WO2007032480A1 - Composés fluorés, leur procédé de production, utilisations des composés, procédé pour abaisser la tension superficielle et procédé pour modifier la surface d’une résine - Google Patents

Composés fluorés, leur procédé de production, utilisations des composés, procédé pour abaisser la tension superficielle et procédé pour modifier la surface d’une résine Download PDF

Info

Publication number
WO2007032480A1
WO2007032480A1 PCT/JP2006/318374 JP2006318374W WO2007032480A1 WO 2007032480 A1 WO2007032480 A1 WO 2007032480A1 JP 2006318374 W JP2006318374 W JP 2006318374W WO 2007032480 A1 WO2007032480 A1 WO 2007032480A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluorine
group
compound
containing compound
integer
Prior art date
Application number
PCT/JP2006/318374
Other languages
English (en)
Japanese (ja)
Inventor
Masato Mitsuhashi
Original Assignee
Agc Seimi Chemical Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agc Seimi Chemical Co., Ltd. filed Critical Agc Seimi Chemical Co., Ltd.
Priority to CN2006800338312A priority Critical patent/CN101263104B/zh
Priority to KR1020087005896A priority patent/KR101288712B1/ko
Priority to JP2007535555A priority patent/JP5139068B2/ja
Publication of WO2007032480A1 publication Critical patent/WO2007032480A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
    • C07C43/137—Saturated ethers containing hydroxy or O-metal groups containing halogen

Definitions

  • Fluorine-containing compound production method thereof, use thereof, surface tension reduction method, and resin surface modification method
  • the present invention relates to a fluorine-containing compound, a method for producing the same, a use of the fluorine-containing compound, a surface tension reducing method using a fluorine-containing compound, and a resin surface modifying method.
  • a fluorine-containing compound having a fluorine-containing alkyl group as a hydrophobic group has a high ability to reduce surface tension. Therefore, when it is added as a surfactant to a coating composition, it has excellent permeability and wettability. And exerts effects such as leveling.
  • As the fluorine-containing compound various structures have been proposed so far.
  • Ordinary fluorine-containing compounds have the property of being hardly soluble in water.
  • fluorine-containing compounds having hydrophilicity fluorine-containing compounds in which hydrophilic groups are made ionic are known.
  • the fluorine-containing compound does not have solubility in an organic solvent.
  • fluorine-containing compound having hydrophilicity As another fluorine-containing compound having hydrophilicity, a fluorine-containing compound having an oxyalkylene group is known (Patent Document 1). Although the fluorine-containing compound is improved in hydrophilicity, the ability to reduce surface tension is poor.
  • Patent Document 1 Japanese Patent Laid-Open No. 04-145041
  • the present invention provides a fluorine-containing compound having excellent ability to reduce surface tension and solubility in water, a method for producing the same, a use thereof, a method for reducing surface tension, and a method for modifying the surface of a resin. Means for solving the problem
  • the fluorine-containing compound of the present invention is a fluorine-containing compound represented by the following formula (I).
  • J 5 is a hydrogen atom, carbon number 1 to: LO alkyl group, or —Z 5 —0— (AkO) n5
  • R 5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or — Z 6 — O— (AkO) — X 6 — R 6 , AkO represents an oxyalkylene group
  • R'-R 6 is a hydrogen atom n6
  • At least one of ⁇ to is a fluorine-containing alkyl group having 1 to 12 carbon atoms which may have an etheric oxygen atom, m represents an integer of 0 to 20, and nl to n6 represent an integer of 0 to 20 Nl + n2 + n3 + n4 + n5 + n6> 0, ⁇ ⁇ 6 represents a single bond or a divalent linking group, and ⁇ 3 to ⁇ 6 represent a single bond or a methylene group.
  • the fluorine-containing compound of the present invention is preferably a fluorine-containing compound represented by the following formula (I1).
  • AkO represents an oxyalkylene group
  • I ⁇ to R 4 represent a hydrogen atom or a monovalent organic group
  • at least one of I ⁇ to R 4 has an etheric oxygen atom.
  • a fluorine-containing alkyl group having 1 to 12 carbon atoms m represents an integer of 0 to 20
  • nl to n4 represents an integer of 0 to 20
  • xi X 4 represents a single bond or a divalent linking group.
  • the total of nl to n6 present in the formula (I) or the formula (1-1) is preferably 4 to 50.
  • R 4 — X 4 — is a hydrogen atom or Rf— (CH) p— CH (OH) — CH— Y— (where p
  • Rf represents a perfluoroalkyl group having 3 to 12 carbon atoms
  • Y represents a single bond or a divalent linking group
  • at least one of R 4 -X 4 is Rf— (CH) p— CH (OH) — CH— Y—
  • m is 1 to 3
  • An integer is shown, and nl + n2 + n3 + n4 is preferably 4-50.
  • the method for producing a fluorine-containing compound of the present invention comprises an etheric oxygen atom at the terminal hydroxyl group of an alkylene oxide adduct obtained by adding an alkylene oxide to glycerol or polyglycerol.
  • a fluorine-containing compound represented by the above formula (I 1) is obtained by reacting a compound having a fluorine-containing alkyl group having 1 to 12 carbon atoms.
  • polyglycerin is represented by “HO— (CH 2 CH (OH) CH 0) n—H”.
  • the method for producing a fluorine-containing compound of the present invention includes an alkylene obtained by adding an alkylene oxide to a compound having a fluorine-containing alkyl group having 1 to 12 carbon atoms which may have an etheric oxygen atom.
  • This is a method for obtaining a fluorine-containing compound represented by the above formula (I1) by reacting glycerin or polyglycerin with the terminal hydroxyl group of an oxide adduct.
  • the surfactant of the present invention contains the fluorine-containing compound of the present invention.
  • the leveling agent of the present invention contains the fluorine-containing compound of the present invention.
  • the anti-fogging agent of the present invention contains the fluorine-containing compound of the present invention.
  • the surface tension reducing method of the present invention is a method of reducing the surface tension of a liquid by adding the fluorine-containing compound of the present invention to the liquid.
  • the resin surface modification method of the present invention is a method of modifying the resin surface by adding the fluorine-containing compound of the present invention to the resin.
  • the fluorine-containing compound of the present invention is superior in surface tension reducing ability and water solubility compared to conventional fluorine-containing compounds.
  • a fluorine-containing compound having excellent ability to reduce surface tension and solubility in water can be produced efficiently with few steps.
  • the surfactant of the present invention is superior in surface tension reducing ability and water solubility compared to conventional surfactants.
  • the leveling agent of the present invention easily dissolves in compositions such as coating materials, resists, water glass, cleaning agents, etching solutions, plating solutions, adhesives, antifungal agents, and agricultural chemicals. Leveling performance that is not affected by the presence of objects can be imparted.
  • the anti-fogging agent of the present invention can quickly develop the anti-fogging performance of a film having high surface transferability. In addition, the anti-fogging performance can be exhibited without inhibiting other functions such as anti-fogging performance.
  • the surface tension of the liquid can be lowered without being limited by the solvent composition of the liquid. Functions such as property, foamability, detergency and emulsification can be imparted.
  • functions such as antistatic properties, antifogging properties, antifogging properties, water repellency and lubricity can be imparted to various types of resins.
  • the fluorine-containing compound of the present invention is a fluorine-containing compound represented by the following formula (I) (hereinafter referred to as compound (I)).
  • J 5 represents a hydrogen atom, carbon number 1 to: LO alkyl group, or —Z 5 —0— (AkO) — X 5 — R 5 n5
  • J 6 represents a hydrogen atom, carbon number 1 to: L0 alkyl group, or — Z 6 — O— (AkO)-n6
  • AkO represents an oxyalkylene group, and from the viewpoint of ease of synthesis, an oxyethylene group is particularly preferable from the viewpoint of solubility in water, which is preferably an oxyethylene group or an oxypropylene group.
  • the oxyalkylene chain composed of a plurality of AkOs may be composed of one or more AkO forces and may be composed of two or more AkO chains. Each oxyalkylene chain may have the same structure or a different structure.
  • R'-R 6 represents a hydrogen atom or a monovalent organic group; At least one of ⁇ ⁇ is a fluorine-containing alkyl group having 1-12 carbon atoms.
  • the fluorine-containing alkyl group means a group in which at least one hydrogen atom in the alkyl group is substituted with a fluorine atom. All the carbon atoms in the fluorine-containing alkyl group are single bonds. Connected together.
  • the fluorine-containing alkyl group may have an etheric oxygen atom inserted between carbon atoms.
  • the fluorine-containing alkyl group is preferably a linear fluorine-containing alkyl group from the viewpoint of the ability to reduce surface tension.
  • the fluorine-containing alkyl group is preferably a perfluoroalkyl group from the viewpoint of the ability to reduce the surface tension.
  • a linear perfluoroalkyl group prepared by a telomerization method is particularly preferred from the viewpoint of ease of synthesis and ability to reduce surface tension.
  • the number of carbon atoms of the fluorine-containing alkyl group is preferably 3-12, more preferably 4-10, and particularly preferably 4-6, from the viewpoints of solubility in water and ability to reduce surface tension.
  • the monovalent organic group is not particularly limited as long as it does not impair the solubility of compound (I) in water.
  • the portion of ⁇ ⁇ that is not a fluorine-containing alkyl group is a hydrogen atom or a carbon atom 1 that is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms in terms of hydrophilicity and ease of synthesis. Particularly preferred is a hydrogen atom, with ⁇ 4 alkyl groups being more preferred.
  • the number of the moiety that is a fluorine-containing alkyl group is preferably 1 to 3, particularly preferably 1 to 2.
  • the average is preferably 1 to 3, and more preferably 1 to 2.5. ,.
  • the number of the fluorine-containing alkyl group is within the above range, the water solubility is improved, which is preferable.
  • m represents an integer of 0 to 20.
  • M is 0 to:
  • LO is preferred 0 to 3 is more preferred 1 to 3 in that compound (I) is easy to handle, exhibits viscosity, and is readily available as a commercial product. Is particularly preferred.
  • nl to n6 represent an integer of 0 to 20, and nl + n2 + n3 + n4 + n5 + n6> 0.
  • Nl + n2 + n3 + n 4 + ⁇ 5 + ⁇ 6 is 4 to 50 forces, especially 10 to 30 forces, because it has good affinity with the solvent and has a good ability to lower the surface tension. .
  • existing nl to n6 are targeted. Specifically, ⁇ 5 and ⁇ 6 do not exist.
  • Nl + n2 + n3 + n4> 0, and nl + n2 + n3 + n4 is preferably 4-50.
  • the surfactant is used as a leveling agent or the like.
  • ⁇ 6 represents a single bond or a divalent linking group. ⁇ 6 are single bonds, Tables 1 and 2 show specific examples of — (CH 2) q—, — (CH 2) p—CO—, — (CH 2) p—CH (OH
  • ⁇ ⁇ Bound to ⁇ 6 is preferably a linking group other than a single bond in terms of ease of raw material preparation and synthesis-(CH) q-,-(CH) p- CO-,-(CH) p— CH (OH) — CH—,-(CH
  • (2-1) to (2-6), (2-9), (2-10), (2-15), (2-20), and (2-23) groups are included.
  • a particularly preferred group is — (CH 2) p—CH (OH) —CH—.
  • CH (OH) 2 -CH 1 1 to 3 is preferable as p, and 1 is particularly preferable.
  • 1-6 is not limited to those shown as specific examples, it may be a ivy structure combination of a plurality of linking groups.
  • Such a structure is-(CH) p- CH (OH)-CH- Y
  • ⁇ is a single bond or a divalent linking group.
  • examples of the divalent linking group of ⁇ include linking groups such as amine. ⁇ (CH) p-CH (OH) -CH ⁇ Y
  • Y is a single bond, it becomes one (CH 2) p—CH (OH) —CH— described above.
  • Z 3 ⁇ Z 6 represents a single bond or a methylene group.
  • the compound (I) is preferably a fluorine-containing compound represented by the following formula (I 1) (hereinafter referred to as compound (I 1)).
  • Compound (1-1) is a compound (I) in which hydrogen atoms are selected as J 5 and J 6 and single bonds are selected as z 3 and z 4 .
  • AkO represents an oxyalkylene group
  • I ⁇ to R 4 represent a hydrogen atom or a monovalent organic group
  • at least one of I ⁇ to R 4 has an etheric oxygen atom.
  • m represents an integer of 0 to 20
  • nl to n4 represents an integer of 0 to 20
  • xi X 4 is a single Indicates a bond or a divalent linking group.
  • an alkylene oxide is added to glycerin or polyglycerin to obtain an alkylene oxide adduct, and then an etheric oxygen is added to the terminal hydroxyl group of the alkylene oxide adduct.
  • the method of making the compound which has a C1-C12 fluorine-containing alkyl group which may have an atom react is mentioned.
  • the alkylene oxide adduct of glycerin can be obtained, for example, by blowing ethylene oxide gas into glycerin or polyglycerin in the presence of a base catalyst when the alkylene oxide is ethylene oxide. At that time, the number of added moles of ethylene oxide can be adjusted by the amount of gas blown. In addition, they are commercially available as New Ox G-450, New TG-330 (1000, 2000, 3000, 4000) manufactured by Nippon Oil and Fats Co., Ltd., and can be easily obtained.
  • Diglycerin alkylene oxide adducts are sold as SC-E450 (750, 1000, 1500, 2000), SC-P400 (750, 1000, 1200, 1600) by Sakamoto Yakuhin Kogyo Co., Ltd. Easy to obtain.
  • the compound having a fluorine-containing alkyl group is particularly preferably a compound having the structure (or group) shown in Table 3, which is preferably a compound having a perfluoroalkyl group.
  • Rf group is a perfluoroalkyl group having 3 to 12 carbon atoms
  • p represents an integer of 0 to 16
  • q represents an integer of 1 to 16
  • r represents an integer of 1 to 16
  • the compound is not limited to the following compounds as long as the compound of the formula (I 1) can be synthesized.
  • the compounds (3-1) to (3-5) are preferred in view of the availability of raw materials and the synthesizing properties (3-1).
  • p is 0, in (3-2) q is 2, in (3-3) p is 1 to 3 in (3-4), and in (3-4) p is 1 in particular.
  • the reaction of the alkylene oxide adduct and the compound having a fluorine-containing alkyl group may be performed in the absence of a solvent or in the presence of a solvent.
  • a solvent include acetone, ethyl acetate, methanol, ethanol, tetrahydrofuran (THF) and the like as long as the raw material is soluble. Since the production process can be simplified and the volumetric efficiency is excellent, the reaction is preferably carried out in the absence of a solvent.
  • the temperature of the fluorine-containing alkyl group introduction reaction is preferably 0 to 150 ° C in terms of ease of control and the like, and a refrigerant medium or a heat medium other than steam is unnecessary and is easy to manufacture. 20-100 ° C is particularly preferred.
  • the pressure of the fluorine-containing alkyl group introduction reaction is preferably normal pressure because it is simple.
  • the temperature and pressure of the fluorine-containing alkyl group introduction reaction are not limited to the above ranges.
  • Examples of the atmosphere of the fluorine-containing alkyl group introduction reaction include air, nitrogen atmosphere, argon atmosphere, helium atmosphere and the like.
  • an acid catalyst or a base catalyst may be used.
  • the raw material charging method in the fluorine-containing alkyl group introduction reaction is not particularly limited.
  • the compound (1-1) obtained by the production method may be used after purification or may be used unpurified depending on the application.
  • the purification means include solvent washing, recrystallization, various chromatography, distillation of residual solvent, use of an adsorbent, and the like.
  • the production method of the compound (I 1) is not limited to the above-mentioned method, and may have an etheric oxygen atom and may have a fluorine-containing alkyl group having 1 to 12 carbon atoms.
  • a method may be used in which glycerin or polyglycerin is reacted with a hydroxyl group at the terminal of an alkylene oxide adduct obtained by adding an alkylene oxide to the alkoxide.
  • an adduct of alkylene oxide for example, when alkylene oxide is ethylene oxide, it can be obtained by blowing ethylene oxide gas into an alcohol derivative having a fluorine-containing alkyl group in the presence of a base catalyst. .
  • the number of moles of ethylene oxide added can be adjusted by the amount of gas blown. It can also be obtained by reacting an alcohol derivative having a fluorine-containing alkyl group with polyoxyethylene glycol.
  • Examples of the reaction between the terminal hydroxyl group of the alkylene oxide adduct and glycerin or polyglycerin include a method in which the hydroxyl group at the terminal of the alkylene oxide adduct is halogenated and reacted with glycerin or polyglycerin.
  • Another example is a method in which the terminal hydroxyl group of glycerol or polyglycerol is halogenated and reacted with an alkylene oxide adduct.
  • a method in which the hydroxyl group at the terminal of the alkylene oxide adduct is nominated is preferred!
  • compound (I) can be produced by replacing glycerin or polyglycerin with trimethylolpropane, pentaerythritol, or dipentaerythritol.
  • the terminal hydroxyl group of an alkylene oxide adduct obtained by adding alkylene oxide to trimethylolpropane, pentaerythritol, or dipentaerythritol has an etheric oxygen atom.
  • a method of reacting a compound having a fluorine-containing alkyl group having 1 to 12 carbon atoms, (ii) having an etheric oxygen atom! / ⁇ a fluorine-containing alkyl group having 1 to 12 carbon atoms To the hydroxyl group at the end of the alkylene oxide adduct obtained by adding alkylene oxide to the compound having Compound (I) can be produced by a method of reacting serine or the like.
  • Alkylene oxide adducts of trimethylolpropane are commercially available as TMP-30U, TMP-60, TMP-F32 manufactured by Nippon Emulsifier Co., Ltd. it can.
  • Pentaerythritol with alkylene oxide is a PNT-40 manufactured by Nippon Emulsifier Co., Ltd.
  • the number of parts that are fluorine-containing alkyl groups can be adjusted by the raw material charge ratio. For example, when 2 moles of the fluorinated alkyl group-containing compound is used per 1 mole of glycerin or polyglycerin, compound (I) having an average number of fluorinated alkyl groups of 2 can be obtained.
  • Compound (I) can be used in various applications because it can exhibit a sufficient surface tension reducing effect even in a small amount.
  • Uses added to liquids such as solvents include penetrants, wettability improvers, leveling agents, paints, emulsifiers, dispersants, fire extinguishing agents, floor waxes, cleaning agents, foaming agents, antifoaming agents, etc. Is mentioned.
  • Applications that are used by adding to cocoa butter include antifogging agents, antifogging agents, foaming agents, antifoaming agents, antistatic agents and the like. It may also be used as a grease diffusion inhibitor by adding to grease.
  • Compound (I) may be used alone or in combination of two or more.
  • the surfactant of the present invention contains compound (I). If necessary, it contains a solvent and other ingredients!
  • organic solvents include alcohols such as methanol, ethanol, 1 propanol, 2-propanol, and t-butanol; esters such as ethyl acetate, methyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • Polarities such as N, N dimethylformamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone Solvent; Glycol ethers such as diethylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; Daricols such as ethylene glycol and propylene glycol; Ethers such as jetyl ether, tetrahydrofuran and dioxane
  • nitrogen-containing solvents such as pyridine and piperazine.
  • the solvent one type may be used alone, or two or more types may be used in combination.
  • Examples of other components include other surfactants, organic substances having affinity for solvents, and inorganic substances such as various salts.
  • examples of other surfactants include commercially available surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants.
  • the surface tension of the liquid can be lowered without being limited by the solvent composition of the liquid. Functions such as property, foamability, detergency and emulsification can be imparted.
  • the leveling agent of the present invention contains compound (I). If necessary, it contains a solvent and other ingredients!
  • solvent examples include water, organic solvents, fluorine-based solvents and the like.
  • Examples of other components include solutes and additives.
  • Examples of solutes include various types of resin.
  • additives include various surfactants, coupling agents, metal oxides, acid / antioxidant agents, antistatic agents, antifungal agents, antifogging agents, ultraviolet ray preventing agents, and photosensitizers.
  • the leveling agent of the present invention is a coating material such as a printing material, photosensitive material, paint, optical material, floor wax; resist, water glass, cleaning agent, etching solution, plating solution, adhesive, antifungal agent, agricultural chemical. Therefore, leveling performance can be provided without being affected by the presence of other compositions.
  • the anti-fogging agent of the present invention contains compound (I). If necessary, other components may be contained.
  • Examples of other components include plasticizers, antifogging agents, ultraviolet absorbers, heat stabilizers, lubricants, stabilizers, antistatic agents, pigments, and dyes.
  • the anti-fogging agent of the present invention is added to the synthetic resin material constituting the agricultural synthetic resin coating material.
  • the synthetic resin material include film-forming thermoplastic synthetic resins. Specifically, monomers such as vinyl chloride, ethylene, propylene, acrylic acid ester, methacrylic acid ester alone or their mutual polymers, or at least one of these monomers and other monomers. Examples thereof include a copolymer with a copolymerizable monomer (for example, vinyl acetate, salt vinylidene, etc.), fluorine-containing resin, polyester, polyamide, and a blend thereof.
  • a copolymer with a copolymerizable monomer for example, vinyl acetate, salt vinylidene, etc.
  • the anti-fogging agent of the present invention can quickly express the anti-fogging performance of a film having a high transferability to the surface of the resin. Further, by taking a structure having an appropriate number of hydrophilic groups, the fog prevention performance can be exhibited without inhibiting other functions such as the antifogging performance.
  • the surface tension reducing method of the present invention is a method for reducing the surface tension of a liquid by adding compound (I) to the liquid.
  • Examples of the liquid include water and organic solvents, and a liquid containing water is preferable.
  • Examples of the organic solvent include alcohols such as methanol, ethanol, 1 propanol, 2-propanol, and t-butanol; esters such as ethyl acetate, methyl acetate, and butyl acetate; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.
  • Polar solvents such as N, N dimethylformamide, dimethyl sulfoxide, sulfolane, N-methylpyrrolidone; glycol ethers such as diethylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; Daricols such as ethylene glycol and propylene glycol; Ethers such as ether, tetrahydrofuran and dioxane
  • the liquid may be a mixed solvent of two or more.
  • the amount of compound (I) added is preferably from 0.001 to 20 parts by mass, particularly preferably from 0.005 to 5 parts by mass with respect to 100 parts by mass of the liquid. In this range, the surface tension can be sufficiently reduced without impairing the properties of other additives.
  • solutes and additives other than the compound (I) may be added.
  • solute examples include various resins. Specifically, acrylic resin, epoxy resin, Examples include alkyd resin, urethane resin, polyimide resin, and fluorine-containing resin. Solutes may be used alone or in combination of two or more.
  • Additives include hydrocarbon surfactants, silicone surfactants, fluorine surfactants, silane coupling agents, titanium coupling agents, metal oxides, antioxidants, antistatic agents, and antifungal agents. Agents, antifogging agents, ultraviolet ray preventing agents, photosensitive agents and the like.
  • the surface tension reducing method of the present invention since the compound (I) has solubility in various solvents, the surface tension of the liquid can be reduced without being limited by the solvent composition. Functions such as leveling, penetrability, foaming, detergency, and emulsification can be imparted.
  • the resin surface modification method of the present invention is a method for modifying the resin surface by adding compound (I) to the resin.
  • the resin examples include poly salt resin, polyethylene, polypropylene, polystyrene, polysalt vinylidene, acrylic resin (polymethyl acrylate, etc.), epoxy resin, fluorine resin, polyurethane, polyester, polycarbonate Polyacetal, polyethylene terephthalate, polyamide, polyimide, melamine resin, phenol resin, urea resin, fluorine resin, and the like.
  • the resin may be a natural resin or a synthetic resin. Further, the resin may be a thermoplastic resin or a thermosetting resin. The resin may be a mixture of two or more.
  • the addition method may be a method in which compound (I) and rosin are directly kneaded, and compound (I) is added to a small amount of rosin or the like to form a masterbatch, It may be added to the method.
  • the amount of compound (I) added is preferably 0.001 to: LO parts by mass, particularly preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin. Within this range, the surface modification performance is maintained by appropriately bleeding out the compound (I) to the surface of the resin.
  • Additives other than the compound (I) and the like may be added to the rosin.
  • Additives include hydrocarbon surfactants, silicone surfactants, fluorosurfactants; plasticizers such as DOP (dioctyl phthalate) and DMP (dimethyl phthalate); Stabilizers such as tiltin laurate, norlium sarcophagus; Antioxidants such as BHA (Butylhydroxyl-sol); Agents: various antistatic agents, flame retardants, colorants, lubricants, antibacterial agents, and the like.
  • plasticizers such as DOP (dioctyl phthalate) and DMP (dimethyl phthalate)
  • Stabilizers such as tiltin laurate, norlium sarcophagus
  • Antioxidants such as BHA (Butylhydroxyl-sol)
  • Agents various antistatic agents, flame retardants, colorants, lubricants, antibacterial agents, and the like.
  • the compatibility between the compound (I) and the resin can be used for various types of resins, such as antistatic properties, antifogging properties, antifogging properties, water repellency, lubricity, etc. Can be provided.
  • the same function can also be imparted by applying the surfactant solution of the present invention to the surface of the resin.
  • the compound (I) of the present invention described above has a structure derived from an alkylene oxide adduct obtained by adding an alkylene oxide to glycerin or polyglycerin, and therefore, compared with a conventional fluorine-containing compound, Excellent solubility in water. Furthermore, since it has a fluorine-containing alkyl group having 1 to 12 carbon atoms, that is, a fluorine-containing group in which all carbon atoms are connected by a single bond, it has an excellent ability to reduce surface tension compared to conventional fluorine-containing compounds. In contrast, the compound described in Patent Document 1 is not saturated with a fluorine-containing group (C F —, C F —) at the terminal.
  • nl + n2 + n3 + n4 is about 20 on average, the same as the raw material.
  • 19 F-NMR and 13 C-NMR were measured for the compound (I-la), and it was confirmed that the compound (I-la) was obtained. The results are shown below.
  • Rf is a perfluoroalkyl group having 3 to 12 carbon atoms, and p represents an integer of 0 to 16)
  • PEG-1000 polyethylene glycol, manufactured by Nippon Oil & Fats Co., Ltd.
  • BF-OEt manufactured by Wako Pure Chemical Industries, Ltd.
  • compound (3-4a) Daikin Chemicals Sales
  • Compound (III) is a compound obtained by changing CF in compound (II) to CF.
  • the fluorine-containing compound of the present invention is characterized by being superior in solubility in each solvent and also having excellent surface tension reducing ability as compared with conventional fluorine-containing compounds, and exhibits a sufficient effect even in a small amount. Can be used for a wide range of purposes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Polyethers (AREA)

Abstract

La présente invention concerne des composés fluorés représentés par la formule générale (I), lesquels sont excellents en termes de capacité à abaisser la tension superficielle et d'hydrosolubilité ; leur procédé de production ; leurs utilisations ; un procédé pour abaisser la tension superficielle ; et un procédé pour modifier la surface d’une résine : (I) où J5 représente un atome d’hydrogène, un groupe alkyle ayant de 1 à 10 atomes de carbone, ou -Z5-O-(AkO)n5-X5-R5 ; J6 représente un atome d’hydrogène, un groupe alkyle ayant de 1 à 10 atomes de carbone, ou -Z6-O-(AkO)n6-X6-R6 ; AkO représente un groupe oxyalkylène ; R1 à R6 représentent chacun un atome d’hydrogène ou un groupe organique monovalent, à condition qu'au moins un des groupes R1 à R6 soit un groupe alkyle fluoré ayant de 1 à 12 atomes de carbone ; m est un nombre entier de 0 à 20 ; n1 à n6 représentent chacun un nombre entier de 0 à 20, à condition que la somme de n1 à n6 soit supérieure à 0 ; X1 à X6 représentent chacun une liaison simple ou un groupe de connexion bivalent ; et Z3 à Z6 représentent chacun une liaison simple ou un groupe méthylène.
PCT/JP2006/318374 2005-09-16 2006-09-15 Composés fluorés, leur procédé de production, utilisations des composés, procédé pour abaisser la tension superficielle et procédé pour modifier la surface d’une résine WO2007032480A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN2006800338312A CN101263104B (zh) 2005-09-16 2006-09-15 含氟化合物、其制造方法、其用途、表面张力降低方法以及树脂表面改性方法
KR1020087005896A KR101288712B1 (ko) 2005-09-16 2006-09-15 불소 함유 화합물, 그 제조 방법, 그 용도, 표면 장력 저하방법, 및 수지 표면 개질 방법
JP2007535555A JP5139068B2 (ja) 2005-09-16 2006-09-15 含フッ素化合物、その製造方法、その用途、表面張力低下方法、および樹脂表面改質方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-269974 2005-09-16
JP2005269974 2005-09-16

Publications (1)

Publication Number Publication Date
WO2007032480A1 true WO2007032480A1 (fr) 2007-03-22

Family

ID=37865063

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/318374 WO2007032480A1 (fr) 2005-09-16 2006-09-15 Composés fluorés, leur procédé de production, utilisations des composés, procédé pour abaisser la tension superficielle et procédé pour modifier la surface d’une résine

Country Status (5)

Country Link
JP (1) JP5139068B2 (fr)
KR (1) KR101288712B1 (fr)
CN (1) CN101263104B (fr)
TW (1) TW200720321A (fr)
WO (1) WO2007032480A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011001650A1 (fr) * 2009-07-03 2011-01-06 Ａｇｃセイミケミカル株式会社 Emulsion de résine aqueuse et composition d'encaustique pour sols
JP2012196943A (ja) * 2011-03-23 2012-10-18 Oji Paper Co Ltd 感熱記録体
JP2012218310A (ja) * 2011-04-11 2012-11-12 Oji Paper Co Ltd 感熱記録体
JPWO2018016544A1 (ja) * 2016-07-22 2019-03-14 富士フイルム株式会社 固体電解質組成物、固体電解質含有シートおよび全固体二次電池ならびに固体電解質含有シートおよび全固体二次電池の製造方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8026289B2 (en) * 2008-10-21 2011-09-27 E.I. Du Pont De Nemours And Company Fluorinated polyoxyalkylene glycol diamide surfactants
KR101319085B1 (ko) * 2009-09-08 2013-10-17 다이킨 고교 가부시키가이샤 신규 비이온계 계면 활성제 및 방무제

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04145041A (ja) * 1990-10-05 1992-05-19 Neos Co Ltd 含フッ素グリセリン誘導体
JPH09296037A (ja) * 1996-05-07 1997-11-18 Kao Corp 含フッ素ポリエーテルおよびその製造方法
JPH10147638A (ja) * 1996-11-19 1998-06-02 Kao Corp グリセロール変性含フッ素ポリエーテル及びその製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3107451B2 (ja) * 1992-03-31 2000-11-06 竹本油脂株式会社 ポリカーボネート樹脂用帯電防止剤及びこれを含有するポリカーボネート樹脂組成物
JP4145041B2 (ja) * 2001-12-05 2008-09-03 日本碍子株式会社 電気化学装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04145041A (ja) * 1990-10-05 1992-05-19 Neos Co Ltd 含フッ素グリセリン誘導体
JPH09296037A (ja) * 1996-05-07 1997-11-18 Kao Corp 含フッ素ポリエーテルおよびその製造方法
JPH10147638A (ja) * 1996-11-19 1998-06-02 Kao Corp グリセロール変性含フッ素ポリエーテル及びその製造方法

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011001650A1 (fr) * 2009-07-03 2011-01-06 Ａｇｃセイミケミカル株式会社 Emulsion de résine aqueuse et composition d'encaustique pour sols
CN102471641A (zh) * 2009-07-03 2012-05-23 Agc清美化学股份有限公司 水性树脂乳液及地板抛光组合物
JP2012196943A (ja) * 2011-03-23 2012-10-18 Oji Paper Co Ltd 感熱記録体
JP2012218310A (ja) * 2011-04-11 2012-11-12 Oji Paper Co Ltd 感熱記録体
JPWO2018016544A1 (ja) * 2016-07-22 2019-03-14 富士フイルム株式会社 固体電解質組成物、固体電解質含有シートおよび全固体二次電池ならびに固体電解質含有シートおよび全固体二次電池の製造方法

Also Published As

Publication number Publication date
CN101263104A (zh) 2008-09-10
JPWO2007032480A1 (ja) 2009-03-19
KR101288712B1 (ko) 2013-07-22
TW200720321A (en) 2007-06-01
CN101263104B (zh) 2012-05-09
JP5139068B2 (ja) 2013-02-06
KR20080044280A (ko) 2008-05-20

Similar Documents

Publication Publication Date Title
WO2007032480A1 (fr) Composés fluorés, leur procédé de production, utilisations des composés, procédé pour abaisser la tension superficielle et procédé pour modifier la surface d’une résine
EP2460790B1 (fr) Composé fluoré, tensioactif fluoré et compositions les contenant
CN101094876A (zh) 含氟聚合物表面活性剂
WO2015025929A1 (fr) Composé bifonctionnel contenant un groupe perfluoro(poly)éther, composition contenant un composé bifonctionnel contenant un groupe perfluoro(poly)éther, et procédés de production dudit composé et de ladite composition
EP2346923B1 (fr) Tensio-actifs de diamide polyoxyalkylène glycol fluoré
JP2005105045A (ja) 界面活性剤組成物
EP2756024B1 (fr) Polyéthers fluorés ou perfluorés linéaires renfermant des groupes terminaux-cf(cf3)cof et leurs dérivés
EP3221382A1 (fr) Dérivés zwitteroniques de (per) fluoropolyéthers
TW202225258A (zh) 新穎的（全）氟聚醚聚合物及其用途
JP2003183242A (ja) 界面活性剤として有用な新規なフッ素含有化合物
JP4411515B2 (ja) フッ素系界面活性剤
JP2006104240A (ja) 含フッ素化合物、界面活性剤およびその組成物
US11708456B2 (en) (Per)fluoropolyether (PFPE) polymers
JP2006137689A (ja) 多分枝状フッ素化合物、その製造方法およびその用途
JP7165017B2 (ja) ペルフルオロエーテル含有化合物及びノニオン系含フッ素界面活性剤
JP2508789B2 (ja) 含フッ素化合物およびその用途
JP6761918B1 (ja) 潤滑油組成物
TW201630972A (zh) 含有鹵化全氟聚醚基的化合物及其製造方法
CN106232575A (zh) 具有聚合性官能团和氟原子团的羧酸酯·氨基甲酸酯化合物及其制造方法
JP4349056B2 (ja) フッ素系界面活性剤
JP2016132771A (ja) 水性塗料用湿潤剤
JP2022086415A (ja) 化合物、及び組成物
JP2001278973A (ja) 含フッ素化合物、その製造方法および用途
JP2009079023A (ja) 含フッ素化合物および界面活性剤組成物ならびに含フッ素化合物を含有する組成物の製造方法
JP2005154668A (ja) 含フッ素熱可塑性エポキシ樹脂

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200680033831.2

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2007535555

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 1020087005896

Country of ref document: KR

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06798037

Country of ref document: EP

Kind code of ref document: A1