WO2005116153A1 - Composition de protection contre l’huile de lubrification et utilisation de celle-ci - Google Patents

Composition de protection contre l’huile de lubrification et utilisation de celle-ci Download PDF

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Publication number
WO2005116153A1
WO2005116153A1 PCT/JP2005/008961 JP2005008961W WO2005116153A1 WO 2005116153 A1 WO2005116153 A1 WO 2005116153A1 JP 2005008961 W JP2005008961 W JP 2005008961W WO 2005116153 A1 WO2005116153 A1 WO 2005116153A1
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Prior art keywords
group
lubricating oil
polymer
agent composition
barrier
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PCT/JP2005/008961
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English (en)
Japanese (ja)
Inventor
Tetsuhito Aihara
Ryo Hirabayashi
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Seimi Chemical Co., Ltd.
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Publication date
Application filed by Seimi Chemical Co., Ltd. filed Critical Seimi Chemical Co., Ltd.
Priority to JP2006513846A priority Critical patent/JP4773953B2/ja
Publication of WO2005116153A1 publication Critical patent/WO2005116153A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C08L43/04—Homopolymers or copolymers of monomers containing silicon

Definitions

  • the present invention relates to a composition having a barrier property against a lubricating oil, a method for forming a film of the composition on the surface of a sliding component to impart a barrier property against a lubricating oil, and a method for providing the composition with a barrier property against a lubricating oil.
  • the present invention relates to a sliding part on which a coating is formed. More specifically, the present invention relates to a barrier agent composition used for preventing seepage of lubricating oil used in sliding parts of precision machines such as watches, motors, lenses of single-lens reflex cameras, etc.
  • the present invention also relates to a method for performing a barrier treatment on the surface of a sliding component and a component adjacent to the sliding component using the composition, and the component subjected to the barrier treatment.
  • lubricating oils such as mineral oil are used as lubricating oils in order to reduce frictional resistance.
  • a lubricating oil is indispensable for preventing the abrasion of the sliding surface, but since it is in a liquid state in a normal state, the lubricating oil may seep from the sliding surface to the peripheral portion.
  • seepage of lubricating oil may lead to adhesion of the lubricant to a peripheral portion.
  • lubricating oil generally accumulates dust with high viscosity and immediately oozes out of the lubricating oil outside of the specified location, causing a machine failure.
  • the oozing of the lubricating oil reduces the holding time of the lubricating oil on the sliding surface, and the necessity of re-application of the lubricating oil increases. For this reason, a barrier agent composition is used for sliding parts of such precision machines or parts close to the sliding parts in order to prevent oozing of lubricating oil. With the integration and miniaturization of components, the demand is increasing.
  • Such a noria agent composition includes a compound having oil repellency when a film is formed. Are dissolved or dispersed in a solvent. The composition is applied to sliding parts and adjacent parts including Z or the peripheral part of the sliding surface to prevent oozing of the lubricating oil and to keep the lubricating oil in necessary parts for a long time, and then dried. used.
  • a fluorine-containing polymer, a fluorine-containing phosphoric acid diester conjugate having one or more perfluoroalkyl groups, and the like have been used.
  • CFC chlorofluorocarbon
  • PFC perfluorocarbon
  • hydrocarbon-based solvents and fluorine-containing aromatic hydrocarbon-based compounds such as meta-xylenehexafluoride are sometimes used. There are problems in toxicity, workability, etc.
  • hydrocarbon-based solvents are often highly flammable and require careful handling.
  • hydrocarbon solvents have low solubility in fluorine-containing water-repellent compounds, and there are many problems.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 01-127080 (Page 1, lower right column, etc.)
  • Patent Document 2 JP-A-2000-1669
  • the present invention provides an emulsion type and microemulsion type using an aqueous medium that is less harmful to the environment, has excellent workability, and can maintain a safe working environment. It is an object of the present invention to provide an aqueous nolia agent composition. Further, by forming a film made of the barrier agent composition of the present invention on sliding parts such as a watch, a motor, a lens of a single-lens reflex camera, and an adjacent portion including Z or a peripheral portion thereof, the sliding surface force can be improved. It is an object of the present invention to provide a method for effectively preventing the oozing of the lubricating oil and a component in which the oozing of the lubricating oil is prevented.
  • the present invention provides a noria agent composition for lubricating oil, comprising: a polymer (A) containing the following polymerized units (al) and (bl); and an aqueous medium (B). It is.
  • a compound containing a polyfluoroalkyl group with an etheric oxygen atom inserted.
  • Polymerized unit (bl) Compound having silicon and unsaturated groups.
  • the polymer (A) used in the barrier agent composition of the present invention is preferably a polymerized unit (al) which is also a polymerized unit that also leads to a compound represented by the following formula (1).
  • Q 1 a single bond or a divalent linking group.
  • R 1 hydrogen atom or methyl group.
  • Rf Polyfluoroalkyl group or ether between carbon-carbon bonds
  • the Rf group-containing compound represented by the formula (1) is an unsaturated ester compound.
  • the polymer (A) used in the barrier agent composition of the present invention has a polymerized unit (bl) represented by the following formula (2) It is preferable that the compound represented by
  • R 2 a hydrogen atom or a methyl group.
  • R 4 and R 5 each independently represent a hydrogen atom, a methyl group
  • Q 2 a single bond or a divalent linking group.
  • n, m and 1 each independently an integer of 0 or 1.
  • the polymer (A) used in the barrier agent composition of the present invention preferably contains a non-fluorinated polymer unit (a2) in addition to the polymer unit (al).
  • the softening point of the polymer (A) used in the noria agent composition of the present invention is preferably from 40 to 150 ° C.
  • the noria agent composition of the present invention contains one or more surfactants.
  • the aqueous medium (B) used for the barrier agent composition of the present invention preferably contains a water-soluble organic solvent having a boiling point of 40 to 200 ° C.
  • the barrier agent composition of the present invention preferably has a surface tension of 10 to 40 mN / m.
  • the concentration of the polymer (A) used in the noria agent composition of the present invention is preferably 0.01 to 40% by weight.
  • the present invention provides the above-mentioned Noria agent composition of lubricating oil, comprising:
  • This is a method in which a coating is applied to the surface of a component close to Z or a sliding component to form a coating, and a barrier performance against lubricating oil is imparted to the sliding component and a component close to the Z or the sliding component.
  • the present invention is a sliding component provided with a film of any of the above lubricating oil noria agent compositions and provided with barrier performance, and a component close to Z or a sliding component.
  • the barrier agent composition of the present invention When the barrier agent composition of the present invention is applied to a sliding part such as a timepiece, a motor, a lens of a single-lens reflex camera, or a nearby part including Z or a peripheral part thereof, lubricating oil from the sliding surface Exudation can be effectively prevented. Further, the barrier agent composition of the present invention is excellent in solubility, robustness of the coating, and uniformity of the coating, and thus effectively acts on both metal and plastic sliding surfaces. In addition, since an aqueous medium is used, the working environment during preparation of the barrier agent composition and application to sliding parts can be kept safe, excellent in workability, and when using sliding parts. Little impact on the environment. BEST MODE FOR CARRYING OUT THE INVENTION
  • the barrier agent composition of the present invention comprises a polymer unit (A) containing a polymer unit derived from a compound having a polyfluoroalkyl group and a polymer unit derived from a compound having a silicon and unsaturated group. And an aqueous medium (B).
  • An emulsion-type and micro-emulsion-type barrier agent composition comprising:
  • the “noria agent composition of lubricating oil” may be simply referred to as “barrier agent”.
  • the polymer (A) in the present invention is a polymer containing specific structural units, that is, a polymer unit (al) and a polymer unit (bl).
  • a polyfluoroalkyl group and a polyfluoroalkyl group having an etheric oxygen atom inserted between carbon and carbon bonds may be collectively referred to as an “Rf group”.
  • a polyfluoroalkyl group having an etheric oxygen atom inserted between the bonds may be collectively referred to as an "Rf group containing an etheric oxygen atom”.
  • Rf group is a superordinate concept of the “Rf group containing an etheric oxygen atom”, and therefore, in the present specification, the term “Rf group” is a generic term for both.
  • the polymerized unit (al) is more preferably a polymerized unit derived from an Rf group or a compound containing an Rf group containing an etheric oxygen atom, and more preferably an unsaturated ester conjugate.
  • the Rf group means a group in which two or more hydrogen atoms of an alkyl group or an alkyl group which may contain an etheric oxygen atom are substituted with a fluorine atom.
  • the number of fluorine atoms in the Rf group must be
  • a perfluoroalkyl group in which substantially all of the hydrogen atoms of the alkyl group have been substituted with fluorine atoms is most preferred, with 60% or more being preferred, and particularly 80% or more being preferred.
  • a perfluoroalkyl group may be referred to as an “RF group” below. It is needless to say that this RF group is included when the Rf group is simply referred to as “RF group”.
  • the Rf group carbon number power of 14 is preferable, and 6 to 12 is particularly preferable.
  • the Rf group may have a straight-chain structure or a branched structure, but preferably has a straight-chain structure. In the case of a branched structure, it is preferable that the branched portion is present at the terminal portion of the Rf group and is a short chain having about 1 to 3 carbon atoms.
  • the Rf group may have a chlorine atom at the terminal.
  • the structure of the terminal component of the Rf group may be CF CF—, CF—, CF C1—, (CF) CF—
  • the carbon number of the RF group is preferably from 4 to 14, particularly preferably from 6 to 12.
  • the RF group may have either a straight chain structure or a branched structure, but is preferably a straight chain structure.
  • the RF group is particularly preferably a linear group represented by F (CF) — [n is an integer of 6 to 12].
  • Rf group containing an etheric oxygen atom examples include Rf groups having an oxypolyfluoroalkylene moiety such as oxypolyfluoroethylene and oxypolyfluoropropylene.
  • the advancing contact angle increases as the chain length of the Rf group increases, and becomes almost constant when the number of carbon atoms is 4 or more.
  • the receding contact angle hardly changes until the chain length of the Rf group is up to 6 carbon atoms, starts to increase when the number of carbon atoms is 7 or more, and becomes maximum when the chain number is 10 carbon atoms.
  • Rf group not containing an etheric oxygen atom examples include, but are not limited to, the following: In the following specific examples, groups corresponding to structurally isomer groups are also included. I will. CF—, CF— [includes both F (CF) —and (CF) CF], CF— [
  • Rf group containing an etheric oxygen atom examples include the following: The Rf group is not limited to these. In the following specific examples, groups corresponding to structurally isomeric groups are also included. F (CF) OCF (CF), F [CF (CF) CF O] CF (CF) CF CF CF
  • u is an integer of 2 to 6.
  • V is an integer of 1 to L1, preferably an integer of 1 to 4.
  • w is an integer from 1 to L1, preferably an integer from 1 to 6; ).
  • the polymerized unit (al) in the present invention is preferably a compound having an Rf group-containing polymerizable unsaturated bond represented by the following formula (1):
  • the Rf group-containing compound represented by the formula (1) is more preferably an unsaturated ester compound.
  • Q 1 a single bond or a divalent linking group.
  • R 1 hydrogen atom or methyl group.
  • Rf a polyfluoroalkyl group or a polyfluoroalkyl group having an ethereal oxygen atom inserted between carbon and carbon bonds.
  • Q 1 in the formula examples include the following. Force Q 1 can be appropriately selected as long as it is a single bond or a divalent linking group, and is not limited to the following examples! /.
  • Force Q 1 can be appropriately selected as long as it is a single bond or a divalent linking group, and is not limited to the following examples! /.
  • N N—, one COO—, one COS—, one CONH—, one COCH—, one CH CH
  • the structure of Q 1 is —Z 1 — (Y 1 )-(Z 1 is —O— or —NH—, Y 1 is a divalent linking group, and n is 0 or 1.
  • Y 1 is a divalent linking group represented by Preferred examples of Y 1 include an alkylene group, an amino group, a sulfol group, and a divalent linking group capable of obtaining a combination thereof. More preferred structures include those in which Y 1 is a linear alkylene group having 1 to 5 carbon atoms.
  • Rf in the formula (1) in order to improve the packing of the Rf group, it is structurally higher.
  • a polyfluoroalkyl group containing no etheric oxygen atom is selected, and in particular, a perfluoroalkyl group containing no etheric oxygen atom is selected.
  • a preferred structure of the Rf group-containing compound represented by the formula (1) includes a compound represented by the formula (3), and the Rf group-containing compound represented by the following formula (3). It is more preferable that the danigata is an unsaturated esteri dani! /.
  • R 1 hydrogen atom or methyl group
  • Z 1 single bond, — O—, -NH- ⁇ 1 : alkylene group having 1 to 5 carbon atoms
  • CH CH-COO- (CH)-(CF)-F ⁇
  • CH CH- COO- (CH)-(CF)-F ⁇
  • CH CH-COO- (CH)-(CF) -F
  • CH CH-COO- (CH)-(CF) -F
  • CH C
  • CH CH- COO- (CH)-(CF)-F
  • CH CH- COO- (CH)-(CF)-F
  • CH CH- COO- (CH)-(CF)-F
  • the polymer unit (al) in the polymer (A) may be only one type or two or more types. In the case of two or more kinds, if the number of carbon atoms in the Rf group is different, the carbon chain length will be longer! Therefore, it is preferably a polymerized unit of two or more monomers having different chain lengths.
  • those having a long carbon chain are those having 7 or more carbon atoms, those having a short carbon chain length, and those having 6 carbon atoms or less.
  • the polymerized unit (bl) is a polymerized unit derived from a compound having silicon and an unsaturated group, and the compound having the polymerized unit (bl) is preferably a compound represented by the following formula (2). ,.
  • R 2 a hydrogen atom or a methyl group.
  • R 4 and R 5 each independently a hydrogen atom, a methyl group
  • an alkoxy group for example, an alkoxy group, a halogen atom,
  • Q 2 a single bond or a divalent linking group.
  • n, m, 1 each independently an integer of 0 or 1.
  • —CH CH—CO—, linear or branched alkylene alkalkylene, alkylenoxy, divalent 4, 5, 6 or 7-membered ring substituents
  • substituents which may have a substituent include a halogen atom (F, Cl, Br, 1), a cyano group, and an alkoxy group (methoxy, ethoxy, butoxy, octyloxy).
  • Q 2 is a single bond, —O—, — (CH 2 CH 2 O) —, —COO
  • n is an integer of 1 to 20
  • a 6-membered aromatic group a linear or branched alkylene group, or a group composed of a combination of these divalent linking groups.
  • a more preferred structure of Q 2 is a single bond , An alkylene group having 1 to 5 carbon atoms, and —COOY 3 — (Y 3 is an alkylene group having 1 to 5 carbon atoms).
  • sliding component and a component at or around Z (hereinafter, also simply referred to as a sliding component).
  • CH CH—SiCl
  • CH CH—Si (OR 6 ) [R 6 is CH—, CH CH—, or (C
  • the polymer unit (bl) in the polymer (A) may be only one type or two or more types.
  • the polymerized unit (bl) in the polymer (A) improves the adhesion to the substrate, and is particularly effective for sliding parts having a polar group on the surface.
  • the polymerized unit (bl) is preferably contained in the polymer (A) in an amount of 0.1 to 50% by mass, particularly preferably 1 to 30% by mass.
  • the polymer (A) preferably contains a polymerized unit (a2) other than the polymerized units (al) and (bl).
  • the polymerization unit (a2) is not particularly limited as long as it is a polymerization unit derived from a monomer having no Rf group and having a polymerizable unsaturated group.
  • the other monomer is selected from known compounds, and one or more kinds can be used.
  • a polymer (A) containing a polymerized unit (a2) of another monomer is employed, the leveling property is improved, the uniformity of the coating is improved, and the coating of the polymer (A) is improved. Control of characteristics and adhesion to sliding parts becomes easier.
  • polymerized unit (a2) examples include polyolefin-based unsaturated esters such as acrylic acid esters, unsaturated esters having an epoxy group, compounds having a vinyl group, compounds having an amino group and a polymerizable unsaturated group, acrylic acid
  • polyolefin-based unsaturated esters such as acrylic acid esters, unsaturated esters having an epoxy group, compounds having a vinyl group, compounds having an amino group and a polymerizable unsaturated group, acrylic acid
  • polyester selected from polyesters of acrylates such as diesters and a polymer unit derived from a compound having a substituted amino group and a polymerizable unsaturated group is preferably selected.
  • R 8 is a group represented by the following numbers 1 to 18:
  • R 9 is number below 1: 18 a group represented by.
  • R 1 () is a group represented by the following numbers 1 to 6, or the like.
  • Example 6 of monomer (polymerized unit (a2))
  • R 11 is a hydrogen atom or a methyl group
  • R 12 organic group.
  • n an integer from l to 4.
  • the fluorine content in the polymer (A) in the present invention is preferably 20% by mass or more, and particularly preferably 40 to 80% by mass. If the fluorine content is less than 20% by mass, the critical surface tension of the surface of the film formed after the barrier treatment increases, and there is a possibility that satisfactory barrier performance may not be obtained.
  • the polymer (A) of the present invention has a moderately large weight average molecular weight! / And improved film strength and water resistance. If the weight average molecular weight is appropriately small, gloss, resolubility, and level The ring properties are improved.
  • the weight average molecular weight of the polymer (A) in the present invention is preferably 1 ⁇ 10 3 to 1 ⁇ 10 7, particularly preferably 1 ⁇ 10 4 to 1 ⁇ 10 5 , and preferably 2 ⁇ 10 4 to 5 10 4. Good.
  • the way in which the polymer units of the polymer (A) are connected may be graft, block or random, and is particularly preferably random.
  • the composition of the present invention contains an aqueous medium (B) together with the polymer (A).
  • the polymer (A) in the composition is preferably dispersed as particles in an aqueous medium described below, and from the viewpoint of dispersion stability, the particle size of the dispersed particles in the composition is preferably It is preferably 10 m or less, more preferably 1 ⁇ m or less.
  • concentration of the polymer (A) in the composition of the present invention a part which is treated so as to be thick enough to obtain a sufficient thickness of the film of the polymer (A) formed upon the Noria treatment Since it is preferable that the thickness is small enough to maintain the dimensional accuracy and aesthetic appearance of the film, 0.01 to 40% by mass is preferable, and 0.03 to 5% by mass is particularly preferable.
  • concentration of the polymer (A) is within this range, the noria performance is good, and the cost for performing the noria treatment using the composition of the present invention is also excellent. Unless the concentration of the polymer (A) is too high or too low, sufficient barrier performance can be obtained.
  • the barrier composition of the present invention can be used for a sliding component by setting a low surface tension with the sliding component.
  • the surface tension is preferably 10 to 40 mNZm (20 to 30 ° C), and more preferably 10 to 30 mNZm, in order to improve the wettability and adhesion to the surface.
  • the surfactant includes a fluorine-based surfactant (hereinafter sometimes referred to as a fluorine-based surfactant (C)).
  • fluorine-based surfactant hereinafter sometimes referred to as a fluorine-based surfactant (C)
  • C fluorine-based surfactant
  • Many fluorine-based surfactants have water- and oil-repellency effects themselves, and it is expected that barrier performance can be improved by adding a fluorine-based surfactant.
  • the surfactant to be added has the same charge as that used in the synthesis, and one of the surfactants is a non-ionic one. Combinations are preferred.
  • Examples of the fluorine-based surfactant (C) include an ionic surfactant having a fluorine atom or a non-ionic surfactant having a fluorine atom.
  • Examples of such a fluorine-based surfactant (C) include an a-fluorine-based surfactant having both an Rf group and an a-on group, a cationic fluorine having both an Rf group and a cationic group.
  • fluorinated surfactant (C) Specific examples of the fluorinated surfactant (C) are described below, but are not limited thereto.
  • such a polymer in which a polymer having an Rf group and capable of lowering the surface tension may be used in place of the fluorosurfactant (C)
  • such a polymer also functions as a kind of binder.
  • increasing the strength of the coating also has the following advantages.
  • the amount of the surfactant added is preferably such that the surfactant concentration in the composition of the present invention is equal to or higher than the critical micelle concentration.
  • the fluorine-based surfactant (C) 0.1% by mass in the composition is sufficient, and it is preferably 0.01 to 0.1% by mass.
  • the composition of the present invention is characterized by containing an aqueous medium (B).
  • the aqueous medium (B) include water or a mixture of water and a water-soluble organic solvent.
  • the water-soluble organic solvent is preferably one having a boiling point of 40 to 200 ° C for ease of drying, and more preferably one having a solubility in water at 20 ° C of 1% by mass or more at 20 ° C.
  • the water-soluble organic solvent examples include ketones, esters, glycols, glyconoate ethers, alcohols and the like. Among them, acetone and isopropyl alcohol, which are preferable to ketones and alcohols, are exemplified.
  • a water-soluble organic solvent By containing a water-soluble organic solvent, the drying property of the coating film and the solubility and stability of the composition can be improved.
  • the aqueous medium (B) contains a water-soluble organic solvent
  • the proportion of water in the aqueous medium (B) is preferably 50 to 99% by mass, while the proportion of the water-soluble organic solvent is 1 to 50%. 5% to 50% by weight is more preferred, and 10 to 30% by weight is particularly preferred.
  • the aqueous medium (B) may be desirable to prevent the aqueous medium (B) from being flammable.
  • the proportion of the water-soluble organic solvent in the aqueous medium) may be set to 0 to 20% by mass, the composition has no flammability and is extremely excellent in use safety.
  • the barrier agent composition of the present invention provides a lubricating oil (hydrocarbon-based lubricating oil having 16 or more carbon atoms, such as normal hexadecane) on the surface of the film when the film is formed on the surface to be treated. ) And the contact angle is 40 degrees or more. If the contact angle of the composition with the lubricant on the coating surface is as described above, it can be considered that sufficient Noria performance is obtained. It comes out.
  • a lubricating oil hydrocarbon-based lubricating oil having 16 or more carbon atoms, such as normal hexadecane
  • the barrier agent composition of the present invention contains other components in addition to those described above within a range that does not adversely affect dispersion stability, barrier properties, wettability to sliding parts, or appearance. Is also good.
  • Dyes for the purpose of distinguishing between untreated parts and the purpose to be treated, and stabilizers for the dyes may be added.
  • flame retardants, defoamers, antistatic agents and the like are also included.
  • the method for producing the polymer (A) of the present invention is not particularly limited, but is preferably synthesized by an emulsion polymerization method in an aqueous medium (B), since the composition of the present invention can be directly obtained.
  • the emulsification polymerization method is preferably carried out by the following method 1 or method 2.
  • each monomer is emulsified by a homomixer or a high-pressure emulsifier in the presence of a medium and an emulsifier, and then polymerized by the action of a polymerization initiation source.
  • the monomer when a gaseous monomer such as vinyl chloride is employed 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 conjugates, and persulfates, or ionizing radiation such as ⁇ -rays can be employed.
  • the medium it is preferable to use the same medium as the aqueous medium (II) constituting the composition of the present invention.
  • the barrier agent composition of the present invention when the barrier agent composition of the present invention is produced by an emulsion polymerization method, the compound represented by the formula (1) or (3) and (2) may be added, if necessary, to other compounds. It is preferable to employ a method of subjecting the monomer (a2) to emulsion polymerization in an aqueous medium (B) in the presence of an emulsifier.
  • the emulsifier may be a fluorine-based surfactant (C) or a non-fluorine-based surfactant. The effect is expected to be improved.
  • the barrier agent composition of the present invention may contain one or more fluorine-based or non-fluorine-based surfactants, these surfactants need not be removed after emulsion polymerization. These surfactants may be added at the time of emulsion polymerization for adjustment.
  • the non-fluorinated surfactant used in the emulsion polymerization includes a non-fluorinated nonionic surfactant having an HLB value of 7 or more and a non-fluorinated cationic surfactant having an alkyl group having 6 or more carbon atoms in the molecule.
  • An activator or a non-fluorine-based surfactant having an alkyl group having 6 or more carbon atoms in the molecule is preferable.
  • the selected non-fluorinated surfactant is easy to obtain the effect of increasing the dispersion stability if it is cationic or ion-based, and easily increases the emulsifying ability if it is nonionic. Therefore, a combined effect can be obtained by using these surfactants in combination.
  • non-fluorinated non-ionic surfactant having an HLB value of 7 or more a known non-ionic surfactant having 5 or more oxyalkylene units in a molecule is preferable.
  • oxyalkylene unit oxyethylene or oxypropylene is preferable.
  • non-fluorinated cationic surfactant having an alkyl group having 6 or more carbon atoms in the molecule include an alkylammonium salt and the like, and a non-fluorinated cationic surfactant having an alkyl group having 6 or more carbon atoms in the molecule.
  • fluorinated aionic surfactant include an alkyl sulfate.
  • the non-fluorinated surfactant in the present invention is not limited to the following, but specific examples thereof are given below.
  • the number of moles of kazuna 8)
  • Moles of oxetylene added 5)
  • stearyltrimethylammonium chloride dioctyldimethylammonium chloride, ammonium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate, and dimethyloctadecylamine
  • non-fluorinated surfactants include polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl Ether and dimethyl octadecylamine acetate are preferred.
  • a surfactant is used at the time of emulsion polymerization, either a fluorine-based surfactant (C) or a non-fluorine-based surfactant may be used, and if necessary, a surfactant having a different ionicity may be used. Two or more kinds may be used in combination.
  • surfactants having different ionic properties it is preferable to combine cationic and nonionic, aionic and nonionic, or nonionic and amphoteric.
  • the barrier agent composition of the present invention may contain a non-fluorine-containing surfactant together with the fluorine-containing surfactant (C). It is preferably 50 to 80% by mass based on the total amount of (C) and the non-fluorinated surfactant.
  • the non-fluorinated surfactant may be the one used during the emulsion polymerization or the one added after the polymerization. The total amount of these surfactants is 0% in the barrier agent of the present invention. 1% by mass is sufficient, and preferably 0.01 to 0.1% by mass.
  • the polymer (A) can also be obtained by solution polymerization using a fluorinated solvent.
  • the fluorinated solvent one having a small environmental destruction factor is desired.
  • the fluorinated solvent that can be suitably used for the polymerization of the polymer (A) include HFCs such as 1,3-bis (trifluoromethyl) benzene and 2,3-dihydrodecafluoro (n-) pentane. , C HF C1 [Asahi Glass
  • HCFC such as "AK-225" manufactured by K.K.
  • the fluorinated solvent is preferably removed after polymerization, and the polymer (A) is dispersed in an aqueous medium (B) in the presence of a fluorinated surfactant (C) to obtain a composition of the present invention! / ,.
  • the barrier agent composition of the present invention is diluted to an arbitrary concentration, and forms a film on the surface of the sliding component according to the purpose or application, so that the necessary sliding component or the vicinity of the sliding component is obtained.
  • the surface of the component (hereinafter, also referred to as a “processed portion”) can be subjected to a lubricating oil barrier treatment.
  • a processing method a general coating processing method can be adopted. For example, there are methods such as dip coating, spray coating, and coating using an aerosol can filled with the composition of the present invention, but are not limited to these methods.
  • a coating can be formed on the surface of the component to be treated by applying the barrier agent composition of the present invention to the surface of the component and then drying it. It is preferred to heat treat the composition after it has been supplied and dried or together with drying. By performing such heat treatment, depending on the surface to be treated A uniform coating can be formed.
  • Drying is preferably performed at a temperature of 60 ° C or higher, and more preferably at a temperature of 100 ° C or higher.
  • the drying temperature does not need to be higher than the softening point of the polymer (A) constituting the barrier agent composition of the present invention, but promotes the formation of a film having a uniform thickness and improves the orientation of the Rf group.
  • the polymer (A) is preferably higher than the softening point.
  • the temperature is preferably 300 ° C. or lower in order to prevent deterioration of the polymer (A).
  • the conditions for the heat treatment may be selected according to the composition of the composition to be applied, the application area, and the like.
  • the reason why the Noria treatment is performed such that a film is formed by heating to improve the Noria performance as compared with the case where a film is simply formed is that the polymer (A) is melted by heating.
  • the film is softened to form a more uniform film, and that the Rf group on the film surface is a force that causes regular rearrangement.
  • Such improvement of the barrier performance by the heat treatment is particularly observed in the case of the polymer (A) containing two or more kinds of polymerized units (al) having different carbon chain lengths in the Rf group.
  • the object of the barrier treatment of the present invention includes a plastic part in addition to the metal part.
  • the minimum film forming temperature of the polymer (A) be low from the necessity of expanding the application range of the barrier agent composition of the present invention. Since the heat resistance temperature of plastics used for electronic components is often around 150 ° C, the drying temperature is lower. The minimum film formation temperature is often derived from the softening point of the polymer. Therefore, the softening point of the polymer (A) is preferably 150 ° C or lower. In order to achieve stable performance, heat treatment at a temperature higher than the minimum film forming temperature is required. However, if the softening point is too low and becomes lower than the operating temperature of the treated component, it will affect the barrier performance and durability. Therefore, considering the ease of film formation and barrier performance and durability, the softening point of the polymer (A) should be 40 to 80 ° C. Is preferred.
  • such a soft point can be measured by a differential scanning calorimeter.
  • a total of 60 g of the raw materials excluding the polymerization initiator is charged into a 100 ml ampoule, and emulsified at 50 ° C for 1 hour.Then, the polymerization initiator is charged, and radical polymerization is performed at 60 ° C for 18 hours. went. After the polymerization, the precipitate was separated by filtration to obtain a dispersion of the polymer (A).
  • the composition of the raw material is monomer (al, bl, a2) 31.7% (in terms of Net), emulsifier (surfactant) 4.4% (in terms of Net), n-dodecylmercaptan 0.
  • the content was 2%, acetone (boiling point: 56.5 ° C) 7.9%, ion-exchanged water 55.5%, and polymerization initiator 0.3%.
  • the polymerization initiator used was 2,2, -azo (2-methylpropionamidine) hydrochloride.
  • the raw material monomer (al, bl, a2) composition and the type of emulsifier are changed as shown in Table 6 (11 types).
  • Table 6 shows the yield relative to the total amount of the monomers and the fluorine concentration in the solid content.
  • the fluorine concentration in Table 6 was calculated from the composition of the polymerization product by the following equation. It was confirmed by gas chromatography of each polymerization product that the peak of the monomer had disappeared.
  • A-151 Triethoxyvinylsilane
  • CHMA cyclohexyl methacrylate
  • IBMA Isobornyl methacrylate
  • StMA Stearyl methacrylate
  • BzMA Benzyl methacrylate
  • Hydrocarbon emulsifier Nonion K-220 (manufactured by NOF Corporation)
  • the softening point of the polymer 4 (the active ingredient of Example 4) was measured. After volatilizing the solvent at room temperature from the polymer dispersion obtained by polymerization, and completely removing water at 110 ° C., the softening point of the polymer was measured. For the measurement of the soft point, DSC-50 manufactured by Shimadzu Corporation was used. The results are shown in Table 7.
  • the particle diameter in the table is the average cumulative diameter (D50) [ ⁇ m] of 50% in volume.
  • the barrier agent composition 1 (Example 1) is a comparative example, and the barrier agent compositions 2 to L 1 (Examples 2 to L 1) are examples.
  • the flammable organic solvent in the examples is less than 1%, and the resulting barrier agent composition is safer to use than flammable, and has less impact on the environment.
  • the emulsion particle diameter of the barrier agent composition of Example 4 was measured.
  • the emulsion particle diameter of the barrier agent composition was 1 m or less, and the dispersion stability was extremely excellent.
  • the results are shown in Table 7.
  • a particle size distribution analyzer “Microtrac UPA” manufactured by Nikkiso Co., Ltd. was used.
  • the surface tension at 25 ° C. of the Noria agent composition of Example 4 was measured.
  • the emulsifier (surfactant) “Surflon S-141” used in preparing the barrier agent composition has a critical micelle concentration of 0.01% or less.
  • the concentration of the fluorine-based surfactant in the barrier agent composition was higher than the critical micelle concentration, and a low surface tension could be maintained.
  • the surface tension was measured using a Wilhelmy surface tensiometer. Table 8 shows the results.
  • the barrier agent composition of each example was diluted 4 times with ion-exchanged water to obtain a treatment liquid to be evaluated.
  • the contact angle of a lubricating oil (“SYNT-A-LUBE" manufactured by Mavis Co., Ltd.) was measured for the treated test piece. The contact angle was measured using a drop-type projection contact angle meter manufactured by Kyowa Interface Science Co., Ltd. Table 9 shows the evaluation results.
  • the noria agent composition containing the polymer (A) having the polymerized unit (al) and the polymerized unit (bl) has sufficiently high barrier performance against lubricating oil. . Further, it can be seen that the noria agent composition containing the polymer (A) having the polymerized unit (a2) which is not limited to the polymerized unit (al) and the polymerized unit (bl) exhibits further higher barrier performance. This is presumably because the adhesion of the barrier agent composition to the test piece (sliding component) is improved.
  • the barrier agent composition of the present invention is applied to a sliding part such as a timepiece, a motor, a lens of a single-lens reflex camera or the like, and a portion near Z or a peripheral portion thereof to form a film. As a result, it is possible to provide a component in which the oozing of the lubricating oil with the sliding surface force is effectively prevented.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Il est prévu une composition comprenant un polymère (A) contenant des unités monomères (a1) dérivées d’un ester insaturé possédant un groupe polyfluoroalkyle et des unités monomères (b1) possédant du silicium et un groupe insaturé de même qu’un milieu aqueux(B) ; un procédé consistant à appliquer la composition à la surface d’une pièce coulissante d’un instrument de précision, comme un moteur ou une caméra reflex à simple lentille, pour former un film de revêtement et ainsi constituer une barrière de protection contre les huiles de lubrification ; et une pièce coulissante revêtue de la composition, la pièce présentant d’excellentes caractéristiques de protection contre les huiles de lubrification.
PCT/JP2005/008961 2004-05-25 2005-05-17 Composition de protection contre l’huile de lubrification et utilisation de celle-ci WO2005116153A1 (fr)

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JP2015528759A (ja) * 2012-07-10 2015-10-01 ザ・スウォッチ・グループ・リサーチ・アンド・ディベロップメント・リミテッド 物品の表面のエピラム化のための作用剤
JP2016188358A (ja) * 2015-03-18 2016-11-04 ザ・スウォッチ・グループ・リサーチ・アンド・ディベロップメント・リミテッド エピラム化剤でコーティングされた表面を含む基板およびこのような基板のエピラム化のための方法
JP2019158469A (ja) * 2018-03-09 2019-09-19 セイコーインスツル株式会社 時計用部品、ムーブメントおよび時計
JP2020040731A (ja) * 2018-09-10 2020-03-19 ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ 医薬品および化粧品用の摺動層を有する包装材および方法、およびその製造のための調製物

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JPS59126109A (ja) * 1982-12-29 1984-07-20 オリンパス光学工業株式会社 グリ−スのにじみ出し防止装置
JPH01127080A (ja) * 1987-11-13 1989-05-19 Seimi Chem Kk 含フッ素化合物被覆膜の形成方法
JP2000001669A (ja) * 1998-06-16 2000-01-07 Seimi Chem Co Ltd 水系オイルバリア組成物およびそれを用いた被処理物
JP2002146271A (ja) * 2000-11-16 2002-05-22 Three M Innovative Properties Co 撥水、撥油および防汚性コーティング組成物

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JPS59126109A (ja) * 1982-12-29 1984-07-20 オリンパス光学工業株式会社 グリ−スのにじみ出し防止装置
JPH01127080A (ja) * 1987-11-13 1989-05-19 Seimi Chem Kk 含フッ素化合物被覆膜の形成方法
JP2000001669A (ja) * 1998-06-16 2000-01-07 Seimi Chem Co Ltd 水系オイルバリア組成物およびそれを用いた被処理物
JP2002146271A (ja) * 2000-11-16 2002-05-22 Three M Innovative Properties Co 撥水、撥油および防汚性コーティング組成物

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015528759A (ja) * 2012-07-10 2015-10-01 ザ・スウォッチ・グループ・リサーチ・アンド・ディベロップメント・リミテッド 物品の表面のエピラム化のための作用剤
JP2016188358A (ja) * 2015-03-18 2016-11-04 ザ・スウォッチ・グループ・リサーチ・アンド・ディベロップメント・リミテッド エピラム化剤でコーティングされた表面を含む基板およびこのような基板のエピラム化のための方法
EP3070152B1 (fr) * 2015-03-18 2018-02-28 The Swatch Group Research and Development Ltd. Substrat comprenant une surface recouverte d'un agent épilame et procédé d'épilamage d'un tel substrat
JP2019158469A (ja) * 2018-03-09 2019-09-19 セイコーインスツル株式会社 時計用部品、ムーブメントおよび時計
JP7026538B2 (ja) 2018-03-09 2022-02-28 セイコーインスツル株式会社 時計用部品、ムーブメントおよび時計
JP2020040731A (ja) * 2018-09-10 2020-03-19 ショット アクチエンゲゼルシャフトＳｃｈｏｔｔ ＡＧ 医薬品および化粧品用の摺動層を有する包装材および方法、およびその製造のための調製物
JP7446748B2 (ja) 2018-09-10 2024-03-11 ショット ファーマ アクチェンゲゼルシャフト ウント コンパニー コマンディートゲゼルシャフト アウフ アクチェン 医薬品および化粧品用の摺動層を有する包装材および方法、およびその製造のための調製物

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TW200604330A (en) 2006-02-01
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JP4773953B2 (ja) 2011-09-14

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