 100℃,
The treatment was carried out in exactly the same manner except that the heat treatment was performed at 50° C. for 3 minutes.

Comparative Example 4 The same process as in Example 1 was carried out except that a thickener that did not contain kerosene was used. The surface of the obtained fabric was observed under a microscope.7 8 Example 4 The same 100% cotton satin fabric used in Example 1 was coated with the following treatment solution. That is, as an insect repellent substance, 1,
2-benzenedicarboxylic acid diethyl ester (boiling point 295
°C) 81% by weight, piperonyl butoxide 5% by weight,
Octyldodecyl myristate 5% by weight and emulsifier 9
50 g/ρ by weight%, blocked isocyanate emulsion Elastron M-207650 g/β manufactured by Dai-Kogyo Seiyaku Co., Ltd. and Catalyst 32 5 g/β manufactured by Dai-Kogyo Seiyaku Co., Ltd. as low-temperature reactive resins.
Amino-modified silicone oil emulsion manufactured by Dainippon Ink Co., Ltd., DIC Silicone Softener 200 (trademark, containing 40% solids) 10 g/j! , epoxy-modified silicone oil emulsion manufactured by Dainippon Ink Co., Ltd., Disoku Silicone Softener 900 (trademark, solid content 4
0% content) 10 g/j! , Ryudai W manufactured by Dainippon Ink Co., Ltd., Reducer Conc 450 (trademark) 400g/7! as a thickener containing kerosene. , and the balance is water, and has a viscosity of 7000 centipoise. After applying the treatment solution to 50 g/m" satin fabric,
Dry at 0°C and heat treat at 130°C for 3 minutes to obtain 0.75% by weight of insect repellent and 0.15% by weight of amino-modified silicone oil based on the fiber structure.

An insect-proof satin fabric to which 0.15% by weight of epoxy-modified silicone oil was applied was obtained.

Table 2 shows the insect repellent effects of the finished fabrics, the fabrics after washing 10 times, and the fabrics after dry cleaning 10 times, and the air permeability of the fabrics after processing.

Furthermore, when the insect-proof satin fabric was used as a side fabric for a feather comforter, no filler material spewed out and it was suitable.

Comparative Example 5 The same 100% cotton satin fabric used in Example 1 was coated with blocked isocyanate emulsion Elastron M-207 manufactured by Dai-Kogyo Seiyaku Co., Ltd. as a low-temperature reactive resin.
650g/β and Catalys manufactured by Dai-Kogyo Seiyaku Co., Ltd.) 32 5g/p, amino-modified silicone oil emulsion manufactured by Dainippon Ink & Chemicals Co., Ltd., Disoku Silicone Softener 200 (trademark, containing 40% solids) Lo
g/j! , epoxy-modified silicone oil emulsion manufactured by Dainippon Ink and Chemicals Co., Ltd., Disoku Silicone Softener 900 (trademark, containing 40% solids) Log/β,
Ryudai W and Reducer Conc 450 (trademark) manufactured by Dainippon Ink Co., Ltd. are used as thickeners containing kerosene.
4oog/l and Meihomer Fzla from Meisei Kasei Co., Ltd. as a foaming agent 10. g/A, and the balance is water, is applied to a foaming machine to obtain a foaming ratio of 20 times and a viscosity of 8.
000 centibois bubbles were made, using a rotary screen made by Toshin Kogyo Co., Ltd., 70 g/m 2
foam was applied to 100% cotton satin fabric.

This was dried at 100°C and heat treated at 150°C for 3 minutes to obtain an insect-proof satin fabric. Table 2 shows the insect repellent effect and air permeability of the finished fabric, the fabric after washing 10 times, and the fabric after dry cleaning 10 times.

Comparative Example 6 The same process as in Example 4 was carried out except that a thickener that did not contain kerosene was used. Observation of the surface of the obtained fabric with a microscope 1 2 (Effects of the invention) This insect repellent fiber structure has a sublimation insect repellent that is durable (it is added to the fiber structure and has excellent safety and insect repellent effects). Furthermore, the method of the present invention enables industrial production of the insect repellent fiber structure.

The present invention is useful when used as a lining or side material for a futon, and in particular, a coated product is effective when used for a feather futon together with the eye closing effect.

Claims (2)

[Claims] (1) An insect repellent fiber structure having a perforated resin film containing a sublimable insect repellent on its surface. (2) A treatment liquid containing an emulsion of a sublimable insect repellent with a boiling point of 200°C or higher, a low-temperature reactive resin, and an organic solvent is applied to the fiber structure, and then heat-treated at a temperature of 150°C or lower. A method for manufacturing an insect-repellent fiber structure.