JP2000309612A - Phosphinic acid oligomers containing fluoroalkyl group, its production, and antimicrobial agent, surfactant and resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain new oligomers represented by a specific formula, having excellent antimicrobial activities, water- and oil-repellency, and high surface- activating performance, and capable of obtaining an antimicrobial agent, a surfactant for a drainage system, and a resin composition having excellent water- and oil-repellency and antifouling properties. SOLUTION: The oligomers are represented by formula I [R1 and R2 are each (CF2)nY (Y is H, fluorine atom or chlorine atom; n is 1-10) or the like; R3 is H or methyl; R4 is 1-18C alkyl; A is an alkylene; m is 1-1,000]. The oligomers can be obtained by reacting fluoroalkanoyl peroxides of formula II, (e.g. diperfluoro-2-methyl-3-oxahexanoyl peroxide) with a phosphinic acid compound having a (meth)acryl group of formula III in a molar ratio of (1:1)-(1:10) at (-20)-150 deg.C reaction temperature in a halogenated aliphatic solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel fluoroalkyl group-containing phosphinic acid oligomer having properties derived from fluorine, a method for producing the same, an antibacterial agent containing the same and having excellent antibacterial activity, and a non-aqueous agent. The present invention relates to a surfactant and a resin composition having excellent water and oil repellency and antifouling property.

[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. It has been widely known that fluoroalkyl group-containing carboxylic acids such as perfluorooctanoic acid exhibit high interfacial properties in an aqueous solution. Examples of the non-aqueous fluorine surfactant include alkyl perfluoroalkanecarboxylates, fluorine surfactants obtained by oligomerization of hexafluoropropene oxide, and polyfluoroacylbenzenes obtained by a Friedel-Crafts reaction with benzene. Has been proposed.

[0003] However, since known fluorine-based surfactants are compounds composed only of a hydrophilic group and a water-repellent group, excellent properties due to fluorine atoms, such as water and oil repellency, can be obtained in various environments. Was difficult to express. In the field of surfactants, surfactants in which fluorine, especially long-chain fluoroalkyl groups have been introduced, may have superior performance due to fluorine as compared to conventional hydrocarbon surfactants. Attention has been paid to low molecular weight surfactants. However,
There is almost no knowledge of high molecular weight surfactants into which fluoroalkyl groups have been introduced. Also, there is almost no knowledge of an antibacterial agent into which a fluoroalkyl group has been introduced.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide novel fluoroalkyl group-containing phosphinic acid oligomers having excellent antibacterial activity, water and oil repellency and high surface activity. An object of the present invention is to provide an antibacterial agent, a non-aqueous surfactant, and a resin composition having excellent water and oil repellency and antifouling properties containing the same.

[0005]

Under these circumstances, the present inventors have conducted intensive studies, and as a result, by reacting a specific fluoroalkanoyl peroxide with a phosphinic acid compound having a (meth) acrylic group, a novel compound has been obtained. Thus, a fluoroalkyl group-containing phosphinic acid oligomer was obtained, and it was found that an antibacterial agent, a surfactant, and a resin composition containing the same as an active ingredient could solve the above problems, and completed the present invention.

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

[0007]

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In the formula, R ¹ and R ² are the same or different and are (CF ₂ ) _n Y or CF (CF ₃ )-[OCF ₂ CF
(CF ₃ )] _p -OC ₃ F ₇ (wherein, Y represents a hydrogen atom, a fluorine atom or a chlorine atom, n represents an integer of 1 to 10, and p represents an integer of 0 to 8), R ³ represents a hydrogen atom or a methyl group; R ⁴ represents a linear or branched alkyl group having 1 to 18 carbon atoms; A represents a linear or branched alkylene group; Indicates 1,000. And a fluoroalkyl group-containing phosphinic acid oligomer represented by｝.

Further, the present invention provides the following general formula (2):

[0010]

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(Wherein R ¹ and R ² are as defined above), and a fluoroalkanoyl peroxide represented by the following general formula (3):

[0012]

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(Wherein R ³ , R ⁴ and A have the same meanings as described above), and a phosphinic acid compound having a (meth) acrylic group represented by the following general formula (1):

[0014]

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In the formula, R ¹ and R ² are the same or different and are (CF ₂ ) _n Y or CF (CF ₃ )-[OCF ₂ CF
(CF ₃ )] _p -OC ₃ F ₇ (wherein, Y represents a hydrogen atom, a fluorine atom or a chlorine atom, n represents an integer of 1 to 10, and p represents an integer of 0 to 8), R ³ represents a hydrogen atom or a methyl group; R ⁴ represents a linear or branched alkyl group having 1 to 18 carbon atoms; A represents a linear or branched alkylene group; Indicates 1,000. The present invention provides a method for producing a fluoroalkyl group-containing phosphinic acid oligomer represented by｝.

Further, the present invention provides an antibacterial agent, a surfactant and a fluoroalkyl group represented by the above general formula (1), which comprise a fluoroalkyl group-containing phosphinic acid oligomer represented by the general formula (1) as an active ingredient. An object of the present invention is to provide a resin composition containing an alkyl group-containing phosphinic acid oligomer.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The fluoroalkyl group-containing phosphinic acid oligomer according to the present invention is represented by the general formula (1). In the formula, R ¹ and R ² are preferably those wherein, in the formula: (CF ₂ ) _n Y, n is 1 to 8, particularly 1 to 5, and Y is a fluorine atom. Also, the formula: CF
(CF ₃₎ - [OCF ₂ CF (CF _{3)] p} - OC ₃ F
_{In 7} , p is 0 to 8, particularly 0 to 6. Preferred of R ³ is a hydrogen atom or a methyl group. Also, R
Preferred of ^{4 is} a linear or branched alkyl group having 1 to 12 carbon atoms. Specific examples of R ⁴ include methyl, ethyl, n-propyl, isopropyl, n-
Butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, isooctyl, n
-Dodecyl group, isododecyl group and the like, among which a methyl group is particularly preferred. Further, A is preferably a linear or branched alkylene group having 1 to 8 carbon atoms. Specific examples of A include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group,
Examples include an ethylethylene group, a propylene group, a butylene group, a hexylene group, and a decylene group. The preferable range of m is 1 to 50, particularly preferably 1 to 10. Further, in the oligomers of the general formula (1) of the present invention, R ¹
And an oligomer in which the fluoroalkyl group represented by R ² is introduced into only one terminal of the oligomer, may be contained at an arbitrary ratio.

Next, a method for producing the fluoroalkyl group-containing phosphinic acid oligomer represented by the general formula (1) according to the present invention will be described. In the general formula (2) as a reaction raw material, preferred groups for R ¹ and R ² are the same as those described above. Specific compounds of the fluoroalkanoyl peroxides represented by the general formula (2) include diperfluoro-2-methyl-3-oxahexanoyl peroxide, diperfluoro-2,5-dimethyl-3 peroxide. , 6-Dioxano nanoyl, diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide, diperfluorobutyryl peroxide, diperfluoroheptanoyl peroxide, diperfluoro peroxide Octanoyl 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 the general formula (3), which is the other reaction raw material, preferred groups for R ³ , R ⁴ and A are the same as those described above. Specific examples of the phosphinic acid compound having a (meth) acrylic group represented by the general formula (3) include methyl (acryloyloxymethyl) phosphinic acid, methyl (methacryloyloxymethyl) phosphinic acid, and ethyl (acryloyloxymethyl). Phosphinic acid, ethyl (methacryloyloxymethyl) phosphinic acid, n-butyl (acryloyloxymethyl) phosphinic acid, n-butyl (methacryloyloxymethyl) phosphinic acid, n-hexadecyl (acryloyloxymethyl) phosphinic acid, n-hexadecyl (methacryloyl) Oxymethyl) phosphinic acid, n-octyl (acryloyloxymethyl) phosphinic acid, n-octyl (methacryloyloxymethyl) phosphinic acid, n-octadecyl (acryloyloxymethyl) phosph Fin acid, n-
Octadecyl (methacryloyloxymethyl) phosphinic acid, n-dodecyl (acryloyloxymethyl) phosphinic acid, n-dodecyl (methacryloyloxymethyl) phosphinic acid, methyl (2-acryloyloxyethyl) phosphinic acid, methyl (2-methacryloyloxyethyl) Phosphinic acid, ethyl (2-acryloyloxyethyl) phosphinic acid, ethyl (2-methacryloyloxyethyl) phosphinic acid, n-butyl (2-acryloyloxyethyl) phosphinic acid, n-butyl (2
-Methacryloyloxyethyl) phosphinic acid, n-hexadecyl (2-acryloyloxyethyl) phosphinic acid, n-hexadecyl (2-methacryloyloxyethyl) phosphinic acid, n-octyl (2-methacryloyloxyethyl) phosphinic acid, n-octyl (2-methacryloyloxyethyl) phosphinic acid, n-octadecyl (2-acryloyloxyethyl) phosphinic acid, n-octadecyl (2-methacryloyloxyethyl) phosphinic acid, n-dodecyl (2-acryloyloxyethyl) phosphinic acid, n -Dodecyl (2-methacryloyloxyethyl) phosphinic acid, methyl (3-acryloyloxypropyl) phosphinic acid, methyl (3
-Methacryloyloxypropyl) phosphinic acid, ethyl (3-acryloyloxypropyl) phosphinic acid,
Ethyl (3-methacryloyloxypropyl) phosphinic acid, n-butyl (3-acryloyloxypropyl)
Phosphinic acid, n-butyl (3-methacryloyloxypropyl) phosphinic acid, n-hexadecyl (3-acryloyloxypropyl) phosphinic acid, n-hexadecyl (3-methacryloyloxypropyl) phosphinic acid, n-octyl (3-acryloyloxy) Propyl)
Phosphinic acid, n-octyl (3-methacryloyloxypropyl) phosphinic acid, n-octadecyl (3-acryloyloxypropyl) phosphinic acid, n-octadecyl (3-methacryloyloxypropyl) phosphinic acid, n-dodecyl (3-acryloyloxy) Propyl) phosphinic acid, n-dodecyl (3-methacryloyloxypropyl) phosphinic acid, methyl (4-acryloyloxybutyl) phosphinic acid, methyl (4-methacryloyloxybutyl) phosphinic acid, ethyl (4-acryloyloxybutyl) phosphinic acid , Ethyl (4-
(Methacryloyloxybutyl) phosphinic acid, n-butyl (4-acryloyloxybutyl) phosphinic acid, n
-Butyl (4-methacryloyloxybutyl) phosphinic acid, n-hexadecyl (4-acryloyloxybutyl) phosphinic acid, n-hexadecyl (4-methacryloyloxybutyl) phosphinic acid, n-octyl (4-
Acryloyloxybutyl) phosphinic acid, n-octyl (4-methacryloyloxybutyl) phosphinic acid,
n-octadecyl (4-acryloyloxybutyl) phosphinic acid, n-octadecyl (4-methacryloyloxybutyl) phosphinic acid, n-dodecyl (4-acryloyloxybutyl) phosphinic acid, n-dodecyl (4
-Methacryloyloxybutyl) phosphinic acid, methyl (5-acryloyloxypentyl) phosphinic acid, methyl (5-methacryloyloxypentyl) phosphinic acid, ethyl (5-acryloyloxypentyl) phosphinic acid, ethyl (5-methacryloyloxypentyl)
Phosphinic acid, n-butyl (5-acryloyloxypentyl) phosphinic acid, n-butyl (5-methacryloyloxypentyl) phosphinic acid, n-hexadecyl (5-acryloyloxypentyl) phosphinic acid, n
-Hexadecyl (5-methacryloyloxypentyl)
Phosphinic acid, n-octyl (5-acryloyloxypentyl) phosphinic acid, n-octyl (5-methacryloyloxypentyl) phosphinic acid, n-octadecyl (5-acryloyloxypentyl) phosphinic acid,
n-octadecyl (5-methacryloyloxypentyl) phosphinic acid, n-dodecyl (5-acryloyloxypentyl) phosphinic acid, n-dodecyl (5-methacryloyloxypentyl) phosphinic acid, methyl (6
-Acryloyloxyhexyl) phosphinic acid, methyl (6-methacryloyloxyhexyl) phosphinic acid,
Ethyl (6-acryloyloxyhexyl) phosphinic acid, ethyl (6-methacryloyloxyhexyl) phosphinic acid, n-butyl (6-acryloyloxyhexyl) phosphinic acid, n-butyl (6-methacryloyloxyhexyl) phosphinic acid, n- Hexadecyl (6-
(Acryloyloxyhexyl) phosphinic acid, n-hexadecyl (6-methacryloyloxyhexyl) phosphinic acid, n-octyl (6-acryloyloxyhexyl) phosphinic acid, n-octyl (6-methacryloyloxyhexyl) phosphinic acid, n-octadecyl ( 6
-Acryloyloxyhexyl) phosphinic acid, n-octadecyl (6-methacryloyloxyhexyl) phosphinic acid, n-dodecyl (6-acryloyloxyhexyl) phosphinic acid, n-dodecyl (6-methacryloyloxyhexyl) phosphinic acid, methyl (7 -Acryloyloxyheptyl) phosphinic acid, methyl (7-methacryloyloxyheptyl) phosphinic acid, ethyl (7-acryloyloxyheptyl) phosphinic acid, ethyl (7-methacryloyloxyheptyl) phosphinic acid, n-butyl (7-acryloyloxyheptyl) ) Phosphinic acid, n-butyl (7-methacryloyloxyheptyl) phosphinic acid, n-hexadecyl (7-acryloyloxyheptyl) phosphinic acid, n-hexadecyl (7-methacryloyl) Oxy heptyl) phosphinic acid, n- octyl (7-acryloyloxy-heptyl)
Phosphinic acid, n-octyl (7-methacryloyloxyheptyl) phosphinic acid, n-octadecyl (7-acryloyloxyheptyl) phosphinic acid, n-octadecyl (7-methacryloyloxyheptyl) phosphinic acid, n-dodecyl (7-acryloyloxy) Heptyl) phosphinic acid, n-dodecyl (7-methacryloyloxyheptyl) phosphinic acid, methyl (8-acryloyloxyoctyl) phosphinic acid, methyl (8-methacryloyloxyoctyl) phosphinic acid, ethyl (8
-Acryloyloxyoctyl) phosphinic acid, ethyl (8-methacryloyloxyoctyl) phosphinic acid,
n-butyl (8-acryloyloxyoctyl) phosphinic acid, n-butyl (8-methacryloyloxyoctyl) phosphinic acid, n-hexadecyl (8-acryloyloxyoctyl) phosphinic acid, n-hexadecyl (8-methacryloyloxyoctyl) phosphine acid,
n-octyl (8-acryloyloxyoctyl) phosphinic acid, n-octyl (8-methacryloyloxyoctyl) phosphinic acid, n-octadecyl (8-acryloyloxyoctyl) phosphinic acid, n-octadecyl (8-methacryloyloxyoctyl) phosphine Acid, n-dodecyl (8-acryloyloxyoctyl)
Phosphinic acid, n-dodecyl (8-methacryloyloxyoctyl) phosphinic acid, and the like.

Next, conditions for reacting the fluoroalkanoyl peroxide with the phosphinic acid compound having a (meth) alkyl group will be described. The molar ratio of the fluoroalkanoyl peroxide to the phosphinic acid compound having a (meth) acryl group is usually from 1: 1 to 1
It is in the range of 0, preferably in the range of 1: 1 to 7.
The reaction can be carried out at normal pressure, and the reaction temperature is usually −20 to 150 ° C., preferably 0 to 100 ° 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 generally 0.5 to 20 hours, preferably 3 to 10 hours. This reaction can be carried out without solvent, but it is preferable to carry out the reaction in a solvent in order to carry out the reaction with fluoroalkanoyl peroxides more smoothly. 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, 1,3-dichloro-1,2,2
3,3-pentafluoropropane and the like can be mentioned, and these can be used alone or in combination of two or more.
Among them, 1,1-dichloro-2,2,3,3,3-
Pentafluoropropane and 1,3-dichloro-1,2,2
A mixed solvent with 2,3,3-pentafluoropropane is preferred. The concentration of the fluoroalkanoyl peroxide in these solvents is preferably in the range of 0.5 to 30% by weight.

The fluoroalkyl group-containing phosphinic acid oligomers thus obtained can be purified, if desired, by conventional purification means such as dialysis, reprecipitation, recrystallization, distillation and column chromatography.

Next, the antibacterial agent of the present invention will be described. In the antibacterial agent of the present invention, preferred examples of the fluoroalkyl group-containing phosphinic acid oligomer as an active ingredient include, in the general formula (1), R ¹ and R ²
In the formula: (CF ₂ ) _n Y, n is 1 to 10, preferably 1 to
8, particularly preferably 1 to 3, and Y is a fluorine atom. The formula: CF (CF ₃ )-[OCF ₂ CF (CF
_{3)] p} - in OC ₃ F _7, p is 0-8, especially 0-2. Further, R ¹ and R ² are preferably the same group. R ³ is preferably a hydrogen atom or a methyl group, and R ⁴ is
Preferably, it is a lower alkyl group having 1 to 8 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and an octyl group. A is preferably a linear or branched alkylene group having 1 to 8 carbon atoms. m is preferably 1 to 5
0, particularly preferably 1 to 10.

The antibacterial agent of the present invention exhibits a broad spectrum of activity particularly effective against various bacteria, fungi, algae, viruses and the like.
It has an algicidal effect on algae. The antibacterial activity varies depending on the type and environment of the antibacterial agent of the present invention.
When the concentration of the fluoroalkyl group-containing phosphinic acid oligomer represented by the formula (1) is 100 ppm, preferably 1000 ppm or more, excellent antibacterial activity is exhibited.

The antibacterial agent according to the present invention may be used in combination with another antibacterial agent. The other antibacterial agent is not particularly limited, and a general antibacterial agent 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, in its preparation,
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 surfactant of the present invention will be described.
I do. In the surfactant of the present invention, the active ingredient
Preferred fluoroalkyl oligomers containing fluoroalkyl groups
A preferable example is that in the general formula (1), R¹And R ^Two
Is of the formula: (CF_Two)_nIn Y, n is 1 to 8, especially 4 to 8
And Y is a fluorine atom. Also, the formula: CF (C
F_Three)-[OCF_TwoCF (CF_Three)]_p-OC_ThreeF
₇In the formula, p is 0 to 8, particularly 2 to 8. Surface activity effects
Is R¹And R^TwoAffects the length of the fluoroalkyl group of
For example, the larger the p in the above formula, the higher the surface activity
Sexual effects tend to be higher. Also, R¹And R^TwoIs
Preferably they are the same group. R^ThreeIs a hydrogen atom or
A tyl group is preferred, and R^FourPreferably has 1 to 5 carbon atoms
Methyl, ethyl, propyl, butyl, pentyl
Is a lower alkyl group. A is a linear group having 1 to 8 carbon atoms
Alternatively, a branched alkylene group is preferable. m is preferably
Is 1 to 50, particularly preferably 1 to 10.

The surfactant of the present invention exhibits an excellent surfactant effect when the amount of the active ingredient is usually 0.5 g / L or more, preferably 1 g / L or more. The surfactant of the present invention can be used in a usual manner, and can be used in combination with other known surfactants. The other surfactant is not particularly limited, and includes, for example, an anionic surfactant, a nonionic surfactant, and a cationic surfactant.

Examples of the anionic surfactant include a sulfonate, a sulfate and a carboxylate. Examples of the sulfonate-based surfactant include alkylbenzene sulfonates having 9 to 15 carbon atoms, alkyl sulfonates having 12 to 16 carbon atoms, alkenes and hydroxyalkane sulfonates, disulfonates,
α-olefin sulfonate and the like. As sulfate surfactants, tallow fatty alcohol, oleyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, monoalcohols such as primary alcohols such as stearyl alcohol or secondary alcohols such as oxo alcohols having 10 to 20 carbon atoms, sulfuric acid monoesters, Examples include hydroxycarboxylic acid, aminocarboxylic acid, hydroxysulfonic acid, aminosulfonic acid, alkylsulfosuccinic acid, sulfosuccinate, and sulfosuccinic alcohol. Also, soaps such as lauric acid, myristic acid, palmitic acid, stearic acid, coconut oil, palm kernel oil, tallow fatty acid and the like can be mentioned.

Examples of the nonionic surfactant include fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid amides, ethylene oxide-propylene oxide block copolymers, polyethylenated carboxylic acid amides, aminooxides and sulfoxides.

Examples of the cationic surfactant include an organic acid salt or an inorganic acid salt of an aliphatic amine having at least one alkyl group having 12 to 18 carbon atoms, a quaternary ammonium salt thereof, and an aryl group such as a benzyl group. And heterocyclic quaternary ammonium salts such as aromatic quaternary ammonium salts, pyridium salts and imidazolium salts, and onium salts such as sulfonyl salts and phosphonium salts. These other surfactants may be present as organic salts such as sodium, potassium, ammonium, mono-, di- or triethanolamine. These compounds may be used alone or in combination of two or more.

As other optional components, components of ordinary detergents, for example, foam stabilizers, foam inhibitors, calcium complexing or precipitating agents, softening agents, alkalis or electrolytes, bleaching agents, bleaching agents Activators, redeposition inhibitors, corrosion inhibitors, bactericidal substances, enzymes, enzyme stabilizers, brighteners, colorants,
It can be used in combination with a fluorescent agent or the like. The surfactant of the present invention has excellent properties due to fluorine atoms such as water repellency and oil repellency, so it has high stability vesicles, pharmaceutical and agrochemical auxiliaries, medical materials, oxygen-enriched films, various lubricants Additives, paints, ink leveling agents, paint movers, resist strippers, foaming agents for cleaning, fiber treatment agents, fluorine resin surface modifiers, and the like.

Next, the resin composition of the present invention will be described. As preferable examples of the fluoroalkyl group-containing phosphonate oligomer contained in the resin composition of the present invention, in the general formula (1), R ¹ and R ² are represented by the formula: (C
In F ₂ ) _n Y, n is 1 to 8, especially 1 to 5, and Y is a fluorine atom. The formula: CF (CF ₃ )-[OCF
₂ CF (CF _{3)] p} - in OC ₃ F _7, p is 0-8, especially 0-2. Preferably, R ¹ and R ² are the same group. Preferred of R ³ is a hydrogen atom or a methyl group. R ⁴ preferably has 1 to 8 carbon atoms.
A lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. A is preferably a linear or branched alkylene group having 1 to 8 carbon atoms. m is preferably 1 to 50, particularly preferably 1 to 10.

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, acrylic rubber, hydrogenated acrylonitrile-butadiene rubber, polysulfide rubber, urethane rubber, acrylsulfonated rubber, silicone rubber and modified products thereof And the like, and these may be a blend rubber of two or more kinds. 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 amount of the fluoroalkyl group-containing phosphinic acid oligomer to be added to the resin is usually 0.01 to 1
0% by weight, preferably 0.5 to 5% by weight. Also,
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 absorbers. , An antioxidant, an extender, a dispersing aid, a vulcanizing agent, a vulcanization accelerator, a vulcanizing aid, a softening agent, an antioxidant, and a plasticizer. The resin composition according to the present invention has excellent water and oil repellency and stain resistance. Further, the fluoroalkyl group-containing phosphinic acid oligomers of the present invention have an excellent anti-AIDS virus action.

[0035]

Next, the present invention will be described in more detail with reference to examples, but this is merely an example and does 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, 5.15 g of n-butyl (3-acryloyloxypropyl) phosphinic acid (22 mmol
l) is a 1: 1 mixed solvent of 1,1-dichloro-2,2,3,3,3-pentafluoropropane and 1,3-dichloro-1,2,2,3,3-pentafluoropropane ( AK-225) dissolved in 40 g, and 1.87 g (4.4 mmol) of diperfluorobutyryl peroxide.
Was quickly added dropwise to the AK-225 solution at room temperature in a nitrogen stream. Thereafter, 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.
Dialysis purification was performed using AK-225 as a solvent. Thereafter, the residue was dried under vacuum to obtain 1.62 g of the oligomer.
(23% yield). The average molecular weight determined by GPC was 3,800. FT-IR, ¹ H-NMR, ¹⁹ F
By -NMR, the fluoroalkyl group-containing phosphinic acid oligomer was confirmed.

FT-IR (KBr, cm ^-1 ): 3,400 (OH), 17
30 (C = O), 1340 (CF 3), 1242 (CF 2) 1 H-NMR (δ, CDCl 3): 0.85~0.99 (CH 3), 1.00~
_{2.45 (CH 2, CH),} 2.61 ~2.80 (CH 2), 3.60~3.79 (CH 2), 4.02
^{_{~4.41 (CH 2) 19 F-}} NMR (δ, CDCl 3, ext.CF 3 COOH): - 4.1 (6
F),-41.2 (4F),-50.5 (4F) From the above analysis results, the obtained product was identified as sample A in Table 1.
It was confirmed to be fluoroalkyl group-containing phosphinic acid oligomers having the structure:

Example 2 n-butyl (3
-Acryloyloxypropyl) phosphinic acid 3.98
g (17 mmol) of diperfluoro-2-methyl-3-peroxide as a reaction raw material fluoroalkanoyl peroxide
Except that 2.17 g (3.3 mmol) of oxyhexanoyl was used, synthesis was performed in the same manner as in Example 1 to obtain 2.46 g of an oligomer (40% yield). The average molecular weight determined by GPC was 4,350. FT-IR, ¹ H
The product was confirmed by -NMR and ¹⁹ F-NMR.

FT-IR (KBr, cm ^-1 ): 3,405 (OH), 17
25 (C = O), 1320 (CF 3), 1240 (CF 2) 1 H-NMR (δ, CDCl 3): 0.89~1.00 (CH 3), 1.05~
_{2.42 (CH 2, CH),} 2.68 ~2.88 (CH 2), 3.63~3.82 (CH 2), 4.00
4.34.38 (CH ₂ ) ¹⁹ F-NMR (δ, CDCl ₃ , ext. CF ₃ COOH): -3.5 to-
8.1 (16F), -53.2 (6F) From the above analysis results, the obtained product is sample B in Table 1.
It was confirmed to be fluoroalkyl group-containing phosphinic acid oligomers having the structure:

Example 3 n-Butyl (3
-Acryloyloxypropyl) phosphinic acid 2.81
g (12 mmol), and 2.47 g (2.5 mmo) of diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide as fluoroalkanoyl peroxide as a reaction raw material.
Except for using l), the synthesis was carried out in the same manner as in Example 1 to obtain 1.48 g of an oligomer (yield: 28%). G
The average molecular weight determined by PC was 2,900. FT
The product was confirmed by -IR, ¹ H-NMR and ¹⁹ F-NMR.

FT-IR (KBr, cm ^-1 ): 3,410 (OH), 17
20 (C = O), 1342 (CF 3), 1245 (CF 2) 1 H-NMR (δ, CDCl 3): 0.95~1.02 (CH 3), 1.09~
_{2.45 (CH 2, CH),} 2.71 ~2.89 (CH 2), 3.60~3.91 (CH 2), 4.02
^{_{~4.42 (CH 2) 19 F-}} NMR (δ, CDCl 3, ext.CF 3 COOH): - 3.7~-
7.9 (26F), -53.8 (6F), -68.7 (2F) Based on the above analysis results, the obtained product was sample C in Table 1.
It was confirmed to be fluoroalkyl group-containing phosphinic acid oligomers having the structure:

Example 4 n-Butyl (3
-Acryloyloxypropyl) phosphinic acid 6.10
g (12 mmol), 1.83 g of diperfluorobutyl peroxide as fluoroalkanoyl peroxide as a reaction raw material
1.82 g of oligomer (23% yield) by synthesizing in the same manner as in Example 1 except that (4.3 mmol) was used.
I got The average molecular weight determined by GPC was 1,800. The product was confirmed by FT-IR, ¹ H-NMR, and ¹⁹ F-NMR.

FT-IR (KBr, cm ^-1 ): 3,402 (OH), 17
25 (C = O), 1330 (CF 3), 1240 (CF 2) 1 H-NMR (δ, CDCl 3): 0.90~1.03 (CH 3), 1.02~
_{2.40 (CH 2, CH),} 2.62 ~2.85 (CH 2), 3.61~3.72 (CH 2), 4.00
^{_{~4.45 (CH 2) 19 F-}} NMR (δ, CDCl 3, ext.CF 3 COOH): - 4.5 (6
F),-41.4 (4F),-51.0 (4F) From the above analysis results, the obtained product was sample D in Table 1.
It was confirmed to be fluoroalkyl group-containing phosphinic acid oligomers having the structure:

Example 5 n-octyl (3-acryloyloxypropyl) phosphinic acid was used as a phosphinic acid compound as a reaction raw material.
94 g (17 mmol) of diperfluoro-2-methyl peroxide as a reaction raw material fluoroalkanoyl peroxide
Except that 2.17 g (3.3 mmol) of 3-oxyhexanoyl was used, the synthesis was carried out in the same manner as in Example 1 to obtain 1.28 g of an oligomer (18% yield). The average molecular weight determined by GPC was 2,100. FT-IR,
^The product was confirmed by ¹ H-NMR and ¹⁹ F-NMR.

FT-IR (KBr, cm ^-1 ): 3,400 (OH), 17
36 (C = O), 1340 (CF 3), 1241 (CF 2) 1 H-NMR (δ, CD 3 OD): 0.79~0.98 (CH 3), 0.80~
2.98 (CH ₂ , CH), 3.85 to 4.45 (CH ₂ ), ¹⁹ F-NMR (δ, CD ₃ OD, ext. CF ₃ COOH): -5.4 to-
8.6 (16F), -54.1 (6F) From the above analysis results, the obtained product was sample E in Table 1.
It was confirmed to be fluoroalkyl group-containing phosphinic acid oligomers having the structure:

Example 6 n-octyl (3-acryloyloxypropyl) phosphinic acid was used as a phosphinic acid compound as a reaction raw material.
35 g (15 mmol) of diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide 2.96 g (3.0) as fluoroalkanoyl peroxide as a reaction raw material
0.73 g (yield 10%) of the oligomer was obtained in the same manner as in Example 1 except that (mmol) was used.
The average molecular weight determined by GPC was 2,550. F
The product was confirmed by T-IR, ¹ H-NMR, and ¹⁹ F-NMR.

FT-IR (KBr, cm ^-1 ): 3,410 (OH), 17
30 (C = O), 1335 (CF 3), 1245 (CF 2) 1 H-NMR (δ, CD 3 OD): 0.75~0.99 (CH 3), 0.81~
2.99 (CH ₂ , CH), 3.80 to 4.47 (CH ₂ ), ¹⁹ F-NMR (δ, CD ₃ OD, ext. CF ₃ COOH): -3.1 to-
7.2 (26F), -50.1 to -58.8 ((6F), -74.5 to -78.5 (2F) Based on the above analysis results, the obtained product was sample F in Table 1.
It was confirmed to be fluoroalkyl group-containing phosphinic acid oligomers having the structure:

[0047]

[Table 1]

(Evaluation of antibacterial activity) The fluoroalkyl group-containing phosphinic acid oligomers of Samples A to D obtained in Examples 1 to 4 were analyzed for Staphylococcus aureus and Pseudomonas aeruginosa. -Antibacterial or bactericidal activity against Arginosa (Pseudomonas aeruginosa) was tested. First, a preculture (0.5 ml) of the bacteria was inoculated into 5 ml of Pennassay medium and cultured with shaking at 37 ° C. for 3 hours. Bacteria are collected by centrifugation (3000 rpm × 5 minutes), and physiological saline containing 10 mM phosphate buffer (pH 7.2)
(PBS). Each oligomer is at a concentration of 1 mg / ml
It was dissolved in PBS. The oligomer and the bacterial suspension (1 ml) were mixed and left at room temperature for 30 minutes. The agar plate was allowed to stand at 37 ° C overnight, and the resulting colonies were counted and the number of colonies (cfu /
(ml). Table 2 shows the results. In the table, "B
"L" is a blank, a sample to which no oligomer was added.

[0049]

[Table 2]

(Evaluation as Surfactant) Examples 1 to 6
The fluoroalkyl group-containing phosphinic acid oligomers of Samples A to F obtained in the above were tested for solubility in various solvents. Table 3 shows the results. In the table, ○ indicates “very soluble”, Δ indicates “not very soluble”, and X indicates “not soluble at all”. The fluoroalkyl group-containing phosphinic acid oligomers of Samples B and C obtained in Examples 2 and 3 were allowed to stand at 25 ° C. overnight, and then m-
Various concentrations of samples were prepared by dissolving in xylene. The surface tension of each sample was measured at a constant temperature of 30 ° C. using a surface tensiometer. The result is shown in FIG.

[0051]

[Table 3]

(Water and oil repellency test) Examples 1, 3 and 4
A mixture of the fluoroalkyl group-containing phosphinic acid oligomers obtained in (Samples A, C and D) and 1% by weight with respect to 0.98 g of polymethyl methacrylate (PMMA) was dissolved in 30 ml of tetrahydrofuran (THF). ,
The pieces were placed in a petri dish having a diameter of 5 cm. 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. The contact angle was measured using a goniometer G-1 manufactured by ERMA.
A blank in which the fluoroalkyl group-containing phosphinic acid oligomer of the present invention was not added to PMMA was used as a blank.

[0053]

[Table 4]

[0054]

The antimicrobial agent containing the fluoroalkyl group-containing phosphinic acid oligomer of the present invention as an active ingredient exhibits a wide activity spectrum particularly effective against various bacteria, fungi, algae, viruses and the like. In addition, it has excellent water and oil repellency and antifouling properties due to fluorine atoms, is useful as a non-aqueous surfactant, and has high stability vesicles, pharmaceutical and agricultural chemicals, medical materials, oxygen-rich materials. Film, additives for various lubricants,
It can be used as a paint, an ink leveling agent, a paint mover, a resist stripping agent, a foaming agent for cleaning, a fluorine resin surface modifier, and the like. Further, the resin composition of the present invention has excellent water and oil repellency and stain resistance.

[Brief description of the drawings]

FIG. 1 is a diagram showing the relationship between the concentration of a xylene solution of the oligomer of the present invention (samples B and C) and the surface tension.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 3/00 112 C09K 3/00 112D 3/18 102 3/18 102 // B01F 17/14 B01F 17 / 14 C09D 7/06 C09D 7/06 (72) Inventor Tadashi Sugiya 9-11-1, Kameido, Koto-ku, Tokyo Nippon Kagaku Kogyo Co., Ltd. Research and Development Division (72) Inventor Yoshiko Inaba Kameido, Koto-ku, Tokyo 9-11-1, Nippon Kagaku Kogyo Co., Ltd. Research and Development Division

Claims (5)

[Claims] 1. The following general formula (1): In the formula, R ¹ and R ² are the same or different, and (CF ₂ ) _n
Y or CF (CF ₃₎ - [OCF ₂ CF (CF _{3)] p} -
OC ₃ F ₇ (wherein, Y represents a hydrogen atom, a fluorine atom or a chlorine atom, n represents an integer of 1 to 10, p represents an integer of 0 to 8), and R ³ represents a hydrogen atom or methyl Represents a group,
R ⁴ represents a linear or branched alkyl group having 1 to 18 carbon atoms, A represents a linear or branched alkylene group,
m represents 1 to 1,000. Fluorinated alkyl group-containing phosphinic acid oligomers represented by｝. 2. The following general formula (2): (Wherein R ¹ and R ² have the same meanings as described above), and a fluoroalkanoyl peroxide represented by the following general formula (3): (Wherein, R ³ , R ⁴ and A have the same meanings as described above), and reacted with a phosphinic acid compound having a (meth) acrylic group represented by the following general formula (1): In the formula, R ¹ and R ² are the same or different, and (CF ₂ ) _n
Y or CF (CF ₃₎ - [OCF ₂ CF (CF _{3)] p} -
OC ₃ F ₇ (wherein, Y represents a hydrogen atom, a fluorine atom or a chlorine atom, n represents an integer of 1 to 10, p represents an integer of 0 to 8), and R ³ represents a hydrogen atom or methyl Represents a group,
R ⁴ represents a linear or branched alkyl group having 1 to 18 carbon atoms, A represents a linear or branched alkylene group,
m represents 1 to 1,000. A method for producing a fluoroalkyl group-containing phosphinic acid oligomer represented by｝. 3. An antibacterial agent comprising a fluoroalkyl group-containing phosphinic acid oligomer represented by the general formula (1) as an active ingredient. 4. A surfactant comprising a fluoroalkyl group-containing phosphinic acid oligomer represented by the general formula (1) as an active ingredient. 5. A resin composition comprising a fluoroalkyl group-containing phosphinic acid oligomer represented by the general formula (1).