JP2001253919A - Fluoroalkyl group-containing trialkylammonium oligomers, method of producing the same, antimicrobial agent, surface treating agent, and resin composition containing the oligomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluoroalkyl group-containing trialkylammonium oligomer having both an excellent functionality of fluorine and a silicon compound and an excellent functionality of an ammonium salt, to provide a method of producing the same, and to provide an antimicrobial agent and a resin compositon. SOLUTION: This fluoroalkyl group-containing trialkylammonium oligomer is represented by general formula (1) [R1 and R2 are each a (CF2)nY or CF (CF3)-[OCF2CF(CF3)]p-OC3F7 (Y is hydrogen atom, fluorine atom or chlorine atom; n is an integer of 1-10; p is an integer of 0-8); R3, R4 and R10 are each hydrogen atom or methyl group; R5 is a 1-5C lower alkyl group; R6 is a 4-22C lower alkyl; R7, R8 and R9 are each an alkyl group or an alkoxy group; Z1 is a morpholinecarbonyl group; Z2 is a straight-chain or branched-chain alkylene group; X is a halogen atom; m is 1-1,000; each constituent unit related to (a), b and c is randomly bonded].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel fluoroalkyl group-containing ammonium oligomer having both the characteristics of fluorine and the characteristics of an ammonium salt and a silicon compound, a process for producing the same, and an antibacterial activity using the same as an active ingredient. The present invention relates to an excellent antibacterial agent, surface treatment agent and resin composition.

[0002]

2. Description of the Related Art Fluoroalkyl group-containing compounds have attracted attention as compounds exhibiting useful properties such as light resistance, water / oil repellency, and physiological activity. Particularly in the field of surfactants, attention is paid to the fact that surfactants into which fluorine, especially long-chain fluoroalkyl groups have been introduced, have superior performance due to fluorine as compared with conventional hydrocarbon surfactants. And there are many reports on low molecular weight surfactants. However, there is almost no knowledge of a high molecular weight surfactant into which a fluoroalkyl group has been introduced.

Conventionally, the surface of a substrate is coated to protect the substrate,
Fluororesins having a fluoroalkyl group, such as fluoroacrylate polymers, are frequently used as surface treatment agents that impart properties such as aesthetics, water / oil repellency, insulating properties, mold release properties, and antifouling properties. However, there are problems such as poor adhesion to inorganic materials such as metals, glass and cement, and substrates such as various plastics. An organic silicon-based compound having a fluoroalkyl group has been proposed as a functional surface treatment agent having both characteristics derived from a fluoroalkyl group and characteristics as a silicon compound, and having excellent water and oil repellency, adhesion to a substrate, and excellent surface lubricity. (JP-A-5-9456).

The present inventors have previously proposed various new functional materials while taking advantage of the fluoroalkyl group. For example, fluoroalkyl group-containing phosphonium oligomers having antibacterial properties (JP-A-11-2465)
77, JP-A-11-246578 and JP-A-11-246579), and fluoroalkyl group-containing phosphonate oligomers useful as surfactants (JP-A-11-246573 and JP-A-11-2465).
No. 74) and fluorinated alkyl group-containing phosphinic acid oligomers (Japanese Patent Application No. 11-45901, Japanese Patent Application No.
-45915).

On the other hand, it has been reported that ammonium salt or phosphonium salt-based polymer compounds exhibit excellent antibacterial activity (Akihiko Kanazawa, Tomoki Ikeda, Tsuyoshi Endo, Surface Vol. 32).
638 (1994)). Compared with low molecular weight antibacterial agents, high-molecular type antibacterial agents are characterized by high density of antibacterial active groups based on polymer characteristics, low toxicity by increasing molecular size, and approach as a polymer material. is there. Examples of ammonium salt-based functional materials having a fluorine function and an antibacterial activity include, for example, trialkylammonium oligomers containing a fluoroalkyl group (Hideo Sawada et al., Oil Chemistry, Vol. 45, pp. 161 (1996)), allyl and diallylammonium Oligomers (Hideo Sawada et al., Proceedings of the 34th Symposium on Oil Chemistry, p. 60, (1995)) have been proposed. These oligomers are also surfactants and exhibit the functionality of fluorine and antibacterial activity. It has been reported.

However, although the above-mentioned trimethylammonium oligomers have high hydrophilicity, they have low solubility in organic solvents, so that it is difficult to apply them as surface modifiers to general-purpose organic materials. In addition, there is a problem that the antibacterial activity is low. Therefore, if it is an organic material that is soluble in ordinary organic solvents and has surface active properties due to fluorine, and is also provided with antibacterial activity at the same time, it has a strong antibacterial property in various fields, especially in recent years. The application to the desired field can be greatly expected.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel fluoroalkyl group-containing trialkylammonium having both the excellent functionality of fluorine and silicon compounds and the excellent functionality of an ammonium salt. An object of the present invention is to provide an oligomer, a method for producing the oligomer, an antibacterial agent containing the oligomer as an active ingredient, a surface treatment agent, and a resin composition containing the same.

[0008]

Under these circumstances, the present inventors have further studied to increase the antibacterial activity of fluoroalkyl group-containing ammonium oligomers. By introducing a trialkylammonium segment having an alkyl group of a specific structure and a silyl group, the antibacterial activity is further enhanced, and the property due to fluorine and the antibacterial property are well-balanced, and further, the surface treatment of a silicon compound. The present inventors have found that novel oligomers having a function with an agent can be obtained, and have completed the present invention.

That is, the present invention provides the following general formula (1):

Embedded image中 where R¹And R^TwoAre the same or different, and (CF_Two)_n
Y or CF (CF_Three)-[OCF_TwoCF (CF_Three)]_p-O
C_ThreeF₇(Where Y is a hydrogen atom, a fluorine atom or a chlorine atom
And n is an integer of 1 to 10, p is an integer of 0 to 8
You. ) And R ^Three, R^Four And R^TenAre the same or different
Represents a hydrogen atom or a methyl group;^FiveIs 1-5 carbon atoms
Represents a lower alkyl group of⁶Is lower with 4 to 22 carbon atoms
Represents an alkyl group;⁷, R⁸And R⁹Are the same or different
Thus, an alkyl group or an alkoxy group having 1 to 10 carbon atoms
And Z¹Represents a morpholine carbonyl group;^TwoIs straight
X represents a chain or branched alkylene group;
And m represents 1 to 1000, and the molar ratio of a: b is
1: 99-99: 1, the total moles of (a + b): c
Is from 1:99 to 99: 1. This is represented by｝
And a fluoroalkyl group-containing trialkyl group,
The invention provides ammonium ammonium oligomers.

Further, the present invention provides a compound represented by the following general formula (2):

Embedded image (Wherein R ¹ and R ² have the same meanings as described above), and a fluoroalkanoyl peroxide represented by the following general formula (3):

Embedded image (Wherein R ³ , R ⁵ , R ⁶ , Z ² and X have the same meanings as described above), and an ammonium salt having a (meth) acrylic group represented by the following general formula (4):

Embedded image (Wherein, R ⁴ , R ⁷ , R ⁸ and R ⁹ have the same meanings as described above) and a silane compound having a vinyl group represented by the following general formula (5):

Embedded image (Wherein R ¹⁰ and Z ¹ have the same meanings as described above), and reacted with a morpholine compound having a (meth) acrylic group represented by the general formula (1):

Embedded image中 where R¹And R^TwoAre the same or different, and (CF_Two)_n
Y or CF (CF_Three)-[OCF_TwoCF (CF_Three)]_p-O
C_ThreeF₇(Where Y is a hydrogen atom, a fluorine atom or a chlorine atom
And n is an integer of 1 to 10, p is an integer of 0 to 8
You. ) And R ^Three, R^Four And R^TenAre the same or different
Represents a hydrogen atom or a methyl group;^FiveIs 1-5 carbon atoms
Represents a lower alkyl group of⁶Is lower with 4 to 22 carbon atoms
Represents an alkyl group;⁷, R⁸And R⁹Are the same or different
Thus, an alkyl group or an alkoxy group having 1 to 10 carbon atoms
And Z¹Represents a morpholine carbonyl group;^TwoIs straight
X represents a chain or branched alkylene group;
And m represents 1 to 1000, and the molar ratio of a: b is
1: 99-99: 1, the total moles of (a + b): c
Is from 1:99 to 99: 1.化 represented by
A compound containing a fluoroalkyl group,
Method for producing lialkyl ammonium oligomers
To provide.

Further, the present invention provides an antibacterial agent comprising a fluoroalkyl group-containing trialkylammonium oligomer represented by the general formula (1) as an active ingredient; the fluoroalkyl group-containing trialkylammonium oligomer, and hydrolysis thereof. , A surface treatment agent comprising as an active ingredient at least one component selected from the group consisting of a hydrolyzed condensate, and a mixture thereof; or a fluoroalkyl group-containing trialkylammonium represented by the general formula (1). An object of the present invention is to provide a resin composition containing oligomers.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The first fluoroal according to the present invention
The alkyl group-containing ammonium oligomer has the general formula
This is represented by (1). Where R¹And R^TwoGood
Preferably, the formula; (CF_Two)_nIn Y, n is 1 to
5, especially 4 to 5, and Y is a fluorine atom. Also,
Formula: (CF_Two)_nY or CF (CF_Three)-[OCF_TwoCF
(CF_Three)] _p-OC_ThreeF₇Wherein p is 0 to 8, especially 0
5 Also, R^ThreeAnd R^Four Is preferably a hydrogen source
I am a child. R^TenIs preferably a hydrogen atom or a methyl group
It is. Z^TwoIs a linear or branched alkylene group
Specifically, a linear or branched alkyl group having 1 to 8 carbon atoms
A alkylene group is preferred, for example, a methylene group, ethylene
Group, trimethylene group, tetramethylene group, pentamethylene
And an ethylene group. R^FiveAs
Is, for example, methyl group, ethyl group, propyl group, butyl
And the like. R⁶As, for example, n-butyl
Group, iso-butyl group, sec-butyl group, n-hexyl
Group, iso-hexyl group, n-heptyl group, iso-
Heptyl group, n-octyl group, iso-octyl group, n
-Dodecyl group, iso-dodecyl group, n-octadecyl
And alkyl groups such as iso-octadecyl group.
You. Also, R^FiveAnd R⁶Are the same but different groups.
You may. R⁷, R⁸Or R⁹As the alkyl group of
Methyl group, ethyl group, n-propyl group, iso-propyl
Group, n-butyl group, iso-butyl group, sec-butyl
Group, n-hexyl group, iso-hexyl group, n-hep
Tyl group, iso-heptyl group, n-octyl group, iso
-Octyl, n-decyl, iso-decyl and the like.
And the alkoxy group is methoxy, ethoxy
Group, propoxy group, butoxy group and the like. X is
A chlorine atom, a boron atom or an iodine atom is preferred. m
The preferred range is 1 to 100, particularly preferably 1 to 50,
Particularly preferably, it is 1 to 10. Further, the copolymerization ratio a: b
Is preferably from 10:90 to 80:20,
The preferred molar ratio of the total mole of (a + b): c is 10: 9
0 to 80:20. Also, the ammonium salt according to a
-Based structural unit, b-based silane-based structural unit and c-based
Ruphorin-based structural units may be randomly linked
No.

Next, a method for producing the fluoroalkyl group-containing ammonium oligomer represented by the general formula (1) according to the present invention will be described. The compound of the general formula (1) includes a fluoroalkanoyl peroxide represented by the general formula (2), an ammonium salt having a (meth) acrylic group represented by the general formula (3), Equation (4)
Is obtained by reacting a silane compound having a vinyl group represented by the formula with a morpholine compound having a (meth) alkyl group represented by the general formula (5).

In the above-mentioned general formula (2) as a reaction raw material, preferred groups for R ¹ and R ² are the same as those described above. Specific examples of the fluoroalkanoyl peroxide represented by the general formula (2) include:
Diperfluoro-2-methyl-3-oxahexanoyl peroxide, diperfluoro-2,5-dimethyl peroxide
3,6-dioxano nanoyl, diperfluoro peroxide
2,5,8-Trimethyl-3,6,9-trioxadodecanoyl, diperfluorobutyryl peroxide, diperfluoroheptanoyl peroxide, diperfluorooctanoyl peroxide and the like. As a method for producing such fluoroalkanoyl peroxides, a known method can be used.For example, a fluoroalkyl group-containing acyl halide can be added to a fluorine-containing aromatic solvent or a fluorine-containing aliphatic solvent such as CFC alternative. And hydrogen peroxide in the presence of an alkali such as sodium hydroxide, potassium hydroxide, potassium bicarbonate, sodium carbonate or potassium carbonate.

In general formula (3), which is the second raw material,
Preferred groups for R ³ , R ⁵ , R ⁶ , Z ² and X are the same as those described above. Specific examples of the ammonium salt having a (meth) acryl group represented by the general formula (3) include tri-n-butyl (acryloyloxymethyl) ammonium chloride and tri-n-
Butyl (methacryloyloxymethyl) ammonium chloride, dimethyl-n-butyl (acryloyloxymethyl) ammonium chloride, dimethyl-n-butyl (methacryloyloxymethyl) ammonium chloride, dimethyl-n-octyl (acryloyloxymethyl) ammonium chloride, dimethyl- n-octyl (methacryloyloxymethyl) ammonium chloride, dimethyl-n-dodecyl (acryloyloxymethyl) ammonium chloride, dimethyl-n-dodecyl (methacryloyloxymethyl) ammonium chloride, tri-n-butyl (2-acryloyloxyethyl) ammonium Chloride, tri-n-butyl (2-
Methacryloyloxyethyl) ammonium chloride, dimethyl-n-butyl (2-acryloyloxyethyl) ammonium chloride, dimethyl-n-butyl (2-methacryloyloxyethyl) ammonium chloride, dimethyl-n-octyl (2-acryloyloxyethyl) ammonium Chloride, dimethyl-n-
Octyl (2-methacryloyloxyethyl) ammonium chloride, dimethyl-n-dodecyl (2-acryloyloxyethyl) ammonium chloride, dimethyl-n-dodecyl (2-methacryloyloxyethyl)
Ammonium chloride, tri-n-butyl (3-acryloyloxypropyl) ammonium chloride, tri-n-butyl (3-acryloyloxypropyl) ammonium chloride, dimethyl-n-butyl (3-acryloyloxypropyl) ammonium chloride,
Dimethyl-n-butyl (3-methacryloyloxypropyl) ammonium chloride, dimethyl-n-octyl (3-acryloyloxypropyl) ammonium chloride, dimethyl-n-octyl (3-methacryloyloxypropyl) ammonium chloride, dimethyl-n-dodecyl (3-acryloyloxymethylpropyl) ammonium chloride, dimethyl-n-dodecyl (3-methacryloyloxypropyl) ammonium chloride, diethyl-n-butyl (acryloyloxymethyl) ammonium chloride, diethyl-n-butyl (methacryloyloxymethyl) ammonium Chloride, diethyl-n-octyl (acryloyloxymethyl) ammonium chloride, diethyl-n-octyl (methacryloy) (Oxymethyl) ammonium chloride, diethyl-n-dodecyl (acryloyloxymethyl) ammonium chloride, diethyl-n-dodecyl (methacryloyloxymethyl) ammonium chloride, diethyl-n-butyl (2-acryloyloxyethyl) ammonium chloride, diethyl-n -Butyl (2-methacryloyloxyethyl) ammonium chloride, dimethyl-n-octyl (2-acryloyloxyethyl) ammonium chloride, dimethyl-n
-Octyl (2-methacryloyloxyethyl) ammonium chloride, dimethyl-n-dodecyl (2-acryloyloxyethyl) ammonium chloride, dimethyl-n-dodecyl (2-methacryloyloxyethyl) ammonium chloride, and the like.

In general formula (4), which is a third raw material,
Preferred examples of R ⁴ and R ^{7 to} R ⁹ include those described above. Examples of the silane compound having a vinyl group represented by the general formula (4) include trimethylvinylsilane, triethylvinylsilane, tri-n-propylvinylsilane, tri-isopropylvinylsilane, and tri-n
-Butylvinylsilane, tri-isobutylvinylsilane, tri-n-octylvinylsilane, trimethoxyvinylsilane, triethoxyvinylsilane, tri-n-propoxyvinylsilane, tri-n-butoxyvinylsilane and the like.

In general formula (5), which is a fourth raw material,
Preferred examples of R ¹⁰ include the same as those described above.
Examples of the morpholine compound having a (meth) acryl group represented by the general formula (5) include N-acryloylmorpholine, N-methacryloylmorpholine, and the like.

In the method for producing a fluoroalkyl group-containing trialkylammonium oligomer represented by the general formula (1), the mixing ratio of the first raw material to the fourth raw material may be a, It is determined by a blending ratio such that it falls within the range of b, c and m. For example, the amount of the ammonium salt having a (meth) acryl group is 1 mol or more, preferably 1 mol per 1 mol of the fluoroalkanoyl peroxide. To 20 mol, and the silane compound having a vinyl group is at least 1 mol, preferably 1 to 10 mol, relative to 1 mol of the fluoroalkanoyl peroxide, and 1 mol to 1 mol of the fluoroalkanoyl peroxide. The morpholine compound having a (meth) acrylic group is 1 mol or more, preferably 1 to 20 mol.

The above reaction can be carried out at normal pressure, and the reaction temperature is usually -20 to 150 ° C., preferably 0 to 150 ° C.
１００100 ° C. If the reaction temperature is lower than −20 ° C., the reaction tends to take a long time. On the other hand, if it exceeds 150 ° C., the pressure in the reaction system increases and the reaction operation tends to be difficult, which is not preferable. The reaction time is usually 0.5
-20 hours, preferably 3-10 hours. This reaction can be carried out without solvent, but it is desirable to carry out the reaction in a solvent in order to smoothly carry out the reaction with fluoroalkanoyl peroxides. As the reaction solvent, a halogenated aliphatic solvent is particularly preferably used. For example, methylene chloride, chloroform, 2-chloro-1,2
Dibromo-1,1,2-trifluoroethane, 1,2
-Dibromohexafluoropropane, 1,2-dibromotetrafluoroethane, fluorotrichloromethane, heptafluoro-2,3,3-trichlorobutane, 1,
1,1,3-tetrachlorotetrafluoropropane,
1,1,2-trichlorotrifluoropropane, 1,
1,2-trichlorotrifluoroethane, 1,1-dichloro-2,2,3,3,3-pentafluoropropane,
Examples thereof include 1,3-dichloro-1,2,2,3,3-pentafluoropropane and the like, and one or more of these can be used in combination. Among them, especially 1,1
A mixed solvent of -dichloro-2,2,3,3,3-pentafluoropropane and 1,3-dichloro-1,2,2,3,3-pentafluoropropane is preferably used.
The concentration of fluoroalkanoyl peroxides in these solvents is preferably in the range of 0.5 to 30% by weight.

Thus, the obtained fluoroalkyl group-containing trialkylammonium oligomer can be easily obtained. In the present invention, dialysis, recrystallization, distillation,
It can be purified by a conventional purification means such as column chromatography.

Next, the antibacterial agent of the present invention will be described.
You. The antibacterial agent according to the present invention has the general formula
Fluoroalkyl group-containing trialkyl represented by (1)
Preferred ammonium oligomers include the following:
It is on the street. In the general formula (1), R¹And R^TwoPreferred
A good example is the formula: (CF_Two)_nFor Y, Y is fluorine
Atom, n is 1-5, especially 1-3, CF (CF_Three)-
[OCF_TwoCF (CF_Three)]_p-OC_ThreeF₇Then, p is 0
-5, especially 0-2. Also, R^ThreeAnd R^Four Preferred
The other is a hydrogen atom or a methyl group. Z ^TwoIs methylene
Groups or ethylene groups are preferred. R^FiveThe preferred group of is carbon
A methyl or ethyl group of the formulas 1 and 2,⁶Preferred
Groups are octyl, dodecyl, octadecyl,
And the like. X is preferably a chlorine atom or a boron atom,
Particularly, a chlorine atom is preferred. The preferred range of m is 1-5
0, particularly preferably 1 to 10. Also, the general formula
In (1), the preferred copolymerization ratio of a: b is 2:
98 to 15:85, sum of a + b: copolymerization ratio of c
Is preferably from 99: 1 to 90:10.

The antibacterial agent of the present invention has a broad spectrum of activity particularly effective against various bacteria, fungi, algae, viruses, etc. Has an algicidal effect. Although the antibacterial activity varies depending on the kind and environment of the antibacterial agent of the present invention, excellent antibacterial activity is obtained when the concentration of the fluoroalkyl group-containing trialkylammonium oligomer represented by the general formula (1) is 100 ppm, preferably 1000 ppm or more. Be demonstrated.

The antibacterial agent according to the present invention may be used in combination with another antibacterial agent. Other antibacterial agents are not particularly limited, and general antibacterial agents can be used. For example, ammonium salts such as dimethyl-n-decylammonium chloride, benzyldimethyl-n-dodecylammonium chloride, benzyldimethyl-n-tetradecylammonium chloride, 5-chloro-2
-Methyl-4-isothiazolin-3-one, 2-bromo-2-nitropropane-1,3-diol, 1,5-pentanedial, phenol, chlorhexidine, popion iodine, alkylpolyaminoethylene glycine chloride, chlorine agent, etc. Examples include organic antibacterial agents and inorganic antibacterial agents such as silver-substituted zeolite and silver-substituted apatite, among which one or two or more can be used in combination. Also, [3- (trimethoxysilyl) -propyl] tri-
It may be used in combination with a silyl phosphonium salt such as n-octylphosphonium chloride and a tetraalkylphosphonium salt such as triethyl-n-hexadecylphosphonium chloride.

The antibacterial agent of the present invention comprises
If necessary, auxiliary agents such as a surfactant, a binder, a coloring agent, a dispersant, a lubricant, and other inorganic or organic diluents and carriers may be blended. The antimicrobial agent according to the present invention may be used in various industrial fields depending on the form of the preparation, for example, slime prevention or control agent in papermaking, water, oil and fat, emulsion, paper, rubber, plastic, fiber, film, paint, etc. Can be provided.

Next, the surface treating agent of the present invention will be described. The surface treating agent according to the present invention comprises a trialkylammonium oligomer having a fluoroalkyl group represented by the general formula (1) as an active ingredient. The general formula (1)
In the above, preferred compounds are the same as those in the case of the antibacterial agent. Further, in the surface treating agent of the present invention, in addition to the fluoroalkyl group-containing trialkylammonium oligomer represented by the general formula (1), a hydrolyzate thereof, a hydrolyzed condensate thereof, and a mixture thereof are used. It can be used in combination with one or more selected components.

The hydrolyzate and hydrolyzed condensate of the oligomer may be obtained by mixing the fluoroalkyl group-containing trialkylammonium oligomer with a mixed solvent of a fluorinated hydrocarbon containing water and an alkyl alcohol or an alkyl alcohol containing water. It is a compound obtained by dissolving in a solvent or alcohol solvent and then subjecting it to hydrolysis or hydrolytic condensation. As the fluorinated hydrocarbon,
1,1,2-trichlorotrifluoroethane, 1,2-
Difluorotetrachloroethane, benzotrifluorofluoride and the like can be preferably used. As the alkyl alcohol, ethanol, isopropanol, butanol and the like can be preferably used. Water concentration is 1
It is preferably in the range of from 30% by weight to 30% by weight. That is, to use the surface treatment agent of the present invention, it is preferable to use the surface treatment agent after diluting it in the above-mentioned solvent. At this time, even when only one or more of the fluoroalkyl group-containing trialkylammonium oligomers represented by the general formula (1) is used, a part or all of the trialkylammonium oligomers are combined with a hydrolyzate and a hydrolyzed condensate. You can also.

The concentration of the active ingredient is preferably in the range of 0.005% by weight to 20% by weight. If the concentration is less than 0.005% by weight, the thickness of the film coated on the substrate after the surface treatment tends to be small, and the water / oil repellency tends to decrease. It is not preferable because the water and oil repellency does not increase any more, and the uniformity of the surface tends to be lowered and peeling tends to occur.

The method for treating the surface treating agent of the present invention includes:
Known coating methods such as brush coating, spraying, roll coating, spin coating, and dip coating can be used. Further, the treatment temperature can be set at a normal temperature, but the temperature can be set to an arbitrary condition for the purpose of adjusting the film formation speed.

The type of the substrate that can be treated with the surface treatment agent of the present invention is not particularly limited. For example, organic materials such as natural fibers, natural resins, wood, polybutene resins, and polyorganic resins can be used. Acrylic acid resin, polyvinyl chloride resin,
Polyester resin, polypropylene resin, polystyrene resin, polycarbonate resin, polyamide resin, polyamine resin, urethane resin, ABS resin, AS resin, thermoplastic acrylic resin, unsaturated polyester resin, epoxy resin, polyimide resin, cellophane resin, alkyd resin, phenol Organic materials such as resin, urea resin, melamine resin, xylene resin, silicone resin or diaryl phthalate resin and modified resins thereof, and, if inorganic, metal powder, metal or nonmetal oxide (including hydrate) , Metal silicates including aluminosilicates, metal carbides, metal nitrides, metal carbonates, metal sulfates, metal phosphates, metal sulfides, metal salts, metal halides or carbon, etc. . For inorganic materials, metal powders, metal or nonmetal oxides (including hydrates), metal silicates including aluminosilicates, metal carbides, metal nitrides, metal carbonates, metal sulfates, metal phosphorus Inorganic materials such as acid salts, metal sulfides, metal salts, metal halides, stainless steel, duralumin, glass, aluminum, and ceramics.

Further, the surface treating agent of the present invention is a medical material,
Various fabrics, clothing, furniture, hangers, tableware, rugs, paper bags,
Cardboard containers, trash cans, trunks, handbags, shoes, jackets, raincoats, tents, carpets, curtains, wood, bricks, concrete, floors, wall tiles, glass, stone, blasters, wallpaper, exterior wall materials, bathroom wall materials, and more Can impart antibacterial properties, water / oil repellency, antifouling properties, surface lubrication properties, etc. to various types such as magnetic tapes, floppy (registered trademark) disks, and hard disks.

Next, the resin composition of the present invention will be described. Preferred examples of the fluoroalkyl group-containing trialkylammonium oligomers contained in the resin composition of the present invention are the same as those in the case of the antibacterial agent.

The resins applicable in the present invention include:
There is no particular limitation, and when used as a rubber composition,
For example, natural rubber, styrene-butadiene rubber (SB
R), acronitrile-butadiene rubber (NBR),
Butyl rubber (IIR), polybutadiene rubber (BR),
Ethylene-propylene rubber (EPPM), chlorobutylene rubber (CR), polyisobutylene rubber, allyl rubber, hydrogenated acrylonitrile-butadiene rubber, polysulfide rubber, urethane rubber, crysulfonated rubber, silicone rubber and modified products thereof And these may be two or more kinds of blended rubbers. In addition, examples of the resin serving as a matrix when obtaining a resin molded product such as a sheet, a film, a container, and a fiber include polyvinyl chloride resin, polyethylene resin, polypropylene resin, polyamide resin, polycarbonate resin, polyester resin, and polystyrene resin. , ABS resin, AS resin, thermoplastic resin such as thermoplastic acrylic resin, epoxy resin, unsaturated polyester resin, diaryl phthalate resin, phenol resin, thermosetting resin such as urea resin, alkyd resin, melanin resin, guanazine resin, Examples include a vinyl resin, an epoxy resin, a polyamine resin, an acrylic resin, a polybutadiene resin, a urethane resin, a silicon resin, a fluorine-containing resin, and modified products thereof.

The addition amount of the fluoroalkyl group-containing trialkylammonium oligomer to the resin is usually 0.01 to 10% by weight, preferably 0.5 to 5% by weight. Other components include inorganic fillers such as white carbon, carbon black, zeolite, calcium carbonate, clay, barium sulfate, and magnesium carbonate, organic fillers such as high styrene resin, lignin, and phenol resin, antibacterial agents, and ultraviolet rays. Examples include an absorbent, an antioxidant, an extender, a dispersing aid, a vulcanizing agent, a vulcanization accelerator, a vulcanizing aid, a softener, an antioxidant, and a plasticizer. The resin composition according to the present invention can impart water repellency, oil repellency and antifouling properties to various resins in addition to antibacterial properties.

[0034]

The present invention will be described in more detail with reference to the following examples, which are merely illustrative and do not limit the present invention. Example 1 2 equipped with a condenser, a thermometer, a stirrer, and a dropping funnel
In a 00 ml four-necked flask, dimethyl-n-octyl (2
1.01 g (3.87 mmol) of -acryloyloxyethyl) ammonium chloride was added to AK-225 (manufactured by Asahi Glass Co., Ltd .; (1,1-dichloro2,2,3,3,3-pentafluoropropane and 1,3-dichloro). 1: 1 mixed solvent of 1,2,2,3,3-pentafluoropropane, the same applies hereinafter))) and dissolved in 50 g of vinyltrimethoxysilane.
1 g (3.87 mmol), 5.48 g (38.0 mmol) of N-acryloylmorpholine and diperflu-2 peroxide
-Methyl-3-oxahexanoyl 2.55 g (3.8
7 mmol) was rapidly added dropwise at room temperature in a nitrogen stream.
The mixture was heated to 40 ° C. and stirred for 5 hours. After the reaction, the solvent was distilled off under reduced pressure, and the resulting crude product was purified by dialysis using AK.
Performed under -225 solvent. Thereafter, the residue was dried in vacuo to give 7.89 g of a co-oligomer (yield 85).
%). The average molecular weight determined by GPC is 240
It was 0. FT-IR, ¹ H-NMR, ¹⁹ F-NMR
, The product was confirmed. The copolymerization ratio a: b: c (ammonium salt: vinyltrimethoxysilane: N-acryloylmorpholine) determined from ¹ H-NMR
Was 6: 92: 2.

FT-IR (KBr, cm ^-1 ): 1031 (CN), 1110
(Si-OR), 1241 ( CF 2), 1365 (CF 3), 1633 (C = O), 2929 (CH) 1 H-NMR (δ, CDCl 3): 0.62 (CH-Si), 1.02~1.08 (CH
_{2 CH 3) 2.01 ~2.71 (CH} , CH 3, CH 2), 2.80~2.88 (OCH 3) 3.10 ~3.78 (CH 2), 3.82~3.98 (CH 2) 4.20 ~4.52 (CH 2) 19 F-NMR _{(δ, CDCl 3, ext.CF 3} COOH): -5.35 ~-1
0.33 (16F), -54.39 (6F) From the above analysis results, the obtained product was sample A in Table 1.
It was confirmed to be a fluoroalkyl group-containing trialkylammonium oligomer having the structure:

Example 2 A condenser equipped with a condenser, a thermometer, a stirrer and a dropping funnel was prepared.
In a 00 ml four-necked flask, dimethyl-n-octyl (2
0.50 g (2 mmol) of -acryloyloxyethyl) ammonium chloride are dissolved in 50 g of AK-225, and 0.296 of vinyltrimethoxysilane is added to this solution.
g (2 mmol), 3.03 g of N-acryloylmorpholine
(21 mmol) and 2.08 g (2 mmol) of diperfur-2,5-dimethyl-3,6-dioxahexanoyl peroxide.
Was quickly added dropwise at room temperature in a nitrogen stream. The mixture was heated to 40 ° C. and stirred for 5 hours. After the reaction, the solvent was distilled off under reduced pressure, and the obtained crude product was purified by dialysis with AK-225.
Performed under solvent. Thereafter, the residue was dried under vacuum to obtain 4.56 g of a cooligomer (yield: 76%). By FT-IR, ¹ H-NMR and ¹⁹ F-NMR,
The product was confirmed. The copolymerization ratio a: b: c (ammonium salt: vinyltrimethoxysilane: N-acryloylmorpholine) determined from ¹ H-NMR was 23:
92: 5.

FT-IR (KBr, cm ^-1 ): 1031 (CN), 1106
(Si-OR), 1251 ( CF 2), 1350 (CF 3), 1631 (C = O), 2867 (CH) 1 H-NMR (δ, CDCl 3): 1.02 ~1.83 (CH 2, CH 3) , 2.2
_{2~2.68 (CH, CH 3, CH} 2), 2.78 ~2.94 (OCH 3), 3.12~3.79
_{(CH 2), 3.81 ~3.85 (} CH 2), 4.18~4.22 (CH 2) 19 F-NMR (δ, CDCl 3, ext.CF 3 COOH): -5.01 ~-
7.74 (26F), -54.34 to -54.62 (6F), -70.07 (2F) Based on the above analysis results, the obtained product was sample B in Table 1.
It was confirmed to be a fluoroalkyl group-containing trialkylammonium oligomer having the structure:

Example 3 2 equipped with a condenser, a thermometer, a stirrer and a dropping funnel
In a 00 ml four-necked flask, dimethyl-n-octyl (2
0.50 g (2 mmol) of -acryloyloxyethyl) ammonium chloride are dissolved in 50 g of AK-225, and 0.296 of vinyltrimethoxysilane is added to this solution.
g (2 mmol), N-acryloylmorpholine 2.63 g
(18 mmol) and diperflu-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide 2.64.
g (2 mmol) was quickly added dropwise at room temperature in a nitrogen stream. The mixture was heated to 40 ° C. and stirred for 5 hours. After the reaction, the solvent was distilled off under reduced pressure, and the obtained crude product was purified by dialysis under an AK-225 solvent. Thereafter, the residue was dried under vacuum to obtain 3.83 g of a cooligomer (yield: 6).
8%). FT-IR, ¹ H-NMR, ¹⁹ F-NM
The product was confirmed by R. In addition, ¹ H-NMR
Ratio a: b: c (ammonium salt: vinyltrimethoxysilane: N-acryloylmorpholine) determined from
Was 11: 86: 3.

FT-IR (KBr, cm ^-1 ): 1031 (CN), 1114
(Si-OR), 1249 ( CF 2), 1361 (CF 3), 1629 (C = O), 2985 (CH) 1 H-NMR (δ, CDCl 3): 1.10 ~1.92 (CH 2, CH 3) , 2.1
_{2~2.79 (CH, CH 3, CH} 2), 2.80 ~3.00 (OCH 3), 3.05~3.80
_{(CH 2), 3.90 ~4.10 (} CH 2), 4.18~4.22 (CH 2) 19 F-NMR (δ, CDCl 3, ext.CF 3 COOH): -5.82 ~-
8.57 (36F), -52.18 to -55.40 (6F), -70.46 to -70.93 (4F) From the above analysis results, the obtained product was sample C in Table 1.
It was confirmed to be a fluoroalkyl group-containing trialkylammonium oligomer having the structure:

Table 1 shows the samples obtained in Examples 1 to 3 (A to
Regarding C), the types of the groups R ¹ , R ² and Z ₁ are shown.

[0041]

[Table 1]

(Solubility Test for Various Solvents) Example 1
The solubility of various fluoroalkyl group-containing ammonium oligomers obtained in Nos. To 3 in various solvents was tested. The results are shown in Table 2. In the table, the symbol ○ indicates “very soluble”, △ indicates “not very soluble”,
× indicates “not melt at all”.

[0043]

[Table 2] In the table, AK-255 is a 1: 1 mixed solvent of 1,1-dichloro-2,2,3,3,3-pentafluoropropane and 1,3-chloro-1,2,2,3,3-pentafluoropropane , THF indicates tetrahydrofuran, and DMSO indicates dimethylsulfoxide.

(Antibacterial activity test) As representatives of Gram-negative bacteria, Escherichia coli IFO3806,
As a representative of Gram-positive bacteria, Staphylococcus aureus (Staphylococcus aureus) IFO12732,
The fluoroalkyl group-containing trialkylammonium oligomers of Samples A, B and C obtained in Examples 1 to 3 were mixed with PMMA resin pellets at a weight ratio of 1% by weight and dissolved in a soluble solvent. The resulting solution was uniformly applied to a Petri dish, and the solvent was evaporated under reduced pressure at room temperature to obtain a film containing the oligomer. A 50 mm × 50 mm square of the film sample was used as a test piece, and a control test piece (PMMA; blank test) was also prepared. A test piece was placed in a sterile petri dish, and a test bacterial solution containing 1.0 × 10 ⁵ cells / ml for Escherichia coli and 2.2 × 10 ⁸ cells / ml for Staphylococcus aureus was added.
5 ml was inoculated on the surface of each test piece. A reinforced polyethylene film was placed thereon, covered, and cultured at 25 ° C. for 24 hours. After the cultivation, each test piece was thoroughly washed with 10 ml of a bouillon medium, cultured in an NA medium at 37 ° C. for 24 hours, the number of viable cells in this medium was measured, and indicated by the number of colonies (cfu / ml). Table 3 shows the results.

[0045]

[Table 3]

(Water and oil repellency test 1) Examples 1 to 3 (A to
C) The fluoroalkyl group-containing trialkylammonium oligomer obtained in C) is converted to polymethyl methacrylate (P
A mixture of 0.98 g of MMA) and 1% by weight was dissolved in 30 ml of THF and placed in a 5 cm-diameter dish. After removing THF by natural drying, it was dried under vacuum for 24 hours, and the contact angles of dodecane and water were measured. Table 4 shows the results. Contact angle measurement is ERMA
The contact angle (degree) was indicated using a goniometer type G-1 made by Toshiba Corporation. A blank in which the fluoroalkyl group-containing ammonium oligomer of the present invention was not added to PMMA was used as a blank. “BL” indicates a blank.

(Water / oil repellency test 2) Examples 1 to 3 (A to
Dissolving the fluoroalkyl group-containing trialkylammonium oligomer obtained in C) in 95% methanol,
A 1% by weight solution was prepared. Next, the glass plate was dipped for 3 minutes, dried at 150 ° C. for 15 minutes, and the contact angle with water and dodecane was measured. Table 5 shows the results. The contact angle was measured by using a goniometer G-1 manufactured by ERMA and expressed as a contact angle (degree). In addition, the thing with respect to the glass which also did not dripping of a solution was made into the blank. “BL” indicates a blank.

[0048]

[Table 4]

Table 4 shows that the fluoroalkyl group-containing trialkylammonium oligomers of the present invention
It can be seen that those treated with exhibit high oil repellency and lipophilicity caused by fluorine.

[0050]

[Table 5]

[0051]

The fluoroalkyl group-containing trialkylammonium oligomers of the present invention have excellent water / oil / oil repellency and antifouling properties due to fluorine atoms, and have properties and properties as surface treatment agents for silicon compounds. It has the excellent antibacterial activity of ammonium salt, and is extremely useful as a new functional material.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 3/00 112 C09K 3/00 112F 3/18 104 3/18 104 F-term (Reference) 4H011 AA02 AA03 BA06 BB04 BB16 DA17 4H020 BA36 4J002 BQ001 FD010 FD180 GA00 GH02 4J100 AL08P AL08R AP16Q BA32P BA72Q BA77Q BC79R CA05 DA01 DA36 FA03 JA01 JA11 JA13 JA20 JA51

Claims (5)

[Claims] 1. The following general formula (1):中 where R¹And R^TwoAre the same or different, and (CF_Two)_n
Y or CF (CF_Three)-[OCF_TwoCF (CF_Three)]_p-O
C_ThreeF₇(Where Y is a hydrogen atom, a fluorine atom or a chlorine atom
And n is an integer of 1 to 10, p is an integer of 0 to 8
You. ) And R ^Three, R^Four And R^TenAre the same or different
Represents a hydrogen atom or a methyl group;^FiveIs 1-5 carbon atoms
Represents a lower alkyl group of⁶Is lower with 4 to 22 carbon atoms
Represents an alkyl group;⁷, R⁸And R⁹Are the same or different
Thus, an alkyl group or an alkoxy group having 1 to 10 carbon atoms
And Z¹Represents a morpholine carbonyl group;^TwoIs straight
X represents a chain or branched alkylene group;
And m represents 1 to 1000, and the molar ratio of a: b is
1: 99-99: 1, the total moles of (a + b): c
Is from 1:99 to 99: 1. This is represented by｝
And a fluoroalkyl group-containing trialkyl group,
Nmonium oligomers. 2. The following general formula (2):(Where R¹And R^TwoIs as defined above. )
Fluoroalkanoyl peroxide, and the following general formula
(3): embedded image(Where R^Three, R^Five, R⁶, Z^TwoAnd X are as defined above.
is there. Ammo having a (meth) acrylic group represented by)
And a salt of the following general formula (4):(Where R^Four , R⁷, R⁸And R⁹Is as defined above
You. ) A silane compound having a vinyl group represented by
General formula (5):(Where R^TenAnd Z¹Is as defined above. )
Reacting morpholine compounds having (meth) acrylic groups
The compound represented by the general formula (1):中 where R¹And R^TwoAre the same or different, and (CF_Two)_n
Y or CF (CF_Three)-[OCF_TwoCF (CF_Three)]_p-O
C_ThreeF₇(Where Y is a hydrogen atom, a fluorine atom or a chlorine atom
And n is an integer of 1 to 10, p is an integer of 0 to 8
You. ) And R ^Three, R^Four And R^TenAre the same or different
Represents a hydrogen atom or a methyl group;^FiveIs 1-5 carbon atoms
Represents a lower alkyl group of⁶Is lower with 4 to 22 carbon atoms
Represents an alkyl group;⁷, R⁸And R⁹Are the same or different
Thus, an alkyl group or an alkoxy group having 1 to 10 carbon atoms
And Z¹Represents a morpholine carbonyl group;^TwoIs straight
X represents a chain or branched alkylene group;
And m represents 1 to 1000, and the molar ratio of a: b is
1: 99-99: 1, the total moles of (a + b): c
Is from 1:99 to 99: 1.化 represented by
A compound containing a fluoroalkyl group,
A method for producing a lialkyl ammonium oligomer. 3. An antimicrobial agent comprising a fluoroalkyl group-containing trialkylammonium oligomer represented by the general formula (1) as an active ingredient. 4. A fluoroalkyl group-containing trialkylammonium oligomer represented by the general formula (1),
A surface treatment agent comprising, as an active ingredient, at least one component selected from the group consisting of the hydrolyzate, the hydrolyzed condensate, and a mixture thereof. 5. A resin composition comprising a fluoroalkyl group-containing trialkylammonium oligomer represented by the general formula (1).