Surface protection composition and an electrical wire equipped with a terminal block

Abstract

Surface protection composition, including: a phosphorus compound (a) represented by the general formula (1) in an amount of 0.1 to 10 wt%, based on the phosphorus element, with respect to the total amount of the composition; at least one, selected from the group, consisting of a phosphorus compound (b1) represented by the general formula (2) and a carboxylic acid compound (b2) represented by the general formula (3), in an amount of 5.0 to 60 wt% of the total amount of the composition; a metal-containing compound (c) in an amount of 0.1 to 10 wt%, based on a metal element, with respect to the total amount of the composition; and a lubricant base oil (d): in which R 1 represents a hydrogen atom 2represents a hydrocarbon group with 4 to 30 carbon atoms with one or more branched chains or one or more carbon-carbon double bonds and R 3 represents a hydrogen atom or a hydrocarbon group with 4 to 30 carbon atoms; in which R 4 represents a hydrogen atom 5 represents a linear hydrocarbon group with 12 to 22 carbon atoms and R 6 represents a hydrogen atom or a hydrocarbon group with 12 to 22 carbon atoms; R 7 -COOH (3) in which R 7 represents a linear hydrocarbon group with 11 to 21 carbon atoms, where the phosphorus compound (b1) does not have a branched chain or a carbon-carbon double bond.

Description

[0001] The present disclosure relates to a surface protection composition and an electrical wire provided with a terminal clamp, and in particular to a surface protection composition having excellent corrosion protection properties for preventing metal corrosion, and to an electrical wire provided with a terminal clamp that has been treated with the composition having excellent corrosion protection properties.

[0002] For metal devices and parts, grease is used for lubrication and corrosion resistance. Patent literature 1, for example, describes a grease containing a perfluoroether base oil, a consistency improver, and barium sulfate or antimony oxide, which is used for machine parts. Patent literature 2 describes a composition containing a lubricant base oil and a gelling agent, which is used to protect a metal surface. ZitatenlistePatentliteratur Patentliteratur 1: JP 4 811 408 B2 Patentliteratur 2: JP H06 - 33 272 A Patentliteratur 3: JP 2018 - 90 690 A Patentliteratur 4: DE 11 2015 000 870 T5 Patentliteratur 5: DE 11 2017 001 618 T5

[0003] The compositions disclosed in patent literature 1 and 2 do not contain a metal-adsorbing component and exhibit weak adsorption to the metal surface. Therefore, when applied to the metal surface, they display poor corrosion protection properties for preventing metal corrosion. Since the grease is a semi-solid or solid material obtained by dispersion of a consistency improver in a lubricant base oil, heating the grease significantly reduces its viscosity and improves its applicability; however, the grease can easily run, and its heat resistance is reduced. Since the composition disclosed in patent literature 2 is a gel-like solid obtained by adding the gelling agent to a lubricant base oil, the composition becomes easily liquefied upon heating, further improving its applicability.In this case, if a suitable gelling agent is selected, the composition may be difficult to leak even under high-temperature conditions; however, the temperature suitable for applying such a composition, which hardly leaks onto the metal surface under high-temperature conditions, tends to be high, which impairs the composition's applicability. Conversely, the composition without a gelling agent has high flowability and can be applied uniformly; however, it is difficult to suppress leakage under high-temperature conditions. Patent literature 4 describes a terminalized, coated, or covered electrical wire in which a composition for a metal surface coating is used.Patent literature 5 describes a surface protection composition that stably protects a metal surface even at high temperatures, and an electrical wire provided with a terminal, which, through the use of the composition, has anti-corrosion properties.

[0004] The purpose of the present disclosure is to provide a surface protection composition with excellent corrosion protection properties as well as uniform applicability and heat resistance, and an electrical wire treated with the composition and equipped with terminal blocks.

[0005] To solve the above problem, the surface protection composition contains a phosphorus compound (a), represented by general formula (1), in an amount of 0.1 to 10 wt% based on the phosphorus element, with respect to the total amount of the composition; at least one selected from the group consisting of a phosphorus compound (b1), represented by general formula (2), and a carboxylic acid compound (b2), represented by general formula (3), in an amount of 5.0 to 60 wt% with respect to the total amount of the composition; a metal-containing compound (c) in an amount of 0.1 to 10 wt% based on the metal element, with respect to the total amount of the composition; and a lubricant base oil (d), wherein R 1 represents a hydrogen atom 2represents a hydrocarbon group with 4 to 30 carbon atoms with one or more branched chains or one or more carbon-carbon double bonds and R 3 represents a hydrogen atom or a hydrocarbon group with 4 to 30 carbon atoms; in which R 4 represents a hydrogen atom 5 represents a linear hydrocarbon group with 12 to 22 carbon atoms and R 6 represents a hydrogen atom or a hydrocarbon group with 12 to 22 carbon atoms; wherein R 7 represents a linear hydrocarbon group with 11 to 21 carbon atoms, wherein the phosphorus compound (b1) does not have a branched chain or a carbon-carbon double bond.

[0006] The surface protection composition has a mass ratio (a):{(b1)+(b2)} of compound (a) to the total of compound (b1) and compound (b2) preferably in the range of 5:95 to 95:5. The metal in compound (c) is preferably at least one metal selected from the group consisting of alkali metals, alkaline earth metals, aluminum, titanium, and zinc. The oil (d) is preferably present in the composition in an amount of 5.0 to 90% by weight of the total composition. The oil (d) preferably has a kinematic viscosity of 10 mmHg. 2 / s or higher at 100°C and a number-average molecular weight of 400 or higher.

[0007] The electrical wire provided with terminals according to the present disclosure comprises a terminal, an electrical conductor and an electrical connecting part formed between the terminal and the electrical conductor, covered with the surface protection composition.

[0008] Since the surface protection composition according to the present disclosure contains compound (a) and compound (c), the composition is adsorbed onto the metal surface to which it is applied. Because compound (a) has a hydrocarbon group with 4 to 30 carbon atoms having a branched chain or a carbon-carbon double bond, and because the composition further contains the oil (d), the composition forms a uniform coating film on a metal surface. Furthermore, the composition contains at least one compound selected from the group consisting of compound (b1) and compound (b2), wherein the compounds have hydrocarbon groups with relatively long straight chains. Therefore, the composition is poorly flowable for the protective composition, even under high-temperature conditions.Therefore, the surface protection composition is excellent in terms of both corrosion protection properties and uniform application and heat resistance.

[0009] In the electrical wire provided with terminals according to the present disclosure, the electrical connection between the terminal and the electrical conductor is covered with the surface protection composition. Consequently, the electrical wire provided with terminals is distinguished by its corrosion protection properties, uniform application of the composition, and heat resistance. Brief description of the drawings Fig. Figure 1 is a perspective view of an electrical wire provided with terminal blocks according to a preferred embodiment of the present disclosure. Fig. 2 is a longitudinal section along line AA in Fig. 1.

[0010] Next, a preferred embodiment of the present disclosure will be described in detail.

[0011] The surface protection composition according to the preferred embodiment of the present disclosure (hereinafter referred to as the present protection composition) comprises a phosphorus compound (a), at least one selected from the group consisting of a phosphorus compound (b1) and a carboxylic acid compound (b2), a metal-containing compound (c) and a lubricant base oil (d) in a predetermined ratio.

[0012] Compound (a) is represented by the general formula (1) shown below. Compound (a) contains a low-polarity part (i.e., a lipophilic part) consisting of a hydrocarbon group and another high-polarity part consisting of a phosphate group. In general formula (1), R represents 1 represents a hydrogen atom, R2 represents a hydrocarbon group with 4 to 30 carbon atoms with one or more branched chains or one or more carbon-carbon double bonds and R 3 represents a hydrogen atom or a hydrocarbon group with 4 to 30 carbon atoms.

[0013] Compound (a), which has a hydrocarbon group with 4 to 30 atoms, is highly compatible with oil (d), similar to a long-chain alkyl compound. Therefore, the protective composition can retain the oil (d), thus preventing its separation. If the number of carbon atoms in the hydrocarbon group is less than 4, compound (a) tends to crystallize, reducing its compatibility with oil (d) and potentially leading to its separation. Conversely, if the number of carbon atoms in the hydrocarbon group exceeds 30, the viscosity of compound (a) becomes so high that the uniform applicability of the protective composition is reduced, even when the oil (d) is mixed.From the perspective of compatibility with the oil (d), the number of carbon atoms in the hydrocarbon group is preferably 5 or more and more preferably 6 or more. Furthermore, from the perspective of uniform applicability of the present protective composition, the number of carbon atoms in the hydrocarbon group is preferably 26 or less and more preferably 22 or less. In addition, compound (a) with one or more branched chains or one or more carbon-carbon double bonds exhibits minimal crystallization and offers sufficient compatibility with the oil (d).

[0014] In the general formula (1) R 3 be a hydrocarbon group that is either the same as or different from the one defined by R 2 The hydrocarbon group shown is preferably R. 3 a hydrogen atom or a hydrocarbon group that is the same as R 2 is.

[0015] Examples of the hydrocarbon group with 4 to 30 carbon atoms with one or more branched chains as R 2 These are an alkyl group with 4 to 30 carbon atoms having one or more branched chains, a cycloalkyl group with 4 to 30 carbon atoms, an alkyl-substituted cycloalkyl group with 4 to 30 carbon atoms, and an alkenyl group with 4 to 30 carbon atoms having one or more branched chains. Preferred examples of the hydrocarbon group with 4 to 30 carbon atoms having one or more branched chains include an isobutyl group, a tert-butyl group, a neopentyl group, an isopentyl group, a 2-ethylhexyl group, an isodecyl group, an isostearyl group, a butyloctyl group, an isomyristyl group, an isocetyl group, a hexyldecyl group, an isobehenyl group, an octyldecyl group, and an octyldodecyl group.

[0016] Examples of the hydrocarbon group with 4 to 30 carbon atoms with one or more carbon-carbon double bonds as R 2 These include an alkenyl group with 4 to 30 carbon atoms and a cycloalkenyl group with 4 to 30 carbon atoms. Preferred examples of the hydrocarbon group with 4 to 30 carbon atoms and one or more carbon-carbon double bonds include a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, and an oleyl group.

[0017] Examples of the hydrocarbon group as R 3These 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. Among them, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, such as the alkyl group, the cycloalkyl group, the alkyl-substituted cycloalkyl group, and the alkenyl group, is preferred. If the hydrocarbon group is such as R 3 the aliphatic hydrocarbon group or the alicyclic hydrocarbon group, the compatibility of compound (a) with the oil (d) is improved.

[0018] The alkyl group can be either linear or branched. Examples of alkyl groups include a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group (a stearyl group), an isostearyl group, a butyloctyl group, a myristyl group, an isomyristyl group, an isocetyl group, a hexyldecyl group, an octyldecyl group, an octyldodecyl group, a behenyl group, and an isobehenyl group.

[0019] Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and cycloheptyl. Examples of alkyl-substituted cycloalkyl groups include methylcyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, diethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylethylcycloheptyl, and diethylcycloheptyl. The substitution position of the alkyl-substituted cycloalkyl group is not specifically indicated.

[0020] The alkenyl group can be either linear or branched. Examples of alkenyl groups include butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, and oleyl.

[0021] Examples of aryl groups include phenyl and naphthyl. Examples of alkyl-substituted aryl groups include tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, and dodecylphenyl. The substitution position of alkyl-substituted aryl groups is not particularly restricted. The alkyl group of alkyl-substituted aryl groups can be linear or branched. Examples of arylalkyl groups include benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl, and phenylhexyl. The alkyl group of arylalkyl groups can be linear or branched.

[0022] Specific examples of the phosphorus compound (a) with a branched chain, represented by the general formula (1) described above, include isobutyl phosphate, 2-ethylhexyl phosphate, isodecyl phosphate, butyl octyl phosphate, isomyristyl phosphate, isocetyl phosphate, hexyl decyl phosphate, isostearyl phosphate, isobehenyl phosphate, octyl decyl phosphate, octyldodecyl phosphate, dibutyl octyl phosphate, diisomyristyl phosphate, diisocetylic phosphate, dihexyl decyl phosphate, diisostearyl phosphate, diisobehenyl phosphate, dioctyl decyl phosphate, dioctyldodecyl phosphate, diisobutyl phosphate, di-2-ethylhexyl phosphate and diisodecyl phosphate.Other specific examples of the phosphorus compound (a) with a carbon-carbon double bond, represented by the general formula (1) described above, include oleyl phosphate, dioley phosphate, palmitoleic phosphate, dipalmitoleic phosphate, elaidy phosphate and dielaidy phosphate.

[0023] The present protective composition contains 0.1 to 10 wt% of compound (a), based on the phosphorus element, in relation to the total amount of the composition. If the content of compound (a) is less than 0.1 wt%, the present protective composition exhibits weak adsorption to a metal surface, and its corrosion suppression effect on the metal surface is reduced. If the content of compound (a) is higher than 10 wt%, a sufficient quantity of at least one of the compounds selected from the group consisting of compound (b1) and compound (b2) may be omitted from the composition, which reduces the anti-flow effect of the present protective composition under high-temperature conditions and impairs its heat resistance.From the perspective of adsorption to a metal surface, the content of compound (a) is preferably 0.5 wt% or more and more preferably 1.0 wt% or more. Furthermore, from the perspective of heat resistance, the content of compound (a) is preferably 8.0 wt% or less and more preferably 5.0 wt% or less. Here, the high-temperature condition refers to a state in which the ambient temperature is 155°C.

[0024] At least one compound selected from the group consisting of compound (b1) and compound (b2) (hereinafter referred to as compound (b1) or (b2)) has a hydrocarbon group with a relatively long straight chain, but no branched chain or carbon-carbon double bond, provided that the phosphorus compound (b1) has no branched chain or carbon-carbon double bond. Therefore, the compound has high crystallinity. When compound (b1) or (b2) crystallizes in the present protective composition, the present protective composition becomes difficult to flow, even when used under high-temperature conditions, and exhibits excellent heat resistance. From this perspective, compound (b1) or (b2) has a hydrocarbon group with a chain of predetermined length as described below.Of the compounds (b1) and (b2), compound (b1) is preferred, for example, because of its higher softening temperature and lower flowability under high temperature conditions.

[0025] The phosphorus compound (b1) is represented by the following general formula (2). Compound (b1) has a part consisting of a low-polarity hydrocarbon group (i.e., a lipophilic part) and another part consisting of a high-polarity phosphate group. In general formula (2), R represents 4 represents a hydrogen atom, R 5 represents a linear hydrocarbon group with 12 to 22 carbon atoms and R 6 represents a hydrogen atom or a hydrocarbon group with 12 to 22 carbon atoms. Preferably, R 6 a hydrogen atom or a hydrocarbon group that is the same as R 5 is.

[0026] If the number of carbon atoms in the hydrocarbon group is called R 5 If the number of carbon atoms in the hydrocarbon group is less than 12, the crystallinity of compound (b1) is low. Therefore, the present protective composition flows under high-temperature conditions and exhibits low heat resistance. On the other hand, if the number of carbon atoms in the hydrocarbon group is expressed as R 5 If the value is greater than 22, the compound (b1) hardly disperses.

[0027] Examples of the linear hydrocarbon group with 12 to 22 carbon atoms as R 5 They include a dodecyl group (a lauryl group), a tridecyl group, a tetradecyl group (a myristyl group), a pentadecyl group, a hexadecyl group (a palmityl group), a heptadecyl group, an octadecyl group (a stearyl group), a nonadecyl group, an eicosyl group, a heneicosyl group and a docosyl group (a behenyl group).

[0028] An example of the hydrocarbon group as R 6 is an alkyl group. If the hydrocarbon group is denoted as R 6 Since it is an aliphatic hydrocarbon group, the compatibility of compound (b1) with the oil (d) is improved.

[0029] The alkyl group is linear. Examples of alkyl groups include a lauryl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a stearyl group, a nonadecyl group, an eicosyl group, a heneicosyl group, a behenyl group, and a myristyl group.

[0030] Specific examples of the phosphorus compound (b1), represented by the general formula (2) described above, include lauryl phosphate, tridecyl phosphate, stearyl phosphate, myristyl phosphate, palmityl phosphate, behenyl phosphate, dilauryl phosphate, ditridecyl phosphate, distearyl phosphate, dimyristyl phosphate, dipalmityl phosphate, dibehenyl phosphate.

[0031] The carboxylic acid compound (b2) is represented by the following general formula (3). The compound (b2) has a part consisting of a low-polarity hydrocarbon group (i.e., a lipophilic part) and another part consisting of a high-polarity carboxylic acid group. R 7 -COOH (3) In the general formula (3) R represents 7 represents a linear hydrocarbon group with 11 to 21 carbon atoms.

[0032] If the number of carbon atoms in the hydrocarbon group is called R 7 If the number of carbon atoms in the hydrocarbon group is less than 11, the crystallinity of compound (b2) is low. Therefore, the present protective composition flows under high-temperature conditions and exhibits low heat resistance. On the other hand, if the number of carbon atoms in the hydrocarbon group is expressed as R 7 If the value is greater than 21, the compound (b2) hardly disperses.

[0033] Examples of the linear hydrocarbon group with 11 to 21 carbon atoms as R 7 They include an undecyl group, a dodecyl group (a lauryl group), a tridecyl group, a tetradecyl group (a myristyl group), a pentadecyl group, a hexadecyl group (a palmityl group), a heptadecyl group, an octadecyl group (a stearyl group), a nonadecyl group, an eicosyl group, and a heneicosyl group.

[0034] Specific examples of the carboxylic acid compound (b2), represented by the general formula (3) described above, include dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), eicosanoic acid, heneicosylic acid, docosanoic acid (behenic acid).

[0035] The present protective composition contains 5.0 to 60 wt% of compound (b1) or (b2) in terms of the total amount of the composition. If the content is below 5.0 wt%, the present protective composition flows under high-temperature conditions and exhibits poor heat resistance. If the content is higher than 60 wt%, the present protective composition solidifies at room temperature due to the high crystallinity of compound (b1) or compound (b2) and hardly flows even when heated, thus preventing the coating film from forming uniformly on the metal surface. This reduces the corrosion suppression effect on the metal surface. Furthermore, the content of compound (a) becomes so relatively low that the present protective composition exhibits weak adsorption on a metal surface and has a low corrosion suppression effect on the metal surface.From the perspective of heat resistance, the content is preferably 10 wt% or higher, more preferably 15 wt% or higher, and even more preferably 20 wt% or higher. Furthermore, from the perspective of uniform application and adsorption to the metal surface, the content is preferably 50 wt% or less, and more preferably 40 wt% or less.

[0036] The mass ratio (a):{(b1)+(b2)} of compounds (a) to the total of compounds (b1) and (b2) is preferably in the range of 5:95 to 95:5. If the content of compound (a) relative to the total of compounds (a), (b1) and (b2) is 5 wt% or more, or if the total content of compounds (b1) and (b2) relative to the total of compounds (a), (b1) and (b2) is 95 wt% or less, the present protective composition exhibits strong adsorption to a metal surface and shows excellent corrosion suppression. If the content of compound (a) is 95 wt% or less, or if the total content of compounds (b1) and (b2) is 5 wt% or more, the present protective composition exhibits minimal flow, even under high-temperature conditions.Accordingly, the mass ratio (a):{(b1)+(b2)} is preferably in a range of 10:90 to 90:10 and more preferably in a range of 30:70 to 70:30.

[0037] The metal-containing compound (c) facilitates the ionization of metal atoms on the metal surface, thereby enabling the adsorption of compound (a) onto the metal surface. In this way, the protective composition can be adsorbed onto the metal surface.

[0038] Examples of the metal-containing compound (c) include a metal hydroxide and a metal oxide. Examples of the metal in compound (c) include an alkali metal such as Li, Na, and K; an alkaline earth metal such as Mg and Ca; aluminum, titanium, and zinc. Compound (c) may consist of a single metal-containing compound containing one of these metals or of two or more metal-containing compounds. If these metals with a relatively high ionization tendency are present in the protective composition, the ionization of the metal atoms at the metal surface is facilitated, allowing compound (a) to be strongly adsorbed onto the metal surface.

[0039] From a hydrophilicity point of view, it is preferred that the metal in compound (c) be a divalent or higher-valent metal, such as an alkaline earth metal, aluminum, titanium, and zinc. Furthermore, from a water resistance point of view, calcium and magnesium are preferred.

[0040] The present protective composition contains 0.1 to 10 wt% of compound (c), based on a metal element, in relation to the total amount of the composition. If the content of compound (c) is less than 0.1 wt%, compound (a) forms ionic bonds on the metal surface and exhibits weak adsorption on the metal surface, thus reducing its corrosion suppression effect. If the content of compound (c) is higher than 10 wt%, the excessive content of the metal-containing compound impairs the properties of the present protective composition and reduces its protective effect. With regard to the adsorption of compound (a), the content of compound (c) is preferably 0.5 wt% or more and more preferably 1.0 wt% or more.Furthermore, the content is preferably 8.0% by mass or less, and more preferably 5.0% by mass or less.

[0041] The present protective composition contains the lubricant base oil. The composition can be a viscous liquid at room temperature by containing the lubricant base oil (d) together with compound (a). If the present protective composition does not contain the oil (d), the composition solidifies at room temperature due to the presence of compound (b1) or (b2), making it difficult for the composition to form the coating film uniformly on the metal surface. By containing the oil (d), the present protective composition forms the coating film uniformly on the metal surface. The content of the oil (d) is preferably 5.0 to 90 wt%, more preferably 10 to 70 wt%, and even more preferably 20 to 70 wt% of the total amount of the composition.

[0042] The oil (d) used here may be a mineral oil, a wax isomerized oil, or a synthetic oil commonly used as a base oil for a lubricant oil, or a mixture of two or more of these oils. Specific examples of the mineral oil used here are paraffinic and naphthenic oils and n-paraffin purified from lubricant oil fractions obtained by distillation of a crude oil under ordinary pressure or by distillation under reduced pressure with a suitable combination of purification treatments such as solvent asphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid purification, and treatment of the lubricant oil fractions with white clay.

[0043] The wax-isomerized oils used here include all oils produced by a hydrogen isomerization treatment of a wax raw material, such as natural wax, for example, paraffin wax obtained by solvent dewaxing of a hydrocarbon oil, or synthetic wax produced by the so-called Fischer-Tropsch synthesis process, in which a mixture of carbon monoxide and hydrogen is brought into contact with a suitable synthetic catalyst at high temperature and high pressure. In the case of using paraffin wax as the wax raw material, it is desirable, since paraffin wax contains large amounts of sulfur and nitrogen, which are unnecessary in the lubricant base oil, to hydrogenate the paraffin wax as needed to produce a wax raw material with reduced sulfur and nitrogen content.

[0044] Although not particularly limited, examples of synthetic oil include a poly-α-olefin, such as a 1-octene oligomer, 1-decene oligomer and ethylene propylene oligomer or a hydrogenated product thereof, isobutene oligomer and a hydrogenated product thereof, isoparaffin, alkylbenzene, alkylnaphthalene, diesters (for example, ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate and di-2-ethylhexyl sebacate), polyol esters (for example, trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol-2-ethylhexanoate and pentaerythritol pelargonate), polyoxyalkylene glycol, dialkyldiphenyl ether and polyphenyl ether.

[0045] The kinematic viscosity (d) of the oil is not particularly limited. It is typically preferably between 1 and 150 mm². 2 / s at 100°C.

[0046] The oil (d) preferably has a kinematic viscosity of 10 mm. 2 / s or higher at 100°C and a number-average molecular weight of 400 or higher. As the kinematic viscosity of the oil (d) increases, the kinematic viscosity of the protective composition also increases, and thus the protective composition becomes poorly flowing under high-temperature conditions, thereby improving its heat resistance. From this perspective, the kinematic viscosity of preferably 15 mm 2 / s or higher and preferably 20 mm 2 / s or higher. Furthermore, from the point of view of applicability, the kinematic viscosity is preferably 150 mm. 2 / s or lower and preferably 120 mm 2 / s or lower. Kinematic viscosity is measured according to JIS K2283.

[0047] If the oil (d) has a number-average molecular weight of 400 or higher, the sufficiently high molecular weight helps to suppress the oxidative degradation of the oil (d) under high-temperature conditions, thereby suppressing the kinematic viscosity that needs to be reduced. If the kinematic viscosity of the oil (d) is kept high under high-temperature conditions, the protective composition itself becomes difficult to flow under high-temperature conditions, thus improving its heat resistance. From this perspective, the number-average molecular weight is preferably 450 or higher. On the other hand, from the point of view of applicability, the number-average molecular weight is preferably 10,000 or lower and more preferably 8,000 or lower.

[0048] The present protective composition may further contain, for example, a stabilizer, a corrosion inhibitor, a dye, a viscosity improver, or a filler, as long as the function of the present protective composition is not impaired. It is preferred that the present protective composition does not contain a consistency improver (i.e., a gelling agent), such as an amide compound, which forms a gel-like, highly consistent material together with the lubricant base oil.

[0049] The present protective composition can be prepared either by mixing compound (a), compound (b1) or (b2), compound (c) and oil (d) all at once, or by first mixing compound (a) and compound (c) and then compound (b1) or (b2) and oil (d).

[0050] The surface of a material to be coated is coated with the protective composition provided by either applying the composition to the surface of the material or immersing the material in the composition. A metal material can be used as the material to be coated. Examples of metal materials include those suitable for use in a metal terminal block or electrical wire conductor, such as copper, copper alloys, aluminum, aluminum alloys, and materials with various types of plating on these metals. When the protective composition is applied to the surface of the material to be coated, it forms a coating film. In this way, the surface of the material is covered with the coating film of the protective composition.The thickness of the coating film is not specifically limited and can, for example, be set in a range of 0.5 to 100 µm.

[0051] The present protective composition, containing compounds (a) and (c), is adsorbed onto the metal surface it covers. Since compound (a) has a hydrocarbon group with 4 to 30 atoms, either with a branched chain or a carbon-carbon double bond, and since the composition also contains oil (d), it forms a uniform coating film on the metal surface. Furthermore, since the composition contains compound (b1) or (b2), which has a linear hydrocarbon group, flow of the composition is suppressed under high-temperature conditions. Thus, the present protective composition exhibits excellent corrosion protection, uniform application, and heat resistance.By containing compound (b1) or (b2), the composition has excellent heat resistance even without a light-curing resin, such as a (meth)acrylic resin.

[0052] This protective composition can be used to prevent corrosion. For example, it can be applied to a surface of a metal part requiring protection, ensuring close contact with the surface, thereby preventing corrosion. The composition can also be used, for instance, to coat the surface of an electrical wire fitted with terminals to prevent corrosion.

[0053] Next, an electrical wire equipped with terminal blocks will be described according to the present disclosure.

[0054] An electrical wire equipped with terminals according to the present disclosure comprises an insulated electrical wire and a terminal connected to a conductor end of the insulated electrical wire. An electrical connection section between the terminal and the electrical wire conductor is covered with the present protective composition. This prevents corrosion at the electrical connection section.

[0055] Fig. Figure 1 is a perspective view of an electrical wire provided with terminal blocks according to a preferred embodiment of the present disclosure, and Fig. Figure 2 is a vertical cross-sectional view along line AA in Fig. 1. As in Fig. 1 and Fig. As shown in Figure 2, an electrical wire 1 equipped with terminals contains an insulated electrical wire 2, which contains an electrical conductor 3 and an insulating sheath (insulator) 4. The insulated electrical wire 2 and a terminal 5 are electrically connected by an electrical connection section 6.

[0056] The terminal block 5 has a tab-shaped connecting part 51, designed as an elongated flat plate to be connected to a terminal, and an electrical wire fixing section 54, which includes a wire sleeve 52 and an insulating sleeve 53 formed at the extended end of the connecting part 51. The terminal block 5 can be formed (or manufactured) by pressing a metal sheet material into a predetermined shape.

[0057] In the electrical connection section 6, the insulating sheath 4 at the end of the sheathed electrical wire 2 is stripped to expose the electrical conductor 3, and the exposed electrical conductor 3 is crimped onto one side of the terminal 5, thereby connecting the sheathed electrical wire 2 to the terminal 5. The wire sleeve 52 of the terminal 5 is crimped over the electrical conductor 3 of the sheathed electrical wire 2 to electrically connect the electrical conductor 3 to the terminal 5. Furthermore, the insulating sleeve 53 of the terminal 5 is crimped over the insulating sheath 4 of the sheathed electrical wire 2.

[0058] In the electrical wire 1, which is fitted with terminals, the region marked by the dashed line is covered with a coating film 7 made of the present protective composition. More precisely, the region extending from the top of the terminal 5, at a section further forward than the distal end of the exposed section of the electrical wire 3 exposed by the insulation 4, to the top of the insulation 4, at a section further rearward than the rearward end of the exposed section of the electrical wire 3 exposed by the insulation 4, is covered with the coating film 7. That is, the sheathed electrical wire 2 is covered with the coating film 7 such that at the distal end 2a of the wire 2, the coating film 7 projects slightly from the distal end of the electrical wire 3 in the direction of the connecting part 51 of the terminal 5.The terminal 5 is covered with the coating film 7, such that at the distal end 5a of the terminal 5 the coating film 7 protrudes slightly from the end section of the insulating sleeve 53 towards the insulating sheath 4 of the sheathed electrical wire 2. As shown in . Fig. As shown in Figure 2, the side surfaces 5b of the terminal 5 are also covered with the coating film 7. A rear surface 5c of the terminal 5 may or may not be covered with the coating film 7. The circumferential edge of the coating film 7 includes a section in contact with the surface of the terminal 5, a section in contact with the surface of the electrical wire conductor 3, and a section in contact with the surface of the insulating sheath 4.

[0059] In this way, the electrical connection section 6 is covered with the coating film 7 to a predetermined thickness along the shape of the outer circumference of the terminal 5 and the sheathed electrical wire 2. Thus, a section of the electrical wire 2 where the conductor 3 is exposed by the insulation 4 is completely covered with the coating film 7, so that it is not exposed to the outside. Accordingly, the electrical connection section 6 is completely covered with the coating film 7. Since the coating film 7 exhibits excellent adsorption to the entire conductor 3, the insulation 4, and the terminal 5, it prevents the ingress of moisture, for example, from the outside, onto the conductor 3 and the electrical connection section 6, which could lead to corrosion of the metal sections.Since the coating film 7 has a strong adhesion, it is also difficult to form a gap between the coating film 7 and the electrical wire conductor 3, the insulation covering 4 and the terminal block 5 at the circumferential edge of the coating film 7, even when the electrical wire is bent, for example in the processes from the manufacture of the cable harness to the attachment of the cable harness to a vehicle, thus maintaining the watertightness and corrosion protection properties.

[0060] The protective composition is applied to a predetermined surface to form the coating film 7. The composition can be applied to form the coating film 7 by known methods such as dripping and brushing.

[0061] The coating film 7 is formed in a predetermined thickness within the predetermined area. Preferably, the thickness is 0.1 mm or less. If the coating film 7 is too thick, it is difficult to insert the terminal 5 into a connector.

[0062] The electrical conductor 3 of the sheathed electrical wire 2 is a stranded wire consisting of a multitude of wires 3a. In this case, the stranded wire can be composed of a single type of metal wire or of two or more types of metal wires. Furthermore, the stranded wire can also consist of organic fibers in addition to the metal wires. A stranded wire composed of a single type of metal wire means that all the metal wires forming the stranded wire are made of the same metal material, while a stranded wire composed of two or more types of metal wires means that the stranded wire contains metal wires made of different metal materials. The stranded wire can also contain reinforcing wires (tensile elements), for example, to reinforce the sheathed electrical wire 2.

[0063] Examples of materials for the metal wire forming the electrical conductor 3 include copper, copper alloys, aluminum, aluminum alloys, or materials with various types of plating on these metals. Reinforcing wire materials can include, for example, copper alloys, titanium, tungsten, or stainless steel. Organic fibers can also be used as reinforcing wire, such as Kevlar. From a weight reduction perspective, the metal wires forming the electrical conductor 3 are preferably made of aluminum, aluminum alloys, or materials with various types of plating on these metals.

[0064] The material for the insulation covering 4 can be, for example, rubber, polyolefin, PVC, or thermoplastic elastomer. These materials can be used individually or in combination. Various additives can be added to the insulation covering material 4 as needed. Examples of these additives include flame retardants, fillers, and colorants.

[0065] The material for terminal block 5 (material for a substrate) can be copper or various copper alloys, including the commonly used brass. The surface of terminal block 5 can be coated with various metals such as tin, nickel, and gold. The surface can be partially coated, for example, including the contact surface, or completely coated.

[0066] While a terminal block with the end of the electrical wire conductor in the Fig.If the electrical wire 1 shown, equipped with terminals, is press-glued, other known electrical connection methods such as welding can also be used instead of press-fitting for the connection. Example

[0067] The present revelation is to be described by means of examples, but the present revelation is not limited to examples. (Production of a surface protection composition)<Probe 1>

[0068] Calcium hydroxide (c1) was added to a methanol solution containing oleic acid phosphate (a1) and lauric acid phosphate (b1-1). The mixture was stirred at room temperature and the methanol was distilled off. A mineral base oil (d1) was then added to the mixture as a lubricant base oil to create a surface protection composition. The compositional ratios of the compounds (in wt%) are shown in Table 1. • Oleic acid phosphate (a1): Phosphorus compound with a hydrocarbon group having 18 carbon atoms, which has a carbon-carbon double bond. • Laurylic acid phosphate (b1-1): Phosphorus compound with a linear hydrocarbon group with 12 carbon atoms. <Proben 2-10>

[0069] Surface protection compositions were prepared in the same manner as Sample 1 according to the content ratios (in mass %) specified in Table 1. • 2-Ethylhexyl phosphate (a2): Phosphorus compound with a hydrocarbon group with 18 carbon atoms and a branched chain. • Lauric acid (β2-1): Linear carboxylic acid with 12 carbon atoms. • Behenic acid (β2-2): Linear carboxylic acid with 22 carbon atoms. <Probe 11>

[0070] A surface protection composition was prepared according to the content ratio (in mass %) specified in Table 1, without compound (b1) and compound (b2). <Probe 12>

[0071] A surface protection composition was prepared according to the content ratio (in mass %) specified in Table 1, excluding compound (a). <Probe 13>

[0072] A surface protection composition was prepared using caprylic acid (x1) instead of compound (b2) according to the content ratio (in mass %) specified in Table 1. • Caprylic acid (x1): Linear carboxylic acid with 8 carbon atoms.<Probe 14>

[0073] A surface protection composition was produced according to the content ratio (in mass %) specified in Table 1, excluding the oil (d). <Proben 15 und 16>

[0074] The surface protection compositions were prepared according to the content ratios (in mass %) shown in Table 1. The amount of compound (b1) is too high in sample 15, while it is too low in sample 16. <auswertung>(Uniform application)

[0075] On a 2 cm x 2 cm copper plate, 0.05 g of each of the surface protection compositions prepared above was spot-applied at 120°C. The condition of the coating film was then assessed by visual observation. If the surface protection composition formed a uniform coating film, it was rated as "good". If the composition formed an uneven coating film, it was rated as "poor". (Heat resistance)

[0076] 0.05 g of each of the surface protection compositions prepared above was spot-applied at 120°C to a position near an edge of a 1 cm x 5 cm strip of copper. The copper plate was then left in a vertical position in an oven heated to 155°C for two hours, with the edge near which the composition was applied facing upwards. The condition of the coating film was assessed by visual observation. If the coating film did not drip from the edge near which the composition was applied, the composition was rated as "excellent." If the coating film partially dripped, the composition was rated as "good." If the coating film completely dripped, the composition was rated as "poor." The conditions, such as temperature, were in accordance with JIS C60068-2-2. (Corrosion protection properties)

[0077] A strip-shaped copper plate measuring 1 cm x 5 cm was fabricated, and a region of the plate 2 cm from one edge was immersed in each of the surface protection compositions heated to 120°C. The copper plate was then suspended in an oven heated to 155°C and left in a vertical position for two hours, with the edge where the composition was applied facing upwards. The plate was then brought back to room temperature to provide a test piece for measurement. The region of the test piece covered with a coating film was used as the cathode electrode, and a separately fabricated aluminum plate was used as the anode electrode. Both electrodes were immersed in a 5% sodium chloride aqueous solution, and the potential difference between the electrodes (i.e., the corrosion current) was measured.A smaller potential difference indicates that the coating film forms more uniformly on the copper plate and exhibits stronger adsorption to the copper plate's surface. Conversely, a larger potential difference indicates that the coating film forms less uniformly on the copper plate and exhibits weaker adsorption to the copper plate's surface. When an untreated, strip-shaped copper plate was suspended in an oven at 155°C without immersion in the surface protection composition and left in a vertical position for two hours, using the untreated copper plate as the cathode electrode, the corrosion current was 80 µA. If the current measured with the test piece treated with the surface protection composition was less than 1 / 5 of the aforementioned current value of 80 µA, the composition was rated as "good" in its surface protection (corrosion protection) properties.If the measured current was less than 1 / 10 of the aforementioned current value, the composition was rated as "excellent". If the current was 1 / 5 of the aforementioned current value or more, the composition was rated as "poor".

[0078] Regarding samples 1 to 10, the surface protection compositions contain compound (a), at least one selected from the group consisting of compound (b1) and compound (b2), compound (c), and oil (d) in specific proportions. Thus, the surface protection compositions exhibit excellent corrosion protection properties as well as excellent uniform application and heat resistance.

[0079] Regarding sample 11, the surface protection composition, which contained neither compound (b1) nor compound (b2), dripped from the metal surface under the high-temperature condition of 155°C. Therefore, the composition exhibited poor heat resistance and poor corrosion protection properties. Regarding sample 12, the surface protection composition, which did not contain compound (a), did not adsorb to the metal surface and exhibited a high corrosion current. Therefore, the composition also exhibited poor corrosion protection properties. Regarding sample 13, the surface protection composition contained the carboxylic acid (x1) with eight carbon atoms instead of compound (b1) or compound (b2). Since acid (x1) has low crystallinity due to its short linear hydrocarbon chain, the surface protection composition dripped from the metal surface under the high-temperature condition of 155°C.Therefore, the composition exhibited poor heat resistance and poor corrosion protection. Since the surface protection composition did not contain the oil (d), it had low flowability and was brittle in sample 14. Consequently, the coating film did not form uniformly. Regarding sample 15, the surface protection composition had low flowability and was brittle due to the high content of compound (b1). Consequently, the coating film did not form uniformly. Since the content of compound (b1) was low, the effect of improving heat resistance through crystallization of compound (b1) was insufficient in sample 16, and the surface protection composition dripped from the metal surface under the high-temperature condition of 155°C. Thus, the composition exhibited poor heat resistance and poor corrosion protection.

[0080] The embodiment of the present disclosure has been specifically described, but the present disclosure is in no way limited to the embodiment described above, but can be modified in various ways within a scope that does not deviate from the idea of ​​the present disclosure.< / auswertung>

Claims

[1] Surface protection composition, comprising: a phosphorus compound (a) represented by the general formula (1) in an amount of 0.1 to 10 wt%, based on the phosphorus element, with respect to the total amount of the composition; at least one, selected from the group, consisting of a phosphorus compound (b1) represented by the general formula (2) and a carboxylic acid compound (b2) represented by the general formula (3), in an amount of 5.0 to 60 wt% of the total amount of the composition; a metal-containing compound (c) in an amount of 0.1 to 10 wt%, based on a metal element, with respect to the total amount of the composition; and a lubricant base oil (d): in which R 1 represents a hydrogen atom 2represents a hydrocarbon group with 4 to 30 carbon atoms with one or more branched chains or one or more carbon-carbon double bonds and R 3 represents a hydrogen atom or a hydrocarbon group with 4 to 30 carbon atoms; in which R 4 represents a hydrogen atom 5 represents a linear hydrocarbon group with 12 to 22 carbon atoms and R 6 represents a hydrogen atom or a hydrocarbon group with 12 to 22 carbon atoms; R 7 -COOH (3) in which R 7 represents a linear hydrocarbon group with 11 to 21 carbon atoms, where the phosphorus compound (b1) does not have a branched chain or a carbon-carbon double bond. [2] Surface protection composition according to claim 1, wherein a mass ratio (a):{(b1)+(b2)} of compound (a) to the totality of compound (b1) and compound (b2) is in a range of 5:95 to 95:

5. [3] Surface protection composition according to claim 1 or 2, wherein a metal in the compound (c) is at least one selected from the group consisting of alkali metals, alkaline earth metals, aluminium, titanium and zinc. [4] Surface protection composition according to any one of claims 1 to 3, wherein the oil (d) is contained in the composition in an amount of 5.0 to 90 wt% of the total amount of the composition. [5] Surface protection composition according to any one of claims 1 to 4, wherein the oil (d) has a kinematic viscosity of 10 mm 2 / s or higher at 100°C and has a number-average molecular weight of 400 or higher. [6] Surface protection composition according to claim 5, wherein the surface protection composition does not contain a consistency improver. [7] Electrical wire equipped with terminals, comprising a terminal block; an electrical conductor; and an electrical connecting part formed between the terminal block and the electrical conductor, which is covered with the surface protection composition according to one of claims 1 to 6.

Images