JPH107731A - Fluoroalkylated function modifier - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a function modifier comprising a specified fluoroalkylated oligomer, having both oil repellency and hydrophilicity possessed by the oligomer, a surface tension lowering action important as a surfactant, and being highly able to incorporate ions of a metal such as calcium. SOLUTION: This modifier comprises a fluoroalkylated oligomer represented by the formula: [wherein Rf is (CF2 )n F or -CF(CF3 O(CF2 CF(CF3 )O)m C3 F7 (wherein n is an integer of 1-15; and m is an integer of 0-6); and x is a natural number); and x is a natural number]. It is desirable that Rf in the formula is C3 F7 , C6 F13 , C7 F15 or -CF(CF3 )O(CF2 CF(CF3 )O)m C3 F7 (wherein m is 0, 1 or 2). Examples of the modifier include a textile processing agent, a paper processing agent, a resin surface treating agent, a metal ion absorber and a surfactant. The number- average molecular weight of this oligomer is desirably in the range of 500-8,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a functionalizing agent containing a novel fluoroalkyl group-containing oligomer.

[0002]

2. Description of the Related Art It is known that a compound having a fluoroalkyl group in an organic compound has high functions such as water and oil repellency, stain resistance, light resistance and durability. Conventionally,
Polymers and oligomers obtained by copolymerizing a compound such as vinylidene chloride or vinyl chloride, which can be copolymerized with a polymerizable compound containing a fluoroalkyl group, are known. It is widely used as a processing agent, a water / oil repellent agent for paper or a water / oil repellent surface treatment agent for glass in the form of an emulsion preparation. However, these fluoroalkyl group-containing copolymers tend to precipitate due to various factors when used as an emulsion preparation, and thus have drawbacks such as poor mechanical stability and long-term storage stability of the emulsion. In addition, these fluoroalkyl group-containing copolymers have poor compatibility with general organic solvents and resins used industrially, so that their use is restricted.

[0003] Further, regarding the surface modification of resins, it has been widely practiced to add a coloring agent, a tactile sensation improving agent, a matting agent, etc. to an elastomer dissolved in a solvent and apply it to the surface of a resin molded product. I have. For the purpose of imparting antifouling properties, water / oil repellency, high wettability and the like to the polyester resin surface, JP-A-59-1
Japanese Patent No. 40280 proposes a modification method using a fluoroalkyl group-containing silicone, but has a drawback that adhesion to a polyester surface is insufficient and water / oil repellency is reduced. To solve this problem, Japanese Patent Application Laid-Open No. 5-254
No. 57 proposes using a component selected from the group consisting of a fluorosilicone oligomer, a hydrolyzate thereof, a hydrolyzed condensate thereof and a mixture thereof as a modifier. With respect to the calcium ion uptake capability, which is one of the usefulness of the present invention described later, an ethylenediamine triacetic acid derivative modified with a long-chain alkyl group such as a lauroyl group is known (JJ Crudden and BA).
Parker, Inform, 6, 1132 (1995)) has the disadvantage of poor ability to take up calcium ions.

Further, a surfactant has a hydrophobic portion and a hydrophilic portion in the molecule, and due to the balance between the hydrophobicity and the hydrophilicity, the surfactant is strongly adsorbed on the two-phase interface between water and oil, so that the free energy at the interface is significantly reduced. The hydrophobic portion is generally a group having a long-chain alkyl group, but a fluorinated alkyl group has been proposed to increase hydrophobicity and reduce the number of carbon atoms, such as perfluoroalkylsulfonyl fluoride and perfluoroalkylcarbonyl. A surfactant in which a polyether group is bonded to fluoride via an amide group or an ester group, and a surfactant in which a perfluoroalkylcarbinol is reacted with ethylene oxide to form a polyether are well known. The former has a very low yield when having a perfluoroalkyl group having 6 or more carbon atoms,
Further, a carboxylic acid ester having a perfluoroalkyl group has a disadvantage that it is easily hydrolyzed. Also,
The latter method is difficult to control the degree of polymerization of ethylene oxide, and is not a satisfactory production method. As described above, various fluorine compounds have been proposed for various uses and purposes, and a fluoroalkyl group-containing oligomer containing a morpholino group as shown in the present invention, and its novel properties and Little is known about its usefulness.

[0005]

Conventional fluoroalkyl group-containing copolymers are often used as emulsion preparations because they are not water-soluble, but the emulsions have poor mechanical stability and long-term storage stability. There are drawbacks,
It has disadvantages such as difficulty in handling because it has extremely low solubility in common organic solvents and water used industrially.
In an attempt to improve solubility, partially cationized ring-bearing fluoropolymers have been proposed (ZYYang
J. Am. Chem. Soc., 116, 4135 (1994)), acetone,
Only soluble in polar solvents such as acetonitrile and dimethylformamide, but not soluble in benzene, chloroform, methanol, etc.

[0006] Further, conventional fluoroalkyl group-containing oligomers all have water and oil repellency, but fluoroalkyl group-containing oligomers having high oil repellency and exhibiting hydrophilicity under hydrophilic conditions are also commercially available. Was sought. Provides a fiber treatment agent that has such oil repellency and hydrophilicity and provides a soil release function that makes it easier to remove stains on fiber products, or a resin surface modifier, etc. to modify various materials and provide high functionality imparting agents It is an object of the present invention to do so. For this purpose, an amphiphilic fluoroalkyl group-containing silicone oligomer having a fluoroalkyl group as a hydrophobic terminal and a polyoxyethylene unit as a hydrophilic part has been studied, but it is high even if the polyoxyethylene unit is lengthened. Hydrophilicity has not been obtained (H.Sa
Wada et al., J. Jpn. Oil Chem. Soc., 43, P65 (1994)).

Further, there is a need for an efficient and powerful adsorbent for removing ions such as calcium and magnesium from washing water and solvents in industrial fields such as electronic materials, and a calcium ion adsorbent in a contact lens cleaning solution. However, since conventionally known absorbents such as calcium ions have poor ability, there is a need for new water-soluble compounds that selectively take in calcium ions and the like. An object of the present invention is to have an amphipathic property that dissolves in water and most common organic solvents and is easy to use, and also has a high oil repellency and a hydrophilic property, and also has a surface tension reducing action important as a surfactant, Furthermore, the present invention provides various functionalizing agents characterized by containing a novel fluoroalkyl group-containing oligomer having a high ability to take in metal ions such as calcium, which has not been found in conventional fluoroalkyl group-containing organic compounds. It is in.

[0008]

According to the present invention, as a means for solving the above-mentioned problems, a function-imparting agent comprising a fluoroalkyl group-containing oligomer represented by the following general formula (A): Is provided.

Embedded image Wherein R _F is-(CF ₂ ) _n F (n = 1 to 15) or
_{-CF (CF 3) O (CF} 2 CF (CF 3) O) m C 3 F 7 (
m = 0 to 6), and x represents a natural number.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The fluoroalkyl group-containing oligomer according to the present invention is a fluoroalkyl group-containing oligomer represented by the general formula (A), wherein R _F in the formula A is — (CF ₂ ) _n F (n = 1).
15) or _{-CF (CF 3) O (CF} 2 CF (CF 3)
O) It is represented by _m C ₃ F ₇ (m = 0 to 6), and x represents a natural number. When R _F is-(CF ₂ ) _n F, if the number of carbon atoms is 16 or more, the production becomes difficult, which is not appropriate. Further, if R _F is -C
_{F (CF 3) O (CF} 2 CF (CF 3) O) when specifically enumerated when represented by _m C ₃ F _7, formula (B), (
C), (D), (E), (F), (G), and (H). R _F is _{-CF (CF 3) O (CF} 2 CF (CF 3) O)
When represented by _m C ₃ F ₇ , if the number of m is 7 or more, the solubility in a solvent is reduced, so that production is difficult.

[0010]

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Embedded imageNumber of oligomers containing fluoroalkyl groups according to the present invention
The average molecular weight is not particularly limited, but may be 500 to 8000.
It is preferably within the range. Furthermore, the general formula in the present invention
The fluoroalkyl group-containing oligomer shown in (A)
In this case, only one end of the fluoroalkyl group R_FIs introduced
Any of these may be included in any ratio. Related to the present invention
The production of oligomers containing fluoroalkyl groups
Fluoroalkanoyl peroxide and acroylmorpholine
It is obtained by reacting. Including fluoroalkyl group
Fluoroalkano peroxide used to produce oligomers
Il is represented by the following general formula (I).

Embedded image In formula I, _{R F - (CF 2) n} F (n = 1~15) , or _{-CF (CF 3) O (CF} 2 CF (CF 3) O) m C 3 F 7 (
m = 0 to 6). If R _F in the formula I is-(CF ₂ ) _n
In the case of F, when the number of carbon atoms is 16 or more, and when R _F in the formula I is represented by —CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _m C ₃ F ₇ , m is The use of fluoroalkanoyl peroxides in the case of 7 or more is difficult because of their poor solubility in the reaction solvent. When R _F in the formula I is — (CF ₂ ) _n F, a perfluoropropyl group, a perfluorohexyl group and a perfluoroheptyl group can be preferably exemplified. Further, when R _F in the formula I is —CF (CF ₃ ) O (
When represented by _{CF 2 CF (CF 3) O} ) m C 3 F 7, peroxide -fluoroalkanoyl is peroxide Jiperufuruoro -2
-Methyl-3-oxahexanoyl, diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide and diperfluoro-2,5,8-trimethyl peroxide
Preferred is 3,6,9-trioxadodecinoyl.

In the production of the fluoroalkyl group-containing oligomer, the molar ratio of each charge when reacting fluoroalkanoyl peroxide with acroylmorpholine is preferably in the range of 1: 0.5 to 1:50, and particularly preferably in the range of 1: 0.5 to 1:50. Preferably it is 1: 1 to 1:10. If the charged molar ratio of acroylmorpholine is less than 0.5 or more than 50, the yield of the desired fluoroalkyl group-containing oligomer is undesirably reduced. The intended fluoroalkyl group-containing oligomer can be obtained by a one-step reaction in which fluoroalkanoyl peroxide and acroylmorpholine are mixed and reacted. Further, the reaction can be carried out at normal pressure. The reaction temperature is -20 to 1
50 ° C is preferable, but 0 to 100 ° C is particularly preferable in consideration of economy and the like. If the temperature is lower than -20 ° C, a long reaction time is required. If the temperature is higher than 150 ° C, the pressure during the reaction increases, which is not preferable. The reaction time is industrially desirably 3 to 10 hours. As a solvent for performing the reaction, a halogenated aliphatic solvent or the like can be used, and AK-225 (1,1-dichloro-
2,2,3,3,3-pentafluoropropane: 1,3
-Dichloro-1,2,2,3,3-pentafluoropropane = 1: 1.35 manufactured by Asahi Glass Co., Ltd.), chloroform,
Methylene chloride, bis (trifluoromethyl) benzene,
Benzotrifluoride, hexafluorobenzene and the like can be used. The concentration of the fluoroalkanoyl peroxide in the reaction solvent is desirably 0.5 to 30% by weight. The product obtained by the production method of the present invention can be purified by a known purification method such as a reprecipitation method, distillation, or gel permeation chromatography (GPC).

The fiber treating agent of the present invention can be used by directly dissolving the fluoroalkyl group-containing oligomer according to the present invention in a solvent, and imparts high oil repellency to the fiber product and imparts to the fiber product surface under hydrophilic conditions. Since it imparts hydrophilicity, it becomes a fiber treatment agent having a soil release function that makes it easier to remove stains on fiber products. When dissolved in a solvent, use the solvent after dissolving in water, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, chloroform, ethyl acetate, dichloromethane, benzene, toluene, m-xylene, acetone, etc. Can be done. When used by dissolving in a solvent, the fibers can be treated by a method such as padding or dipping. In this case, the adhesion amount of the fluoroalkyl group-containing oligomer according to the present invention to the textile is 0.1 to 1 with respect to the weight of the textile in consideration of economy, effects, and the like.
It is preferably set to 0%, and particularly preferably set to 0.2 to 3%. The fiber treating agent of the present invention also combines the fluoroalkyl group-containing oligomer according to the present invention with other water-soluble or water-dispersible other resin components commonly used for padding and water-based coating as shown below. Thereby, durable water and oil repellency can be obtained. That is, various types of emulsions and aqueous solutions such as acrylic, urethane, polyester, polyvinyl acetate or synthetic rubber latex used to bind organic and inorganic particulates, powders, microcapsules, etc. to fibers. Resin binder, acrylic resin emulsion used as a binder for nonwoven fabrics and carpets, self-crosslinking thermosetting acrylic emulsion used for anti-wrinkle, pilling, thickening, durable hardening or soft finishing, It can be used by blending it with various resin components such as urethane emulsion for water-based sueding and rebound resilience, or W / 0 type urethane emulsion used for moisture permeable waterproofing. Furthermore, those having compatibility such as amino-modified, epoxy-modified, carboxy-modified emulsions of dimethyl silicone oil used for the purpose of improving texture, and water-soluble proteins such as collagen and silk protein used for the purpose of improving tactile sensation. As long as they are used, they can be used in combination with any one of them, and two or more of these can be used in combination.

In this case, since the fluoroalkyl group-containing oligomer according to the present invention is dissolved in water, it can be easily mixed with the above-mentioned resin preparation. The mixing ratio of the fluoroalkyl group-containing oligomer to the organic resin component cannot be specified unconditionally because the amount of the processing solution that can be attached to the fiber varies greatly depending on the processing method. The amount of the group-containing oligomer is blended in the range of 0.01 to 15 parts by weight. More preferably, it is blended so as to be in the range of 0.05 to 10 parts by weight. If the amount is less than 0.01 part by weight, the effects of water / oil repellency and stain resistance cannot be obtained.
On the other hand, if the amount exceeds 15 parts by weight, no further increase in the contact angle of oil or water is recognized, and the performance of the base resin may be impaired. In addition, the amount of the fluoroalkyl group-containing oligomer according to the present invention attached to the fiber product is 0.1% with respect to the weight of the fiber product in consideration of economy, effects, and the like.
It is preferably set to 10 to 10%, and particularly preferably set to 0.2 to 3%. The method of treating the fiber substrate with the fiber treating agent of the present invention uses padding, dipping,
A method such as coating or printing can be selected. In this case, if necessary, other water and oil repellents, softeners, texture improvers, tactile sensation improvers, coloring agents, antibacterial agents, thickeners and the like can be used in combination. Further, it is also possible to mix and add the fluoroalkyl group-containing oligomer according to the present invention to commercially available emulsions or aqueous solutions for processing various fibers.

The fiber treating agent of the present invention can also use an elastomer which is usually used for coating or laminating as an organic resin component to which the fluoroalkyl group-containing oligomer according to the present invention is added. The organic resin component is not particularly limited, and is a known resin composition conventionally used for fiber processing, for example, a general-purpose resin such as a urethane resin or an acrylic resin, a fluororesin, a polyester resin, a vinyl chloride resin, or a chlorsulfonated resin. A polymer material containing polyethylene resin or silicone as a main component can be used, and two or more of these can be used in combination. Further, the organic resin composition of the present invention may be dissolved or dispersed in an organic solvent. In this case, the fluoroalkyl group-containing oligomer according to the present invention can be used in a wide range of solvents such as methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, chloroform, dichloromethane, ethyl acetate, benzene, toluene, m-xylene, and acetone. Since it is dissolved, it can be easily mixed with the organic resin component.
In this case, the mixing ratio of the fluoroalkyl group-containing oligomer to the organic resin component cannot be specified unconditionally because the amount of the treatment liquid that can be attached to the fiber varies greatly depending on the processing method. Is blended so that the amount of the fluoroalkyl group-containing oligomer is in the range of 0.01 to 15 parts by weight. More preferably, it is blended so as to be in the range of 0.05 to 10 parts by weight. If the amount is less than 0.01 part by weight, the effects of water / oil repellency and stain resistance cannot be obtained. On the other hand, if the amount exceeds 15 parts by weight, no further increase in the contact angle of oil or water is recognized, and the performance of the base resin may be impaired.

In the present invention, the above-mentioned polyurethane is used in a form dissolved in a solvent. When the polyurethane is formed by wet coagulation, it is appropriate to dissolve it in water or a water-miscible solvent that can be extracted with a water-miscible solvent,
For example, N, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, tetramethylurea, N, N-dimethylacetamide, dioxane, butylcarbinol and the like can be used alone or in combination.
In this case, acetone or methyl ethyl ketone may be added to the extent that the polyurethane does not solidify. When the polyurethane is used in a dry coating in which the polyurethane is directly heated and dried immediately after coating, a solvent such as toluene, xylene, ethyl acetate, butyl acetate, or isopropyl alcohol other than the above solvents can be added in a range where the polyurethane does not solidify. . In the present invention, the mixing of the fluoroalkyl group-containing oligomer with the polyurethane can be mixed when the polyurethane elastomer is dissolved in the solvent.

When the organic resin used in the fiber treating agent of the present invention is an acrylic resin, any of commonly used acrylic copolymers can be used, but a functional group having an active hydrogen such as a hydroxyl group can be used. A group-containing acrylic copolymer can be more preferably used. As the acrylic copolymer, for example, an ethylenically unsaturated monomer copolymer containing a hydroxyl group or a carboxyl group can be used. As an example, an ethylenically unsaturated monomer having no hydroxyl group and no carboxyl group represented by the following formula (J) can be used. And a combination of a monomer and an ethylenically unsaturated monomer having a hydroxyl group or a carboxyl group represented by the following formula (K).

Embedded image [In formula J, R ₃ is hydrogen or an alkyl group having 1 to 2 carbon atoms, R ₄ is an alkyl group, an allyl group, a halogen-substituted alkyl group, a halogen-substituted allyl group, a nitrile group, or an alkoxycarbonyl having 2 to 24 carbon atoms. Shows a group]

Embedded image [In the formula K, R ₅ represents a hydrogen, an alkyl group or a carboxyalkyl group, R ₆ represents a hydrogen or a carboxyl group, R ₇ represents a hydrogen or a hydroxyalkyl group, and n represents 0 or a natural number.] Examples of the ethylenically unsaturated monomer having no hydroxyl group and no carboxyl group include acrylonitrile, alkyl acrylates such as methyl acrylate and butyl acrylate, alkyl methacrylates such as ethyl methacrylate and butyl acrylate, and styrene. Examples of the ethylenically unsaturated monomer having a hydroxyl group or a carboxyl group represented by the above) include ethylenically unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid, 2-hydroxyethyl acrylate and hydroxypropyl. Hydroxyl such as acrylate Hydroxy acrylate, hydroxyalkyl methacrylate such as 2-hydroxyethyl methacrylate and hydroxypropyl methacrylate, 3-chloro-2-hydroxyalkyl methacrylate, and the like can be used. Each of the monomers represented by the formula (J) or (K) can be used in combination of two or more. In the present invention, the blending of the fluoroalkyl group-containing oligomer into the acrylic resin is performed by mixing the acrylic copolymer and the crosslinking agent with ketones such as methyl ethyl ketone, aromatic hydrocarbons such as xylene and toluene, ethyl acetate, butyl acetate and the like. By mixing them in a solution of an ester or an organic solvent such as a halogenated hydrocarbon such as trichloroethylene.

Examples of the cross-linking agent include amino resin-based cross-linking agents such as methylolated amino resins obtained by the reaction of an amino component such as melamine, urea, benzoguanamine, acetoguanamine, steloganamine, spiroguanamine, dicyandiamide and aldehyde, and toluylene-2. , 4-diisocyanate, toluylene-2,6-diisocyanate, diphenylmethane-4,4′-diisocyanate,
Aromatic, aliphatic and cycloaliphatic isocyanate-based crosslinking agents such as xylene diisocyanate, 1,5-naphthylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate can be used. The organic resin component used in the fiber treatment agent of the present invention, as a polymer substance containing silicone as a main component, hydrogen at the end, an alkyl group,
A product obtained by a dehydrocondensation reaction, a dealcoholization condensation reaction or an addition reaction of a silicone prepolymer having a hydroxyl group according to the following reaction formula can be used.

Dehydrocondensation reaction type

Embedded image Alcohol-free condensation reaction type

Embedded image Addition reaction type

Embedded image In the present invention, the fluoroalkyl group-containing oligomer is blended with the above-mentioned polymer substance containing a silicone prepolymer as a main component, and the catalyst containing the silicone prepolymer and a metal such as platinum, zinc, tin or the like is mixed with benzene, toluene, xylene or the like. Or a mixture thereof in a solution of an aromatic hydrocarbon or a halogenated hydrocarbon such as trichloroethylene or tetrachloroethylene alone or in a mixed solvent. When the mixed solution is processed into a fiber product, a silica-based reinforcing filler, a flame retardant, a moisture permeability improving agent, a coloring agent, and the like can be added as necessary. In addition, as the organic resin used in the fiber treating agent of the present invention, a polymer containing vinyl chloride as a main component, a chlorsulfonated polyethylene alone or a copolymer, or a mixture thereof can be used.
The compounding of the fluoroalkyl group-containing oligomer with these organic resin components is carried out by mixing these organic resin components with a solution obtained by dissolving the organic resin components in a solvent or kneading these organic resin components with an inorganic filler, a colorant or a plasticizer. It is performed by a method such as occasional addition. In the fiber treatment agent of the present invention,
The method of compounding the fluoroalkyl group-containing oligomer into the organic resin component is not particularly limited, as it may be uniformly dissolved or dispersed in the organic resin component. The most common mixing method is a stirring blade and a motor. And a mixing method that requires a shearing force such as a high-speed stirring / dispersing device, a bead mill, a ball mill, or the like. Further, the fluoroalkyl group-containing oligomer according to the present invention can be mixed and added to a commercially available organic resin-containing coating processing agent for fiber processing dissolved or dispersed in a solvent. Further, the fiber treatment agent of the present invention, if necessary,
Preservatives, stabilizers, coloring agents, pH adjusters and the like can also be added.

The method of applying the fiber treating agent combined with the elastomer to the fiber base fabric is performed by a usual coating method such as a floating knife coater, knife over roll coater, reverse roll coater, gravure coater, rotary screen, kiss roll coater and the like. Just do it. The method for wet coagulation film formation, the method for drying after coating, and the like may be conventionally performed in the same manner as in the case of processing using respective organic resin components. Also, it can be coated on release paper, transferred to a fiber base cloth, and laminated. In the use of the fiber treatment agent of the present invention,
The fluoroalkyl group-containing oligomer according to the present invention,
When added to a resin emulsion or an elastomer, the resin component such as the emulsion is uniformly dispersed in the resin emulsion or the like until the resin component is dried or cured. The fluoroalkyl group of the concerned fluoroalkyl group-containing oligomer moves to the surface of the resin component and is oriented due to the affinity of fluorine. This imparts functions such as water repellency and oil repellency and antifouling properties to the fiber. The fiber base fabric for processing the fiber processing agent of the present invention covers a wide range of materials such as chemical fibers such as nylon and polyester, natural fibers such as cotton and wool, and blends thereof.

Next, by using the paper treating agent of the present invention, oil repellency, stain resistance and the like can be imparted to the surface of the paper. In this case, the paper can be processed by an arbitrary method according to the material of the paper and the dosage form of the preparation. That is, the fluoroalkyl group-containing oligomer according to the present invention can be used by dissolving it in a solvent as it is, and high oil repellency and stain resistance can be imparted to paper products. The solvent that dissolves the fluoroalkyl group can be selected from water, methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, chloroform, ethyl acetate, dichloromethane, benzene, toluene, m-xylene, acetone, etc. I can do it. The paper treating agent of the present invention can be used in combination with other water repellents, oil repellents, anti-slip agents, surface strength improvers, sizing agents, flame retardants, and the like, if necessary.
As other water repellents and oil repellents, paraffin wax and synthetic products generally used for water repellency of paper can be used, and when used in combination with the fluoroalkyl group-containing oligomer according to the present invention, the water repellent and oil repellent are used. The oil resistance can be improved and the water resistance of the fluoroalkyl group-containing oligomer according to the present invention can be improved. Examples of the water repellent include water-soluble or emulsion-based polyethylene wax, paraffin wax or a metal salt thereof, silicone wax,
Fluorine resin emulsion, silicone resin emulsion, alkyl ethylene urea, N-methylol fatty acid amide and the like can be used alone or in combination. Examples of anti-slip agents include styrene-acrylic and styrene-maleic acid-based emulsion preparations and colloidal silica. Examples of the surface strength improver include starch, oxidized starch and modified products thereof, carboxymethyl cellulose, polyvinyl alcohol and polyacrylamide, and derivatives and modified products thereof.

The concentration of the fluoroalkyl group-containing oligomer according to the present invention is 0.5 to 2%.
The processing liquid is adjusted so that the paper is immersed in a tab size or the like, or the paper is applied by calender coating, coating using an off-machine coater or on-machine coater, or spray coating. After adhering to the surface, 90-15
It can be processed by drying at 0 ° C for 1 to 20 minutes. Further, an internal addition method in which paper is made by adding to and mixing with pulp is also possible. Paper products treated with the paper treating agent of the present invention include butter,
It can be widely used for general wrapping paper such as paperboard, hamburger, fried chicken and other wrapping paper used for containers of chocolate and the like, kraft paper, liner, cardboard base paper and the like. Next, the resin surface treatment agent of the present invention can be used for surface treatment of various resin products to impart antifouling property, water / oil repellency, heat resistance, chemical resistance and the like.

The resin surface treating agent of the present invention is combined with a synthetic resin component as a binder component in order to improve the water resistance, solvent resistance, abrasion resistance and adhesion of the fluoroalkyl group-containing oligomer according to the present invention. It is preferable to use it. Conventionally used elastomers can be used as the organic resin composition for the binder. The organic resin component of the elastomer is not particularly limited, and a known resin composition generally used conventionally, for example, a general-purpose resin such as a urethane resin and an acrylic resin, an acrylic urethane resin, a silicone-modified urethane resin, and a chloride resin Synthetic resins such as vinyl resin, epoxy resin, polyolefin-based resin, fluororesin, and polyester resin can be used, and two or more of these can be used in combination. Also,
The organic resin composition may be used not only for its role as a binder but also for its functions such as a tactile sensation improving effect, gloss control, heat resistance, and chemical resistance. The organic resin composition may be one dissolved or dispersed in an organic solvent, and the fluoroalkyl group-containing oligomer of the present invention may be dissolved in a compatible organic solvent and mixed and added. The organic solvent to be used can be widely selected from methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, chloroform, ethyl acetate, dichloromethane, benzene, toluene, m-xylene, acetone and the like.

The physical properties and the like of the organic resin component of the resin surface treating agent of the present invention are not particularly limited. However, when a resin product is treated with the resin surface treating agent of the present invention and then vacuum-formed, the 100% modulus value is 80kgf
/ Cm ² or less. If the 100% modulus exceeds 80 kgf / cm ² , it is not preferable because the elongation following property of the skin coating layer decreases during molding such as vacuum molding. The resin surface treatment agent of the present invention, if necessary,
Beads such as acrylic resin and urethane resin for imparting a suede touch feeling, etc., natural product powder such as collagen and cellulose or urea formalin resin powder, pigments and dyes for adjusting color tone, alkylphenol, alkylenebisphenol or alkylphenol. Antioxidants such as thioethers, ultraviolet absorbers such as phenyl salicylate, 2-hydroxyphenylbenzotriazole, 2-hydroxybenzophenone or 2-hydroxy-4-methoxybenzophenone, and other necessary amounts of stabilizers and plasticizers are added. You can do it. When used in combination with an organic resin composition, the mixing ratio of the fluoroalkyl group-containing oligomer according to the present invention with the organic resin composition is a treatment liquid that can be adhered to a substrate by a method using a resin surface treatment agent. Although it cannot be specified unconditionally because the amount is greatly different, the fluoroalkyl group-containing oligomer according to the present invention is preferably 0.01 to 15 parts by weight, more preferably 0.05 to 100 parts by weight of the solid content of the organic resin component. -10 parts by weight are added. Also, commercially available resin surface treatment agents in which an organic resin component is dissolved or dispersed in a solvent, for example, a surface used for surface treatment of PVC leather, PVC sheet, polyolefin resin sheet, PVC wallpaper, synthetic leather or artificial leather, etc. When using a treating agent or the like, the fluoroalkyl group-containing oligomer according to the present invention can be added and mixed for use.

The resin surface treating agent of the present invention can be applied to a wide range of resin products by known coating methods such as brush coating, spray coating, roll coating, gravure coating, knife coating, and dip coating. If necessary, a primer such as chlorinated polypropylene can be used as a primer before applying the resin surface treating agent of the present invention. Examples of resin products treated with the resin surface treating agent of the present invention include olefin resins, ABS resins, and AS resins used for home appliances, vehicle interior parts, stationery, furniture, other household goods, and the like.
Resin, resin molded products molded with vinyl chloride resin or urethane resin, olefin resin, polyester resin, various films or sheets made of vinyl chloride resin or urethane resin, vehicle interior materials and furniture, shoes, bags,
Examples include vinyl chloride leather used for stationery and the like, and polyurethane resin artificial leather and synthetic leather used for apparel and shoes, bags, vehicle interior materials, furniture, stationery and the like.

Further, the fluoroalkyl group-containing oligomer according to the present invention has amphiphilicity and surface tension lowering property, and imparts wettability, spreadability, fluidity, dispersibility and emulsifying property.
Since it has the effect of improving, it can be used as a surfactant in various fields. Specifically, emulsifiers for polymerization in the fields of plastics and rubber, stabilizers for latex, additives for controlling spreading and uneven coating,
It can be used as an emulsifier or dispersant for a wide variety of preparations such as toiletry products, agricultural chemicals, textile processing chemicals, paints, pigments, dyes, inks and the like.

The fluoroalkyl group-containing oligomer according to the present invention has a property of taking in metal ions such as calcium ions, and thus can be used as a metal ion scavenger. Specifically, bleaching and dyeing in the textile industry, refining process of metals such as calcium ions, magnesium ions, manganese ions, and copper ions that inhibit the finish,
Removal in the bleaching and dyeing processes, removal of metals such as iron, copper, manganese, aluminum and calcium ions that cause bleaching instability, color reversion and pitch troubles in the paper and pulp industries, rubber・ Used in the metal industry such as copper ion, manganese ion, iron ion, and zinc ion, which cause decay, coagulation, and precipitation of fats and amino acids in rubber latex in the polymer industry, and in the electronic materials and photographic industries. It can be used for removing calcium ions and magnesium ions from washing water and the like, or for removing calcium ions from contact lens washing liquid. In this case, the amount of the fluoroalkyl group-containing oligomer according to the present invention to be used cannot be specified unconditionally because it is used in accordance with the metal ion concentration of the target solution from which metal ions are to be removed. The alkyl group-containing oligomer is water, methanol,
It is soluble in a wide range of solvents such as ethanol, tetrahydrofuran, dimethylsulfoxide, dimethylformamide, chloroform, ethyl acetate, dichloromethane, benzene, toluene, m-xylene, and acetone, so select from these solvents according to the purpose of use. May be used by dissolving in a solvent to be used.

[0027]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

(Synthesis Example 1) Diperfluoro-2-peroxide
3.29 g (5 mmol) of methyl-3-oxahexanoyl was added to AK
-225 (1,1-dichloro-2,2,3,3,3-pentafluoropropane: 1,3-dichloro-1,2,2
2,3,3-pentafluoropropane = 1: 1.35 dissolved in 21 g of Asahi Glass Co., Ltd.
9 g (24 mmol) dissolved in 70 g of AK-225 was added, and the mixture was stirred at 45 ° C. for 5 hours under a nitrogen stream. After the completion of the reaction, the concentrate from which the reaction solvent was removed was purified by a reprecipitation method using AK-225 and hexane, then the solvent was removed, and the residue was dried under vacuum to obtain 4.6 g of a purified product. The purified product was analyzed by IR, ¹ H-NMR and ¹⁹ F-NMR, and the results are shown in Table 1. This purified product was a fluoroalkyl group-containing oligomer having a compound represented by the following structural formula (L) as a constituent unit.

Embedded image

[Table 1]

(Synthesis Example 2) Diperfluoro-2-peroxide
5 mmol of methyl-3-oxahexanoyl was added to 7 mmol (6.93 g) of diperfluoro-2,5-dimethyl-3,6-dioxananoyl peroxide and 24 mmol of acroylmorpholine.
Was changed to 37 mmol (5.22 g).
The reaction was carried out in the same manner as described above, and R _{F of the} general formula (A) was -CF
6.9 g of a fluoroalkyl group-containing oligomer having a compound represented by (CF ₃ ) OCF ₂ CF (CF ₃ ) OC ₃ F ₇ was obtained. The number average molecular weight of this purified product was 4730
Met.

(Synthesis Example 3) Diperfluoro-2-peroxide
5 mmol of methyl-3-oxahexanoyl was added to 5 mmol (6.61 g) of diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecinoyl peroxide, and the reaction solvent was added to the same amount of benzotrifluoride. , Except for each,
The reaction was carried out in the same manner as in Synthesis Example 1 to obtain R of the above general formula (A).
_F is _{-CF (CF 3) O (CF} 2 CF (CF 3) O) 2 C 3 F
6.0 g of a fluoroalkyl group-containing oligomer having the compound represented by ₇ as a constitutional unit was obtained. The number average molecular weight of this purified product was 7,290.

(Synthesis Example 4) Diperfluoro-2-peroxide
The reaction was carried out in the same manner as in Synthesis Example 1 except that 5 mmol of methyl-3-oxahexanoyl was replaced with 5 mmol (2.13 g) of diperfluorobutyryl peroxide, and R _{F of the} general formula (A) was C
₃ was obtained a fluoroalkyl group containing oligomer 4.7g of a constitutional unit of a compound represented by F _7. The number average molecular weight of this product was 1700.

(Synthesis Example 5) 5 mmol of diperfluorobutyryl peroxide was added to 5 mmol of diperfluoroheptanoyl peroxide
(3.63 g), the reaction was carried out in the same manner as in Synthesis Example 4 except that the reaction solvent was replaced with the same amount of bis (trifluoromethyl) benzene, and the R _{F of the} general formula (A) was C ₆ F 5.8 g of a fluoroalkyl group-containing oligomer having the compound represented by ₁₃ as a constitutional unit was obtained.

Synthesis Example 6 Diperfluorobutyryl peroxide (5 mmol) was converted to diperfluorooctanoyl peroxide (5 mmol).
(4.13 g) in 30 mmol of acroylmorpholine
(4.24 g), except that each was replaced, the reaction was carried out in the same manner as in Synthesis Example 4 to obtain a fluoroalkyl group-containing oligomer having a compound represented by the above formula (A) in which R _F is represented by C ₇ F _15. 5.0 g were obtained.

(Example 1) Fiber treatment agent Butyl acrylate, ethyl acrylate, acrylonitrile and 2-hydroxymethacrylate were copolymerized in a weight ratio of 60: 28: 10: 2, respectively, and dissolved in toluene. Solid content 22%, viscosity 40,00
A solution A of 0 cps was prepared. To 100 parts by weight of this solution A, 1 part by weight of the fluoroalkyl group-containing oligomer of Synthesis Example 1 dissolved in 10 parts by weight of dimethylformamide was added and mixed to prepare a fiber treating agent solution B. Separately, n
-Butanol: xylene = 3: 2 (weight ratio) mixed solution, 50% of amino resin based crosslinking agent 2,4,6-tri (N-methoxymethyl, N-methyl) amino-1,3,5-triazine A solution C and a 50% solution D of a cross-linking catalyst alkylbenzenesulfonic acid were prepared with isopropyl alcohol. The solutions B, C, D and toluene were each in a weight ratio,
100: 1: 0.4: 15 was mixed at a ratio of 1 to prepare a coating solution, and 50 g / m ² was calendered in advance (conditions: temperature 170 ° C., pressure 30 kg / cm). Warp: 120 yarns / inch of 70 denier yarn, weft: 90 yarns / inch of 70 denier yarn) using a floating knife coater. After application, 1
After drying at 10 ° C. for 1 minute and further heating at 160 ° C. for 1 minute, an acrylic resin-based processed cloth was obtained.

(Example 2) Fiber treatment agent The same operation as in Example 1 was performed except that the fluoroalkyl group-containing oligomer of Synthesis Example 1 in Example 1 was replaced with the fluoroalkyl group-containing oligomer of Synthesis Example 5. Thus, an acrylic resin-based cloth was obtained.

Comparative Example 1 Fiber Treatment Agent A solution E was prepared by adding 10 parts by weight of toluene to 100 parts by weight of the solution A of Example 1. The solution B in the preparation of the coating solution 1 of Example 1 was replaced with the solution E instead of the solution E.
Was prepared in the same manner as in Example 1 except that was prepared.

(Effect Example 1) The water repellency and oil repellency of the processed cloth and the untreated calender-treated cloth obtained in Examples 1 and 2 and Comparative Example 1 were evaluated. The results are shown in Table 3. Each evaluation method is shown below. Water repellency: Performed based on JIS L-1092 (92) spray test method. The water repellency was represented by the following water repellency score of 50 to 100 points. 50 points: the whole surface was wet. 70 points: Half of the surface wet, usually small individual wets penetrating the cloth. 80 points: Small individual droplet-like wetness on the surface. 90 points: those that do not wet the surface but have small water droplets attached. 100 points: No wet or water droplets adhered to the surface. Oil repellency: A few drops of the test solution shown in Table 2 were placed at two places on the test-treated paper and discriminated by the permeation state after 30 seconds (AAT)
CC-TM118-1966).

[0038]

[Table 2]

[0039]

[Table 3]

Example 3 Fiber treatment agent A polybutylene obtained by polycondensation of 1,4-butanediol and adipic acid was placed in a 300 cc flask equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser. 40.0 g of adipate, 9.0 g of diphenylmethane-4,4'-diisocyanate and the antioxidant Irganox 1
010 (manufactured by Ciba Geigy) and 20.0 g of dimethylformamide were charged, and the mixture was reacted for 1 hour while maintaining the solution temperature at 60 ° C. while stirring under a nitrogen stream. 4
The mixture was cooled to 0 ° C., and a mixed solution of 1.0 g of ethylene glycol and 5.0 g of dimethylformamide was uniformly dropped over about 1 hour. Further, the reaction temperature was raised to 80 ° C. and 25.0 g
The stirring was continued for 10 hours while adding toluene in three portions each time the solution viscosity increased. n-butanol
1 g was dissolved in 20.0 g of dimethylformamide and added. After confirming that the viscosity of the reaction solution did not increase,
2 g of the fluorosilicone oligomer of Synthesis Example 1 was diluted and added to 15.0 g of dimethylformamide, and stirring was stopped to obtain a fiber treating agent solution F. To 100 parts by weight of the solution F, 3.5 parts by weight of an isocyanate crosslinking agent Coronate L (manufactured by Nippon Polyurethane Industry Co., Ltd.) and 20 parts by weight of methyl ethyl ketone were added to prepare a coating solution, which was previously calendered (condition: 170 ° C. temperature). , Pressure 30kg / c
m) Polyester plain woven fabric (290 weft yarns / 30 denier yarns / inch) was applied using a floating knife coater. After the application, the coating was dried at 120 ° C. for 2 minutes, and further heated at 160 ° C. for 1 minute to obtain a urethane resin-based processed cloth.

Example 4, Effect Example 2 Fiber treatment agent The fluoroalkyl group-containing oligomer of Synthesis Example 5 was dissolved in tetrahydrofuran to prepare a 1% dilution. Immerse the refined cotton cloth for 1 minute in this solution (80% squeezing rate)
After that, it was air-dried in a draft. 0.5 ml each of salad oil was attached to the processed cloth and the cotton cloth before processing using a dropper and left in a constant temperature and humidity room at 20 ° C. and a relative humidity of 65% for one week. JIS L-02
After washing according to No. 17 (103 method), the degree of oil stain was compared. As a result, the cloth treated with the fluoroalkyl group-containing oligomer of Synthesis Example 5 had no trace of stain on salad oil, whereas the stain on salad oil of unprocessed cotton cloth clearly remained. The soil release function of the fiber treatment agent was confirmed.

Example 5 Fiber treatment agent The fluoroalkyl group-containing oligomer prepared in Synthesis Example 1 was dissolved in water to form a 1% solution, and 40 parts of this solution was added to a commercially available acrylic resin emulsion RI-637 (non-volatile). Min 4
5%, 10 parts of Takamatsu Oil & Fat Co., Ltd.) and 50 parts of water were added and mixed to prepare a fiber treatment liquid. After immersing nylon taffeta in this treatment liquid for 3 minutes, the mixture was squeezed with a mangle roll to a squeezing ratio of 100%, and then dried at 110 ° C. for 5 minutes. This treated cloth after drying was confirmed to have water repellency and oil repellency.

(Example 6, Effect Example 3) Paper Treatment Agent Each of the fluoroalkyl group-containing oligomers of Synthesis Examples 1 and 4 to 6 was dissolved in tetrahydrofuran at 1% to prepare a paper treatment agent. Next, this solution was impregnated with non-size kraft paper (basis weight 70 g / m ² ) at an impregnation rate of 90% using a size press machine, and then dried at 100 ° C. for 30 seconds. After leaving the treated paper in a constant temperature and humidity room at 20 ° C. and a relative humidity of 65% overnight, the oil repellency was evaluated. The oil repellency was evaluated by the following method, and the results are shown in Table 4. Oil repellency evaluation method: A few drops of the test solution shown in Table 2 above were placed on two places on the test paper, and discrimination was made based on the permeation state after 30 seconds (AATCC-TM118-1966).

[0044]

[Table 4]

Example 7, Effect Example 4 Resin Surface Treatment Agent The fluoroalkyl group-containing oligomers of Synthesis Examples 1 and 6 were each dissolved in tetrahydrofuran at a concentration of 1%.
A polyethylene terephthalate film previously immersed in methanol for 2 hours and degreased was immersed in this solution for 1 minute, and then dried by heating at 100 ° C. for 10 minutes. For the purpose of determining the oil repellency, the contact angle of this treated film with respect to dodecane was measured, and is shown in Table 5. As a comparative control, the contact angle with respect to dodecane of the polyethylene terephthalate film subjected to only the degreasing treatment was measured.

[0046]

[Table 5]

(Example 8) Resin surface treating agent N, N-dimethylformamide / methyl ethyl ketone =
A polyether type polyurethane resin having a 100% modulus of 30 kgf / cm ² and an elongation of 800% was dissolved in a 30/70 (% by weight) mixed solvent at a concentration of 16.5% by weight. To 100 parts of this solution, 10 parts of a solution obtained by dissolving the fluoroalkyl group-containing oligomer of Synthesis Example 1 in N, N-dimethylformamide at 3.3% by weight was added to prepare a resin surface treating agent. Using a gravure coater (120 mesh), the resin surface treating agent was applied twice to a 0.5 mm thick vinyl chloride sheet kneaded with a white pigment and dried at 80 ° C. for 30 seconds to obtain a surface treated chloride. A vinyl sheet was produced.

(Example 9) Resin surface treatment agent The same operation as in Example 8 was performed, except that the fluoroalkyl group-containing oligomer of Synthesis Example 1 in Example 8 was replaced with the fluoroalkyl group-containing oligomer of Synthesis Example 5. A surface-treated vinyl chloride sheet was produced.

Comparative Example 2 Resin Surface Treatment Agent The polyether-type polyurethane resin used in Example 8 was mixed with a mixed solvent of N, N-dimethylformamide / methyl ethyl ketone = 30/70 (% by weight) at 15.0% by weight. At a concentration of. This is a gravure coater (1
20 mesh), and applied twice to a 0.5 mm thick vinyl chloride sheet kneaded and colored with white pigment.
It dried at 30 degreeC for 30 second, and produced the surface-treated vinyl chloride sheet.

(Effect Example 5) The antifouling properties of the surface-treated PVC sheets produced in Examples 8 and 9 and Comparative Example 2 were evaluated by the following method. The results are shown in Table 6. Antifouling evaluation: On a treated PVC sheet, black oil-based ink pen (manufactured by Magic Ink Co., Ltd., large type), black ballpoint pen (Zebra Co., No. 5000), red crayon (Sakura Crepas Co., Ltd.) 1c with black water-based felt-tip pen (P520, S520) and coffee liquid
An m-width line was drawn. After standing at room temperature for 24 hours, the black oil-based ink pen, black ball-point pen and red crayon were wiped with a cloth soaked with ethanol, and the black aqueous felt-tip pen and coffee liquid were wiped with a cloth soaked with a neutral detergent diluted with water. went. The degree of dirt after the wiping operation was evaluated on the following five levels. Stain resistance index 5: Stain can be completely removed. ４ 4: Slight traces of dirt remain. ３3: Dirt can be removed to some extent, but remains clearly. 〃2: Dirt can be slightly removed. １ ： 1: Dirt can hardly be removed.

[0051]

[Table 6]

(Effect Example 6) Surfactant effect (surface tension lowering property) Aqueous solution of fluoroalkyl group-containing oligomer prepared in Synthesis Examples 1, 3, and 4, and fluoroalkyl group-containing oligomer prepared in Synthesis Examples 2 and 3 M-xylene solution was prepared, and the surface tension at 30 ° C. was measured by the Wilhelmy method (using an ST-1 model manufactured by Shimadzu Corporation; the gas phase was air). The results are summarized in Table 7. As Comparative Control Example M, an aqueous solution of a homoyl oligomer of acroylmorpholine represented by the following structural formula (M) (number average molecular weight Mn = 3750, Mw / Mn = 1.99) was prepared, and the surface tension was measured.

Embedded image

[0053]

[Table 7]

(Effect 7) Calcium ion absorption ability The ability of the fluoroalkyl group-containing oligomer prepared in Synthesis Examples 1 and 4 to take in calcium ions in an aqueous solution was measured by the following method. Calibration curve preparation: Measure the electromotive force of a standard solution of an aqueous solution of calcium chloride with a known concentration using a calcium ion electrode (pH / ion meter: using F-23 type manufactured by Horiba, Ltd.) to determine the electromotive force versus the concentration. Create a calibration curve for Since potassium chloride is used as an ionic strength regulator at that time, the standard solution of the calcium chloride aqueous solution was prepared by dissolving calcium chloride in a 0.1 mol / L aqueous solution of potassium chloride. Preparation of test solution: The fluoroalkyl group-containing oligomers of Examples 1 and 4 were added to a 0.1 mol / L aqueous solution of potassium chloride in an amount of 0.5%.
Dissolve at a concentration of g / L. Measurement: Calcium chloride was added in a variable amount to the test solution, and the electromotive force at the calcium ion electrode at each concentration was measured in the same manner as when the calibration curve was prepared. The difference is the amount of calcium ions incorporated into the oligomer. The calcium ion uptake ability of the fluoroalkyl group-containing oligomer of the present invention is determined by comparing calcium ion (Ca ²⁺ ) and morpholino group (Mo) in the oligomer.
It was determined as a ratio of two (Ca ²⁺ / 2Mo), and the results are summarized in Table 8. An aqueous solution of acroylmorpholine (a reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was used as Comparative Control Example N, and a homo-oligomer of acroylmorpholine represented by the structural formula (M) (number average molecular weight Mn = 37) was used as Comparative Control Example M.
50, an aqueous solution of Mw / Mn = 1.99) was prepared, and the calcium ion uptake ability was measured.

[0055]

[Table 8]

[0056]

The fluoroalkyl group-containing oligomer according to the present invention is a novel compound and exhibits amphipathic solubility in water and most common organic solvents. In addition to the same excellent oil repellency, surface tension lowering properties, heat resistance, cold resistance, oil resistance, chemical resistance, and mold release properties as the conventional fluoroalkyl group-containing oligomers, it also has hydrophilic properties. Have. Therefore, the functional additive of the present invention has a high effect as a fiber treatment agent, a paper treatment agent, and a resin surface treatment agent. In addition, the fluoroalkyl group-containing oligomer according to the present invention has the ability to absorb metal ions and has a high effect of lowering the surface tension. Therefore, the function-imparting agent of the present invention can be used as a metal ion absorbent or a surfactant. Has a high effect.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location // C09D 139/04 PGL D06M 13/42

Claims (7)

[Claims] 1. A function-imparting agent comprising a fluoroalkyl group-containing oligomer represented by the following general formula (1). Embedded image Wherein the _{R F - (CF 2) n} F, or, -CF (CF
_{3) O (CF 2 CF (} CF 3) O) m C 3 F 7 ( wherein, n 1
An integer of 0 to 15, m represents an integer of 0 to 6), and x represents a natural number. 2. The functionalizing agent according to claim 1, which is a fiber treating agent. 3. The functionalizing agent according to claim 1, which is a paper treating agent. 4. The functionalizing agent according to claim 1, which is a resin surface treating agent. 5. The function-imparting agent according to claim 1, which is a surfactant. 6. The function-imparting agent according to claim 1, which is a metal ion absorbent. 7. The method according to claim 1, wherein R _{F in the} general formula (1) is C ₃ F ₇ ,
₆ F _13, C ₇ F ₁₅ or _{-CF (CF 3) O (CF} 2 C
The function-imparting agent according to claim 1, wherein F (CF ₃ ) O) _m C ₃ F ₇ (m = 0, 1, 2).