JP2021001364A - Surface protective agent composition and coated wire with terminal - Google Patents

Abstract

To provide a surface protective agent composition that shows excellent curability when turned into a thin film, while having excellent anti-corrosive performance to prevent metal corrosion, and a coated wire with a terminal using the same.SOLUTION: A surface protective agent composition contains, based on the total amount of the composition, a phosphorus compound of a specific structure (a) 0.1-10 mass% in terms of phosphorus element, a metal-containing compound (b-1) 0.1-10 mass% in terms of metal element or an amine compound (b-2) 0.1-5.0 mass% in terms of nitrogen element, a (meth) acrylate having a hydrocarbon chain with 4 or more carbon atoms (c) of 1.0-70 mass%, an acylphosphine oxide photopolymerization initiator (d) of 0.1-10 mass%, and at least one selected from an arylphosphine compound of a specific structure (e-1) and an arylphosphite compound of a specific structure (e-2) of 0.1-10 mass%.SELECTED DRAWING: Figure 1

Description

The present application relates to a surface protective agent composition and a coated electric wire with a terminal, and more particularly, to a surface protective agent composition having an excellent anticorrosive performance to prevent metal corrosion and a coated electric wire having an excellent anticorrosive performance using the same. is there.

Grease is used in metal equipment and metal parts for lubrication and anticorrosion purposes. For example, Patent Document 1 describes that a grease containing a perfluoroether base oil, a thickener, barium sulfate or antimony oxide is used for mechanical parts. Further, for example, Patent Document 2 describes that, as a composition for protecting a metal surface, a lubricating oil base oil to which a gelling agent is added is used.

Japanese Patent No. 4811408 Japanese Unexamined Patent Publication No. 06-33272 International Release 2017/018546

Since the compositions of Patent Documents 1 and 2 do not contain a metal adsorbing component, they are inferior in adsorption power to the metal surface and inferior in anticorrosion performance to prevent metal corrosion when applied to the metal surface.

Further, when the metal surface to which the composition is applied has a complicated shape, the composition may flow out from the metal surface after the composition is applied, so that the composition on the metal surface becomes a thin film. When the composition of the thin film is cured by a radical reaction, it is susceptible to oxygen inhibition, which may cause insufficient curing. As a result, the anticorrosive performance for preventing metal corrosion may deteriorate.

The problem to be solved in this application is to provide a surface protective agent composition which is excellent in anticorrosion performance to prevent metal corrosion and is also excellent in curability even when it is made into a thin film, and a coated electric wire with a terminal using the same. It is in.

上記一般式（１）において、Ｒ^１は水素原子を示し、Ｒ^２は炭素数４〜３０の炭化水素基を示し、Ｒ^３は水素原子または炭素数４〜３０の炭化水素基を示す。

上記一般式（２）において、Ｒ^４はアリール基を示し、Ｒ^５およびＲ^６は炭化水素基を示す。

上記一般式（３）において、Ｒ^７はアリール基を示し、Ｒ^８およびＲ^９は炭化水素基を示す。 In order to solve the above problems, the surface protective agent composition according to the present application has the following (a), which is 0.1 to 10% by mass in terms of phosphorus element based on the total amount of the composition, and the following (b-1). However, based on the total amount of the composition, 0.1 to 10% by mass as the metal element equivalent amount, or (b-2) below is 0.1 to 5.0 as the nitrogen element equivalent amount based on the total amount of the composition. By mass%, the following (c) is 1.0 to 70% by mass based on the total amount of the composition, and the following (d) is 0.1 to 10% by mass based on the total amount of the composition, and the following (e-). The gist is that at least one selected from 1) and (e-2) below is blended in an amount of 0.1 to 10% by mass based on the total amount of the composition.
(A) Phosphine compound (b-1) represented by the following general formula (1), metal-containing compound (b-2) amine compound (c) (meth) acrylate (d) having a hydrocarbon chain having 4 or more carbon atoms. Acylphosphine oxide-based photopolymerization initiator (e-1) Arylphosphine compound represented by the following general formula (2) (e-2) Arylphosphine compound represented by the following general formula (3)

In the above general formula (1), R ¹ represents a hydrogen atom, R ² represents a hydrocarbon group having 4 to 30 carbon atoms, and R ³ represents a hydrogen atom or a hydrocarbon group having 4 to 30 carbon atoms.

In the above general formula (2), R ⁴ represents an aryl group, and R ⁵ and R ⁶ represent a hydrocarbon group.

In the above general formula (3), R ⁷ represents an aryl group, and R ⁸ and R ⁹ represent a hydrocarbon group.

In the surface protective agent composition according to the present application, the total of the above (a), the above (b-1) and the above (b-2) and the mass ratio of the above (c) are ((a) + (b−). 1) + (b-2)): (c) = 98: 2 to 10:90 is preferable. Further, it is preferable that the metal of the metal-containing compound of (b-1) is at least one selected from alkali metal, alkaline earth metal, aluminum, titanium and zinc. Further, it is preferable that at least one of the hydrocarbon groups having 4 to 30 carbon atoms in (a) has one or more branched chains or one or more carbon-carbon double bonds. The surface protective agent composition according to the present application may further contain (f) in an amount of 10 to 90% by mass based on the total amount of the composition.

The gist of the coated electric wire with a terminal according to the present application is that the electrical connection portion between the terminal fitting and the electric wire conductor is covered with the cured product of the surface protective agent composition according to the present application.

According to the surface protective agent composition according to the present application, the phosphorus compound (a) and the metal-containing compound (b-1) or the amine compound (b-2) are blended to be coated. It can be adsorbed on the metal surface. Further, by blending the (meth) acrylate of (c) and the photopolymerization initiator of (d), it can be cured by a radical reaction. The photopolymerization initiator (d) is an acylphosphine oxide-based photopolymerization initiator, and at least one selected from the arylphosphine compound (e-1) and the arylphosphine compound (e-2). Since the seeds are mixed, it has excellent curability even when it is made into a thin film. As a result, it is excellent in anticorrosion performance for preventing metal corrosion and also excellent in curability even when it is made into a thin film.

According to the coated electric wire with a terminal according to the present application, since the electrical connection portion between the terminal fitting and the electric wire conductor is covered with the cured product of the above surface protective agent composition, the anticorrosive performance for preventing metal corrosion is achieved. It is also excellent in curability even when it is made into a thin film.

FIG. 1 is a perspective view of a covered electric wire with a terminal according to an embodiment. FIG. 2 is a vertical cross-sectional view taken along the line AA in FIG.

Next, the embodiments of the present disclosure will be described in detail.

The surface protective agent composition according to the present disclosure (hereinafter, may be referred to as the present protective agent composition) includes the following (a), the following (b-1), the following (b-2), and the following (). c), at least one selected from the following (d), the following (e-1) and the following (e-2) are blended in a specific ratio. The protective agent composition may be further blended with the following (f) in a specific ratio.

上記一般式（１）において、Ｒ^１は水素原子を示し、Ｒ^２は炭素数４〜３０の炭化水素基を示し、Ｒ^３は水素原子または炭素数４〜３０の炭化水素基を示す。 (A) is a phosphorus compound represented by the following general formula (1). The phosphorus compound represented by the following general formula (1) has a low-polarity portion (lipophilic portion) composed of a hydrocarbon group and a highly polar portion containing a phosphoric acid group.

In the above general formula (1), R ¹ represents a hydrogen atom, R ² represents a hydrocarbon group having 4 to 30 carbon atoms, and R ³ represents a hydrogen atom or a hydrocarbon group having 4 to 30 carbon atoms.

Since (a) has a hydrocarbon group having 4 to 30 carbon atoms, it is excellent in compatibility with (c) having a hydrocarbon chain having 4 or more carbon atoms. Further, when the protective agent composition contains (f) a lubricating oil base oil, the compatibility between (a) and (f) is improved. When the number of carbon atoms of the hydrocarbon group is less than 4, (a) is easily crystallized, and the compatibility with (c) and (f) is lowered. On the other hand, when the number of carbon atoms of this hydrocarbon group exceeds 30, the viscosity of (a) becomes too high, and even if (c) and (f) are blended, the coatability of the surface protective agent composition deteriorates. .. From the viewpoint of compatibility with (c) and (f), the number of carbon atoms of the hydrocarbon group is more preferably 5 or more, still more preferably 6 or more. Further, from the viewpoint of coatability of the protective agent composition, the number of carbon atoms of the hydrocarbon group is more preferably 26 or less, still more preferably 22 or less.

In the above general formula (1), R ³ may or may not be the same hydrocarbon group as R ² . R ³ is preferably a hydrogen atom or the same hydrocarbon group as R ² .

Examples of the hydrocarbon group in the general formula (1) 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. Of these, alkyl groups, cycloalkyl groups, alkyl-substituted cycloalkyl groups, and alkenyl groups, which are aliphatic hydrocarbon groups or alicyclic hydrocarbon groups, are preferable. When the hydrocarbon group (a) is an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, (a) and (f) lubrication when the protective agent composition contains (f) a lubricating oil base oil. The compatibility of oil-based oils is improved.

The alkyl group may be linear or branched. The alkyl groups include butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group and tetradecyl group. Group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group (stearyl group), isostearyl group, butyloctyl group, myristyl group, isomyristyl group, isosetyl group, hexyldecyl group, octyldecyl group, octyldodecyl group, behenyl group , Isobehenyl group and the like.

Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like. Alkyl-substituted cycloalkyl groups include methylcyclopentyl group, dimethylcyclopentyl group, methylethylcyclopentyl group, diethylcyclopentyl group, methylcyclohexyl group, dimethylcyclohexyl group, methylethylcyclohexyl group, diethylcyclohexyl group, methylcycloheptyl group and dimethylcyclo. Examples thereof include a petit group, a methylethylcycloheptyl group and a diethylcycloheptyl group. Alkyl Substitution The substitution position of the cycloalkyl group is not particularly limited.

The alkenyl group may be linear or branched chain. The alkenyl group includes 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 and an octadecenyl group. , Oleyl group and the like.

Examples of the aryl group include a phenyl group and a naphthyl group. The alkyl-substituted aryl groups include tolyl group, xsilyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group and decylphenyl group. Examples include an undecylphenyl group and a dodecylphenyl group. The substitution position of the alkyl-substituted aryl group is not particularly limited. The alkyl group of the alkyl-substituted aryl 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, a phenylhexyl group and the like. The alkyl group of the arylalkyl group may be linear or branched.

In (a), at least one of the hydrocarbon groups having 4 to 30 carbon atoms is preferably a hydrocarbon group having 8 to 30 carbon atoms. Further, in (a), at least one of the hydrocarbon groups having 4 to 30 carbon atoms preferably has one or more branched chains or one or more carbon-carbon double bonds. When the hydrocarbon group (a) has a branched chain or a carbon-carbon double bond, the orientation of the hydrocarbon groups (a) is suppressed, the crystallinity of (a) is lowered, and the hydrocarbon group has a hydrocarbon chain. The compatibility between (c) and (a) is improved. Further, when the protective agent composition contains (f) a lubricating oil base oil, the compatibility between (a) and (f) the lubricating oil base oil is improved.

Specific phosphorus compounds represented by the above general formula (1) include butyl octyl acid phosphate, isomilystyl acid phosphate, isosetyl acid phosphite, hexyldecyl acid phosphate, isostearyl acid phosphate, and isobehenyl. Acid Phosphate, Octyl Decyl Acid Phosphate, Octyldodecyl 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-Isomyristyl Acid Phosphate, Di-Isosetyl Acid Phosphate, Di-Hexyldecyl Acid Phosphate, Di- Isostearyl Acid Phosphate, Di-Isobehenyl Acid Phosphate, Di-octyldecyl Acid Phosphate, Di-octyldodecyl Acid Phosphate, Di-Isobutyl Acid Phosphate, Di-2-ethylhexyl Acid Phosphate, Di-Isodecyl Examples thereof include acid phosphate, di-tridecyl acid phosphate, di-oleyl acid phosphate, di-myristyl acid phosphate, and di-palmityl acid phosphate.

In (a), 0.1 to 10% by mass is blended as a phosphorus element equivalent amount based on the total amount of the composition. When the amount of (a) is less than 0.1% by mass in terms of phosphorus element on the basis of the total amount of the composition, the adsorption force of the surface protective agent composition to the metal surface is weak, and the effect of suppressing the corrosion of the metal surface is effective. Low. When the amount of (a) is more than 10% by mass in terms of phosphorus element on the basis of the total amount of the composition, the amount of (c) is relatively too small, and the surface protective agent composition is irradiated with light and cured. Even if it is allowed to form a gel having a high melting point, the heat resistance is not sufficient. Further, from the viewpoint of the adsorption force on the metal surface, (a) is more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more in terms of phosphorus element equivalent amount based on the total amount of the composition. .. Further, from the viewpoint of heat resistance, (a) is more preferably 8.0% by mass or less, still more preferably 5.0% by mass or less in terms of phosphorus element conversion amount based on the total amount of the composition.

(B-1) is a metal-containing compound. (B-2) is an amine compound. In the present protective agent composition, only one of (b-1) and (b-2) may be blended, or both (b-1) and (b-2) may be blended. May be good. On the metal surface to which the protective agent composition is applied, ionization of the metal on the metal surface is promoted by (b-1) and (b-2), and the phosphorus compound of (a) can be adsorbed on the metal surface. .. As a result, the protective agent composition can be adsorbed on the metal surface.

Examples of the metal-containing compound include metal hydroxides and metal oxides. Examples of the metal of the metal-containing compound include alkali metals such as Li, Na and K, alkaline earth metals such as Mg and Ca, aluminum, titanium and zinc. (B-1) may be composed of only one kind of metal-containing compound composed of any one of these metals, or may be composed of two or more kinds. Since these metals have a relatively high ionization tendency, coexistence in the present protective agent composition promotes ionization of the metal on the metal surface, and the phosphorus compound (a) can be strongly adsorbed on the metal surface.

From the viewpoint of hydrophilicity, the metal of the metal-containing compound is preferably an alkaline earth metal, aluminum, titanium, zinc or the like having a valence of 2 or more. Further, Ca and Mg are more preferable from the viewpoint of water resistance and the like.

(B-1) is blended in an amount of 0.1 to 10% by mass as a metal element equivalent amount based on the total amount of the composition. When the amount of (b-1) is less than 0.1% by mass in terms of metal element based on the total amount of the composition, the phosphorus compound of (a) forms an ionic bond on the metal surface and is adsorbed on the metal surface. The force is weak, and the effect of suppressing the corrosion of the metal surface by the surface protective agent composition is low. Further, when the amount of (b-1) is more than 10% by mass in terms of the metal element equivalent amount based on the total amount of the composition, the influence of the excess metal-containing compound becomes large and the protective effect cannot be obtained. Further, from the viewpoint of the adsorption power of the phosphorus compound of (a), (b-1) is more preferably 0.5% by mass or more, still more preferably 1.0 as a metal element equivalent amount based on the total amount of the composition. It is mass% or more. In addition, (b-1) is more preferably 8.0% by mass or less, still more preferably 5.0% by mass or less as a metal element equivalent amount based on the total amount of the composition.

Examples of the amine compound include an organic amine compound having a hydrocarbon group having 2 to 100 carbon atoms. Preferably, it is an organic amine compound having a hydrocarbon group having 2 to 22 carbon atoms. Further, from the viewpoint of oxidation stability and the like, those having a hydrocarbon having 8 or more carbon atoms are more preferable. The amine compound may be any of primary to tertiary.

More specifically, the amine compounds include octylamine, laurylamine, myristylamine, stearylamine, behenylamine, oleylamine, beef alkylamine, cured beef alkylamine, aniline, benzylamine, cyclohexylamine, diethylamine, and dipropylamine. Examples thereof include dibutylamine, diphenylamine, dibenzylamine, dicyclohexylamine, triethylamine, tributylamine, dimethyloctylamine, dimethyldecylamine, dimethylstearylamine, dimethyl cowfat alkylamine, dimethyl-cured beef fat alkylamine and dimethyloleylamine. These may be used alone as (b-2), or may be used in combination of two or more. Of these, octylamine and stearylamine are preferable.

(B-2) is blended in an amount of 0.1 to 5.0% by mass as a nitrogen element equivalent amount based on the total amount of the composition. When the amount of (b-2) is less than 0.1% by mass in terms of nitrogen element based on the total amount of the composition, the phosphorus compound of (a) forms an ionic bond on the metal surface and is adsorbed on the metal surface. The force is weak, and the effect of suppressing the corrosion of the metal surface by the surface protective agent composition is low. Further, if the amount of (b-2) is more than 5.0% by mass in terms of nitrogen element based on the total amount of the composition, the influence of the excess amine compound becomes large and the protective effect cannot be obtained. Further, from the viewpoint of the adsorption power of the phosphorus compound of (a), (b-2) is more preferably 0.3% by mass or more, still more preferably 0.5 in terms of nitrogen element conversion amount based on the total amount of the composition. It is mass% or more. Further, (b-2) is more preferably 3.0% by mass or less, still more preferably 2.0% by mass or less in terms of nitrogen element conversion amount based on the total amount of the composition.

(C) is a (meth) acrylate having a hydrocarbon chain having 4 or more carbon atoms. Most (meth) acrylates are liquid at room temperature. (C) has an excellent compatibility with (a) having a hydrocarbon group having 4 or more carbon atoms because it has a hydrocarbon chain having 4 or more carbon atoms. Therefore, the present protective agent composition can be easily applied uniformly even at room temperature and has excellent coatability.

In (c), the hydrocarbon chain having 4 or more carbon atoms may be linear, branched chain, or cyclic. It may also contain one or more carbon-carbon double bonds. A hydrocarbon chain having 4 or more carbon atoms is preferably a hydrocarbon chain having 8 or more carbon atoms. Further, a hydrocarbon chain having 30 or less carbon atoms is preferable. More preferably, it is a hydrocarbon chain having 22 or less carbon atoms. Examples of the hydrocarbon chain having 4 or more carbon atoms include an alkyl chain, a cycloalkyl chain, an alkyl-substituted cycloalkyl chain, an alkenyl chain, an aryl chain, an alkyl-substituted aryl chain, and an arylalkyl chain. Among these, an aliphatic hydrocarbon chain, an alkyl chain which is an alicyclic hydrocarbon chain, a cycloalkyl chain, an alkyl-substituted cycloalkyl chain, and an alkenyl chain are preferable.

(C) may be a (meth) acrylate having two or more carbon-carbon double bonds and a hydrocarbon chain having four or more carbon atoms, or carbon having one carbon-carbon double bond. It may be a (meth) acrylate having a hydrocarbon chain of several 4 or more. Further, a (meth) acrylate having two or more carbon-carbon double bonds and having a hydrocarbon chain having four or more carbon atoms and a hydrocarbon chain having one carbon-carbon double bond and having four or more carbon atoms are used. It may be a combination of having (meth) acrylates. In (c), since it has two or more carbon-carbon double bonds, it becomes a polymer having a three-dimensional structure by photopolymerization, and it becomes difficult to melt at a high temperature. Since (a) has excellent compatibility with (c), (a) is retained in the polymer of (c). As a result, (a) is less likely to flow out at high temperatures, so that the cured product of the present protective agent composition is less likely to melt at high temperatures and has excellent heat resistance. Here, under high temperature means under a temperature of 155 ° C.

The carbon-carbon double bond includes a carbon-carbon double bond contained in a (meth) acryloyl group and a carbon-carbon double bond contained in an alkenyl group. The (meth) acrylate having two or more carbon-carbon double bonds may be a monofunctional (meth) acrylate as long as it has an alkenyl group, or is bifunctional regardless of whether or not it has an alkenyl group. The above polyfunctional (meth) acrylate may be used. The (meth) acrylate contains one or both of acrylate and methacrylate.

Examples of the (meth) acrylate of (c) include monofunctional (meth) acrylates such as dicyclopentenyl (meth) acrylate and dicyclopentenyloxyethyl (meth) acrylate, butanediol di (meth) acrylate, and hexanediol di (meth). Meta) acrylate, nonanediol di (meth) acrylate, decanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, EO adduct di (meth) acrylate of bisphenol A, di (meth) acrylate of polyol of hydrogenated bisphenol A EO adduct or PO adduct, bis [4- (2-) Acryloyloxyethoxy) phenyl] Polyfunctional (meth) acrylates such as fluorene, trimethylpropantri (meth) acrylate, and pentaerythritol tri (meth) acrylate can be mentioned. These may be used alone as (c), or may be used in combination of two or more.

(C) is blended in an amount of 1.0 to 70% by mass based on the total amount of the composition. When the amount of (c) is less than 1.0% by mass based on the total amount of the composition, the effect of making the cured product of the surface protective agent composition difficult to melt at a high temperature is low. Further, if the amount of (c) is more than 70% by mass based on the total amount of the composition, the amount of (a) is relatively too small, so that the adsorption force of the surface protective agent composition on the metal surface is weak. , The effect of suppressing corrosion of the metal surface is low. Further, from the viewpoint of making it difficult to melt at a high temperature, (c) is more preferably 5.0% by mass or more, still more preferably 10% by mass or more, based on the total amount of the composition. Further, from the viewpoint of the adsorption force to the metal surface, (c) is more preferably 50% by mass or less, still more preferably 30% by mass or less based on the total amount of the composition.

Further, the blending amount of (c) is the sum of (a), (b-1) and (b-2) in relation to (a), (b-1) and (b-2), and ( The mass ratio of c) is preferably in the range of ((a) + (b-1) + (b-2)) :( c) = 98: 2 to 10:90. When the blending amount of (c) with respect to the total of (a), (b-1), (b-2) and (c) is 2.0% by mass or more, or (a), (b-1) When the blending amount of (a) + (b-1) + (b-2) is 98% by mass or less based on the total of (b-2) and (c), the cured product of the present protective agent composition is heated to a high temperature. It is highly effective in making it difficult to melt underneath. From this viewpoint, the blending amount of (c) with respect to the total of (a), (b-1), (b-2), and (c) is more preferably 5.0% by mass or more, still more preferably 10. It is 20% by mass or more and 20% by mass or more. Further, when the blending amount of (c) with respect to the total of (a), (b-1), (b-2), and (c) is 70% by mass or less, or (a), (b-1) When the blending amount of (a) + (b-1) + (b-2) with respect to the total of (b-2) and (c) is 30% by mass or more, the protective agent composition is applied to the metal surface. It has strong adsorption power and is highly effective in suppressing corrosion of metal surfaces. From this viewpoint, the blending amount of (c) with respect to the total of (a), (b-1), (b-2), and (c) is more preferably 60% by mass or less, still more preferably 50% by mass. It is as follows.

(D) is an acylphosphine oxide-based photopolymerization initiator. (D) is not particularly limited as long as it is an acylphosphine oxide-based photopolymerization initiator. Examples of (d) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide. In (d), only one kind of acylphosphine oxide-based photopolymerization initiator may be used, or two or more kinds thereof may be used. Examples of commercially available acylphosphine oxide-based photopolymerization initiators include Omnirad TPO series and Ominirad 819 series (trade name of IGM Resins BV).

(D) is blended in an amount of 0.1 to 10% by mass based on the total amount of the composition. When the amount of (d) is less than 0.1% by mass based on the total amount of the composition, the surface protective agent composition is insufficiently cured even when irradiated with light, and the effect of suppressing corrosion of the metal surface is low. Further, when the amount of (d) is more than 10% by mass based on the total amount of the composition, the cured product becomes non-uniform, and the effect of suppressing corrosion of the metal surface is low. Further, from the viewpoint of being more excellent in curability of the cured product, (d) is more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more based on the total amount of the composition. Further, from the viewpoint of being more excellent in the uniformity of the cured product, (d) is more preferably 5.0% by mass or less, still more preferably 3.0% by mass or less based on the total amount of the composition.

上記一般式（２）において、Ｒ^４はアリール基を示し、Ｒ^５およびＲ^６は炭化水素基を示す。Ｒ^５およびＲ^６の炭化水素基は、炭素数１〜３０の炭化水素基であることが好ましい。 (E-1) is an arylphosphine compound represented by the following general formula (2).

In the above general formula (2), R ⁴ represents an aryl group, and R ⁵ and R ⁶ represent a hydrocarbon group. The hydrocarbon groups of R ⁵ and R ⁶ are preferably hydrocarbon groups having 1 to 30 carbon atoms.

The hydrocarbon group in the general formula (2) includes an alkyl group, a cycloalkyl group, an alkyl-substituted cycloalkyl group, an alkenyl group, an aryl group, and an alkyl-substituted aryl group, similarly to the hydrocarbon group in the general formula (1). Arylalkyl groups and the like can be mentioned. Further, the alkyl group, cycloalkyl group, alkyl-substituted cycloalkyl group, alkenyl group, aryl group, alkyl-substituted aryl group and arylalkyl group referred to here are the same as those in the above general formula (1).

The aryl group R ⁴ in the general formula (2), other unsubstituted aryl group, alkyl-substituted aryl groups are included. Aryl group R ^4, alkyl-substituted aryl group is the same as those in formula (1).

The arylphosphine compound represented by the general formula (2) may be a monoarylphosphine compound having one aryl group such as a monoaryldialkylphosphine compound, or may have 2 aryl groups such as a diarylmonoalkylphosphine compound. It may be a diarylphosphine compound having three, a triarylphosphine compound having three aryl groups, or a combination of two or more of these. As the arylphosphine compound represented by the general formula (2), a large amount of aryl groups is preferable, and a triarylphosphine compound is particularly preferable, from the viewpoint of having a high effect of retaining and stabilizing radicals.

More specifically, the arylphosphine compound represented by the general formula (2) includes triphenylphosphine, tris (o-tolyl) phosphine, tris (p-tolyl) phosphine, tris (m-tolyl) phosphine and the like. Can be mentioned.

上記一般式（３）において、Ｒ^７はアリール基を示し、Ｒ^８およびＲ^９は炭化水素基を示す。Ｒ^８およびＲ^９の炭化水素基は、炭素数１〜３０の炭化水素基であることが好ましい。 (E-2) is an aryl phosphite compound represented by the following general formula (3).

In the above general formula (3), R ⁷ represents an aryl group, and R ⁸ and R ⁹ represent a hydrocarbon group. The hydrocarbon groups of R ⁸ and R ⁹ are preferably hydrocarbon groups having 1 to 30 carbon atoms.

The hydrocarbon group in the general formula (3) includes an alkyl group, a cycloalkyl group, an alkyl-substituted cycloalkyl group, an alkenyl group, an aryl group, and an alkyl-substituted aryl group, similarly to the hydrocarbon group in the general formula (1). Arylalkyl groups and the like can be mentioned. Further, the alkyl group, cycloalkyl group, alkyl-substituted cycloalkyl group, alkenyl group, aryl group, alkyl-substituted aryl group and arylalkyl group referred to here are the same as those in the above general formula (1).

The aryl group of R ⁷ in the above general formula (3) includes not only an unsubstituted aryl group but also an alkyl-substituted aryl group. The aryl group and alkyl-substituted aryl group of R ⁷ are the same as those in the above general formula (1).

The aryl phosphite compound represented by the general formula (3) may be a monoaryl phosphite compound having one aryl group such as a monoaryl dialkyl phosphite compound, or a diaryl monoalkyl phosphite compound or the like. It may be a diarylphosphite compound having two aryl groups, a triarylphosphite compound having three aryl groups, or a combination of two or more of these. Good. As the aryl phosphite compound represented by the general formula (3), it is preferable that the aryl phosphite compound has a large number of aryl groups from the viewpoint of having a high effect of retaining and stabilizing radicals, and the triaryl phosphite compound is particularly preferable.

More specifically, the arylphosphine compound represented by the above general formula (3) includes triphenylphosphine (triphenyl phosphate), tris (o-tolyl) phosphite, and tris (p-tolyl). Examples thereof include phosphite and tris (m-tolyl) phosphite.

Of (e-1) and (e-2), (e-1) is more preferable. Of (e-1), triphenylphosphine is more preferable. Of (e-2), triphenylphosphite is more preferable.

At least one selected from (e-1) and (e-2) is blended in an amount of 0.1 to 10% by mass based on the total amount of the composition. When the blending amount is less than 0.1% by mass based on the total amount of the composition, the curability (thin film curability) when the surface protective agent composition is made into a thin film is low. Further, if the blending amount exceeds 10% by mass based on the total amount of the composition, the cured product becomes non-uniform, and the effect of suppressing corrosion of the metal surface is low. From the viewpoint of being more excellent in thin film curability, the blending amount is more preferably 0.5% by mass or more, still more preferably 1.0% by mass or more based on the total amount of the composition. Further, from the viewpoint of being more excellent in the uniformity of the cured product, the blending amount is more preferably 5.0% by mass or less, still more preferably 3.0% by mass or less based on the total amount of the composition.

(F) is a lubricating oil base oil. When the protective agent composition contains (f), the coatability of the protective agent composition at room temperature is improved. It is preferable that (f) is blended in an amount of 10 to 90% by mass based on the total amount of the composition. More preferably, it is 30 to 70% by mass.

As the lubricating oil base oil, any mineral oil, wax isomerized oil, or a mixture of two or more kinds of synthetic oils, which are used as the base oils of ordinary lubricating oils, can be used. As the mineral oil, specifically, for example, the lubricating oil distillate obtained by atmospheric distillation and vacuum distillation of crude oil is subjected to solvent delamination, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, and hydrogen. Paraffin-based, naphthen-based oils, normal paraffins, etc. purified by appropriately combining refining treatments such as chemical purification, sulfuric acid washing, and white clay treatment can be used.

The wax isomerization oil is a so-called Fischer-Tropsch synthesis in which a natural wax such as petroleum slack wax obtained by removing a hydrocarbon oil from a solvent or a mixture of carbon monoxide and hydrogen is brought into contact with an applicable synthetic catalyst at high temperature and high pressure. A wax raw material such as a synthetic wax produced by the method can be prepared by hydrogen isomerization treatment. When slack wax is used as a wax raw material, slack wax contains a large amount of sulfur and nitrogen, which are not necessary for the lubricating oil base oil. Therefore, if necessary, hydrogenate the slack wax to obtain sulfur and nitrogen. It is desirable to use wax with reduced nitrogen as a raw material.

The synthetic oil is not particularly limited, but polyα-olefin such as 1-octene oligomer, 1-decene oligomer, ethylene-propylene oligomer or its hydride, isobutylene oligomer or its hydride, isoparaffin, alkylbenzene, alkylnaphthalene, etc. Diesters (ditridecylglutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, etc.), polyol esters (trimethylolpropanecapried, trimethylpropanepelargonate, pentaerythritol-2) -Ethylhexanoate, pentaerythritol pelargonate, etc.), polyoxyalkylene glycol, dialkyldiphenyl ether, polyphenyl ether and the like.

The kinematic viscosity of the lubricating oil base oil is not particularly limited, but is usually preferably in the range of 1 to 150 mm ² / s at 100 ° C. Further, it is more preferable that the kinematic viscosity at 100 ° C. is in the range of ² to 130 mm ² / s because it is excellent in volatility and ease of handling during production. The kinematic viscosity is measured according to JIS K2283.

In the present protective agent composition, a stabilizer, a corrosion inhibitor, a dye, a thickener, a filler and the like may be blended as long as the functions of the present disclosure are not impaired.

The protective agent composition comprises at least one selected from (a), (b-1) or (b-2), (c), (d), (e-1) and (e-2). It may be prepared by mixing together, or after (a) and (b-1) or (b-2) are mixed, (c), (d), (e-1) and ( It may be prepared by further adding and mixing at least one selected from e-2). When the protective agent composition contains (f) or an additive, (a), (b-1) or (b-2), (c), (d), (e-1) and (e). It may be prepared by mixing at least one selected from (2), (f) and an additive together, or (a) and (b-1) or (b-2) are mixed. After that, at least one selected from (c), (d), (e-1) and (e-2), (f) and an additive may be further added and mixed. Good.

The protective agent composition is coated on the surface of the material to be coated by applying the protective agent composition to the surface of the material to be coated or by immersing the material to be coated in the protective agent composition. Examples of the material to be coated include a metal material. Examples of the metal type of the metal material include Cu, Cu alloy, Al, Al alloy, and metal materials obtained by various plating thereof, which are preferably used in terminal fittings, electric wire conductors, and the like. The protective agent composition can be cured by coating the surface of the material to be coated with light such as ultraviolet rays. As a result, the surface of the material to be coated is covered with the cured product of the present protective agent composition. The film thickness of the cured product of the present protective agent composition is not particularly limited, and may be adjusted to about 0.5 to 100 μm.

According to the present protective agent composition having the above constitution, the phosphorus compound (a) and the metal-containing compound (b-1) or the amine compound (b-2) were blended and applied. It can be adsorbed on the metal surface. Further, by blending the (meth) acrylate of (c) and the photopolymerization initiator of (d), it can be cured by a radical reaction. Then, the photopolymerization initiator (d) is an acylphosphine oxide-based photopolymerization initiator, and the arylphosphine compound (e-1) and the arylphosphine compound (e-2) are blended together with the acylphosphine oxide-based photopolymerization initiator. It has excellent curability even when it is made into a thin film. As a result, it is excellent in anticorrosion performance for preventing metal corrosion and also excellent in curability even when it is made into a thin film.

The effect of improving the thin film curability of the protective agent composition is that the acylphosphine oxide-based photopolymerization initiator (d) and the arylphosphin compound (e-1) and the arylphosphite compound (e-2) mutually. By the action, the radical generated from (d) is retained in (e-1) or (e-2), stabilized (extended), and then used in the polymerization reaction of the (meth) acrylate of (c). It is presumed that it has been achieved from the fact that it is done.

It is presumed that the transfer of radicals from (d) to (e-1) or (e-2) is due to the similarity of these chemical structures. If the photopolymerization initiator is not an acylphosphine oxide-based photopolymerization initiator but another type of photopolymerization initiator, the effect of improving the thin film curability cannot be obtained.

Further, the transfer of radicals from (d) to (e-1) or (e-2) is due to the fact that (e-1) or (e-2) is a trivalent phosphorus having an unshared electron pair. It is presumed. Even if a pentavalent arylphosphite compound is used in place of the arylphosphine compound (e-1), the effect of improving the thin film curability cannot be obtained. Further, even if a pentavalent aryl phosphite compound (phosphate ester) is used instead of the aryl phosphite compound (phosphite ester) which is (e-2), the effect of improving the thin film curability cannot be obtained. ..

It is presumed that the stabilization (prolongation of life) of radicals by (e-1) or (e-2) is due to the resonance structure in which radicals are easily stabilized. Both (e-1) and (e-2) have an aromatic ring resonance structure. Even if trialkylphosphine is used instead of (e-1), the effect of improving the thin film curability cannot be obtained. Further, even if trialkylphosphite is used instead of (e-2), the effect of improving the thin film curability cannot be obtained.

The protective agent composition contains the (meth) acrylate of (c). In addition, the lubricating oil base oil of (f) may be blended. As a result, a liquid having a low viscosity can be obtained at room temperature, and a thin film of the present protective agent composition can be formed by coating at room temperature. The thin film refers to a film having a thickness of about several μm to 10 μm. The radical curable composition of the thin film is susceptible to oxygen inhibition and is prone to insufficient curing. As a result, the anticorrosive performance for preventing metal corrosion is lowered. According to the present protective agent composition, since it is excellent in curability even when it is made into a thin film, it is possible to maintain anticorrosion performance which prevents metal corrosion even when it is made into a thin film. By being excellent in thin film curability, the present protective agent composition can be a stable cured film even on a complicated structure surface.

This protective agent composition can be used for anticorrosion applications and the like. For example, it can be used for anticorrosion to prevent metal corrosion by adhering to the surface of a metal member to be surface-protected and covering the metal surface. Further, as an anticorrosive application, for example, it can be used as an anticorrosive agent for a coated electric wire with a terminal.

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

The coated wire with a terminal according to the present disclosure comprises a wire with a terminal fitting connected to a conductor terminal of an insulated wire, and the electrical connection portion between the terminal fitting and the wire conductor is covered with a cured product of the protective agent composition. .. This prevents corrosion at the electrical connections.

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

The terminal fitting 5 is a wire fixing portion composed of a tab-shaped connecting portion 51 made of an elongated flat plate connected to the mating terminal, a wire barrel 52 extendingly formed at the end of the connecting portion 51, and an insulation barrel 53. Has 54. The terminal fitting 5 can be formed (processed) into a predetermined shape by pressing a metal plate material.

In the electric connection portion 6, the insulating coating 4 of the end of the coated electric wire 2 is peeled off to expose the electric wire conductor 3, and the exposed electric wire conductor 3 is crimped to one side of the terminal fitting 5 to be crimped to the coated 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, and 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 coated electric wire 2.

In the coated electric wire 1 with terminals, the range indicated by the alternate long and short dash line is covered with the cured product 7 of the protective agent composition. Specifically, the insulating coating 4 exposed from the insulating coating 4 of the electric wire conductor 3 from the surface of the terminal fitting 5 ahead of the tip, and the portion exposed from the insulating coating 4 of the electric wire conductor 3 after the rear end. The area up to the surface of is covered with the cured product 7. That is, the tip 2a side of the covered electric wire 2 is covered with the cured product 7 so as to slightly protrude from the tip of the electric wire conductor 3 toward the connection portion 51 side of the terminal fitting 5. The tip 5a side of the terminal fitting 5 is covered with the cured product 7 so as to slightly protrude from the end of the insulation barrel 53 to the insulating coating 4 side of the coated electric wire 2. Then, as shown in FIG. 2, the side surface 5b of the terminal fitting 5 is also covered with the cured product 7. The back surface 5c of the terminal fitting 5 may or may not be covered with the cured product 7. The peripheral end of the cured product 7 is composed of 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 cured product 7 to a predetermined thickness along the outer peripheral shapes of the terminal fitting 5 and the covered electric wire 2. As a result, the exposed portion of the electric wire conductor 3 of the covered electric wire 2 is completely covered with the cured product 7 so as not to be exposed to the outside. Therefore, the electrical connection 6 is completely covered by the cured product 7. Since the cured product 7 has excellent adhesion to all of the electric wire conductor 3, the insulating coating 4, and the terminal fitting 5, the cured product 7 allows moisture or the like to enter the electric wire conductor 3 and the electrical connection portion 6 from the outside, and the metal portion is removed. Prevents corrosion. Further, since the adhesiveness is excellent, for example, even if the electric wire is bent in the process from the manufacture of the wire harness to the attachment to the vehicle, the cured product 7 and the electric wire conductor 3 and the insulating coating 4 are formed at the peripheral end of the cured product 7. , It is difficult to form a gap between any of the terminal fittings 5, and the waterproof and anticorrosion functions are maintained.

The protective agent composition forming the cured product 7 is applied to a predetermined range. A known means such as a dropping method and a coating method can be used for applying the protective agent composition for forming the cured product 7.

The cured product 7 is formed with a predetermined thickness and in a predetermined range. The thickness is preferably 0.1 mm or less. If the cured product 7 becomes too thick, it becomes difficult to insert the terminal fitting 5 into the connector.

The electric wire conductor 3 of the covered electric wire 2 is composed of a stranded wire formed by twisting a plurality of strands 3a. In this case, the stranded wire may be composed of one kind of metal wire or two or more kinds of metal wire. Further, the stranded wire may include a wire made of an organic fiber or the like in addition to the metal wire. Note that being composed of one type of metal wire means that all the metal wires constituting the stranded wire are made of the same metal material, and being composed of two or more types of metal wire is twisted. It means that the wire contains a metal wire made of different metal materials. The stranded wire may include a reinforcing wire (tension member) or the like for reinforcing the coated electric wire 2.

Examples of the material of the metal wire constituting the electric wire conductor 3 include copper, copper alloy, aluminum, aluminum alloy, and materials obtained by various plating on these materials. Further, as the material of the metal wire as the reinforcing wire, copper alloy, titanium, tungsten, stainless steel and the like can be exemplified. Moreover, as an organic fiber as a reinforcing wire, Kevlar and the like can be mentioned. As the metal wire constituting the electric wire conductor 3, from the viewpoint of weight reduction, aluminum, an aluminum alloy, or a material obtained by various plating on these materials is preferable.

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

In the coated electric wire 1 with terminals shown in FIG. 1, the terminal fittings are crimp-connected to the end of the electric wire conductor, but other known electrical connection methods such as welding may be used instead of the crimp connection.

Hereinafter, the present disclosure will be described with reference to examples, but the present disclosure is not limited to the examples.

<Preparation of surface protective agent composition>
(Sample 1)
Calcium hydroxide was added to a methanol solution of oleyl acid phosphate, stirred at room temperature, and then methanol was distilled off. Then, isobornyl acrylate and an acylphosphine oxide-based photopolymerization initiator (IGM Resins B.V.) Omnirad TPO H "), triphenylphosphine (PPh ₃ ) and lubricating oil base oil (mineral base oil) were blended to prepare a surface protectant composition. The compounding composition (mass%) is as shown in Table 1.
-Oleyl acid phosphate: a phosphorus compound having a carbon-carbon double bond and having a hydrocarbon group having 18 carbon atoms.-Isobornyl acrylate: an acrylate having a cyclic hydrocarbon chain having 10 carbon atoms.

(Samples 2 to 19)
A surface protective agent composition was prepared in the same manner as in Sample 1 with the compounding composition (mass%) shown in Table 1. Sample 13 does not contain a lubricating oil base oil. In Sample 4, an amine compound is used instead of the metal-containing compound.
-2-Ethylhexyl acid phosphate: a phosphorus compound having a branched chain and having an 8-carbon hydrocarbon group-octylamine: an 8-carbon aliphatic primary amine-nonanediol diacrylate: a 9-carbon straight-chain hydrocarbon Diacrylate neopentyl glycol diacrylate having a hydrogen chain: Diacrylate having a branched hydrocarbon chain having 5 carbon atoms / Tetraethylene glycol diacrylate: Diacrylate having a straight chain hydrocarbon chain having 2 carbon atoms Omnirad 819 : Acylphosphine oxide-based photopolymerization initiator ・ Omnirad 184: α-hydroxyalkylphenone-based photopolymerization initiator ・ Omnirad 369: α-aminoalkylphenone-based photopolymerization initiator ・ Omnirad 651: benzylketal-based photopolymerization initiator ・ Omnirad MBF: Intramolecular hydrogen abstraction type photopolymerization initiator ・ Irgacure OXE01: Oxym ester-based photopolymerization initiator ・ Triphenylphosphite: P (OPh) ₃
-Trioctylphosphine: P ((CH ₂ ) ₇ CH ₃ ) ₃
-Triphenylphosphine: O = P (OPh) ₃

(Sample 21)
A surface protective agent composition was prepared in the same manner as in Sample 1 except that none of (a), (b-1), and (b-2) was blended.

(Sample 22)
A surface protective agent composition was prepared in the same manner as in Sample 1 except that (d) was not blended.

(Sample 23)
A surface protective agent composition was prepared in the same manner as in Sample 1 except that neither (e-1) nor (e-2) was blended.

(Sample 24)
A surface protective agent composition was prepared in the same manner as in Sample 1 except that (x-4) was blended instead of (c).

(Samples 25-29)
In the same manner as in Sample 1, except that any one of (y-3), (y-4), (y-5), (y-6), and (y-7) was blended in place of (d). , A surface protectant composition was prepared.

(Samples 30 to 31)
A surface protective agent composition was prepared in the same manner as in Sample 1 except that either (z-3) or (z-4) was blended in place of (e-1) or (e-2).

(Samples 32 to 33)
A surface protective agent composition was prepared in the same manner as in Sample 1 except that a large amount of (d) or (e-1) was blended.

<Evaluation>
(Measurement of thin film curing rate)
Each of the prepared surface protective agent compositions was formed into a thin film (thickness 4.6 μm) on a 2 cm × 2 cm copper plate with a # 2 bar coater, and a UV lamp (100 mW / cm ² manufactured by SEN Special Light Source Co., Ltd.) was formed on the surface of the thin film. The film was cured by irradiating with a spatula for 20 seconds, and immediately scraped off the entire thin film with a spatula made of polytetrafluoroethylene to prepare a sample for measuring the thin film curing rate. The infrared spectrum (4000-400 cm ^-1 ) of the measurement sample is measured using a Fourier transform infrared spectrophotometer (FT-IR), and 811 cm based on the unsaturated double bond of the acrylate contained in the measurement sample. ^-1 infrared absorption peak area Aa, the infrared absorption peak area Ab of 1735 cm ^-1 based on the ester bond of acrylate respectively calculated, was determined the ratio Aa / Ab. Thin film cure rate based on the ratio Aa ₀ / Ab measured for the same composition with a cure rate of 0% (not cured) and the ratio Aa ₁₀₀ / Ab measured for the same composition with a cure rate of 100% (complete cure). Asked. In the completely cured product, the infrared absorption peak of 811 cm ^{-1 due} to the unsaturated double bond of the acrylate disappeared, and Aa ₁₀₀ / Ab = 0. When the thin film curing rate is 90% or more by this measuring method, it can be said that the thin film curing property is high.

(Corrosion current)
A strip-shaped copper plate of 1 cm × 5 cm is immersed 2 cm from one end in each of the prepared surface protective agent compositions, and after taking out, a thin film (thickness 4.6 μm) is formed with a # 2 bar coater, and the surface of the thin film The thin film was cured by irradiating with a UV lamp (100 mW / cm ² manufactured by SEN Special Light Source Co., Ltd.) for 30 seconds. This was used as a test piece for measurement. The portion of the test piece for measurement covered with a thin film was used as a cathode electrode, and an Al plate prepared separately was used as an anode electrode, and the electrode was immersed in a 5% NaCl aqueous solution to measure the potential difference (corrosion current). It can be said that the smaller the potential difference, the more uniformly the thin film is present on the strip-shaped copper plate, and the stronger the adsorption force of the thin film on the surface of the strip-shaped copper plate. On the other hand, it can be said that the larger the potential difference is, the more uneven the thin film on the strip-shaped copper plate is, or the weaker the adsorption force of the thin film on the surface of the strip-shaped copper plate is. When an untreated strip-shaped copper plate not immersed in the surface protective agent composition is used as the cathode electrode, the corrosion current value is 80 μA, and the current value is less than 1/5 of this value in comparison with this. If there is, it can be judged that the effect of surface protection (corrosion prevention) is high.

The surface protective agent composition of Samples 1 to 19 is selected from (a), (b-1) or (b-2), (c), (d), (e-1) and (e-2). At least one of them is blended in a specific ratio. Therefore, it is excellent in anticorrosion performance to prevent metal corrosion and also excellent in thin film curability.

Since the surface protective agent composition of sample 21 does not contain any of (a), (b-1), and (b-2), it becomes a cured product after UV irradiation, but it is adsorbed on the metal surface. However, the corrosion current is high and the anticorrosion performance to prevent metal corrosion is inferior. Since the surface protective agent composition of sample 22 does not contain (d), it does not cure even when irradiated with UV, has a high corrosion current, and is inferior in anticorrosion performance for preventing metal corrosion. In the surface protective agent composition of sample 24, tetraethylene glycol diacrylate having no hydrocarbon chain having 4 or more carbon atoms is used instead of (c), so that the compatibility with (a) is low. , A uniform cured product was not formed. Therefore, the corrosion current is high, and the anticorrosion performance for preventing metal corrosion is inferior.

The surface protective agent composition of sample 23 does not contain either (e-1) or (e-2). In the surface protectant composition of Samples 25 to 29, a photopolymerization initiator that is not an acylphosphine oxide type is used instead of (d). In the surface protective agent composition of Sample 30, trioctylphosphine is used instead of (e-1). Triphenylphosphine is used instead of (e-1) in the surface protective agent composition of Sample 31. All of these results in inferior thin film curability. In the surface protectant composition of Samples 1 to 19, an acylphosphine oxide-based photopolymerization initiator is used as the photopolymerization initiator, and triphenylphosphine as (e-1) or triphenyl as (e-2). Phosphite is used, and in these combinations, the thin film curability is excellent. From this, in order to have excellent thin film curability, it is necessary to use a trivalent phosphorus atom having an unshared electron pair and a phosphorus compound having an aromatic ring in combination with an acylphosphine oxide-based photopolymerization initiator. It can be seen that it is.

The acylphosphine oxide-based photopolymerization initiator has a similar chemical structure to triphenylphosphine as (e-1) and triphenylphosphine as (e-2), and easily interacts with each other (e-1). Triphenylphosphine as () and triphenylphosphine as (e-2) are phosphorus compounds having a trivalent phosphorus atom having an unshared electron pair, and can exchange radicals with (d), (e). Since triphenylphosphine as -1) and triphenylphosphine as (e-2) have an aromatic ring, radicals can be easily stabilized, which also explains the improved curing of thin film curability.

The surface protective agent compositions of the samples 32 and 33 contain too much (d) or (e-1). Therefore, the cured product is non-uniform, the corrosion current is high, and the anticorrosion performance for preventing metal corrosion is inferior.

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

1 Coated wire with terminal 2 Coated wire 3 Wire conductor 4 Insulation coating (insulator)
5 Terminal bracket 6 Electrical connection 7 Hardened product

Claims (6)

The following (a) is 0.1 to 10% by mass as the phosphorus element equivalent amount based on the total amount of the composition.
The following (b-1) is 0.1 to 10% by mass as the metal element equivalent amount based on the total composition amount, or the following (b-2) is the nitrogen element equivalent amount based on the total composition amount. 0.1 to 5.0% by mass,
The following (c) is 1.0 to 70% by mass based on the total amount of the composition.
The following (d) is 0.1 to 10% by mass based on the total amount of the composition.
At least one selected from the following (e-1) and the following (e-2) is 0.1 to 10% by mass based on the total amount of the composition.
A surface protective agent composition that is compounded.
(A) Phosphine compound (b-1) represented by the following general formula (1), metal-containing compound (b-2) amine compound (c) (meth) acrylate (d) having a hydrocarbon chain having 4 or more carbon atoms. Acylphosphine oxide-based photopolymerization initiator (e-1) Arylphosphine compound represented by the following general formula (2) (e-2) Arylphosphine compound represented by the following general formula (3)

In the above general formula (1), R ¹ represents a hydrogen atom, R ² represents a hydrocarbon group having 4 to 30 carbon atoms, and R ³ represents a hydrogen atom or a hydrocarbon group having 4 to 30 carbon atoms.

In the above general formula (2), R ⁴ represents an aryl group, and R ⁵ and R ⁶ represent a hydrocarbon group.

In the above general formula (3), R ⁷ represents an aryl group, and R ⁸ and R ⁹ represent a hydrocarbon group. The total of the above (a), the above (b-1) and the above (b-2) and the mass ratio of the above (c) are ((a) + (b-1) + (b-2)) :. c) The surface protective agent composition according to claim 1, which is in the range of 98: 2 to 10:90. The surface protective agent composition according to claim 1 or 2, wherein the metal (b-1) is at least one selected from alkali metals, alkaline earth metals, aluminum, titanium, and zinc. The present invention according to any one of claims 1 to 3, wherein at least one of the hydrocarbon groups having 4 to 30 carbon atoms in (a) has one or more branched chains or one or more carbon-carbon double bonds. The surface protective agent composition described. The surface protective agent composition according to any one of claims 1 to 4, wherein the following (f) is blended in an amount of 10 to 90% by mass based on the total amount of the composition.
(F) Lubricating oil Base oil A coated electric wire with a terminal, wherein the electrical connection portion between the terminal fitting and the electric wire conductor is covered with the cured product of the surface protective agent composition according to any one of claims 1 to 5.

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