KR20220027037A - Coating composition - Google Patents

Abstract

The present invention is to provide a coating composition capable of forming a coating film that has excellent drying and curing properties and a coating film appearance and is excellent in oil resistance, solvent resistance, chemical resistance, water (hot water) resistance, and anticorrosion, even coating, drying and curing under the low temperature of 15℃ or lower. The present invention relates to a coating composition, a coating film, a coating film-attached substrate, and a manufacturing method thereof. The coating composition comprises: an aromatic epoxy compound (A); an amine-based curing agent (B); a silane coupling agent (C); and a solvent (D1), and may contain a high boiling point compound (E1). The curing agent (B) contains at least one selected from the group consisting of an alicyclic amine, a modified product of the alicyclic amine, an aromatic amine, and a modified product of the aromatic amine. The solvent (D1) is a solvent other than water, that has a boiling point at 1 atom of lower than 200℃ and contains a hydroxy group in a molecule. The compound (E1) is a compound that has a boiling point at 1 atm of 200℃ or higher and lower than 250℃ and contains a hydroxy group in a molecule. Each of the contents of the solvent (D1) and the compound (E1) is 30-150 parts by mass and 0-20 parts by mass with respect to 100 parts by mass of the solid content of the compound (A).

Description

Coating composition {Coating composition}

The present invention relates to a coating composition, a coating film, a substrate with a coating film, and a method for manufacturing the same.

A ship is equipped with a cargo tank specific to a ship type in addition to a ship bottom, waterline part, outboard part, exposed deck, engine room, fuel oil tank, a cascade tank, a lubricating oil tank, a water ballast tank, etc. depending on a ship type. Examples of the ship having such a cargo tank include a bulk carrier for loading solid cargo, an oil tanker for loading crude oil, and an LNG tanker for loading liquefied natural gas (LNG), and various types of ships travel around the world. is sailing

Among these ships, chemical tankers having tanks ranging from many to several dozen and equipped with unloading pumps and pipelines are excellent in transporting small quantities of various types of liquid chemical products with high added value.

The cargo transported by the chemical tanker spans various fields, and specific examples thereof include petrochemical products, animal oils, vegetable oils, organic substances such as molasses, and inorganic substances such as hydrochloric acid and sodium hydroxide. The inner surface of the tank in contact with the cargo is usually protected by stainless steel or formed from an epoxy resin paint or inorganic zinc paint for the purpose of suppressing corrosion by the cargo or maintaining high quality standards of the cargo. Protection by a coating film is performed.

As an epoxy resin-based coating composition used for this purpose, Patent Document 1 discloses a composition containing an epoxy functional resin, an amine curing agent, and an organosilicon compound.

Japanese Patent Publication No. 2017-508598

The epoxy resin-based paint to be coated on the inner surface of the tank, such as the chemical tanker, is determined based on the operation plan of each chemical tanker in charge of cargo transportation. In terms of coating properties, a composition having good drying and curing properties even at low temperatures is excellent in terms of coating workability, and therefore, it is desired by the paint builders.

Conventional compositions such as the composition described in Patent Document 1, for example, when a coating film is formed under a low temperature of 15 ° C. or less, resistance to liquid chemicals, etc. in various fields, water (hot water) resistance and corrosion resistance are insufficient. As there is a trend, there is room for improvement.

In addition, in the case of a paint used for the above purpose, particularly, in the case of a paint containing an alicyclic amine and a modified product thereof as a curing agent, in the case of coating under a low temperature of 15 ° C. or less, the surface of the coating film derived from the curing agent contained is dried. It was also found that shallow cracks on the surface of the coating film (hereinafter also referred to as "checking") occurred during the drying and curing process.

The checking is a shallow crack (crack that does not reach the substrate) on the surface of the coating film as shown in FIG. 1, for example, a large difference occurs in the dry and cured state of the surface layer of the coating film and the inside of the coating film, so that the balance of the contractile force of the coating film It is a coating film defect thought to be caused by the collapse of In the coating film where the checking has occurred, irregular irregularities are formed, and in particular, in the part that becomes the valley of the coating film, since the cleaning operation in the tank cannot be sufficiently performed, there is a possibility that contamination of new cargo may occur due to contamination of previously loaded loads, and , there is a possibility that the substrate may be corroded because it is less than or equal to the film thickness that can protect the substrate.

From these facts, since repair is required for the coating film in which the checking has occurred, the labor and cost are unnecessary for the repair.

In addition, a large difference occurs in the drying and curing conditions of the surface layer of the coating film and the inside of the coating film, mainly in the case of painting and drying and curing under low temperatures such as winter. It is also conceivable that such high-temperature drying and curing is a great burden on the paint contractor in terms of facilities and costs for setting the temperature to a high temperature, especially in winter.

The present invention is an invention intended to solve the problems accompanying the prior art, and has good drying/curing properties and coating film appearance even in the case of coating and drying/curing under a low temperature of 15° C. or less, and also oil resistance, solvent resistance, and resistance An object of the present invention is to provide a coating composition capable of forming a coating film having excellent chemical properties, water (hot water) resistance and corrosion resistance.

MEANS TO SOLVE THE PROBLEM As a result of repeating earnest examination about the method of solving the said subject, the present inventors discovered that the said subject could be solved according to a predetermined|prescribed coating composition, and came to complete this invention. A configuration example of the present invention is as follows.

<1> the aromatic epoxy compound (A), the amine-based curing agent (B), the silane coupling agent (C), and the solvent (D1) may be included, and the high boiling point compound (E1) may be included;

The amine-based curing agent (B) includes at least one selected from the group consisting of alicyclic amines, modified products of alicyclic amines, aromatic amines and modified products of aromatic amines,

The solvent (D1) is a solvent other than water that has a boiling point of less than 200° C. at 1 atm and contains a hydroxyl group in its molecule;

The high boiling point compound (E1) is a compound having a boiling point of 200° C. or higher and less than 250° C. at 1 atm, and containing a hydroxyl group in the molecule;

Content of the said solvent (D1) is 30-150 mass parts with respect to 100 mass parts of solid content of the said aromatic epoxy compound (A),

The content of the high boiling point compound (E1) is 0 to 20 parts by mass based on 100 parts by mass of the solid content of the aromatic epoxy compound (A),

paint composition.

<2> The coating composition according to <1>, wherein the aromatic epoxy compound (A) contains a novolac epoxy resin (A1).

<3> The coating composition according to <2>, wherein the content of the novolak epoxy resin (A1) is 30 mass% or more with respect to 100 mass% of the solid content of the aromatic epoxy compound (A).

<4> 　The aromatic epoxy compound (A) further comprises at least one bisphenol type epoxy resin (A2) selected from the group consisting of bisphenol A type epoxy resin, bisphenol AD type epoxy resin, and bisphenol F type epoxy resin, The coating composition according to <2> or <3>.

<5> 　 The coating composition according to any one of <1> to <4>, wherein the solvent (D1) contains a glycol ether-based solvent.

<6> 　 further containing a pigment (F),

The pigment volume concentration (PVC) of the paint composition is 20-50%,

The coating composition according to any one of <1> to <5>.

<7> 　 The coating composition according to any one of <1> to <6>, wherein the content of the silane coupling agent (C) is 0.1 to 30 parts by mass with respect to 100 parts by mass of the solid content of the aromatic epoxy compound (A).

<8> A coating film formed from the coating composition in any one of <1>-<7>.

<9> A base material with a coating film containing the coating film as described in <8>, and a base material.

<10> The base material with a coating film as described in <9> whose said base material is an inner surface of a tank.

<11> 　 The manufacturing method of the base material with a coating film including the following processes [1] and [2].

[1] Step of coating the coating composition according to any one of <1> to <7> on the substrate

[2] Step of drying the coated coating composition to form a coating film

According to the present invention, even in the case of coating and drying and curing under a low temperature of 15° C. or less, a coating film having good drying and curing properties and a coating film appearance can be formed. and cost can be reduced. In addition, the obtained coating film has excellent oil resistance, solvent resistance, chemical resistance, water (hot water) resistance, and corrosion resistance, so it can be used suitably for steel structures such as ships and bridges, especially cargo tanks in contact with liquid chemical products, etc. , the inner surface of pipelines, etc., and the inner surface of tanks such as cascade tanks, fuel oil tanks and lubricating oil tanks in contact with high-temperature water or boiling water of 50 to 120°C and/or heated chemicals.

BRIEF DESCRIPTION OF THE DRAWINGS It is an external appearance photograph which shows an example (an example of a checked state) of evaluation criteria 1-3 in evaluation of the coating-film external appearance of an Example.
Fig. 2 is a schematic view of a test plate with a sheath or the like used in the corrosion resistance test of Examples.

《Paint composition》

The coating composition (hereinafter also referred to as "the present composition") of one embodiment of the present invention is an aromatic epoxy compound (A) (hereinafter also referred to as "component (A)"). The same is true for other components.], a specific amine-based curing agent (B), a silane coupling agent (C), and a specific solvent (D1) may be included, and a specific high boiling point compound (E1) may be included, and further, the compound (A) ), the content of the solvent (D1) and the compound (E1) is within a specific range.

Although this composition does not need to contain the pigment (F), it is preferable that the pigment (F) is contained.

According to such a present composition, the coating film which shows the said effect can be formed.

In the case of a conventional coating composition, resistance to liquid chemical products, etc., water (hot water) resistance, and corrosion resistance across various fields are insufficient, and, when painting, drying and curing under a low temperature of 15° C. or less, drying/curing properties and coating film appearance In the past, there has been no coating composition capable of simultaneously satisfying high resistance to liquid chemicals, excellent drying/curing properties under low temperature, and appearance of a coating film.

On the other hand, according to the present invention, even when a coating film is formed by coating, drying and curing at a low temperature, the occurrence of checking can be suppressed, and the drying and curing properties are excellent, and furthermore, oil resistance, solvent resistance, chemical resistance, water resistance A coating film excellent also in (hydrothermal) property and corrosion resistance can be easily formed.

The reason why a coating film having good drying and curing properties and a coating film appearance can be formed even at a low temperature by using the present composition is not necessarily clear, but it can be considered as follows.

Since the solvent is volatilized immediately after being applied to the coating material after being applied to the substrate, drying starts from the coating film surface layer and finally reaches the inside of the coating film. There are various factors that affect the drying speed of the coating film, but the effect of temperature is particularly large. do. It is thought that a check becomes easy to occur when the state from which such a dry state differs greatly arises over a long term.

Moreover, the present inventors discovered that it is easy to migrate to a coating-film surface layer especially under a low temperature, and drying and hardening are easy to advance only in a coating-film surface layer in some amine-type hardening|curing agents. Especially under low temperature, in addition to the difference in molecular weight of the epoxy resin in the coating film and the amine-based curing agent, and insufficient affinity, the innumerable voids (intervals caused by air entering) present in the applied composition and coating film It is thought that this is because it is not in the ideal proximity state for the reaction. That is, if there are many such voids, a delay occurs in the reaction inside the coating film, and if the affinity between the epoxy resin and the amine curing agent is insufficient, the reaction inside the coating film is delayed as well as unreacted amine curing agent. It is estimated that it becomes easy to transfer to the surface layer.

On the other hand, as the reason that this composition exhibits the said effect, this composition contains a component (C) and a specific amount of a specific component (D1) together with specific components (A) and (B), so that the parenthesis of each component in a coating film is It is estimated that not only can chemical conversion be improved, but it is because generation|occurrence|production of the space|gap in a composition or a coating film can be suppressed.

Specifically, the specific component (D1) improves the affinity of the components (A) and (B) in the coating film, and in particular even at low temperatures, the reaction of both proceeds ideally, so the drying property of the coating film is improved. Moreover, since it becomes difficult for an unreacted component (B) to transfer to the surface layer, it is thought that checking can be suppressed.

In addition, when the present composition contains component (F), component (F) and components (A) and (B), which are reactive resin components, form a chemical bond via component (C), and the component (F) By suppressing the space|gap which tends to generate|occur|produce in the periphery, since the said reactive resin component becomes an ideal proximity state, it is thought that drying and hardening property of a coating film improve, and, as a result, checking is suppressed.

From the above facts, the present composition can also be said to be a check inhibitory coating composition under low temperature. In addition, according to the present composition, since a coating film exhibiting the above effect can be easily formed, it is suitable for a substrate that is coated and dried and cured at 15° C. or less, specifically, outdoors, in a painting factory, and inside a tank. It is used, and is particularly suitably used on the inner surface of a cargo tank for transporting chemical products and the like. In addition, since the present composition has good drying and curing properties, it can be suitably used even in the case of painting repairs that are more imminent in the coating process.

In the present invention, excellent oil resistance, solvent resistance and chemical resistance specifically refer to oils such as heavy oil, gasoline, naphtha, palm oil, methanol, ethanol, xylene, benzene, methyl isobutyl ketone, 1,2 -Excellent resistance to chemicals such as solvents such as dichloroethane and ethyl acetate, aqueous sodium hydroxide solution, and dilute sulfuric acid.

Since these oils, solvents, and chemicals have a large influence on the coating film, it is considered that the coating films having resistance to these oils, solvents and chemicals have resistance to general oils, solvents and chemicals.

The present composition may be a one-component composition, but is usually a two-component composition comprising a main component containing component (A) and a curing agent component containing component (B). Moreover, it is good also as a three-component type or more composition as needed.

These main components, curing agent components, etc. are usually stored, stored, transported, etc. in separate containers, and mixed immediately before use.

The pigment volume concentration (PVC) of the composition is preferably 20% or more, more preferably 25% or more, from the viewpoint of easily obtaining a composition excellent in coating workability, drying/curing properties and corrosion resistance, Further, it is preferably 50% or less, more preferably 45% or less, still more preferably less than 40%.

If the PVC is below the lower limit, checking may occur in the coating film, especially when it is coated and dried/cured under low temperature, and the drying/curability tends to be poor, and furthermore, the corrosion resistance tends to decrease. Moreover, when the said upper limit is exceeded, there exists a tendency for the coating workability of this composition and the corrosion resistance of the coating film obtained to fall.

The PVC refers to the volume concentration of the total pigment (F) with respect to the volume of the nonvolatile matter in the present composition. PVC can be specifically calculated|required from the following formula (1).

PVC [%] = the sum of the volumes of all pigments in the composition x 100 / the volume of the non-volatile matter in the composition... (1)

The volume of the non-volatile matter in the present composition can be calculated from the non-volatile fraction and true density of the present composition. Even if the said non-volatile fraction and a true density are measured values, it does not matter even if it is the value computed from the raw material to be used.

The non-volatile fraction of the present composition (the content of the heated residue in the present composition) can be calculated as follows.

In accordance with JIS K 5601-1-2: 2008, 1±0.1 g of this composition (eg, the composition immediately after mixing the main component and the curing agent component) is weighed out on a flat-bottomed plate, and the mass is known using a wire. It is calculated by spreading uniformly, leaving it to stand at 23°C for 24 hours, drying it at 110°C for 1 hour and 1 atm pressure, subtracting the mass of the wire from the obtained heating residue, and setting it as a value of mass percentage.

The volume of the pigment can be calculated from the mass and true density of the pigment used. Even if the mass and true density of the said pigment are measured values, it does not matter even if it is the value computed from the raw material to be used. As a measured value, it is computable by isolate|separating a pigment and other components from the nonvolatile matter of this composition, and measuring the mass and true density of the separated pigment, for example.

In addition, in the present specification, among the raw materials (eg, component (A)) constituting the main component or the curing agent component, each solvent (the above component (D1) and the following solvent (D2)) among the main component and the curing agent component) The ingredient is called “solid content”.

<Aromatic Epoxy Compound (A)>

The aromatic epoxy compound (A) is not particularly limited as long as it is an aromatic epoxy compound containing an aromatic ring and an epoxy group in the molecule, and a conventionally known aromatic epoxy compound can be used. Specific examples of component (A) include at least one bisphenol type epoxy resin (A2) selected from the group consisting of novolac epoxy resins (A1), bisphenol A type epoxy resins, bisphenol AD type epoxy resins, and bisphenol F type epoxy resins; Aromatic epoxy compounds (A3) other than resin (A1) and (A2) are mentioned.

By using component (A), a coating film excellent in oil resistance, solvent resistance, chemical resistance, and corrosion resistance can be easily formed.

A component (A) may be used individually by 1 type, and may use 2 or more types. When using 2 or more types, you may use 2 or more types of arbitrary components chosen from the said resin (A1), the said resin (A2), and the said compound (A3).

The content of the solid content of the component (A) in the composition is, from the viewpoint of being able to easily form a coating film having better adhesion to the substrate, coating film strength, oil resistance, solvent resistance, chemical resistance and corrosion resistance, etc., the present composition Preferably it is 10-60 mass % with respect to 100 mass % of non-volatile matter, More preferably, it is 15-50 mass %.

<Novolac Epoxy Resin (A1)>

It is preferable that this composition contains a novolac epoxy resin (A1) especially from points, such as being able to easily form the coating film excellent in oil resistance, solvent resistance, and chemical resistance.

A component (A1) may be used individually by 1 type, and may use 2 or more types.

As a component (A1), the aromatic polymer, oligomer, etc. which contain the structural unit derived from phenol or cresol, and contain two or more epoxy groups in a molecule|numerator are mentioned. As such a component (A1), a phenol novolak-type epoxy resin and a cresol novolak-type epoxy resin are mentioned, for example.

A component (A1) may use a commercial item, As this commercial item, "D.E.N. 425" (manufactured by The Dow Chemical Company, epoxy equivalents 169 to 175, weight average number of epoxy functional groups 2.5, solid content 100% by mass), "D.E.N. 431" (manufactured by The Dow Chemical Company, epoxy equivalents of 172 to 179, weight average number of epoxy functional groups 2.8, solid content 100% by mass), "D.E.N. 438" (manufactured by The Dow Chemical Company, epoxy equivalents of 176 to 181, weight average number of epoxy functional groups 3.6, solid content 100% by mass), and "D.E.N. 439" (manufactured by The Dow Chemical Company, epoxy equivalent 191-210, weight average number of epoxy functional groups 3.8, solid content 100% by mass), cresol novolac-type epoxy resin "EPICLON N-673" (DIC Co., Ltd., epoxy equivalent) 208 to 212, the number of weight average epoxy functional groups 5.4, and solid content 100% by mass).

In addition, an epoxy equivalent is computed based on JISK7236:2001.

The weight average number of epoxy functional groups of the solid content of the component (A1) is excellent in oil resistance, solvent resistance and drying/curing properties, and from the viewpoint of being able to easily form a coating film that does not easily generate deep cracks, preferably 2.5 or more, More preferably, it is 2.8 or more, More preferably, it is 6.0 or less, More preferably, it is 4.5 or less.

When the number of weight average epoxy functional groups of component (A1) is less than the said lower limit, the coating film obtained may be inferior in oiliness and solvent resistance, and also tends to be inferior also in drying and hardenability to some extent by extension. Moreover, when the said upper limit is exceeded, as a result of the internal stress of the coating film obtained becomes large, it exists in the tendency for deep cracks to generate|occur|produce in a coating film, and corrosion resistance may be especially impaired.

The said weight average number of epoxy functional groups is computed by dividing the weight average molecular weight of an epoxy compound by the epoxy equivalent of this epoxy compound.

The weight average molecular weight can be measured using a gel permeation chromatography (GPC) method, for example, under the following measurement conditions.

·Measuring conditions

Apparatus: "HLC-8320GPC" (manufactured by Tosoh Corporation)

Column: "TSKgel Super H4000" + "TSKgel Super H2000" + "TSKgel Super H2000" (all manufactured by Tosoh Corporation)

Eluent: tetrahydrofuran (THF)

Flow rate: 0.6 ml/min

Detector: ShoDex RI-104 manufactured by Showa Denko Co., Ltd.

Column thermostat temperature: 40°C

Standard material: polystyrene

When the present composition contains the component (A1), the content of the solid content is, in particular, from the viewpoint of easily forming a coating film excellent in oil resistance, solvent resistance and chemical resistance, the solid content of the component (A) is 100 mass %, preferably 30 mass% or more, more preferably 40 mass% or more, still more preferably 50 mass% or more, and 100 mass% or less, preferably 90 mass% or less, more preferably 80 mass% or less.

<Bisphenol type epoxy resin (A2)>

The composition may contain at least one bisphenol type epoxy resin (A2) selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol AD type epoxy resin, and a bisphenol F type epoxy resin, and a component (A1) and a component (A2) ) is preferred. By using these components (A1) and (A2) together with the components (B), (C) and (D1), the checking of the coating film is further suppressed even when it is coated, dried and cured at a low temperature of 15° C. or less. can do.

A component (A2) may be used individually by 1 type, and may use 2 or more types.

Component (A2) is a compound other than component (A1).

Examples of the component (A2) include aromatic polymers, oligomers, etc. which contain a structural unit derived from any one of bisphenol A, bisphenol AD, and bisphenol F and contain two or more epoxy groups in the molecule. As such a component (A2), For example, Bisphenol A, such as bisphenol A diglycidyl ether, bisphenol A (poly) propylene oxide diglycidyl ether, bisphenol A (poly) ethylene oxide diglycidyl ether, Condensation products, such as type|mold diglycidyl ether and bisphenol F type|mold diglycidyl ether, are mentioned.

As such a component (A2), a bisphenol A epoxy resin and a bisphenol F epoxy resin are preferable, and a bisphenol A epoxy resin is more preferable.

The component (A2) may use the compound synthesize|combined by a conventionally well-known method, and may use a commercial item.

As said commercial item, it is liquid at normal temperature (25 degreeC, hereinafter the same.), for example, "E-028" (Otake Meishin Chemical Co., Ltd. product, bisphenol A type epoxy resin, epoxy equivalent 180-190, viscosity 12,000 to 15,000 mPa·s/25°C), “jER807” (manufactured by Mitsubishi Chemical Co., Ltd., bisphenol F-type epoxy resin, epoxy equivalent 160 to 175, viscosity 3,000 to 4,500 mPa·s/25°C), etc. are mentioned. . As a semi-solid thing at normal temperature, "jER834" (made by Mitsubishi Chemical Co., Ltd., bisphenol A epoxy resin, epoxy equivalent 230-270) etc. are mentioned. As a solid thing at room temperature, "jER1001" (Mitsubishi Chemical Co., Ltd. product, bisphenol A type epoxy resin, epoxy equivalent 450-500), "jER1004" (Mitsubishi Chemical Co., Ltd. product, bisphenol A type epoxy resin, epoxy equivalent 875) -975), "jER1007" (manufactured by Mitsubishi Chemical Co., Ltd., bisphenol A epoxy resin, epoxy equivalent: 1,750 to 2,200), "jER4005P" (manufactured by Mitsubishi Chemical, bisphenol F epoxy resin, epoxy equivalent 950 to 1,200) ) and the like.

The epoxy equivalent of the solid content of the component (A2) is preferably 200 or more, more preferably from the viewpoint of being able to further suppress the checking of the coating film even when it is coated and dried and cured at a low temperature of 15° C. or less, in particular. is 400 or more, preferably 2200 or less, and more preferably 1200 or less.

When the present composition contains the component (A2), the solid content thereof can suppress checking even when coated and dried and cured at a low temperature of 15° C. or less, and has excellent drying and curing properties, and furthermore, oil resistance , Preferably a 10 mass % or more with respect to 100 mass % of solid content of component (A) from points, such as being able to easily form a coating film excellent in solvent resistance, chemical resistance and corrosion resistance, More preferably, 20 mass % More preferably, it is 70 mass % or less preferably, More preferably, it is 60 mass % or less, More preferably, it is 50 mass % or less.

When content of component (A2) is less than the said minimum, especially when coating, drying and hardening under low temperature of 15 degrees C or less, checking may generate|occur|produce in a coating film. Moreover, when the said upper limit is exceeded, drying and sclerosis|hardenability may be inferior to the coating film obtained to some extent, and there exists a tendency for oil resistance and solvent resistance to also fall.

<Aromatic epoxy compounds (A3) other than the above components (A1) and (A2)>

The aromatic epoxy compound (A3) is not particularly limited as long as it is an aromatic epoxy compound other than the components (A1) and (A2). For example, a polymer containing an aromatic ring in the molecule and two or more epoxy groups in the molecule , oligomers, and reactive diluents.

A component (A3) may be used individually by 1 type, and may use 2 or more types.

Specific examples of the polymer or oligomer in the component (A3) include a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, and a glycidylamine type epoxy resin.

Examples of the reactive diluent include phenyl glycidyl ether, o-cresyl glycidyl ether, and alkylphenyl glycidyl ether (alkyl group having 1 to 20 carbon atoms, preferably 1 to 5 carbon atoms, for example: methylphenyl glycidyl Dil ether, ethylphenyl glycidyl ether, propylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether), phenol glycidyl ether, alkylphenol glycidyl ether, phenol (EO) _n glycidyl ether (repetition number n=3-20, EO _{: -C2H4O-} ), and resorcinol diglycidyl ether are mentioned.

The epoxy equivalent of the solid content of the component (A3) is preferably 210 or less, and more preferably 100 to 210 from the viewpoints of being able to easily form a coating film having more excellent solvent resistance and chemical resistance.

<Amine-based curing agent (B)>

The amine-based curing agent (B) includes at least one selected from the group consisting of an alicyclic amine, a modified product of an alicyclic amine, an aromatic amine, and a modified product of an aromatic amine.

By using this component (B) together with the components (A), (C) and (D1), a coating film excellent in oil resistance, solvent resistance, chemical resistance and corrosion resistance can be easily formed.

A component (B) may be used individually by 1 type, and may use 2 or more types.

The alicyclic amine is preferably an alicyclic polyamine, and the alicyclic polyamine is specifically 1,4-cyclohexanediamine and diaminodicyclohexylmethane (especially 4,4'-methylenebiscyclohexylamine). ), 4,4'-isopropylidenebiscyclohexylamine, norbornanediamine, bis(aminomethyl)cyclohexane, isophoronediamine, mensendiamine (MDA), 2,4-di(4-aminocyclohexylmethyl) ) and aniline.

As the aromatic amine, an aromatic polyamine is preferable. Examples of the aromatic polyamine include bis(aminoalkyl)benzene, bis(aminoalkyl)naphthalene, and a compound having two or more primary amino groups bonded to a benzene ring. there is.

Specific examples of the aromatic polyamine include o-xylylenediamine, m-xylylenediamine (MXDA), p-xylylenediamine, phenylenediamine, naphthalenediamine, diaminodiphenylmethane, 2,2- Bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4, 4'-diaminodiphenylmethane, diaminodiethylphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy -4,4'-diaminobiphenyl, bis(aminomethyl)naphthalene, bis(aminoethyl)naphthalene, etc. are mentioned.

Examples of the modified product of the alicyclic amine and the aromatic amine include a Mannich modified product of an alicyclic amine and/or an aromatic amine, an epoxy adduct of an alicyclic amine and/or an aromatic amine, an alicyclic amine and/or an aromatic amine. The epoxy adduct of a Mannich-modified product of an amine, a styrene-modified product of an alicyclic amine and/or an aromatic amine, or a fatty acid modified product of an alicyclic amine and/or an aromatic amine can be mentioned.

Among these, from the viewpoint of being able to easily form a coating film excellent in solvent resistance and chemical resistance, Mannich-modified products of alicyclic amines and/or aromatic amines, epoxides of alicyclic amines and/or aromatic amines A duct or an epoxy adduct of a Mannich-modified product of an alicyclic amine and/or an aromatic amine is preferable.

Specifically, as the Mannich-modified product, one or two or more phenols, one or two or more aldehydes, and one or two or more amines selected from alicyclic amines and aromatic amines are Mannich. The Mannich-modified amine obtained by condensation is mentioned.

As said phenols, monovalent|monohydric or polyhydric may be sufficient, and although mononuclear or polynuclear may be sufficient, monovalent|monohydric mononuclear phenol is preferable.

Specific examples of the phenols include phenol which is a monovalent mononuclear phenol; resorcinol and hydroquinone which are divalent mononuclear phenols; 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2, which are divalent polynuclear phenols; 6-dihydroxynaphthalene is mentioned.

Further, examples of the phenols include alkylphenol (the number of carbon atoms in the alkyl group: 1 to 10, preferably 1 to 5), halogenated phenol, and alkoxyphenol (the number of carbon atoms in the alkoxy group: 1 to 10, preferably 1 to 5). ), bisphenol A, and bisphenol F.

Examples of the alkylphenol include monohydric phenols such as methylphenol (o, m or p-cresol), ethylphenol, butylphenol, t-butylphenol, octylphenol, nonylphenol, dodecylphenol, and dinonylphenol, , Examples of the halogenated phenol include monohydric phenols such as chlorophenol, and examples of the alkoxyphenol include methoxyphenol.

The phenols may be phenols containing an unsaturated substituent, and the phenols containing an unsaturated substituent include at least one monohydroxyphenyl group in the molecule, and a part of hydrogen atoms in the phenyl group, that is, 1 to 5 of these hydrogen atoms The compound etc. which were substituted with the unsaturated hydrocarbon group are mentioned.

As said unsaturated hydrocarbon group, the phenyl group containing a C1-C30 alkylene group and a C1-C30 alkylene group is mentioned, for example.

Specific examples of the unsaturated substituent-containing phenol include cardanol, isopropenyl phenol, diisopropenyl phenol, butenyl phenol, isobutenyl phenol, cyclohexenyl phenol, and monostyrenated phenol (C ₆ H ₅ -CH=CH-C ₆ H ₄ -OH) and distyrene-ized phenol ((C ₆ H ₅ -CH=CH) ₂ -C ₆ H ₃ -OH).

Among these, as said phenols, a phenol is preferable.

As said aldehydes, formaldehyde, paraformaldehyde, acetaldehyde, etc. are mentioned, Among these, formaldehyde is preferable.

In the case of the Mannich condensation, for example, phenols, aldehydes, and amines may be used in equimolar amounts in theory, but usually, the amount of aldehydes is 0.5 to 2.5 moles per 1 mole of phenols, and the amount of amines is 0.5 to 2.5 moles. It is used in an amount of 2.5 moles and heated at a temperature of about 50 to 180° C. for about 3 to 12 hours.

After completion of the reaction, for example, the reaction product may be heated under reduced pressure to remove moisture and unreacted material.

As said epoxy adduct, 1 type or 2 or more types of amines, such as an alicyclic amine, an aromatic amine, the said Mannich modified product, and 1 type or 2 or more types of epoxy compounds, such as a bisphenol A type epoxy compound, are obtained by reacting .

Preferably the usage-amount of the epoxy resin with respect to 100 mass parts of said amines is 5-50 mass parts.

Examples of the epoxy compound include bisphenol A diglycidyl ether; bisphenol F diglycidyl ether; styrene oxide; cyclohexene oxide; (alkyl) phenols such as phenol, cresol, and t-butylphenol; glycidyl ethers such as butanol, 2-ethylhexanol, and alcohol having 8 to 14 carbon atoms; alkyl glycidyl ethers (eg, Epodil 759 (manufactured by Evonik)).

As component (B), among these, an alicyclic polyamine and its modified product are preferable from the viewpoint of being able to easily form a coating film which is more excellent in solvent resistance, chemical resistance, etc., and the polyamine which has a cyclohexane ring is more 4,4'-methylenebiscyclohexylamine, 2,4-di(4-aminocyclohexylmethyl)aniline, and modified products thereof are particularly preferable.

A commercial item may be used as said alicyclic polyamine, As this commercial item, "Ancamine 2264", "Amicure PACM" (above manufactured by Evonik), etc. are mentioned.

The component (B) may contain an amine curing agent other than an alicyclic amine, a modified product of an alicyclic amine, an aromatic amine, and a modified product of an aromatic amine.

The other amine-based curing agent is not particularly limited, and a conventionally known amine-based curing agent can be used, and specifically, an amine compound such as an aliphatic or heterocyclic amine-based curing agent can be used. Moreover, you may use these modified substances.

In the case of using the other amine-based curing agent, an alicyclic amine, a modified product of an alicyclic amine among the component (B), in particular, in terms of being able to easily form a coating film having better oil resistance, solvent resistance and chemical resistance, The content of the solid content of the aromatic amine and the modified product of the aromatic amine is preferably 30 mass % or more, more preferably 50 mass % or more with respect to 100 mass % of the solid content of component (B). Do.

In the present composition, the total content of the solid content of the components (A) and (B) has a high crosslinking density, and a coating film having superior oil resistance, solvent resistance, chemical resistance and corrosion resistance, etc. can be easily formed. In the present composition, it is preferably 15 to 70 mass%, more preferably 20 to 60 mass%, based on 100 mass% of the nonvolatile matter of the present composition.

The content of the component (B) in the composition can easily obtain a composition excellent in drying and curing properties, and can easily form a coating film excellent in oil resistance, solvent resistance, chemical resistance and corrosion resistance, etc. The reaction ratio calculated by (2) is preferably 0.5 or more, more preferably 0.6 or more, and preferably 1.3 or less, more preferably 1.0 or less.

When the reaction ratio is less than the above lower limit, the amount of unreacted epoxy groups in the composition (coating film) increases, so that drying and curing properties tend to be inferior.

Reaction ratio = a (blending amount of solid content of component (B) / equivalent of active hydrogen in solid content of component (B)) + (blending amount of solid content of component having reactivity with component (A) / reactivity with respect to component (A) The functional group equivalent of the solid content of the component having) ｝ / ｛ (the compounding amount of the solid content of the component (A) / the epoxy equivalent of the solid content of the component (A)) + (the compounding amount of the solid content of the component having reactivity with the component (B) / component ( Functional group equivalent of the solid content of the component having reactivity with B) ... (2)

Here, as "a component having reactivity with respect to component (B)" in said Formula (2), the silane coupling agent (C) mentioned later is mentioned, for example, Furthermore, "with respect to component (A)" As a reactive component", the silane coupling agent (C) mentioned later is mentioned, for example. The "functional group equivalent" of each component means the mass (g) per 1 mol functional group obtained by dividing the number of mols of the functional groups contained therein from the mass of 1 mol of the solid content of these components.

As the silane coupling agent (C) to be described later, since a silane coupling agent having an amino group or an epoxy group as a reactive group can be used, depending on the type of the reactive group, whether the silane coupling agent has reactivity with the component (A); It is necessary to judge whether it has reactivity with respect to component (B), and to compute a reaction ratio.

<Silane coupling agent (C)>

The composition comprises a silane coupling agent (C).

By using the component (C) together with the components (A), (B) and (D1), it is possible to easily form a coating film excellent in adhesion to the substrate, and to apply coating and drying at a low temperature of 15° C. or less. Even when it hardens|cures, the checking of a coating film can be suppressed, Furthermore, drying and sclerosis|hardenability can be improved.

A component (C) may be used individually by 1 type, and may use 2 or more types.

Component C) is not particularly limited, and a conventionally known compound can be used, but it is a compound that has two or more hydrolysable groups in the same molecule and can contribute to improvement of adhesion to a substrate, decrease in viscosity of the present composition, etc. It is preferable, and it is more preferable that it is a compound represented by the following formula.

[n is 0 or 1, and X is a functional group capable of reacting with an organic substance (eg, an amino group, a vinyl group, an epoxy group, a mercapto group, a halogeno group, a group in which a part of the hydrocarbon group is substituted with these groups, or a hydrocarbon group) A group in which a part of the group is substituted with an ether bond or the like is partially substituted with these groups.), Me is a methyl group, and Y represents a hydrolyzable group (eg, an alkoxy group such as a methoxy group or an ethoxy group).

Among these, by using an epoxy group-containing alkoxysilane compound in which X is an epoxy group, the adhesion of the resulting coating film to the substrate is further improved, and even when coated, dried and cured at a low temperature of 15° C. or less, the checking of the coating film is more suppression, and furthermore, drying and sclerosis|hardenability can be improved.

As a preferable component (C), specifically, "KBM403" (manufactured by Shin-Etsu Chemical Industries, Ltd.), which is γ-glycidoxypropyltrimethoxysilane, “Sylaace S-510” (manufactured by JNC Corporation) and the like.

The content of component (C) in the composition is 100 nonvolatile matter of the composition from the viewpoint of being able to easily form a coating film excellent in adhesion to a substrate, drying/curing properties, oil resistance, solvent resistance, chemical resistance and corrosion resistance. Preferably it is 0.05-15 mass % with respect to mass %, More preferably, it is 0.1-10 mass %, More preferably, it is 0.2-5 mass %.

Further, the content of the component (C) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, still more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the solid content of the component (A). .

When the content of the component (C) is less than the above lower limit, the adhesion to the substrate tends to decrease, and checking may occur in the coating film coated and dried/cured under a low temperature of 15° C. or less, and furthermore, drying/curing may occur. The hardenability also tends to be somewhat inferior. In addition, when the above upper limit is exceeded, as a result of increasing the internal stress of the obtained coating film, there is a tendency that deep cracks are likely to occur in the coating film, and oil resistance, solvent resistance, chemical resistance, and corrosion resistance may be impaired.

<Solvent (D1)>

This composition contains a solvent (D1) other than water which has a boiling point in 1 atm of less than 200 degreeC, and contains a hydroxyl group in a molecule|numerator.

By including component (D1), even when a semi-solid or solid compound is used as component (A), especially component (A), a uniform solution can be obtained, and a coating composition having appropriate coating workability can be easily obtained can In addition, by using a specific amount of component (D1) together with the above components (A), (B) and (C), it is possible to suppress checking of the coating film at the time of coating and drying/curing under low temperature, and drying/curing It is also excellent in curability, and furthermore, a coating film excellent in oil resistance, solvent resistance, chemical resistance and corrosion resistance can be easily formed.

A component (D1) may be used individually by 1 type, and may use 2 or more types.

Examples of the component (D1) include an alcohol-based solvent, a glycol ether-based solvent, an alcohol ester-based solvent, and an alcohol ketone-based solvent. Among these, from the point of being able to suppress more the checking of the coating film at the time of coating and drying and hardening under low temperature, and further improving drying and sclerosis|hardenability, component (D1) is an alcohol solvent, glycol ether It is preferable that it is a system solvent, and it is more preferable that it is a glycol ether system solvent.

The alcohol-based solvent is a solvent having a hydroxyl group in the molecule, and specifically, methyl alcohol, ethyl alcohol, isopropyl alcohol, normal propyl alcohol, isobutyl alcohol, normal butyl alcohol, 2-ethylbutyl alcohol, and 2-ethylhexyl alcohol. and monohydric alcohols such as , cyclohexanol, methylamyl alcohol and phenol, and dihydric alcohols such as ethylene glycol and propylene glycol.

The glycol ether solvent is a solvent having both a hydroxyl group and an ether group in the molecule, and specifically, propylene glycol monomethyl ether (1-methoxy-2-propanol), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Ethylene glycol monobutyl ether (butyl cellosolve), 3-methoxy-3-methyl-1-butanol, ethylene glycol monopropyl ether, etc. are mentioned.

The boiling point at 1 atmosphere of component (D1) is preferable from the viewpoint of being able to suppress residual solvent in the obtained dry coating film, and in particular, a coating film excellent in oil resistance, solvent resistance, chemical resistance and corrosion resistance can be easily obtained. Preferably it is 180 degrees C or less, More preferably, it is 170 degrees C or less, More preferably, it is 150 degrees C or less.

The content of component (D1) in the composition can suppress the checking of the coating film even when it is coated and dried and cured at a low temperature of 15° C. or less, and furthermore, it is excellent in drying and curing properties, and oil resistance, solvent resistance, and resistance From the viewpoint of being able to easily form a coating film having better chemical properties and corrosion resistance, etc., it is preferably 5 to 30 mass%, more preferably 10 to 25 mass%, based on 100 mass% of the composition, It is 30-150 mass parts with respect to 100 mass parts of solid content of A), Preferably it is 40-110 mass parts, Preferably it is 50-500 mass parts with respect to 100 mass parts of solid content of component (B), More preferably 100 to 400 parts by mass.

When content of component (D1) is less than the said minimum, when coating, drying and hardening under low temperature of 15 degreeC or less, it exists in the tendency for it to become difficult to suppress the checking of a coating film.

<High boiling point compound (E1)>

The composition may contain a high boiling point compound (E1) having a boiling point of 200°C or more and less than 250°C at 1 atm and containing a hydroxyl group in the molecule.

By using the component (E1), it is thought that the checking of the coating film can be more suppressed, especially when it is coated and dried and cured under low temperature, and since it is easy to remain in the dry coating film, the oil resistance, solvent resistance and It is thought that chemical-resistance is easy to fall. For this reason, when it contains component (E1), the content is restrict|limited.

When this composition contains a component (E1), this component (E1) may be used individually by 1 type, and may use 2 or more types.

Examples of the component (E1) include alcohol solvents, glycol ether solvents, alcohol ester solvents, alcohol ketone solvents, and the like. Alcohol solvents, such as phenol, xylenol, and cresol, and glycol ether solvents, such as ethylene glycol phenyl ether, diethylene glycol monobutyl ether, and triethylene glycol monobutyl ether, are mentioned.

The content of component (E1) in the composition can suppress the checking of the coating film even when it is coated and dried and cured at a low temperature of 15° C. or less, and furthermore, it has excellent drying and curing properties, and oil resistance, solvent resistance, and resistance It is 0-20 mass parts with respect to 100 mass parts of solid content of component (A) from points, such as being able to form easily the more excellent coating film, such as chemical|chemical property and corrosion resistance, Preferably it is 0-10 mass parts.

When the content of component (E1) exceeds the above upper limit, the amount of component (E1) remaining in the obtained dry coating film increases, so that various coating film performances such as oil resistance, solvent resistance, chemical resistance and corrosion resistance tend to decrease. there is.

＜Other ingredients＞

In this composition, as other components other than the above components (A) to (E1), a pigment (F), a non-aromatic epoxy compound, an anti-sagging agent (anti-settling agent), a surfactant (eg, Japanese Patent Laid-Open No. 2-298563) (surfactant described in ), dispersant, defoaming agent, leveling agent, surface conditioning agent, curing accelerator (eg tertiary amine), imidazole-based compound, solvent (D2) having a boiling point of less than 200 ° C at 1 atm other than component (D1) Various components, such as a high boiling point compound (E2) whose boiling point at 1 atmospheric pressure other than component (E1) is 200 degreeC or more and less than 250 degreeC, can be mix|blended suitably.

These may use 1 type, respectively, and may use 2 or more types.

In addition, non-reactive components having a boiling point of 250° C. or higher at 1 atm have a very strong tendency to remain in the dry coating film, and particularly tend to easily lower the oil resistance, solvent resistance and chemical resistance of the obtained coating film. desirable.

<Pigment (F)>

The present composition can easily form a coating film particularly excellent in corrosion resistance, and even when it is coated, dried and cured at a low temperature of 15° C. or less, the checking of the coating film can be further suppressed. It is preferable to contain pigments (F), such as a pigment and a rust preventive pigment.

When the present composition is a two-component composition, the pigment (F) may be blended with either one of the main component and the curing agent component, or may be blended with both, but is preferably blended with the main component.

<Pigment of constitution>

Examples of the extender pigment include zinc oxide, talc, silica, mica, clay, potassium feldspar, glass flake, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium sulfate (eg barite powder), gypsum. , and fibrous fillers such as rock wool and glass fiber. Among these, talc, silica, mica, clay, calcium carbonate, kaolin, barium sulfate, potassium feldspar, gypsum, and glass flake are preferable.

When the present composition contains an extender pigment, its content is usually 10-80 mass%, preferably 20-75 mass%, more preferably 30-70 mass%, based on 100 mass% of solid content of the main component, Preferably it is 20-70 mass % with respect to 100 mass % of non-volatile matter of a composition, More preferably, it is 30-60 mass %.

<Color pigment>

As said color pigment, conventionally well-known inorganic pigments, such as carbon black, titanium dioxide (titanium white), iron oxide (Bengala), yellow iron oxide, ultramarine, organic pigments, such as cyanine blue, cyanine green, etc. can be used. Among these, titanium white, carbon black, and Bengala are preferable.

When the present composition contains a coloring pigment, its content is usually 1 to 50 mass%, preferably 1 to 20 mass%, more preferably 2 to 10 mass%, based on 100 mass% of the solid content of the main component, Preferably it is 1-20 mass % with respect to 100 mass % of non-volatile matter of a composition.

<Non-aromatic epoxy compound>

When the present composition is a two-component composition, the non-aromatic epoxy compound is preferably blended with the main component.

The non-aromatic epoxy compound is not particularly limited as long as it is a non-aromatic epoxy compound containing an epoxy group in its molecule, but for example, a hydrogenated novolac-type epoxy resin, a hydrogenated bisphenol F-type epoxy resin, an aliphatic epoxy resin, an alicyclic Epoxy resins such as epoxy resins, and alkyl glycidyl ethers (alkyl groups having 1 to 13 carbon atoms), 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycyl Cydyl ether, cyclohexanedimethanol diglycidyl ether, mono or polyalkylene glycol diglycidyl ether (alkylene group having 1 to 5 carbon atoms, e.g.: ethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether Reactive diluents, such as dil ether, polypropylene glycol diglycidyl ether), and trimethylol propane triglycidyl ether, are mentioned.

As a commercial item of the said reactive diluent, "ERYSIS GE-22" (made by CVC Thermoset Specialties, epoxy equivalent 155, solid content 100 mass %) which is cyclohexane dimethanol diglycidyl ether is mentioned, for example.

<Anti-sagging agent (anti-settling agent)>

Examples of the anti-sagging agent (anti-settling agent) include organic clay waxes such as Al, Ca and Cu stearate salts, lecithin salts, and alkylsulfonates, polyethylene wax, amide wax, hydrogenated castor oil wax, hydrogenated castor oil wax, and A mixture of amide waxes, synthetic finely divided silica, polyethylene oxide wax, and the like can be used. Among them, amide wax, synthetic finely divided silica, polyethylene oxide wax and organoclay wax are preferable.

As such anti-sagging agent (anti-settling agent), "Disparon 305", "Disparon 4200-20", "Disparon 6650" manufactured by Kusumoto Chemical Co., Ltd.; "ASAT-" manufactured by Ito Oil Co., Ltd. 250F"; Products, such as "Flonon RCM-300" by Kyoeisha Chemical Co., Ltd. product, are mentioned.

When the present composition contains an anti-sagging agent (anti-settling agent), the content thereof is, for example, 0.1 to 10 mass% with respect to 100 mass% of the main component.

<curing accelerator>

The composition preferably contains a curing accelerator capable of contributing to the adjustment of the curing rate, particularly the acceleration. When the present composition is a two-component composition, the curing accelerator is preferably blended with the curing agent component.

Examples of the curing accelerator include conventionally known curing accelerators used in coating compositions, and tertiary amines are preferred from the viewpoints of obtaining a coating composition having superior curing rate and low-temperature curing properties.

The tertiary amine is not particularly limited, and for example, triethanolamine, dialkylaminoethanol, triethylenediamine [1,4-diazabicyclo[2.2.2]octane], 2,4,6-tri(dimethyl aminomethyl) phenol (eg, brand name "versamin EH30" (manufactured by BASF Japan Co., Ltd.), brand name "ancamine K-54" (manufactured by Evonik)) is mentioned.

When the present composition contains a curing accelerator, the content thereof is preferably 0.01 to 5 mass%, more preferably 0.05 to 3 mass%, based on 100 mass% of the nonvolatile matter of the present composition.

<Imidazole compound>

This composition may contain the imidazole type compound.

The imidazole-based compound can efficiently and rapidly advance the polymerization of the epoxy groups of the component (A).

When the present composition is a two-component composition, the imidazole-based compound is preferably blended with the curing agent component.

The imidazole-based compound is not particularly limited as long as it has an imidazole group, but 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-heptadecylimidazole, etc. are preferable. Among these, 1-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl- 4-methylimidazole is preferred.

When this composition contains an imidazole type compound, the content becomes like this. Preferably it is 0.01-5 mass parts with respect to 100 mass parts of solid content of component (A).

<Solvent (D2) and high boiling point compound (E2)>

The composition contains a solvent (D2) other than component (D1) having a boiling point of less than 200°C at 1 atm, that is, a solvent (D2) having a boiling point of less than 200°C at 1 atm and containing no hydroxyl group in the molecule. may be included. In addition, the present composition is a high boiling point compound (E2) other than component (E1) having a boiling point of 200°C or more and less than 250°C at 1 atm, that is, a boiling point of 200°C or more and less than 250°C at 1 atm, and a hydroxyl group The high boiling point compound (E2) which is not contained in a molecule|numerator may be included.

Although it does not restrict|limit especially as component (D2) and (E2), For example, an aromatic hydrocarbon type compound (solvent), an aliphatic hydrocarbon type compound (solvent), a ketone type compound (solvent), an ester type compound (solvent), an ether type compound A compound (solvent) and a halogenated hydrocarbon type compound (solvent) are mentioned.

The aromatic hydrocarbon-based compound (solvent) is a compound (solvent) having a benzene ring in the molecule, and examples thereof include benzene, toluene, xylene, ethylbenzene, styrene monomer, C9 aromatic hydrocarbon mixture, and C10 aromatic hydrocarbon mixture.

As the aliphatic hydrocarbon compound (solvent), a paraffinic hydrocarbon compound (solvent) represented by the molecular formula C _n H _2n+2 , an olefinic hydrocarbon compound (solvent) represented by the molecular formula C _n H _2n , one or more saturated rings in the molecule and a naphthenic hydrocarbon compound (solvent) represented by the molecular formula C _n H _2n , and specifically, mineral spirit, n-hexane, n-octane, 2,2,2-trimethylpentane, isooctane, n - Nonane, cyclohexane, methylcyclohexane, etc. are mentioned.

The ketone-based compound (solvent) is a compound (solvent) having a ketone group represented by R-C(=O)-R' (R,R' is an alkyl group, etc.) in a molecule, acetone, methyl ethyl ketone, methyl isobutyl Ketone, methyl amyl ketone, cyclohexanone, etc. are mentioned.

The ester compound (solvent) is a compound (solvent) having an ester group represented by R-C(=O)-OR' (R and R' is an alkyl group, etc.) in the molecule, and is ethyl acetate, butyl acetate, or isobutyl acetate. and the like.

When the present composition contains component (D2), its content is preferably 0 to 80 parts by mass, more preferably 0 to 70 parts by mass, still more preferably 0 to 100 parts by mass of the solid content of component (A). -60 parts by mass.

When content of component (D2) exceeds the said upper limit, when coating, drying and hardening under low temperature of 15 degreeC or less, it exists in the tendency for a checking to become easy to generate|occur|produce in a coating film.

When this composition contains component (E2), Preferably the content is 0-20 mass parts with respect to 100 mass parts of solid content of component (A), More preferably, it is 0-10 mass parts.

When the content of component (E2) exceeds the above upper limit, when coating, drying and curing under a low temperature of 15° C. or less, checking tends to occur in the coating film, and the component (E2) remaining in the obtained dry coating film ), various coating film properties such as oil resistance, solvent resistance, chemical resistance and corrosion resistance tend to decrease.

When the present composition contains both the component (E1) and the component (E2), the total content is such that various coating film properties such as oil resistance, solvent resistance, chemical resistance and corrosion resistance of the obtained dry coating film are not significantly impaired. , Preferably it is 0-20 mass parts with respect to 100 mass parts of solid content of a component (A), More preferably, it is 0-10 mass parts.

The content of components (D1), (D2), (E1) and (E2) in the composition is not particularly limited, and may be appropriately adjusted according to the coating method at the time of coating the composition, but the coating workability of the composition, etc. Considering this, the concentration of the nonvolatile matter in the composition is preferably 55 to 98 mass%, more preferably 65 to 95 mass%.

This composition may contain water as a component (D2).

When the present composition contains water, its content is preferably 5 mass% or less, more preferably less than 3.5 mass%, still more preferably 3 mass% or less, with respect to 100 mass% of the nonvolatile matter of the present composition, the lower limit is not particularly limited, and is, for example, 0.1 mass% or more.

<Preparation of this composition>

The present composition is preferably prepared by mixing and kneading the main component and the curing agent component, each individually prepared in advance, at the time of use.

The main component can be prepared by mixing each component constituting it, stirring and kneading. In this case, it is preferable to use, for example, an SG mill or a high-speed disper, and to disperse the blended ingredients as uniformly as possible while maintaining the mill base temperature at 55 to 60° C. for about 30 minutes.

On the other hand, although the curing agent component differs depending on the components to be blended, each component constituting it may be mixed and uniformly dispersed with a stirrer.

<Use of this composition>

According to this composition, a coating film (layer) having various performances such as oil resistance, solvent resistance, chemical resistance, water (hot water) resistance, and corrosion resistance can be formed. The method also includes interelectrode corrosion, dissimilar metal contact corrosion, stress corrosion and the like.

The present composition is capable of forming a coating film having excellent performance thereof, so that steel structures such as ships and bridges, especially chemical substances, are transported or stored by land transport or sea transport, etc., in cargo tanks (eg, product carriers or It is preferably used for inner surfaces of tanks such as chemical tankers), cascade tanks, fuel oil tanks, and lubricating oil tanks, and is preferably used for structures in contact with chemical substances such as inner surfaces of pipelines. In addition to this use, in places where maintenance is difficult for seawater desalination devices, offshore structures, etc., around dams and sluice gates, piping, water storage tanks, water storage tanks, etc. in plants that use seawater, river water or industrial water as cooling water, use It is also suitable for use as a pool for storing finished nuclear fuel.

≪Method for producing a coating film, a substrate with a coating film, and a substrate with a coating film»

The coating film of one embodiment of the present invention (hereinafter also referred to as “the present coating film”) is formed using the present composition, and the substrate with a coating film of one embodiment of the present composition is a laminate comprising the present coating film and an object (substrate) to be coated it's a chain

Although it does not restrict|limit especially as said base material, It is preferable that it is a base material which anticorrosive property is requested|required from that the effect of this invention can be exhibited more.

Examples of such a substrate include steel (iron, steel, ferroalloy, carbon steel, mild steel, alloy steel, stainless steel, etc.), non-ferrous metals (zinc, aluminum, etc.), and the surface of the substrate may be coated with a shop primer or the like.

In addition, when, for example, mild steel (SS400, etc.) is used as the base material, the base material is adjusted (e.g., the maximum height roughness (Rz) is 30 to 75 It is preferable to adjust it so that it may become about micrometer).

Although the dry film thickness in particular of this coating film is not restrict|limited, From the point of being able to obtain a coating film which has sufficient corrosion resistance etc., it is 50-500 micrometers normally, Preferably it is 200-400 micrometers.

As the method for forming the present coating film, a desired film thickness may be formed by one coating (one-time application), or a coating film having a desired film thickness may be formed by two or more coatings (two or more coatings). It is preferable to form a coating film so that film thickness management may become easy and it may become a target dry film thickness by the point, such as being able to reduce the residual solvent in a coating film easily by two or more coats.

The manufacturing method (hereinafter also referred to as "the present method") of the base material with a coating film of one Embodiment of this invention includes the following processes [1] and [2].

Step [1]: A step of coating the composition on a substrate

Step [2]: A step of drying the coated composition to form a coating film

In addition, for example, when the present composition contains the imidazole-based compound, the present composition may include the following step [3] if necessary, thereby forming a coating film having better oil resistance, solvent resistance, chemical resistance, etc. can do.

Step [3]: A step of heating the coating film obtained in the step [2] at 60 to 150°C

<Process [1]>

The coating method in the step [1] is not particularly limited, and for example, the surface of the base material may be coated in accordance with common methods such as airless spray coating, air spray coating, brush coating, and roller coating, but large structures In the case of coating with , spray coating is preferable from the viewpoint of being able to easily coat a large-area base material.

The spray coating conditions may be appropriately adjusted according to the dry film thickness to be formed. For example, in the case of airless spray, primary (air) pressure: about 0.4 to 0.8 MPa, secondary (paint) pressure: 10 About -26 MPa and about 50-120 cm/sec of key movement speed are preferable.

Moreover, what is necessary is just to coat so that the dry film thickness of the coating film obtained may become the said range.

For the viscosity of the composition suitable for spray coating, an E-type viscometer (manufactured by TOKIMEC, FMD type) was used as a measuring instrument. The viscosity under the measurement conditions at 23°C is preferably 1,000 to 6,000 mPa·s, more preferably 1,500 to 3,500 mPa·s.

<Process [2]>

The drying conditions in the step [2] are not particularly limited, and may be appropriately set depending on the method for forming the coating film, the type of the substrate, the use, the coating environment, etc., but the drying temperature is preferably 0 to 60° C., more preferably It is usually 5-40℃. In addition, although it is usually dried and hardened under natural conditions, you may force-dry by heating or blowing according to the objective.

Since the present composition is excellent in drying and curing properties under low temperature, it can be dried at a temperature of 15° C. or less, and further 10° C. or less, and the effect of the present invention is more exhibited compared with the conventional composition. Drying at temperature is preferred.

Since the composition can be dried even at such a temperature, it is suitably used when coating a substrate that cannot be heated or is not easy to heat, and even if it is coated on such a substrate under a low temperature such as winter, a desired coating film can be formed. there is.

<Process [3]>

The heating conditions in the step [3] are not particularly limited, but the heating temperature is preferably 60 to 150°C, and the heating time is preferably 5 to 24 hours, more preferably 6 to 20 hours.

As such a heating method, for example, (a) the surface of the coating film obtained in the step [2] is brought into contact with warm seawater or water, (b) the surface of the coating film obtained in the step [2] is heated with hot air, or ( c) Several methods, such as spraying hot water on the surface of the coating film obtained in the said process [2], are mentioned.

In addition, in the case of performing the step [3], in the case of forming a coating film by the above-mentioned two or more coatings, in particular, two coatings, after performing the steps [1] and [2], on the obtained coating film, the steps [1], [ It is preferable to carry out 2] and [3]. Moreover, when forming a coating film by application|coating three or more times, it is preferable to perform process [3], after repeating a series of processes of process [1] and [2] 3 times or more. In addition, it is preferable to perform process [3] once at the end of the process of forming a coating film.

Example

The preferred aspects of the present invention will be described in more detail below based on Examples, but the present invention is not limited to these Examples.

[Examples 1 to 12 and Comparative Examples 1 to 4]

Each component constituting the main component shown in Table 1 was added to a plastic container according to the amount (numerical value) shown in Table 1, an appropriate amount of glass beads was put there, and dispersed in a paint shaker for 1 to 2 hours. Then, after removing the glass beads, the mixture was stirred using a high-speed disper and dispersed at 56 to 60°C for about 30 minutes. Then, the main component was prepared by cooling to 30 degrees C or less.

Further, each component constituting the curing agent component described in Table 1 was added to a container according to the amount (numerical value) described in Table 1, and the curing agent component was prepared by dispersing it with a table-top stirrer.

The prepared main component and hardening|curing agent component were mixed, and the coating composition was prepared.

In addition, description of each component described in Table 1 is shown in Table 2. In Table 1, the numerical value of each component constituting the main component and the curing agent component represents parts by mass, respectively.

(1) Drying test

Based on JISK5600-3-3:1999 (curing drying property), the dryness of the obtained coating composition was tested. Specifically, each coating composition obtained in Examples and Comparative Examples was applied to the surface of a cold-rolled steel sheet (maximum height roughness (Rz): 0 µm) having dimensions of 150 mm × 70 mm × 0.8 mm (thickness) with a film applicator. was used so that the dry film thickness was about 200 µm, respectively, and the curing drying time of each coating composition was evaluated according to the following criteria. A result is shown in Table 3. In each coating composition used, the main component and the curing agent component obtained in Examples and Comparative Examples were mixed immediately before this test.

(Evaluation standard)

5: Hardening and drying time at 10°C is less than 24 hours

4: Curing and drying time at 10°C is 24 hours or more and less than 32 hours

3: Curing and drying time at 10°C is 32 hours or more and less than 40 hours

2: Curing and drying time at 10°C is 40 hours or more and less than 48 hours

1: Curing and drying time at 10°C is 48 hours or more

(2) Evaluation of the appearance of the coating film

The following reference|standard evaluated the external appearance of the coating film of the test board with a coating film produced at 10 degreeC in the same way as the said dryness test. A result is shown in Table 3.

(Evaluation standard)

5: Checking did not occur at all in the coating film

4: Checking area is less than 1% of the entire surface of the coating film

3: Checking area is 1% or more but less than 5% of the entire surface of the coating film

2: Checking area is 5% or more but less than 10% of the entire surface of the coating film

1: Checking area is 10% or more of the entire surface of the coating film

Appearance photographs showing an example of the evaluations 1 to 3 are shown in FIG. 1 . In addition, the checking generation area means the total area of the stripe-shaped part as shown in FIG. 1 with respect to the coating-film whole surface formed on the base material.

[Production of trial version]

A sandblasted steel sheet (maximum height roughness Rz: 30 to 75 µm) of SS400 having dimensions of 150 mm x 70 mm x 2.3 mm (thickness) was prepared. On the surface of this steel sheet, each coating composition prepared as mentioned above was coated so that it might become a dry film thickness of 300 micrometers, respectively, using air spray. Then, the steel plate with a coating film (test plate A) was produced by drying for 10 days in 23 degreeC and 50%Rh atmosphere. Each obtained test plate A was used for each test mentioned later. A result is shown in Table 3.

In addition, all of the pencil hardness of the coating film in the obtained test board A were "H" or more. In this invention, pencil hardness was measured based on JISK5600-5-4:1999.

Moreover, after each coating composition was coated similarly to the above, the steel plate with a coating film dried under low temperature (test plate B) was produced by drying for 10 days in 10 degreeC and 50%Rh atmosphere. Each of the obtained test plates B was subjected to tests (3) and (4) described later. A result is shown in Table 3.

(3) Corrosion resistance test

Based on JISK5600-6-2:2016, the corrosion resistance of each obtained test board A and B was tested.

The sheath 2 reaching the steel plate from the coating film side was put in the position shown in FIG. 2 of each obtained test plate A and B. The test plate 1 with the sheath 2 was immersed in 3% saline at 40°C for 90 days so that the sheath 2 side was down (in the direction shown in FIG. 2). After immersion, 11 cuts 3 are placed upward in order from the left end of the sheath 2 as if the sheath 2 is equally divided at intervals of 5 mm, and 10 measurement parts between each cut 3 ( In 4), the peeling length (length from the sheath 2) of the steel plate and the coating film was measured. The average value of 10 points|pieces of the measured peeling length was evaluated based on the following reference|standard.

(Evaluation standard)

4: Peeling length is less than 5 mm

3: The peeling length is 5 mm or more and less than 10 mm

2: The peeling length is 10 mm or more and less than 15 mm

1: The peeling length is 15 mm or more

(4) Hot water resistance test

In accordance with JIS K 5600-6-2: 2016, the appearance of the coating film and the state of the steel plate under the coating film after each of the obtained test plates A and B were immersed in tap water at 85° C. for 90 days were evaluated according to the following standards. . In addition, as for the state of the steel plate under the coating film, the coating film of 1 cm<2> was removed with a cutter knife etc., and the area occupied by rust in the location where the steel plate base material was exposed was evaluated.

(Evaluation standard)

5: No swelling on the outside of the coating, no rust under the coating (on the steel plate)

4: There is no swelling in the appearance of the coating film, and the area occupied by rust under the coating film (on the steel plate) is less than 1%

3: There is no swelling in the appearance of the coating film, but the area occupied by rust under the coating film (on the steel plate) is 1% or more and less than 5%

2: Swelling is seen in less than 5% of the entire surface of the coating film, and/or the area occupied by rust under the coating film (on the steel plate) is 5% or more and less than 20%

1: Swelling is seen in 5% or more of the coating film area, deep cracks are seen in a part of the coating film surface, and the area occupied by rust under the coating film (on the steel plate) is 20% or more

(5) Oil resistance test

Based on JISK5600-6-1:2016, the oil resistance of each obtained test board A was tested.

Each obtained test plate A was immersed in naphtha at room temperature for 180 days. The test plate after immersion in naphtha was evaluated by the following criteria.

(Evaluation standard)

5: There was no rust on the steel plate, no swelling on the coating film, and the pencil hardness of the coating film was H or more (H, 2H, 3H...)

4: There was no generation of rust on the steel sheet, no swelling occurred in the coating film, and the pencil hardness of the coating film was F to 4B.

3: There was no rust on the steel plate, no swelling on the coating film, and the pencil hardness of the coating film was 5B or less (5B, 6B, 7B...)

2: Slight rust occurred on the steel plate, and swelling occurred in the coating film.

1: Rust occurred in the steel plate, and swelling occurred in the coating film.

(6) Solvent resistance test

Based on JISK5600-6-1:2016, the solvent resistance of each obtained test board A was tested.

Each of the obtained test panels A was immersed in various solvents such as methanol, benzene, methyl isobutyl ketone, ethyl acetate or 1,2-dichloroethane at room temperature for 180 days. The test plate after immersion was evaluated by the same criteria as the said oil resistance test.

(7) Chemical resistance test

Based on JISK5600-6-1:2016, the chemical-resistance of each obtained test board A was tested.

Each obtained test panel A was immersed in 3% sulfuric acid or 30% sodium hydroxide aqueous solution in various chemicals at room temperature for 180 days. The test plate after immersion was evaluated by the same criteria as the said oil resistance test.

1: trial version
2: sheath
3: cut
4: Measuring part

Claims (11)

The aromatic epoxy compound (A), the amine-based curing agent (B), the silane coupling agent (C), and the solvent (D1) may be included, and the high boiling point compound (E1) may be included;
The amine-based curing agent (B) includes at least one selected from the group consisting of alicyclic amines, modified products of alicyclic amines, aromatic amines and modified products of aromatic amines,
The solvent (D1) is a solvent other than water that has a boiling point of less than 200° C. at 1 atm and contains a hydroxyl group in its molecule;
The high boiling point compound (E1) is a compound having a boiling point of 200° C. or more and less than 250° C. at 1 atm, and containing a hydroxyl group in the molecule;
Content of the said solvent (D1) is 30-150 mass parts with respect to 100 mass parts of solid content of the said aromatic epoxy compound (A),
The content of the high boiling point compound (E1) is 0 to 20 parts by mass based on 100 parts by mass of the solid content of the aromatic epoxy compound (A),
paint composition. The method of claim 1,
The coating composition in which the said aromatic epoxy compound (A) contains a novolak epoxy resin (A1). 3. The method of claim 2,
The coating composition, wherein the content of the novolac epoxy resin (A1) is 30 mass % or more with respect to 100 mass % of the solid content of the aromatic epoxy compound (A). 3. The method of claim 2,
The aromatic epoxy compound (A) further comprises at least one bisphenol type epoxy resin (A2) selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol AD type epoxy resin, and a bisphenol F type epoxy resin. The method of claim 1,
The coating composition, wherein the solvent (D1) contains a glycol ether-based solvent. According to claim 1,
It further contains a pigment (F),
The pigment volume concentration of the paint composition is 20-50%,
paint composition. According to claim 1,
The coating composition in which content of the said silane coupling agent (C) is 0.1-30 mass parts with respect to 100 mass parts of solid content of the said aromatic epoxy compound (A). A coating film formed from the coating composition according to any one of claims 1 to 7. A substrate with a coating film comprising the coating film according to claim 8 and the substrate. 10. The method of claim 9,
A base material with a coating film, wherein the base material is an inner surface of a tank. A method for producing a substrate with a coating film, comprising the steps [1] and [2] below.
[1] A step of coating the base material with the coating composition according to any one of items 1 to 7
[2] Step of drying the coated coating composition to form a coating film

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