JPH045205A - Antibacterial treating agent - Google Patents

Abstract

PURPOSE:To provide the subject treating agent imparting durable antimicrobial, hydrophilic, antistatic and yellowing-preventing properties, etc., to fiber products, etc., by compounding an organosilane having a specific quaternary ammonium salt group with an organopolysiloxane having a specified substituent. CONSTITUTION:An antimicrobial treating agent comprises 100 pts.wt. of a quaternary ammonium salt of formula I (R is monovalent hydrocarbon; R<1> is 10-22C monovalent hydrocarbon; R<2> is divalent hydrocarbon; R<3> is alkyl, alkoxyalkyl; X is halogen; a is 0,1) (e.g. a compound of formula II) and 1-100 pts.wt. of an organic polysiloxane having at least one of three groups of formulas III, IV and V R<4> is an end-capping group; M is H, monovalent hydrocarbon, triorganosilyl, ammonium, alkali metal; m is 1-50; n is 0-50; m+n=1-60) in the molecule (e.g. a compound of formula VI). The agent imparts excellent antimicrobial property to fiber products, building products, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an antibacterial treatment agent that imparts excellent antibacterial properties to textile materials, building materials, and the like.

[Prior art and its problems] Molds such as black mold, blue mold, Aspergillus mold, spider mold, or white fungi that exist in the atmosphere, large &! Bacteria,
Bacteria such as Staphylococcus aureus, Corynebacterium, Durham-negative rod-shaped bacteria, Bacillus spp., Bacillus spp., and Coccus spp.
They breed using human sweat, fat, food and drink, etc. adhering to casual wear, bed sheets, covers, interior materials of aircraft, ships, vehicles, etc. as a source of nutrition.
It causes athlete's foot, discoloration, and bad odor.

Traditionally, breeding tin compounds, to solve such problems
Methods of treatment with breeding mercury compounds, halogenated phenol compounds, breeding copper compounds, quaternary ammonium salt-containing cationic surfactants, quaternary ammonium salt-containing vinyl polymers, etc. are known. However, these known methods have poor durability against washing, insufficient effectiveness, environmental pollution during processing, toxicity, etc., and have not been widely used. Ta. Later, an organosilane antibacterial agent containing a quaternary ammonium salt was developed, and as it has almost no toxicity to the human body, it attracted much attention, and numerous patent applications related to it (for example, Japanese Patent Publication No. 45-36320) .

Special Publication No. 52-19860, Special Publication No. 53-1858
4, JP-A-53-139653, JP-A-5
7-51874, JP 59-21777, JP 59-71480, JP 59-130
871, JP-A-59-228371, JP-A-60-48908, etc.).

However, if organosilane containing a quaternary ammonium salt is treated alone on fibers, etc., it will develop strong water repellency and electrostatic properties, so it will become electrostatically charged and dirt will easily adhere to it.
It has drawbacks such as lack of long-lasting effects because it easily falls off when washed or the like.

Therefore, the present inventors first improved durability by using an organosilane that grows a quaternary ammonium salt and an organopolysiloxane that grows an alkoxy group and a polyoxyalkylene group in one molecule. We developed a treatment agent with excellent hydrophilicity, antistatic properties, and antibacterial properties, and filed a patent application (Japanese Patent Application Laid-open No. 148285/1985).

However, since organosilanes that grow quaternary ammonium salts are used, the disadvantage of yellowing of treated textile products cannot be avoided.

Problems to be Solved by the Invention] The present invention aims to eliminate the above-mentioned drawbacks, and provides durable antibacterial, hydrophilic, and antistatic properties to textile materials, as well as anti-yellowing properties. The object of the present invention is to provide an antibacterial treatment agent that imparts antibacterial properties and also improves lubricity.

[Means for solving the IK problem and their effects] The above-mentioned purpose is as follows:
22's 1-branched hydrogen group I R'' is a 2-branched hydrogen group +
R" is an alkyl group or alkoxyalkyl i,
X is a halogen atom, and a is 0 or 1. ) is a quaternary ammonium salt-growing organosilane.
100 parts by weight (B) Bonded to silicon atom, formula -R2S i (R)-(OR3)a--formula -R2-COOM and formula -8
2-0-(C2H,0h-(03H80)-ll-R4
(In the formula, R is a unilateral hydrogen group I, R2 is a bilateral hydrogen group I, R'' is an alkyl group or an alkoxyalkyl group + RJ is a terminal capping group, and 2M is a hydrogen atom.

a group selected from monovalent hydrocarbon groups, triorganosilyl groups, ammonium and alkali metals, a is 0 or L
m is 1 to 50. n is 0 to 50°m+n is 1 to 60. ) can be achieved by using an antibacterial treatment agent characterized by consisting of 1 to 100 parts by weight of organopolysiloxane, each of which is present in a small amount (one individual per molecule).

To explain this, component (A) used in the present invention is a component necessary for exhibiting antibacterial properties, and is an organosilane that grows a quaternary ammonium salt represented by the formula. In the formula, R represents the same or different monovalent hydrocarbon groups, including alkyl groups such as methyl, ethyl, and propyl groups, alkenyl groups such as vinyl and allyl groups, and 2-phenylethyl groups. , 2-phenylpropyl group, substituted alkyl group such as 3.3.3-trifluoropropyl group, phenyl group, aryl group such as tolyl group, or substituted aryl group.

Among these, methyl group is preferred.

R1 is a monovalent hydrocarbon group having 10 to 220 carbon atoms, and includes alkyl groups such as decyl, undecyl, dodecyl, tridecyl, octadecyl, and icosyl, undecenyl, dodecenyl, and octadecenyl groups. Examples include alkenyl groups and aryl groups such as phenyl groups. Among these, preferably carbon number 12
~20 monovalent hydrocarbon groups.

R2 is a divalent hydrocarbon group, preferably having 2 to 1 carbon atoms.
O is an alkylene group, and examples thereof include an ethylene group, an n-propylene group, an isopropylene group, a butylene group, and a pentylene group. Among these, ethylene group or propylene group is preferred.

R3 is an alkyl group or an alkoxyalkyl group,
These include methyl, ethyl, propyl, butyl,
Examples include methoxyethoxy group. Among these, methyl group or ethyl group is preferred.

X is a halogen atom, examples of which include chlorine, bromine, and iodine. Among these, a chlorine atom is preferred.

a is 0 or I. Since this component improves hydrolyzability, its partially hydrolyzed condensate may be used.

The organopolysiloxane (B) component used in the present invention reacts with the (A) component to impart durable hydrophilicity, antistatic properties, and anti-yellowing properties to textile materials, and also provides lubricating properties. It is also a component that imparts sex. It also has the effect of making the antibacterial properties developed by the component (A) durable through the reaction between the component (B) and the component (A). This organopolysiloxane has a silicon atom in its main chain with the formula -R2S l (R)@(OR”)s-
m formula -R2-COOM and formula
-R2-Q-(C2Ha 0)1HC3He OhR'
Each of the three types of groups shown in It may be present both at the terminal and in the side chain.The organopolysiloxane constituting the main chain is preferably linear, but part or all of it may be branched, cyclic, or network-like. , a homopolymer, a block copolymer, or a random copolymer.The organopolysiloxane used in the present invention is preferably liquid at room temperature, and those represented by the following general formula are preferably used. Ru.

In the formula, R is the same or different monovalent hydrocarbon group, including alkyl groups such as methyl, ethyl, propyl, and octyl, alkenyl groups such as vinyl and allyl groups, and phenyl groups. , aryl group such as naphthyl group, 2
Examples include aralkyl groups such as -phenylethyl group and 2-phenylpropyl group, alkaryl groups such as tolyl group and xenyl group, and cycloalkyl groups such as cyclohexyl group. Preferably it is a methyl group. R2 is a divalent hydrocarbon group, and examples thereof include an ethylene group, an alkylene group such as an n-pro and lene group, an isopropylene group, a butylene group, an arylene group such as a phenylene group,
Ethylene group is typical. However, if M in the -R'C00M group is an alkali metal, %
R2 is preferably an alkylene group having about 8 to 16 carbon atoms.

-R"-S L (R) s (OR') !-a group reacts with component (A) and at the same time crosslinks to impart durability of the effect. R1 is an alkyl group or an alkoxyalkyl group Examples include methyl group, ethyl group, propyl group, butyl group, and methoxyethoxy group, and among these, methyl group or ethyl group is preferable.a
is 0 or 1, preferably 0.

The formula -R9C00M group prevents yellowing of fibrous materials, etc. in which component (A) is present.

M is a hydrogen atom, a monovalent hydrocarbon group such as a methyl group, an ethyl group, a propyl group, an octyl group, or a phenyl group, a triorganosilyl group such as a trimethylsilyl group or a dimethylethylsilyl group, ammonium, sodium, potassium, lithium, or rubidium. , and alkali metals such as cesium. Preferably it is a hydrogen atom, sodium or potassium.

Formula -R2-0-(C2H40ToTSakiC3H,0),
The -R' group imparts hydrophilicity and W1ws prevention properties and facilitates dissolution and dispersion in water. R- is a terminal capping group, and includes a hydrogen atom, a methyl group, an ethyl group, a propyl group, an octyl group,
Examples include monovalent hydrocarbon groups such as a phenyl group, and acyl groups such as an acetyl group, a propionyl group, and a butyryl group. m
is 1-50. n is 0 to 50. m+n is 1-60.

Preferably m+n is in the range of 10-50.

A is the R group described above.

R2S l (R) m (OR3) 3-s group.

-R2-COOM group and R2-0(C2H40)7(CsHeOHR' group. W is 1 to 1000, and this diorganosiloxane unit provides lubricity and flexibility to fiber materials etc. The preferred range of W is from 10 to 500, more preferably from 20 to 300.X
is in the range of 1 to 50, preferably in the range of 2 to 20.

y is 1-50, preferably 2-10. 2 is 1-50, preferably 2-10. W+x+
y+z is 4 to 1000, preferably 20 to 50
It is in the range of 0.

The ratio of component (B) to component (A) is 1 to 100 parts by weight of component (B) per 100 parts by weight of component (A)! The amount is preferably 2 to 301 parts.

An example of the method for producing the organopolysiloxane component (B) is as follows: (CHa)aSIO[(C)la)2Si
Okos@[CHa()I)SiO]+5Si(CHa)
CH2:CHCOO)1°CTo=
CHCH20(CaHaO)TrH and CHe=CH
5ICQCHs) Obtained by addition reaction with a in the presence of a platinum-based catalyst.

The processing agent of the present invention can be obtained simply by mixing predetermined amounts of component (A) and component (B).

Although this mixture may be used as it is, it is usually used in the form of a solution in an organic solvent, an aqueous solution, or an emulsion of water and a surfactant. 1! 'Suitable solvents include, for example, toluene, xylene, benzene, n-ethanol, heptane, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl acetate, butyl acetate, mineral turpentine, perchloroethylene. , chlorocene, etc. Examples of the surfactant include higher alcohol polyoxyalkylene adducts, higher fatty acid polyoxyalkylene adducts, higher fatty acid sorbitan esters, and alkylene phenol polyoxyalkylene adducts.

Furthermore, the antibacterial treatment agent of the present invention may be used in combination with conventionally known curing catalysts, crosslinking agents, silane coupling agents, lubricity imparting agents, heat resistant agents, flame retardants, etc., as required.

As curing catalysts, there are conventionally known silanol condensation catalysts, which include breeding salts such as zinc, tin, and zirconium, and include zinc stearate, zinc oleate, dibutyltin dioleate, cyphthyltin dilaurate, and zirconium stearate. Illustrated. Examples of the crosslinking agent include silanol group-containing organopolysiloxane.

There are no particular limitations on the treatment method, and methods such as spray roll coating, brushing, and dipping may be used to adhere the agent to the object to be treated, such as a fiber material. The amount of the treatment agent of the present invention to be applied varies depending on the type of the object to be treated and is not particularly limited, but in the case of aN materials, it is recommended to apply the treatment agent in a solid content of 0.1 to 5% by weight based on the weight of the fiber material. Common. In addition, after the treatment agent of the present invention is applied to a fiber material, etc., it may be left at room temperature, but in order to maintain work efficiency and durability, it is further heated at a temperature of 50 to 110°C. It is preferable.

The objects to which the treatment agent of the present invention can be applied include various fibers and their mismatched products, paper, wood, ceramics, natural or synthetic leather, cellophane, sheet-like objects such as plastic films, foam-like objects such as synthetic resin foam, synthetic resin molded products,
Examples include natural or synthetic rubber molded articles, metal molded articles, glass molded articles, and powdered materials such as inorganic powder or synthetic resin powder.

Textile materials are particularly difficult to treat, including hair, wool, silk, linen, cotton, natural fibers such as asbestos, recycled fibers such as rayon and acetate, polyester, polyamide, vinylon, polyester, etc. Examples include acrylonitrile, polyethylene, polypropylene, synthetic fibers such as spandex, glass fibers, carbon fibers, and silicone carbide fibers. Examples of shapes include staples, filaments, tows, and threads, and examples of acts include knitted fabrics, woven fabrics, nonwoven fabrics, resin-treated fabrics, and sewn products of these.

The antibacterial treatment agent of the present invention has durable antibacterial properties.

It imparts hydrophilicity, anti-static properties, anti-Il properties, and lubricity, making it suitable for shoes, shoe soles, socks, underwear, casual wear 9 gloves, mufflers, and scarves.

Yougetsu is used as a treatment agent for pajamas, sheets, pillowcases, duvet covers, seat covers, tablecloths, bags, bedding, etc., where sweat and fat easily accumulate. In addition, the kitchen, washroom,
Yougetsu is used as a treatment agent for tiles, boards, walls, etc. in humid areas such as toilets and bathrooms.

[Example] Next, the present invention will be explained with reference to an example. In the examples, parts and % are parts by weight and! The viscosity is the value at 25°C.

Furthermore, component (A) and component (B) used in the examples are represented by the following chemical structural formula.

(B) Component 0-(CaH40)+2H Q-CCmHaQ)msccjHaO)xILH5IC
OCHs)s Q-CCzHaO>Iz-COCIh
CaHsO(Ca)lao)as(CzH@OJ*s tlc; Hz Comparative example CHs C viscosity 1880C5t O(CaHaOhs(CsHsO)ascIhl
Viscosity 1100C5t O-(CaH40)+*tl In addition, each test item described in the example was measured by the following method.

■Water Absorption Test Cloths before and after washing were arranged horizontally on top of the paper, a drop of water was dropped on them using a dropper, and the time (seconds) it took for the water droplets to diffuse and disappear was measured.

■Charging property test After leaving each treated fabric in an atmosphere of 20°C and 65% relative humidity for one week, use a Kyoto University Kaken type rotary static tester to apply friction to a cotton cloth (Kanakin No. 3). The frictional charging voltage (V) was measured after 60 seconds by rotating 800 times/minute using a .

■Silicone residual rate Using a fluorescent X-ray analyzer manufactured by Rigaku Denki Kogyo Co., Ltd., we measured the number of silicon atoms in the silicone particles adhering to the cloth before and after washing. The silicone residual rate (%) after washing was determined.

■ Yellowing degree After drying the cloth subjected to the water absorption test for one day and night at room temperature,
After heat treatment for 5 minutes in a hot air circulation oven at ℃, 4 layers of cloth were stacked and the three color stimulus values x, y, and z were measured using a 5M color computer manufactured by Suga Test Instruments Co., Ltd. The degree of yellowing (ΔYI) was calculated by calculation.

△YI=YI2-YI.

Example I A treatment solution (a) was prepared by mixing 3 parts of the organopolysiloxane B-1, 10 parts of the organosilane A-1, and 987 parts of methyl isobutyl ketone.

At the same ratio as above, the treatment solution (
b), (c), (d), and (e), and as comparative examples, (f), (g), and (h) were prepared. Furthermore, as a comparative example, a treatment solution (
i) was prepared.

Next, fluorescently whitened white 50% cotton 50% polyester blend knitted fabric of 40x20α size was immersed in each treatment solution for 30 seconds, and then a mangle roller was used to adjust the squeezing rate to 100%. After drying at room temperature for 5 hours, dry in a hot air circulation oven at 110℃ for 10 minutes.
Heat treatment was performed for a minute.

This treated fabric was cut into two, and one of the fabrics was washed once in an automatic reversing washing machine under the following conditions, then washed twice in water under the same conditions except for the detergent, and then washed at room temperature. It was dried with.

Bath ratio: 1:50 Temperature: 40°C Detergent: Monogen (neutral detergent manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Time: 10 minutes Regarding the treated fabrics obtained in this way before and after washing, water absorption,? The 4f conductivity, silicone residual rate, and yellowing were examined using the measurement methods described above.

The results are shown in the construction table. As shown in Table 1, the fabrics treated with the composition of the present invention had better water absorption, antistatic properties, and yellowing resistance than those of the comparative examples, and were also excellent in durability against washing.

j111 Table Example 2 Prepare one pair of commercially available shoe insoles made of expanded polyethylene foam, and use a simple spray gun to apply the treatment solution (a) prepared in Example 1 to the left foot insoles. After spraying for 5 seconds and leaving at room temperature day and night, heat treatment was performed at 60° C. for 30 minutes.

Next, the insole for the left foot treated with treatment solution (a) and the insole for the untreated right foot were inserted into new canvas shoes, and the shoes were worn indoors at 28° C. for about 10 hours a day for one month. In addition, the socks are nylon! I wore a new one every day that did not have 00% antibacterial treatment. After one month, the insole was removed and Example 1
In the same manner as above, the strength of the odor was evaluated by the electrostatic test and the sensitivity test.

Next, the insole used was washed and rinsed under the same conditions as in Example 1, and was worn in the same manner for an additional month. Thereafter, the insole was taken out, and the strength of the odor was evaluated by an electrostatic test and a sensitivity test.

As shown in Table 2, the insole treated with the treatment liquid of the present invention had excellent antibacterial properties, antistatic properties, and excellent durability against washing.

As shown in Table 2, the squeezing ratio was adjusted to 100%, and after squeezing, the sample was dried at room temperature for a day and a night. The socks treated in this manner were heat treated at 150° C. for 5 minutes, and the reduction in whiteness before and after the treatment was visually evaluated. In addition, the fit, lubricity, and sweat absorption were examined through a wearing test.

The results are shown in Table 3, and the socks treated with the treatment agent of the present invention were not colored (excellent fit, lubricating properties, and good sweat absorption). In the treatment solutions (a) and (i) used, treatment solutions (a)'-w and (i) were prepared in exactly the same manner except that water was used instead of methyl isobutyl ketone as the dispersion solvent.
)-w was prepared.

Next, three pairs of fluorescent white 100% cotton socks (knitted fabric, no antibacterial treatment) were washed under the washing conditions of Example 1, and two of the pairs were heated to 60°C (a). -W and (i) After immersing in the treatment solutions of -w for 60 minutes, a mangle roller was used. Since it is used in combination with organopolysiloxane, which has at least one of each of three types of specific groups that bond to silicon atoms in each molecule, it has antibacterial properties, hydrophilicity, and antistatic properties that are durable for textile materials, etc. In addition to imparting properties and lubricity, this material also has the characteristic of preventing yellowing of 11M materials and the like when organosilane containing a quaternary ammonium salt is used.

Claims (1)

[Claims] (A) Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is a monovalent hydrocarbon group, R^1 is a carbon number of 10 to 2
2 is a monovalent hydrocarbon group, R^ is a divalent hydrocarbon group, R^3 is an alkyl group or an alkoxyalkyl group, X is a halogen atom, and a is 0 or 1. 100 parts by weight of an organosilane having a quaternary ammonium salt represented by
Formula -R^2-COOM and formula -R^2-O-(C_2H_4O)_m(C_3H_
6O)_n, R^4 (wherein, R is a monovalent hydrocarbon group, R^
2 is a divalent hydrocarbon group, R^3 is an alkyl group or alkoxyalkyl group, R^4 is a terminal capping group, M is a hydrogen atom,
a group selected from monovalent hydrocarbon groups, triorganosilyl groups, ammonium and alkali metals, a is 0 or 1,
m is 1-50, n is 0-50, and m+n is 1-60. 1. An antibacterial treatment agent characterized by comprising 1 to 100 parts by weight of an organopolysiloxane containing at least one of each of the three groups represented by the following in one molecule.