JP2022112515A - Primer and anti-corrosion structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a primer or the like that demonstrates improved workability when applied to a substrate and also allows the resultant primer layer to have high heat resistance.

SOLUTION: This primer comprises a main agent and a hardener. The main agent contains a silicone compound, and has a viscosity of 16 Pa s or more and 600 Pa s or less at 23°C.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

TECHNICAL FIELD The present invention relates to a primer and an anti-corrosion structure comprising a primer layer formed of the primer.

Conventionally, it is known to use a primer (undercoat material) when forming some layer on a substrate.

Such a primer is used, for example, when forming an anticorrosion layer in the production of an anticorrosion structure (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 as the base is used. After forming a primer layer by applying the primer to the surface, an anticorrosion tape is wound around the surface of the metal member on which the primer layer is formed to form an anticorrosion layer, thereby producing an anticorrosion structure. It is

Further, as the primer, a primer containing a main agent and a curing agent is known. In such a primer containing the main agent and the curing agent, the main agent contains a silicone compound in order to improve heat resistance and the like. It is also known to have

JP 2018-168455 A

By the way, when the primer containing the silicone compound as the main agent is applied onto the substrate to form the primer layer, the primer can be applied with good workability.
The primer layer formed by applying the primer is placed in a high temperature environment (for example,
200° C. environment), the primer layer may crack.
That is, the primer layer may fail to exhibit sufficient heat resistance.
In addition, although the primer layer formed by applying the primer to the substrate exhibits sufficient heat resistance, workability (workability) of coating the primer onto the substrate may be deteriorated.

However, sufficient studies have not yet been made on how to make the obtained primer layer excellent in heat resistance while improving the coating workability when the primer is applied to the substrate (while ensuring the workability). Hard to say.

Accordingly, the present invention provides a primer that has good coating workability when applied to a substrate (can ensure workability) and that can make the resulting primer layer excellent in heat resistance, and the primer. An object of the present invention is to provide an anti-corrosion structure comprising a primer layer formed by

As a result of extensive studies by the present inventors, in a primer comprising a main agent and a curing agent, the main agent contains a silicone compound and has a viscosity of 16 Pa s or more and 600 at 23 ° C.
By setting the viscosity to be Pa s or less, the workability of applying the primer to the substrate is improved (the workability can be secured), and the primer layer obtained by applying the primer is It has been found that the heat resistance is excellent.
As a result, the present invention has been conceived.

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 of 16 Pa·s or more and 600 Pa·s or less at 23°C.

According to such a configuration, the primer has good coating workability when applied to a substrate (can ensure workability), and the obtained primer layer can have excellent heat resistance.

In the primer,
The main agent has an infrared absorption spectrum of 1200 cm ⁻
It has ^one or more peaks in the range of 1 or more and 1300 cm ^-1 or less and the range of 2800 cm ^-1 or more and 2900 cm ^-1 or less, and 2800 cm ^-1 or more and 2900 cm ^-1
1200 cm ⁻¹ or more 1300 c for height h ₁ of the highest peak appearing in the following range
The ratio h ₂ /h ₁ of the height h ₂ of the highest peak appearing in the range of m ⁻¹ or less is 25 or more and 250
It is preferable that:

According to such a configuration, the primer layer obtained by applying the primer can be further 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 applied to the substrate (can ensure workability), and the obtained primer layer can be excellent in heat resistance. In addition to, the primer layer can be excellent in corrosion resistance.

In the primer,
It is preferable to further contain an antirust agent.

According to such a configuration, when the primer layer formed by the primer is placed on the surface of a metal member such as a metal pipe, the metal member can be prevented from rusting.

In the primer,
It is preferably used as an anti-corrosion paste.

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

The anti-corrosion structure according to the present invention is
A primer is used as an anti-corrosion paste to be applied to the object to be anti-corrosion, 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 of 16 Pa·s or more and 600 Pa·s or less at 23°C.

According to such a configuration, the primer has good coating workability when applied to a substrate (can ensure workability), and the obtained primer layer can have excellent heat resistance.
That is, the anticorrosion structure can be made excellent in heat resistance while forming the primer layer by applying the primer with good coating workability.

In the anticorrosion structure,
Further comprising an anticorrosion layer composed of an anticorrosion tape laminated on the primer layer,
The anticorrosion tape has a fiber sheet and a compound supported by the fiber sheet and containing a silicone compound,
It is preferable that the water content of the compound is 1000 ppm or less.

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

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

According to such a configuration, it is possible to further suppress the acceleration of hardening of the compound carried on the surface layer portion of the fiber sheet, thereby more appropriately controlling the hardening of the compound of the anticorrosion tape. .
As a result, the anticorrosion structure can be made more excellent in heat resistance.

In the anticorrosion structure,
It is preferable that the fiber sheet has a mass reduction rate of 10% by mass or less after heat treatment 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 pipe and the anticorrosion tape can be maintained. can be done.
As a result, the anticorrosion structure can be made 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 can be relatively easily impregnated with the compound. That is, the anticorrosion tape is more sufficiently impregnated with the compound.
Therefore, the anticorrosion tape is further sufficiently hardened in a state of being wound around a metal member such as a metal pipe, thereby further suppressing the formation of a gap between the metal member and the anticorrosion tape. be able to.
Thereby, the anti-corrosion structure can be made more excellent in heat resistance.

In the anticorrosion structure,
Further comprising a topcoat layer laminated on the anticorrosion layer,
The topcoat layer is formed of a topcoat containing oil,
It is preferable that the oil contains a silicone compound.

According to such a configuration, in the state of being laminated on the anticorrosion layer composed of the anticorrosion tape containing the silicone compound, the anticorrosion layer has a relatively high affinity with the anticorrosion layer, and the oil agent is applied to the anticorrosion layer. becomes easier to impregnate.
That is, since a gap is less likely to occur between the topcoat layer and the anticorrosion layer, the anticorrosion property of the anticorrosion structure can be further enhanced.

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

With such a configuration, the top coat can be easily applied to the anticorrosion layer.
In the anticorrosion structure, the topcoat layer can be formed on the anticorrosion layer with a relatively uniform thickness.

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

According to such a configuration, the tin-based catalyst can be moved into the anticorrosion layer from the topcoat layer formed by the topcoat, so that the curing reaction in the anticorrosion layer proceeds more easily.

In the anticorrosion structure,
further comprising an anti-corrosion mastic layer disposed between the primer layer and the anti-corrosion layer and formed of an anti-corrosion mastic;
The anticorrosion mastic layer preferably contains a silicone compound.

According to such a configuration, when the anti-corrosion mastic layer is in contact with the primer layer and the anti-corrosion layer, the anti-corrosion mastic layer has a relatively high affinity with the primer layer and the anti-corrosion layer. becomes.
That is, since it becomes difficult for a gap to occur between the anticorrosion mastic layer and 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 layer is formed by filling the anticorrosion mastic layer between the primer layer and the anticorrosion layer, the filling is relatively easy. The anti-corrosion mastic layer can have relatively good shape retention.

In the anticorrosion structure,
It is preferable that the anticorrosive mastic has a mass reduction rate of 20% by mass or less after heat treatment at 300° C. for 24 hours.

According to such a configuration, after the anticorrosion mastic layer is formed by filling the space between the primer layer and the anticorrosion layer, the anticorrosion mastic layer can have a relatively high density. .
Thereby, the anti-corrosion structure can be made more excellent in heat resistance.

According to the present invention, the coating workability when coating on a substrate is improved (workability can be secured).
Moreover, a primer that can make the obtained primer layer excellent in heat resistance,
And it is possible to provide an anti-corrosion structure comprising a primer layer formed by the primer.

BRIEF DESCRIPTION OF THE DRAWINGS Sectional drawing which shows the structure of the anti-corrosion structure which concerns on one Embodiment of this invention.

An embodiment of the present invention will be described below.

[Primer]
A primer according to one embodiment of the present invention (hereinafter also referred to as a primer according to this embodiment)
contains a main agent and a curing agent.
The primer is preferably used as an anticorrosion paste.
Therefore, below, the primer which concerns on this embodiment demonstrates the example used as an anti-corrosion paste. That is, an example in which the primer according to the present embodiment is applied to the surface of the metal member to form a primer layer 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. Since 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) include straight silicone oil, reactive modified silicone oil, and non-reactive modified silicone oil.
Examples of straight silicone oils include dimethylsilicone oil, methylphenylsilicone oil, and methylhydrogensilicone oil.
The reactive modified silicone oil has an amine group, an epoxy group, a carbinol group, a mercapto group, a carboxyl group, a methacrylic group, a polyether group, a phenol group, a silanol group, an acrylic groups, acid anhydride groups and the like are added.
Examples of the non-reactive modified silicone oil include those having a polyether group, an aralkyl group, a fluoroalkyl group, a long-chain alkyl group, a fatty acid ester, a fatty acid amide, etc. added to a side chain, one end, or both ends. be done.
Commercially available silicone compounds such as those described above include YF3800 (manufactured by Momentive Performance Materials Japan), YF3905 (manufactured by Momentive Performance Materials Japan), YF3057 (Momentive Performance Materials)・Manufactured by Momentive Performance Materials Japan), YF3807 (manufactured by Momentive Performance Materials Japan), YF3802 (manufactured by Momentive Performance Materials Japan), YF3897 (manufactured by Momentive Performance Materials Japan) ), KF9701 (manufactured by Shin-Etsu Chemical Co., Ltd.), PAM-E (
Shin-Etsu Chemical Co., Ltd.), KF-8008 (Shin-Etsu Chemical Co., Ltd.), KF-105 (Shin-Etsu Chemical Co., Ltd.), K
F-2201 (manufactured by Shin-Etsu Chemical Co., Ltd.), WAXKER (registered trademark) SILICONE FLUI
D AK 0.65 to 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 AK100-10,000
(manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), DOWSIL (registered trademark) SF 8427 Flu
id (manufactured by Dow Toray), DOWSIL (registered trademark) BY 16-750 Fluid (
manufactured by Dow and Toray Industries, Inc.).

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 main agent has a viscosity of 16 Pa·s or more and 600 Pa·s or less at 23°C, and more importantly that the viscosity at 23°C is 16 Pa·s or more and 150 Pa·s or less.
By the viscosity of the main agent at 23 ° C. being 16 Pa s or more and 600 Pa s or less,
Since the primer containing the main agent exhibits an appropriate viscosity, when the primer containing the main agent is applied to a substrate (for example, a metal member), it can be applied (to ensure workability). Therefore, when the primer layer formed by applying the primer is exposed to a high-temperature environment (for example, an environment of 200° C.), cracking of the primer layer can be suppressed. That is, the primer layer has excellent heat resistance.
As a result, when the primer is applied to the substrate, the resulting primer layer can be made excellent in heat resistance while improving the coating workability (while ensuring workability).
In addition, since 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 moderate viscosity. The primer layer formed by applying the primer was exposed to a high-temperature environment (for example, an environment of 200 ° C.). Occasionally, cracking of the primer layer can be suppressed. That is, the primer layer has excellent heat resistance.
As a result, it is possible to make the obtained primer layer excellent in heat resistance while further improving the coating workability when the primer is applied to the substrate.
Moreover, the anticorrosion structure provided with such a primer layer can also exhibit sufficient heat resistance.
Furthermore, by forming an anticorrosion layer by winding an anticorrosion tape around the primer layer,
When the anti-corrosion structure is obtained, in the anti-corrosion structure, the adhesion of the anti-corrosion layer to the metal member via the primer layer can be sufficiently ensured, and the anti-corrosion layer and the metal member can be sufficiently secured. can be made sufficiently small.
Thereby, the anti-corrosion structure can exhibit more sufficient heat resistance.

The measurement of the viscosity at 23°C can be carried out at a temperature of 23±1°C using a BH type viscometer manufactured by Tokimec as a measuring device.
The number of the rotor to be used and the number of rotations 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 speed: 10rpm
・When V exceeds 100 Pa·s and is 250 Pa·s or less (100<V≦150) Rotor number to be used: No. 6, rotor 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 speed: 4 rpm

The main agent has an infrared absorption spectrum of 1200 cm ⁻
It is preferable to have ^one or more peaks in the range of 1 to 1300 cm ⁻¹ and in the range of 2800 cm ⁻¹ to 2900 cm ⁻¹ .
In addition, the main agent has a ratio h ₂ of the highest peak appearing in the range of 1200 cm ^-1 to 1300 cm ^-1 to the height h ₁ of the highest peak appearing in the range of 2800 cm ^-1 to 2900 cm ^-1 ₂ /h ₁ is preferably 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 exhibit much more sufficient heat resistance.

The IR measurement of the main agent can be obtained by using Nicolet iS10 manufactured by Thermo Fisher Scientific as a measuring device and adopting the following measurement conditions.
In addition, when the main agent contains a solid content, the solid content is removed by centrifugation in advance, and then the IR measurement of the main agent is performed. For centrifugation, a condition of processing at 47000 rpm for 15 minutes using a Himac CS100GX can be adopted.

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

The main agent includes, in addition to the silicone compound, a resin component, a rust inhibitor, an inorganic filler, and
It may contain a thickening agent.

Examples of the resin component include silane compounds.
Examples of the silane compound include polyalkoxysilane compounds and silicate oligomers having a methoxy group or ethoxy group on a side chain or end, and silane coupling agents modified with an epoxy group, an acid anhydride, or the like.
Examples of commercially available silane compounds include XR31-B2733 (Momentive
Performance Materials Japan Co., Ltd.), XR31-B2230 (Momentive Performance Materials Japan Co., Ltd.), Methyl Silicate 51 (Colcoat Co., Ltd.), Methyl Silicate 53 (Colcote Co., Ltd.), Ethyl Silicate 48 ( Colcoat Co., Ltd.), Silicate 45 (Tama Chemical Industry Co., Ltd.), WACKER (registered trademark) SI
LANE M1-TRIMETHOXY (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), WACKE
R (registered trademark) SILANE M2-DIMETHOXY (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.), KBM-22 (manufactured by Shin-Etsu Chemical Co., Ltd.), XIAMETE
R (registered trademark) OFS-6388 Silane (manufactured by Dow Chemical Japan), DOWS
IL (registered trademark) Z-6329 Silane (manufactured by Dow Toray Industries, Inc.) and the like.

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

Examples of rust inhibitors include inorganic rust inhibitors and organic rust inhibitors.
Examples of the inorganic rust inhibitor include chromates, molybdates, tungstates, phosphates, tripolyphosphates, phosphites, hypophosphites, silicates, borates, Phosphorus compounds, zinc oxide, iron oxide, zinc, mica-like iron oxide and the like.
Among these, phosphates, tripolyphosphates, phosphites, zinc oxide and the like are preferably used.
Examples of the organic rust inhibitor include tannic acid, carboxylic acid (oleic acid, dimer acid, naphthenic acid, etc.), carboxylic acid metal soap (lanolin Ca, naphthene Zn, oxidized wax Ca, oxidized wax Ba, etc.), sulfone Acid salts (Na sulfonate, Ca sulfonate, Ba sulfonate, etc.), amine salts, esters (esters obtained by reacting higher fatty acids with glycerin, sorbitan monoisostearate, sorbitan monooleate, etc.).
Commercially available rust inhibitors include K-WHITE#82 (manufactured by Tayca) and K-WHITE#1.
05 (manufactured by Tayca), K-WHITE#108 (manufactured by Tayca), EXPERT NP-5
30 (manufactured by Toho Pigment Industry Co., Ltd.), EXPERT-1530 (manufactured by Toho Pigment Industry Co., Ltd.), EXPER
T-1600 (manufactured by Toho Pigment Industry Co., Ltd.), Heucophos ZPA (manufactured by Heubach Japan), Heucophos ZAM-PLUS (manufactured by Heubach Japan) and the like.

When the main agent contains the antirust agent, the content thereof is preferably 0.1% by mass or more and 25% by mass or less, 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, 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.
Such minerals include sepiolite, attapulgite, fumed silica, bentonite, smectite, hectorite, montmorillonite, and the like.
Moreover, those obtained by organically chemically modifying these minerals may be used.
Commercially available thickeners include LAPONITE-EP (manufactured by BYK), LAPONI
TE-B (manufactured by BYK), Aerosil (registered trademark) 130 (manufactured by Evonik), Aerosil (registered trademark) 200 (manufactured by Evonik), Aerosil (registered trademark) R972 (Ev
onik), Esben N-400 (manufactured by Hojun), PANSIL (manufactured by TOLSA), PANSIL 100 (manufactured by TOLSA), PANSIL 400 (manufactured by TOLSA) and the like.

When the main agent contains the thickener, the content thereof is preferably 0.1% by mass or more and 30% by mass or less, 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 dehydration condensation between the silicone compounds contained in the main agent is accelerated, and in the anticorrosion tape containing a silicone compound and a crosslinking agent, as described later, the silicone compound and the silicone compound are crosslinked. Examples include those having a catalytic ability to promote dehydration condensation with agents.
Examples of the catalyst include organic titanium compounds such as titanium tetraisopropoxide, titanium tetra-normal butoxide, butyl titanate dimer, titanium acetylacetonate, titanium octylene glycolate, and titanium ethylacetoacetate; aluminum tris(acetylacetonate); , aluminum tris(ethylacetoacetate)
zirconium tetra(acetylacetonate), zirconium tributoxyacetylacetonate, zirconium dibutoxydiacetylacetonate, zirconium tetra-normal propoxide, zirconium tetraisopropoxide,
Organic zirconium compounds such as zirconium tetra-normal butoxide, zirconium acylate, zirconium tributoxy stearate, zirconium octoate, zirconyl (2-ethylhexanoate), zirconium (2-ethylhexoate); dibutyltin dioctoate, dibutyltin Organic tin compounds such as dilaurate and dibutyl tin di(2-ethylhexanoate); metal salts of acids; amine compounds such as hexylamine and dodecylamine phosphate, and salts thereof; benzyltriethylammonium acetate; dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine;
These may be used individually by 1 type, and may be used in combination of 2 or more type.
Among these catalysts, organic tin compounds, tin naphthenate, tin oleate, tin butyrate, It is particularly preferred to use tin-based catalysts such as dibutyltin, octyltin and dioctyltin.
Commercially available tin-based catalysts include CE621 (manufactured by Momentive Performance Materials Japan), CE611 (manufactured by Momentive Performance Materials Japan), and CE601 (Momentive Performance Materials).
Japan Co., Ltd.), Neostan U-303 (manufactured by Nitto Kasei Co., Ltd.), Neostan U-81
0 (manufactured by Nitto Kasei Co., Ltd.).

7. The curing agent preferably contains 3% by mass or more and 80% by mass or less of the catalyst.
It is more preferable that the content is not less than 40% by mass and not more than 40% by mass.

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,
and an anticorrosion layer formed by winding an anticorrosion tape in which a compound containing a reaction-curable compound (for example, a silicone compound) is supported on a fiber sheet, wherein the anticorrosion layer is formed from the primer layer to the anticorrosion layer. A tin-based catalyst can be transferred.
As a result, the curing reaction of the compound having the reaction curing property in the anticorrosion layer can be further facilitated.

The curing agent preferably contains a pH adjuster for adjusting the pH of the curing agent in addition to the catalyst.
Examples of the pH adjuster include inorganic acids such as phosphoric acid, hydrochloric acid, nitric acid, 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, acid anhydrides; Examples include additives exhibiting acidity such as material-based silicone oil.
Commercially available products of the acid anhydride-based silane coupling agent include X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.), and commercial products of the acid anhydride-based silicone oil include X-22-1
68AS (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-168A (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-168B
(manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-168P5-B (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

When the curing agent contains, in addition to the catalyst, a pH adjuster for adjusting the pH of the curing agent, when adding the curing agent to the main agent to obtain a primer, the catalyst and 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,
As will be shown in Examples below, it is possible to further suppress corrosion of the surface of metal members (for example, metal pipes such as gas pipes) by inorganic salts such as NaCl.

The pH of the curing agent is preferably 2 or more and 5 or less.
When the curing agent has a pH of 2 or more and 5 or less, the curing of the silicone compound can proceed more sufficiently in the anticorrosive 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 made sufficiently small.
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 an amount of the measurement sample that makes the mass of the tin catalyst 1 g in a beaker, and weigh the measurement sample.
(2) Add 50 NaCl aqueous solution (NaCl concentration 10 g/L) to the beaker containing the measurement sample.
mL is added and stirred so that the measurement sample and the NaCl aqueous solution are well mixed.
(3) After standing for 10 minutes after stirring, the water layer was collected, and the collected water layer was measured according to JIS K7.
371:2000.

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

The metal member 10 is used as a pipeline for transporting fluids. metal member 10
is provided with a plurality of cylindrical tubes having flanges 11 , and the tubes are connected by the flanges 11 . Flanges 11 of adjacent pipes are fixed with bolts 12 and nuts 13 . That is, the metal member 10 has a cylindrical shape, and the outer surface of the metal member 10 is uneven due to the flange portion 11, the bolt 12, the nut 13, and the like.

The anticorrosion structure 100 according to the present embodiment has the primer layer 1, so that the anticorrosion layer 2
and the metal member 10 can be filled, and corrosion of the metal member 10 can be suppressed.
The primer layer 1 is formed by thinly applying the primer according to the present embodiment to the entire outer surface of the cylindrical metal member 10 . Therefore, on the outer surface of the primer layer 1,
The unevenness is formed 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 transferred into the anticorrosion layer 2 .
When the anticorrosive layer 2 contains a silicone compound as a compound, as will be described later, a catalyst such as a tin-based catalyst is moved into the anticorrosive layer 2 to cause a curing reaction of the silicone compound. can be promoted.

In the anti-corrosion structure 100 according to this embodiment, the anti-corrosion layer 2 is made of an anti-corrosion tape.

As the anticorrosion tape constituting the anticorrosion layer 2, one 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), polyparaphenylenebenzobisoxazole fiber (PBO fiber), poly Examples include those constructed using tetrafluoroethylene fibers (PTFE fibers), nylon fibers, and the like.
A nonwoven fabric is preferably used as the fiber sheet. In addition, in this specification,
Non-woven fabric is a concept that includes felt.
The nonwoven fabric has a basis weight (mass per unit area) of 30 g/m ² or more and 150 g/
It is preferable to use one with 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 nonwoven fabric, those produced by various known methods such as spunbond, chemical bond, needle punch, and stitch bond can be employed.
Among the nonwoven fabrics produced by the above-mentioned various methods, it is preferable to use a spunlaced 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 heat treatment at 300° C. for 24 hours.
By using the fiber sheet having the above characteristics, the anticorrosion tape can be made more excellent in heat resistance, and 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 is 3 relative to the mass of the fiber sheet before exposure to 300°C.
It means the percentage loss of mass of the fiber sheet after exposure to 00° C. for 24 hours.

The compound has reaction curability. The compound can have reaction hardenability by including a compound having reaction hardenability.
When the compound contains the reaction-curable compound, it preferably contains a cross-linking agent for crosslinking the reaction-curable compound.
The compound preferably contains a reaction-curing silicone compound as the reaction-curing compound.
Examples of such silicone compounds include straight silicone oil, reactive modified silicone oil, and non-reactive modified silicone oil.
Examples of straight silicone oils include dimethylsilicone oil, methylphenylsilicone oil, and methylhydrogensilicone oil.
The reactive modified silicone oil has an amine group, an epoxy group, a carbinol group, a mercapto group, a carboxyl group, a methacrylic group, a polyether group, a phenol group, a silanol group, an acrylic groups, acid anhydride groups and the like are added.
Examples of the non-reactive modified silicone oil include those having a polyether group, an aralkyl group, a fluoroalkyl group, a long-chain alkyl group, a fatty acid ester, a fatty acid amide, etc. added to a side chain, one end, or both ends. be done.
Commercially available silicone compounds such as those described above include YF3800 (manufactured by Momentive Performance Materials Japan), YF3905 (manufactured by Momentive Performance Materials Japan), YF3057 (Momentive Performance Materials)・Manufactured by Momentive Performance Materials Japan), YF3807 (manufactured by Momentive Performance Materials Japan), YF3802 (manufactured by Momentive Performance Materials Japan), YF3897 (manufactured by Momentive Performance Materials Japan) ), KF9701 (manufactured by Shin-Etsu Chemical Co., Ltd.), PAM-E (
Shin-Etsu Chemical Co., Ltd.), KF-8008 (Shin-Etsu Chemical Co., Ltd.), KF-105 (Shin-Etsu Chemical Co., Ltd.), K
F-2201 (manufactured by Shin-Etsu Chemical Co., Ltd.), WAXKER (registered trademark) SILICONE FLUI
D AK 0.65 to 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 AK100-10,000
(manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), DOWSIL (registered trademark) SF 8427 Flu
id (manufactured by Dow Toray), DOWSIL (registered trademark) BY 16-750 Fluid (
manufactured by Dow and Toray Industries, Inc.).

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, the silicone compound preferably has a silanol group as a reactive group, or an alkoxysilyl group that 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. A chain silicone having hydroxyl groups at both ends such as polydimethylsiloxane diol Oils are particularly preferred.
The silicone oil preferably has a kinematic viscosity at 25° C. of 1000 mm ² /s or more and 5000 mm ² /s or less 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 silicone compounds that condense with the above-described polydimethylsiloxane diol or the like by dealcoholization.
Examples of such silicone compounds include polyalkoxysilane compounds and silicate oligomers having methoxy or ethoxy groups in side chains or terminals, and silane coupling agents modified with epoxy groups or 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 Methyl Silicate 51 (manufactured by Colcoat). ), methyl silicate 53 (manufactured by Colcoat), methyl silicate 48 (manufactured by Colcoat), silicate 45 (manufactured by Tama Chemical Industry), WACKER (registered trademark) SILAN
E M1-TRIMETHOXY (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), WACKER (registered trademark) SILANE M2-DIMETHOXY (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.),
KBM-13 (manufactured by Shin-Etsu Chemical Co., Ltd.), KBM-22 (manufactured by Shin-Etsu Chemical Co., Ltd.), XIAMETER (registered trademark) OFS-6383 Silane (manufactured by Dow Chemical Japan), DOWSIL (
registered trademark) Z-6329 Silane (manufactured by Dow Toray Industries, Inc.).

As such a silicone compound, one having one or more alkoxy groups is suitable.
A polyalkoxypolysiloxane represented by the following general formula (1) is preferably used as a cross-linking agent for cross-linking the above silicone oil having a chain structure.
Among 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１
００以下の整数である）

(R in formula (1) is an alkyl group with the same or different carbon atoms, n is 1 or more 1
is an integer less than or equal to 00)

Specific names of the cross-linking agent include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, vinyltrimethoxysilane, and phenyltrimethoxysilane. trifunctional alkoxysilanes such as; tetramethoxysilane, tetraethoxysilane,
Tetrafunctional alkoxysilanes such as tetrapropoxysilane; methyltripropenoxysilane, methyltriacetoxysilane, vinyltriacetoxysilane, methyltri(butanoxime)silane, propyltri(butanoxime)silane, phenyltri(butanoxime)silane, propyltri( butanoxime)silane, tetra(butanoxime)silane, 3,3,3
-trifluoropropyltri(butanoxime)silane, 3-chloropropyltri(butanoxime)silane, methyltri(propanoxime)silane, methyltri(pentanoxime)
silane, methyltri(isopentanoxime)silane, vinyltri(cyclopentanoxime)silane, methyltri(cyclohexanoxime)silane, and the like.
The crosslinker 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, 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.

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 with respect to 100 parts by mass of the silicone compound,
It is more preferably 0.1 parts by mass or more and 7 parts by mass or less.

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

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.
Further, when the compound contains calcium carbonate and calcium hydroxide as the inorganic filler, the ratio of the content of calcium carbonate to the content of aluminum hydroxide (content of calcium carbonate / content of aluminum hydroxide amount) is preferably 1 or more and 5 or less.

Further, the silicone oil and the inorganic filler are preferably contained in the compound at a mass ratio (silicone oil:inorganic filler) of 20:80 to 40:60.
The total mass ratio of the silicone oil and the inorganic filler is 50% of the compound.
It is preferably at least 80% by mass, particularly preferably at least 90% by mass.

The compound preferably has a water content of 1000 ppm or less.
Since the water content of the compound is 1000 ppm or less, the anticorrosion tape is wound 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. Sometimes it is possible to better control the cure of the anti-corrosion tape compound.
As a result, in addition to being able to exhibit sufficient heat resistance in the anticorrosion structure 100,
Sufficient corrosion resistance can also be exhibited.
The reason for this is considered by the inventors as follows.

As a result of intensive studies by the present inventors, when the water content of the compound containing the silicone compound is relatively high (the water content exceeds 1000 ppm), among the compounds supported on the fiber sheet, the fiber sheet The curing of the compound carried on the surface layer portion of the fiber sheet progresses faster than the compound carried on the inside of the fiber sheet, and the curing of the compound carried on the inside of the fiber sheet does not progress sufficiently.
Such a phenomenon occurs when the primer layer 1 is laminated on one side of the anticorrosion layer 2 and the topcoat layer 3 is laminated on the other side, as in the anticorrosion structure 100 according to the present embodiment. ,
It becomes more pronounced when the catalyst contained in these layers migrates to the anticorrosion layer 2 . In particular,
The surface layer of the anticorrosion layer 2 hardens due to the hardening reaction that occurs in the surface layer of the anticorrosion layer 2, so that the catalyst cannot sufficiently move into the interior of the anticorrosion layer 2, and the surface layer of the anticorrosion layer 2 is selectively cured. It becomes hardened.
However, when the water content of the compound is a relatively small value of 1000 ppm or less, it is considered that the accelerated hardening of the compound supported on the surface layer portion of the fiber sheet can be suppressed.
Also, as described above, even when the catalyst moves from the primer layer 1 and the topcoat layer 3 to the anticorrosion layer 2, it is possible to suppress the accelerated curing of the compound supported on the surface layer portion of the fiber sheet. It is considered that the catalyst can be sufficiently transferred to the compound supported inside the fiber sheet.
Based on the above, the present inventors have found that the anticorrosion structure 100 according to the present embodiment appropriately controls the curing of the compound supported by the fiber sheet, so that in addition to sufficient heat resistance, sufficient anticorrosion properties are obtained. I think that it is becoming something that can also demonstrate

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

- Measuring device: coulometric titration moisture measuring device (manufactured by Mitsubishi Chemical Analytic Tech, model CA-200), heating and vaporization device (manufactured by Mitsubishi Chemical Analytic Tech, model VA-200)
・Measurement conditions: Heat vaporization method (heated at 150°C)
・Anolyte: Aquamicron AKX (manufactured by Mitsubishi Chemical Corporation)
・ Catholyte: Aquamicron CXU (manufactured by Mitsubishi Chemical Corporation)

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

The measurement of the viscosity at 23°C can be carried out at a temperature of 23±1°C using a BH type viscometer manufactured by Tokimec as a measuring device.
The number of the rotor to be used and the number of rotations 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 speed: 10rpm
・When V exceeds 100 Pa·s and is 250 Pa·s or less (100<V≦150) Rotor number to be used: No. 6, rotor 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 speed: 4 rpm

The topcoat layer 3 can be formed by applying a topcoat 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).
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, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of the non-reactive modified silicone oil include a side chain, one terminal, or both terminals having a polyether group. , aralkyl groups, fluoroalkyl groups, long-chain alkyl groups, fatty acid esters, and aliphatic amides.
As a commercial product of silicone oil, Shin-Etsu Chemical Co., Ltd. trade name "KF96-50cp
” and the trade name “KF96-1000cp”.

The topcoat preferably contains a catalyst. As the catalyst, the dehydration condensation between the silicone compounds contained in the main agent is accelerated, and in the anticorrosion tape containing a silicone compound and a crosslinking agent, as described later, the silicone compound and the silicone compound are crosslinked. Examples include those having a catalytic ability to promote dehydration condensation with agents.
Examples of the catalyst include organic titanium compounds such as titanium tetraisopropoxide, titanium tetra-normal butoxide, butyl titanate dimer, titanium acetylacetonate, titanium octylene glycolate, and titanium ethylacetoacetate; aluminum tris(acetylacetonate); , aluminum tris(ethylacetoacetate)
zirconium tetra(acetylacetonate), zirconium tributoxyacetylacetonate, zirconium dibutoxydiacetylacetonate, zirconium tetra-normal propoxide, zirconium tetraisopropoxide,
Organic zirconium compounds such as zirconium tetra-normal butoxide, zirconium acylate, zirconium tributoxy stearate, zirconium octoate, zirconyl (2-ethylhexanoate), zirconium (2-ethylhexoate); dibutyltin dioctoate, dibutyltin Organic tin compounds such as dilaurate and dibutyltin di(2-ethylhexanoate); organic carboxylic compounds such as tin naphthenate, tin oleate, tin butyrate, dibutyltin, octyltin, dioctyltin, cobalt naphthenate, and zinc stearate; metal salts of acids; amine compounds such as hexylamine and dodecylamine phosphate, and salts thereof; benzyltriethylammonium acetate; dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine;
These may be used individually by 1 type, and may be used in combination of 2 or more type.
Among these catalysts, organic tin compounds, tin naphthenate, tin oleate, tin butyrate, It is particularly preferred to use tin-based catalysts such as dibutyltin, octyltin and dioctyltin.
Commercially available tin-based catalysts include CE621 (manufactured by Momentive Performance Materials Japan), CE611 (manufactured by Momentive Performance Materials Japan), CE601 (Momentive Performance Materials).
Japan Co., Ltd.), Neostan U-303 (manufactured by Nitto Kasei Co., Ltd.), Neostan U-81
0 (manufactured by Nitto Kasei Co., Ltd.).

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

The topcoat may contain colorants, thickeners, and the like. Commercially available coloring agents include "ALPASTE" (trade name) manufactured by Toyo Aluminum Co., Ltd.; can be mentioned.

The top coat preferably has a viscosity of 0.05 Pa·s or more and 100 Pa·s or less at 23°C.
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 measurement of the viscosity at 23°C can be carried out at a temperature of 23±1°C using a BH type viscometer manufactured by Tokimec as a measuring device.
The number of the rotor to be used and the number of rotations 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 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 speed: 10 rpm
・When V exceeds 10 Pa·s and is 50 Pa·s or less (10<V≦50) Number of rotor to be used: No. 6, rotor speed: 20rpm
・When V exceeds 50 Pa·s and is 100 Pa·s or less (50<V≦100) Rotor number to be used: No. 6, rotor speed: 10rpm

The anti-corrosion mastic layer 4 is formed by filling the concave portions of the primer layer 1 with anti-corrosion mastic so as to reduce the unevenness of the primer layer 1 .
In the anti-corrosion structure 100 according to this embodiment, the anti-corrosion mastic layer 4 is formed by filling the gap between the primer layer 1 and the anti-corrosion layer 2 with the anti-corrosion mastic. As a result, corrosion of the metal member 10 is further suppressed in the anti-corrosion structure 100 according to this embodiment.

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).
Examples of the silicone oil include straight silicone oil, reactive modified silicone oil, and non-reactive modified silicone oil.
Examples of straight silicone oils include dimethylsilicone oil, methylphenylsilicone oil, and methylhydrogensilicone oil.
As the reactive modified silicone oil, 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, an acrylic groups, acid anhydride groups and the like 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 a side chain, one end, or both ends. be done.
Commercially available silicone compounds such as those described above include YF3800 (manufactured by Momentive Performance Materials Japan), YF3905 (manufactured by Momentive Performance Materials Japan), YF3057 (Momentive Performance Materials)・Manufactured by Momentive Performance Materials Japan), YF3807 (manufactured by Momentive Performance Materials Japan), YF3802 (manufactured by Momentive Performance Materials Japan), YF3897 (manufactured by Momentive Performance Materials Japan) ), KF9701 (manufactured by Shin-Etsu Chemical Co., Ltd.), PAM-E (
Shin-Etsu Chemical Co., Ltd.), KF-8008 (Shin-Etsu Chemical Co., Ltd.), KF-105 (Shin-Etsu Chemical Co., Ltd.), K
F-2201 (manufactured by Shin-Etsu Chemical Co., Ltd.), WAXKER (registered trademark) SILICONE FLUI
D AK 0.65 to 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 AK100-10,000
(manufactured by Asahi Kasei Wacker Silicone Co., Ltd.), DOWSIL (registered trademark) SF 8427 Flu
id (manufactured by Dow Toray), DOWSIL (registered trademark) BY 16-750 Fluid (
manufactured by Dow and Toray Industries, Inc.).

The anticorrosion mastic may contain inorganic fillers. Examples of the inorganic filler include aluminum hydroxide, magnesium hydroxide, talc, silica, clay, calcium carbonate, mica, mica-like iron oxide, and metal powder.
The anti-corrosion mastic may contain lightening agents and flame retardants. Examples of the weighting agent include silica balloons, and examples of the flame retardant include aluminum hydroxide.

The anticorrosive 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, the filling is relatively easy.
The anti-corrosion mastic layer 4 can have relatively sufficient shape retention.
The consistency of the anticorrosive mastic is JIS K2235-1991 "petroleum wax 5
. It means a value measured at 23°C based on the 10 Consistency Test Method.

The anti-corrosion mastic preferably has a mass reduction rate of 20% by mass or less after heat treatment at 300° C. for 24 hours.
Since the mass reduction rate is 20% by mass or less, after filling the anticorrosion mastic between the primer layer 1 and the anticorrosion layer 2 to form the anticorrosion mastic layer 4, the anticorrosion mastic layer 4 has a relatively high density. can be
Thereby, the anti-corrosion structure 100 can be made more excellent in heat resistance.
Weight loss of said anti-corrosion mastic means the ratio of weight loss of said anti-corrosion mastic after exposure to 300°C for 24 hours to the weight of said anti-corrosion mastic before exposure to 300°C.

The primer and anticorrosion structure according to the present invention are not limited to the above embodiments. Moreover, the primer and anticorrosion structure according to the present invention are not limited by the above-described effects. Various modifications can be made to the primer and anticorrosion structure according to the present invention without departing from the gist of the present invention.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. The following examples are intended to further illustrate the invention and are not intended to limit the scope of the invention.

<Primer main agent>
A silicone compound A (main component (oil)), a silane compound A as a resin, a rust inhibitor, calcium carbonate as an inorganic filler, and a thickener were added at room temperature (
23±1° C.) to prepare primer main ingredients A to L.
Further, the main primer agent J was placed in a constant temperature bath at 40°C and held for 3 months to prepare a main primer agent J', and the main primer agent K was placed in a constant temperature bath at 40°C and held for 3 months. was prepared as the base primer K' (see Table 1B below).
That is, the primer main agent J' and the primer main agent K' were prepared so as to promote storage.
Viscosity at 23° C. was measured as a property of main primer agents A to L, main primer agent J′, and main primer agent K′.
The viscosities at 23°C of the main primer agents A to L, the main primer agent J', and the main primer agent K' were measured as follows.
Specifically, using a BH type viscometer manufactured by Tokimec as a measuring device, the temperature is 23 ± 1
°C.
The number of the rotor to be used and the number of rotations of the rotor were 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 speed: 10rpm
・V exceeds 100 Pa s and is 250 Pa s or less (100 < V ≤ 250)
Rotor number to be used: No. 6, rotor 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 speed: 4 rpm

In addition, the main primer agents A to L, the main primer agent J′, and the main primer agent K′ were subjected to IR measurement, and the obtained infrared absorption spectrum showed 1200 cm ⁻¹ or more13
The value of the height h ₁ of the highest peak appearing in the range of 00 cm ⁻¹ or less (height of the peak appearing at 1258 cm ⁻¹ ), and the height of the highest peak appearing in the range of 2800 cm ⁻¹ or more and 2900 cm ⁻¹ or less The value of h ₂ (the height of the peak appearing at 2840 cm ⁻¹ ) was determined, and the ratio of the value of h ₂ to the value of h ₁ was determined.
IR measurement of main primer agents A to L, main primer agent J', and main primer agent K' was performed as follows.
Specifically, Nico manufactured by Thermo Fisher Scientific Co., Ltd.
It was obtained by using let iS10 and adopting the following measurement conditions.
In addition, when the main agent contained a solid content, the solid content was removed 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 conditions of processing at 47000 rpm for 15 minutes were adopted.

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

Furthermore, the applicability of main primer agents A to L, main primer agent J', and main primer agent K' was evaluated.
The applicability of the main primer agents A to L, the main primer agent J', and the main primer agent K' is
Substrate (SPCC-SB (planar dimensions 150 mm × 75 mm, thickness 3.2 mm) on one side (coated surface) adjusted to an arithmetic average roughness Ra of 2 μm or more and 10 μm or less by sandblasting)
The workability when each primer main agent was applied with a finger to one side of the primer so that the coating amount was 300 g/m ² was judged according to the following criteria.

5 points: When the primer main agent is applied to the substrate with fingers, it is extremely easy to scoop and apply, so workability is extremely good. Therefore, the surface after application is uniformly finished.
4 points: When the primer main agent is applied to the substrate with fingers, it is relatively easy to scoop and spread relatively easily, 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 fingers, it is somewhat difficult to scoop it up due to its slightly high viscosity, and there is some resistance when spreading it, but the workability is relatively good.
2 points: When the primer main agent is applied to the substrate with fingers, it is difficult to scoop it up due to its high viscosity, and the resistance to spread is large, but the application is sufficiently possible.
1 point: When the primer main agent is applied to the substrate with a finger, it is extremely difficult to scoop it up due to 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 to spread is small, the base primer runs off the substrate.

Further, the main primer agents A to L, the main primer agent J', and the main primer agent K' were evaluated for cracks after coating (hereinafter also simply referred to as cracks).
The cracks of the main primer agents A to L, the main primer agent J', and the main primer agent K' were obtained by sandblasting one side (coated surface) of the substrate (SPCC-SB (planar dimensions: 150 mm x 75 mm, thickness: 3.2 mm) and arithmetically averaging. (Roughness Ra adjusted to 2 μm or more and 10 μm or less) was applied with a finger to one side of each primer base so that the coating amount was 300 g / m ² , and then dried at room temperature (23 ± 1 ° C.) for 24 hours. After that, the substrate was left in a drier at 200° C. for 1 month, the substrate was taken out from the drier, and the surface of the substrate (primer-coated surface) was visually evaluated.
When no cracks were visually observed in the primer main agent after application, it was evaluated as "excellent", and when cracks were observed, it was evaluated as "improper".

Table 1A below shows the viscosity measurement results at 23° C. for the main primers A to L, h
_A value of ₁ , a value of h2, _a value of _h2 /h1, evaluation results of applicability, and evaluation results of cracks are shown.
In addition, in Table 1B below, 23 ° C.
, the viscosity measurement results, the h ₂ /h ₁ value, the applicability evaluation results, and the crack evaluation results.
In Tables 1A and 1B below, silicone compound A is "YF3807" manufactured by Momentive Performance Materials Japan, and silane compound A is "YF3807" manufactured by Momentive Performance Materials Japan. XR31-B2
733", the rust inhibitor is trade name "K-WHITE#82" manufactured by Tayca, and the thickener is trade name "Aerosil (registered trademark) 130" manufactured by Evonik.

From Table 1A, for each of the main primer agents B to G, the applicability evaluation was 5 points, and the crack evaluation was "excellent."
In addition, both the primer main agent H and the primer main agent I were rated as 4 points for applicability and rated as "excellent" for cracking.
Furthermore, both the main primer agent J and the main primer agent K were rated as 3 points for applicability and as "excellent" for cracking.
Further, from Table 1B, both the main primer agent J' and the main primer agent K' were rated as 2 points for applicability and rated as "excellent" for cracking.
From these results, it can be seen that the main primers B to I are highly evaluated for applicability, and are also excellently evaluated for cracking.
In addition, it can be seen that the main primer agent J and the main primer agent K are relatively excellent in applicability evaluation and also excellent in evaluation of cracking.
Furthermore, with respect to the main primer agent J' and the main primer agent K', the applicability was evaluated as sufficiently workable, and the evaluation of cracking was excellent.
From the above, when the viscosity of the primer main agent at 23 ° C. is 16 Pa s or more and 600 Pa s or less, the applicability is evaluated as being sufficiently workable, and the crack is evaluated as being excellent. In particular, the viscosity at 23 ° C. is 16 Pa ·
s or more and 150 Pa·s or less, the applicability is evaluated to be extremely excellent or relatively excellent, and cracking is also evaluated to be excellent.
On the other hand, with respect to the primer main agent A, the applicability was evaluated as 5 points, which is extremely excellent, but the evaluation of cracking was "improper", indicating that it was evaluated as poor. At the same time, regarding the primer main agent L, the evaluation of cracking was "excellent", and although it was evaluated as excellent, the evaluation of the applicability was 1 point, indicating that the application was not possible.
The reason why primer main agent A was evaluated as “impossible” for cracking is that primer main agent A has more functional groups that contribute to the cross-linking reaction than silane compound A, which has fewer functional groups that contribute to the cross-linking reaction. It is considered that the reason for this is that the cross-linking reaction proceeded excessively due to the presence of a large excess amount of the cross-linking reaction.
On the other hand, since the primer main agent L contains a large excess amount of the silicone compound A compared to the silane compound A, excessive progress of the cross-linking reaction is suppressed, and it is considered that the crack evaluation was "excellent". be done.
In addition, the reason why the applicability evaluation of the main primer L was 1 point was that the viscosity of the main primer L was a high value (750 Pa s) exceeding 600 Pa s, so the resistance when spreading was large. This is thought to be the cause.

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

(1) Put an amount of the measurement sample that makes the mass of the tin catalyst 1 g in a beaker, and weigh the measurement sample.
(2) Add 50 NaCl aqueous solution (NaCl concentration 10 g/L) to the beaker containing the measurement sample.
mL is added and stirred so that the measurement sample and the NaCl aqueous solution are well mixed.
(3) After standing for 10 minutes after stirring, the water layer was collected, and the collected water layer was measured according to JIS K7.
371:2000.

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

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

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

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

Regarding heat resistance, the primer according to Example 1 was applied to an iron plate (planar dimensions: 15 cm x 7 cm, thickness: 3.2 mm) as a substrate at a coating amount of 300 g/m ² , and the primer was dried at room temperature (23 ± 1 ° C.) for 2 hours.
After curing for 4 hours, a primer layer was formed on the substrate, and the substrate with the primer layer formed thereon was divided into two layers.
After being left in an environment of 50°C for 3 months, the surface condition of the primer layer was visually observed,
It carried out by evaluating by the following references|standards.

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

The corrosiveness on the saltwater plate was evaluated as follows.

(1) Apply the primer according to each example to the substrate to which salt is attached (the amount of application is 300 g
/m ² ).
(2) After the substrate coated with the primer is left at room temperature (23±1° C.) for 24 hours, the primer is cured at 200° C. for 24 hours to form a primer layer on the substrate.
(3) Crosscut treatment is performed on the primer layer. The cross-cutting treatment is carried out by applying the blade of a cutter knife perpendicularly to the upper surface of the primer layer and making two crossing cuts of 10 cm in length.
(4) An aqueous solution containing salt (salinity concentration 5 wt%, pH 6.2) is applied to the primer layer after the cross-cut treatment using a salt spray device (manufactured by Suga Test Instruments Co., Ltd., model: STP-90V-4Z).
7.2) was sprayed for 72 hours, and then the progress of corrosion was visually observed. The aqueous solution containing salt was sprayed in an environment of 35°C, and the amount of spray was 1.5 mL ± 80 cm ² .
0.5 mL. This test condition complies with JIS Z 2371:2015.
(5) Evaluate "Excellent", "Good", and "Poor" according to the following criteria. Yu: (A
～B grade) Almost no rust. Good: (Class C to D) Slightly rusted. Impossible: Class E More than half rusted.

Table 3 below shows the results of evaluating the applicability, heat resistance, and corrosiveness on a saltwater plate.
It was shown to.

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

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

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

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

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

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

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

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

[Example 10]
A primer according to Example 10 was produced in the same manner as in Example 1, except that the main component was the main component K shown in Table 1A above.
Also in Example 10, a mixture in which the catalyst (tin catalyst) constituting the curing agent E and the 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 applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 3 below.

[Example 11]
Example 11 was prepared in the same manner as in Example 1, except that the main agent J' shown in Table 1B was used as the main agent.
was prepared.
Also in Example 11, the catalyst (tin catalyst) constituting the curing agent E was added to the main agent J'.
and a premixed mixture of a pH adjuster (anhydride coupling agent) was added.
The primer according to Example 11 was evaluated for applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 3 below.

[Example 12]
Example 12 was prepared in the same manner as in Example 1, except that the main agent K' shown in Table 1B was used as the main agent.
was prepared.
Also in Example 12, the catalyst (tin catalyst) constituting the curing agent E was added to the main agent K'.
and a premixed mixture of a pH adjuster (anhydride coupling agent) was added.
The primer according to Example 12 was evaluated for applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 3 below.

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

[Comparative Example 2]
A primer according to Comparative Example 2 was produced in the same manner as in Example 1, except that the main agent A shown in Table 1A was used as the main agent.
Also in Comparative Example 2, a mixture in which the catalyst (tin catalyst) constituting the curing agent E and the 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 applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 3 below.

[Comparative Example 3]
A primer according to Comparative Example 3 was prepared in the same manner as in Example 1, except that the main agent L shown in Table 1A was used as the main agent.
Also in Comparative Example 3, a mixture in which the catalyst (tin catalyst) constituting the curing agent E and the 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 applicability, heat resistance, and corrosiveness on a saltwater 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 "not acceptable" in terms of heat resistance and corrosiveness on a saltwater plate.
In addition, the primer according to each example was evaluated as 2 points or more in the item of applicability, and it can be seen that it is sufficiently workable.
Further, the primers according to Examples 1 to 8 were evaluated as 4 points 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 the respective comparative examples were evaluated as "not good" in either item of heat resistance or corrosiveness on a saltwater plate.
In particular, the primer according to Comparative Example 3 was evaluated as 1 point in the item of applicability, indicating that the primer cannot be applied.

Next, primers according to Examples 13 to 22 were produced by fixing the type of the main agent and changing the type of curing agent, and the difference in properties of these primers was evaluated.

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

[Example 14]
A 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 was used as the curing agent.
Also in Example 14, a mixture in which the catalyst (tin catalyst) constituting the curing agent B and the pH adjuster (acetic acid) were mixed in advance was added to the main agent H.
The primer according to Example 14 was evaluated for applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 4 below.

[Example 15]
A 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 was used as the curing agent.
Also in Example 15, to the main agent H, a mixture in which the catalyst (tin catalyst) constituting the curing agent C and the pH adjuster (acid anhydride coupling agent) were mixed in advance was added.
The primer according to Example 15 was evaluated for applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 4 below.

[Example 16]
A 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 was used as the curing agent.
Also in Example 16, a mixture in which the catalyst (tin catalyst) constituting the curing agent D and the 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 saltwater plate.
These results are shown in Table 4 below.

[Example 17]
A 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 was used as the curing agent.
Also in Example 17, to the main agent H, a mixture in which the catalyst (tin catalyst) constituting the curing agent F and the pH adjuster (acid anhydride coupling agent) were mixed in advance was added.
The primer according to Example 17 was evaluated for applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 4 below.

[Example 18]
A 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 was used as the curing agent.
Also in Example 18, to the main agent H, a mixture in which the catalyst (tin catalyst) constituting the curing agent G and the pH adjuster (acid anhydride coupling agent) were mixed in advance was added.
The primer according to Example 18 was evaluated for applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 4 below.

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

[Example 20]
A 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, to the main agent H, a mixture in which the catalyst (tin catalyst) constituting the curing agent I and the pH adjuster (acid anhydride oil) were mixed in advance was added.
The primer according to Example 20 was evaluated for applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 4 below.

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

[Example 22]
A 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 was used as the curing agent.
Also in Example 22, a mixture in which the catalyst (tin catalyst) constituting the curing agent K and the 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 applicability, heat resistance, and corrosiveness on a saltwater 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, in any of the primers according to Examples 13 to 22, the coatability is excellent and the heat resistance is excellent. It turned out to be
On the other hand, the primer according to Example 13 using curing agent A and Example 21 using curing agent J
and the primer according to Example 22 using the curing agent K, the evaluation of corrosiveness on the saltwater plate was "impossible", whereas the primer according to Example 14 using a curing agent other than this ~2
It was found that the primer according to 0 gave at least a "good" or better evaluation for corrosion on a saltwater plate.
From this, it was found that by containing a curing agent having a pH of 2 or more and 5 or less, the primer becomes excellent in corrosiveness on the salt water plate.
This is because by adjusting the pH of the curing agent to 2 or more and 5 or less, in addition to improving the adhesion of the primer to a metal member (for example, a metal pipe such as a gas pipe), the crosslinking reaction of the main agent of the primer It is thought that one of the reasons for this is that the
On the other hand, a primer containing a curing agent with a pH of less than 2 and a curing agent with a pH of more than 5 reduces the adhesion to the metal member, so that the primer formed by the metal member and the primer It is thought that the surface of the metal member was corroded by the salt water that entered through the gap between the primer layer and the primer layer.

Next, a primer according to Example 23 was produced by changing the method of adding the catalyst and pH adjuster that constitute the curing agent to the main base of the primer, and the difference in the properties of the primer was evaluated.
The primer according to Example 23 uses the main agent H shown in Table 1A above and the curing agent E shown in Table 2 above. (anhydride coupling agent) separately.
More specifically, the primer according to Example 23 was produced by first adding a pH adjuster that constitutes the curing agent E to the main agent H, and then adding a catalyst that constitutes the curing agent E. .
The primer according to Example 23 was evaluated for applicability, heat resistance, and corrosion resistance on a saltwater plate. The corrosiveness evaluation of the plate was "excellent".
That is, the primer according to Example 23, which was produced by separately adding the catalyst and the pH adjuster that constitute the curing agent, to the main agent of the primer, was found to have particularly good corrosiveness evaluation on a saltwater plate. Do you get it.
One reason for this is thought to be that the adhesion of the primer to the metal member was further improved by adding the catalyst and pH adjuster that make up the curing agent separately to the main base of the primer. be done.

<Top coat>
The catalyst, the main component (oil), the colorant, and the thickener were mixed at room temperature in the mass ratios shown in Table 5 below to obtain topcoats according to Examples 24 to 28, and Comparative Examples 4 and A top coat according to No. 5 was produced.
In Example 24, a tin-based catalyst "CE611" (manufactured by Momentive Performance Materials Japan Co., Ltd.) was used as the catalyst, and a silicone oil "KF96-50cp" (Shin-Etsu manufactured by Kagaku Kogyo Co., Ltd.), and as a coloring agent,
Alpaste" (manufactured by Toyo Aluminum Co., Ltd.) was used.
In Example 25, the same catalyst, main component (oil), and colorant as in Example 24 were used, and "Aerosil (registered trademark) 130" (manufactured by Nippon Aerosil Co., Ltd.) was used as the 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 were used,
As the main component (oil), silicone oil "KF96-1000cp" (manufactured by Shin-Etsu Chemical Co., Ltd.) was used.
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 at 23° C. was measured for the topcoat of each example.
The viscosity of the topcoat of each example at 23°C was measured using a BH viscometer manufactured by Tokimec under conditions of a temperature of 23 ± 1°C.
The number of the rotor to be used and the number of rotations of the rotor were 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 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 speed: 10 rpm
・When V exceeds 10 Pa·s and is 50 Pa·s or less (10<V≦50) Number of rotor to be used: No. 6, rotor speed: 20rpm
・When V exceeds 50 Pa·s and is 100 Pa·s or less (50<V≦100) Roller number to be used: No. 6, rotor speed: 10rpm

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

For the curability of the tape, a blast plate (planar dimension 7 cm × 15 cm, thickness: 3.2 m
m) Primer (including "YF3807" manufactured by Momentive Performance Materials Japan Co., Ltd. as the main agent of the primer, and "CE611" manufactured by Momentive Performance Materials Japan Co., Ltd. as the curing agent ( After forming a primer layer on the blast plate by applying 300 g/m ² of a primer containing a tin-based catalyst), an anti-corrosion tape ( The entire area of the primer layer is covered with the anticorrosion tape according to Example 1 described above), and then the topcoat according to each example is applied on the anticorrosion tape at 200 g / m ² and at 2
After forming a top coat layer by curing for 4 hours, it was evaluated by visually observing whether or not the tapes were in close contact with each other.
The curability of the tape was evaluated according to the following criteria.

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

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

Excellent: After application, unevenness is eliminated, the surface is smoothed, and the entire topcoat layer is sufficiently thin.
Good: After application, unevenness disappeared and the surface was smoothed, but there were portions where the topcoat layer was not thinned.
Impossible: Unevenness does not disappear after application, and the surface does not become smooth.

Regarding the runnability, when the topcoat is applied to the substrate using a brush, the operator visually observes how much resistance the operator feels and whether or not streaks are formed on the surface of the topcoat layer by the brush. It was evaluated by checking with Evaluation was performed according to the following criteria.

Excellent: No streaks are formed on the surface of the topcoat layer by the brush, and the operator feels light resistance (that is, extremely good coatability).
Good: Although no streaks were formed on the surface of the topcoat layer by the brush, the operator felt a little heavy resistance (that is, the applicability was slightly good).
Poor: Streaks are formed on the surface of the topcoat layer by the brush, and the operator feels extremely heavy resistance (that is, applicability is considerably poor).

The dripping/pooling property was evaluated by visually observing whether dripping or pooling occurred after the top coat was applied to the substrate. Evaluation was performed according to the following criteria.

Excellent: No dripping or pooling occurs after application.
Good: No dripping occurs after application, but local pooling occurs.
Poor: Topcoat drips off substrate after application.

Table 5 below shows the results of evaluation of tape curability, leveling properties, running properties, and dripping and pooling properties.

From Table 5, it can be seen that the top coat according to each example has tape curability, leveling property, running property,
In addition, none of the items were evaluated as "poor" in any item of dripping/liquid pooling property.
On the other hand, the top coats according to the respective comparative examples were evaluated as "improper" in any of the items of tape curability, leveling property, running property, and dripping/liquid pooling property. was there.

<Mastic>
The main component (oil), the inorganic filler, the weighting agent, and the flame retardant were mixed at room temperature in the mass ratios shown in Table 6 below, and the mastics according to Examples 29 to 31 and Comparative Example 6 were prepared. A mastic according to ~8 was made.
In Example 29, "YF3057" (silicone oil) was used as the main component (oil).
Manufactured by Momentive Performance Materials Japan. hereinafter also referred to as silicone compound B), pyrogenic silica and calcium carbonate are used as inorganic fillers, silica balloon "Glass Bubbles K46" (manufactured by 3M) is used as a lightweight agent, and flame retardants are Aluminum hydroxide was used.
In Example 30, Example 31, Comparative Example 7, and Comparative Example 8, the same main component (oil), inorganic filler, weighting agent, and flame retardant as in Example 29 were used.
In Comparative Example 6, as the main component (oil), isoprene (poly ip manufactured by Idemitsu Kosan Co., Ltd.)
was used, 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 mastic according to each example.
In addition, the mastic according to each example was subjected to a slump test and evaluated for changes in apparent density.

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

(1) Measure the initial mass of the mastic according to each example.
(2) The mastic according to each example is placed in an oven whose internal temperature has been 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 ratio of mass reduction after exposure to 300° C. for 24 hours to the initial mass 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) A mastic is molded into a rectangular parallelepiped shape (2.5 cm×10 cm in plan view and 2.5 cm in thickness).
(2) Two pieces of L-shaped steel are arranged so that one side faces each other with a gap of 50 mm (one side is arranged in the vertical direction), and two mastics are molded into a rectangular parallelepiped shape. It is placed so as to straddle both of the L-shaped steels.
(3) Measure how much the mastic sag after heating at 80° C. for 24 hours.
The degree of sagging of the mastic is measured with reference to the upper edge of one surface of the L-shaped steel.

The results are shown in Table 6 below.

The change in apparent density was evaluated by determining the presence or absence of apparent density.
For the presence or absence of change in apparent density, the mastic placed on the test jig was photographed immediately after being placed and after being heated at 80° C. for 24 hours after being placed. Photographs were compared to visually determine whether or not the volume had changed.
Specifically, if the volume V2 after being heated at 80° C. for 24 hours after being placed is 2/3 or less of the volume V1 immediately after placement, it is determined that there is a change in volume. and V
When the volume of V2 exceeded 2/3 of 1, it was evaluated as "none" as no change in volume.
The results are shown in Table 6 below.

As can be seen from Table 6, the mastics according to the respective examples showed no change in apparent density, and the results of the slump test were all good at 10 mm or less.
In contrast, the mastic according to Comparative Example 6 had a good slump test result of 10 mm or less, but a change in apparent density was observed.
In addition, although the mastics according to Comparative Examples 7 and 8 did not show any change in apparent density, they were samples for performing a slump test (planar dimensions: 2.5 cm x 10 cm, thickness: 2.5 cm).
It was not possible to even perform a slump test because it could not be molded into a uniform shape.

REFERENCE SIGNS LIST 1 primer layer 2 anticorrosion layer 3 topcoat layer 4 anticorrosion mastic layer 10 metal member 11 flange 12 bolt 13 nut 100 anticorrosion structure

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

[Example 14]
A primer according to Example 14 was prepared in the same manner as in Reference Example 1 , except that the curing agent B shown in Table 2 was used as the curing agent.
Also in Example 14, a mixture in which the catalyst (tin catalyst) constituting the curing agent B and the pH adjuster (acetic acid) were mixed in advance was added to the main agent H.
The primer according to Example 14 was evaluated for applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 4 below.

[Example 15]
A primer according to Example 15 was produced in the same manner as in Reference Example 1 , except that the curing agent C shown in Table 2 was used as the curing agent.
Also in Example 15, to the main agent H, a mixture in which the catalyst (tin catalyst) constituting the curing agent C and the pH adjuster (acid anhydride coupling agent) were mixed in advance was added.
The primer according to Example 15 was evaluated for applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 4 below.

[Example 16]
A primer according to Example 16 was prepared in the same manner as in Reference Example 1 , except that the curing agent D shown in Table 2 was used as the curing agent.
Also in Example 16, a mixture in which the catalyst (tin catalyst) constituting the curing agent D and the 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 saltwater plate.
These results are shown in Table 4 below.

[Example 17]
A primer according to Example 17 was produced in the same manner as in Reference Example 1 , except that the curing agent F shown in Table 2 was used as the curing agent.
Also in Example 17, to the main agent H, a mixture in which the catalyst (tin catalyst) constituting the curing agent F and the pH adjuster (acid anhydride coupling agent) were mixed in advance was added.
The primer according to Example 17 was evaluated for applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 4 below.

[Example 18]
A primer according to Example 18 was produced in the same manner as in Reference Example 1 , except that the curing agent G shown in Table 2 was used as the curing agent.
Also in Example 18, to the main agent H, a mixture in which the catalyst (tin catalyst) constituting the curing agent G and the pH adjuster (acid anhydride coupling agent) were mixed in advance was added.
The primer according to Example 18 was evaluated for applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 4 below.

[Example 19]
A primer according to Example 19 was produced in the same manner as in Reference Example 1 , except that the curing agent H shown in Table 2 was used as the curing agent.
Also in Example 19, to the main agent H, a mixture in which the catalyst (tin catalyst) constituting the curing agent H and the pH adjuster (acid anhydride oil) were mixed in advance was added.
The primer according to Example 19 was evaluated for applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 4 below.

[Example 20]
A primer according to Example 20 was prepared in the same manner as in Reference Example 1 , except that Curing Agent I shown in Table 2 above was used as the curing agent.
Also in Example 20, to the main agent H, a mixture in which the catalyst (tin catalyst) constituting the curing agent I and the pH adjuster (acid anhydride oil) were mixed in advance was added.
The primer according to Example 20 was evaluated for applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 4 below.

[ Reference example 2 ]
A primer according to Reference Example 2 was prepared in the same manner as in Reference Example 1 , except that the curing agent J shown in Table 2 was used as the curing agent.
The primer according to Reference Example 2 was evaluated for applicability, heat resistance, and corrosiveness on a saltwater plate.
These results are shown in Table 4 below.

[ Reference example 3 ]
A primer according to Reference Example 3 was prepared in the same manner as in Reference Example 1 , except that the curing agent K shown in Table 2 was used as the curing agent.
Also in Reference Example 3 , a mixture in which the catalyst (tin catalyst) constituting the curing agent K and the pH adjuster (amine-based silane coupling agent) were mixed in advance was added to the main agent H.
The primer according to Reference Example 3 was evaluated for applicability, heat resistance, and corrosiveness on a saltwater 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, in any of the primers according to Reference Examples 1 to 3 and Examples 14 to 20 , the coatability is excellent, and was found to be excellent in heat resistance.
On the other hand, in the primer according to Reference Example 1 using the curing agent A, the primer according to Reference Example 2 using the curing agent J, and the primer according to Reference Example 3 using the curing agent K, corrosion on the salt water plate While the corrosion evaluation was "improper", the primers according to Examples 14 to 20 using other curing agents were found to be at least "good" or higher in corrosion evaluation on the saltwater plate. rice field.
From this, it was found that by containing a curing agent having a pH of 2 or more and 5 or less, the primer becomes excellent in corrosiveness on the salt water plate.
This is because by adjusting the pH of the curing agent to 2 or more and 5 or less, in addition to improving the adhesion of the primer to metal members (for example, metal pipes such as gas pipes), the crosslinking reaction of the main agent of the primer It is thought that one of the reasons for this is that the
On the other hand, a primer containing a curing agent with a pH of less than 2 and a curing agent with a pH of more than 5 reduces the adhesion to the metal member, so that the primer formed by the metal member and the primer It is thought that the surface of the metal member was corroded by the salt water that entered through the gap between the primer layer and the primer layer.

Claims (16)

Equipped with a main agent and a curing agent,
A primer, wherein the main agent contains a silicone compound and has a viscosity of 16 Pa·s or more and 600 Pa·s or less at 23°C. The main agent has an infrared absorption spectrum of 1200 cm ⁻
It has ^one or more peaks in the range of 1 to 1300 cm ⁻¹ and the range of 2800 cm ⁻¹ to 2900 cm ⁻¹ , and 2800 cm ⁻¹ to 2900 cm ⁻¹ .
1200 cm ⁻¹ or more for height h ₁ of the highest peak appearing in the range of ¹ or less 1300
The ratio h ₂ /h ₁ of the height h ₂ of the highest peak appearing in the range of cm ⁻¹ or less is 25 or more and 25
The primer according to claim 1, which is 0 or less. The primer according to claim 1 or 2, wherein the curing agent has a pH of 2 or more and 5 or less as measured by the method specified in JIS K7371:2000. 4. The primer according to any one of claims 1 to 3, further comprising a rust inhibitor. 5. The primer according to any one of claims 1 to 4, which is used as an anticorrosion paste. A primer is used as an anti-corrosion paste to be applied to the object to be anti-corrosion, and a primer layer formed by the primer is provided,
The primer contains a main agent and a curing agent,
The anticorrosion structure, wherein the main agent contains a silicone compound and has a viscosity of 16 Pa·s or more and 600 Pa·s or less at 23°C. Further comprising an anticorrosion layer composed of an anticorrosion tape laminated on the primer layer,
The anticorrosion tape has a fiber sheet and a compound supported by the fiber sheet and containing a silicone compound,
The anti-corrosion structure according to claim 6, wherein the compound has a moisture content of 1000 ppm or less. The anti-corrosion structure according to claim 7, wherein the compound contains a reaction-curable silicone compound as the silicone compound, and has a viscosity of 25 Pa·s or more and 250 Pa·s or less at 23°C. The anti-corrosion structure according to claim 7 or 8, wherein the fiber sheet has a mass reduction rate of 10% by mass or less after heat treatment at 300°C for 24 hours. The anti-corrosion structure according to any one of claims 7 to 9, wherein the fiber sheet has a basis weight of 30 g/ ^m2 or more and 150 g/ ^m2 or less. Further comprising a topcoat layer laminated on the anticorrosion layer,
The topcoat layer is formed of a topcoat containing oil,
The anticorrosion structure according to any one of claims 7 to 10, wherein the oil contains a silicone compound. The anticorrosion structure according to claim 11, wherein the top coat has a viscosity of 0.05 Pa·s or more and 100 Pa·s or less at 23°C. 13. The anticorrosion structure according to claim 11 or 12, wherein said topcoat further comprises a tin-based catalyst. further comprising an anti-corrosion mastic layer disposed between the primer layer and the anti-corrosion layer and formed of an anti-corrosion mastic;
14. Anticorrosion structure according to any one of claims 7 to 13, wherein the anticorrosion mastic layer comprises a silicone compound. The anticorrosion structure according to claim 14, wherein the anticorrosion mastic has a consistency of 40 or more and 150 or less. The anti-corrosion structure according to claim 14 or 15, wherein the anti-corrosion mastic has a mass reduction rate of 20% by mass or less after heat treatment at 300°C for 24 hours.

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