JPH0244951B2 - - Google Patents

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a fiber 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,
66 etc., which has excellent deodorizing effects but lacks washing durability. It is safe to say that the antibacterial effect is not intended and is almost non-existent. 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 effect is recognized in the sense of antibacterial effects, it is difficult to prevent odor from textile products that have not been treated with antibacterial treatment or from the external environment. Antibacterial-treated textile products cannot be expected to be effective in preventing even the transference of bad odors. 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. A textile product that is resistant to washing and has both the functions of preventing the growth of microorganisms that produce bad odors, cutting off the source of bad odors, and deodorizing by absorbing the transfer of bad odors from the surrounding external environment has not yet been completed. The current situation is that there is no such thing. (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 effects and antibacterial substances. (Means for Solving the Problems) The present invention provides 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 as a solid content of 0.05 to 4% by weight (all weight % is The present invention provides a durable deodorizing fiber structure having a perforated synthetic resin film on the fiber surface that contains (based on the weight of the fiber structure itself), and has washing durability that has not been solved with conventional methods. Moreover, it can maintain excellent deodorizing and antibacterial effects for a long period of time. The deodorizing substance in the present invention is a substance separated by dry distillation from a plant of the Camellia family, particularly its leaves, and preferably has a boiling point of 180° to 200°C at 20 mmHg. Particularly preferably (a) it exhibits maximum absorption at 276±2 mμ in the ultraviolet absorption spectrum of a 1000 times aqueous solution, (b) boiling point: 180° to 200°C (20mmHg) (c) refractive index: n ²⁰ _D = 1.418±0.02 ( D) Optical rotation: n ²⁰ _D = +0.007゜±0.002゜ (E) Specific gravity: d ²⁰ ₂₀ = 1.025±0.002 (However, the above (C), (D) and (E) are in a 20% by weight propylene glycol solution. It is a material with physical properties of (measured value). As the antibacterial substance used in the present invention, any known antibacterial substance can be used. A preferred example is an organosilicon quaternary ammonium salt.
For example, 3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride, which is commercially available as Polon MF50 (trademark: Shin-Etsu Chemical Co., Ltd.), can be used. Alternatively, diphenyl ether compounds can also be used. For example, the commercially available Nitsukanon AB
(Nicca Chemical Co., Ltd., solid content 20%) can be applied to fibers at 0.2% to particularly suppress Staphylococcus aureus. The solid content of this deodorizing substance is 0.1 to 10% by weight, preferably 0.5 to 7% by weight, based on the weight of the fiber structure itself (excluding deodorizing substance, antibacterial substance, and synthetic resin), and 0.05 to 4% by weight of the antibacterial substance. %,Preferably
0.2 to 2% by weight is contained in the perforated synthetic resin film and 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 a fibrous structure can be achieved by using an emulsified treatment liquid made by adding a water-immiscible organic solvent 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. The processing liquid preferably has a viscosity of 3,000 to 20,000 centipoise, particularly 5,000 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 0.1 to 10% by weight (as a solid content) of a deodorizing substance and 0.05 to 4% by weight (as a solid content) of an antibacterial substance separated by dry distillation from a plant of the Camellia family.
(all percentages by weight are based on the weight of the fiber structure itself), including synthetic resin or its precursor, water, water-immiscible organic solvent, and emulsifier, 3000 to 20000
A durable deodorizer having a perforated synthetic resin film containing a deodorizing substance and an antibacterial substance on the fiber surface, which involves applying a treatment liquid having a centipoise viscosity to a fiber structure, followed by drying and heat treatment. A method for manufacturing a fiber structure is provided. 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,
Dimethylol dihydroxyethylene urea, dimethylol ethylene urea, dimethylol dimethoxyethylene urea, dimethylol butylene urea, tetramethylol acetylene diurea, dimethylol propylene urea, dimethylol-5-hydroxypropylene urea, dimethylol triazone, dimethylol uron, Examples include tetramethylolethylenebistriazon. In one embodiment, 0.2 to 5.0% by weight solids of an aminoplast resin or its precursor monomer and its catalyst are mixed with kerosene, water and an emulsifier. In addition, increase the viscosity to 3000~
Adjust to 20,000 centipoise and prepare a processing solution. This is applied to the fiber structure by a coating method. Or add a foaming agent to increase the viscosity to 3000~
It is adjusted to 20,000 centipoise and applied to the fiber structure by a foam processing method. Next, after drying at 100° to 130°C, the aminoplast resin film having many small pores is fixed to the fiber structure by heat treatment at 150°C for 3 minutes. Examples of the urethane-based resin include ether-based and ester-based polyurethane resins. An emulsion of the polyurethane can be used, for example, one produced in a solvent system as known in the art, emulsionized with a suitable emulsifier, and the solvent appropriately recovered. Examples of specific products include Bondi Tsuku 1610 manufactured by Dainippon Ink Co., Ltd.
Bonditsuku 1660, Bonditsuku 1640 (all trademarks), Izerax manufactured by Hodogaya Chemical Co., Ltd.
S4040N (trademark), Evafanol NS-2, Evaphanol S-5, Evafanol KH (all trademarks) manufactured by NICCA Chemical Co., Ltd., and the like.
In one embodiment, a urethane resin with a solid content of 0.2 to 15.0% by weight based on the weight of the fiber structure is adjusted to a viscosity of 5,000 to 10,000 centipoise with a thickener containing kerosene, water, and an emulsifier. Make a liquid. This is applied to the fiber structure by a coating method. Alternatively, the viscosity is adjusted to 5,000 to 10,000 centipoise by further adding a foaming agent and the above-mentioned thickener, and the mixture is applied to the fiber structure by a foam processing method. Next, after drying at 100° to 130°C, heat treatment is performed at 150°C for 3 minutes, and a polyurethane resin film with many small pores is fixed to the fibrous structure. As acrylic resin, 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, stearyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, methoxypolyethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-
Hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 1,4-
Mention may be made of homo- or copolymer emulsions of butylene glycol monoacrylate or emulsions of mixtures of these homopolymers.
In one embodiment, a thickener containing kerosene, water, and an emulsifier is added to an acrylic resin with a solid content of 0.2 to 15.0% by weight based on the weight of the fiber structure to adjust the viscosity to 5000 to 10000 centipoise. to make a processing solution. This is applied to the fiber structure by a coating process. Alternatively, a foaming agent may be further added to adjust the viscosity to 5,000 to 10,000 centipoise, and the foaming agent may be applied to the fiber structure by a foam processing method. next
After drying at 100° to 130°C, heat treatment at 150°C for 3 minutes fixes the acrylic resin, which has many small holes, to the fiber structure. In addition, epoxy-modified silicone oil emulsion, such as Deutsuku Silicone Softener A-900 (trademark) manufactured by Dainippon Ink Co., Ltd., may be used to adjust the texture of the fiber structure.
An amino-modified silicone oil emulsion, such as Deutsuku Silicone Softner 200 (trademark) manufactured by Dainippon Ink Co., Ltd., is applied in an amount of 0.2 to 0.8% by weight as a solid content based on the weight of the fiber structure. The thickening agent containing kerosene, water and emulsifier used in the above coating processing method and foam processing is Ryudai-W, a product of Dainippon Ink Co., Ltd.
Examples include Reducer Conc 450 (trademark).
The amount used is 40-70% by weight in solution concentration. Devices used in the coating process include knife coaters, air doctor coaters, blade coaters, reverse roll coaters, gravure coaters, kiss coaters, and the like. The amount of coating liquid applied varies depending on the material used for the fiber structure, the basis weight, etc., but is generally 10 to 80 g/m ² , preferably 20 to 70 g/m ² . Suitable foaming agents used in foam processing include about 10 to 50 foaming agents, preferably about 12 to 20 foaming agents per molecule.
ethylene oxide adducts of mixed C ₁₁ to C ₁₅ linear secondary alcohols having ethylene oxide units;
Ethylene oxide adducts of linear primary alcohols having 10 to 16 carbon atoms, 5 to about 50 ethylene oxides of alkylphenols having 8 to 12 carbon atoms
fatty acid alkanolamide such as coconut fatty acid monoethanolamide, disodium N-octadecyl sulfosuccinate, tetrasodium N-
Sulfosuccinate ester salts such as (1,2-dicarboxyethyl)-N-octadecyl sulfosuccinate, diamyl ester of sodium sulfosuccinate, dihexyl ester of sodium sulfosuccinate, dioctyl ester of sodium sulfosuccinate, etc. In addition to nonionic and anionic surfactants, distearylpyridinium chloride, N-coco-β-aminopropionic acid (N-talo- or N-lauryl derivatives) or its sodium salt, stearyldimethylbenzylammonium chloride, betaine Cationic or amphoteric surfactants such as cationic or amphoteric surfactants can also be used. These foaming agents are 0.05% based on the weight of the fiber structure.
-5% by weight, preferably 0.1-3% by weight is used. Generally known methods and machines are used to perform foam processing on fibrous structures, such as FFT foam applicator from Gaston County, RSF scale from Stoekl, Universal Quarter from Toshin Kogyo Co., Kyustar foam applicator from Kyustar, etc. Fabcon FFT by Fabcon
A foam processing machine such as a system such as a rotary screen manufactured by Toshin Kogyo Co., Ltd., a kiss coater, a gravure coater, a 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/m ² . (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 350 ml airtight container, and 1 ml of 0.3% trimethylamine or 1.4 ml of 0.3% trimethylamine was added. After adding 0.5 ml of % ammonia and sealing, after leaving it for 1 hour, take 1 ml of head spaer gas and perform gas chromatography analysis.Meanwhile, conduct a blank test in the same way (only 1 ml of 0.3% trimethylamine without adding deodorizing cloth, or 1.4% ammonia
(0.5 ml only) to determine the removal rate. The antibacterial effect is shown by the bacterial reduction rate measured by the shake flask method. Washing durability was also examined by washing 10 times using the JISL0217-103 method, and then determining the removal rate using the above method. Example 1 On a 100% cotton, 40-count satin fabric with a basis weight of 130 g/m ² that has been desizing, scouring, mercerization, and printing using a known method, a soft cloth made by Shiraimatsu Shinyaku Co., Ltd., which is dry-distilled from tea leaves as a deodorizing substance, is applied. Yushiraimatsu (trademark)
(Contains 50% solid content) 60g/, 3 as an antibacterial substance
-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride as solid content
40% containing Poron MF50 (trademark, Shin-Etsu Chemical Co., Ltd.) 30g/, Bondi Tsuku 1610 manufactured by Dainippon Ink Co., Ltd. as urethane emulsion resin
(trademark) (contains 40% solids) 90g/, amino-modified silicone oil emulsion manufactured by Dainippon Ink Co., Ltd., Deitsuku Silicone Softner 200 (trademark)
(Contains 40% solids) 10g/, epoxy-modified silicone oil emulsion manufactured by Dainippon Ink Co., Ltd., Deitsku Silicone Softner A-900 (trademark)
(Contains 40% solids) 10g/, as a thickener containing kerosene, Ryudai W Reducer Conc 450 (trademark) manufactured by Dainippon Ink Co., Ltd. 400g/,
After coating 50g/ ^m2 of a coating mixture with a viscosity of 7000 centipoise and the balance being water, it was heated to 100°C.
and heat treated at 150°C for 3 minutes. 1.15% by weight of deodorizing substance, antibacterial substance based on the weight of the fiber structure
0.46% by weight, 1.38% by weight of urethane resin, 0.15% by weight of amino-modified silicone oil, and 0.15% by weight of epoxy-modified silicone oil. A deodorizing and antibacterial cotton sateen fabric was obtained in which a polyurethane resin film having small pores contained a deodorizing substance and an antibacterial substance. Table 1 shows the odor removal rate of trimethylamine and ammonia after 1 hour and the antibacterial effect of the obtained processed fabric and the fabric after washing 10 times. Example 2 Desizing, scouring, bleaching, mercerization,
A gear bagine made of dyed 65% polyester, 35% cotton, and 40th grit with a basis weight of 250 g/m ² was used. As a deodorizing substance, 200g/200g/trade name of Shiraimatsu Shinyaku Co., Ltd. (containing 50% solid content), and as an antibacterial substance, the above-mentioned Poron MF50 (40% solid content) 35
g/, Boncoat R-3020 manufactured by Dainippon Ink Co., Ltd. (solid content 40%) as acrylic ester
300g/, as a thickener, Reudai W Reiderucer Conc 450, a product of Dainippon Ink Co., Ltd.
400g/, 10g/Meihomer F218 from Meisei Chemical Co., Ltd. as a foaming agent, and the balance water was applied to a foaming machine, and the foaming ratio was 20 times and the viscosity was
Create 8000 centipoise foam and use a rotary screen manufactured by Toshin Kogyo Co., Ltd. to produce 70 g/m ²
foam was applied to the polyester cotton blend gear bagin. After drying at 100°C, it was heat treated at 150°C for 3 minutes.
A deodorizing antibacterial polyester cotton fabric with a polyacrylic resin film having many small pores, which contains 1.75% by weight of deodorizing substances, 0.39% by weight of antibacterial substances, and 3.36% by weight of acrylic esters based on the weight of the fiber structure. Obtained. Table 1 shows the odor removal rate and antibacterial effect of trimethylamine and ammonia after 1 hour on the processed fabric and the fabric after washing 10 times. Example 3 A 100% rayon 100%, 30 count, plain fabric with a weight of 195 g/m ² that had been desized, scoured, bleached, and dyed using a conventionally known method was coated with a deodorizing substance called FRESHIUSHI LIIMATSU manufactured by Shiraimatsu Shinyaku Co., Ltd. (Contains 50% solids) 60
g/, Poron MF50 as an antibacterial substance (solid content 40
% content) 40g/, Sumitex Resin M-3 manufactured by Sumitomo Chemical Co., Ltd. as aminoplast resin
(Contains 80% solids) 60g/, Catalyst
ACX8g/, Reudai W Reducer Conc 450, a product of Dainippon Ink Co., Ltd., as a thickener
A coating mixture of 400 g/m 2 and a viscosity of 7000 centipoise, the remainder being water, was applied at 60 g/m ² , dried at 100° C., and heat-treated at 150° C. for 3 minutes. 1.9% by weight of deodorizing substance based on the weight of the fiber structure;
Antibacterial substance 0.41% by weight, Sumitekus Resin M-
A deodorant rayon plain fabric having a small pore Sumitex Resin M3 resin coating containing 31.5% by weight was obtained. Table 1 shows the odor removal rate after 1 hour of trimethylamine and ammonia and the antibacterial effect of the obtained fabric after processing and the fabric after washing 10 times. Comparative Example 1 100% printed cotton same as used in Example 1
40th satin fabric with a basis weight of 130g/ ^m2 , 60g of fresh lima pine (containing 50% solid content) manufactured by Shiraimatsu Shinyaku Co., Ltd. as a deodorizing substance, and 40g of Poron MF50 (containing 40% solid content) as an antibacterial substance. After applying 50 g/ ^m2 of a coating mixture solution with a viscosity of 7,000 centipoise consisting of 400 g of Reudai W Reducer Conc 450 manufactured by Dainippon Ink Co., Ltd. as a thickener and the balance being water, dry at 100°C. and heat treated at 150°C for 3 minutes. 1.15% by weight of deodorizing substances and antibacterial substances based on the weight of the fiber structure.
A deodorizing satin fabric containing 0.62% by weight was obtained. Table 1 shows the odor removal rate after 1 hour and the antibacterial effect of trimethylamine and ammonia on the obtained fabric after processing and the fabric after washing 10 times.

[Table] (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. The deodorizing effect and antibacterial effect are further improved because the synthetic resin containing the deodorant and antibacterial agent is not in the form of a crackless film but has minute cracks and minute pores. The odor removal effect on malodorous substances other than the two exemplified subodor substances was similarly confirmed. Not only the processed fiber structure of the present invention but also after 10 washings showed an excellent odor removal effect comparable to that described in JP-A-59-66. In addition, the antibacterial effect and washing resistance are excellent. In addition, the fibrous structure has a soft feel.

Claims (1)

[Scope of 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 from tea leaves by dry distillation.
A fibrous structure according to claim 1 having a boiling point of 180° to 200° C. below mmHg. 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 comprises 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 solids), antibacterial substances 0.05-4
% by weight (as solids) (all % by weight relative to the weight of the fiber structure itself), including synthetic resin or its precursor, water, water-immiscible organic solvents, and emulsifiers, with a concentration of 3000 to 20000 centipoise. A viscous treatment liquid is applied to the fiber structure, then dried,
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 including heat treatment. 7. The method according to claim 6, wherein the treatment liquid is foamed by further containing a foaming agent, and 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. The method according to any one of claims 6 to 8, wherein the organic solvent is kerosene.