JP7084699B2 - A method for manufacturing a pressure-sensitive adhesive composition for metal protection, a pressure-sensitive adhesive tape for metal protection, and a connection protection structure. - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention relates to a metal protective pressure-sensitive adhesive composition, a method for manufacturing a metal protective pressure-sensitive adhesive tape and a connection portion protective structure, specifically, a metal protective pressure-sensitive adhesive composition, and a metal protective feeling provided therein. The present invention relates to a pressure-sensitive adhesive tape and a method for manufacturing a connection portion protection structure using the pressure-sensitive adhesive tape.

Conventionally, butyl rubber has excellent weather resistance, electrical insulation, impact resistance, and gas permeability as a pressure-sensitive adhesive material, and is used in various applications. For example, an insulator in which crosslinked butyl rubber is used in combination with a vinyl chloride resin has been proposed (see, for example, Patent Document 1).

In Patent Document 1, it is proposed that the insulator covers the conductor of the insulated wire.

JP-A-2015-149141

However, since the crosslinked butyl rubber described in Patent Document 1 is crosslinked, the insulator has a problem that the workability is low and it is difficult to form it as a pressure-sensitive adhesive tape.

Therefore, it is tentatively proposed to improve the processability of the insulator by using uncrosslinked butyl rubber instead of crosslinked butyl rubber.

However, such uncrosslinked butyl rubber tends to have a low molecular weight (prone to cause so-called metal damage) in the presence of a metal, specifically, due to contact with a conductor, and therefore, the outer shape should be maintained for a long period of time. There is a problem that durability is reduced. That is, it is a phenomenon in which radical species derived from oxygen contained in water or air are combined with a metal to rapidly accelerate the deterioration of butyl rubber.

Therefore, the inventors of the present application have been pressure-sensitive for metal protection, which can suppress metal damage even in the presence of heat and oxygen that cannot be removed in the usage environment while containing butyl rubber having excellent processability. As a result of diligent studies on the adhesive composition, the following invention has been completed.

The present invention (1) is a pressure-sensitive adhesive composition for metal protection, which comprises a butyl rubber, a metal damage suppressing function based on metal capture, and a metal damage-oxidation suppressing coexisting component having both an oxidation suppressing function. including.

Since this pressure-sensitive adhesive composition for metal protection contains butyl rubber instead of crosslinked butyl rubber, it is excellent in processability.

Further, in the pressure-sensitive adhesive composition for metal protection, the metal damage-oxidation suppression coexisting component captures the metal even if the pressure-sensitive adhesive composition for metal protection comes into contact with the metal due to its metal damage suppression function. Further, due to its oxidation suppressing function, it is possible to suppress deterioration of butyl rubber due to metal damage by capturing radical species derived from oxygen contained in water or air.

In the present invention (2), the pressure-sensitive metal protection component according to (1), wherein the metal damage-oxidation suppression combined component contains a first metal damage suppression agent having both a metal damage suppression function and an oxidation suppression function. Contains an adhesive composition.

In this pressure-sensitive adhesive composition for metal protection, the metal damage-oxidation suppression coexisting component contains a first metal damage suppression agent having both a metal damage suppression function and an oxidation suppression function. It can exert both a harm suppression function and an oxidation suppression function. Therefore, the pressure-sensitive adhesive composition for metal protection can be simply formulated.

In the present invention (3), the pressure-sensitive adhesive for metal protection according to (2), wherein the first metal damage inhibitor is at least one selected from the group consisting of an aromatic amine compound and a hydrazine compound. Contains the composition.

In this pressure-sensitive adhesive composition for metal protection, since the first metal damage suppressant is at least one selected from the group consisting of an aromatic amine compound and a hydrazine compound, the first metal damage suppressant is a metal. Can be more reliably captured and the deterioration of butyl rubber due to metal damage can be suppressed.

The present invention (4) includes the pressure-sensitive adhesive composition for metal protection according to (2) or (3), wherein the first metal damage suppressant is a copper damage suppressant.

In the pressure-sensitive adhesive composition for metal protection, the copper damage inhibitor can more reliably capture copper and further reliably suppress the deterioration of butyl rubber due to copper damage.

In the present invention (5), the metal damage-oxidation suppressing coexisting component does not have an oxidation suppressing function, and contains a second metal damage suppressing agent having a metal damage suppressing function, and an oxidation suppressing agent (1). ) Shall contain the metal protective pressure sensitive adhesive composition.

In this pressure-sensitive adhesive composition for metal protection, the ratio of the oxidation inhibitor to the second metal damage inhibitor can be changed depending on the environment.

In the present invention (6), the pressure-sensitive adhesive composition for metal protection according to (5), wherein the second metal damage inhibitor is at least one selected from the group consisting of an amide compound and a benzotriazole compound. Including things.

In this pressure-sensitive adhesive composition for metal protection, since the second metal damage suppressant is at least one selected from the group consisting of an amide compound and a benzotriazole compound, the second metal damage suppressant is a metal. Can be more reliably captured and the deterioration of butyl rubber due to metal damage can be suppressed.

The present invention (7) includes the pressure-sensitive adhesive composition for metal protection according to (5) or (6), wherein the second metal damage suppressant is a copper damage suppressant.

In the pressure-sensitive adhesive composition for metal protection, the copper damage inhibitor can more reliably capture copper and further reliably suppress the deterioration of butyl rubber due to copper damage.

The present invention (8) is the pressure-sensitive adhesive for metal protection according to any one of (1) to (7), wherein the toluene insoluble content of the pressure-sensitive adhesive composition for metal protection is 10% by mass or less. Contains the agent composition.

Since the toluene insoluble content of the pressure-sensitive adhesive composition for metal protection is 10% by mass or less, the processability is further improved.

The present invention (9) further includes the pressure-sensitive adhesive composition for metal protection according to any one of (1) to (8), which contains a filler.

Since the pressure-sensitive adhesive composition for metal protection contains a filler, it is excellent in processability and reinforcing property.

The present invention (10) contains the pressure-sensitive adhesive component containing the butyl rubber, and the ratio of the filler is 100 parts by mass or more and less than 600 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive component. (9) Contains the pressure-sensitive adhesive composition for metal protection according to (9).

Since the ratio of the filler is 100 parts by mass or more with respect to 100 parts by mass of the pressure-sensitive adhesive component, the reinforcing effect can be sufficiently improved. Since the ratio of the filler is less than 600 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive component, the pressure-sensitive adhesive composition for metal protection has excellent pressure-sensitive adhesiveness, excellent self-bonding property, and excellent self-bonding property. Workability can be ensured.

INDUSTRIAL APPLICABILITY The present invention (11) is a metal composed of a base material and a pressure-sensitive adhesive composition for metal protection according to any one of (1) to (10), which is arranged on one surface in the thickness direction of the base material. Includes a metal protective pressure sensitive adhesive tape with a protective pressure sensitive adhesive layer.

Since this pressure-sensitive adhesive tape for metal protection includes the pressure-sensitive adhesive layer for metal protection made of the above-mentioned pressure-sensitive adhesive composition for metal protection, even if the pressure-sensitive adhesive layer for metal protection comes into contact with metal, the metal Harm-oxidation suppression The coexisting component can capture metals and radical species, and can prevent the butyl rubber of the pressure-sensitive adhesive layer for metal protection from deteriorating due to metal damage.

In the present invention (12), a first conductor portion having a passivation film formed on its surface, a first electric wire provided with a first coating layer covering the passivation film, a second conductor portion and the second conductor are provided. In the step of preparing the second electric wire provided with the second coating layer covering the portion and the pressure-sensitive adhesive tape for metal protection according to (8), a part of the first coating layer is removed to obtain the passivation. A step of exposing the film from the first coating layer, a step of removing the exposed passivation film to expose the first conductor portion from the passivation film, and a step of removing a part of the second coating layer. , The step of exposing the second conductor portion from the second coating layer, and the step of bundling the exposed first conductor portion and the second conductor portion and coating them with the metal protective pressure-sensitive adhesive tape. Includes a method of manufacturing a connection protection structure.

When the connection part including the first conductor part having the passivation film formed on the surface is covered with the metal protective pressure-sensitive adhesive tape, if the first conductor part is covered with the passivation film, the metal protection pressure-sensitive part is used. No metal damage is caused by the first conductor portion in the adhesive layer, and the durability of the connection portion is not deteriorated.

However, if the passivation film is removed, the first conductor portion is exposed from the passivation film, and the connection portion including the first conductor portion is covered with the metal protective pressure-sensitive adhesive tape, the metal protection pressure-sensitive adhesive layer is obtained. Is in contact with at least the first conductor portion. Then, in the pressure-sensitive adhesive layer for metal protection, the metal forming the first conductor portion causes metal damage, and the durability of the connecting portion is lowered.

On the other hand, in the method for manufacturing a connection portion protection structure of the present invention, the passivation film is removed to expose the first conductor portion from the passivation film, and the connection portion including the first conductor portion is exposed to a pressure-sensitive adhesive tape for metal protection. Since the pressure-sensitive adhesive layer for metal protection contains a metal-damage-oxidation-suppressing coexisting component, the metal-damage-oxidation-suppressing co-component captures metals and radical species, and the butyl rubber is metal-damaged. It is possible to suppress deterioration due to. Therefore, it is possible to manufacture a connection portion protection structure having excellent durability.

In the present invention (13), the first conductor portion is made of at least one metal selected from the group consisting of copper, iron, cobalt, nickel, manganese, vanadium, titanium, calcium, silver, zinc, aluminum and magnesium. , (12) includes the method for manufacturing the connection portion protection structure.

In this method for manufacturing the connection portion protection structure, the metal damage-oxidation suppression coexisting component can capture the above-mentioned specific metal and radical species to prevent the butyl rubber from being deteriorated by the metal damage. Therefore, it is possible to manufacture a connection portion protection structure having excellent durability.

The pressure-sensitive adhesive composition for metal protection of the present invention is excellent in processability and can suppress deterioration of butyl rubber due to metal damage.

The pressure-sensitive adhesive tape for metal protection of the present invention can suppress deterioration of the butyl rubber of the pressure-sensitive adhesive layer for metal protection due to metal damage.

In the method for manufacturing a connection portion protection structure of the present invention, a connection portion protection structure having excellent durability can be manufactured.

FIG. 1 shows a schematic cross-sectional view of an embodiment of the pressure-sensitive adhesive tape for metal protection of the present invention. FIG. 2 shows a manufacturing process diagram of an embodiment of the method for manufacturing a connection portion protection structure of the present invention using the pressure-sensitive adhesive tape for metal protection shown in FIG. 1, and FIG. 2A shows a first electric wire and a first wire. 2 The process of preparing the electric wire and the fixing member, FIG. 2B shows the process of fixing to the first electric wire and the second electric wire by the fixing member, FIG. 2C, the process of fixing the first electric wire and the metal protective pressure-sensitive adhesive tape. The process of manufacturing the connection part protection structure by protecting the connection part of the 2nd electric wire is shown. 3A and 3B are views illustrating a mode in which the metal protective pressure-sensitive adhesive layer forms a protective layer, in which FIG. 3A is a metal protective pressure-sensitive adhesive tape of a first electric wire and a second electric wire. FIG. 3B, a cross-sectional view immediately after winding the connection portion, shows an embodiment in which the pressure-sensitive adhesive layer for metal protection is self-fused to form a single protective layer. FIG. 4 shows a cross-sectional view of an embodiment in which a metal vapor deposition plate is protected by using a metal protective pressure-sensitive adhesive tape to manufacture a connection portion protection structure.

An embodiment of the pressure-sensitive adhesive composition for metal protection of the present invention will be described.

1. 1. Pressure-sensitive adhesive composition for metal protection The pressure-sensitive adhesive composition for metal protection is, for example, a pressure-sensitive adhesive composition for metal protection (specifically, metal damage) that causes harm (metal damage) from the metal contained in the protected object. , Butyl rubber, which will be described later), is a composition that can protect the object to be protected while suppressing the reception. Further, the pressure-sensitive adhesive composition for metal protection is, for example, a composition capable of protecting the protection target while suppressing the metal damage caused by a metal that is not the protection target from being received by the pressure-sensitive adhesive composition for metal protection. be. Preferably, the pressure-sensitive adhesive composition for metal protection is a composition capable of protecting the protection target while suppressing the metal damage from the metal contained in the protection target to the metal protection pressure-sensitive adhesive composition. be.

The pressure-sensitive adhesive composition for metal protection contains a pressure-sensitive adhesive component and a metal damage-oxidation suppressing coexisting component having both a metal damage suppressing function and an oxidation suppressing function as essential components.

2. 2. Pressure-sensitive adhesive component The pressure-sensitive adhesive component contains butyl rubber.

Butyl rubber is contained as an essential component in the pressure-sensitive adhesive component. Further, the butyl rubber imparts self-bonding property to the metal protective pressure-sensitive adhesive composition (specifically, the metal protective pressure-sensitive adhesive tape 1 described later). Butyl rubber is a synthetic rubber (copolymer) obtained by copolymerizing isobutylene and isoprene.

The copolymer in butyl rubber is uncrosslinked (uncrosslinked butyl rubber).

Butyl rubber contains a double bond. The content ratio (unsaturation degree) of the double bond in the butyl rubber is, for example, 0.1 mol% or more, preferably 0.5 mol% or more, and for example, 5 mol% or less, preferably 2 mol% or less. Is. If the content ratio of the double bond in butyl rubber is equal to or higher than the above-mentioned lower limit, it may cause metal damage described later, but such metal damage can be suppressed by the metal damage-oxidation suppression combined component. .. On the other hand, if the content ratio of the double bond in the butyl rubber is not more than the upper limit, the toluene-soluble content can be set in the range described later, and excellent processability of the pressure-sensitive adhesive composition for metal protection can be ensured. Can be done.

The content of double bonds in butyl rubber is calculated by infrared spectroscopy.

The Mooney viscosity (ML1 + 4, at 100 ° C.) of butyl rubber is, for example, 25 or more, preferably 30 or more, and for example, 90 or less, preferably 60 or less. Mooney viscosity is measured according to JIS K 6300.

As the butyl rubber, a commercially available product can be used, and for example, JSR BUTYL series (manufactured by JSR Corporation) or the like can be used.

The proportion of butyl rubber is, for example, 20% by mass or more, preferably 30% by mass or more, and for example, less than 70% by mass, preferably 60% by mass or less, based on the pressure-sensitive adhesive component. The proportion of butyl rubber is, for example, 2% by mass or more, preferably 5% by mass or more, and for example, 30% by mass or less, preferably 20% by mass, based on the pressure-sensitive adhesive composition for metal protection. It is as follows.

The pressure-sensitive adhesive component can contain a rubber component other than butyl rubber (hereinafter, simply referred to as “rubber component”).

The rubber component is contained as an optional component in the pressure-sensitive adhesive component. Examples of the rubber component include an uncrosslinked rubber component such as isobutylene rubber, styrene-butadiene rubber, and isoprene rubber. More preferably, isobutylene is mentioned.

Specific examples of isobutylene include high molecular weight isobutylene. Such high molecular weight isobutylene has, for example, a viscosity average molecular weight of 300,000 or more, preferably 500,000 or more, more preferably 700,000 or more, still more preferably 900,000 or more, and 3 million or less. It preferably has a viscosity average molecular weight of 2 million or less, more preferably 1.5 million or less.

As the rubber component, a commercially available product can be used, and for example, an Opanol series (manufactured by BASF) can be used as the high molecular weight isobutylene.

The content of the crosslinked rubber component (crosslinked butyl rubber, etc.) in the pressure-sensitive adhesive component is permissible as long as it does not impair the effect of the present invention, for example. The pressure-sensitive adhesive component preferably does not contain a crosslinked rubber component.

The ratio of the rubber component is, for example, 30 parts by mass or more, preferably 50 parts by mass or more, and for example, 500 parts by mass or less, preferably 250 parts by mass or less with respect to 100 parts by mass of butyl rubber. The ratio of the rubber component to the pressure-sensitive adhesive component is, for example, 20% by mass or more, preferably 30% by mass or more, and for example, 80% by mass or less, preferably 70% by mass or less. be. Further, the ratio of the rubber component is, for example, 5% by mass or more, preferably 7% by mass or more, and for example, 50% by mass or less, preferably 50% by mass, based on the pressure-sensitive adhesive composition for metal protection. It is 40% by mass or less.

The ratio of the pressure-sensitive adhesive component is, for example, 10% by mass or more, preferably 20% by mass or more, and for example, 50% by mass or less, preferably 50% by mass, based on the pressure-sensitive adhesive composition for metal protection. It is 35% by mass or less.

3. 3. Metal damage-oxidation suppression coexisting component The metal damage-oxidation suppression coexisting component is a component having both a metal damage suppression function based on the capture of metal and an oxidation suppression function based on the capture of radical species.

The metal damage-oxidation suppression coexisting component is contained as an essential component in the pressure-sensitive adhesive composition for metal protection. The metal damage-oxidation suppression coexisting component can capture metals (described later) and radical species derived from oxygen contained in water or air. The radical species mainly contains oxygen radicals, and may also contain peroxide radicals, alkyl radicals, alkoxy radicals and the like.

Therefore, the metal damage-oxidation suppression coexisting component is a component that suppresses deterioration of the pressure-sensitive adhesive component due to contact with the metal to be protected of the pressure-sensitive adhesive composition for metal protection. Preferably, the metal-damage-oxidation-suppressing coexisting component is derived from the metal-damage of butyl rubber due to contact between the metal and the metal-protecting pressure-sensitive adhesive composition by trapping the metal, as well as water and air. It is a metal and radical species trapping type metal damage-oxidation suppression coexisting component that prevents metal damage of butyl rubber due to radical species. The metal-damage-oxidation-suppressing component is also a ligand capable of coordinating with a metal (specifically, a metal atom and / or a metal cation, which will be described later) to form a metal complex.

The form of the metal captured by the metal damage-oxidation suppression coexisting component is not particularly limited, and may be metal particles, metal atoms, metal ions (metal cations), or the like. It is preferably a metal cation.

The type of metal is not particularly limited, and examples thereof include copper, iron, cobalt, nickel, manganese, vanadium, titanium, calcium, silver, zinc, aluminum, and magnesium. These metals may be one kind or two or more kinds. In particular, the metal damage-oxidation suppression coexisting component is preferably used as a copper damage inhibitor that captures copper (specifically, copper ions).

Specifically, the metal damage-oxidation suppressing coexisting component is, for example, a first aspect of being a first metal damage suppressing agent, for example, a second aspect of being a second metal damage suppressing agent and an oxidation suppressing agent. For example, a third aspect of the first metal damage inhibitor and the oxidation inhibitor, for example, a fourth aspect of the first metal damage inhibitor, the second metal damage inhibitor and the oxidation inhibitor. Be done.

Preferably, the first aspect, the second aspect, and the third aspect are mentioned.

More preferably, the first aspect and the second aspect are mentioned.

More preferably, the first aspect is mentioned.

3-1. First aspect (first metal damage inhibitor)
The first metal damage inhibitor has both a metal damage suppressing function and an oxidation suppressing function. More specifically, the first metal damage inhibitor is a metal damage-oxidation inhibitor having both a metal damage prevention function and an antioxidant function. Preferably, the first metal damage inhibitor is a first copper damage inhibitor.

The first metal damage inhibitor is not particularly limited as long as it has both a metal damage suppressing function and an oxidation suppressing function, and examples thereof include aromatic amine compounds, hydrazine compounds, thiol compounds, and phenol compounds. Preferred are aromatic amine compounds and hydrazine compounds from the viewpoint that they are well coordinated to copper ions to efficiently form a complex, while the possibility of corroding the metal to be protected is low. Sulfur-based compounds (specifically, Noxeller TCA (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.), etc.) are metal damage suppressants, but because they have metal corrosiveness, they can be used as the first metal damage suppressant. Not suitable. That is, the first metal damage suppressant preferably does not have metal corrosiveness.

Examples of the aromatic amine compound include N, N'-di-2-naphthyl-p-phenylenediamine (see formula (1) below) and N-phenyl-N'-(1,3-dimethylbutyl) -p. -Examples include phenylenediamine compounds such as phenylenediamine (see formula (2) below).

Equation (1):

Equation (2):

Examples of the hydrazine compound include 2', 3-bis [[3- [3,5-di-t-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide (see the following formula (3)). Be done.

Equation (3):

Preferred examples of the aromatic amine compound include N, N'-di-2-naphthyl-p-phenylenediamine. N, N'-di-2-naphthyl-p-phenylenediamine is distinct, unlike N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine, which has a melting point (44 ° C or higher). It does not show a melting point and is therefore less likely to cause bleeding.

N, N'-di-2-naphthyl-p-phenylenediamine has a softening point of 225 ° C. or higher.

The first metal damage inhibitor can be used alone or in combination of two or more. Preferred are the single use of the aromatic amine compound and the single use of the hydrazine compound.

As the first metal damage inhibitor, a commercially available product can be used. For example, as an aromatic amine compound, Nocrack White (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., see the above formula (1), N, N'-di. -2-naphthyl-p-phenylenediamine), Nocrack 6C (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., see formula (2) above, N-phenyl-N'-(1,3-dimethylbutyl) -p-phenylenediamine) Etc. can be used. Further, as a hydrazine compound, Irganox MD1024 (manufactured by BASF, see the above formula (3), 2', 3-bis [[3- [3,5-di-t-butyl-4-hydroxyphenyl] propionyl]]]. Propionohydrazide) or the like can be used.

The ratio of the first metal damage inhibitor is, for example, 0.3 parts by mass or more, preferably 0.6 parts by mass or more, and more preferably 1.2 parts by mass or more with respect to 100 parts by mass of butyl rubber. Further, for example, it is 15 parts by mass or less, preferably 6 parts by mass or less, and more preferably 3 parts by mass or less. The ratio of the first metal damage inhibitor is, for example, 0.1 part by mass or more, preferably 0.2 part by mass or more, and more preferably 0.5 with respect to 100 parts by mass of the pressure-sensitive adhesive component. It is 5 parts by mass or more, and for example, 5 parts by mass or less, preferably 2 parts by mass or less, and more preferably 1 part by mass or less. The ratio of the first metal damage inhibitor is, for example, 0.01% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1 with respect to the pressure-sensitive adhesive composition for metal protection. It is by mass or more, and is, for example, 1% by mass or less, preferably 0.5% by mass or less, and more preferably 0.25% by mass or less.

When the ratio of the first metal damage inhibitor is not less than the above-mentioned lower limit, deterioration of butyl rubber due to metals and radical species can be effectively suppressed (preferably prevented). On the other hand, when the ratio of the first metal damage inhibitor is equal to or less than the above-mentioned upper limit, the excessive content of the first metal damage inhibitor is suppressed, the influence on the pressure-sensitive adhesiveness is small, and the manufacturing cost is reduced. Can be reduced.

3-2. Second Embodiment (1) Second Metal Damage Suppressant The second metal damage suppressant does not have an oxidation suppression function but has a metal damage suppression function. More specifically, the second metal damage inhibitor is a second metal damage inhibitor (specifically, a second copper damage inhibitor) that does not have an antioxidant function and has a metal damage prevention function. be.

Examples of the second metal damage inhibitor include amide compounds and benzotriazole compounds.

Examples of the amide compound include N- (2H-1,2,4-triazole-5-yl) salicylamide (see the following formula (4)).

Equation (4):

Examples of the benzotriazole compound include 1,2,3-benzotriazole (see the following formula (5)).
Equation (5):

As the second metal damage inhibitor, a commercially available product can be used, for example, as an amide compound, Adecastab CDA-1 (manufactured by ADEKA, see the above formula (4), N- (2H-1,2,4-). As the triazole-5-yl) salicylamide) and the benzotriazole compound, BT-120 (manufactured by Johoku Chemical Industry Co., Ltd., see the above formula (5), 1,2,3-benzotriazole) and the like can be used.

The second metal damage inhibitor can be used alone or in combination of two or more. Preferred are the single use of the amide compound and the single use of the benzotriazole compound. The second metal damage inhibitor is more preferably the use of an amide compound alone. The amide compound is more excellent in the metal damage suppressing function than the benzotriazole compound.

The ratio of the second metal damage inhibitor is the same as the ratio of the first metal damage inhibitor described above.

(2) Oxidation inhibitor The oxidation inhibitor does not have a metal damage suppressing function, but has an oxidation suppressing function. That is, the oxidation inhibitor has only an oxidation inhibitory function.

As the oxidation inhibitor, for example, a primary oxidation inhibitor (primary antioxidant) capable of suppressing deterioration of butyl rubber caused by a radical species derived from oxygen contained in water or air in combination with a metal, for example, a peroxy radical. Examples thereof include antioxidants such as secondary antioxidants (secondary antioxidants) that can prevent chain reactions due to decomposition and stabilization of radicals.

Examples of the primary oxidation inhibitor include hindered phenol compounds such as pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

Examples of the secondary oxidation inhibitor include phosphorus compounds such as tris (2,4-di-t-butylphenyl) phosphite, and sulfur compounds such as sulfur-containing imidazole compounds such as 2-mercaptobenzimidazole. Will be.

The oxidation inhibitor can be used alone or in combination of two or more.

Preferred are primary oxidation inhibitors, more preferably hindered phenol compounds, and more preferably pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

As the oxidation inhibitor, a commercially available product can be used. For example, as a hindered phenol compound, Sonnox 1010 (manufactured by Sonwon Co., Ltd., pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl)) can be used. ) Propionate] (see formula (7)), Irgaphos 168 (BASF, Tris (2,4-di-t-butylphenyl) phosphite) as a phosphorus compound, Nocrack MB (Ouchi Shinko Kagaku Co., Ltd.) as a sulfur compound. , 2-Mercaptobenzimidazole) and the like can be used.

The ratio of the oxidation inhibitor is appropriately set according to the ratio of the first metal damage inhibitor and / or the second metal damage inhibitor and the exposed environment. Specifically, the ratio of the oxidation inhibitor is, for example, 50 parts by mass or more, preferably 75 parts by mass or more, and for example, 300 parts by mass with respect to 100 parts by mass of the first metal damage inhibitor. Hereinafter, it is preferably 200 parts by mass or less. The ratio of the oxidation inhibitor is, for example, 50 parts by mass or more, preferably 75 parts by mass or more, and more preferably 300 parts by mass or less, based on 100 parts by mass of the second metal damage inhibitor. Is also 200 parts by mass or less. The ratio of the oxidation inhibitor is, for example, 0.5 parts by mass or more, preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and, for example, 10 parts by mass with respect to 100 parts by mass of butyl rubber. By mass or less, preferably 5 parts by mass or less, more preferably 3 parts by mass or less. The ratio of the oxidation inhibitor is, for example, 0.1 part by mass or more, preferably 0.2 part by mass or more, and more preferably 0.5 part by mass or more with respect to 100 parts by mass of the pressure-sensitive adhesive component. Further, for example, it is 5 parts by mass or less, preferably 2 parts by mass or less, and more preferably 1 part by mass or less.

When the ratio of the oxidation inhibitor is equal to or higher than the above-mentioned lower limit, deterioration of butyl rubber can be further suppressed. When the ratio of the oxidation inhibitor is not more than the above-mentioned upper limit, it is possible to suppress an increase in manufacturing cost while maintaining the pressure-sensitive adhesiveness while exhibiting the above-mentioned effect of suppressing deterioration of butyl rubber.

3-3. Formulation of First Metal Damage Inhibitor and Oxidation Inhibitor in Third Aspect The proportion of the first metal hazard inhibitor in the third embodiment is the same as the proportion of the first metal damage inhibitor in the first embodiment. Is.

The proportion of the antioxidant in the third aspect is the same as the proportion of the antioxidant in the second aspect. In particular, the ratio of the oxidation inhibitor is, for example, 50 parts by mass or more, preferably 75 parts by mass or more, and more preferably 300 parts by mass or less, with respect to 100 parts by mass of the first metal damage inhibitor. Is 200 parts by mass or less.

3-4. Comparison of the first aspect to the third aspect In the first aspect, the metal damage-oxidation suppression coexisting component needs to contain only the first metal damage suppression agent, so that it is different from the second to fourth aspects. 3. The pressure-sensitive adhesive composition for metal protection can be simply formulated.

Further, in the second aspect, the ratio of the oxidation inhibitor to the second metal damage inhibitor can be freely changed according to the environment exposed to water or air.

Further, in the third aspect, due to the oxidation suppressing function of the first metal damage suppressing agent and the oxidation suppressing function of the oxidation inhibitor, a poor environment, specifically, construction in which air enters, high temperature and high humidity. Metals can be well protected even in the environment.

3-5. Ratio of metal damage-oxidation inhibitory component The ratio of metal damage-oxidation inhibitory component (in the second aspect and the third aspect, the total amount of the metal damage inhibitor and the oxidation inhibitor) is 100 mass of butyl rubber. For example, 0.5 parts by mass or more, preferably 1 part by mass or more, more preferably 2 parts by mass or more, and for example, 30 parts by mass or less, preferably 10 parts by mass or less. More preferably, it is 5 parts by mass or less. The ratio of the metal damage-oxidation suppression coexisting component is, for example, 0.2 parts by mass or more, preferably 0.5 parts by mass or more, and more preferably 1 part by mass with respect to 100 parts by mass of the pressure-sensitive adhesive component. It is 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 2 parts by mass or less. The ratio of the metal damage-oxidation suppressing coexisting component is, for example, 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0. It is 1% by mass or more, and is, for example, 2% by mass or less, preferably 1% by mass or less, and more preferably 0.5% by mass or less.

4. Other Optional Components The pressure-sensitive adhesive composition for metal protection can further contain a filler, a softener, and a tackifier as optional components.

4-1. Fillers Fillers can reinforce metal protective pressure sensitive adhesive compositions. Examples of the filler include insulating fillers such as magnesium oxide, calcium carbonate, magnesium silicate, mica, calcined aluminum silicate, diatomaceous earth, mica powder, bentonite, silica, alumina, titanium oxide, and glass balloon, for example, carbon black and aluminum. Examples include powder, conductive fillers such as aluminum hydroxide, and the like. The filler can be used alone or in combination of two or more.

When the pressure-sensitive adhesive composition for metal protection is used for insulating applications, an insulating filler is preferably used, and more preferably, a calcined aluminum silicate and diatomaceous earth are used in combination.

The average particle size of the filler is, for example, 0.1 μm or more, preferably 1 μm or more, and for example, 50 μm or less, preferably 10 μm or less.

As the filler, a commercially available product can be used, and examples thereof include SATINTONE WHITETEX (manufactured by BASF) as a calcined aluminum silicate and Radiolite series (manufactured by Showa Kagaku Kogyo Co., Ltd.) as diatomaceous earth.

The ratio of the filler is, for example, 2000 parts by mass or less, preferably 1500 parts by mass or less, more preferably 1000 parts by mass or less, still more preferably 600 parts by mass or less, and more preferably 600 parts by mass or less with respect to 100 parts by mass of butyl rubber. For example, it is 100 parts by mass or more, preferably 250 parts by mass or more, more preferably 300 parts by mass or more, and further preferably 400 parts by mass or more. The ratio of the filler is, for example, 1000 parts by mass or less, preferably less than 600 parts by mass, more preferably 300 parts by mass or less, and further preferably 200 parts by mass or less with respect to 100 parts by mass of the pressure-sensitive adhesive component. Further, for example, it is 50 parts by mass or more, preferably 80 parts by mass or more, more preferably 100 parts by mass or more, and further preferably 130 parts by mass or more. The proportion of the filler is, for example, 100% by mass or less, preferably 75% by mass or less, more preferably 50% by mass or less, and, for example, the proportion of the pressure-sensitive adhesive composition for metal protection. It is 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, and particularly preferably 40% by mass or more.

When calcined aluminum silicate and diatomaceous soil are used together as a filler, the ratio of calcined aluminum silicate is, for example, 25 parts by mass or more, preferably 40 parts by mass or more with respect to 100 parts by mass of the pressure-sensitive adhesive component. Further, for example, it is 300 parts by mass or less, preferably 180 parts by mass or less, more preferably 150 parts by mass or less, further preferably 80 parts by mass or less, particularly preferably 50 parts by mass or less, and of diatomaceous soil. The ratio is, for example, 50 parts by mass or more, preferably 100 parts by mass or more, and more preferably 500 parts by mass or less, preferably 400 parts by mass or less, more preferably with respect to 100 parts by mass of the pressure-sensitive adhesive component. Is 300 parts by mass or less, more preferably 200 parts by mass or less. The ratio of calcined aluminum silicate to diatomaceous earth (calcined aluminum silicate / diatomaceous earth) is, for example, 0.25 or more, preferably 0.3 or more, and for example, 0.5 or less, preferably 0.5. Is less than.

When the ratio of the filler is not more than the above-mentioned upper limit, excellent pressure-sensitive adhesiveness and excellent processability of the pressure-sensitive adhesive composition for metal protection can be ensured. Specifically, the self-bonding property of the butyl rubber contained in the pressure-sensitive adhesive component can be ensured. On the other hand, if the ratio of the filler is equal to or higher than the above-mentioned lower limit, the reinforcing effect can be sufficiently improved. Further, in the pressure-sensitive adhesive composition for metal protection, excellent insulating properties based on the filler, particularly the insulating filler, can be ensured.

The processability means workability when preparing a kneaded material of a pressure-sensitive adhesive composition for metal protection and / or when rolling the kneaded material into a pressure-sensitive adhesive layer for metal protection. .. Therefore, when the ratio of the filler is not more than the above-mentioned upper limit, it is possible to prevent the workability when rolling the kneaded product from being lowered. Deterioration of workability during rolling and stretching means, for example, that streaks occur in the molded product and the smoothness of the pressure-sensitive adhesive composition for metal protection cannot be guaranteed, and that the pressure-sensitive adhesive composition for metal protection is missing (pinhole). Is to occur.

On the other hand, when the ratio of the filler is not more than the above-mentioned lower limit, the rubber elastic property of the pressure-sensitive adhesive composition for metal protection can be prevented from becoming too strong, and the kneaded product can be smoothly prepared. Deterioration of workability during preparation of kneaded product means, for example, that it is not possible to prepare a uniform kneaded product due to the formation of lumps (granular matter), and that the kneaded product is difficult to separate from the molding roll in rolling (described later) (difficult to peel off). Is to become.

4-2. Softeners Examples of softeners include low molecular weight polyisobutylene and liquid polybutene. Preferred softeners include low molecular weight polyisobutylene and liquid polybutene.

The low molecular weight polyisobutylene has, for example, a viscosity average molecular weight of less than 300,000, preferably 250,000 or less, more preferably 60,000 or less, and, for example, a viscosity of 30,000 or more, preferably 100,000 or more. Has an average molecular weight.

The liquid polybutene has, for example, a number average molecular weight of 1,000 or more, preferably 1,100 or more, more preferably 1,200 or more. Further, the liquid polybutene has, for example, a number average molecular weight of 3,000 or less, preferably 2,000 or less.

These softeners can be used alone or in combination. Preferred are the combined use of low molecular weight polyisobutylene and liquid polybutene.

The ratio of the softening agent is, for example, 25 parts by mass or more, preferably 50 parts by mass or more, and for example, 200 parts by mass or less, preferably 150 parts by mass or less with respect to 100 parts by mass of the pressure-sensitive adhesive component. Is. When the low molecular weight polyisobutylene and the liquid polybutene are used in combination, the ratio of the low molecular weight polyisobutylene is, for example, 5 parts by mass or more, preferably 15 parts by mass or more with respect to 100 parts by mass of the pressure-sensitive adhesive component. Further, for example, 100 parts by mass or less, preferably 80 parts by mass or less, and the ratio of the liquid polybutene is, for example, 25 parts by mass or more, preferably 40 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive component. It is 5 parts by mass or more, and is, for example, 150 parts by mass or less, preferably 75 parts by mass or less. The ratio of the ratio of low molecular weight polyisobutylene to the ratio of liquid polybutene (low molecular weight polyisobutylene / liquid polybutene) is, for example, less than 2, preferably 1.5 or less, and for example, 0.1 or more. , Preferably 0.3 or more.

4-3. Adhesive-imparting agent Examples of the tackifier include a rosin-based resin, a terpene-based resin, a Kumaron inden-based resin, a phenol-based resin, a phenol formalin-based resin, a xylene formalin-based resin, and a petroleum-based resin. As the tackifier, a terpene-based resin is preferable.

The tackifier can be used alone or in combination.

The ratio of the tackifier is, for example, 1 part by mass or more, preferably 3 parts by mass or more, and for example, 40 parts by mass or less, preferably 30 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive component. It is as follows.

The pressure-sensitive adhesive composition for metal protection contains an appropriate ratio of additives such as lubricants, rocking agents, pigments, scorch inhibitors, plasticizers, ultraviolet absorbers, colorants, antifungal agents, and flame retardants. Can be contained in.

5. Preparation of pressure-sensitive adhesive composition for metal protection and toluene insoluble content Each of the above components is blended in the above proportions and kneaded with a kneader, extruder (single-screw extruder, twin-screw extruder, etc.), for example. A pressure-sensitive adhesive composition for metal protection is prepared as a kneaded product.

The toluene insoluble content of this pressure-sensitive adhesive composition for metal protection is, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less. Also, for example, it is 0% by mass or more. When the toluene insoluble content of the pressure-sensitive adhesive composition for metal protection is not more than the above-mentioned upper limit, the processability of the pressure-sensitive adhesive composition for metal protection can be further improved.

The toluene insoluble content of the pressure-sensitive adhesive composition for metal protection is the toluene-insoluble content in the pressure-sensitive adhesive composition for metal protection other than ash, and is insoluble in toluene in the pressure-sensitive adhesive composition for metal protection excluding the filler. Minutes.

In the case of a metal protective pressure sensitive adhesive composition containing no filler, in order to measure the toluene insoluble content of the metal protective pressure sensitive adhesive composition, about 0.1 g of the metal protective pressure sensitive adhesive composition is collected. And weigh this precisely (obtain the mass number of the metal protective pressure sensitive adhesive composition containing no filler). Then, the pressure-sensitive adhesive composition for metal protection containing no finely weighed filler is immersed in 30 g of toluene at 25 ° C. for 1 week. Then they are filtered and the filters are dried. Then, the obtained filter medium (solid content) is precisely weighed. Then, the percentage of the mass number of the finely weighed solid content to the mass number of the pressure-sensitive adhesive composition for metal protection that does not contain the finely weighed filler (the mass number of the finely weighed solid content / [contains the finely weighed filler). No mass number of pressure-sensitive adhesive composition for metal protection] × 100), and the toluene insoluble content is calculated.

In the case of a pressure-sensitive adhesive composition for metal protection containing a filler, first, the ash content is measured by thermogravimetric analysis (TGA), and the filler ratio per mass is determined. Subsequently, about 0.1 g is collected and weighed (obtaining the mass number of the metal protective pressure-sensitive adhesive composition containing the filler). Then, the metal protective pressure-sensitive adhesive composition containing the finely weighed filler is immersed in 30 g of toluene at 25 ° C. for 1 week. Then they are filtered and the filters are dried. Then, the obtained filter medium (solid content) is precisely weighed. Then, the filler amount is calculated from the mass number of the metal protective pressure-sensitive adhesive composition containing the precisely weighed filler, which is the value obtained by subtracting the filler amount calculated based on the filler ratio from the mass number of the precisely weighed solid content. Percentage to the subtracted value (mass number of finely weighed solid content-filler amount calculated from TGA / [mass number of pressure-sensitive adhesive composition for metal protection containing finely weighed filler-filler calculated from TGA Amount] × 100), and the toluene insoluble content is calculated.

6. Manufacture of pressure-sensitive adhesive tape for metal protection Then, the kneaded product is rolled into a tape shape from the kneaded product by, for example, by calendar molding, extrusion molding, press molding, or the like (that is,). , Tape the pressure-sensitive adhesive composition for metal protection). As shown in FIG. 1, specifically, the pressure-sensitive adhesive layer 2 for metal protection is arranged on the upper surface of the base material 3 (an example of one surface in the thickness direction).

The base material 3 is a support layer that supports the pressure-sensitive adhesive layer 2 for metal protection, and protects the periphery of the pressure-sensitive adhesive layer 2 for metal protection and / or the pressure-sensitive adhesive layer 2 for metal protection from being contaminated. It is a layer. Further, the base material 3 prevents the metal protective pressure-sensitive adhesive layers 2 adjacent to each other in the thickness direction from being pressure-sensitively adhered to each other when the metal protective pressure-sensitive adhesive layer 2 is wound in a roll shape. Moreover, it is also a separator for smoothly feeding out the metal protective pressure-sensitive adhesive tape 1 from the roll. The base material 3 has a tape shape that extends long in one direction in the plane direction (direction orthogonal to the thickness direction).

The base material 3 is made of a flexible material, and examples of such a material include polyethylene terephthalate, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyacrylonitrile, cellulose, and acetyl cellulose. Preferred is polyvinyl chloride. The thickness of the base material 3 is, for example, 10 μm or more, preferably 100 μm or more, and for example, 1500 μm or less, preferably 750 μm or less.

The pressure-sensitive adhesive layer 2 for metal protection is arranged on the entire upper surface of the base material 3. The metal protective pressure-sensitive adhesive layer 2 has a tape shape along the extending direction (long direction) of the base material 3. The thickness of the pressure-sensitive adhesive layer 2 for metal protection is, for example, 200 μm or more, preferably 400 μm or more, and for example, 2,000 μm or less, preferably 1500 μm or less.

As a result, the metal protective pressure-sensitive adhesive tape 1 including the base material 3 and the metal protective pressure-sensitive adhesive layer 2 in order is manufactured. That is, the metal protective pressure-sensitive adhesive tape 1 includes a base material 3 and a metal protective pressure-sensitive adhesive layer 2 arranged on the upper surface of the base material 3. Preferably, the metal protective pressure-sensitive adhesive tape 1 is composed of only the base material 3 and the metal protective pressure-sensitive adhesive layer 2.

The thickness of the metal protective pressure-sensitive adhesive tape 1 is, for example, 300 μm or more, preferably 500 μm or more, and for example, 3000 μm or less, preferably 2000 μm or less.

7. Uses of Pressure-Sensitive Adhesive Tape for Metal Protection The use of the pressure-sensitive adhesive tape 1 for metal protection is not particularly limited, and specifically, the pressure-sensitive adhesive tape 1 for metal protection is used for, for example, for wire protection, for example, vapor deposition. It is used for plate protection applications such as electronic board wiring and copper plate protection applications, for example, copper plate drawing processing applications.

7-1. Conductor Protection Application Next, an embodiment in which the pressure-sensitive adhesive tape 1 for metal protection is used as a conductor protection application, specifically, an embodiment of a method for manufacturing a connection portion protection structure will be described.

(1) Preparation of First Electric Wire, Second Electric Wire, and Fixing Member In this embodiment, as shown in FIG. 2A, first, the first electric wire 5, the second electric wire 9, and the fixing member 10 are prepared, respectively. do.

(I) First electric wire The first electric wire 5 has a shape extending in one direction. The first electric wire 5 includes, for example, a first conductor portion 6 and a first coating layer 7 that covers the first conductor portion 6.

The first conductor portion 6 has a conducting wire 8 extending in a direction in which the first electric wire 5 extends. The conductor 8 has, for example, a substantially circular cross section.

The lead wire 8 is made of at least one metal selected from the group consisting of, for example, copper, iron, cobalt, nickel, manganese, vanadium, titanium, calcium, silver, zinc, aluminum and magnesium. Therefore, the first conductor portion 6 is made of the above-mentioned conductor.

The conductor 8 is preferably made of copper, a copper alloy, or aluminum. The conductor 8 is more preferably made of copper.

If the conducting wire 8 is made of copper, excellent conductivity can be imparted to the conducting wire 8, and even if it comes into contact with the pressure-sensitive adhesive tape 1 for metal protection, a metal damage suppressing agent (in this case, a copper damage suppressing agent) is used. , Deterioration of the pressure-sensitive adhesive tape 1 for metal protection due to copper damage is suppressed.

The first coating layer 7 has a substantially annular shape in cross section. The first coating layer 7 is made of an insulating material such as an insulating resin.

(Ii) Second electric wire The second electric wire 9 is an electric wire connected to the first electric wire 5. The second electric wire 9 has a configuration similar to that of the first electric wire 5 described above, and includes a second conductor portion 26 and a second coating layer 27.

(Iii) Fixing member The fixing member 10 has a substantially C-shaped cross section. The fixing member 10 extends slightly in the longitudinal direction of the transmission line 5. The fixing member 10 has a substantially cylindrical shape having an opening 11. The fixing member 10 is made of the above-mentioned conductor (specifically, metal).

(2) Electrical connection of the first electric wire and the second electric wire Next, the first electric wire 5 and the second electric wire 9 are electrically connected.

Specifically, as shown in FIG. 2A, first, one end of the first covering layer 7 in the first electric wire 5 is removed. As a result, one end of the first conductor portion 6 is exposed from the first coating layer 7. The length of the exposed portion of the first conductor portion 6 is, for example, 3 mm or more, preferably 10 mm or more, and for example, 500 mm or less, preferably 300 mm or less.

Subsequently, the passivation film formed on the surface of the first conductor portion 6 is removed. Specifically, the surface (radial outer surface) of the first conductor portion 6 (the outermost conducting wire 8) is cut (polished) with, for example, a knife or a metal brush. The passivation film is, for example, a thin film formed of a metal forming the first conductor portion 6 and / or a thin film formed of an additive (organic stabilizer or the like) treated on the surface of the first conductor portion 6. Is. More specifically, the passivation film includes a stabilized metal oxide film, a rust preventive film, and a surface coating film by metal plating.

As a result, the inside of the first conductor portion 6 is exposed (exposed) to the outside.

Separately, the second covering layer 27 at one end of the second electric wire 9 is removed to expose one end of the second conductor portion 26 in the second electric wire 9. The length of the exposed portion of the second conductor portion 26 is the same as that of the first conductor portion 6.

After that, as shown in FIG. 2B, one end of the second conductor portion 26 is applied (contacted) to one end of the first conductor portion 6. Subsequently, the contact portions where the second conductor portion 26 and the first conductor portion 6 come into contact with each other are inserted into the opening portion 11 of the fixing member 10, and they are housed in the fixing member 10. Subsequently, the fixing member 10 is crimped so that the opening 11 is closed. As a result, one end of the second conductor portion 26 and one end of the first conductor portion 6 are fixed by the fixing member 10. The contact state between the second conductor portion 26 and the first conductor portion 6 is fixed by the fixing member 10.

Then, the service line 9 and the transmission line 5 are electrically connected (conducting). As a result, the second conductor portion 26, the first conductor portion 6, and the connecting portion 12 including the fixing member 10 are configured.

(3) Protection of the connection portion with the metal protective pressure-sensitive adhesive tape Then, the first electric wire 5 and the second electric wire 9 are protected by the metal protective pressure-sensitive adhesive tape 1. Specifically, the first electric wire 5 and the second electric wire 9 that are in contact with each other are covered with the metal protective pressure-sensitive adhesive tape 1.

For example, as shown in FIG. 2B, the metal protective pressure-sensitive adhesive tape so that the metal protective pressure-sensitive adhesive layer 2 of the metal protective pressure-sensitive adhesive tape 1 faces the first electric wire 5 and the second electric wire 9. 1 is arranged to face the first electric wire 5 and the second electric wire 9, and as shown in FIG. 2C, the metal protective pressure-sensitive adhesive tape 1 is wound around the first electric wire 5.

At this time, as shown in FIG. 3A, one side portion of the metal protective pressure-sensitive adhesive tape 1 to be wound around the first electric wire 5 and the second electric wire 9 in the width direction is the first electric wire 5 and the second electric wire 9. Metal protective pressure-sensitive adhesive tape 1 so as to overlap the other side portion of the metal protective pressure-sensitive adhesive tape 1 already wound around the electric wire 9 in the thickness direction (diametrical direction of the first electric wire 5). Is wound around the first electric wire 5 and the second electric wire 9. That is, the metal protective pressure-sensitive adhesive tape 1 is wound around the first electric wire 5 and the second electric wire 9 so as to have a spiral shape overlapping with each other. Although not shown, the wound metal protective pressure-sensitive adhesive tape 1 may have a plurality of layers in the radial direction of the first electric wire 5 and the second electric wire 9.

As a result, the connecting portion 12 including the first electric wire 5 and the second electric wire 9 is configured.

After that, as shown in FIG. 3B, the metal protective pressure-sensitive adhesive layers 2 of the metal protective pressure-sensitive adhesive tape 1 overlapping in the thickness direction are fused (self-fused) to each other, thereby giving a feeling of metal protection. The pressure-bonding layer 2 forms a single protective layer (coating layer) 14 made of a metal-protecting pressure-sensitive adhesive composition.

As a result, the first electric wire 5 and the second electric wire 9 are protected by the metal protective pressure-sensitive adhesive tape 1. Specifically, the connecting portion 12 is covered with a metal protective pressure-sensitive adhesive tape 1 (a protective layer 14 formed from the protective layer 14).

As a result, a connection portion protection structure 30 in which the first electric wire 5 and the second electric wire 9 are protected by the metal protective pressure-sensitive adhesive tape 1 is manufactured.

8. Action Effect However, there are three means for suppressing deterioration of butyl rubber and improving durability.

The first means is a method of reducing double bonds (allyl hydrogen), which is the cause of deterioration of butyl rubber (crosslinking butyl rubber). For example, deterioration can be suppressed by cross-linking the butyl rubber described in Patent Document 1. However, by cross-linking the butyl rubber, the insulator becomes hard, the workability is deteriorated, and the self-adhesiveness is particularly poor. In addition, a method of reducing the blending amount of butyl rubber and lowering the ratio of rubber having a double bond is tentatively proposed. It can lead to loss of sex. Further, a means for softening the hardened property of the crosslinked butyl rubber with a softening agent or the like is tried, but as the ratio of the butyl rubber of the insulator decreases, the above-mentioned property peculiar to butyl rubber is lost.

The second means is to add a filler and increase the amount of the filler. Compared to raw rubber alone, the addition of a filler has the effect of lowering rubber elasticity and improving workability. Furthermore, due to the radical trap function of the filler, it can be expected that the durability will be improved as compared with the butyl rubber alone. It was found that this radical trap function is superior or inferior depending on, for example, the type and amount of the metal compound as an impurity contained in the filler, in addition to the filler type. However, there is a limit to the blending amount, and for example, if the blending amount is a certain amount or more, the butyl rubber has a hard property and tends to lose the pressure-sensitive adhesiveness. In addition, it leads to a decrease in electrical insulation.

Therefore, as a third means, it is possible to improve the processability and self-fusion property of the insulator by using uncrosslinked butyl rubber while ensuring processability by containing a certain amount of filler. It will be tentative. However, such uncrosslinked butyl rubber tends to have a low molecular weight due to contact with a conductor (so-called metal damage is likely to occur), so that the outer shape cannot be maintained for a long period of time and the durability is lowered. There is a problem.

(1) On the other hand, since this pressure-sensitive adhesive composition for metal protection contains butyl rubber instead of crosslinked butyl rubber, it is excellent in processability.

Further, the pressure-sensitive adhesive composition for metal protection contains a metal damage suppressing function based on the capture of metal and a metal damage-oxidation suppressing coexisting component having both an oxidation suppressing function. Therefore, even if the pressure-sensitive adhesive composition for metal protection comes into contact with the metal, the metal damage suppressant captures the metal, and further, due to its oxidation suppressing function, radical species derived from oxygen contained in water or air. By capturing the radical, it is possible to prevent the butyl rubber from deteriorating due to metal damage.

(2) In the first aspect of this pressure-sensitive adhesive composition for metal protection, the metal damage-oxidation suppression combined component contains a first metal damage suppression agent having both a metal damage suppression function and an oxidation suppression function. Therefore, one agent can exert both a metal damage suppressing function and an oxidation suppressing function. Therefore, the pressure-sensitive adhesive composition for metal protection can be simply formulated.

(3) In the first aspect, if the first metal damage suppressant is at least one selected from the group consisting of an aromatic amine compound and a hydrazine compound, the first metal damage suppressant further increases the metal. It can be reliably captured and the deterioration of butyl rubber due to metal damage can be suppressed.

(4) In the first aspect, the copper damage inhibitor can more reliably capture copper and further reliably suppress the deterioration of butyl rubber due to copper damage.

(5) On the other hand, in the second aspect, the metal damage-oxidation suppressing coexisting component contains a second metal damage suppressing agent having no oxidation suppressing function and having a metal damage suppressing function, and an oxidation suppressing agent. .. Therefore, the ratio of the oxidation inhibitor to the second metal damage inhibitor can be changed depending on the environment in which the pressure-sensitive adhesive composition for metal protection is exposed to water or air.

(6) Then, in this second aspect, if the second metal damage suppressant is at least one selected from the group consisting of an amide compound and a benzotriazole compound, the second metal damage suppressant is a metal. It can be more reliably captured and the deterioration of butyl rubber due to metal damage can be suppressed.

(7) In this second aspect, in the pressure-sensitive adhesive composition for metal protection, the copper damage inhibitor more reliably captures copper, and the butyl rubber is more reliably deteriorated by copper damage. It can be suppressed.

(8) When the toluene insoluble content of the pressure-sensitive adhesive composition for metal protection is 10% by mass or less, the processability is further improved.

(9) The pressure-sensitive adhesive composition for metal protection is excellent in processability and reinforcing property if it contains a filler.

(10) When the ratio of the filler is 100 parts by mass or more with respect to 100 parts by mass of the pressure-sensitive adhesive component, the reinforcing effect can be sufficiently improved. Further, in the pressure-sensitive adhesive composition for metal protection, excellent insulating properties based on the filler, particularly the insulating filler, can be ensured. Further, the processability of the pressure-sensitive adhesive composition for metal protection can be further improved. Specifically, a kneaded product of a pressure-sensitive adhesive composition for metal protection can be smoothly prepared.

When the ratio of the filler is less than 600 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive component, excellent pressure-sensitive adhesiveness and excellent self-bonding property of the pressure-sensitive adhesive composition for metal protection are ensured. be able to. In addition, excellent processability of the pressure-sensitive adhesive composition for metal protection can be ensured. Specifically, it is possible to prevent the workability when rolling the kneaded product of the pressure-sensitive adhesive composition for metal protection from being lowered. Further, the self-bonding property of the butyl rubber contained in the pressure-sensitive adhesive component can be ensured.

(11) Since the metal-protecting pressure-sensitive adhesive tape 1 includes the metal-protecting pressure-sensitive adhesive layer 2 made of the above-mentioned metal-protecting pressure-sensitive adhesive composition, the metal-protecting pressure-sensitive adhesive layer 2 is made of metal. Even if they come into contact with each other, the metal damage-oxidation suppression coexisting component can capture the metal and the radical species, and it is possible to suppress the deterioration of the butyl rubber of the metal protective pressure-sensitive adhesive layer 2 due to the metal damage.

(12) When the connection portion 12 including the first conductor portion 6 having the passivation film formed on the surface is coated with the metal protective pressure-sensitive adhesive tape 1, the first conductor portion 6 is covered with the passivation film. For example, in the pressure-sensitive adhesive layer 2 for metal protection, metal damage caused by the first conductor portion 6 does not occur, and the durability of the connecting portion does not deteriorate.

However, if the passivation film is removed, the first conductor portion 6 is exposed from the passivation film, and the connection portion 12 including the first conductor portion 6 is covered with the metal protective pressure-sensitive adhesive tape 1, the metal protection The pressure-sensitive adhesive layer 2 comes into contact with at least the first conductor portion 6. Then, in the pressure-sensitive adhesive layer 2 for metal protection, the metal forming the first conductor portion 6 causes metal damage, and the durability of the connecting portion is lowered.

On the other hand, in this method of manufacturing the connection portion protection structure, the passivation film is removed, the first conductor portion 6 is exposed from the passivation film, and the connection portion 12 including the first conductor portion 6 is pressure-sensitive for metal protection. Even if it is covered with the tape 1, the metal-protecting pressure-sensitive adhesive layer 2 contains a metal-damage-oxidation-suppressing coexisting component having both a metal-damage suppressing function and an oxidation-suppressing function. Can capture metals and radical species and prevent butyl rubber from deteriorating due to metal damage. Therefore, it is possible to manufacture the connection portion protection structure 30 having excellent durability.

(13) In this method for manufacturing the connection portion protection structure, the butyl rubber captures the metal damage-oxidation suppression coexisting component having both the metal damage suppression function and the oxidation suppression function, the above-mentioned specific metal and radical species, and the butyl rubber. Deterioration due to metal damage can be suppressed. Therefore, it is possible to manufacture the connection portion protection structure 30 having excellent durability.

9. Other Aspects In the following description, detailed description of the same members and processes as in the above-described embodiment will be omitted.

In one embodiment described above, as shown in FIG. 2A, the fixing member 10 has a substantially C-shaped cross section, but the shape and examples of the fixing member 10 are not limited thereto. The fixing member 10 may be, for example, a terminal having another shape such as a T-shaped connector or a Giboshi terminal, a sleeve, or a connector.

In the above-described embodiment, the second conductor portion 26 (conductor wire 8) in the second electric wire 9 is not cut (polished), but if a dynamic film is formed on the surface of the second conductor portion 26, Similar to the first conductor portion 6, a dynamic film on the surface of the second conductor portion 26 can be formed.

Further, for example, although not shown, a transmission line may be mentioned as an example of the first electric wire, and a lead-in wire may be mentioned as an example of the second electric wire. The type of transmission line is not particularly limited, and is, for example, a low voltage electric wire and a high voltage electric wire. A drop line is a branch line for distributing electricity from a transmission line.

In one embodiment described above, as shown in FIGS. 2A to 2C, FIGS. 3A and 3B, the metal protective pressure-sensitive adhesive tape 1 is used to protect the connection portion 12 of the first electric wire 5 and the second electric wire 9. It is used for.

However, the use of the pressure-sensitive adhesive tape 1 for metal protection is not limited to this. For example, as shown in FIG. 4, it can also be used, for example, to protect the metal vapor deposition plate 13.

The metal vapor deposition plate 13 is, for example, a plate forming a container in a vapor deposition apparatus, a lead frame for electronic components, and the like. The metal vapor deposition plate 13 is made of the same kind of metal as described above, and is preferably made of copper or nickel-palladium alloy plating.

The above-mentioned pressure-sensitive adhesive tape 1 for metal protection is attached to the inner wall of the metal vapor deposition plate 13.

Further, in the above-described embodiment, the connecting portion 12 includes the first conductor portion 6, the second conductor portion 26, and the fixing member 10, but for example, although not shown, the connecting portion 12 does not include the fixing member 10. , The first conductor portion 6 and the second conductor portion 26 may be provided. It is also possible to manufacture the connection portion protection structure 30 by protecting and fixing such a connection portion 12 with the metal protective pressure-sensitive adhesive tape 1.

Further, in the above-described embodiment, the metal protective pressure-sensitive adhesive tape 1 is wound around the connection portion 12 so as to overlap in the thickness direction. For example, although not shown, the metal protective pressure-sensitive adhesive tape 1 is wound. Can also be wound around the connecting portion 12 so that they do not overlap in the thickness direction and are adjacent to each other in the circumferential direction.

Further, as shown by the solid line in FIG. 1, in the metal protective pressure-sensitive adhesive tape 1, the metal protective pressure-sensitive adhesive layer 2 is arranged only on the upper surface of the base material 3. However, for example, as shown by the solid line and the virtual line in FIG. 1, the metal protective pressure-sensitive adhesive layer 2 may be arranged on both the upper surface and the lower surface of the base material 3.

Further, in the present specification, tape is synonymous with sheet, film, etc., and these are not clearly distinguished from each other.

Each of the above-described embodiments can exhibit the same effects as those of the above-described embodiment.

Specific numerical values such as ratios (blending ratio, content ratio), physical property values, parameters, etc. used in the following description are the ratios (blending) corresponding to those described in the above-mentioned "form for carrying out the invention". Percentage, content ratio), physical property value, parameter, etc. to the upper limit value (value defined as "less than or equal to", "less than") or lower limit value (value defined as "greater than or equal to", "excess") Can be replaced.

In addition, parts and% mean parts by mass and% by mass, respectively, unless otherwise specified.

Examples 1 to 15 and Comparative Examples 1 to 5
Each component was blended according to the blending formulations shown in Tables 1 to 3 and kneaded at 110 ° C. for 15 minutes in a kneader to prepare a pressure-sensitive adhesive composition for metal protection as a kneaded product.

Subsequently, a tape-shaped pressure-sensitive adhesive layer 2 for metal protection having a thickness of 530 μm was formed on the surface of the base material 3 made of a polyvinyl chloride tape having a thickness of 170 μm.

As a result, the metal protective pressure-sensitive adhesive tape 1 provided with the base material 3 and the metal protective pressure-sensitive adhesive layer 2 was manufactured.

(evaluation)
The following evaluations were carried out and the results are shown in Tables 1 to 3.

1. 1. Workability The workability at the time of molding into the pressure-sensitive adhesive layer 2 for metal protection was evaluated according to the following criteria.
A: The pressure-sensitive adhesive layer 2 for metal protection could be smoothly formed.
B: The pressure-sensitive adhesive layer 2 for metal protection could be formed, but a slight dispersion failure occurred.
C: The pressure-sensitive adhesive layer 2 for metal protection could not be formed, resulting in poor dispersion.

2. 2. Self-bonding property The space of the overlapping part created when winding the transparent acrylic pipe with a diameter of 100 mm so that the width of the overlapping part is 1/2 of the total width (with 1/2 half wrap). After 10 days, it was observed from the back side.
A: There is no space in the overlapping part.
B: Space remains in the overlapping part.

3. 3. Suppression of Copper Damage Based on the formulations shown in Tables 1 to 3, a pressure-sensitive adhesive composition for metal protection was prepared, cut into 10 mm × 10 mm, and the surface was polished with an abrasive into a copper plate. I pasted it. These were put into a dryer at 100 ° C. After that, the surface condition and fluidity of the pressure-sensitive adhesive composition for metal protection were visually confirmed. Copper damage was evaluated according to the following criteria.
A: The shape of the pressure-sensitive adhesive composition for metal protection was maintained even after 2 weeks.
B: After 2 weeks, the shape of the pressure-sensitive adhesive composition for metal protection was almost retained, but the surface was partially glossy and softened.
C: After 1 week, the shape of the pressure-sensitive adhesive composition for metal protection was almost retained, but the surface was partially glossy and softened.

4. Toluene insoluble content First, the ash content of the pressure-sensitive adhesive composition for metal protection was measured by thermal mass analysis (TGA), and the filler ratio per mass was determined. Subsequently, about 0.1 g of the pressure-sensitive adhesive composition for metal protection was collected and weighed precisely. Then, the pressure-sensitive adhesive composition for metal protection was immersed in 30 g of toluene at 25 ° C. for 1 week. Then they were filtered and the filters dried. Then, the obtained filter medium (solid content) was precisely weighed. Then, a percentage (precision) of the value obtained by subtracting the filler amount calculated based on the filler ratio from the mass number of the precisely weighed solid content to the value obtained by subtracting the filler amount from the mass number of the pressure-sensitive adhesive composition for metal protection. The toluene insoluble content was calculated as the mass number of the weighed solid content-the amount of filler calculated from TGA / [the mass number of the pressure-sensitive adhesive composition for metal protection-the amount of filler calculated from TGA] x 100).

5. Comprehensive evaluation Comprehensive evaluation of pressure-sensitive adhesive tape for metal protection based on the above-mentioned "1. Workability", "2. Self-bonding", "3. Suppression of copper damage" and "4. Toluene insoluble matter". Was judged according to the following criteria.
A: All evaluation items are judged as A. These can be implemented as a pressure-sensitive adhesive tape for metal protection, satisfying all the characteristics, and can be used in a harsher environment such as high temperature, high humidity, and copper damage than the next B judgment.
B: Among the evaluation items, even one has a B judgment. These can be implemented as pressure-sensitive adhesive tapes for metal protection.
C: Among the evaluation items, even one has a C judgment. These are not feasible as pressure sensitive adhesive tapes for metal protection.

Details of each component shown in Tables 1 to 3 are shown below.

JSR BUTYL 268 (butyl rubber): double bond content (unsaturation) 0.8 mol%, Mooney viscosity 32 (ML1 + 8, 125 ° C), JSR KALAR 5275 (partially crosslinked butyl rubber): Mooney viscosity 65-72 (ML1 + 3, 127 ° C), glass transition temperature -70 ° C, Royal Elastomers Opanol N100 (high molecular weight polyisobutylene): viscosity average molecular weight 1.1 million, glass transition temperature -64 ° C, BASF Tetrax 4T (low molecular weight) Polyisobutylene): viscosity average molecular weight 40,000, JX Nikko Nisseki Energy Co., Ltd. HV-300 (polybutene): number average molecular weight 1,400
YS resin PX1150) (terpene resin): softening point 115 ± 5 ° C.
Calcined aluminum silicate: SATINTONE WHITETEX, average particle size 1.4 μm, Mitsui & Co. (BASF)
Triazole soil: Radiolite F, average particle size 7 μm, Showa Kagaku Kogyo Nocrack White (N, N'-di-2-naphthyl-p-phenylenediamine): aromatic amine compound, see formula (1) above, first Metal damage suppressant, softening point 225 ° C or higher, Ilganox MD1024 (2', 3-bis [[3- [3,5-di-t-butyl-4-hydroxyphenyl] propionyl] manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.] ] Propionohydrazide): Hydrazide compound, first metal damage inhibitor, see formula (3) above, melting point 225-227 ° C, BASF Adecastab CDA-1 (N- (2H-1,2,4-triazole) -5-yl) salicylamide): amide compound, second metal damage inhibitor, see formula (4) above, melting point 315-325 ° C., ADEKA BT-120 (1,2,3-benzotriazole) :. Benzotriazole compound, second metal damage inhibitor, see formula (5) above, melting point 95 ° C or higher, Sonnox 1010 manufactured by Johoku Chemical Industry Co., Ltd. (Pentaerytritoltetrakis [3- (3,5-di-tert-butyl-) 4-Hydroxyphenyl) propionate]): Hydrazide phenol compound, antioxidant (primary antioxidant), melting point 110-125 ° C, manufactured by Songwon Co., Ltd.

1 Pressure-sensitive adhesive tape for metal protection 2 Pressure-sensitive adhesive layer for metal protection 3 Base material 5 First wire 6 First conductor part 7 First coating layer 9 Second wire 10 Fixing member 12 Connection part 26 Second conductor part 27 Second covering part 30 Connection part protection structure

Claims (10)

Butyl rubber and
It contains a metal damage-oxidation suppression coexisting component that has both a metal damage suppression function based on metal capture and an oxidation suppression function based on radical species capture.
The metal damage-oxidation suppression combined component contains a first metal damage suppression agent having both a metal damage suppression function and an oxidation suppression function.
The first metal damage inhibitor is at least one selected from the group consisting of N, N'-di-2-naphthyl-p-phenylenediamine and hydrazine compounds. Pressure adhesive composition. The pressure-sensitive adhesive composition for metal protection according to claim 1, wherein the first metal damage suppressant is a copper damage suppressant. Butyl rubber and
It contains a metal damage-oxidation suppression coexisting component that has both a metal damage suppression function based on metal capture and an oxidation suppression function based on radical species capture.
The metal-damage-oxidation-suppressing coexisting component is
A second metal damage inhibitor that does not have an oxidation suppression function and has a metal damage suppression function,
It is characterized by containing an oxidation inhibitor.
The second metal damage inhibitor is at least one selected from the group consisting of an amide compound and a benzotriazole compound.
Pressure-sensitive adhesive composition for metal protection. The pressure-sensitive adhesive composition for metal protection according to claim 3, wherein the second metal damage suppressant is a copper damage suppressant. The pressure-sensitive adhesive composition for metal protection according to any one of claims 1 to 4 , wherein the toluene insoluble content of the pressure-sensitive adhesive composition for metal protection is 10% by mass or less. The pressure-sensitive adhesive composition for metal protection according to any one of claims 1 to 5 , further comprising a filler. Contains the pressure-sensitive adhesive component containing the butyl rubber,
The pressure-sensitive adhesive composition for metal protection according to claim 6 , wherein the ratio of the filler is 100 parts by mass or more and less than 600 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive component. .. With the base material
It is characterized by comprising a metal protective pressure-sensitive adhesive layer which is arranged on one surface in the thickness direction of the base material and is made of the metal protective pressure-sensitive adhesive composition according to any one of claims 1 to 7 . Pressure-sensitive adhesive tape for metal protection. A first conductor portion having a passivation film formed on its surface, a first electric wire provided with a first coating layer covering the passivation film, and a second coating covering the second conductor portion and the second conductor portion. The step of preparing the second electric wire provided with the layer and the pressure-sensitive adhesive tape for metal protection according to claim 8 .
A step of removing a part of the first coating layer to expose the passivation film from the first coating layer.
A step of removing the exposed passivation film to expose the first conductor portion from the passivation film.
A step of removing a part of the second coating layer to expose the second conductor portion from the second coating layer, and
A method for manufacturing a connection portion protection structure, comprising a step of bundling the exposed first conductor portion and the second conductor portion and covering them with the metal protective pressure-sensitive adhesive tape. The first conductor portion is made of at least one metal selected from the group consisting of copper, iron, cobalt, nickel, manganese, vanadium, titanium, calcium, silver, zinc, aluminum and magnesium. Item 9. The method for manufacturing a connection portion protection structure according to Item 9.

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