WO2004033579A1

WO2004033579A1 - Oil-barrier composition

Info

Publication number: WO2004033579A1
Application number: PCT/JP2003/012774
Authority: WO
Inventors: Yutaka Fukatsu; Shunji Odaka; Tetsuhito Aihara
Original assignee: Seimi Chemical Co., Ltd.
Priority date: 2002-10-10
Filing date: 2003-10-06
Publication date: 2004-04-22
Also published as: TW200415231A; CN1703479A; JP4537854B2; MY135472A; AU2003268772A1; TWI250201B; JPWO2004033579A1; CN1294224C; HK1082517A1

Abstract

A water-based oil-barrier composition employing an aqueous medium. The oil-barrier composition is characterized in that it comprises a polymer (A) containing the following monomer units (a1), a surfactant (B), and an aqueous medium (C), and that the surfactant (B) comprises at least 50 wt.% fluorochemical surfactant (B1) based on the total amount of the surfactant (B). Monomer units (a1): monomer units derived from an unsaturated ester containing a polyfluoroalkyl group or monomer units derived from an unsaturated ester containing a polyfluoroalkyl group having an etheric oxygen atom inserted in a carbon-carbon bond.

Description

Oil barrier composition

TECHNICAL FIELD The present invention relates to a composition having an oil barrier effect and a method for producing the composition.

You. More specifically, precision machinery such as watches, motors, and lenses for single-lens reflex cameras

The present invention relates to a composition having a filler effect used to prevent the bleeding of a lubricant used in a sliding portion, and a method for producing the composition. The present invention also relates to a method for oil-barrier-treating the surface of a sliding component and a component adjacent to the sliding component using the composition, and a component subjected to the oil-barrier treatment.

BACKGROUND ART Lubricants such as mineral oil are used on sliding surfaces of sliding parts of precision machines such as lenses of watches, watches, and single-lens reflex cameras in order to reduce frictional resistance. Although such a lubricant is indispensable for preventing the sliding surface from being worn, the lubricant, which is usually in a liquid state, may ooze from the sliding surface to the peripheral portion. In precision machinery such as those described above, since multiple parts are usually arranged in a narrow area, oozing of lubricant may lead to adhesion of lubricant to other parts in the surrounding area Usually, a highly viscous lubricant tends to accumulate dust and the like, and the oozing of the lubricating oil to places other than the desired places may cause a machine failure. In addition, the oozing of the lubricant reduces the retention time of the lubricant on the sliding surface, thereby reducing the necessity of reapplying the lubricant. increase. Therefore, an oil barrier composition is used for a sliding part of such a precision machine or a part close to the sliding part in order to prevent oozing of a lubricant.

The oil barrier composition is obtained by dissolving or dispersing an oil-repellent compound in a medium. The sliding of sliding parts is required to prevent oozing of lubricant and to keep it in necessary parts for a long time. It is applied to the periphery of the moving surface and dried before use. As the oil-repellent compound, a fluorinated polymer or a fluorinated phosphoric diester compound having one or more perfluoroalkyl groups is used. Further, as the medium, a fluorine-containing aromatic hydrocarbon compound such as black fluorocarbon (CFC), perfluorocarbon (PFC) or meta-xylenehexafluoride is used.

However, CFCs have a restriction on the use of CFCs because they destroy the ozone layer, and PFCs have a high global warming potential and pose environmental problems. In addition, fluorine-containing aromatic hydrocarbon compounds have problems in toxicity, workability, and the like. Thus, there is a need for an aqueous oil barrier composition using an aqueous medium that does not affect the environment. However, among the above oil-repellent compounds, the fluorine-containing polymer or the fluorine-containing compound having two or more perfluoroalkyl groups has low solubility in water, so that when an aqueous medium is used, It is not possible to dissolve the required amount of active ingredient to exhibit sufficient oil barrier performance. In addition, when a hydrocarbon-based surfactant is added for solubilization, there is a problem that oil barrier performance and durability are reduced. For example, as a composition obtained by dissolving a fluorine-containing polymer in an aqueous medium, a composition for preventing the solder flux from climbing up is disclosed. 1 1-1 5 4 7 8 3 Publication). However, even if the soldering flux is solid at room temperature or liquid, the solid component is dissolved in a volatile solvent such as isopropyl alcohol, and isopropyl alcohol is heated by soldering. Since only the solid components are volatilized and remain on the substrate at the product stage, the required oil repellency is not high as compared with the oil barrier effect on the lubricant intended for the present application. Therefore, as a surfactant, together with a fluorine-based surfactant, a non-fluorinated cationic surfactant having an alkyl group having 6 or more carbon atoms in the molecule or a non-fluorinated surfactant having an alkyl group having 6 or more carbon atoms in the molecule It is said that it is preferable to use an anionic surfactant in combination, and the amount of the non-fluorinated surfactant contained in the surfactant is the total of the fluorine-based surfactant and the non-fluorinated surfactant. It is stated that it is preferably 50 to 80% by mass based on the amount. That is, it is said that it is preferable to include a larger amount of the non-fluorine-based surfactant. The reason why the amount of the non-fluorinated surfactant is preferably larger is that the emulsifying action during the production of the composition is excellent, and the dispersion stability of the oil-repellent compound is high. This is because the composition is excellent in handleability.

In addition, parts having a sliding surface treated with an oil barrier agent often contain oil such as press oil adhered in a previous step such as press working. However, the conventional oil barrier composition cannot form a coating film in a portion where oil remains, and when such a portion is treated with a conventional oil barrier agent, a component to be treated in advance is required. There is a need for a process to wash the oil with a halogenated organic solvent such as trichlene to remove the remaining oil. For example, as a water-based oil barrier composition, a fluorinated phosphoric acid monoester compound having one perfluoroalkyl group An oil barrier composition in which is dissolved in an aqueous medium is disclosed (see Japanese Patent Application Laid-Open No. 2000-16669). Although this oil-paria composition is excellent in solubility in water, it does not contain a fluorinated surfactant, so the surface tension is not low enough to form a coating film on the oil, and the remaining oil is removed. A removal step is required. Further, in the fluorinated phosphoric acid monoester used, the phosphoric acid moiety is adsorbed on the metal component when applied to the component, and the fluoroalkyl group moiety becomes free. For this reason, the coating film after drying has insufficient adhesion compared to an oil barrier agent using a fluorine-containing polymer.

In view of the above, an object of the present invention is to provide an aqueous oil barrier composition using an aqueous medium, which does not affect the environment. By applying such an oil barrier composition to a peripheral portion of a sliding surface such as a timepiece, a motor, and a lens of a single-lens reflex camera, oozing of a lubricant from the sliding surface is effectively prevented. Such an oil barrier composition exerts an excellent oil barrier effect even when a part in which oil components such as press oil adhered in the previous process remain is treated as it is. Disclosure of the invention

The present invention has been made to solve the above problems, a polymer containing the following polymerized units of (a ¹⁾ (A), surfactant (B), and an aqueous medium (C), a wherein the surfactant (B) is E Mar Ji type oil barrier, which comprises a fluorine-based surface active agent in the total mass of the surfactant (B) and (B ¹⁾ 5 0 wt% or more It is intended to provide a composition.

Polymerized unit (a ¹ ): a polymerized unit of an unsaturated ester containing a polyfluoroalkyl group, Or a polymerized unit of an unsaturated ester containing a polyfluoroalkyl group having an etheric oxygen atom inserted between carbon-carbon bonds.

In the oil barrier composition of the present invention, in the polymer (A), the proportion of the polymerized units (a ¹⁾ is preferably at least 90 mass%.

In the oil barrier composition of the present invention, it is more preferable that all the polymer units constituting the polymer (A) are polymer units (a ¹ ).

In the oil barrier composition of the present invention, the surfactant (B) is preferably a fluorine-based surfactant (B ¹ ).

In the oil barrier composition of the present invention, it is preferable that the polymerized unit (a ¹ ) is a polymerized unit of a compound represented by the following formula (1).

CH ₂ -CR ¹ COO-Q ¹ -R ^f …… Equation (1.)

However, in the formula (1), Q ¹ , R ¹ , and R ^f are as follows.

Q ¹ : a single bond or a divalent linking group.

R ¹ : hydrogen atom or methyl group.

R ^f : a polyfluoroalkyl group or a polyfluoroalkyl group having an etheric oxygen atom inserted between carbon-carbon bonds.

In the oil barrier composition of the present invention, the aqueous medium (C) is preferably water or a mixed solution of water and a water-soluble organic solvent having a boiling point of 40 to 200 ° C.

The oil barrier composition of the present invention preferably has a surface tension of 3 OmN / m or less at room temperature (25 ° C).

In the oil barrier composition of the present invention, it is preferable that the emulsion of the polymer (A) has a cumulative average diameter of 10 m or less. The present invention is also characterized in that a polymer (A) is synthesized by emulsion polymerization in the presence of an emulsifier, and a fluorosurfactant (B ¹ ) is further added to the obtained polymer (A). A method for producing the oil barrier composition of the present invention is provided.

The method for producing the oil barrier composition of the present invention comprises synthesizing the polymer (A) by emulsion polymerization in an aqueous medium (C) in the presence of a fluorine-based surfactant (B ¹ ) as an emulsifier. Is preferred.

According to the present invention, an oil barrier composition is applied to a surface of a component, dried and heat-treated, and the surface of a component close to a sliding component is subjected to an oil barrier treatment. Provide a method.

The present invention also provides a sliding component whose surface has been subjected to the oil-paria treatment and a component close to the sliding component, which is obtained by the method of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the polymer (A) is a polymer containing a specific structural unit, that is, a polymerized unit (a ¹ ). In the following, a polyfluoroalkyl group and a polyfluoroalkyl group having an etheric oxygen atom inserted between carbon-carbon bonds are collectively referred to as “R ^f group”. An alkyl group having an etheric oxygen atom inserted between an alkyl group and a carbon-carbon bond is generically referred to as an “alkyl group which may contain an etheric oxygen atom”. Acrylate and methacrylate are collectively referred to as (meth) acrylate, and the same applies to other (meth) acrylic acids.

The polymerized unit (a ¹ ) is a polymerized unit of an unsaturated ester containing an R ^f group. R ^f group Represents a group in which two or more hydrogen atoms of an alkyl group which may contain an etheric oxygen atom are substituted with a fluorine atom. The number of fluorine atoms in the R ^f group is represented by [(the number of fluorine atoms in the R ^f group) / (a hydrogen atom contained in an alkyl group which may contain an etheric oxygen atom having a structure corresponding to the R ^f group). Number)] XI When expressed by 00%, the oil barrier performance is easily exhibited, so that it is preferably 60% or more, particularly preferably 80% or more.

As the ^the R ^f group having an etheric oxygen atom, O carboxymethyl polyfurfuryl O b Echiren, is O carboxymethyl polyfurfuryl O b ^the R ^f group containing an alkylene unit components such as old carboxymethyl polyfurfuryl O b propylene like. The ^Rf group preferably has 4 to 14 carbon atoms, and particularly preferably 6 to 12 carbon atoms. When the carbon number of the ^Rf group is within the above range, the oil barrier performance is sufficient and the polymerized unit (a ¹ ) can be easily obtained. The R ^f group may have either a straight-chain structure or a branched structure, but more preferably a straight-chain structure. In the case of a branched structure, the branched portion is preferably present at the terminal portion of the ^Rf group, and is preferably a short chain having about 1 to 3 carbon atoms. Further, in the terminal portion of the Rr group, a chlorine atom may be partially present instead of a fluorine atom. Examples of the structure of the terminal portion of the R ^f group in which a chlorine atom may be present include structures such as CF ₃ CF 2 —, CF 2 H—, CF ₂ C 1 —, and (CF ₃ ) 2 CF— Is mentioned.

In the present invention, the ^Rf group is an alkyl group which may contain an etheric oxygen atom because oil barrier performance is easily developed, and substantially all of the hydrogen atoms of Is preferably a perfluorinated alkyl group which may contain an oxygen atom (hereinafter referred to as an R '"group). The number of carbon atoms of the R ^F group is preferably 4 to 14, more preferably 6 to 12. R ^F group Is within the above range And the oil barrier performance is sufficient, and it is easy to obtain the polymerized unit (a ¹ ). The R ^F group may have either a linear structure or a branched structure, but is preferably a group having a linear structure from the viewpoint of oil barrier performance. The R ^F group is preferably a group in which substantially all of the hydrogen atoms of the alkyl group have been replaced by fluorine atoms (ie, a group that does not contain an etheric oxygen atom). In particular, F (CF ₂ ) _n — To an integer of to 12].

Specific examples of the R ^f group include, but are not limited to, the following structures. In the following specific examples, groups corresponding to structurally isomeric groups are also included.

Examples of R ^f groups that do not contain an etheric oxygen atom.

_{_{_{C 2 F s -, C 3}}} F 7 - [F (CF 2) 3 -, and (CF ₃₎ includes both _{_{2 CF-], C 4 - [}} F (CF 2) 4 -, (CF 3) 2 CFCF ₂ , (CF ₃ ) 3 C 1, F (CF ₂ ) ₂ CF (CF,)-including), C ₅ F ,,-[F (CF ₂ ) 5 1, (CF ₃ ) 2 CF _{_{(CF 2) 2 -, (}} CF 3) 3 CCF 2 _{_{one, F (CF 2) 2 CF}} (CF 3) comprises a structural isomeric groups such as CF ₂ one], C e F, 3 - [F (CF ₂ ) a C (CF ₃ ) 2, etc.], C s F 17 -1, C 10 F 21 -1, C 12 F 25 ― C 15 F 31, HC t F 21 ― ( t 整数 an integer from 1 to 18), (CF ₃ ) ₂ CFC _S F _2S — (s is an integer from 1 to 15), etc. Examples of R ^f groups containing an etheric oxygen atom.

F (CF ₂ ) 5 OCF (CF ₃ ) I, F [CF (CF ₃ ) CF ₂ O] _s CF (CF ₃ ) CF ₂ CF ₂ ―, F [CF (CF.,) CF ₂ O], CF _{(CF 3) -, F [} CF (CF 3) CF 2 〇] _u CF _₂ CF ₂ _{one, F (CF, CF 2 CF} 2 O) v CF, CF 2 -, F (CF 2 CF 2 O) w CF ₂ CF ₂ ― (s and t are An integer from 1 to 10 to respective independently ease whether we 1-3 integer to obtain the appropriate polymer units (a ¹⁾ are preferred. u is an integer from 2 to 6. V is an integer from 1 11 integer ease of 1-4 availability of the person to polymerized units (a ¹⁾ are preferred. w is an integer from 1 11 corresponding polymer units (a ¹⁾ an integer ease of 1-6 availability are preferred. ) Such.

Polymerized units in the present invention (a ¹⁾ from easy availability of the corresponding polymer units (a ^1), R ^f group-containing (meth) Akurireto polymerization unit is good preferable represented by the following formula (1) .

CH ₂ = CR ^] COO-Q ¹ — R ^f …… Equation (1)

However, the symbols in the formula have the following meanings.

Q ¹ : a single bond or a divalent linking group.

R ¹ : hydrogen atom or methyl group.

R ^r : R ^f group.

Q ¹ in the formula is preferably a divalent organic linking group, and particularly preferably those listed in the specific examples described below. R ^f in the formula is preferably a polyfluoroalkyl group containing no etheric oxygen atom, and particularly preferably a perfluoroalkyl group containing no etheric oxygen atom. Specific examples of the ^Rf group-containing (meth) acrylate represented by the formula (1) include the following compounds.

F (CF ₂ ) 8 (CH ₂ ) ■> OCOCH = CH ₂ , F (CF ₂ ) ₈ (CH _a ) ₂ 〇COC (CH ₃ ) = CH ₂ , F (CF _a ) _H (Ch) ₃ 〇 COCH = CH _2. , F (CF ₂ ) 7 CH, OCOCH = CH ₂ , F (CF ₂ ), ₍ , (CH ₂ ) ₂ OCOC ( _CH.¾ ) = CH _a , H (CF ₂ ) _s (CH ,) ₂ OCOC (CH ₃ ) = CH ₂ , (CF.,) 2 CF (CF ₂ ) 6 (CH ₂ ) ₂ OCOC (CH ₃ ) = CH ₂ , F (CF ₂ ) s S0 ₂ N (CH ₂ CH ₂ CH ₃ ) ― ( CH ₂ ) ₂ 〇C〇 CH = CH ₂ .

The number of the polymerized units (a ¹ ) in the polymer (A) may be one or more. Polymer (A) may contain polymerized units (a ¹⁾ other than the polymerized units. The polymerization unit other than the polymerization unit (a ') is not particularly limited as long as it is a monomer unit having no ^Rf group and having a polymerizable unsaturated group (hereinafter, referred to as other monomer). Not done. As the other monomer, a known or well-known compound is employed, and one kind or two or more kinds can be used.

Other monomers include polyolefin-based unsaturated esters such as acrylates, unsaturated esters having an epoxy group, compounds having a vinyl group, compounds having an amino group and a polymerizable unsaturated group, and compounds having a polymerizable property with silicon. Examples include compounds having an unsaturated group, and compounds having a substituted amino group and a polymerizable unsaturated group. When the polymer (A) is a copolymer comprising polymerized units other than (a ^1), the proportion of the polymer (A) in the polymerized units (a ¹⁾ is preferably at least 80 wt%, in particular 90 It is preferably at least mass%. When the ratio of the polymerized unit (a ') in the polymer (A) is within the above range, the oil barrier performance is good.

The fluorine content in the polymer (A) of the present invention is preferably 30% by mass or more, particularly preferably 45 to 95% by mass. When the fluorine content in the polymer (A) is within the above range, the oil barrier performance is good.

The weight average molecular weight of the polymer (A) is preferably from ^{1 X 1 0 3 ~ 1 X} 1 0 7, especially 1 X 10 ⁴ ~1 X 10 ⁵ preferred. In addition, when the polymer (A) In the case of a polymer containing units, the sequence of the polymerized units may be professional, and particularly preferably random.

In addition, in the oil barrier composition of the present invention, the cumulative average diameter of the emulsion of the polymer (A) is preferably 10 μηι or less, more preferably 6 m or less, and more preferably 1 m or less. Is more preferable, and particularly preferably 0.1 m or less. When the cumulative average diameter of the emulsion of the polymer (A) is 10 m or less, the dispersion stability as the emulsion is excellent, and there is no possibility that an operation such as re-stirring is required at the time of coating. The film has excellent homogeneity, and there is no possibility that the oil barrier performance is reduced.

Here, in the present invention, the cumulative average diameter is assumed to be a group of one particle, and when the particle size distribution is obtained, when the total volume of the particle group is set to 100% and the cumulative curve is obtained, The particle size (m) at which the cumulative curve reaches 50%. The composition of the present invention contains a surfactant (B) and an aqueous medium (C), in addition to the polymer (A) described above. The polymer (A) in the composition is preferably dispersed as particles in an aqueous medium (C) described below. The concentration of the polymer (A) in the composition of the present invention is preferably from 0.01 to 10% by mass, particularly preferably from 0.1 to 5% by mass. When the concentration of the polymer (A) is within the above range, the oil barrier performance is good, and the cost when performing the oil barrier treatment using the composition of the present invention is also excellent.

In the present invention, the surfactant (B) is a fluorinated surfactant (B ¹ ) containing at least 50% by mass of the fluorine-based surfactant (B ¹ ) in the total mass of the surfactant (B). The surfactant is a surfactant whose main component is fluorinated surfactant (B ¹ ). As long as it is enclosed, it may contain a non-fluorinated surfactant (B ² ). It is more preferable that the surfactant (B) contains 90% by mass or more of the fluorine-based surfactant (B ¹ ) based on the total mass of the surfactant (B). ') Is particularly preferred.

If the content of the fluorinated surfactant to the total weight of the surfactant (Β) (Β ¹⁾ is less than 50 wt%, it is impossible to obtain a desired oil barrier performance, also the durability of the composition Inferior and not practical.

Examples of the fluorine-based surfactant (beta ¹⁾ of the present invention, Roh two on-surfactant having an ionic surfactant or a fluorine atom that having a fluorine atom can be mentioned, et al are. Further, fluorine-based Surfactant (beta ^1), ^the R ^f group and Anion group and Anion fluorine-based surfactant having both a fluorinated cationic surfactant having both ^the R ^f group and a cationic group Any of a surfactant, an amphoteric surfactant having an ^Rf group, a cationic group and an anionic group, and a nonionic surfactant having an ^Rf group and a hydrophilic group may be used.

The trade names of fluorine-based cationic surfactants include “Surflon (registered trademark) S-121J” manufactured by Seimi Chemical Co., Ltd. “Florald FC — 134” manufactured by Suriem, and Dainippon Ink & Chemicals, Inc. “MegaFac F-150”. The trade names of fluorine-based anionic surfactants include “Surflon (registered trademark) S-111” manufactured by Seimi Chemical Co., Ltd., “Florald (registered trademark) FC-143” manufactured by Surichem, and Dainippon Japan. "MegaFac (registered trademark) F-120" manufactured by Ink Chemical Industry Co., Ltd. The trade names of the fluorine-based amphoteric surfactant include “Surflon (registered trademark) S-132” and “Surflon (registered trademark)” manufactured by Seimi Chemical Co., Ltd. S-1311 "," Florald (registered trademark) FX-172 "manufactured by Sliem Co., Ltd., and" MegaFac (registered trademark) F-120 "manufactured by Dainippon Ink and Chemicals, Inc. The trade names of fluorine-based nonionic surfactants include “Surflon (registered trademark) S-145” manufactured by Seimi Chemical Co., Ltd., “Florald (registered trademark) FC-170” manufactured by SLEEM, and Dainippon Ink and Chemicals, Inc. “MegaFac (registered trademark) F-141”.

Examples of the non-fluorinated surfactant (B ² ) that may be included in the surfactant (B) include a non-fluorinated non-ionic surfactant having an HLB value of Ί or more and an alkyl group having 6 or more carbon atoms in the molecule. And a non-fluorinated anionic surfactant having an alkyl group having 6 or more carbon atoms in the molecule.

As the non-fluorinated nonionic surfactant having an HLB value of 7 or more, a known nonionic surfactant containing 5 or more oxyalkylene units in a molecule is preferable. As the oxyalkylene unit, ethylene xylene or oxypropylene is preferred. Examples of the non-fluorinated cationic surfactant having an alkyl group having 6 or more carbon atoms in the molecule include an alkyl ammonium salt and the like, and a non-fluorinated cationic surfactant having an alkyl group having 6 or more carbon atoms in the molecule. Examples of the anionic surfactant include an alkyl sulfate.

Specific examples of the non-fluorinated surfactant (B ² ) in the present invention are shown below. Polyoxyethylene lauryl ether (HLB = 14.5, mole number of oxyethylene added = 9), polyoxyethylene polyoxypropylene cetyl ether (HLB = 9.5, mole number of oxyethylene added = 1, mole number of oxypropylene added = 8), polyoxyethylene octyl phenyl ether (HLB = 11.5, Mole number of added len = 10), polyoxyxetylene nonyl phenyl ether (HLB = 8.0, mole of oxyethylene added = 5), salted stearyl trimethyl ammonium, dioctyl dimethyl ammonium, lauryl Ammonium sulfate, sodium boroxyethylene lauryl ether sulfate, and dimethyl octadecylamine acetate. Of these, non-fluorinated surfactants (B ² ) include polyoxyethylene lauryl ether, polyoxyethylene octylphenyl, polyoxyethylene noenyl ether, and dimethyloctane. Decylamine acetate and the like are preferred.

The surfactant (B) is preferably contained in the composition in an amount of 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 5% by mass. If the amount of the surfactant (B) is less than 0.001% by mass, the wettability of the composition to the substrate may be insufficient. If the amount is more than 10% by mass, the formed coating film adheres to the substrate. There is a problem that the performance is low.

Further, the composition of the present invention contains an aqueous medium (C). Examples of the aqueous medium (C) include water or a mixture of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include ketones, esters, glycols, glycol ethers, and alcohols. When the aqueous medium (C) contains a water-soluble organic solvent, the proportion of water in the aqueous medium (C) is preferably 50 to 95% by mass, while the proportion of the water-soluble organic solvent is 5 to 50% by mass. preferable.

Further, the water-soluble organic solvent preferably has a boiling point of 40 to 200 from the viewpoint of easy drying. Further, the aqueous medium (C) is preferably an organic solvent having a solubility in water at 20 ° C of 1% by mass or more. The composition of the present invention preferably has a surface tension at room temperature (25) of 3 OmNZm or less, more preferably 2 OmN / m or less. If the surface tension of the composition at room temperature (25 T) is 3 OmNZm or less, the oil barrier properties are good, and the surface of the component may be damaged during the pre-process such as press oil used in press working. It is highly likely to adhere, for example, lower than the surface tension of oils such as higher fatty acid esters, so it has excellent wettability and adhesion to the surface where oils adhere. For this reason, it is possible to treat with the composition without washing and removing the oil attached to the surface to be treated.

When the composition of the present invention forms a coating film on the surface to be treated, a lubricant (for example, a hydrocarbon-based lubricating oil having 16 or more carbon atoms, specifically, (For example, normal hexadecane) is 50 ° or more. When the contact angle of the lubricant on the surface of the composition coating film is within the above range, the oil barrier performance is excellent.

The composition of the present invention may contain components other than those described above as long as the components do not adversely affect the dispersion stability, the oil barrier property, the wettability to the substrate, or the appearance. Such other components include, for example, a pH regulator for preventing corrosion, a protective agent, a dye for controlling the concentration of the polymer in the liquid, a dye stabilizer, and a flame retardant. Or an antistatic agent.

The oil barrier composition of the present invention may be produced by any method as long as a composition having the desired composition and physical properties described above is obtained. Therefore, the polymerized units containing polymerized units (a ¹⁾ is a solution polymerization in a fluorinated solvent in the polymer (A) was synthesized, after removal of the fluorine-containing solvent, a fluorine-based polymer was analyzed by (A) Surfactant

(Β ′) may be dispersed in the aqueous medium (C) to produce the composition of the present invention. Les ^ As this available fluorinated solvents, 1, 3- bis (Torifuruorome chill) benzene, 2, 3-dihydro-deca full O b (n-) of pentane HF (:, CHF ₅ C 1 ₂ ( HCFC such as “AK-2225” (trade name, manufactured by Asahi Glass Co., Ltd.), provided that the monomer containing the polymerized unit (a ¹ ) and, if necessary, another monomer are used as an emulsifier. It is preferable to synthesize the polymer (A) by emulsion polymerization in the presence, since the composition of the present invention can be directly obtained.

When the polymer (A) is synthesized by emulsion polymerization, it is preferable to carry out the method 1 or 2 below.

[Method 1] A method in which a monomer is emulsified in the presence of a medium and an emulsifier, and then polymerized with stirring.

[Method 2] Before adding a polymerization initiator, a method in which a monomer is emulsified by a homomixer or a high-pressure emulsifier in the presence of a medium and an emulsifier, and then a polymerization is initiated by a polymerization initiator.

In any of the above methods, when a gaseous monomer such as vinyl chloride is used as the monomer, the monomer may be continuously supplied under pressure using a pressure vessel. The polymerization initiation source is not particularly limited, and ordinary polymerization initiators such as organic peroxides, azo compounds, and persulfates, or ionizing radiation such as alpha rays can be used.

It is preferable to use the same medium as the aqueous medium (C).

That is, when the composition of the present invention is produced by synthesizing the polymer (A) by emulsion polymerization, a monomer containing the polymerized unit (a ′), preferably a monomer represented by the formula (1) And, if necessary, another monomer in an aqueous medium (C) in the presence of an emulsifier. It is preferable to synthesize the polymer (A) in combination.

In all of the above methods, the emulsifier may be the surfactant (B). In this case, the emulsifier may be the fluorine-based surfactant (B ¹ ) or the non-fluorine-based surfactant (B ² ) It may be. However, it is preferable to use the fluorine-containing surfactant (B ¹ ) since the composition of the present invention can be directly obtained. As the surfactant (B), two or more surfactants having different ionic properties may be used in combination. However, when surfactants having different ionic properties are used, it is preferable to combine cationic and nonionic, anionic and nonionic, or nonionic and amphoteric.

In the present invention, the composition of the composition, specifically, the weight average molecular weight of the polymer (A), the polymer (A), the surfactant (B) and the aqueous medium (C) in the composition It is easy to adjust the content, the content of the fluorinated surfactant (B ¹ ) in the surfactant (B), and the physical properties, specifically, the surface tension of the composition, etc. to the above-mentioned preferred ranges. From the above, it is preferable to prepare the composition of the present invention by adding a fluorine-containing surfactant (B ¹ ) after the emulsion polymerization.

According to the composition of the present invention, the surface of a sliding component or a component near the sliding component (hereinafter, also referred to as a “component to be treated”) that needs to be subjected to an oil barrier treatment depending on the purpose or application is used. Oil barrier treatment can be performed. As a processing method, a general coating method can be adopted. For example, there are methods such as dip coating, spray coating, and coating with an aerosol can filled with the composition of the present invention.

By coating the composition of the present invention on the surface of the component to be treated and then drying it, a coating film can be formed on the surface. After the composition is applied and dried, it is preferable to further heat-treat the composition. By performing such a heat treatment, the surface of the workpiece is chipped. It is possible to form a continuous film without any depression. The drying conditions and the heat treatment conditions may be appropriately selected according to the composition of the composition to be applied, the application area, and the like.For example, as the drying conditions, in Examples described later, drying is performed at 60 for 15 minutes. As a condition, in Examples described later, the heat treatment is performed at 120 for 10 minutes.

(Example)

Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

[Synthesis example of Polymer 1]

F (CF ₂ ) (CH ₂ ) OCOC H = CH ₂ 219 g, Fluorosurfactant S-131 (solid content: 30%, manufactured by Semi Chemical Co., Ltd.) 4 g, 48.2 g of acetone, and 266 g of ion-exchanged water were added, and pre-emulsification was performed with 5 for 1 hour. Thereafter, 2 g of 2,2′-azobis (2-methylpropionamidine) hydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the autoclave was purged with nitrogen.

Stirring speed is about 200 rpm (20L cylindrical vessel Φ = 26 cm, anchor wing (Φ = 18 cm)). The temperature is raised to 60 ° C and polymerization is performed for 18 hours with stirring. After cooling, gas chromatography ( As a result of analysis by GC), the conversion of F (CF ₂ ) (CH ₂ ), OCOCH = CH ₂ was 99% or more, indicating that the polymerization reaction proceeded smoothly. Thereafter, the mixture was filtered with a filter having a pore size of 6 im to obtain a milky white emulsion. The solid content of the emulsion was 36.0%.

[Synthesis example of Polymer 2]

F (CF,) „(CH ₂ ), OCOC in 1 liter glass autoclave H = CH ₂ 17 g, hydrocarbon surfactant K-220 (manufactured by NOF Corporation) 2 Owt.% Aqueous solution 133 g, acetone 47.6 g, ion-exchanged water 201 g, 50 Pre-emulsification for 1 hour. Thereafter, 1.9 g of 2,2′-azobis (2-methylpropionamidine) hydrochloride (V-50, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the autoclave was purged with nitrogen.

The temperature was raised to 60 ° C with stirring under the same conditions as for Polymer 1, polymerization was carried out for 18 hours, and after cooling, analyzed by gas chromatography (GC), F (CF 2) ₈ (CH ₂ ) 2 OCOCH = The reaction rate of CH ₂ was 99% or more, indicating that the polymerization reaction proceeded smoothly. Thereafter, the mixture was filtered through a filter having a pore size of 6 m to obtain a milky white emulsion. The solid content of the emulsion was 40.9%.

[Preparation of Composition 1]

Surflon (registered trademark) S-11 (solid content: 30%, manufactured by Seimi Chemical Co., Ltd.) was diluted with a 20% aqueous ethanol solution to prepare a solution II having a solid content of 0.2%. Emulsion (solid content: 36%) synthesized in Synthesis Example of Polymer 1 was diluted with the prepared solution (2) to prepare Composition 1 in which Polymer 1 had a solid content of 2%.

With respect to the obtained composition, the cumulative average diameter of the emulsion of Polymer 1 was measured by a dynamic light reflection method using a particle size analyzer MI CROTRAC UP A (MODEL: 9230, manufactured by Nikkiso Co., Ltd.). The measured value of the cumulative average diameter was 0.011 rn.

[Preparation of composition 2]

Emulsion (solid content: 40%) prepared in Synthesis Example of Polymer 2 was diluted with Solution (2) prepared in Preparation Example of Composition 1 to obtain Composition 2 having a solid content concentration of Polymer 2 of 2%. Prepared. With respect to the obtained composition, the cumulative average diameter of the emulsion of the polymer 2 was measured in the same manner as in the composition 1. The measured value of the cumulative average diameter was 0.0689.

[Preparation of Composition 3]

Emulsion (solid content: 36%) prepared in Synthesis Example of Polymer 1 was mixed with a 0.2 wt.% Aqueous solution of Surflon (registered trademark) S-111 (solid content: 30%, manufactured by Seimi Chemical Co.), Composition 3 was prepared by diluting the polymer 1 with ion-exchanged water so that the solid content concentration of the polymer 1 was 0.4% and the solid content concentration of S-111 was 0.04%.

With respect to the obtained composition, the cumulative average diameter of the emulsion of the polymer 1 was measured in the same manner as in the composition 1. The measured value of the cumulative average diameter was 0.0119 im.

[Preparation of Composition 4] ''

The procedure is the same as in the synthesis example of polymer 1, except that the stirring speed at the time of polymerization is 120 rpm (20 L cylindrical vessel Φ = 26 cm, anchor wing (<i = 18 cm)). The concentration of the polymer is 0.2% by weight of a 0.2% aqueous solution of Surflon (registered trademark) S-111 (solid content: 30%, manufactured by Seimi Chemical Co., Ltd.) and ion-exchanged water. Composition 4 was prepared by diluting the solution so as to have a solid content concentration of 0.4% and S-111 of 0.04%.

With respect to the obtained composition, the cumulative average diameter of the emulsion of the polymer was measured in the same manner as in composition 1. The measured value of the cumulative average diameter was 0.3178 m.

[Performance evaluation method and evaluation results]

• (1) Wetting at room temperature (25 ° C) to evaluate the wettability of Compositions 1 and 2. Surface tension was measured with a Wilhelmi surface tensiometer. Table 1 shows the results (unit: mNZm).

Eclectic 1

(2) Evaluation of oil barrier performance (Part 1)

An iron plate of 10 cm × 10 cm × 1 mm was immersed in each of Compositions 1 and 2 for 1 minute. Furthermore, drying and heat treatment were performed at 120 ° C. for 10 minutes to form a coating film on the surface. The normal hexadecane contact angle on the surface after the formation of the coating film was measured with a drop-type projection contact angle meter manufactured by Kyowa Kaisei Kagaku. In addition, the iron plate with the droplets was left for a certain period of time at room temperature (25 ° C) or 9 O, respectively, and the change over time of the normal hexadecane contact angle was measured. Table 2 shows the average values of the contact angles.

Composition Normal hexadecane contact angle)

Immediately after treatment Leave at room temperature (25 ° C) 90 ° C

1 After 2 After 10 days 1 After 2 days After 10 days Untreated 10 or less 10 or less 10 or less 10 or less 10 or less 10 or less 10 or less Composition 1 82 82 82 82 62 58 58 Composition 2 30 10 or less 10 or less 10 10 or less 10 or less 10 or less 10 or less (3) Evaluation of oil barrier performance (Part 2)

Normal hexadecane force contact on the surface in the same manner as in (2) except that the same steel plate as in (2) was brush-painted with the oil used for press working (AK-280 Cosmo Oil, Lubricant) The angle was measured with a drop-type projection contact angle meter manufactured by Kyowa Interface Science Co., Ltd. Table 3 shows the average values of the contact angles. Table 3

Composition Contact angle of normal hexadecane (°)

(4) Evaluation of oil barrier performance (Part 3)

After immersion in press oil (AK-280, manufactured by Cosmo Oil Vulcante) for 1 minute, heat-dried glass plates were immersed in Compositions 3 and 4 for 1 minute each, and then 60. After drying for 15 minutes at C, a coating film was formed on the surface, and the contact angle of normal hexadecane force on the surface of the glass plate was measured with a droplet-type projection contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). . Table 4 shows the average values of the contact angles. Table 4

Industrial applicability

Since the oil barrier composition of the present invention uses an aqueous medium, it does not have to worry about ozone layer destruction and global warming, and exhibits excellent oil barrier performance. Since the composition has almost no odor problem, it is very advantageous in working environment. In addition, the composition can be processed as it is even if the oil used in the previous process such as press working is adhered to the part to be processed, so that a cleaning step for removing the oil is required. It can be omitted and the process can be simplified.

Claims

The scope of the claims

1. It comprises a polymer (A) containing the following polymerized unit (a ¹ ), a surfactant (B), and an aqueous medium (C) ′, wherein the surfactant (B) comprises the surfactant (B) An oil barrier composition comprising the fluorosurfactant (B ¹ ) in an amount of 50% by mass or more based on the total mass of the oil barrier composition.

2. The in the polymer (A), the proportion of the polymerized units (a ¹⁾ is Oirubaria composition according to claim 1 Ru der least 90 mass%.

3. The oil barrier composition according to claim ^{1, wherein} all the polymerized units constituting the polymer (A) are polymerized units (a1).

4. The surfactant (B) is Oirubaria composition according to any one of claims 1 to 3, which is all fluorinated surfactant (B ^1).

5. The polymer units (a ¹⁾ is Oirubaria composition according to any one of claims 1 to 4 polymerized units of the compound represented by the following formula (1).

CH ₂ = CR 'COO-Q ¹ — R ^f …… Equation (1)

However, in the formula (1), Q ¹ , R ¹ , and R ^f are as follows.

Q ': a single bond or a divalent linking group.

R ': a hydrogen atom or a methyl group.

R ^r : polyfluoroalkyl group or etheric oxygen atom between carbon-carbon bonds Polyfluoroalkyl group into which a child has been inserted.

6. The oil barrier composition according to claim 1, wherein the aqueous medium (C) is water or a mixed solution of water and a water-soluble organic solvent having a boiling point of 40 to 20 O ^.

7. The oil barrier composition according to any one of claims 1 to 6, wherein the composition has a surface tension at room temperature (25) of 3 OmNZm or less.

8. The oil barrier composition according to claim 1, wherein a cumulative average diameter of the emulsion of the polymer (A) is 10 μm or less.

9. Emulsifier presence, polymer (Alpha) was synthesized by emulsion polymerization, which comprises adding the resulting polymer (Alpha) in a fluorine-based surfactant (beta ^1), claim

9. A method for producing the oil barrier composition according to any one of 1 to 8.

1 0. As an emulsifier in the presence of a fluorinated surfactant (beta ^1), according to claim 9, wherein the synthesis of the polymer (Alpha) by emulsion polymerization in an aqueous medium (C) A method for producing an oil barrier composition.

11. The oil barrier composition according to any one of claims 1 to 8, or the barrier composition produced by the method for producing an oil barrier composition according to claim 9 or 10, applied to the surface of the component. A method of performing oil barrier treatment on the surface of a sliding part or a part near the sliding part, which is characterized by drying or heat treatment.

12. A sliding part whose surface is subjected to an oil barrier treatment or a part close to the sliding part, obtained by the method according to claim 11.