JPH107738A - Fluoroalkylated function modifier - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a function modifier comprising a specified fluoroalkylated oligomer, having amphipathic properties and both oil repellency and hydrophicity possessed by the oligomer and a surface tension lowering action important as a surface, and being highly able to incorporate ions of a metal. SOLUTION: This modifier comprises a fluoroalkylated oligomer represented by the formula: [wherein Rf is a 1-25C fluoroalkyl which may be interrupted by an oxygen atom; Z is trimethylene or tetramethylene; and x and y are each 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)n C3 F7 (wherein n is an integer of 0-6), and Z is trimiethylene. Examples of the modifier include a textile processing agent, a paper processing agent, a resin surface treating agent, a surfactant, and a metal ion absorber. The number-average molecular weight of this oilgomer is desirably in the range of 500-10,000.

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, but a novel fluoroalkyl group-containing oligomer as shown in the present invention, and its novel properties and usefulness, Little is known.

[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.

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 dissolving in water or a polar organic solvent and to be easy to use, and to have both high oil repellency and hydrophilicity and a surface tension lowering 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 may be interrupted by an oxygen atom, and has 1 carbon atom.
-25 represents a fluoroalkyl group, Z represents trimethylene or tetramethylene, and x and y represent natural numbers]

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The fluoroalkyl group-containing oligomer in the present invention is a fluoroalkyl group-containing oligomer represented by the general formula (A), wherein R _{F in} formula A may be interrupted by an oxygen atom, and has 1 to 25 carbon atoms. Group,
The fluoroalkyl group of cases may be linear or branched, preferably - (CF ₂₎ a perfluoroalkyl group represented by _m F _(m = _1~15 integer) or -CF,
_{(CF 3) O (CF 2} CF (CF 3) O) n C 3 F 7 (n = 0
(An integer of from 6 to 6). When m is 16 or more or n is 7 or more, the solubility of the corresponding fluoroalkanoyl peroxide in the corresponding solvent is poor, and the production becomes difficult, which is not preferable.
R _F is particularly perfluoropropyl group, a perfluorohexyl group and a perfluoroheptyl group, -CF (CF ₃₎ O
_{C 3 F 7, -CF (CF} 3) O (CF 2 CF (CF 3) O
C ₃ F ₇ and _{-CF (CF 3) OCF 2 CF} (CF 3) O
Preferred is CF ₂ CF (CF ₃ ) OC ₃ F ₇ .

The fluoroalkyl group-containing oligomer according to the present invention is represented by the general formula (A). The value of x / (x + y) ranges from 0.10 to 0.90, preferably from 0.1 to 0.90.
35 to 0.75. If it is less than 0.10 or more than 0.90, the function of the functionality-imparting agent of the present invention such as the ability to take in calcium ions decreases, which is not preferable. Further, the number average molecular weight Mn of the fluoroalkyl group-containing oligomer in the present invention is preferably in the range of 500 to 10,000. If the Mn is less than 500 or more than 10,000, production becomes difficult. In the fluoroalkyl group-containing oligomer represented by the general formula (A) of the present invention, a fluoroalkyl group R _F may contain a fluoroalkyl group containing oligomer introduced only at one end.

[0011] In the present invention, the fluoroalkyl group-containing
The production of ligomers is based on certain fluoroalkanoyl peroxides.
And acrylic acid and N-vinyl-2-pyrrolidone or N
-Possible by reacting vinyl-2-piperidone
It is. Fluoroalkyl group-containing oligo in the present invention
The fluoroalkanoyl peroxide used in the production of
A fluoroalkanoyl represented by the following general formula (B)
You.

Embedded image In the formula B, R _F may be interrupted by an oxygen atom and has 1 carbon atom.
-25 fluoroalkyl groups. Specific examples of fluoroalkanoyl peroxide include diperfluorobutyryl peroxide (structural formula C), diperfluoro-2-methyl-3-oxahexanoyl peroxide (structural formula D), and diperfluoro-2,5 peroxide. -Dimethyl-3,6-dioxanonanoyl (structural formula E) and the like are preferred.

Embedded image

Embedded image

Embedded image In the production of the fluoroalkyl group-containing oligomer in the present invention, fluoroalkanoyl peroxide and acrylic acid and N-vinyl-2-pyrrolidone or N-vinyl-2
-The range of the charged amount when reacting piperidone is 7.0 to 15.0 m of fluoroalkanoyl peroxide.
ol% is preferred. The molar ratio of the charged acrylic acid and N-vinyl-2-pyrrolidone or N-vinyl-2-piperidone is preferably from 1: 0.4 to 1.2.

The reaction can be carried out at normal pressure, and the reaction temperature is preferably in the range of -20 to + 150 ° C, particularly preferably in the range of 0 to + 100 ° C. If the reaction temperature is lower than −20 ° C., the reaction requires a long time, and if it exceeds + 150 ° C., the pressure during the reaction increases, and the reaction operation becomes difficult. Further, the reaction can be carried out at a reaction temperature in the range of 0.5 to 20 hours, and is desirably industrially in the range of 3 to 10 hours. In the method for producing a fluoroalkyl group-containing oligomer according to the present invention, by reacting the fluoroalkanoyl peroxide with acrylic acid and N-vinyl-2-pyrrolidone or N-vinyl-2-piperidone under the various reaction conditions, Although a desired fluoroalkyl group-containing oligomer can be obtained by a one-step reaction, it is preferable to use a solvent in order to handle and react the fluoroalkanoyl peroxide more smoothly. As the solvent,
Halogenated aliphatic solvents and halogenated aromatic solvents are particularly preferred. Specifically, for example, methylene chloride, chloroform, carbon tetrachloride, 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.), 2-chloro-
1,2-dibromo-1,1,2-trifluoroethane,
1,2-dibromohexafluoropropane, 1,2-dibromotetrafluoroethane, 1,1-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-2,3,3-trichlorobutane, 1,1,1,
3-tetrachlorotetrafluoropropane, 1,1,1
-Trichloropentafluoropropane, 1,1,2-trichloropentafluoroethane and the like, hexafluorobenzene, benzotrifluoride, bis (trifluoromethyl) benzene and the like can be used.
K225 (manufactured by Asahi Glass Co., Ltd.) is preferred. When the solvent is used, the concentration of the fluoroalkanoyl peroxide (B) in the reaction solvent is desirably 0.5 to 30% by weight. Further, two or more kinds of solvents may be used as a mixture. The reaction product obtained by the above production method can be purified by a known method such as column chromatography, reprecipitation, or dialysis.

The fiber treating agent of the present invention is a water-soluble or water-dispersible other resin component commonly used for padding and water-based coating of the fluoroalkyl group-containing oligomer according to the present invention as described below. By combining with, durable water and oil repellency can be obtained. That is, various emulsion types 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. Acrylic resin emulsion used as a mold resin binder, 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 mixing with various resin components such as urethane emulsion for water-based sueding and rebound resilience, and W / 0 type urethane emulsion used for moisture permeable and 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 dissolves in water, it can be easily mixed with the 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.

Further, as the fiber treating agent of the present invention, an elastomer generally used for coating or laminating as an organic resin component to which the fluoroalkyl group-containing oligomer according to the present invention is added can be selected. 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, since the fluoroalkyl group-containing oligomer according to the present invention dissolves in a wide range of solvents such as methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, chloroform, dichloromethane, ethyl acetate, and acetone, the above-mentioned organic compound can be easily prepared. It can be mixed with resin components. 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, a hydroxyl group or a carboxyl group-containing ethylenically unsaturated monomer copolymer can be used. As an example, an ethylenically unsaturated monomer having no hydroxyl group and no carboxyl group represented by the following formula (F) is 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 (G).

Embedded image [In the formula F, R ₁ is hydrogen or an alkyl group having 1 to 2 carbon atoms, R ₂ 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 G, R ₃ represents hydrogen, an alkyl group or a carboxyalkyl group, R ₄ represents a hydrogen or a carboxyl group, R ₅ 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 (F) or (G) 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 unit hydrogen such as xylene and toluene, ethyl acetate, and butyl acetate. This is carried out by mixing or dispersing in a solution dissolved in an organic solvent such as an ester or a halogenated hydrocarbon such as trichloroethylene.

Examples of the cross-linking agent include amino resin-based cross-linking agents such as methylolated amino resin obtained by reacting an aldehyde with an amino component such as melamine, urea, benzoguanamine, acetoguanamine, steloguanamine, spiroguanamine, dicyandiamide, 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 treating agent of the present invention may be a high molecular substance containing silicone as a main component.
A product obtained by a dehydrocondensation reaction, a dealcoholization condensation reaction or an addition reaction of a silicone prepolymer having a hydrogen, an alkyl group or a hydroxyl group at a terminal by 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. This is carried out by mixing or dispersing 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 into these organic resin components is as follows:
It is carried out by a method of mixing or dissolving or mixing and dispersing these organic resin components in a solution in which a solvent is dissolved, or a method of adding these organic resin components when kneading with an inorganic filler, a coloring agent or a plasticizer. In the fiber treating agent of the present invention, the method of blending the fluoroalkyl group-containing oligomer into the organic resin component is not particularly limited since the method may be such that it is uniformly dissolved or dispersed in the organic resin component. In addition to the mixing method, which can be performed by rotating and mixing with a stirring blade and a motor, the mixing can also be performed by a mixing method that applies a shearing force such as a high-speed stirring disperser, a bead mill, a ball mill, or the like.

It is also possible to mix and add a fluoroalkyl group-containing oligomer according to the present invention to a commercially available organic resin-containing coating agent for fiber processing dissolved or dispersed in a solvent. Further, the fiber treating agent of the present invention may optionally contain a preservative, a stabilizer, a coloring agent, a pH adjuster, and the like. The method of applying the fiber treating agent combined with the elastomer to the fiber base fabric may be performed by a usual coating method such as a floating knife coater, a knife over roll coater, a reverse roll coater, a gravure coater, a rotary screen, a kiss roll coater, and the like. . The method for wet coagulation film formation, the method for drying after coating, and the like may be performed in the same manner as in the case of processing using the 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 treating agent of the present invention, the fluoroalkyl group-containing oligomer according to the present invention may be added to a resin emulsion or an elastomer or the like until the resin component such as the emulsion is dried or cured. When the resin component such as an emulsion is dried or cured, the fluoroalkyl group of the fluoroalkyl group-containing oligomer according to the present invention moves to the surface of the resin component due to the affinity of fluorine. Orient. 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 includes synthetic fibers such as nylon and polyester, cotton, and the like.
It covers a wide range of natural fibers such as wool and their blends. 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. Solvents that dissolve the fluoroalkyl group include water, methanol, ethanol,
It can be selected from tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, chloroform, ethyl acetate, dichloromethane, acetone and the like.

The paper treating agent of the present invention may optionally contain other water repellents, oil repellents, anti-slip agents, surface strength improvers, sizing agents,
It is also possible to use a flame retardant or the like in combination. 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-based wax, fluorine-based resin emulsion, silicone-based resin emulsion, alkylethylene urea, N-methylol fatty acid amide, or the like alone or Can be mixed and used. 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. In the paper treating agent of the present invention, 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 or dispersed in an organic solvent and mixed and added. The organic solvent used can be widely selected from methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, chloroform, ethyl acetate, dichloromethane, acetone and the like.

The physical properties and the like of the organic resin component of the resin surface treatment agent of the present invention are not particularly limited. However, when a resin product is treated with the resin surface treatment 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, natural product powder such as collagen and cellulose or urea formalin resin powder, pigments and dyes for adjusting color tone, gloss adjuster, alkylphenol, alkylenebisphenol Or alkylphenol
Antioxidants such as thioether, phenyl salicylate,
UV absorbers such as 2-hydroxyphenylbenzotriazole, 2-hydroxybenzophenone or 2-hydroxy-4-methoxybenzophenone, as well as stabilizers and plasticizers can be added in necessary amounts. 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. Since the amount is greatly different, it cannot be specified unconditionally, but the solid content of the organic resin component is 100%.
The fluoroalkyl group-containing oligomer according to the present invention is added in an amount of preferably 0.01 to 15 parts by weight, more preferably 0.05 to 10 parts by weight, relative to parts by weight.

A commercially available resin surface treating agent in which an organic resin component is dissolved or dispersed in a solvent, for example, used for surface treatment of PVC leather, PVC sheet, polyolefin resin sheet, PVC wallpaper, synthetic leather or artificial leather. It is also possible to add and mix the fluoroalkyl group-containing oligomer according to the present invention when using a surface treatment agent or the like to be used or a paint or the like used for a plastic molded product. The resin surface treatment agent of the present invention, brush coating,
A wide variety of resin products can be surface-treated by known coating methods such as 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 thereof include vinyl chloride leather used for stationery and the like, and urethane resin artificial leather and synthetic leather used for apparel and shoes, bags, vehicle interior materials, furniture, stationery and the like.

The fluoroalkyl group-containing oligomer according to the present invention has amphiphilicity and surface tension lowering properties and imparts wettability, spreadability, fluidity, dispersibility, and emulsifying properties.
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. Further, 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 of metals such as calcium ions, magnesium ions, manganese ions, and copper ions that hinder the finish, bleaching, removal in the dyeing process,
Removal of metals such as iron ion, copper ion, manganese ion, aluminum ion and calcium ion which cause bleaching instability, color return, pitch trouble, etc. in paper and pulp industry, and fat of rubber latex in rubber and polymer industry Metals, such as copper ions, manganese ions, iron ions, and zinc ions, which cause decay, coagulation, and precipitation of amino acids, etc., and calcium ions and magnesium from washing water used in electronic materials and the photo industry. It can be widely used for removing metal components of ions or removing calcium ions from a contact lens cleaning solution. 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, ethanol, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, chloroform, ethyl acetate, dichloromethane,
Since it is dissolved in a wide range of solvents such as acetone, it may be dissolved in a solvent selected from these solvents according to the purpose of use.

[0028]

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) AK-225 containing 5 mmol of diperfluoro-2-methyl-3-oxahexanoyl peroxide in 24 mmol of acrylic acid and 24 mmol of N-vinyl-2-pyrrolidone
(1,1-dichloro-2,2,3,3,3-pentafluoropropane: 1,3-dichloro-1,2,2,3,3
-Pentafluoropropane = 1: 1.35 Asahi Glass Co., Ltd.)
90 g of the solution was added and reacted at 40 ° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solvent was removed by suction filtration, and the product was sufficiently washed with hexane. Thereafter, vacuum drying with heating at 40 to 50 ° C. for 24 hours was performed to remove the solvent and the like. The yield was 46%. The molecular weight of the obtained product was measured by gel permeation (hereinafter abbreviated as GPC) (in terms of polystyrene). As a result, Mn = 1080, Mw / Mn = 1.52 (where Mn is the number average molecular weight and Mw is the weight average molecular weight) And analyzed by infrared spectroscopy (hereinafter abbreviated as IR) and nuclear magnetic resonance (abbreviated as ¹ H-NMR and ¹⁹ F-NMR) (see below). It was a fluoroalkyl group-containing oligomer having the indicated compound as a constitutional unit. The analysis results are shown below. Table 1 shows the ratios of x and y in the structural formula L from the results of ¹ H-NMR analysis (hereinafter, the ratios of x and y up to Synthesis Example 7 are similarly shown).

IR (cm ^-1 ): 3453 (OH), 1722 (C = O), 16
47 (C = O), 1296 (CF ₃ ), 1238 (CF ₂ ) ¹ H-NMR (D ₂ O) δ: 1.58 to 2.58 (CH ₂ , CH), 3.2
8 to 3.69 (CH ₂ ) ¹⁹ F-NMR (D ₂ O _, ext.CF ₃ COOH) δ: −5.89 to −7.13 (1
6F), -57.54 (6F)

Embedded image (In the formula, R _F is CF (CF ₃ ) OC ₃ F _7. )

(Synthesis Example 2) The reaction and synthesis were carried out in the same manner as in Synthesis Example 1 except that 24 mmol of acrylic acid, 14 mmol of N-vinyl-2-pyrrolidone and 5 mmol of diperfluoro-2-methyl-3-oxahexanoyl peroxide were used. Purification was performed. Yield was 52%. The obtained product was analyzed by GPC. As a result, Mn was 1070, Mw / Mn was 1.47, and IR,
As a result of analysis by ¹ H-NMR and ¹⁹ F-NMR,
It was a fluoroalkyl group-containing oligomer having the compound represented by Structural Formula H as a constituent unit. (Where R _F is CF
(CF ₃ ) OC ₃ F ₇ . )

(Synthesis Example 3) The fluoroalkanoyl peroxide was changed to 37 mmol of acrylic acid and 37 mmol of N-vinyl-2-pyrrolidone to obtain diperfluorobutyryl peroxide.
The reaction and purification were carried out in the same manner as in Synthesis Example 1 except that the amount was changed to mmol. The yield was 24%. The obtained product was analyzed by GPC, and as a result, Mn = 1130 and Mw / Mn = 1.80. The product was analyzed by IR, ¹ H-NMR, and ¹⁹ F-NMR. The oligomer was a fluoroalkyl group-containing oligomer having the compound as a structural unit. (Where
R _F is CF _3. )

(Synthesis Example 4) Fluoroalkanoyl peroxide was converted to diperfluorobutyryl peroxide by changing to 27 mmol of acrylic acid and 22 mmol of N-vinyl-2-pyrrolidone.
The reaction and purification were carried out in the same manner as in Synthesis Example 1 except that the amount was changed to mmol. The yield was 36%. The obtained product was analyzed by GPC and found to have Mn = 2000 and Mw / Mn = 1.42. The product was analyzed by IR, ¹ H-NMR, and ¹⁹ F-NMR, and as a result, represented by Structural Formula H The oligomer was a fluoroalkyl group-containing oligomer having the compound as a structural unit. (Where
R _F is CF _3. )

(Synthesis Example 5) Fluoroalkanoyl peroxide was changed to diperfluoro-2,5-dimethyl-3,6-dioxahexananoyl peroxide by changing to 13 mmol of acrylic acid and 13 mmol of N-vinyl-2-pyrrolidone. The reaction and purification were carried out in the same manner as in Synthesis Example 1 except that the amount was changed to 3 mmol.
The yield was 24%. The obtained product was analyzed by GPC. As a result, Mn = 2190 and Mw / Mn = 1.18.
As a result of analysis by R, ¹ H-NMR and ¹⁹ F-NMR, it was found to be a fluoroalkyl group-containing oligomer having a compound represented by Structural Formula H as a constituent unit. (In the formula, R _F is CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OC ₃ F _7. )

(Synthesis Example 6) 13 mmol of acrylic acid, 8 mmol of N-vinyl-2-pyrrolidone and diperfluoro peroxide
2,5-dimethyl-3,6-dioxahexananoyl
The reaction and purification were carried out in the same manner as in Synthesis Example 1 except that the amount was changed to 3 mmol. The yield was 44%. The obtained product was analyzed by GPC, and as a result, Mn = 2230 and Mw / Mn = 1.48. The product was analyzed by IR, ¹ H-NMR, and ¹⁹ F-NMR. The oligomer was a fluoroalkyl group-containing oligomer having the compound as a structural unit. (Where R _F is CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OC ₃ F
₇ )

(Synthesis Example 7) Reaction and purification were carried out in the same manner as in Synthesis Example 1 except that 24 mmol of acrylic acid, 24 mmol of N-vinyl-2-piperidone and 5 mmol of diperfluoro-2-methyl-3-oxahexanoyl peroxide were used. Was done. The yield is
It was 49%. The obtained product was analyzed by GPC, a Mn = 1100, Mw / Mn = 1.55, IR, 1
As a result of analysis by H-NMR and ¹⁹ F-NMR, it was found to be a fluoroalkyl group-containing oligomer having a compound represented by Structural Formula I as a constitutional unit.

Embedded image (In the formula, R _F is CF (CF ₃ ) OC ₃ F _7. )

Comparative Example 1 A reaction was carried out in the same manner as in Synthesis Example 1 except that 48 mmol of acrylic acid and 5 mmol of diperfluoro-2-methyl-3-oxahexanoyl peroxide were used without adding N-vinyl-2-pyrrolidone. And purification. The yield was 45%. The obtained product was analyzed by GPC, and as a result, Mn = 6700, Mw / Mn = 1.43, and IR,
As a result of analysis by ¹ H-NMR and ¹⁹ F-NMR,
It was a fluoroalkyl group-containing oligomer having the compound represented by Structural Formula J as a structural unit.

Embedded image (Where R _F is CF (CF ₃ ) OC ₃ F ₇ , where n is a natural number)

Comparative Example 2 12 mmol of acrylic acid and 16.4 mmol of N-vinyl-2-pyrrolidone were added to V-50 (2,2 ′).
100 g of an aqueous solution containing 3 mmol of -azobis (2-amidinopropane) dihydrochloride; manufactured by Wako Pure Chemical Industries, Ltd.
Was added thereto and reacted at 40 ° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, unreacted monomers were removed by dialysis, and the product was sufficiently washed with hexane. After that, vacuum drying with heating at 40 to 50 ° C. for 24 hours was performed to remove the solvent and the like. The yield was 39%. As a result of analyzing the obtained product by GPC,
Mn = 12700, Mw / Mn = 2.23, IR, ¹ H−
As a result of analysis by NMR and ¹⁹ F-NMR, acrylic acid having a compound represented by the structural formula K as a constituent unit and N-
It was a copolymer of vinyl-2-pyrrolidone. ¹ H-N
Table 1 shows the ratio of x and y in the structural formula K from the results of MR analysis.

Embedded image

[0038]

[Table 1]

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. Solution A having a solid content of 22% and a viscosity of 40,000 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, a mixed solution of n-butanol: xylene = 3: 2 (weight ratio) is used as an amino resin-based crosslinking agent 2,4,6-tri (N-methoxymethyl, N-methyl) amino-1,3,5-triazine. 50% solution C of
And 50% solution D of alkylbenzene sulfonic acid as a crosslinking catalyst was prepared with isopropyl alcohol. Solutions B, C,
D and toluene in a weight ratio of 100: 1: 0.4:
Mixing at a ratio of 15 to prepare 1 coating solution, 50g / m ²
Nylon plain woven cloth (warp: 90 denier yarns 90 / inch), previously calendered (condition: temperature 170 ° C, pressure 30 kg / cm ² )
Was applied using a floating knife coater.
After the application, the coating was dried at 110 ° C. for 1 minute, and further heated at 160 ° C. for 1 minute to obtain an acrylic resin-based work cloth.

(Example 2) Fiber treatment agent The same operation as in Example 1 was carried out except that the fluorosilicone oligomer of Synthesis Example 1 in Example 1 was replaced with a fluoroalkyl group-containing oligomer of Synthesis Example 7. A resin-based work cloth was obtained.

Comparative Example 3 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. An acrylic resin-based work cloth was obtained in the same manner as in Example 1 except that the coating liquid 2 was prepared in place of the solution B in the preparation of the coating liquid 1 in Example 1.

(Effect Example 1) Water repellency and oil repellency of the processed cloths and the untreated calendered cloths obtained in Examples 1 and 2 and Comparative Example 3 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 expressed by the following water repellency score of 50 to 100 points. 50 points: The whole surface was wet. 70 points: Half of the surface is wet, usually small individual wetness penetrating the cloth. 80 points: Small individual water droplets 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 on the surface. Oil repellency: A few drops of the test solution shown in Table 2 were placed at two places on the test paper, and discrimination was made based on the permeation state after 30 seconds (AATCC-TM1
18-1966).

[0043]

[Table 2]

[0044]

[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, 0.3 g of Irganox 1010 (manufactured by Ciba-Geigy) and 20.g of dimethylformamide.
0 g, and the solution temperature was increased to 60 while stirring under a nitrogen stream.
C. and kept for 1 hour. After cooling to 40 ° C., a mixed solution of 1.0 g of ethylene glycol and 5.0 g of dimethylformamide was uniformly added dropwise over about 1 hour. Further increase the reaction temperature
The temperature was raised to 80 ° C., and stirring was continued for 10 hours while adding 25.0 g of toluene in three portions each time the solution viscosity increased.
After dissolving 0.1 g of n-butanol in 20.0 g of dimethylformamide and confirming that the viscosity of the reaction solution did not increase, the fluorosilicone oligomer of Synthesis Example 1 was synthesized.
2 g diluted in 15.0 g of dimethylformamide and added,
The 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-based 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 (conditions: 170 ° C., pressure 30kg / cm) polyester plain woven cloth (30 denier yarn for both warp and weft)
90 pieces / inch) using a floating knife coater. After application, dry at 120 ° C for 2 minutes,
Heating was performed at 60 ° C. for 1 minute to obtain a urethane resin-based processed cloth.

Example 4 Fiber treatment agent The fluoroalkyl group-containing oligomer prepared in Synthesis Example 2 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 parts, 10 parts of Takamatsu Yushi Co., Ltd.) and 50 parts of water were added and mixed to prepare a fiber treatment solution. Nylon taffeta was immersed in this treatment solution for 3 minutes, squeezed with a mangle roll to a squeezing ratio of 100%, and dried at 110 ° C. for 5 minutes. This treated cloth after drying was confirmed to have water repellency and oil repellency.

(Example 5, Effect Example 2) Paper Treatment Agent Each of the fluoroalkyl group-containing oligomers of Synthesis Examples 2, 4, 5, and 7 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 ) using a size press.
After impregnation at 90%, it was dried at 100 ° C. for 30 seconds.
The treated paper was left overnight in a thermo-hygrostat at 20 ° C. and 65% relative humidity, and then evaluated for oil repellency. Oil repellency evaluation,
The following method was used, and the results are shown in Table 4. Oil repellency evaluation method: A few drops of the test solution shown in Table 2 were placed at two places on the test paper, and discrimination was made based on the permeation state after 30 seconds (AATCC-TM118-1966).

[0048]

[Table 4]

Example 6, Effect Example 3 Resin Surface Treatment Agent The fluoroalkyl group-containing oligomers of Synthesis Examples 2 and 6 were each dissolved in tetrahydrofuran at a concentration of 1%.
A polyethylene terephthalate film preliminarily 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.

[0050]

[Table 5]

(Example 7) Resin surface treating agent N, N-dimethylformamide / methyl ethyl ketone =
30/70 (wt%) mixed solvent with 100% modulus 3
A polyether-type polyurethane resin having 0 kgf / cm ² and an elongation of 800% was dissolved at a concentration of 16.5% by weight. This solution
To 100 parts, 10 parts of a solution obtained by dissolving the fluoroalkyl group-containing oligomer of Synthesis Example 2 in N, N-dimethylformamide at 3.3% by weight was added to prepare a resin surface treating agent. Using a gravure coater (120 mesh), apply this resin surface treatment agent twice to a 0.5 mm thick vinyl chloride sheet kneaded with a white pigment and dried at 80 ° C for 30 seconds.
A surface-treated vinyl chloride sheet was produced.

(Example 8) Resin surface treating agent The same operation as in Example 7 was performed, except that the fluoroalkyl group-containing oligomer of Synthesis Example 2 in Example 7 was replaced with the fluoroalkyl group-containing oligomer of Synthesis Example 6. A surface-treated vinyl chloride sheet was produced.

Comparative Example 4 Resin Surface Treatment Agent The polyether type polyurethane resin used in Example 7 was mixed with a mixed solvent of N, N-dimethylformamide / methyl ethyl ketone = 30/70 (% by weight) at a concentration of 15.0% by weight. And dissolved. This was mixed with a white pigment using a gravure coater (120 mesh) and colored 0.5 mm.
After coating twice on a thick vinyl chloride sheet, it was dried at 80 ° C. for 30 seconds to produce a surface-treated vinyl chloride sheet.

(Effect Example 4) The antifouling properties of the surface-treated PVC sheets produced in Examples 7 and 8 and Comparative Example 4 were evaluated by the following method. The results are shown in Table 6. Antifouling evaluation: On the treated PVC sheet, black oil-based ink pen (Magic Ink Co., Ltd., large type), black ballpoint pen (Zebra Co., No. 5000), red crayon (Sakura Crepas Co., Ltd.) , A black water-based felt-tip pen (S520, manufactured by Pentel Co., Ltd.) and a 1 cm-wide line were drawn with a coffee liquid. 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.

[0055]

[Table 6]

(Effect Example 5) Surfactant Effect (Surface Tension Decreasing Property) The surface tension at 30 ° C. of the aqueous solution of the fluoroalkyl group-containing oligomer prepared in Synthesis Examples 2, 4, and 6 was determined by Wilhelmy.
As a result of the measurement by the method (using ST-1 type manufactured by Shimadzu Corporation. The gas phase is air), the surface tension of water was reduced by adding a small amount. The surface tension of the aqueous solution of 0.1 g / L oligomer is 35 mN / m for the oligomer of Synthesis Example 2 and the oligomer of Synthesis Example 4 is for the surface tension of the 0.1 g / L aqueous oligomer solution, whereas the surface tension value of the added water is 71 mN / m.
The oligomer of Synthesis Example 6 showed a value of 17 mN / m. The critical micelle concentration of the oligomer of Synthesis Example 6 was 0.02 g / L. These oligomers were easily dissolved in purified water.

(Effect Example 6) Metal ion absorbing ability The oligomer prepared in Synthesis Examples 2, 4, and 6 and Comparative Examples 1 and 2, polyacrylic acid (Mn = 2000, a reagent of Aldrich Chemical Company), poly N-vinyl- The ability of 2-pyrrolidone (Mn = 10000, Tokyo Chemical Co., Ltd.) 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: use F-23 manufactured by Horiba, Ltd.)
Then, a calibration curve of the electromotive force versus the concentration is created. At that time,
Potassium chloride is used as an ionic strength regulator. Therefore, the standard solution of the calcium chloride aqueous solution is 0.1 mol / L
It was prepared by dissolving calcium chloride in an aqueous solution of potassium chloride at a concentration.

Preparation of test solution: The oligomers obtained in Examples 2, 4, 6 and Comparative Examples 1 and 2 are dissolved in a 0.1 mol / L aqueous solution of potassium chloride at a concentration of 0.5 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. Comparing the calcium ion uptake capacity with the ratio (Ca / A) of the calcium ion (Ca) and the carboxylate group (A) in the oligomer, it was found that in an aqueous solution having a concentration of 25 mmol / L calcium ion, Synthesis Example 2 was obtained.
Oligomers of Ca / A = 20, oligomers of Synthesis Example 4 had a Ca / A = 6, and oligomers of Synthesis Example 6 had a Ca / A = 30, indicating high calcium ion uptake ability. On the other hand, the oligomer of Comparative Example 1 was Ca / A = 2, and the oligomer of Comparative Example 2 was
Oligomer is Ca / A = 2 and polyacrylic acid is Ca / A
A = 2, and poly N-vinyl-2-pyrrolidone is Ca /
A = 0, and the calcium ion uptake ability was very small.

[0059]

Industrial Applicability The fluoroalkyl group-containing oligomer according to the present invention is a novel compound and has an amphipathic property which is soluble in water and a polar organic solvent. In addition, it has a wide range of properties such as excellent oil repellency, heat resistance, cold resistance, oil resistance, chemical resistance, and mold release properties similar to conventional fluoroalkyl group-containing oligomers. The agent has a high effect also 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,
Since the effect of lowering the surface tension is high, the function-imparting agent of the present invention has a high effect as a metal ion absorbent or a surfactant.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location D06M 13/398 C09D 133/02 PFY // C09D 133/02 PFY 139/04 PGL 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 R _F may be interrupted by an oxygen atom, and has 1 carbon atom.
-25 represents a fluoroalkyl group, Z represents trimethylene or tetramethylene, and x and y represent natural numbers] 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
F (CF ₃ ) O) _n C ₃ F ₇ (n = 0 to 6)
7. The agent according to claim 1, wherein Z is trimethylene.