JPS62250281A - Durable deodorizing and antibacterial fiber structure havingperforated film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a textile structure that is durable against washing and has both deodorizing and antibacterial effects.

(Prior Art) Many conventional deodorizing and antibacterial treatments of fibers have been proposed and put into practical use.

For example, as a deodorizing treatment for textile products, there is Japanese Patent Application Laid-Open No. 59-66, etc., which is excellent in deodorizing effect but lacks washing durability. It is safe to say that antibacterial effects are not intended and are highly unlikely.

In addition, there are antibacterial treatments such as JP-A-59-223371, but they do not have a deodorizing effect. In other words, many antibacterial textile products that prevent the growth of fungi that produce bad odors have been proposed, and although their deodorizing effects have been recognized in the sense that they are based on their antibacterial effects, there are many antibacterial textile products that prevent the growth of fungi that produce bad odors. Antibacterial treated fiber IIA products cannot be expected to have the effect of deodorizing even the deepest parts of the odor. In addition, although deodorizing processed fiber products have the effect of preventing bad odors from the external environment, they do not have the effect of preventing the growth of microorganisms that produce bad odors and thus have a limited deodorizing effect.

There is still no durable textile product that can prevent the growth of microorganisms that cause bad odors, block the source of bad odors, and absorb and deodorize the transfer of bad odors from the surrounding external environment. The current situation is that it is not completed.

(Problems to be Solved by the Invention) An object of the present invention is to provide a fiber structure that is durable against washing and has both excellent deodorizing and antibacterial effects.

(Means for Solving the Problems) The present invention consists of a deodorizing substance separated by dry distillation from a plant of the Camellia family in a solid content of 0.1 to 10% by weight, and an antibacterial substance in a solid content of 0.05 to 4% by weight ( The purpose is to provide a durable deodorizing and antibacterial W4 fiber structure that has a perforated synthetic resin coating on the fiber surface that contains (all percentages by weight are based on the weight of the fiber structure itself), which has not been solved by conventional methods. It has a certain washing durability and can maintain excellent deodorizing and antibacterial effects for a long period of time.

The deodorizing substance in the present invention is separated by dry distillation from a plant of the Camellia family, particularly its leaves, and preferably contains 20 mHC
It is a substance with a boiling point of 1800-200°C. Particularly preferably (a) it exhibits a maximum absorption at 276±2 mμ in the ultraviolet absorption spectrum of a 1000 times aqueous solution, and (b) boiling point =
1800-200°C (20mm f1g) (c) Refractive index: n2°-n. −°“°1°°°′ (d) Optical rotation: n = + 0.007°±0.00
2゜(E) Specific gravity: 6 1.025±0.002(
However, the above (c), (d) and (e) are 20ffi amount%
It has the following physical properties (measured in a propylene glycol solution).

As the antibacterial substance used in the present invention, any known antibacterial substance can be used. As a preferred example, organosilicon 4
grade ammonium salts. For example, Poron HF
50 (Trademark: Shin-Etsu Chemical Co., Ltd.) 3-(trimethoxysilyl)propyldimethyloctadecylammonium chloride can be used.Alternatively, diphenyl ether compounds can also be used.For example, commercially available Nitzkanone AB(
NICCA CHEMICAL CO., LTD., solid content: 20%) to the fibers.
Staphylococcus aureus can be especially suppressed by applying 2%.

The solid content of this deodorant substance is 0.1 to 0.1 to the weight of the fiber structure itself (excluding deodorant substances, antibacterial substances, and synthetic resins).
10% by weight, preferably 0.5-7% by weight, and 0.05-4% by weight, preferably 0.2-2% by weight of the antibacterial substance are contained in the perforated synthetic resin coating. It is fixed to the fibrous structure.

In the present invention, it is necessary that the synthetic resin film containing the deodorizing substance and the antibacterial substance has a large number of small pores. In the present invention, by using such a porous film, not only the deodorizing and antibacterial performance is further improved, but also the washing durability of the deodorizing and antibacterial performance is further improved. It is particularly surprising that washing resistance is improved by incorporating deodorizing and antibacterial substances into the porous film.

Formation of such a porous film on the surface of the 1iliIf structure is achieved by using an emulsified treatment liquid made by adding an organic solvent that is immiscible with water to a deodorizing substance, an antibacterial substance, a synthetic resin or its precursor, and water. be done. It is thought that by applying such a treatment liquid to a fibrous structure and then heating it, the organic solvent evaporates, leaving a large number of small pores in the synthetic resin film. Processing liquid is 3,000~20.00
It is preferred to have a viscosity of 0, in particular s, ooo to 10,000 centipoise.

Examples of organic solvents that are immiscible with water include hydrocarbons such as kerosene and various halogenated hydrocarbons.

Kerosene is particularly preferred because of its ease of handling and the state of the pores it forms.

That is, the present invention also provides a deodorizing substance separated by dry distillation from Camelliaaceae plants (0.1 to 10% by weight as a small matrix content), and an antibacterial substance y3o, os ~ 4% by weight (as a solid content) (a small matrix content). % is based on the weight of the fiber structure itself), a processing liquid containing a synthetic resin or its precursor, water, an organic solvent immiscible with water, and an emulsifier, and having a viscosity of 3.000 to 20.000 centipoise. A method for producing a durable deodorizing and antibacterial fiber structure having a perforated synthetic resin film containing a deodorizing substance and an antibacterial substance on the fiber surface, the method comprising applying WA to the fiber structure, followed by drying and heat treatment. I will provide a.

The synthetic resin containing the deodorizing substance is preferably an aminoplast resin, a urethane resin, or an acrylic resin. For example, aminoplast resins include trimethylolmelamine, hexamethylolmelamine, dimethyloldihydroxyethyleneurea, dimethylolethyleneurea, dimethyloldimethoxyethyleneurea, dimethylolbutyleneurea,
Tetramethylol acetylene urea, dimethylol propylene urea, dimethylol-5-hydroxypropylene urea, dimethylol triazone, dimethylol uron,
Examples include tetramethylolethylenebistriazon.

In one embodiment, the fiber structure itself contains kerosene, water, and an emulsifier in the aminoplast resin or its monomer, which is usually its precursor, and its catalyst in a solid content of 0.2 to 5.0 fJi% based on the fiber structure itself. A processing liquid is prepared by adding a thickener and adjusting the viscosity to 3.000 to 20.00 poise. This is applied to the fiber structure by a coating method.

Or further add a foaming agent to increase the viscosity from 3.000 to 20.00.
It is adjusted to 0 centipoise and applied to the fiber structure by a foam processing method. Next, after drying at 1000-130℃,
The aminoplast resin film having a large number of small pores is fixed to the fiber structure by heat treatment for 3 minutes at °C.

Examples of the urethane-based resin include ether-based and ester-based polyurethane resins. An emulsion of the polyurethane can be used, for example, produced in a solvent-based manner as is known in the art, emulsified with a suitable emulsifier, and the solvent appropriately recovered. An example of a specific product is Bondic 1610, a product of Dainippon Ink Co., Ltd. Bondic 1660, Bondic 164
0 (all trademarks), Izerax 3404ON (trademark) manufactured by Hodogaya Chemical Co., Ltd., Evaphanol MS-2, Evaphanol S-5, and Evaphanol 11 (all trademarks) manufactured by NICCA Chemical Co., Ltd. .

- To describe the actual ffA aspect, the solid content of the fiber structure itself is 0.2 to 15. OIfm% urethane resin is mixed with a thickener containing kerosene, water and an emulsifier to give a viscosity of 5,000 to io, oo.

Adjust to centipoise and prepare a processing solution. This is applied to the fiber structure by a coating method.

Or further add a foaming agent and the above thickener to increase the viscosity to 5J)00
-10,000 centipoise and applied to the fibrous structure by foam processing. Next, after drying at ~130[deg.]C, heat treatment is performed at 150[deg.]C for 3 minutes, and a polyurethane resin film having many small holes is fixed to the fibrous structure.

Examples of acrylic resins include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, tridecyl acrylate, and stearyl. Acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, methoxypolyethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 1,4-butylene glycol mono Mention may be made of homo- or copolymer emulsions of acrylates or emulsions of mixtures of these homopolymers.

In one embodiment, a thickener containing kerosene, water, and an emulsifier is added to an acrylic resin in an amount of 0.2 to 15.0% by weight based on the weight of the fiber structure, including the solid content, to reduce the viscosity to 5%. Adjust to .000~io, ooo centipoise! I! Make a liquid. This is applied to the fiber structure by a coating process. Alternatively, a foaming agent is further added to adjust the viscosity to 5,000 to io,00 centiboise, and the mixture is applied to the fiber@@M material by a foam processing method. Next 100'~
After drying at 130°C, heat treatment at 150°C for 3 minutes causes the acrylic resin with many small holes to be fixed to the fiber structure. In addition, to adjust the texture of the fiber structure, if necessary, use an epoxy-modified silicone oil emulsion such as Dick Silicone Softner ^-900 (trademark) manufactured by Dainippon Ink Co., Ltd., or an amino-modified silicone oil emulsion such as Dainippon Ink Co., Ltd. Deutsuku Silicone Softner 200 (trademark), a product of the company, is applied in a solids content of 0.22 to 0.8% by weight, based on the weight of the fibrous structure.

The thickening agent containing kerosene, water and emulsifier used in the above coating processing method and foam processing is Ryudai Liide 1-Sirconc 4, a product of Dainippon Ink Co., Ltd.
50 (trademark), etc., and the amount used is 4 in terms of solution concentration.
It is 0 to 70% by weight.

Equipment used in the coating process includes a knife coater, an air doctor coater, a blade coke, a reverse roll coater, a gravure coater, a kiss coater, and the like.

The amount of coating liquid applied depends on the material used for the fiber structure,
Although it varies depending on the basis weight etc., it is generally 10 to 80 g/TIt, preferably 20 to 700 g/m.

Suitable foaming agents used in foam processing include ethylene oxide adducts of mixed C11-C15 linear secondary alcohols having about 10 to 50, preferably about 12 to 20, ethylene oxide positions in the molecule; Ethylene oxide adducts of 10 to 16 linear primary alcohols, 5 to about 50 ethylene oxides, preferably 7 to 2 of C8 to 12 alkylphenols.
fatty acid alkanolamides such as coconut fatty acid monoethanolamide, cinnamonium N-octadecyl sulfosuccinate, tetrasodium N-(1,2-dicarboxyethyl>-N-octadecyl sulfosuccinate), Sulfosuccinate ester salts, such as cyamyl ester of sodium sulfosuccinate, dioctyl ester of sodium sulfosuccinate, dioctyl ester of sodium sulfosuccinate, etc.
In addition to nonionic and anionic surfactants such as distearylpyridinium chloride, N-coco-
Cationic or amphoteric surfactants such as beta-aminopropionic acid (N-tallow or N-lauryl derivatives) or its sodium salt, stearyldimethylbenzylammonium chloride, betaine can also be used.

These foaming agents are 0.95 to 5 for fiber structure type
% by weight, preferably from 0.1 to 3% by weight.

Foam processing can be carried out on textile structures using commonly known methods and machines such as the FFT foam applicator manufactured by Gaston Calanti, the R3F scale manufactured by Stokl, the universal quarter manufactured by Toshin Kogyo Co., Ltd., and the cue manufactured by Custar. A foam processing machine such as a Starfoam applicator or a Fabcon FFT system manufactured by Fabcon, a rotary screen manufactured by Toshin Kogyo Co., Ltd., a kiss coater, a gravure coater, a textile printing machine, etc. may be used. The coating size of the foaming liquid varies depending on the material used for the fiber structure, the basis weight, etc., but is generally 10.
~80g/m.

(Example) The present invention will be explained in detail in the following examples. Regarding the deodorizing effect in the examples, one sample (deodorizing cloth 20 cm x 25 cm) was placed in a 350rni sealed container, and 0.3% trimethylamine 11r11 or 0.3% trimethylamine 11r11 or After adding 0.5% of 1.4% ammonia and sealing, after leaving it for 1 hour, remove 1 volume of head spae gas and conduct gas chromatography analysis.Meanwhile, conduct a blank test in the same way (0.5% without adding deodorizing cloth). 3% trimethylamine 111t1 only or 1.4% ammonia 0.5d
) to determine the removal rate.

The antibacterial effect is shown by the bacterial reduction rate measured by the shake flask method.

Washing) R durability is washing using JISLO217-103 method)
After performing R 10 times, the removal rate by the above method was determined and investigated.

Example 1 Cotton 10 desizing, scouring, mercerization, and printing by known methods
Fresh Shiraimatsu (trademark) manufactured by Shiraimatsu Shinyaku Co., Ltd., separated by dry distillation from tea leaves as a deodorizing substance (contains 50% solid content) 60g/JJ, Polon containing 40% solid content of 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride as an antibacterial substance.
F50 (trademark, Shin-Etsu Chemical Co., Ltd.) 30qlf
l, Bondic 1610 (trademark) manufactured by Dainippon Ink Co., Ltd. (solid content 4) as a urethane emulsion resin.
0% content) 90 (1/N, Dainippon Ink Co., Ltd. amino-modified silicone oil emulsion, Dick Silicone Softner 200 (trademark) (solid content 40% content>i
.

g/, l! , epoxy-modified silicone oil emulsion manufactured by Dainippon Ink Co., Ltd., Dick Silicone Softener A-900 (trademark) (contains 40% solids) 10Q#!
, Ryudai W Reducer Conc 450 (trademark) manufactured by Dainippon Ink Co., Ltd. as a thickener containing kerosene.
400 (1#!, and the remainder is water, with a viscosity of 7,
000 centivoise coating mixture at 50o/m
After coating, it was dried at 100°C and pretreated at 150°C for 3 minutes. Deodorant substance 1.15% by weight, antibacterial substance 0.46% by weight, urethane resin 1.38% by weight based on the weight of the fiber structure
Weight %, amine-modified silicone oil 0. IJJ% and 0.15% epoxy modified silicone oil were added.

A deodorizing antibacterial cotton sateen fabric containing a deodorizing substance and an antibacterial substance in a polyurethane resin film having small pores was prepared (q). Table 1 shows the odor removal rate and antibacterial effect after 1 hour.

Example 2 65% polyester, 35% cotton, 40-count fabric weight 250, desizing, scouring, bleaching, mercerizing, and dyeing by known methods
o/m gabardine was used. As a deodorizing substance, use the product name Fresh Shiraimatsu (solid content 5) manufactured by Shiraimatsu Shinyaku Co., Ltd.
0% content >200g#, the above-mentioned Poron HF50 (solid content 40%) 35g/l as an antibacterial substance, Boncoat R-3020 (solid content 40%) 300 (]/, manufactured by Dainippon Ink Co., Ltd. as an acrylic ester) 1!
Ryudai W manufactured by Dainippon Ink Co., Ltd. as a thickener
Reducer Conc 450400Q/β, and as a foaming agent Meihomer F21810g from Meisei Chemical Co., Ltd.
/ , 1! , and the balance being water, was applied to a foaming machine to produce foam with a foaming ratio of 20 times, a viscosity of a, and ooo centipoise, and a foam of 70(]/m using a rotary screen manufactured by Toshin Kogyo Co., Ltd.) was applied to polyester cotton blend gabardine. After drying at 100°C, 150'C
was heat-treated for 3 minutes. A polyacrylic resin with many small pores that contains 1.75% by weight of deodorizing substances, 0.39% by weight of antibacterial substances, and 3.36% by weight of acrylic ester based on the weight of the fiber structure. A deodorizing and antibacterial polyester cotton fabric with a film was obtained. Table 1 shows the odor removal rate and antibacterial effect of trimethylamine and ammonia after 1 hour for the fabric after processing and the fabric after 110 washes.

Example 3 100% rayon, 30 count date 195 (1/m plain woven fabric) drawn, scoured, bleached, and dyed using commonly known methods.
As a deodorizing substance, brand name: Fresh Shiraimatsu (50% solids content) manufactured by Shiraimatsu Shinyaku Co., Ltd. 60g/, 1!
, Poron HF50 (containing 40% solid content) 40 g/l as an antibacterial substance, Sumitex Resin M-3 (containing 80% solid content) manufactured by Sumitomo Chemical Co., Ltd. 60 (1#!), Catalyst ACX 8 g/l as an aminoplast resin. fl,
Ryudai W manufactured by Dainippon Ink Co., Ltd. as a thickener
Reducer Conc 450400g/, 1! , and the balance was water and had a viscosity of 7.000 centipoise at 60 g/TIi, dried at 100° C., and heat-treated at 150° C. for 3 minutes. Deodorant '141.9% by weight, antibacterial substance 0.41% by weight of fiber structure Φ
A deodorant rayon plain woven fabric having a Sumitex Resicit 13 resin film with small pores and containing 1.5% by weight of Sumitex Resin M-3 was obtained.

Table 1 shows the odor removal rate and antibacterial effect of trimedelamine and ammonia after 1 hour using the obtained processed fabric and the fabric after washing 810 times.

Comparative Example 1 Fresh white pine (solid content 50%) manufactured by Shiraimatsu Shinyaku Co., Ltd. was added as a deodorizing substance to the same printed 100% cotton 40 count satin fabric with a weight of 130 (]/m as used in Example 1. Contains) 60 (]/, 1!, Poron as an antibacterial substance) iF50 (Contains 40% solid content) 401J/,
1! , Ryudai W Reducer Conc 450400g/, 1! manufactured by Dainippon Ink Co., Ltd. as a thickener! ,
After applying 50g/'rIi of a coating mixture solution with a viscosity of 7,000 centipoise and the balance being water, 1
It was dried at 00°C and heat treated at 150°C for 3 minutes.

A deodorizing satin fabric was obtained in which 1.15% by weight of a deodorizing substance and 0.62% by weight of an antibacterial substance were added to the weight of the fiber structure.

Table 1 shows the odor removal rate and antibacterial effect of trimethylamine and ammonia after 1 hour on the obtained fabric after processing and the fabric after washing 10 times.

(Effects of the invention) ゛ The higher the odor removal rate, the better the deodorizing effect, and the higher the bacteria reduction rate, the better the antibacterial effect.

As can be seen from Table 1, the present invention has high deodorizing and antibacterial effects even after 10 washes. Deodorizing effect.

The antibacterial effect is further improved because the synthetic resin containing the deodorant and antibacterial agent is not a crackless film but has minute cracks and minute pores.

The odor removal effect on malodorous substances other than the two exemplified malodorous substances was similarly confirmed. Processed products of the fiber structure of the present invention are not only available, but also after 10 washes).
It showed an excellent odor removal effect comparable to that described in Publication No. 9-66. In addition, the antibacterial effect and washing resistance are excellent. In addition, the fibrous structure has a soft feel.

Claims (9)

[Claims] (1) 0.1 to 10% by weight of a deodorizing substance dry-distilled from plants of the Camellia family and 0.05 to 4% by weight of an antibacterial substance as a solid content (both weight% is the weight of the fiber structure itself) A durable deodorizing and antibacterial fiber structure having a perforated synthetic resin coating on the surface of the fibers. (2) Deodorizing substances are separated by dry distillation from tea leaves, 20m
A fibrous structure according to claim 1 having a boiling point of 180 DEG to 200 DEG C. under mHg. (3) The fiber structure according to any one of claims 1 to 2, wherein the antibacterial substance is an organosilicon quaternary ammonium salt or a diphenyl ether compound. (4) The fibrous structure according to any one of claims 1 to 3, wherein the synthetic resin is an aminoplast resin, an acrylic resin, or a urethane resin. (5) The fiber structure according to any one of claims 1 to 4, wherein the fiber structure includes a woven fabric, knitted fabric, or nonwoven fabric selected from the group consisting of natural fibers, synthetic fibers, and regenerated fibers. (6) Deodorizing substance separated by dry distillation from plants of the Camellia family 0.1~
10% by weight (as solid content), antibacterial substance 0.05-4
Weight% (as solid content) (all weight% are based on the weight of the fiber structure itself), synthetic resin or its precursor, water,
Contains an organic solvent immiscible with water and an emulsifier, 3,000
Applying a treatment liquid having a viscosity of 0 to 20,000 centipoise to the fiber structure, followed by drying and heat treatment to form a perforated film of a synthetic resin containing a deodorizing substance and an antibacterial substance on the fiber surface. A method for manufacturing a durable deodorizing and antibacterial fiber structure. (7) The processing liquid is foamed by further containing a foaming agent,
7. The method according to claim 6, wherein the treatment liquid is applied to the fiber structure by coating. (8) The method according to claim 6, wherein the treatment liquid is an emulsion, and the treatment liquid is applied to the fiber structure by coating. (9) Claims 6 to 6, wherein the organic solvent is kerosene.
The method described in any one of Section 8.