JPS63288273A - Durability enhancer for antibacterial and antifungal processing of fiber material - 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 [Industrial Application Field] The present invention is directed to the use of 2,4,4'-trichloro-2', which is known as an antibacterial and fungicidal agent for sanitary processing of synthetic fibers and natural fibers.
- in combination with compounds such as hydroxydiphenyl ether and/or quaternary ammonium salts and/or 2-(4-thiazolyl)-benzimidazole and/or 2-methoxycarbonylaminobenzimidazole; The present invention relates to a durability improving agent for antibacterial and antifungal processing to improve durability.

[Conventional technology]

Studies on imparting antibacterial and antifungal properties have been progressing in the clothing and non-clothing fields, but the antibacterial and antifungal properties of textile products treated with the above-mentioned antibacterial and antifungal agents are not very effective immediately after processing. However, the drawback is that the antibacterial and antifungal effect is lost due to repeated washing and cleaning, and there is a strong demand for the development of textile products that have a durable antibacterial and antifungal effect.

[Problem that the invention seeks to solve]

As a result of intensive research in order to meet the above demands, the present inventors discovered that N-
It has been discovered that methylolmelamine and N-methylolurea have the effect of improving durability. However, when 31 N-methylols are used together, the problem arises that more or less formalin remains, and it may not be possible to use it depending on the purpose.

The present inventors conducted intensive research on non-formalin-based compounds to solve such problems, and as a result, discovered that hydrophobic latent reactive urethane compounds have the effect of improving durability. completed.

[Means for solving problems]

According to the present invention, there is provided a durability improver for antibacterial and antifungal processing of textile materials, which comprises a compound having two or more active hydrogens, or a compound obtained by adding an alkylene oxide to the compound, and an organic isocyanate. react,
Furthermore, it comprises at least one hydrophobic latent reactive urethane compound whose terminal isocyanate group is masked.

The hydrophobic latent reactive urethane compound useful in the present invention is
These are shown below.

In other words, it is a compound having two or more active hydrogen atoms, which is converted into a polyalkyl ether if necessary to have a molecular weight of 300.
It is a hydrophobic latent reactive urethane compound having a urethane bond in its structure and a masked isocyanate group at the end, which is obtained by polyaddition reaction of a polyether compound with a molecular weight of 0 or less, preferably 1000 or less, with an organic isocyanate.

Examples of compounds having two or more active hydrogens include hydroxyl group-containing compounds such as ethylene glycol, propylene glycol, butylene glycol, butanediol, glycerin, trimethylolpropane, triethanolamine diglycerin, pentaerythritol, sorbitan, and sorbitol, or ethylene diamine. , hexamethylene diamine, diethylene triamine, etc.
There are class amines. When addition polymerizing an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide to such an active hydrogen-containing compound as necessary, whether it is individual addition polymerization or random addition polymerization,
Alternatively, block addition polymerization may be used. The polyether compound thus synthesized may be either hydrophilic or hydrophobic. In addition, the molecular weight of these compounds is 3000 or less,
Preferably it is 1000 or less.

Examples of organic isocyanate compounds to be reacted with such polyetherified polyol compounds include tetramethylene diisocyanate, hexamethylene diisocyanate,
Examples include aliphatic polyisocyanates such as cyclohexylene diisocyanate and isophorone diisocyanate.

When a terminal hydroxyl compound and an organic isocyanate compound as described above are reacted, a urethane compound containing a terminal isocyanate group can be obtained by reacting at a reaction molar ratio of hydroxyl group to isocyanate group of about I:l to 1:2. The terminal isocyanate group may then be masked with a stabilizer, or the organic isocyanate may be masked with a stabilizer and then reacted with a terminal hydroxy compound. Examples of the above-mentioned stabilizers include methanol, ethanol, aliphatic mercaptan, ε-caprolactam, methyl ethyl ketoxime, acetylacetone, ethyl acetoacetate, diethyl malonate, hydrocyanic acid, sodium bisulfite, and the like.

The hydrophobic latent reactive urethane compound obtained with the above 90 comb can be diluted with various solvents when used in a solvent system, and can be emulsified and dispersed using various surfactants when used in an aqueous system. . The amount of surfactant used as an emulsifier is generally about 3 to 100 parts by weight of the urethane compound.
50 parts by weight, and when this urethane compound is applied to fibers, the isocyanate groups are regenerated by heat treatment, and the regenerated isocyanate groups are crosslinked with a compound having active hydrogen to maintain sufficient performance. It is preferable to use the surfactant in the smallest amount possible.

As a method for imparting a durable antibacterial and antifungal effect, the hydrophobic latent reactive urethane compound obtained here is emulsified and dispersed alone, and 2,4゜4'-trichloro-
2'-hydroxydiphenyl ether and/or 2-
It can be treated in combination with an antibacterial and fungicidal agent typified by (4-thiazolyl)-benzimidazole and/or 2-methoxycarbonylbenzimidazole, or can be treated by emulsifying and dispersing at the same time. The amount of the hydrophobic latent reactive urethane compound to be used is 0.0% based on the weight of the textile product.
It is 1 to 10%, preferably 0.5 to 5%.

〔Example〕

The present invention will be further explained below with reference to Examples.

Production Example 1 17 parts of ethylene oxide in 60 parts of ethylenediamine without catalyst
After dehydration, addition polymerization of 465 parts of propylene oxide on a potassium hydroxide catalyst yielded a polyether with an average molecular weight of 700. After dehydration, methyl ethyl ketoxime was added to 70 parts of this polyether and 68 parts of hexamethylene diisocyanate. A hydrophobic urethane compound was obtained by reacting the masked product with 36 parts. 5 parts of a 2 mol adduct of nonylphenol with EO (ethylene oxide) and 10 parts of an 0 50 mol adduct of nonylphenol were mixed and dissolved in 300 parts of this urethane compound, and 685 parts of water was added to perform emulsification and dispersion to obtain emulsion A. .

Production Example 2 Addition polymerization of 220 parts of ethylene oxide on sodium hydroxide catalyst to 92 parts of glycerin was carried out to obtain an average molecular weight of 310, and 62 parts of this polyether and 132 parts of isophorone diisocyanate were added.
52 parts of methyl ethyl ketoxime were added to obtain a hydrophobic urethane compound. This urethane compound 30
To 0 parts, 1hxo part of bisphenol A with 4 moles of EO added and 20 parts of 60060 moles of bisphenol A with EO 30 parts of methyl oleate were added and dissolved, and 640 parts of water was added to emulsify and disperse to obtain emulsion B.

Production Example 3: Dissolve 20 parts of sarconium, 10 parts of EO4 molar adduct of nonylphenol, and 20 parts of E050050 molar adduct of nonylphenol, and add 700 parts of water to emulsify and disperse to obtain emulsion C containing 10% of the active ingredient of an antibacterial agent. Ta.

Production Example 4 100 parts of the hydrophobic urethane compound obtained in Production Example 1,
200 parts of 2-(4-thiazolyl)-benzimidazole, 10 parts of Ly-780™ E0 of nonylphenol
670 parts of water was added to 20 parts of 20 mole adduct sulfate ester soda and dispersed in an Ajihomo mixer to obtain a dispersion containing 20% of the active ingredient of a fungicide.

Production Example 5 (Comparative Example) 204 mol adduct of 100 parts of 2.4.4'-trichloro-2'-hydroxydiphenyl ether, 30 parts of benzalkonium chloride, 20 parts of nonylphenol, 50 parts
8,020 moles of nonylphenol adduct were mixed and dissolved, and water was added to emulsify and disperse the mixture to make a total volume of 1,000, to obtain emulsion E containing 10% of the active ingredient of an antibacterial agent.

Production Example 6 (Comparative Example) 100 parts of 2.4.4'-trichloro-2'-hydroxydiphenyl ether, 20 parts of sodium alkylbenzenesulfonate, 30 parts of 204 mole adduct of nonylphenol, 8020 moles of 50 parts of nonylphenol. Mix and dissolve the adduct, add water to emulsify and disperse, and reduce the total amount to 100%
0, and emulsion F containing 10% of the active ingredient of the antibacterial agent was obtained.

Production Example 7 (Comparative Example) 780 parts of water was added to 200 parts of 2-(4-thiazolyl)-benzimidazole, 10 parts of Tween 80.10 parts of sodium alkylbenzenesulfonate, and dispersed in a homomixer to prevent mildew. A dispersion G containing 20% of the active ingredient of the agent was obtained.

Production Example 8 (Comparative Example) 780 parts of water was added to 200 parts of 2-methoxycarbonylbenzimidazole, 10 parts of Tween, 80.10 parts of sodium alkylbenzenesulfonate, and dispersed with a homomixer to obtain the active ingredient of the antifungal agent. A 20% dispersion H was obtained.

The chemicals synthesized, emulsified, and dispersed as described above were treated on various fibers under the following conditions, and the antibacterial activity against various bacteria and mold after washing was tested.

Test conditions> 1. Test fiber cotton broadcloth (No. 40), nylon, acrylic, wool muslin, polyester/cotton (65/35), polyester 2, chemical treatment conditions The chemicals shown in the manufacturing example were applied using the pad method under the following conditions.
Each was treated singly or in combination. The adhesion concentration (% o, w, f,) of each drug per weight of fiber is as shown below.

Emulsion A: 2% o, wJ, Emulsion B: 2% o, w,
f.

Emulsion Cat% o, w, f, Dispersion D: 1% o, w
, f.

Emulsion E: 1% o, w, f, Emulsion F: 1% o, w
, f.

Dispersion G: 1% o, w, (, Dispersion H: 1% o, w, f
.

Squeezing rate: 100% Pre-drying: 105℃ x 2 minutes Curing: 120℃ x 2 minutes (acrylic, wool muslin) 150℃
× 3 minutes (cotton, polyester/cotton) 160°C × 2 minutes (nylon) 180°C × 30 seconds (polyester) 3. Washing conditions: Detergent according to JIS L-0217 method 103: New Beads (trademark) 2 g /j! The washing method uses a household washing machine, and the detergent is New Beads 2g/(
! Use. Washing (<) 40'c x 5 minutes, (El)
One wash consisted of rinsing (overflow) for 2 minutes, (c) dehydration, (d) rinsing (overflow) for 2 minutes, and (v) dehydration.The cloth was washed up to 30 times, and an antibacterial activity test was conducted on the cloth for each wash.

4. Antibacterial test method Test bacteria: 5taphylococcus aureus 209
P (abbreviation S, a,) Klebsiella pneu
moniae IFO13277 (abbreviation: p) Test method: Halo test method is AATCCTEST? ! ETIIO
Ro9oc: The seedling reduction rate was determined in accordance with the Society Law by the Textile Sanitary Processing Council, and the retest method was used in conjunction with the evaluation of effectiveness.

Effect judgment method (-): Valid (no breeding of the dead) (+): Invalid (
5. Antifungal test method Test fungus: Penicillium citrjnum IFO6
026 (abbreviation P, c,) 8. supergillus niger IPO63
41 (abbreviation A, n,) Tricophyton mentagrophyte
s IFO5466 (abbreviation ↑, m,) Test method: The mold resistance test is based on the mold resistance test method described in JIS Z 2911.

Effect evaluation method: (=): Effective (no mold growth observed) (+): Ineffective (
6. Antibacterial test results Table 1: Table 2 Table 3 7. Antifungal test results Table 4 Table 5 [Effects of the invention] As is clear from Tables 1 to 5, the antibacterial test results are effective against bacteria and mold. All fibers treated with antibacterial agents and antifungal agents containing hydrophobic latent reactive urethane compounds, or treated in combination, have shown durability over 30 washes.

In comparison, fibers treated solely with antibacterial and antifungal agents do not exhibit durability.

Claims (1)

[Claims] A fiber material made of at least one hydrophobic latent reactive urethane compound obtained by reacting a compound having one or more active hydrogens or a compound obtained by adding an alkylene oxide to the above compound with an organic isocyanate, and further masking the terminal isocyanate group. A durability improver for antibacterial and antifungal processing.