JP7054586B1 - Primer and anticorrosion structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a primer or the like which can improve the coating workability at the time of coating on a substrate and can make the obtained primer layer excellent in heat resistance. A primer according to the present invention comprises a main agent and a curing agent, and the main agent contains a silicone compound and has a viscosity at 23 ° C. of 16 Pa · s or more and 600 Pa · s or less. [Selection diagram] None

Description

The present invention relates to a primer and an anticorrosion structure comprising a primer layer formed by the primer.

Conventionally, it has been known to use a primer (primer) when forming some layer on a substrate.

Such a primer is used, for example, in the production of an anticorrosion structure when forming an anticorrosion layer (for example, Patent Document 1).
In Patent Document 1, a metal member (for example, a gas pipe, a water pipe, and a metal pipe such as a pipe for transporting a liquid raw material such as oil) is used as a base, and the metal member serving as the base is used. It is shown that an anticorrosion structure is produced by applying the primer to the surface to form a primer layer and then wrapping an anticorrosion tape around the surface of the metal member on which the primer layer is formed to form an anticorrosion layer. Has been done.

Further, as the primer, one containing a main agent and a curing agent is known, and in such a primer containing the main agent and the curing agent, a silicone compound is contained in the main agent in order to improve heat resistance and the like. Some are known.

Japanese Unexamined Patent Publication No. 2018-168455

By the way, when a primer containing the silicone compound as the main agent is applied onto the substrate to form a primer layer, the primer can be applied with good workability, but the primer layer formed by applying the primer has a high temperature. When exposed to an environment (for example, an environment of 200 ° C.), the primer layer may be cracked. That is, the primer layer may not exhibit sufficient heat resistance.
Further, although the primer layer formed by applying the primer to the substrate exhibits sufficient heat resistance, the workability (workability) of applying the primer to the substrate may deteriorate.

However, sufficient studies have been made on making the obtained primer layer excellent in heat resistance while improving the coating workability when applying the primer to the substrate (while ensuring workability). It is hard to say that it is.

Therefore, the present invention provides a primer that improves coating workability when coated on a substrate (can ensure workability), and can make the obtained primer layer excellent in heat resistance, and the primer. It is an object of the present invention to provide an anticorrosion structure including a primer layer formed by the above.

As a result of diligent studies by the present inventors, in a primer containing a main agent and a curing agent, the main agent contains a silicone compound and has a viscosity at 23 ° C. of 16 Pa · s or more and 600 Pa · s or less. It has been found that the coating workability when the primer is applied to the substrate is improved (workability can be ensured), and the primer layer obtained by applying the primer has excellent heat resistance. rice field.
Then, he came up with the present invention.

That is, the primer according to the present invention is
Equipped with a main agent and a curing agent,
The main agent contains a silicone compound and has a viscosity at 23 ° C. of 16 Pa · s or more and 600 Pa · s or less.

According to such a configuration, the primer has good coating workability when coated on the substrate (workability can be ensured), and the obtained primer layer can be made excellent in heat resistance.

In the primer,
The main agent has one or more peaks in the range of 1200 cm ^-1 or more and 1300 cm ^-1 or less and 2800 cm ^-1 or more and 2900 cm ^-1 or less in the infrared absorption spectrum obtained by IR measurement. The ratio of the highest peak height h ₂ appearing in the range of 1200 cm ^-1 or more and 1300 cm ^-1 to the highest peak height h ₁ appearing in the range of 2800 cm ^-1 or more and 2900 cm ^-1 is h ₂ / h ₁ . , 25 or more and 250 or less is preferable.

According to such a configuration, the primer layer obtained by applying the primer can be made more excellent in heat resistance.

In the primer,
The curing agent preferably has a pH of 2 or more and 5 or less as measured by the method specified in JIS K7371: 2000.

According to such a configuration, the primer has good coating workability when the substrate is coated (workability can be ensured), and the obtained primer layer can be made excellent in heat resistance. In addition, the primer layer can be made to have excellent anticorrosion properties.

In the primer,
It is preferable to further contain a rust preventive.

According to such a configuration, when the primer layer formed by the primer is arranged on the surface of a metal member such as a metal tube, it is possible to prevent the metal member from rusting.

In the primer,
It is preferably used as an anticorrosion paste.

According to such a configuration, the primer used as the anticorrosion paste can be applied to the substrate with good coating workability (securing workability), and the anticorrosion structure includes a primer layer formed by using the primer as the anticorrosion paste. The body can be made to have excellent heat resistance.

The anticorrosion structure according to the present invention is
A primer is used as an anticorrosion paste applied to an object to be anticorrosion, and a primer layer formed by the primer is provided.
The primer contains a main agent and a curing agent.
The main agent contains a silicone compound and has a viscosity at 23 ° C. of 16 Pa · s or more and 600 Pa · s or less.

According to such a configuration, the primer has good coating workability when coated on the substrate (workability can be ensured), and the obtained primer layer can be made excellent in heat resistance.
That is, the anticorrosion structure can be made excellent in heat resistance while the primer is applied with good coating workability to form the primer layer.

In the anticorrosion structure,
Further provided with an anticorrosion layer made of anticorrosion tape laminated on the primer layer,
The anticorrosion tape comprises a fiber sheet and a compound supported on the fiber sheet and containing a silicone compound.
The water content of the compound is preferably 1000 ppm or less.

According to such a configuration, it is possible to suppress the promotion of the curing reaction of the compound supported on the surface layer portion of the fiber sheet, whereby the curing of the compound of the anticorrosion tape can be appropriately controlled.
As a result, the anticorrosion structure can be made even more excellent in heat resistance.

In the anticorrosion structure,
It is preferable that the compound contains a silicone compound having reaction curability as the silicone compound and has a viscosity at 23 ° C. of 25 Pa · s or more and 250 Pa · s or less.

According to such a configuration, the promotion of curing of the compound supported on the surface layer portion of the fiber sheet can be further suppressed, whereby the curing of the compound of the anticorrosion tape can be controlled more appropriately. ..
As a result, the anticorrosion structure can be made even more excellent in heat resistance.

In the anticorrosion structure,
The fiber sheet preferably has a mass reduction rate of 10% by mass or less after being heat-treated at 300 ° C. for 24 hours.

According to such a configuration, even when exposed to a high temperature of 300 ° C. for a long time of 24 hours, the adhesion between the surface of a metal member such as a metal tube and the anticorrosion tape is maintained. Can be done.
As a result, the anticorrosion structure can be made even more excellent in heat resistance.

In the anticorrosion structure,
The fiber sheet preferably has a basis weight of 30 g / m ² or more and 150 g / m ² or less.

According to such a configuration, the fiber sheet is relatively easy to impregnate with the compound. That is, the anticorrosion tape is more sufficiently impregnated with the compound.
Therefore, in a state of being wound around a metal member such as a metal tube, the anticorrosion tape is further sufficiently cured to further suppress the formation of a gap between the metal member and the anticorrosion tape. be able to.
As a result, the anticorrosion structure can be made even more excellent in heat resistance.

In the anticorrosion structure,
Further provided with a top coat layer laminated on the anticorrosion layer,
The top coat layer is formed of a top coat containing oil.
The oil content preferably contains a silicone compound.

According to such a configuration, the affinity with the anticorrosion layer becomes relatively high in a state of being laminated on the anticorrosion layer made of the anticorrosion tape containing the silicone compound, and the oil agent is applied to the anticorrosion layer. Is easy to impregnate.
That is, since a gap is less likely to occur between the top coat layer and the anticorrosion layer, the anticorrosion property of the anticorrosion structure can be further improved.

In the anticorrosion structure,
The top coat preferably has a viscosity at 23 ° C. of 0.05 Pa · s or more and 100 Pa · s or less.

According to such a configuration, the top coat can be easily applied to the anticorrosion layer. Therefore, in the anticorrosion structure, the topcoat layer is formed on the anticorrosion layer with a relatively uniform thickness. Can be done.

In the anticorrosion structure,
The topcoat preferably further contains a tin-based catalyst.

According to such a configuration, the tin-based catalyst can be moved from the top coat layer formed by the top coat into the anticorrosion layer, so that the curing reaction in the anticorrosion layer can be further promoted.

In the anticorrosion structure,
Further provided with an anticorrosion mastic layer disposed between the primer layer and the anticorrosion layer and formed of an anticorrosion mastic.
The anticorrosion mastic layer preferably contains a silicone compound.

According to such a configuration, when the anticorrosion mastic layer is brought into contact with the primer layer and the anticorrosion layer, the affinity between the anticorrosion mastic layer and the primer layer and the anticorrosion layer is relatively high. It becomes.
That is, since a gap is less likely to occur between the anticorrosion mastic layer, the primer layer, and the anticorrosion layer, the anticorrosion property of the anticorrosion structure can be further enhanced.

In the anticorrosion structure,
The anticorrosion mastic preferably has a consistency of 40 or more and 150 or less.

According to such a configuration, when the anticorrosion mastic is filled between the primer layer and the anticorrosion layer to form the anticorrosion mastic layer, in addition to being relatively easy to fill, after filling, the said. The anticorrosion mastic layer can be made to have relatively sufficient shape retention.

In the anticorrosion structure,
The anticorrosion mastic preferably has a mass reduction rate of 20% by mass or less after being heat-treated at 300 ° C. for 24 hours.

According to such a configuration, after the anticorrosion mastic is filled between the primer layer and the anticorrosion layer to form the anticorrosion mastic layer, the anticorrosion mastic layer can be made relatively dense. ..
As a result, the anticorrosion structure can be made even more excellent in heat resistance.

According to the present invention, a primer that improves coating workability when coated on a substrate (can ensure workability) and can make the obtained primer layer excellent in heat resistance, and the primer. It is possible to provide an anticorrosion structure including a primer layer formed by the above.

The cross-sectional view which shows the structure of the anticorrosion structure which concerns on one Embodiment of this invention.

Hereinafter, an embodiment of the present invention will be described.

[Primer]
The primer according to the embodiment of the present invention (hereinafter, also referred to as the primer according to the present embodiment) includes a main agent and a curing agent.
The primer is preferably used as an anticorrosion paste.
Therefore, an example in which the primer according to the present embodiment is used as an anticorrosion paste will be described below. That is, an example in which the primer according to the present embodiment is applied to the surface of the metal member and a primer layer is formed on the surface of the metal member to prevent corrosion of the surface of the metal member will be described.

The main agent contains a silicone compound. When the main agent contains a silicone compound, the primer has excellent heat resistance.
The silicone compound is preferably contained in the primer as a main component (oil). Examples of the silicone compound as the main component (oil content) include straight silicone oil, reactive modified silicone oil, and non-reactive modified silicone oil.
Examples of the straight silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil.
The reactive modified silicone oil includes an amine group, an epoxy group, a carbinol group, a mercapto group, a carboxyl group, a methacryl group, a polyether group, a phenol group, a silanol group, and an acrylic on the side chain, one end, and both ends. Examples include those to which a group, an acid anhydride group, etc. are added.
Examples of the non-reactive modified silicone oil include those to which a polyether group, an aralkyl group, a fluoroalkyl group, a long-chain alkyl group, a fatty acid ester, a fatty acid amide, etc. are added to the side chain, one end, and both ends. Be done.
Commercially available products of the above-mentioned silicone compounds include YF3800 (manufactured by Momentive Performance Materials Japan), YF3905 (manufactured by Momentive Performance Materials Japan), and YF3057 (manufactured by Momentive Performance Materials).・ YF3807 (Momentive Performance Materials Japan), YF3802 (Momentive Performance Materials Japan), YF3897 (Momentive Performance Materials Japan) ), KF9701 (manufactured by Shin-Etsu Chemical Co., Ltd.), PAM-E (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-8008 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-105 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-2201 (manufactured by Shin-Etsu Chemical Co., Ltd.), WAXKER (registered trademark) SILICONE FLUID AK 0.65-10 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), WAXKER (registered trademark) SILICONE FLUID AK20-5,000 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) WAXKER (registered trademark) SILICONE FLUID AK100 000 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), DOWNSIL (registered trademark) SF 8427 Fluid (manufactured by Dow Toray Co., Ltd.), DOWNSIL (registered trademark) BY 16-750 Fluid (manufactured by Dow Toray Co., Ltd.) and the like.

The main agent preferably contains 20% by mass or more and 80% by mass or less of the silicone compound, and more preferably 35% by mass or more and 65% by mass or less.

It is important that the viscosity of the main agent at 23 ° C. is 16 Pa · s or more and 600 Pa · s or less, and it is more important that the viscosity at 23 ° C. is 16 Pa · s or more and 150 Pa · s or less.
When the viscosity of the main agent at 23 ° C. is 16 Pa · s or more and 600 Pa · s or less, the primer containing the main agent exhibits an appropriate viscosity. Therefore, the primer containing the main agent is used as a substrate (for example, a metal member). In addition to being able to be applied (to ensure workability), the primer layer formed by applying the primer was exposed to a high temperature environment (for example, an environment of 200 ° C.). Occasionally, it is possible to suppress the occurrence of cracks in the primer layer. That is, the primer layer has excellent heat resistance.
As a result, when the primer is applied to the substrate, the obtained primer layer can be made excellent in heat resistance while improving the coating workability (while ensuring the workability).
Further, when the viscosity of the main agent at 23 ° C. is 16 Pa · s or more and 150 Pa · s or less, the primer containing the main agent exhibits a more appropriate viscosity. Therefore, the primer containing the main agent is used as a substrate (for example, a metal). In addition to further improving the coating workability when coating the material (manufacturing member), the primer layer formed by applying the primer was exposed to a high temperature environment (for example, an environment of 200 ° C.). Occasionally, it is possible to suppress the occurrence of cracks in the primer layer. That is, the primer layer has excellent heat resistance.
As a result, the obtained primer layer can be made excellent in heat resistance while further improving the coating workability when the primer is applied to the substrate.
Further, the anticorrosion structure provided with such a primer layer can also exhibit sufficient heat resistance.
Further, when an anticorrosion structure is obtained by wrapping an anticorrosion tape around the primer layer to form an anticorrosion layer, the anticorrosion layer to the metal member via the primer layer in the anticorrosion structure. The adhesiveness can be sufficiently ensured, and the gap between the anticorrosion layer and the metal member can be sufficiently reduced.
As a result, the anticorrosion structure can exhibit more sufficient heat resistance.

The viscosity at 23 ° C. can be measured using a BH type viscometer manufactured by Tokimec as a measuring device under the condition of a temperature of 23 ± 1 ° C.
The number of the rotor to be used and the rotation speed of the rotor are selected according to the viscosity value V as follows.

When V is 100 Pa · s or less (V ≦ 100) Rotor number to be used: No. 6. Rotor rotation speed: 10 rpm
When V exceeds 100 Pa · s and 250 Pa · s or less (100 <V ≦ 150) Rotor number to be used: No. 6. Rotor rotation speed: 4 rpm
When V exceeds 250 Pa · s and is 1000 Pa · s or less (250 <V ≦ 1000) Rotor number to be used: No. 7. Rotor rotation speed: 4 rpm

The main agent has one or more peaks in the range of 1200 cm ^-1 or more and 1300 cm ^-1 or less and 2800 cm ^-1 or more and 2900 cm ^-1 or less in the infrared absorption spectrum obtained by IR measurement. It is preferable to have.
In addition, the main agent has a ratio h of the highest peak height h ₂ appearing in the range of 1200 cm ^-1 or more and 1300 cm ^-1 or less to the height h ₁ of the highest peak appearing in the range of 2800 cm ^-1 or more and 2900 cm ^-1 or less. It is preferable that ₂ / h ₁ is 25 or more and 250 or less.
When h ₂ / h ₁ is 25 or more and 250 or less, the primer layer formed by the primer can be made to exhibit even more sufficient heat resistance.

The IR measurement of the main agent can be obtained by using Nicolet iS10 manufactured by Thermo Fisher Scientific Co., Ltd. as a measuring device and adopting the following measurement conditions.
If the main agent contains a solid content, the solid content is previously centrifuged to remove the solid content, and then the IR measurement of the main agent is performed. For centrifugation, CS100GX manufactured by HIMAC is used, and the condition of processing at 47,000 rpm for 15 minutes can be adopted.

<Measurement conditions>
Measurement method: ATR method Window material used: Diamond
Resolution: 4 cm ^-1
Accumulation number: 64 times

The main agent may contain a resin component, a rust preventive, an inorganic filler, and a thickener in addition to the silicone compound.

Examples of the resin component include a silane compound.
Examples of the silane compound include polyalkoxysilane compounds having a methoxy group or an ethoxy group at the side chain or the terminal, a silicate oligomer, a silane coupling agent modified with an epoxy group or an acid anhydride, and the like.
Commercially available products of the silane compound include, for example, XR31-B2733 (manufactured by Momentive Performance Materials Japan), XR31-B2230 (manufactured by Momentive Performance Materials Japan), and Methyl Silicone 51 (Colcoat). , Methyl silicate 53 (manufactured by Corcote), Ethyl silicate 48 (manufactured by Corcote), Silica 45 (manufactured by Tama Chemical Industry Co., Ltd.), WACKER (registered trademark) SILANE M1-TRIMETHOXY (manufactured by Asahi Kasei Wacker Silicone), WACKER (Registered Trademark) SILANE M2-DIMETHOXY (manufactured by Asahi Kasei Wacker Silicone), KBM-13 (manufactured by Shinetsu Chemical Co., Ltd.), KBM-22 (manufactured by Shinetsu Chemical Co., Ltd.), XIAMETER (registered trademark) OFS-6388 Silane (Dow Chemical Japan) , DOWNSIL (registered trademark) Z-6329 Silane (manufactured by Dow Toray Co., Ltd.) and the like.

When the main agent contains the resin component, the content thereof is preferably 1% by mass or more and 80% by mass or less, and more preferably 5% by mass or more and 50% by mass or less.

Examples of the rust preventive agent include an inorganic rust preventive agent and an organic rust preventive agent.
Examples of the inorganic rust preventive agent include chromate, molybdenate, tungstate, phosphate, tripolyphosphate, phosphite, hypophosphite, silicate, borate, and the like. Examples thereof include phosphorus compounds, zinc oxide, iron oxide, zinc, and mica-like iron oxide.
Among these, it is preferable to use phosphate, tripolyphosphate, phosphite, zinc oxide and the like.
Examples of the organic rust preventive agent include tannic acid, carboxylic acid (oleic acid, dimer acid, naphthenic acid, etc.), carboxylic acid metal soap (lanolin Ca, naphthen Zn, oxide wax Ca, oxide wax Ba, etc.), and sulfone. Examples thereof include acid salts (Na sulphonate, Ca sulphonate, Ba sulphonate, etc.), amine salts, esters (esters obtained by reacting higher fatty acids with glycerin, sorbitan monoisostearate, sorbitan monoolate, etc.).
Commercially available rust preventives include K-WHITE # 82 (manufactured by TAYCA), K-WHITE # 105 (manufactured by TAYCA), K-WHITE # 108 (manufactured by TAYCA), and EXPERT NP-530 (Toho Pigment Industry). EXPERT-1530 (manufactured by Toho Pigment Industry Co., Ltd.), EXPERT-1600 (manufactured by Toho Pigment Industry Co., Ltd.), Heucophos ZPA (manufactured by Hoybach Japan), Heucophos ZAM-PLUS (manufactured by Hoibach Japan), etc. Be done.

When the main agent contains the rust preventive, the content thereof is preferably 0.1% by mass or more and 25% by mass or less, and more preferably 1% by mass or more and 15% by mass or less.

Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, talc, silica, clay, calcium carbonate, bentonite, mica, mica-like iron oxide, and metal powder.

When the main agent contains the inorganic filler, the content thereof is preferably 10% by mass or more and 60% by mass or less, and more preferably 20% by mass or more and 45% by mass or less.

Examples of the thickener include minerals containing silicate as a main component.
Examples of such minerals include sepiolite, attapargite, fumed silica, bentonite, smectite, hectorite, montmorillonite and the like.
Further, organically chemically modified minerals may be used.
Commercially available thickeners include LAPONITE-EP (manufactured by BYK), LAPONITE-B (manufactured by BYK), Aerosil (registered trademark) 130 (manufactured by Evonik), and Aerosil (registered trademark) 200 (manufactured by Evonik). ), Aerosil (registered trademark) R972 (manufactured by Evonik), Esben N-400 (manufactured by Hojun), PANSIL (manufactured by TOOLSA), PANSIL 100 (manufactured by TORSA), PANSIL 400 (manufactured by TORSA), etc. ..

When the main agent contains the thickener, the content thereof is preferably 0.1% by mass or more and 30% by mass or less, and more preferably 0.5% by mass or more and 10% by mass or less. preferable.

The curing agent contains a catalyst. As the catalyst, the silicone compounds contained in the main agent promote dehydration condensation, or in an anticorrosion tape containing the silicone compound and a cross-linking agent as described later, the silicone compounds or the silicone compound and the cross-linking are used. Examples thereof include those having a catalytic ability to promote dehydration condensation with an agent.
Examples of the catalyst include organic titanium compounds such as titanium tetraisopropoxide, titanium tetranormalbutoxide, butyl titanate dimer, titanium acetylacetonate, titanium octylene glycolate, and titanium ethylacetacetate; aluminum tris (acetylacetonate). , Aluminum tris (ethylacetacetate) and other organic aluminum compounds; zirconium tetra (acetylacetonate), zirconium tributoxyacetylacetonate, zirconium dibutoxydiacetylacetonate, zirconium tetranormal propoxide, zirconium tetraisopropoxide, zirconium tetra Organic zirconium compounds such as normal butoxide, zirconium acylate, zirconium tributoxystearate, zirconium octate, zirconyl (2-ethylhexanoate), zirconium (2-ethylhexoate); dibutyltin dioctote, dibutyltin dilaurate, Organic tin compounds such as dibutyltin di (2-ethylhexanoate); organic carboxylic acids such as tin naphthenate, tin oleate, tin butylate, dibutyltin, octyltin, dioctyltin, cobalt naphthenate, zinc stearate. Examples thereof include an amine compound such as hexylamine and dodecylamine phosphate, and a salt thereof; benzyltriethylammonium acetate; dialkylhydroxylamine such as dimethylhydroxylamine and diethylhydroxylamine; and an organic silicon compound containing a guanidyl group.
These may be used alone or in combination of two or more.
Among these catalysts, organic tin compounds, tin naphthenate, tin oleate, tin butyrate, from the viewpoint of facilitating dehydration condensation between the silicone compounds and dehydration condensation between the silicone compound and the cross-linking agent. It is particularly preferable to use a tin-based catalyst such as dibutyl tin, octyl tin, or dioctyl tin.
Commercially available tin-based catalysts include CE621 (manufactured by Momentive Performance Materials Japan), CE611 (manufactured by Momentive Performance Materials Japan), and CE601 (manufactured by Momentive Performance Materials Japan). Examples include Neostan U-303 (manufactured by Nitto Kasei Co., Ltd.) and Neostan U-810 (manufactured by Nitto Kasei Co., Ltd.).

The curing agent preferably contains the catalyst in an amount of 3% by mass or more and 80% by mass or less, and more preferably 7% by mass or more and 40% by mass or less.

Since the curing agent contains a catalyst such as a tin-based catalyst, the primer layer formed by applying the primer according to the present embodiment to the entire surface of the metal member and the primer layer have reaction curability. In an anticorrosion structure comprising an anticorrosion layer formed by winding an anticorrosion tape having a compound containing a compound (for example, a silicone compound) supported on a fiber sheet, the tin-based catalyst is applied from the primer layer to the anticorrosion layer. Can be moved.
This makes it easier to proceed with the curing reaction of the reaction-curable compound in the anticorrosion layer.

The curing agent preferably contains, in addition to the catalyst, a pH adjusting agent for adjusting the pH of the curing agent.
Examples of the pH adjusting agent include inorganic acids such as phosphoric acid, hydrochloric acid, nitrate and sulfuric acid; organic acids such as phthalic acid, tartaric acid, citric acid, formic acid, oxalic acid and acetic acid; acid anhydride-based silane coupling agents and acid anhydride. Examples thereof include additives showing acidity such as physical silicone oil.
Examples of the commercially available acid anhydride-based silane coupling agent include X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.), and examples of the commercially available acid anhydride-based silicone oil include X-22-168AS (Shin-Etsu Chemical Co., Ltd.). Examples thereof include X-22-168A (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-168B (manufactured by Shin-Etsu Chemical Co., Ltd.), and X-22-168P5-B (manufactured by Shin-Etsu Chemical Co., Ltd.).

When the curing agent contains a pH adjusting agent for adjusting the pH of the curing agent in addition to the catalyst, the catalyst and the catalyst are used when the curing agent is added to the main agent to obtain a primer. It is preferable to add the pH adjuster separately to the main agent, and it is more preferable to add the curing agent after adding the pH adjuster.
As described above, by separately adding the catalyst and the pH adjuster to the main agent, the surface of the metal member (for example, a metal pipe such as a gas pipe) can be made as shown in the section of Examples described later. Corrosion by inorganic salts such as NaCl can be further suppressed.

The pH of the curing agent is preferably 2 or more and 5 or less.
When the pH of the curing agent is 2 or more and 5 or less, the curing of the silicone compound can proceed more sufficiently in the anticorrosion layer laminated on the primer layer formed by the primer.
As a result, the adhesion of the anticorrosion layer to the surface of the metal member via the primer layer can be sufficiently ensured, and the gap between the anticorrosion layer and the metal member can be sufficiently reduced.
As a result, the anticorrosion structure including the primer layer and the anticorrosion layer laminated on the primer layer can exhibit sufficient heat resistance.

The pH of the curing agent can be measured as follows.

(1) Put the measurement sample in an amount such that the mass of the tin catalyst is 1 g in a beaker, and weigh the measurement sample.
(2) Add 50 mL of an aqueous NaCl solution (NaCl concentration 10 g / L) to the beaker containing the measurement sample, and stir so that the measurement sample and the aqueous NaCl solution are well mixed.
(3) After stirring and allowing to stand for 10 minutes, an aqueous layer is collected, and the pH of the collected aqueous layer is measured by the method specified in JIS K7371: 2000.

[Anti-corrosion structure]
Next, the anticorrosion structure according to the embodiment of the present invention (hereinafter, also referred to as the anticorrosion structure according to the present embodiment) will be described.
The anticorrosion structure according to this embodiment has two or more layers.
Further, as shown in FIG. 1, the anticorrosion structure 100 according to the present embodiment is in contact with the surface of the metal member 10 and is formed by a primer according to the present embodiment as an anticorrosion paste for anticorrosion of an object. It includes a primer layer 1 and an anticorrosion layer 2 formed by an anticorrosion tape.
Further, the anticorrosion structure 100 according to the present embodiment has a protective layer (topcoat layer 3) formed of the protective layer forming composition on the outer side (opposite side of the primer layer 1 side) of the anticorrosion layer 2. Further prepare.
Further, the anticorrosion structure 100 according to the present embodiment further includes an anticorrosion mastic layer 4 arranged between the primer layer 1 and the anticorrosion layer 2 and formed by the anticorrosion mastic.

The metal member 10 is used as a pipeline for transporting a fluid. The metal member 10 includes a plurality of cylindrical pipes having a flange portion 11, and the pipes are connected to each other by the flange portion 11. The flange portions 11 of the adjacent pipes are fixed to each other by bolts 12 and nuts 13. That is, the metal member 10 has a cylindrical shape, and the outer surface is formed with irregularities by the flange portion 11, the bolt 12, the nut 13, and the like.

By having the primer layer 1, the anticorrosion structure 100 according to the present embodiment can fill the gap between the anticorrosion layer 2 and the metal member 10, and can suppress the corrosion of the metal member 10. ..
The primer layer 1 is formed by applying a thin layer of the primer according to the present embodiment to the entire outer surface of the cylindrical metal member 10. Therefore, unevenness is formed on the outer surface of the primer layer 1 by the unevenness formed on the metal member 10.
Further, when the primer layer 1 contains a catalyst such as a tin-based catalyst, the catalyst can be moved into the anticorrosion layer 2.
Then, as described later, when the anticorrosion layer 2 contains a silicone compound as a compound, the curing reaction of the silicone compound is carried out by moving a catalyst such as a tin-based catalyst into the anticorrosion layer 2. Can be promoted.

In the anticorrosion structure 100 according to the present embodiment, the anticorrosion layer 2 is formed of an anticorrosion tape.

As the anticorrosion tape constituting the anticorrosion layer 2, a tape having a fiber sheet and a compound supported on the fiber sheet can be used.

Examples of the fiber sheet include polyethylene terephthalate fiber (PET fiber), aramid fiber, polyphenylene sulfide fiber (PPS fiber), polyacrylonitrile-based carbon fiber (PAN-based carbon fiber), polyparaphenylene benzobisoxazole fiber (PBO fiber), and poly. Examples thereof include those made of tetrafluoroethylene fiber (PTFE fiber), nylon fiber and the like.
It is preferable to use a non-woven fabric as the fiber sheet. In addition, in this specification, a non-woven fabric is a concept including felt.
As the non-woven fabric, it is preferable to use a non-woven fabric having a basis weight (mass per unit area) of 30 g / m ² or more and 150 g / m ² or less.
The nonwoven fabric is preferably formed using fibers having a thickness of 1.5 decitex or more and 4 decitex or less.

As the non-woven fabric, those produced by various known methods such as spun bond, chemical bond, needle punch, stitch bond and the like can be adopted.
Among the non-woven fabrics produced by the above-mentioned various methods, it is preferable to use the spunlace nonwoven fabric from the viewpoint that the strength in the longitudinal direction of the fiber sheet can be excellent. It is more preferable to use a non-woven fabric.

The fiber sheet preferably has a mass reduction rate of 10% by mass or less after being heat-treated at 300 ° C. for 24 hours.
By using the fiber sheet having the above-mentioned characteristics, the anticorrosion tape can be made more excellent in heat resistance, and by extension, in the anticorrosion structure, the anticorrosion layer formed by the anticorrosion tape. Can be made more excellent in heat resistance.
The mass reduction rate of the fiber sheet means the reduction rate of the mass of the fiber sheet after exposure to 300 ° C. for 24 hours with respect to the mass of the fiber sheet before exposure to 300 ° C.

The compound has reaction curability. The compound can be made to have reaction curability by containing a compound having reaction curability.
When the compound contains the reaction-curable compound, it is preferable that the compound contains a cross-linking agent for cross-linking the reaction-curable compound.
The compound preferably contains a reaction-curable silicone compound as the reaction-curable compound.
Examples of such silicone compounds include straight silicone oils, reactive modified silicone oils, non-reactive modified silicone oils and the like.
Examples of the straight silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil.
The reactive modified silicone oil includes an amine group, an epoxy group, a carbinol group, a mercapto group, a carboxyl group, a methacryl group, a polyether group, a phenol group, a silanol group, and an acrylic on the side chain, one end, and both ends. Examples include those to which a group, an acid anhydride group, etc. are added.
Examples of the non-reactive modified silicone oil include those to which a polyether group, an aralkyl group, a fluoroalkyl group, a long-chain alkyl group, a fatty acid ester, a fatty acid amide, etc. are added to the side chain, one end, and both ends. Be done.
Commercially available products of the above-mentioned silicone compounds include YF3800 (manufactured by Momentive Performance Materials Japan), YF3905 (manufactured by Momentive Performance Materials Japan), and YF3057 (manufactured by Momentive Performance Materials).・ YF3807 (Momentive Performance Materials Japan), YF3802 (Momentive Performance Materials Japan), YF3897 (Momentive Performance Materials Japan) ), KF9701 (manufactured by Shin-Etsu Chemical Co., Ltd.), PAM-E (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-8008 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-105 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-2201 (manufactured by Shin-Etsu Chemical Co., Ltd.), WAXKER (registered trademark) SILICONE FLUID AK 0.65-10 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), WAXKER (registered trademark) SILICONE FLUID AK20-5,000 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) WAXKER (registered trademark) SILICONE FLUID AK100 000 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), DOWNSIL (registered trademark) SF 8427 Fluid (manufactured by Dow Toray Co., Ltd.), DOWNSIL (registered trademark) BY 16-750 Fluid (manufactured by Dow Toray Co., Ltd.) and the like.

The compound is preferably a substance that cures by a condensation reaction from the viewpoint of allowing the curing reaction to proceed satisfactorily even at room temperature (23 ± 1 ° C.). Therefore, it is preferable that the silicone compound has a silanol group as a reactive group or an alkoxysilyl group which becomes a silanol group by hydrolysis.
Specifically, the silicone compound is preferably a silicone oil having a chain structure or a branched structure having a plurality of hydroxyl groups in the molecule, and a chain silicone having hydroxyl groups at both ends such as polydimethylsiloxanediol. It is particularly preferred to be oil.
The silicone oil preferably has a kinematic viscosity of 1000 mm ² / s or more and 5000 mm ² / s or less at 25 ° C. as measured by JIS K2283 "Crude oil and petroleum products-kinematic viscosity test method and viscosity index calculation method".

Examples of the cross-linking agent include a silicone compound that is condensed with the above-mentioned polydimethylsiloxane diol or the like by dealcoholization.
Examples of such silicone compounds include polyalkoxysilane compounds having methoxy groups and ethoxy groups at the side chains and terminals, silicate oligomers, and silane coupling agents modified with epoxy groups and acid anhydrides.
Commercially available products of such silicone compounds include XR31-B2733 (manufactured by Momentive Performance Materials Japan), XR31-B2230 (manufactured by Momentive Performance Materials Japan), and Methylsilicate 51 (manufactured by Corcote). ), Methyl silicate 53 (manufactured by Corcote), Methyl silicate 48 (manufactured by Corcote), Silica 45 (manufactured by Tama Chemical Industry Co., Ltd.), WACKER (registered trademark) SILANE M1-TRIMETHOXY (manufactured by Asahi Kasei Wacker Silicone), WACKER (registered) Trademarks) SILANE M2-DIMETHOXY (manufactured by Asahi Kasei Wacker Silicone), KBM-13 (manufactured by Shinetsu Chemical Co., Ltd.), KBM-22 (manufactured by Shinetsu Chemical Co., Ltd.), XIAMETER (registered trademark) OFS-6383 Silane (manufactured by Dow Chemical Japan) ), DOWNSIL (registered trademark) Z-6329 Silane (manufactured by Dow Toray Co., Ltd.) and the like.

As such a silicone compound, a compound having one or more alkoxy groups is suitable.
As the cross-linking agent for cross-linking the above-mentioned silicone oil having a chain structure, it is preferable to use polyalkoxypolysiloxane represented by the following general formula (1).
Among the polyalkoxypolysiloxanes represented by the following general formula (1), it is particularly preferable to use ethyl silicate.

（なお、式（１）中のＲは、同一の又は異なる炭素数のアルキル基であり、ｎは１以上１００以下の整数である）

(Note that R in the formula (1) is an alkyl group having the same or different carbon atoms, and n is an integer of 1 or more and 100 or less).

Specific names of the cross-linking agent include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, vinyltrimethoxysilane, and phenyltrimethoxysilane. Trifunctional alkoxysilanes such as; tetrafunctional alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane; methyltripropenoxysilane, methyltriacetoxysilane, vinyltriacetoxysilane, methyltri (butanoxim) silane, propyl Tri (butanoxim) silane, phenyltri (butanoxim) silane, propyltri (butanoxim) silane, tetra (butanoxim) silane, 3,3,3-trifluoropropyltri (butanoxim) silane, 3-chloropropyltri (butanoxim) silane , Methyltri (propanoxime) silane, Methyltri (pentanoxime) silane, Methyltri (isopentanoxim) silane, Vinyltri (cyclopentanoxime) silane, Methyltri (cyclohexanoxime) silane and the like.
The cross-linking agent may be an alkylpolysiloxane such as methylpolysiloxane or ethylpolysiloxane.

A silane coupling agent may be used as the cross-linking agent. As the silane coupling agent, one having an amino group is preferably used.
Examples of the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and N-2- (amino). Ethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl -3-Aminopropyltrimethoxysilane and the like can be mentioned.

When the compound contains the cross-linking agent, the content thereof is preferably 0.05 parts by mass or more and 10 parts by mass or less, preferably 0.1 parts by mass or more, with respect to 100 parts by mass of the silicone compound. It is more preferably 7 parts by mass or less.

The molar ratio (-OR: -OH) of the alkoxy group (-OR) of the cross-linking agent to the hydroxyl group (-OH) of the silicone oil is usually in the range of 1: 100 to 100:10, and 1: It is preferably in the range of 10 to 10: 1.

The compound may contain an inorganic filler.

Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, talc, silica, clay, calcium carbonate, bentonite, mica, mica-like iron oxide, and metal powder.
The compound preferably contains calcium carbonate and calcium hydroxide as the inorganic filler.
When the compound contains the inorganic filler, the content thereof is preferably 50 parts by mass or more and 400 parts by mass or less with respect to 100 parts by mass of the silicone compound.
When the compound contains calcium carbonate and calcium hydroxide as the inorganic filler, the ratio of the calcium carbonate content to the aluminum hydroxide content (calcium carbonate content / aluminum hydroxide content). The amount) is preferably 1 or more and 5 or less.

Further, it is preferable that the silicone oil and the inorganic filler are contained in the compound so that the mass ratio (silicone oil: inorganic filler) is 20:80 to 40:60.
The total mass ratio of the silicone oil and the inorganic filler is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more of the compound.

The compound preferably has a water content of 1000 ppm or less.
When the water content of the compound is 1000 ppm or less, the anticorrosion tape is wrapped around the primer layer 1 formed by applying the primer to the surface of the metal member 10 to form the anticorrosion layer 2, and the compound is cured. Occasionally, the curing of the anticorrosion tape compound can be adequately controlled.
As a result, in addition to being able to exhibit sufficient heat resistance to the anticorrosion structure 100, it is also possible to exhibit sufficient anticorrosion properties.
The present inventors consider the reason as follows.

As a result of diligent studies by the present inventors, when the water content of the compound containing the silicone compound is relatively high (when the water content is such that it exceeds 1000 ppm), among the compounds supported on the fiber sheet, the fiber sheet The curing of the compound supported on the surface layer portion of the fiber sheet proceeds faster than the compound supported on the inside of the fiber sheet, and the curing of the compound supported on the inside of the fiber sheet does not proceed sufficiently.
Such a phenomenon occurs when the primer layer 1 is laminated on one side of the anticorrosion layer 2 and the top coat layer 3 is laminated on the other side as in the anticorrosion structure 100 according to the present embodiment. , It becomes more remarkable when the catalyst contained in these layers moves to the anticorrosion layer 2. Specifically, the curing reaction that occurs in the surface layer portion of the anticorrosion layer 2 cures the surface layer portion of the anticorrosion layer 2, so that the catalyst cannot sufficiently move inside the anticorrosion layer 2 and the surface layer of the anticorrosion layer 2 The part will be selectively cured.
However, when the water content of the compound is a relatively small value of 1000 ppm or less, it is considered that the promotion of curing of the compound supported on the surface layer portion of the fiber sheet can be suppressed.
Further, as described above, even when the catalyst is transferred from the primer layer 1 and the top coat layer 3 to the anticorrosion layer 2, the curing of the compound supported on the surface layer portion of the fiber sheet is suppressed from being promoted. It is considered that the catalyst has been sufficiently transferred to the compound supported on the inside of the fiber sheet.
Based on the above, in the anticorrosion structure 100 according to the present embodiment, the present inventors appropriately control the curing of the compound supported on the fiber sheet, so that in addition to sufficient heat resistance, sufficient anticorrosion properties are obtained. I think that it can also be demonstrated.

The water content of the compound can be measured by the Karl Fischer titration method. The details of the measuring device and the measuring conditions are as follows.

-Measuring device: Coulometric titration type moisture measuring device (Mitsubishi Chemical Analytech Co., CA-200 type), Heat vaporizer (Mitsubishi Chemical Analytech Co., VA-200 type)
-Measurement conditions: Heating vaporization method (heating at 150 ° C)
・ Anode solution: Aquamicron AKX (manufactured by Mitsubishi Chemical Corporation)
・ Cathode solution: Aquamicron CXU (manufactured by Mitsubishi Chemical Corporation)

The compound preferably has a viscosity at 23 ° C. of 25 Pa · s or more and 250 Pa · s or less.

The viscosity at 23 ° C. can be measured using a BH type viscometer manufactured by Tokimec as a measuring device under the condition of a temperature of 23 ± 1 ° C.
The number of the rotor to be used and the rotation speed of the rotor are selected according to the viscosity value V as follows.

When V is 100 Pa · s or less (V ≦ 100) Rotor number to be used: No. 6. Rotor rotation speed: 10 rpm
When V exceeds 100 Pa · s and 250 Pa · s or less (100 <V ≦ 150) Rotor number to be used: No. 6. Rotor rotation speed: 4 rpm
When V exceeds 250 Pa · s and is 1000 Pa · s or less (250 <V ≦ 1000) Rotor number to be used: No. 7. Rotor rotation speed: 4 rpm

The top coat layer 3 can be formed by applying the top coat to the surface of the anticorrosion layer 2.
The top coat contains a main component (oil), and the main component (oil) contains a silicone compound. It is preferable to use silicone oil as the main component (oil content).
Examples of the silicone oil include straight silicone oil and non-reactive modified silicone oil.
Examples of the straight silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil, and examples of the non-reactive modified silicone oil include polyether groups on the side chain, one end, or both ends. , Silicone oil to which an aralkyl group, a fluoroalkyl group, a long-chain alkyl group, a fatty acid ester, an aliphatic amide, etc. are added.
Examples of commercially available silicone oil products include the trade name "KF96-50cp" manufactured by Shin-Etsu Chemical Co., Ltd. and the trade name "KF96-1000cp".

The top coat preferably contains a catalyst. As the catalyst, the silicone compounds contained in the main agent promote dehydration condensation, or in an anticorrosion tape containing the silicone compound and a cross-linking agent as described later, the silicone compounds or the silicone compound and the cross-linking are used. Examples thereof include those having a catalytic ability to promote dehydration condensation with an agent.
Examples of the catalyst include organic titanium compounds such as titanium tetraisopropoxide, titanium tetranormalbutoxide, butyl titanate dimer, titanium acetylacetonate, titanium octylene glycolate, and titanium ethylacetacetate; aluminum tris (acetylacetonate). , Aluminum tris (ethylacetacetate) and other organic aluminum compounds; zirconium tetra (acetylacetonate), zirconium tributoxyacetylacetonate, zirconium dibutoxydiacetylacetonate, zirconium tetranormal propoxide, zirconium tetraisopropoxide, zirconium tetra Organic zirconium compounds such as normal butoxide, zirconium acylate, zirconium tributoxystearate, zirconium octate, zirconyl (2-ethylhexanoate), zirconium (2-ethylhexoate); dibutyltin dioctote, dibutyltin dilaurate, Organic tin compounds such as dibutyltin di (2-ethylhexanoate); organic carboxylic acids such as tin naphthenate, tin oleate, tin butylate, dibutyltin, octyltin, dioctyltin, cobalt naphthenate, zinc stearate. Examples thereof include an amine compound such as hexylamine and dodecylamine phosphate, and a salt thereof; benzyltriethylammonium acetate; dialkylhydroxylamine such as dimethylhydroxylamine and diethylhydroxylamine; and an organic silicon compound containing a guanidyl group.
These may be used alone or in combination of two or more.
Among these catalysts, organic tin compounds, tin naphthenate, tin oleate, tin butyrate, from the viewpoint of facilitating dehydration condensation between the silicone compounds and dehydration condensation between the silicone compound and the cross-linking agent. It is particularly preferable to use a tin-based catalyst such as dibutyl tin, octyl tin, or dioctyl tin.
Commercially available tin-based catalysts include CE621 (manufactured by Momentive Performance Materials Japan), CE611 (manufactured by Momentive Performance Materials Japan), and CE601 (manufactured by Momentive Performance Materials Japan). Examples include Neostan U-303 (manufactured by Nitto Kasei Co., Ltd.) and Neostan U-810 (manufactured by Nitto Kasei Co., Ltd.).

Since the top coat contains a catalyst such as a tin-based catalyst, a catalyst such as a tin-based catalyst can be transferred from the top coat layer 3 formed by the top coat to the anticorrosion layer 2.
This makes it easier to proceed with the curing reaction of the reaction-curable compound in the anticorrosion layer 2.

The top coat may contain a colorant, a thickener and the like. As a commercial product of the colorant, the trade name "Alpaste" manufactured by Toyo Aluminum Co., Ltd. can be mentioned, and as a commercial product of the thickener, the trade name "Aerosil (registered trademark) 130" manufactured by Nippon Aerosil Co., Ltd. can be mentioned. Can be mentioned.

The top coat preferably has a viscosity at 23 ° C. of 0.05 Pa · s or more and 100 Pa · s or less.
When the viscosity of the top coat is within the above numerical range, the top coat can be easily applied to the anticorrosion layer 2.
Therefore, in the anticorrosion structure 100, the topcoat layer 3 can be formed on the anticorrosion layer 2 with a relatively uniform thickness.

The viscosity at 23 ° C. can be measured using a BH type viscometer manufactured by Tokimec as a measuring device under the condition of a temperature of 23 ± 1 ° C.
The number of the rotor to be used and the rotation speed of the rotor are selected according to the viscosity value V as follows.

・ When V is 4 Pa · s or less (V ≦ 4) Rotor number to be used: No. 2. Rotor rotation speed: 10 rpm
When V exceeds 4 Pa · s and is 10 Pa · s or less (4 <V ≦ 10) Rotor number to be used: No. 3. Rotor rotation speed: 10 rpm
When V exceeds 10 Pa · s and is 50 Pa · s or less (10 <V ≦ 50) Rotor number to be used: No. 6. Rotor rotation speed: 20 rpm
When V exceeds 50 Pa · s and is 100 Pa · s or less (50 <V ≦ 100) Rotor number to be used: No. 6. Rotor rotation speed: 10 rpm

The anticorrosion mastic layer 4 is formed by filling the recesses of the primer layer 1 with anticorrosion mastics in order to reduce the unevenness of the primer layer 1.
In the anticorrosion structure 100 according to the present embodiment, the anticorrosion mastic layer 4 is formed by filling the gap between the primer layer 1 and the anticorrosion layer 2 with the anticorrosion mastic. As a result, in the anticorrosion structure 100 according to the present embodiment, the corrosion of the metal member 10 is further suppressed.

The anticorrosion mastic contains a main component (oil), and the main component (oil) contains a silicone compound. It is preferable to use silicone oil as the main component (oil content).
Examples of the silicone oil include straight silicone oil, reactive modified silicone oil, non-reactive modified silicone oil and the like.
Examples of the straight silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, and methyl hydrogen silicone oil.
The reactive modified silicone oil includes an amine group, an epoxy group, a carbinol group, a mercapto group, a carboxyl group, a methacryl group, a polyether group, a phenol group, a silanol group, and an acrylic on the side chain, one end, and both ends. Examples include those to which a group, an acid anhydride group, etc. are added.
Examples of the non-reactive modified silicone oil include those to which a polyether group, an aralkyl group, a fluoroalkyl group, a long-chain alkyl group, a fatty acid ester, a fatty acid amide, etc. are added to the side chain, one end, and both ends. Be done.
Commercially available products of the above-mentioned silicone compounds include YF3800 (manufactured by Momentive Performance Materials Japan), YF3905 (manufactured by Momentive Performance Materials Japan), and YF3057 (manufactured by Momentive Performance Materials).・ YF3807 (Momentive Performance Materials Japan), YF3802 (Momentive Performance Materials Japan), YF3897 (Momentive Performance Materials Japan) ), KF9701 (manufactured by Shin-Etsu Chemical Co., Ltd.), PAM-E (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-8008 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-105 (manufactured by Shin-Etsu Chemical Co., Ltd.), KF-2201 (manufactured by Shin-Etsu Chemical Co., Ltd.), WAXKER (registered trademark) SILICONE FLUID AK 0.65-10 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), WAXKER (registered trademark) SILICONE FLUID AK20-5,000 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) WAXKER (registered trademark) SILICONE FLUID AK100 000 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), DOWNSIL (registered trademark) SF 8427 Fluid (manufactured by Dow Toray Co., Ltd.), DOWNSIL (registered trademark) BY 16-750 Fluid (manufactured by Dow Toray Co., Ltd.) and the like.

The anticorrosion mastic may contain an inorganic filler. Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, talc, silica, clay, calcium carbonate, mica, mica-like iron oxide, and metal powder.
The anticorrosion mastic may contain a lightening agent or a flame retardant. Examples of the lightening agent include silica balloons, and examples of the flame retardant include aluminum hydroxide.

The anticorrosion mastic preferably has a consistency of 40 or more and 150 or less.
As a result, when the anticorrosion mastic is filled between the primer layer 1 and the anticorrosion layer 2 to form the anticorrosion mastic layer 4, it is relatively easy to fill, and after filling, the anticorrosion mastic layer 4 is formed. It can be made to have relatively sufficient shape retention.
The consistency of the anticorrosion mastic means a value measured at 23 ° C. based on JIS K2235-1991 "Petroleum wax 5.10 Consistency test method".

The anticorrosion mastic preferably has a mass reduction rate of 20% by mass or less after being heat-treated at 300 ° C. for 24 hours.
When the mass reduction rate is 20% by mass or less, the anticorrosion mastic is filled between the primer layer 1 and the anticorrosion layer 2 to form the anticorrosion mastic layer 4, and then the anticorrosion mastic layer 4 is relatively dense. Can be.
As a result, the anticorrosion structure 100 can be made even more excellent in heat resistance.
The mass reduction rate of the anticorrosion mastic means the reduction ratio of the mass of the anticorrosion mastic after exposure to 300 ° C. for 24 hours with respect to the mass of the anticorrosion mastic before exposure to 300 ° C.

The primer and the anticorrosion structure according to the present invention are not limited to the above-described embodiment. Further, the primer and the anticorrosion structure according to the present invention are not limited by the above-mentioned effects. The primer and anticorrosion structure according to the present invention can be variously modified without departing from the gist of the present invention.

Next, the present invention will be described in more detail with reference to examples. The following examples are for the purpose of explaining the present invention in more detail, and do not limit the scope of the present invention.

<Primer main agent>
Silicone compound A (main component (oil)), silane compound A as a resin, rust preventive, calcium carbonate as an inorganic filler, and thickener at room temperature (23 ±) at the mass ratio shown in Table 1A below. 1 ° C.) was kneaded to prepare primer main agents A to L.
Further, a primer main agent J placed in a constant temperature bath at 40 ° C. and held for 3 months was prepared as a primer main agent J', and a primer main agent K was placed in a constant temperature bath at 40 ° C. and held for 3 months. Was prepared as a primer main agent K'(see Table 1B below).
That is, the primer main agent J'and the primer main agent K'are prepared so as to promote storage.
As the characteristics of the primer main agents A to L, the primer main agent J', and the primer main agent K', the viscosity at 23 ° C. was measured.
The viscosities of the primer main agents A to L, the primer main agent J', and the primer main agent K'at 23 ° C. were measured as follows.
Specifically, as a measuring device, a BH type viscometer manufactured by Tokimec Co., Ltd. was used, and the measurement was performed under the condition of a temperature of 23 ± 1 ° C.
The number of the rotor to be used and the rotation speed of the rotor were selected as follows according to the value V of the viscosity.

When V is 100 Pa · s or less (V ≦ 100) Rotor number to be used: No. 6. Rotor rotation speed: 10 rpm
・ V exceeds 100 Pa · s and 250 Pa · s or less (100 <V ≦ 250)
Rotor number to be used: No. 6. Rotor rotation speed: 4 rpm
・ V exceeds 250 Pa · s and is 1000 Pa · s or less (250 <V ≦ 1000)
Rotor number to be used: No. 7. Rotor rotation speed: 4 rpm

In addition, IR measurements were performed on the primer main agents A to L, the primer main agents J', and the primer main agent K', and in the obtained infrared absorption spectrum, the highest peak appearing in the range of 1200 cm ^-1 or more and 1300 cm ^-1 or less. The value of the height h ₁ (the height of the peak appearing at 1258 cm ^-1 ) and the value of the highest peak height h ₂ appearing in the range of 2800 cm ^-1 or more and 2900 cm ^-1 or less (the peak appearing at 2840 cm ^-1 ). The ratio of the value of h ₂ to the value of h ₁ was calculated.
The IR measurements of the primer main agents A to L, the primer main agent J', and the primer main agent K'were performed as follows.
Specifically, it was obtained by using Nicolet iS10 manufactured by Thermo Fisher Scientific Co., Ltd. as a measuring device and adopting the following measurement conditions.
When the main agent contained a solid content, the solid content was separated by centrifugation in advance and then the IR measurement of the main agent was performed. For the centrifugation, CS100GX manufactured by HIMAC was used, and the condition of processing at 47,000 rpm for 15 minutes was adopted.

<Measurement conditions>
Measurement method: ATR method Window material used: Diamond
Resolution: 4 cm ^-1
Accumulation number: 64 times

Further, the coatability of the primer main agents A to L, the primer main agent J', and the primer main agent K'was evaluated.
The applicability of the primer main agents A to L, the primer main agent J', and the primer main agent K'is calculated by sandblasting one side (applied surface) of the substrate (SPCC-SB (planar dimension 150 mm × 75 mm, thickness 3.2 mm)). The workability when each primer base material is applied with a finger so that the application amount is 300 g / m ² on one side of the average roughness Ra adjusted to 2 μm or more and 10 μm or less shall be judged according to the following criteria. Was done by.

5 points: When the primer main agent is applied to the substrate with a finger, it is extremely easy to scoop and apply, so the workability is extremely good. Therefore, the surface after application is uniformly finished.
4 points: When applying the primer main agent to the substrate with a finger, it is relatively easy to scoop and spread, so workability is good. On the other hand, the uniformity of the surface after coating is slightly inferior to that of 5 points.
3 points: When the primer main agent is applied to the substrate with a finger, it is a little difficult to scoop because it has a slightly high viscosity, and although there is some resistance when spreading it, the workability is relatively good.
2 points: When the primer main agent is applied to the substrate with a finger, it is difficult to scoop it because of its high viscosity, and although the resistance when spreading it is large, it can be sufficiently applied.
1 point: When the primer main agent is applied to the substrate with a finger, it is extremely difficult to scoop because of its extremely high viscosity, and the resistance when spreading is extremely large, making it impossible to apply. That is, it cannot be constructed. Alternatively, although the resistance when spreading is small, the primer base material drips from the substrate.

In addition, the primer main agents A to L, the primer main agent J', and the primer main agent K'were evaluated for cracks after application (hereinafter, also simply referred to as cracks).
For the cracks of the primer main agents A to L, the primer main agent J', and the primer main agent K', arithmetically average one side (coated surface) of the substrate (SPCC-SB (planar dimension 150 mm × 75 mm, thickness 3.2 mm) by sandblasting). Roughness Ra is adjusted to 2 μm or more and 10 μm or less), and each primer main agent is applied with a finger so that the coating amount is 300 g / m ² , and then dried at room temperature (23 ± 1 ° C.) for 24 hours. Then, after leaving the substrate in a dryer at 200 ° C. for one month, the substrate was taken out from the dryer, and the surface of the substrate (the surface coated with the primer) was visually evaluated.
Then, visually, those in which no cracks were found in the primer main agent after application were evaluated as "excellent", and those in which cracks were found were evaluated as "impossible".

Table 1A below shows the measurement results of the viscosities of the primer main agents A to L at 23 ° C., the value of h ₁ , the value of h ₂ , the value of h ₂ / h ₁ , the evaluation result of coatability, and the evaluation of cracks. The results are shown.
In addition, Table 1B below shows the measurement results of viscosity at 23 ° C., the value of h ₂ / h ₁ , the evaluation result of coatability, and the evaluation result of cracks for the primer main agent J'and the primer main agent K'. ..
In Tables 1A and 1B below, the silicone compound A is "YF3807" manufactured by Momentive Performance Materials Japan, and the silane compound A is "YF3807" manufactured by Momentive Performance Materials Japan. XR31-B2733 ”, the rust preventive agent is the trade name“ K-WHITE # 82 ”manufactured by Teika, and the thickener is the trade name“ Aerosil® 130 ”manufactured by Evonik.

From Table 1A, for each of the primer main agent B to the primer main agent G, the applicability was evaluated at 5 points, and the crack was evaluated as “excellent”.
In addition, regarding the primer main agent H and the primer main agent I, the evaluation of coatability was 4 points, and the evaluation of crack was "excellent".
Further, regarding the primer main agent J and the primer main agent K, the evaluation of the coatability was 3 points, and the evaluation of the crack was "excellent".
Further, from Table 1B, for both the primer main agent J'and the primer main agent K', the evaluation of the coatability was 2 points, and the evaluation of the crack was "excellent".
From these results, it can be seen that the primer base agent B to the primer base agent I are extremely excellent in the evaluation of coatability and also in the evaluation of cracking.
Further, it can be seen that the primer main agent J and the primer main agent K are relatively excellent in the evaluation of coatability and also excellent in the evaluation of cracks.
Further, regarding the primer main agent J'and the primer main agent K', the applicability is evaluated to be sufficiently applicable, and it can be seen that the evaluation of cracks is excellent.
From the above, it can be seen that when the viscosity of the primer main agent at 23 ° C. is 16 Pa · s or more and 600 Pa · s or less, it is evaluated that the coatability is sufficiently applicable and the crack is excellent. In particular, when the viscosity at 23 ° C. is 16 Pa · s or more and 150 Pa · s or less, it is evaluated that the coatability is extremely excellent or relatively excellent, and that the crack is also excellent. ..
On the other hand, regarding the primer main agent A, the applicability was evaluated as 5 points, which was extremely excellent, but the crack evaluation was "impossible", and it was evaluated as defective. At the same time, regarding the primer main agent L, although the crack evaluation is "excellent" and the evaluation is excellent, the applicability evaluation is 1 point, and it can be seen that the evaluation is not possible.
The reason why the crack evaluation of the primer main agent A was "impossible" was that the primer main agent A compared the silane compound A, which has many functional groups contributing to the crosslinking reaction, with the silicone compound A, which has few functional groups contributing to the crosslinking reaction. It is considered that the cause is that the cross-linking reaction proceeded excessively because it contained a large excess amount.
On the other hand, since the primer main agent L contains a large excess amount of the silicone compound A as compared with the silane compound A, it is considered that the cross-linking reaction is suppressed from proceeding excessively and the crack evaluation becomes “excellent”. Be done.
Further, regarding the primer main agent L, the evaluation of the coatability was 1 point because the viscosity of the primer main agent L was a high value (750 Pa ・ s) exceeding 600 Pa · s, so that the resistance at the time of spreading increased. It is thought that this is the cause.

<Primer hardener>
As shown in Table 2 below, the curing agents A to K were obtained by adjusting the catalyst to a predetermined pH using a pH adjusting agent.
The pH of the curing agents A to K was measured as follows.

(1) Put the measurement sample in an amount such that the mass of the tin catalyst is 1 g in a beaker, and weigh the measurement sample.
(2) Add 50 mL of an aqueous NaCl solution (NaCl concentration 10 g / L) to the beaker containing the measurement sample, and stir so that the measurement sample and the aqueous NaCl solution are well mixed.
(3) After stirring and allowing to stand for 10 minutes, an aqueous layer is collected, and the pH of the collected aqueous layer is measured by the method specified in JIS K7371: 2000.

Table 2 below shows the pH measurement results for the curing agents A to K.

First, the curing agent type was fixed, the main agent type was changed, and the primers according to Examples 1 to 12 and the primers according to Comparative Examples 2 and 3 were prepared, and the difference in the characteristics of those primers was evaluated.
The primer according to Comparative Example 1 was prepared using a synthetic oil-based resin. As the synthetic oil-based resin, the trade name "Nitto Harmac XG XG-P" manufactured by Nitto Denko Corporation was used.

[Example 1]
The main agent B shown in Table 1A and the curing agent E shown in Table 2 above were combined to prepare a primer according to Example 1.
In Example 1, a mixture in which a catalyst (tin catalyst) constituting the curing agent E and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent B.
The primer according to Example 1 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.

The coatability was evaluated in the same manner as the coatability of the primer main agent described above.

Regarding heat resistance, the primer according to Example 1 was applied to an iron plate (planar dimension 15 cm × 7 cm, thickness 3.2 mm) as a substrate at a coating amount of 300 g / m ² , and 24 at room temperature (23 ± 1 ° C.). After curing for a long time to form a primer layer on the substrate and leaving the substrate on which the primer layer was formed for 3 months in an environment of 250 ° C., the surface condition of the primer layer was visually observed, and the following criteria were used. It was done by evaluating in.

Excellent: No cracks are found on the surface of the primer layer.
Possible: Cracks are observed on the entire surface of the primer layer.
Impossible: The surface of the primer layer is found to be powdered (thermally decomposed by heating).

The corrosiveness of the salt water plate was evaluated as follows.

(1) The primer according to each example is applied to a substrate to which salt is attached (the amount of application is 300 g / m ² ).
(2) The substrate after applying the primer is left at room temperature (23 ± 1 ° C.) for 24 hours, and then the primer is cured at 200 ° C. for 24 hours to form a primer layer on the substrate.
(3) The primer layer is cross-cut. The cross-cut process is carried out by applying a cutter knife blade so as to be perpendicular to the upper surface of the primer layer and making two notches having a length of 10 cm that intersect each other.
(4) An aqueous solution containing salt (salt concentration 5 wt%, pH 6.2 to 7) was used on the primer layer after the cross-cut treatment using a salt spray device (manufactured by Suga Test Instruments Co., Ltd., model: STP-90V-4Z). After spraying 2.) for 72 hours, visually observe the progress of corrosion. The aqueous solution containing salt is sprayed in an environment of 35 ° C., and the spray amount is 1.5 mL ± 0.5 mL with respect to 80 cm ² . This test condition is in accordance with JIS Z 2371: 2015.
(5) "Excellent", "Good", and "Impossible" are evaluated according to the following criteria. Yu: (Class A to B) Almost no rust. Good: (C to D grade) Slightly rusted. Impossible: Class E Half or more rusted.

The results of evaluation of coatability, heat resistance, and corrosiveness on a salt water plate are shown in Table 3 below.

[Example 2]
Primers according to Example 2 were prepared in the same manner as in Example 1 except that the main agent was the main agent C shown in Table 1A.
Also in Example 2, a mixture in which a catalyst (tin catalyst) constituting the curing agent E and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent C.
The primer according to Example 2 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 3 below.

[Example 3]
Primers according to Example 3 were prepared in the same manner as in Example 1 except that the main agent was the main agent D shown in Table 1A.
Also in Example 3, a mixture in which a catalyst (tin catalyst) constituting the curing agent E and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent D.
The primer according to Example 3 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 3 below.

[Example 4]
Primers according to Example 4 were prepared in the same manner as in Example 1 except that the main agent was the main agent E shown in Table 1A above.
Also in Example 4, a mixture in which a catalyst (tin catalyst) constituting the curing agent E and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent E.
The primer according to Example 4 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 3 below.

[Example 5]
Primers according to Example 5 were prepared in the same manner as in Example 1 except that the main agent was the main agent F shown in Table 1A.
Also in Example 5, a mixture in which a catalyst (tin catalyst) constituting the curing agent E and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent F.
The primer according to Example 5 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 3 below.

[Example 6]
Primers according to Example 6 were prepared in the same manner as in Example 1 except that the main agent was the main agent G shown in Table 1A.
Also in Example 6, a mixture in which a catalyst (tin catalyst) constituting the curing agent E and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent G.
The primer according to Example 6 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 3 below.

[Example 7]
Primers according to Example 7 were prepared in the same manner as in Example 1 except that the main agent was the main agent H shown in Table 1A.
Also in Example 7, a mixture in which a catalyst (tin catalyst) constituting the curing agent E and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent H.
The primer according to Example 7 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 3 below.

[Example 8]
Primers according to Example 8 were prepared in the same manner as in Example 1 except that the main agent was the main agent I shown in Table 1A.
Also in Example 8, a mixture in which a catalyst (tin catalyst) constituting the curing agent E and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent I.
The primer according to Example 8 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 3 below.

[Example 9]
Primers according to Example 9 were prepared in the same manner as in Example 1 except that the main agent was the main agent J shown in Table 1A.
Also in Example 9, a mixture in which a catalyst (tin catalyst) constituting the curing agent E and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent J.
The primer according to Example 9 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 3 below.

[Example 10]
Primers according to Example 10 were prepared in the same manner as in Example 1 except that the main agent was the main agent K shown in Table 1A.
Also in Example 10, a mixture in which a catalyst (tin catalyst) constituting the curing agent E and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent K.
The primer according to Example 10 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 3 below.

[Example 11]
Primers according to Example 11 were prepared in the same manner as in Example 1 except that the main agent was J'shown in Table 1B above.
Also in Example 11, a mixture in which a catalyst (tin catalyst) constituting the curing agent E and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent J'.
The primer according to Example 11 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 3 below.

[Example 12]
Primers according to Example 12 were prepared in the same manner as in Example 1 except that the main agent was K'shown in Table 1B above.
Also in Example 12, a mixture in which a catalyst (tin catalyst) constituting the curing agent E and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent K'.
The primer according to Example 12 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 3 below.

[Comparative Example 1]
A primer according to Comparative Example 1 was prepared using a synthetic oil-based resin.
The primer according to Comparative Example 1 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 3 below.

[Comparative Example 2]
Primers according to Comparative Example 2 were prepared in the same manner as in Example 1 except that the main agent was the main agent A shown in Table 1A.
Also in Comparative Example 2, a mixture in which a catalyst (tin catalyst) constituting the curing agent E and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent A.
The primer according to Comparative Example 2 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 3 below.

[Comparative Example 3]
Primers according to Comparative Example 3 were prepared in the same manner as in Example 1 except that the main agent was the main agent L shown in Table 1A.
Also in Comparative Example 3, a mixture in which a catalyst (tin catalyst) constituting the curing agent E and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent L.
The primer according to Comparative Example 3 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 3 below.

From Table 3, it can be seen that none of the primers according to each example was evaluated as "impossible" in terms of heat resistance and corrosiveness on a salt water plate.
Further, the primers according to each example are evaluated at 2 points or more in the item of coatability, and it can be seen that they can be sufficiently applied.
Further, the primers according to Examples 1 to 8 are evaluated with a score of 4 or more in the item of coatability, and it can be seen that they are particularly excellent in coatability.
On the other hand, it can be seen that the primers according to each comparative example are evaluated as "impossible" in any of the items of heat resistance and corrosiveness in the salt water plate.
Further, in particular, the primer according to Comparative Example 3 was evaluated as 1 point in the item of coatability, and it can be seen that construction is not possible.

Next, the main agent type was fixed, the curing agent type was changed, and the primers according to Examples 13 to 22 were prepared, and the difference in the characteristics of those primers was evaluated.

[Example 13]
The main agent H shown in Table 1A above and the curing agent A shown in Table 2 above were combined to prepare a primer according to Example 13.
Also in Example 13, a mixture in which a catalyst (tin catalyst) constituting the curing agent A and a pH adjuster (acetic acid) were mixed in advance was added to the main agent H.
The primer according to Example 13 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 4 below.

[Example 14]
The primer according to Example 14 was prepared in the same manner as in Example 13 except that the curing agent B shown in Table 2 above was used as the curing agent.
Also in Example 14, a mixture in which a catalyst (tin catalyst) constituting the curing agent B and a pH adjuster (acetic acid) were mixed in advance was added to the main agent H.
The primer according to Example 14 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 4 below.

[Example 15]
The primer according to Example 15 was prepared in the same manner as in Example 13 except that the curing agent C shown in Table 2 above was used as the curing agent.
Also in Example 15, a mixture in which a catalyst (tin catalyst) constituting the curing agent C and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent H.
The primer according to Example 15 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 4 below.

[Example 16]
The primer according to Example 16 was prepared in the same manner as in Example 13 except that the curing agent D shown in Table 2 above was used as the curing agent.
Also in Example 16, a mixture in which a catalyst (tin catalyst) constituting the curing agent D and a pH adjuster (acetic acid) were mixed in advance was added to the main agent H.
The primer according to Example 16 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 4 below.

[Example 17]
The primer according to Example 17 was prepared in the same manner as in Example 13 except that the curing agent F shown in Table 2 above was used as the curing agent.
Also in Example 17, a mixture in which a catalyst (tin catalyst) constituting the curing agent F and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent H.
The primer according to Example 17 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 4 below.

[Example 18]
The primer according to Example 18 was prepared in the same manner as in Example 13 except that the curing agent G shown in Table 2 above was used as the curing agent.
Also in Example 18, a mixture in which a catalyst (tin catalyst) constituting the curing agent G and a pH adjuster (acid anhydride coupling agent) were mixed in advance was added to the main agent H.
The primer according to Example 18 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 4 below.

[Example 19]
The primer according to Example 19 was prepared in the same manner as in Example 13 except that the curing agent H shown in Table 2 above was used as the curing agent.
Also in Example 19, a mixture in which a catalyst (tin catalyst) constituting the curing agent H and a pH adjuster (acid anhydride oil) were mixed in advance was added to the main agent H.
The primer according to Example 19 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 4 below.

[Example 20]
The primer according to Example 20 was prepared in the same manner as in Example 13 except that the curing agent I shown in Table 2 above was used as the curing agent.
Also in Example 20, a mixture in which a catalyst (tin catalyst) constituting the curing agent I and a pH adjuster (acid anhydride oil) were mixed in advance was added to the main agent H.
The primer according to Example 20 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 4 below.

[Example 21]
The primer according to Example 21 was prepared in the same manner as in Example 13 except that the curing agent J shown in Table 2 above was used as the curing agent.
The primer according to Example 21 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 4 below.

[Example 22]
The primer according to Example 22 was prepared in the same manner as in Example 13 except that the curing agent K shown in Table 2 above was used as the curing agent.
Also in Example 22, a mixture in which a catalyst (tin catalyst) constituting the curing agent K and a pH adjuster (amine-based silane coupling agent) were mixed in advance was added to the main agent H.
The primer according to Example 22 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate.
These results are shown in Table 4 below.

From Table 4, even when any of the curing agents shown in Table 2 is used, that is, any of the primers according to Examples 13 to 22 has excellent coatability and heat resistance. It turned out to be.
On the other hand, the primer according to Example 13 using the curing agent A, the primer according to Example 21 using the curing agent J, and the primer according to Example 22 using the curing agent K are corroded on the salt water plate. It was found that the evaluation of the property was "impossible", whereas the primer according to Examples 14 to 20 using other curing agents had an evaluation of corrosion on the salt water plate at least "good" or higher. rice field.
From this, it was found that the primer becomes excellent in corrosiveness in a salt water plate by containing a curing agent having a pH of 2 or more and 5 or less.
This is because by adjusting the pH of the curing agent to 2 or more and 5 or less, the adhesion of the primer to a metal member (for example, a metal tube such as a gas pipe) is improved, and the cross-linking reaction of the primer main agent is performed. It is thought that this is partly due to the fact that the metal has come to progress at an appropriate speed.
On the other hand, in the primer containing the curing agent having a pH of less than 2 and the curing agent having a pH of more than 5, the adhesion to the metal member is lowered, so that the primer is formed by the metal member and the primer. It is considered that the surface of the metal member was corroded by the salt water due to the infiltration of salt water through the gap with the primer layer.

Next, the method of adding the catalyst and the pH adjuster constituting the curing agent to the primer main agent was changed to prepare the primer according to Example 23, and the difference in the characteristics of the primer was evaluated.
As the primer according to Example 23, the main agent H shown in Table 1A above and the curing agent E shown in Table 2 above are used, and the catalyst (tin catalyst) and the pH adjuster constituting the curing agent E are used as the main agent H. It was prepared by adding (acid anhydride coupling agent) separately.
More specifically, the pH adjuster constituting the curing agent E was first added to the main agent H, and then the catalyst constituting the curing agent E was added to prepare the primer according to Example 23. ..
When the primer according to Example 23 was evaluated for coatability, heat resistance, and corrosiveness on a salt water plate, the coatability was evaluated as "excellent", the heat resistance was evaluated as "excellent", and the salt water was evaluated. The evaluation of corrosiveness on the plate was "excellent".
That is, in the primer according to Example 23 prepared by separately adding the catalyst and the pH adjuster constituting the curing agent to the primer main agent, the evaluation of corrosiveness on the salt water plate is particularly good. Do you get it.
It is considered that this is partly because the adhesion of the primer to the metal member was further improved by adding the catalyst and the pH adjuster constituting the curing agent separately to the primer main agent. Be done.

<Top coat>
The catalyst, the main component (oil), the colorant, and the thickener were mixed at room temperature at the mass ratios shown in Table 5 below, and the top coats according to Examples 24 to 28, and Comparative Examples 4 and 4 and The top coat according to No. 5 was prepared.
In Example 24, a tin-based catalyst "CE611" (manufactured by Momentive Performance Materials Japan Co., Ltd.) is used as a catalyst, and a silicone oil "KF96-50cp" (Shin-Etsu) is used as a main component (oil). (Made by Chemical Industry Co., Ltd.) was used, and "Alpaste" (manufactured by Toyo Aluminum Co., Ltd.) was used as a colorant.
In Example 25, the same catalyst, main component (oil), and colorant as in Example 24 are used, and "Aerosil (registered trademark) 130" (manufactured by Nippon Aerosil Co., Ltd.) is used as a thickener. board.
In Example 26, the same catalyst, main component (oil), colorant, and thickener as in Example 25 were used.
In Example 27, the same catalyst, colorant, and thickener as in Example 25 are used, and the main component (oil content) is silicone oil "KF96-1000 cp" (manufactured by Shin-Etsu Chemical Co., Ltd.). Using.
In Example 28, the same catalyst, main component (oil), colorant, and thickener as in Example 27 were used.
In Comparative Example 4, a water-based resin (acrylic emulsion resin) was used as the main component (oil), and carbon (BLACK FLTR CONC manufactured by Dainichiseika Kogyo Co., Ltd.) and titanium white (manufactured by Dainichiseika Kogyo Co., Ltd.) were used as colorants. TB807 Pearl) was used.
In Comparative Example 5, the same catalyst, main component (oil), colorant, and thickener as in Example 27 were used.

The viscosity of the top coat according to each example was measured at 23 ° C.
The viscosity of the top coat according to each example at 23 ° C. was measured using a BH type viscometer manufactured by Tokimec Co., Ltd. under the condition of a temperature of 23 ± 1 ° C.
The number of the rotor to be used and the rotation speed of the rotor were selected as follows according to the value V of the viscosity.

・ When V is 4 Pa · s or less (V ≦ 4) Rotor number to be used: No. 2. Rotor rotation speed: 10 rpm
When V exceeds 4 Pa · s and is 10 Pa · s or less (4 <V ≦ 10) Rotor number to be used: No. 3. Rotor rotation speed: 10 rpm
When V exceeds 10 Pa · s and is 50 Pa · s or less (10 <V ≦ 50) Rotor number to be used: No. 6. Rotor rotation speed: 20 rpm
When V exceeds 50 Pa · s and is 100 Pa · s or less (50 <V ≦ 100) Roller number to be used: No. 6. Rotor rotation speed: 10 rpm

In addition, the curability, leveling property, running property, and dripping / pooling property of the tape were evaluated for the top coat according to each example.

Regarding the curability of the tape, a primer (Momentive Performance Materials Japan Co., Ltd.'s "YF3807" as a primer main agent is applied to the entire surface of the blast plate (planar dimension 7 cm x 15 cm, thickness: 3.2 mm). After applying a primer containing "CE611" (tin-based catalyst) manufactured by Momentive Performance Materials Japan Co., Ltd. as a curing agent at 300 g / m ² to form a primer layer on the blast plate. The entire area of the primer layer is covered with an anticorrosion tape (anticorrosion tape according to the above-mentioned Example 1) so that overlap occurs (so that a double portion is generated), and then each example is placed on the anticorrosion tape. After applying the top coat of the above to 200 g / m ² and curing at room temperature (23 ± 1 ° C.) for 24 hours to form a top coat layer, visually check whether the tapes are in close contact with each other. Evaluated by observing.
The curability of the tape was evaluated according to the following criteria.

Yu: The tapes are in close contact with each other.
Impossible: The tapes are not in close contact with each other.

The leveling property was evaluated by visually confirming the unevenness of the surface of the top coat layer formed by applying the top coat to the substrate. The evaluation was performed according to the following criteria.

Excellent: After coating, the unevenness disappears, the surface becomes smooth, and the entire top coat layer is sufficiently thinned.
Good: After application, the unevenness disappears and the surface is smoothed, but there are some parts of the topcoat layer that are not thinned.
Impossible: After application, unevenness does not disappear and the surface does not become smooth.

Regarding the runnability, visually check how much resistance the operator feels when applying the top coat to the substrate using a brush and whether or not streaks due to the brush are formed on the surface of the top coat layer. It was evaluated by confirming at. The evaluation was performed according to the following criteria.

Excellent: No streaks due to the brush are formed on the surface of the top coat layer, and the resistance felt by the operator is light (that is, the coatability is extremely good).
Good: Although no streaks due to the brush are formed on the surface of the top coat layer, the resistance felt by the operator is a little heavy (that is, the applicability is a little good).
Impossible: A streak due to a brush is formed on the surface of the top coat layer, and the resistance felt by the operator is extremely heavy (that is, the applicability is considerably inferior).

The dripping / dripping property was evaluated by visually observing whether or not dripping or dripping occurred after the top coat was applied to the substrate. The evaluation was performed according to the following criteria.

Excellent: No dripping or dripping occurs after application.
Good: No dripping occurs after application, but liquid pools occur locally.
Impossible: Top coat drips from the substrate after application.

The results of evaluation of the curability, leveling property, running property, and dripping / pooling property of the tape are shown in Table 5 below.

From Table 5, none of the top coats according to each example was evaluated as "impossible" in any of the items of tape curability, leveling property, running property, and dripping / pooling property. ..
On the other hand, the top coats according to each comparative example are evaluated as "impossible" in any of the items of tape curability, leveling property, running property, and dripping / pooling property. was there.

<Mastic>
The main component (oil), the inorganic filler, the lightening agent, and the flame retardant were mixed at room temperature at the mass ratios shown in Table 6 below, and the mastics according to Examples 29 to 31 and Comparative Example 6 were mixed. The mastics according to 8 were prepared.
In Example 29, the silicone oil "YF3057" (manufactured by Momentive Performance Materials Japan, hereinafter also referred to as silicone compound B) is used as the main component (oil), and the calcined silica is used as the inorganic filler. And calcium carbonate were used, "Glass Bubbles K46" (manufactured by 3M), which is a silica balloon, was used as a lightweight agent, and aluminum hydroxide was used as a flame retardant.
In Example 30, Example 31, Comparative Example 7, and Comparative Example 8, the same main component (oil), inorganic filler, lightweight agent, and flame retardant as in Example 29 were used.
In Comparative Example 6, isoprene (poly ip manufactured by Idemitsu Kosan Co., Ltd.) was used as the main component (oil), calcium carbonate was used as the inorganic filler, and aluminum hydroxide was used as the flame retardant.

The mass reduction rate and consistency were measured for the mastics according to each example.
In addition, a slump test was conducted on the mastics related to each example, and changes in apparent density were evaluated.

The mass loss rate was measured by determining the mass loss rate after heat treatment at 300 ° C. for 24 hours.
The mass loss rate after heat treatment at 300 ° C. for 24 hours was determined as follows.

(1) The initial mass of the mastic according to each example is measured.
(2) The mastic according to each example is placed in an oven whose internal temperature is adjusted to 300 ° C., exposed for 24 hours, and then the mass of the mastic according to each example is measured.
(3) For the mastic according to each example, the reduction ratio of the mass after exposure to the initial mass at 300 ° C. for 24 hours is calculated.

The results are shown in Table 6 below.

The consistency was measured at 23 ° C. based on JIS K2235-1991 "Petroleum wax 5.10 Consistency test method".
The results are shown in Table 6 below.

The slump test was performed according to the following procedure.

(1) The mastic is formed into a rectangular parallelepiped shape (planar dimension 2.5 cm × 10 cm, thickness 2.5 cm).
(2) Two L-shaped steels are placed 50 mm apart so that one side faces each other (placed so that one side rises in the vertical direction), and two rectangular parallelepiped shaped mastics are placed. Place it so that it straddles both of the L-shaped steels.
(3) After heating at 80 ° C. for 24 hours, how much the mastic hangs down is measured. It should be noted that the degree of sagging of the mastic is measured with reference to the upper end edge of one surface of the L-shaped steel.

The results are shown in Table 6 below.

The evaluation of the change in the apparent density was performed by judging whether or not there was an apparent density.
The presence or absence of changes in the apparent density was photographed by taking photographs of the mastic placed on the test jig, the state immediately after the placement and the state after heating at 80 ° C. for 24 hours after the placement. By comparing the photographs, it was visually judged whether or not the volume had changed.
Specifically, the volume V1 immediately after being placed has a volume V2 of 2/3 or less after being heated at 80 ° C. for 24 hours after being placed, and it is considered as having a volume change. It was evaluated as "None" because the volume of V2 was more than 2/3 with respect to V1 and there was no volume change.
The results are shown in Table 6 below.

From Table 6, in the mastics according to each example, no change in apparent density was observed, and the results of the slump test were all good at 10 mm or less.
On the other hand, in the mastic according to Comparative Example 6, although the result of the slump test was as good as 10 mm or less, a change in apparent density was observed.
Further, although the mastics according to Comparative Examples 7 and 8 did not show any change in the apparent density, they could not be molded into a sample (planar dimension 2.5 cm × 10 cm, thickness 2.5 cm) for performing the slump test. , I couldn't even do the slump test.

1 Primer layer 2 Anti-corrosion layer 3 Top coat layer 4 Anti-corrosion mastic layer 10 Metal member 11 Flange part 12 Bolt 13 Nut 100 Anti-corrosion structure

Claims (10)

A primer as an anticorrosion paste applied to an object to be anticorrosed is used, and a primer layer formed by the primer and an anticorrosion layer made of an anticorrosion tape laminated on the primer layer are provided.
The primer contains a main agent and a curing agent.
The main agent contains a silicone compound and has a viscosity at 23 ° C. of 16 Pa · s or more and 600 Pa · s or less .
The anticorrosion tape comprises a fiber sheet and a compound supported on the fiber sheet and containing a silicone compound.
The water content of the compound is 1000 ppm or less.
Anticorrosion structure. The anticorrosion structure according to claim 1 , wherein the compound contains a silicone compound having reaction curability as the silicone compound, and has a viscosity at 23 ° C. of 25 Pa · s or more and 250 Pa · s or less. The anticorrosion structure according to claim 1 or 2 , wherein the fiber sheet has a mass reduction rate of 10% by mass or less after being heat-treated at 300 ° C. for 24 hours. The anticorrosion structure according to any one of claims 1 to 3 , wherein the fiber sheet has a basis weight of 30 g / m ² or more and 150 g / m ² or less. Further provided with a top coat layer laminated on the anticorrosion layer,
The top coat layer is formed of a top coat containing oil.
The anticorrosion structure according to any one of claims 1 to 4 , wherein the oil contains a silicone compound. The anticorrosion structure according to claim 5 , wherein the top coat has a viscosity at 23 ° C. of 0.05 Pa · s or more and 100 Pa · s or less. The anticorrosion structure according to claim 5 or 6 , wherein the top coat further contains a tin-based catalyst. An anticorrosion mastic layer arranged between the primer layer and the anticorrosion layer and formed of an anticorrosion mastic is further provided.
The anticorrosion structure according to any one of claims 1 to 7 , wherein the anticorrosion mastic layer contains a silicone compound. The anticorrosion structure according to claim 8 , wherein the anticorrosion mastic has a consistency of 40 or more and 150 or less. The anticorrosion structure according to claim 8 or 9 , wherein the anticorrosion mastic has a mass reduction rate of 20% by mass or less after being heat-treated at 300 ° C. for 24 hours.

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