JP6446383B2 - Surface protective agent composition and coated electric wire with terminal - Google Patents

Description

  The present invention relates to a surface protective agent composition and a coated electric wire with a terminal, and more particularly, to a surface protective agent composition excellent in anticorrosive performance for preventing metal corrosion and a coated electric wire with terminal excellent in anticorrosive performance using the same. is there.

  Grease is used for lubrication and corrosion prevention in metal equipment and metal parts. For example, Patent Document 1 describes that a grease containing a perfluoroether base oil, a thickener, barium sulfate or antimony oxide is used for a machine part. Patent Document 2 discloses that a volatile liquid having a boiling point of 300 ° C. or less is 30 to 95% by mass, a lubricant and / or a rust preventive agent is 1 to 50% by mass, and a compound having an amide group is 0.1 to 0.1%. A surface treatment agent containing 50% by mass has been proposed.

Japanese Patent No. 4811408 International Publication No. 2009/022629

  The grease of Patent Document 1 has low adhesion to metal, and may flow out from the metal surface particularly in a high temperature environment, and it is difficult to stably protect the metal surface. This is presumably because the grease of Patent Document 1 is not chemically bonded to the metal surface and is only in close contact with the metal surface by the van der Waals force having a weak suction force. Further, the surface treatment agent of Patent Document 2 also has low adhesion to metal, and may flow out of the metal surface particularly in a high temperature environment, and it is difficult to stably protect the metal surface.

  The problem to be solved by the present invention is to provide a surface protective agent composition that stably protects a metal surface even when exposed to a high temperature, and a coated electric wire with a terminal using the same.

ただし、Ｘ^１〜Ｘ^７は、それぞれ個別に酸素原子または硫黄原子を示し、Ｒ^１１〜Ｒ^１３は、それぞれ個別に水素基または炭素数１〜３０の炭化水素基を示し、かつこれらのうちの少なくとも１つは炭素数１〜３０の炭化水素基であり、Ｒ^１４〜Ｒ^１６は、それぞれ個別に水素基または炭素数１〜３０の炭化水素基を示し、かつこれらのうちの少なくとも１つは炭素数１〜３０の炭化水素基である。 In order to solve the above problems, a surface protective agent composition according to the present invention is represented by a viscous substance (A) composed of a lubricating base oil and an amide compound, the following general formulas (1) and (2): The composition (B) of the phosphorus compound and metal which consist of 1 type or 2 types or more of the compound which is said, and the mass ratio of said (A) and said (B) is (A) :( B) = 50. : The range of 50 to 98: 2, and the lubricating base oil has a kinematic viscosity at 100 ° C. of 10 mm ² / s or more and a number average molecular weight of 400 or more. .

^However, X 1 to X ⁷ are each independently an oxygen atom or a sulfur ^atom, R 11 ^{to R 13} are each independently a hydrocarbon group of a hydrogen group or a C1-30, and of these At least one is a hydrocarbon group having 1 to 30 carbon atoms, R ^{14 to} R ¹⁶ each independently represents a hydrogen group or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of these is It is a C1-C30 hydrocarbon group.

  The surface protective agent composition according to the present invention preferably has a shear viscosity at 100 ° C. of 1000 mPa · s or more.

The amide compound is preferably one or more of compounds represented by the following general formulas (3) to (5).
(Chemical formula 3)
^{R 21 -CO-NH-R 22} (3)
(Chemical formula 4)
^{R 23 -CO-NH-Y 31} -NH-CO-R 24 (4)
(Chemical formula 5)
^{R 25 -NH-CO-Y 32} -CO-NH-R 26 (5)
^However, R 21 ^{to R 26} are each an individual chain saturated or unsaturated hydrocarbon group of 5-25 carbon ^{atoms, R 22} can be ^{hydrogen, Y 31} and ^{Y 32} has a number of carbon A divalent hydrocarbon group having 1 to 10 carbon atoms selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, a phenylene group, or an alkylphenylene group having 7 to 10 carbon atoms.

  The amide compound is preferably a fatty acid amide having a melting point in the range of 20 to 200 ° C.

  The phosphorus compound preferably has one or more branched chain structures or one or more carbon-carbon double bond structures in the structure of the hydrocarbon group.

  The metal forming the composition with the phosphorus compound is preferably at least one selected from alkali metals, alkaline earth metals, aluminum, titanium, and zinc.

The molecular weight of the phosphorus compound and metal composition is preferably 3000 or less.
The surface protective agent composition according to the present invention is preferably used for anticorrosion to prevent metal corrosion by covering the metal surface with the surface of the metal member to be surface protected.

  The covered electric wire with a terminal according to the present invention is characterized in that the electrical connection portion between the terminal fitting and the electric wire conductor is covered with the above surface protective agent composition.

According to the surface protective agent composition of the present invention, a viscous substance (A) composed of a lubricating base oil and an amide compound, 1 of the compounds represented by the above general formulas (1) and (2) The composition (B) of the phosphorus compound and metal which consist of a seed | species or 2 or more types is contained, The mass ratio of said (A) and said (B) is (A) :( B) = 50: 50-98. : The above-mentioned lubricating base oil has a kinematic viscosity at 100 ° C. of 10 mm ² / s or more and a number average molecular weight of 400 or more, and is oxidized and deteriorated even when exposed to high temperatures. It is difficult and maintains a high viscosity, so that outflow is suppressed even when exposed to high temperatures. Thereby, even if it exposes to high temperature, a metal surface can be protected stably.

  The surface protective agent composition according to the present invention has a shear viscosity at 100 ° C. of 1000 mPa · s or more, so that the outflow is easily suppressed even when exposed to high temperatures.

  In the surface protective agent composition according to the present invention, when the specific phosphorus compound has one or more branched chain structures or one or more carbon-carbon double bond structures in the structure of the hydrocarbon group, a lubricating oil group Compatibility with oil is improved.

  Further, when the metal forming the composition with the specific phosphorus compound is at least one selected from alkali metals, alkaline earth metals, aluminum, titanium, and zinc, the adhesion when applied to the metal surface is improved. To do.

  Moreover, compatibility with a lubricating base oil improves that the molecular weight of the composition of a specific phosphorus compound and a metal is 3000 or less.

  And according to the covered electric wire with a terminal which concerns on this invention, since the electrical-connection part of a terminal metal fitting and an electric wire conductor is covered by said surface protective agent composition, even if it exposes to high temperature, a terminal metal fitting and an electric wire The metal surface such as a conductor is stably protected and the anticorrosion performance is maintained.

It is a perspective view of a covered electric wire with a terminal concerning one embodiment of the present invention. FIG. 2 is a longitudinal sectional view taken along line AA in FIG. 1.

  Next, an embodiment of the present invention will be described in detail.

  The surface protective agent composition according to the present invention (hereinafter sometimes referred to as the present protective agent composition) includes a viscous substance (A) composed of a lubricating base oil and an amide compound, a specific phosphorus compound, And a composition (B) with a metal.

  As the lubricating base oil, any mineral oil, wax isomerized oil or synthetic oil used as a normal lubricating base oil can be used, or a mixture of two or more kinds can be used. Specific examples of mineral oils include, for example, a lubricating oil fraction obtained by subjecting crude oil to atmospheric distillation and vacuum distillation, solvent dewaxing, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrogen Oils such as paraffinic and naphthenic oils, normal paraffins, and the like that are purified by appropriately combining purification treatments such as chemical purification, sulfuric acid washing, and clay treatment can be used.

  As wax isomerized oil, natural wax such as petroleum slack wax obtained by dewaxing hydrocarbon oil, or so-called Fischer Tropsch synthesis in which a mixture of carbon monoxide and hydrogen is contacted with a synthesis catalyst applicable at high temperature and high pressure. Those prepared by hydroisomerizing a wax raw material such as synthetic wax produced by the method can be used. When slack wax is used as a wax raw material, slack wax contains a large amount of sulfur and nitrogen, and these are not necessary for lubricating base oils. It is desirable to use a wax having a reduced content as a raw material.

  The synthetic oil is not particularly limited, but is a poly α-olefin such as 1-octene oligomer, 1-decene oligomer, ethylene-propylene oligomer or the hydride thereof, isobutene oligomer or the hydride thereof, isoparaffin, alkylbenzene, alkylnaphthalene, Diesters (ditridecylglutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, etc.), polyol esters (trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2) -Ethyl hexanoate, pentaerythritol pelargonate, etc.), polyoxyalkylene glycol, dialkyl diphenyl ether, polyphenyl ether Etc. The.

As the lubricating base oil, one having a kinematic viscosity at 100 ° C. of 10 mm ² / s or more and a number average molecular weight of 400 or more is used. Since the kinematic viscosity of the present protective agent composition is increased by increasing the kinematic viscosity of the lubricating base oil, it is easy to suppress outflow when exposed to high temperatures. From this viewpoint, the kinematic viscosity is more preferably 15 mm ² / s or more, and further preferably 20 mm ² / s or more. From the viewpoint of ease of application, the kinematic viscosity is more preferably 150 mm ² / s or less, and still more preferably 120 mm ² / s or less. Moreover, since it is excellent in volatility and the handleability at the time of manufacture, it is preferable that kinematic viscosity in 100 degreeC is in the range of 2-130 mm < ² > / s. The kinematic viscosity is measured according to JIS K2283.

  Since the lubricating base oil has a number average molecular weight of 400 or more, the molecular weight is high, and oxidative degradation when exposed to high temperatures is suppressed, thereby suppressing a decrease in the kinematic viscosity. Since the kinematic viscosity of the lubricating base oil is kept high even when exposed to high temperatures, the outflow when exposed to high temperatures is suppressed. From this viewpoint, the number average molecular weight is more preferably 450 or more. From the viewpoint of ease of application, the number average molecular weight is more preferably 10,000 or less, and still more preferably 8000 or less.

  The amide compound forms a network structure by hydrogen bonding in the lubricating base oil. Thereby, viscosity is provided to lubricating base oil and it becomes a grease-like viscous substance. That is, by using it together with the lubricating base oil, a gel-like material is formed at room temperature. That is, the amide compound gels (semi-solidifies) a liquid lubricating base oil at room temperature. The viscous substance is held on the coated surface of the material to be coated at room temperature or under heating due to its viscosity.

  The amide compound is a compound having one or more amide groups (—NH—CO—), and a monoamide compound having one amide group or a bisamide compound having two amide groups can be preferably used.

As the amide compound, for example, compounds represented by the following general formulas (3) to (5) can be preferably used. These may be used individually by 1 type and may be used in combination of 2 or more type.
(Chemical formula 3)
^{R 21 -CO-NH-R 22} (3)
(Chemical formula 4)
^{R 23 -CO-NH-Y 31} -NH-CO-R 24 (4)
(Chemical formula 5)
^{R 25 -NH-CO-Y 32} -CO-NH-R 26 (5)

In the general formulas (3) to (5), R ^{21 to} R ²⁶ each independently represents a saturated or unsaturated chain hydrocarbon group having 5 to 25 carbon atoms, and R ²² may be hydrogen. Y ³¹ and Y ³² represent a divalent hydrocarbon group having 1 to 10 carbon atoms selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, a phenylene group, or an alkylphenylene group having 7 to 10 carbon atoms. In the general formulas (3) to (5), part of hydrogen of the hydrocarbon group constituting R ^{21 to} R ²⁶ may be substituted with a hydroxyl group (—OH).

Specific examples of the amide compound represented by the general formula (3) include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxy stearic acid amide, saturated fatty acid amides, oleic acid amides, Elca Examples include unsaturated fatty acid amides such as acid amides, stearyl stearic acid amides, oleyl oleic acid amides, oleyl stearic acid amides, stearyl oleic acid amides and the like, substituted amides with saturated or unsaturated long chain fatty acids and long chain amines, and the like. Among these, an amide compound in which R ²¹ is a saturated chain hydrocarbon group having 12 to 20 carbon atoms and R ²² is a hydrogen group in the general formula (3), R ²¹ and R ²² in the general formula (3) Amide in which at least one of R ²¹ and R ²² is a saturated chain hydrocarbon group having 12 to 20 carbon atoms in the general formula (3), such as an amide compound each having a saturated chain hydrocarbon group having 12 to 20 carbon atoms Compounds are preferred. More specifically, stearyl stearamide is preferred.

Specific examples of the amide compound represented by the general formula (4) include ethylene bis stearic acid amide, ethylene bis isostearic acid amide, ethylene bis oleic acid amide, methylene bis lauric acid amide, hexamethylene bis oleic acid amide, Examples include hexamethylene bishydroxystearic acid amide and m-xylylene bisstearic acid amide. Among these, an amide compound in which R ²³ is a saturated chain hydrocarbon group having 12 to 20 carbon atoms and R ²⁴ is a hydrogen group in the general formula (4), and R ²³ and R ²⁴ in the general formula (4) Amide in which at least one of R ²³ and R ²⁴ is a saturated chain hydrocarbon group having 12 to 20 carbon atoms in the general formula (4), such as an amide compound each having a saturated chain hydrocarbon group having 12 to 20 carbon atoms Compounds are preferred. More specifically, ethylene bis stearamide is preferable.

Specific examples of the amide compound represented by the general formula (5) include N, N′-distearyl sebacic acid amide. Among these, an amide compound in which R ²⁵ is a saturated chain hydrocarbon group having 12 to 20 carbon atoms and R ²⁶ is a hydrogen group in the general formula (5), and R ²⁵ and R ²⁶ in the general formula (5) An amide compound in which at least one of R ²⁵ and R ²⁶ is a saturated chain hydrocarbon group having 12 to 20 carbon atoms in the general formula (5), such as an amide compound each having a saturated chain hydrocarbon group having 12 to 20 carbon atoms Compounds are preferred.

  The amide compound has a melting point of 20 ° C. or higher from the viewpoint of easily maintaining a gel (semi-solid) at room temperature when mixed with a lubricating base oil, and easily maintaining a gel (semi-solid) at normal temperature. It is preferable that More preferably, it is 50 degreeC or more, More preferably, it is 80 degreeC or more, Most preferably, it is 120 degreeC or more. Moreover, it is preferable that melting | fusing point is 200 degrees C or less. More preferably, it is 180 degrees C or less, More preferably, it is 150 degrees C or less. Moreover, it is preferable that the molecular weight of an amide compound exists in the range of 100-1000. More preferably, it exists in the range of 150-800.

  The content of the amide compound is a lubricating oil that is easy to maintain a gel (semi-solid) at room temperature when mixed with a lubricant base oil, and is easy to maintain a gel (semi-solid) at normal temperature. It is preferable that it is 1 mass part or more with respect to 100 mass parts of base oil. More preferably, it is 2 mass parts or more, More preferably, it is 5 mass parts or more. Moreover, it is preferable that it is 70 mass parts or less with respect to 100 mass parts of lubricating base oil. More preferably, it is 60 mass parts or less, More preferably, it is 50 mass parts or less.

ただし、Ｘ^１〜Ｘ^７は、それぞれ個別に酸素原子または硫黄原子を示し、Ｒ^１１〜Ｒ^１３は、それぞれ個別に水素基または炭素数１〜３０の炭化水素基を示し、かつこれらのうちの少なくとも１つは炭素数１〜３０の炭化水素基であり、Ｒ^１４〜Ｒ^１６は、それぞれ個別に水素基または炭素数１〜３０の炭化水素基を示し、かつこれらのうちの少なくとも１つは炭素数１〜３０の炭化水素基である。 The specific phosphorus compound is composed of one or more compounds represented by the following general formulas (1) and (2).

^However, X 1 to X ⁷ are each independently an oxygen atom or a sulfur ^atom, R 11 ^{to R 13} are each independently a hydrocarbon group of a hydrogen group or a C1-30, and of these At least one is a hydrocarbon group having 1 to 30 carbon atoms, R ^{14 to} R ¹⁶ each independently represents a hydrogen group or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of these is It is a C1-C30 hydrocarbon group.

  Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkyl-substituted cycloalkyl group, an alkenyl group, an aryl group, an alkyl-substituted aryl group, and an arylalkyl group.

  As the alkyl group, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group , Hexadecyl group, heptadecyl group, octadecyl group and the like. These may be linear or branched.

  Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. Examples of the alkyl-substituted cycloalkyl group include methylcyclopentyl group, dimethylcyclopentyl group, methylethylcyclopentyl group, diethylcyclopentyl group, methylcyclohexyl group, dimethylcyclohexyl group, methylethylcyclohexyl group, diethylcyclohexyl group, methylcycloheptyl group, dimethylcyclohexyl group. Examples thereof include a butyl group, a methylethylcycloheptyl group, and a diethylcycloheptyl group. The substitution position of the alkyl-substituted cycloalkyl group is not particularly limited. The alkyl group may be linear or branched.

  Alkenyl groups include butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl Etc. These may be linear or branched.

  Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the alkyl-substituted aryl group include tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, An undecylphenyl group, a dodecylphenyl group, etc. are mentioned. The substitution position of the alkyl-substituted aryl group is not particularly limited. The alkyl group may be linear or branched. Examples of the arylalkyl group include a benzyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, and a phenylhexyl group. The alkyl group may be linear or branched.

X ^{1 to} X ⁷ are preferably all oxygen atoms. The hydrocarbon group having 1 to 30 carbon atoms of R ^{11 to} R ¹⁶ is preferably a hydrocarbon group having 4 to 30 carbon atoms, and more preferably a hydrocarbon group having 8 to 30 carbon atoms.

X ^{1 to} X ⁷ are preferably all oxygen atoms. It is preferable that at least one of R ^{11 to} R ¹³ is a hydrogen group and at least one is a hydrocarbon group having 1 to 30 carbon atoms. Moreover, it is preferable that at least one of R ^{14 to} R ¹⁶ is a hydrogen group and at least one is a hydrocarbon group having 1 to 30 carbon atoms.

  Examples of the phosphorus compound represented by the general formula (1) include phosphorous acid, monothiophosphorous acid, dithiophosphorous acid, phosphorous acid monoester, monothiophosphorous acid monoester, dithiophosphorous acid monoester, phosphorous acid Acid diesters, monothiophosphite diesters, dithiophosphite diesters, phosphite triesters, monothiophosphite triesters, dithiophosphite triesters and the like. These may be used individually by 1 type as a phosphorus compound represented by General formula (1), and may be used in combination of 2 or more type.

  Examples of the phosphorus compound represented by the general formula (2) include phosphoric acid, monothiophosphoric acid, dithiophosphoric acid, phosphoric monoester, monothiophosphoric monoester, dithiophosphoric monoester, phosphoric diester, monothiophosphoric diester, dithiophosphoric diester, Examples thereof include phosphoric acid triesters, monothiophosphoric acid triesters, and dithiophosphoric acid triesters. These may be used individually by 1 type as a phosphorus compound represented by General formula (2), and may be used in combination of 2 or more type.

As the phosphorus compound, the phosphorus compound represented by the general formula (2) from the viewpoint of improving the compatibility with (A), improving the adhesion, and improving the adhesion to the metal surface to be protected. Is more preferable. Moreover, among the phosphorus compounds represented by the general formula (2), an acidic phosphate ester represented by the following general formula (6) or the general formula (7) is particularly preferable.
(Chemical Formula 8)
P (= O) (-OR < ¹⁴ >) (-OH) ₂ ... (6)
(Chemical 9)
P (= O) (-OR < ¹⁴ >) ₂ (-OH) (7)

  Examples of the metal used in the composition with the specific phosphorus compound include alkali metals such as Li, Na, and K, alkaline earth metals such as Mg and Ca, aluminum, titanium, and zinc. These may be used alone or in combination of two or more. Since these metals have a relatively high ionization tendency, a high adsorptivity can be obtained on the metal surface. Further, for example, since the ionization tendency is higher than that of Sn, the ion binding property to Sn can be improved. Among these, Ca and Mg are more preferable from the viewpoint of water resistance. The metal used in the composition with the phosphorus compound preferably has a valence of 2 or more from the viewpoint of increasing the molecular weight of the composition and improving heat resistance.

  Examples of the metal supply source in the composition of the specific phosphorus compound and the metal include a metal hydroxide and a metal carboxylate. Examples of the carboxylic acid of the metal salt of carboxylic acid include salicylic acid, benzoic acid, and phthalic acid. The metal salt of the carboxylic acid is a neutral salt, and may be a basic salt or an overbased salt. Of these, overbased salicylic acid and the like are preferable from the viewpoints of solubility during reaction, reactivity of metal ions, and the like.

  In the composition of the specific phosphorus compound and the metal, when at least one of the hydrocarbon groups of the specific phosphorus compound is a hydrocarbon group having 4 to 30 carbon atoms, the lubricating base oil that is a long-chain alkyl compound Contributes to compatibility. The hydrocarbon group is an organic group composed of carbon and hydrogen, and does not contain a hetero element such as N, O, or S. The hydrocarbon group of the specific phosphorus compound is preferably an aliphatic hydrocarbon group or an alicyclic hydrocarbon group because of compatibility with the lubricating base oil that is a long-chain alkyl compound. More preferably, it is an aliphatic hydrocarbon group.

  Examples of the aliphatic hydrocarbon group include an alkyl group composed of a saturated hydrocarbon and an alkenyl group composed of an unsaturated hydrocarbon, and any of these may be used. The alkyl group or alkenyl group which is an aliphatic hydrocarbon group may have a linear or branched structure. However, when the alkyl group is a linear alkyl group such as an n-butyl group or an n-octyl group, the alkyl groups are easily oriented with each other, and the crystallinity of the composition of the specific phosphorus compound and the metal becomes high. The compatibility with the lubricating base oil tends to decrease. From this viewpoint, when the hydrocarbon group is an alkyl group, a branched alkyl group is preferable to a linear alkyl group. On the other hand, an alkenyl group has one or more carbon-carbon double bond structures, so that the crystallinity is not so high even if it is linear. For this reason, the alkenyl group may be linear or branched.

  When the number of carbon atoms of at least one hydrocarbon group is less than 4, the specific phosphorus compound is inorganic. In addition, certain phosphorus compounds have a strong tendency to crystallize. If it does so, compatibility with lubricating base oil will be bad, and it will not mix with base oil. On the other hand, if the hydrocarbon group has more than 30 carbon atoms, the viscosity of the specific phosphorus compound becomes too high, and the fluidity tends to decrease. The number of carbon atoms of the hydrocarbon group is more preferably 5 or more, still more preferably 6 or more, from the viewpoint of compatibility with the lubricating base oil. Moreover, as carbon number of a hydrocarbon group, from viewpoints of fluidity | liquidity etc., More preferably, it is 26 or less, More preferably, it is 22 or less.

  Moreover, the composition of a specific phosphorus compound and metal has both a phosphoric acid group (polar group) and a nonpolar group (hydrocarbon group of an ester site) in the molecule. Can exist in an associated layer state, so even a non-polymer can be a highly viscous liquid. When it is a viscous liquid, it can be brought into close contact with the metal surface by utilizing physical adsorption by van der Waals force when applied to the metal surface. This viscosity is assumed to be obtained by entanglement of chain molecular chains. Therefore, from this viewpoint, it is preferable to design in a direction that does not promote crystallization of a specific phosphorus compound. Specifically, the carbon number of the hydrocarbon group is 4 to 30, and the hydrocarbon group has one or more branched chain structures or one or more carbon-carbon double bond structures.

  From the viewpoint of tackiness, the specific phosphorus compound needs to be a composition with a metal. When a specific phosphorus compound itself that is not in a composition with a metal is used, the polarity of the phosphate group portion is small, the association property (cohesiveness) between the phosphate groups that are polar groups is low, and a highly viscous liquid do not become. For this reason, adhesiveness (viscosity) is low. Moreover, even if it is a composition with ammonia or an amine, the polarity of the phosphoric acid group part is small, the association property (aggregation property) of the phosphoric acid groups which are polar groups is low, and it does not become a highly viscous liquid. For this reason, adhesiveness (viscosity) is low.

  More specifically, as the hydrocarbon group, oleyl group, stearyl group, isostearyl group, 2-ethylhexyl group, butyloctyl group, isomyristyl group, isocetyl group, hexyldecyl group, octyldecyl group, octyldecyl group, An isobehenyl group etc. are mentioned.

  Specific acid phosphates include butyl octyl acid phosphate, isomyristyl acid phosphate, isocetyl acid phosphate, hexyl decyl acid phosphate, isostearyl acid phosphate, isobehenyl acid phosphate, octyl decyl Acid phosphate, octyl decyl acid phosphate, isobutyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, myristyl Acid phosphate, palmityl acid phosphate, di-butyl octyl acid phosphate, di-i Myristyl acid phosphate, di-isocetyl acid phosphate, di-hexyl decyl acid phosphate, di-isostearyl acid phosphate, di-isobehenyl acid phosphate, di-octyl decyl acid phosphate, di-octyl decyl acid Phosphate, di-isobutyl acid phosphate, di-2-ethylhexyl acid phosphate, di-isodecyl acid phosphate, di-tridecyl acid phosphate, di-oleyl acid phosphate, di-myristyl acid phosphate, di -Palmitic acid phosphate etc. are mentioned. Among these, oleyl acid phosphate and isostearyl acid phosphate are preferable from the viewpoints of non-crystallinity and molecular chain entanglement with a lubricating base oil.

  The molecular weight of the composition of the specific phosphorus compound and metal is preferably 3000 or less because the compatibility with the viscous material is improved by fine dispersion. More preferably, it is 2500 or less. Moreover, it is preferable that it is 80 or more from viewpoints, such as separation suppression by high concentration of a polar group. More preferably, it is 100 or more. The molecular weight can be obtained by calculation.

  In the present protective agent composition, in addition to the viscous substance (A) and the composition (B), an organic solvent, a stabilizer, a corrosion inhibitor, Dyes, thickeners, fillers and the like can be added.

  In the present protective agent composition, the mass ratio of the viscous substance (A) to the composition (B) is in the range of (A) :( B) = 50: 50 to 98: 2. Thereby, it is excellent in adhesiveness with a metal, does not flow out from the metal surface under high temperature conditions, and stably protects the metal surface. Moreover, the thickness as a membrane | film | coat is ensured and the outstanding anticorrosion performance is exhibited. In the present protective agent composition, the mass ratio of the viscous substance (A) and the composition (B) is preferably (A) from the viewpoint of ensuring the thickness as a film and ensuring the adhesion to the metal. (B) = in the range of 60:40 to 95: 5, more preferably in the range of (A) :( B) = 70: 30 to 90:10.

  The protective agent composition preferably has a shear viscosity at 100 ° C. of 1000 mPa · s or more. Thereby, even if it exposes to high temperature, an outflow is easy to be suppressed. From this viewpoint, the shear viscosity is more preferably 1100 mPa · s or more, and still more preferably 1200 mPa · s or more. On the other hand, the shear viscosity is preferably 2500 mPa · s or less, more preferably 2000 mPa · s or less, considering the ease of application. The shear viscosity is represented by the viscosity at a temperature of 100 ° C. and a shear rate of 100 / s according to JIS K7117-2. The viscosity can be measured using a cone-plate rotational viscometer. The shear viscosity can be adjusted by the kinematic viscosity of the lubricating base oil, the viscous material (A), the content of the composition (B), the content of the amide compound, and the like.

  The protective agent composition preferably has a softening point of 150 ° C. or lower. Thereby, the material deterioration by the heating at the time of application | coating is suppressed. In this respect, the softening point is more preferably 140 ° C. or lower, and further preferably the softening point is 130 ° C. or lower. On the other hand, from the viewpoint of maintaining the anticorrosion performance even when exposed to high temperatures, the present protective agent composition preferably has a softening point of 100 ° C or higher. More preferably, it is 110 degreeC or more, More preferably, it is 120 degreeC or more. The softening point of the present protective agent composition can be adjusted by the type (melting point) of the amide compound in the viscous substance (A), the content of the viscous substance (A), the content of the amide compound, and the like.

  This protective agent composition can be obtained by mixing the viscous substance (A), the composition (B), and the component added as needed. It can also be obtained by mixing a lubricating base oil, an amide compound, a composition (B), and components added as necessary.

In the present protective agent composition, a viscous film is retained on the coated surface after application due to the viscosity of the viscous substance. If an amide compound having a higher melting point is used, the same consistency as that at room temperature is maintained at a high temperature below the melting point, and the viscous film is held on the coated surface. A composition of a specific phosphorus compound and a metal acts as a metal adsorbing component, and contributes to an improvement in adhesion of the viscous film on the metal surface. Since the lubricating base oil has a kinematic viscosity at 100 ° C. of 10 mm ² / s or more and a number average molecular weight of 400 or more, the lubricating base oil is not easily oxidized and deteriorated even when exposed to high temperatures, and maintains a high viscosity. As mentioned above, this protective agent composition suppresses outflow even when exposed to high temperatures, and stably protects the metal surface even when exposed to high temperatures. The protective agent composition can be coated on the surface of the material to be coated by applying the protective agent composition on the surface of the material to be coated or immersing the material to be coated in the protective agent composition.

  The film thickness of the viscous film applied to the surface of the material to be coated is preferably 100 μm or less from the viewpoint of preventing outflow from the coating site and preventing leakage. More preferably, it is 50 μm or less. On the other hand, from the viewpoint of the mechanical strength of the viscous film to be applied, the thickness is preferably not less than a predetermined thickness. Examples of the lower limit of the film thickness include 0.5 μm, 2 μm, and 5 μm.

  This protective agent composition can be used for anticorrosion applications and the like. For example, it can be used as an anticorrosion agent that adheres to the surface of a metal member to be surface protected and covers the metal surface to prevent metal corrosion. Moreover, as an anticorrosion use, it can use, for example as an anticorrosive of a covered electric wire with a terminal.

  Next, the covered electric wire with a terminal according to the present invention will be described.

  The coated electric wire with a terminal according to the present invention is the one in which the terminal metal fitting is connected to the conductor terminal of the insulated electric wire, and the viscous material composed of the lubricant base oil and the amide compound of the present protective agent composition, and the specified The electrical connection part of a terminal metal fitting and an electric wire conductor was covered with the viscous film containing the composition of said phosphorus compound and a metal. This prevents corrosion at the electrical connection.

  FIG. 1 is a perspective view of a covered electric wire with a terminal according to an embodiment of the present invention, and FIG. 2 is a longitudinal sectional view taken along line AA in FIG. As shown in FIGS. 1 and 2, the terminal-equipped covered electric wire 1 is configured such that the electric wire conductor 3 of the covered electric wire 2 in which the electric wire conductor 3 is covered with the insulating coating (insulator) 4 and the terminal fitting 5 are electrically connected by the electric connection portion 6. Connected.

  The terminal fitting 5 includes a tab-like connection portion 51 made of an elongated flat plate connected to a counterpart terminal, a wire barrel 52 extending at the end of the connection portion 51, and an electric wire fixing portion made of an insulation barrel 53. 54. The terminal fitting 5 can be formed (processed) into a predetermined shape by pressing a metal plate.

  In the electrical connection portion 6, the insulation coating 4 at the end of the covered electric wire 2 is peeled off to expose the electric wire conductor 3, and the exposed electric wire conductor 3 is pressure-bonded to one side of the terminal fitting 5, thereby covering the electric wire 2. And the terminal fitting 5 are connected. The wire barrel 52 of the terminal fitting 5 is crimped from above the wire conductor 3 of the covered electric wire 2 so that the wire conductor 3 and the terminal fitting 5 are electrically connected. Further, the insulation barrel 53 of the terminal fitting 5 is crimped from above the insulating coating 4 of the covered electric wire 2.

  In the covered electric wire 1 with a terminal, the range shown by the alternate long and short dash line is covered with the viscous film 7 obtained from the present protective agent composition. Specifically, among the portions exposed from the insulation coating 4 of the wire conductor 3, the insulation coating 4 after the rear end of the portion exposed from the insulation coating 4 of the wire conductor 3 from the surface of the terminal fitting 5 ahead of the tip. The range up to the surface of is covered with the viscous film 7. That is, the tip 2 a side of the covered electric wire 2 is covered with the viscous film 7 so as to slightly protrude from the tip of the wire conductor 3 to the connecting portion 51 side of the terminal fitting 5. The distal end 5 a side of the terminal fitting 5 is covered with the viscous film 7 so as to slightly protrude from the end of the insulation barrel 53 to the insulating coating 4 side of the covered electric wire 2. As shown in FIG. 2, the side surface 5 b of the terminal fitting 5 is also covered with the viscous film 7. In addition, the back surface 5c of the terminal metal fitting 5 may not be covered with the viscous film 7, and may be covered. The peripheral end of the viscous film 7 includes a portion that contacts the surface of the terminal fitting 5, a portion that contacts the surface of the electric wire conductor 3, and a portion that contacts the surface of the insulating coating 4.

  In this way, the electrical connection portion 6 is covered with the viscous film 7 with a predetermined thickness along the outer peripheral shape of the terminal fitting 5 and the covered electric wire 2. As a result, the exposed portion of the wire conductor 3 of the covered wire 2 is completely covered with the viscous film 7 and is not exposed to the outside. Therefore, the electrical connection 6 is completely covered by the viscous film 7. Since the viscous film 7 is excellent in adhesion to all of the electric wire conductor 3, the insulation coating 4, and the terminal fitting 5, moisture or the like enters the electric conductor 3 and the electrical connection portion 6 from the outside by the viscous film 7. Prevent the metal parts from corroding. Moreover, since it is excellent in adhesiveness, for example, even when an electric wire is bent in the process from manufacture of a wire harness to attachment to a vehicle, the viscous film 7 and the electric wire conductor 3 are formed at the peripheral edge of the viscous film 7. In addition, it is difficult to form a gap between any of the insulating coating 4 and the terminal fitting 5, and waterproofness and anticorrosion function are maintained.

  The present protective agent composition for forming the viscous film 7 is applied in a predetermined range. Application | coating of this protective agent composition which forms the viscous film | membrane 7 can use well-known means, such as a dripping method and a coating method.

  The viscous film 7 is formed in a predetermined range with a predetermined thickness. The thickness is preferably within a range of 0.01 to 0.1 mm. If the viscous film 7 becomes too thick, it becomes difficult to insert the terminal fitting 5 into the connector. If the viscous film 7 becomes too thin, the anticorrosion performance tends to be lowered.

  The electric wire conductor 3 of the covered electric wire 2 is made of a stranded wire formed by twisting a plurality of strands 3a. In this case, the stranded wire may be composed of one type of metal strand or may be composed of two or more types of metal strand. Moreover, the twisted wire may contain the strand etc. which consist of organic fibers other than a metal strand. Note that “consisting of one type of metal strand” means that all the metal strands constituting the stranded wire are made of the same metal material, and “consisting of two or more types of metal strands” This means that the wire contains metal wires made of different metal materials. The stranded wire may include a reinforcing wire (tension member) for reinforcing the covered electric wire 2.

  Examples of the material of the metal wire constituting the wire conductor 3 include copper, a copper alloy, aluminum, an aluminum alloy, or a material obtained by applying various platings to these materials. Examples of the material of the metal strand as the reinforcing wire include copper alloy, titanium, tungsten, and stainless steel. Examples of the organic fiber as the reinforcing wire include Kevlar. As a metal strand which comprises the electric wire conductor 3, from the viewpoint of weight reduction, the material by which various plating was given to aluminum, aluminum alloy, or these materials is preferable.

  Examples of the material for the insulating coating 4 include rubber, polyolefin, PVC, and thermoplastic elastomer. These may be used alone or in combination of two or more. Various additives may be appropriately added to the material of the insulating coating 4. Examples of the additive include a flame retardant, a filler, a colorant and the like.

  Examples of the material (material for the base material) of the terminal fitting 5 include various copper alloys and copper in addition to brass that is generally used. A part (for example, a contact) or the entire surface of the terminal fitting 5 may be plated with various metals such as tin, nickel, and gold.

  In addition, in the covered electric wire 1 with a terminal shown in FIG. 1, the terminal metal fitting is crimped and connected to the end of the electric wire conductor, but other known electrical connection methods such as welding may be used instead of the crimping connection.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited by an Example.

(Preparation of viscous material)
A viscous substance was prepared by mixing a lubricating base oil and an amide compound in the composition shown in Table 1.
Lubricating base oil A: Mineral base oil (number average molecular weight Mn = 500, kinematic viscosity = 32.0 mm ² / s (100 ° C.))
Lubricating base oil B: Mineral base oil (number average molecular weight Mn = 400, kinematic viscosity = 11.1 mm ² / s (100 ° C.))
Lubricating base oil C: Synthetic base oil (number average molecular weight Mn = 1000, kinematic viscosity = 50.0 mm ² / s (100 ° C.))
Lubricating base oil D: Synthetic base oil (number average molecular weight Mn = 7000, kinematic viscosity = 100.0 mm ² / s (100 ° C.))
Lubricating base oil E: Mineral base oil (number average molecular weight Mn = 350, kinematic viscosity = 8.0 mm ² / s (100 ° C.))
Amide compound: ethylenebisstearylamide (melting point 150 ° C., molecular weight 592), Nippon Kasei's “Sripax E”

(Preparation of composition of phosphorus compound and metal)
<Preparation Example 1> OL-Ca
To a 500 ml flask, add 50 g (acid number 0.163 mol) and 50 ml of methanol of oleyl acid phosphate (“Phoslex A18D” manufactured by SC Organic Chemical Co., Ltd., molecular weight 467 (average), acid value 183 mg KOH / g) and stir at room temperature. A homogeneous solution was obtained. Thereto, 6.04 g (0.0815 mol) of calcium hydroxide was added. The suspension was stirred at room temperature for 24 hours. After confirming that the precipitate of calcium hydroxide had disappeared, the suspension was filtered, and methanol and produced water were distilled off under reduced pressure using a rotary evaporator. Next, after adding 50 mL of toluene, the product water was distilled off azeotropically by distilling off under reduced pressure in the same manner to obtain a target product which was a clear viscous product.

<Preparation of surface protective agent composition>
In the blending composition (parts by mass) shown in Table 1, the viscous substance and the composition of the phosphorus compound and metal (phosphorus composition) are mixed at a predetermined ratio under heating at 160 ° C. Thus, a surface protective agent composition was prepared.

<Measurement of shear viscosity>
Using a cone-plate type rotational viscometer, the viscosity of the surface protective agent composition was measured at a temperature of 100 ° C. and a shear rate of 100 / s according to JIS K7117-2.

(Appearance observation after high temperature test)
As shown in FIG. 1, the surface protective agent composition heated to 160 ° C. and liquefied was applied so as to cover the copper terminal of the covered electric wire with terminal and the electrical connection portion of the aluminum electric wire. Then, it was left in a constant temperature bath at 100 ° C. for 168 hours. Before and after this high-temperature test, the appearance was observed. If no change in appearance was observed, a good “◯” was given, and the surface protective agent composition was flowing out of the terminal or the viscous film was thermally deformed. Defect “x”.

(After anticorrosion performance test, high temperature test)
As shown in FIG. 1, the surface protective agent composition heated to 160 ° C. and liquefied was applied so as to cover the copper terminal of the covered electric wire with terminal and the electrical connection portion of the aluminum electric wire. Then, it was left in a constant temperature bath at 100 ° C. for 168 hours. Next, a neutral salt spray test was performed at 35 ° C. (salt solution concentration 50 g / L) in accordance with JIS C0024, and rust generation after 120 hours was visually evaluated. In the case of 10 test points (N = 10), the case where even one rust was confirmed was “X”, and the case where no rust was confirmed was “◯”.

From Examples 1 to 4 and Comparative Example 3, the lubricating oil base oil has a kinematic viscosity at 100 ° C. of 10 mm ² / s or more and a number average molecular weight of 400 or more, so that it is a surface protective agent even when exposed to high temperatures. It can be seen that the outflow of the composition is suppressed and the anticorrosion performance is maintained even when exposed to high temperatures. And from Example 1, Example 6, Example 8, Comparative Example 1, and Comparative Example 2, a viscous substance (A) composed of a lubricating base oil and an amide compound and a phosphorus-based composition (B) It can be seen that when the mass ratio is within the predetermined range of the present application, the outflow of the surface protective agent composition is suppressed even when exposed to high temperatures, and the anticorrosion performance is maintained even when exposed to high temperatures.

  In Comparative Example 1, since the amount of the phosphorus-based composition (B) is small, the adhesion to the metal surface is inferior and the anticorrosion performance is not satisfied. Since the comparative example 2 has few viscous substances (A), it will flow out when exposed to high temperature. Thereby, it does not satisfy anticorrosion performance. In Comparative Example 3, since the viscosity of the lubricating base oil is low and the number average molecular weight is small, it flows out when exposed to high temperatures. This also does not satisfy the anticorrosion performance. Since Comparative Example 4 does not include the phosphorus composition (B) and the amide compound, the adhesion to the metal surface is inferior and the anticorrosion performance is not satisfied. Also, it flows out when exposed to high temperatures. This also does not satisfy the anticorrosion performance.

  Although the embodiments of the present invention have been described in detail above, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the gist of the present invention.

1 Coated electric wire with terminal 2 Coated electric wire 3 Electric wire conductor 4 Insulation coating (insulator)
5 Terminal fitting 6 Electrical connection 7 Viscous film

Claims (9)

A viscous substance (A) composed of a lubricating base oil and an amide compound,
Containing a phosphorus compound and metal composition (B) comprising one or more of the compounds represented by the following general formulas (1) and (2),
The mass ratio of (A) and (B) is within the range of (A) :( B) = 50: 50 to 98: 2.
The lubricant base oil has a kinematic viscosity at 100 ° C. of 10 mm ² / s or more and a number average molecular weight of 400 or more.

^However, X 1 to X ⁷ are each independently an oxygen atom or a sulfur ^atom, R 11 ^{to R 13} are each independently a hydrocarbon group of a hydrogen group or a C1-30, and of these At least one is a hydrocarbon group having 1 to 30 carbon atoms, R ^{14 to} R ¹⁶ each independently represents a hydrogen group or a hydrocarbon group having 1 to 30 carbon atoms, and at least one of these is It is a C1-C30 hydrocarbon group.   The surface protective agent composition according to claim 1, wherein the shear viscosity at 100 ° C. is 1000 mPa · s or more. The surface protective agent composition according to claim 1 or 2, wherein the amide compound is one or more of compounds represented by the following general formulas (3) to (5).
(Chemical formula 3)
^{R 21 -CO-NH-R 22} (3)
(Chemical formula 4)
^{R 23 -CO-NH-Y 31} -NH-CO-R 24 (4)
(Chemical formula 5)
^{R 25 -NH-CO-Y 32} -CO-NH-R 26 (5)
^However, R 21 ^{to R 26} are each an individual chain saturated or unsaturated hydrocarbon group of 5-25 carbon ^{atoms, R 22} can be ^{hydrogen, Y 31} and ^{Y 32} has a number of carbon A divalent hydrocarbon group having 1 to 10 carbon atoms selected from the group consisting of an alkylene group having 1 to 10 carbon atoms, a phenylene group, or an alkylphenylene group having 7 to 10 carbon atoms.   The surface protecting agent composition according to any one of claims 1 to 3, wherein the amide compound is a fatty acid amide having a melting point in the range of 20 to 200 ° C.   5. The phosphorous compound according to claim 1, wherein the structure of the hydrocarbon group has one or more branched chain structures or one or more carbon-carbon double bond structures. Surface protectant composition.   The metal forming the composition with the phosphorus compound is at least one selected from alkali metals, alkaline earth metals, aluminum, titanium, and zinc, according to any one of claims 1 to 5. The surface protection agent composition as described.   The molecular weight of the composition of the said phosphorus compound and a metal is 3000 or less, The surface protection agent composition of any one of Claim 1 to 6 characterized by the above-mentioned.   The surface protective agent composition according to any one of claims 1 to 7, wherein the surface protective agent composition is used for anticorrosion to adhere to the surface of a metal member to be surface-protected and cover the metal surface to prevent metal corrosion. object.   A covered electric wire with a terminal, wherein an electrical connection portion between the terminal fitting and the electric wire conductor is covered with the surface protective agent composition according to any one of claims 1 to 8.

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