JP6616722B2 - Film forming material - Google Patents

Description

  The present invention relates to a novel film forming material.

When painting on buildings, civil engineering structures, etc., a coating is required to ensure adhesion to the base materials (inorganic base materials such as concrete, mortar, slate plate, calcium silicate plate, etc.) After applying a primer as a forming material, a top coat is applied.
Furthermore, recently, there are many cases where painting is performed on the old paint film surface that has deteriorated over time. In such a case, the topcoat material is applied after selecting and applying a primer material in order to ensure adhesion and the like in accordance with the deterioration state of the old paint film surface.

  The undercoat material used here has a great role of improving the adhesion between the base material and the old paint film surface and the overcoat material.

  Conventionally, as such an undercoat material, an appropriate undercoat material has been selected according to the type and state of the base material and the old paint film surface. For example, an epoxy-based primer as described in Patent Documents 1 and 2 is one of the primer materials that have been used for general purposes.

JP2000-319582 JP-A-11-199648

However, in recent years, with the diversification of buildings, civil engineering structures, etc., the types of base materials and coating films have increased, and the selection of primer materials has become complicated.
Furthermore, coating surfaces having high functions such as high durability and antifouling properties have also appeared, and existing undercoat materials have become unable to handle these coating surfaces.

  As a result of intensive studies on such problems, the present inventors have determined that an epoxy-based film-forming material containing an epoxy resin and an amine curing agent includes an epoxy resin having a specific epoxy equivalent and an amine curing agent having a specific active hydrogen equivalent. By using it in combination, it discovered that it showed the outstanding adhesiveness with respect to various base materials and a coating film, and completed this invention.

That is, the present invention has the following characteristics.
1. A film-forming material containing an epoxy resin and an amine curing agent,
The epoxy equivalent of the epoxy resin is 500 g / eq or more and 2000 g / eq or less,
The active hydrogen equivalent of the amine curing agent is 50 g / eq or more and 200 g / eq or less,
An active hydrogen equivalent of the amine curing agent and an epoxy equivalent of the epoxy resin are less than 0.4 in terms of [active hydrogen equivalent of the amine curing agent / epoxy equivalent of the epoxy resin].

  The film forming material of the present invention exhibits excellent adhesion to a wide range of substrates and coating surfaces.

The epoxy resin used in the present invention has an epoxy equivalent (per solid content) of 500 g / eq to 2000 g / eq, preferably 600 g / eq to 1500 g / eq.
The amine curing agent used in the present invention has an active hydrogen equivalent (per solid content) of 50 g / eq to 200 g / eq, preferably 60 g / eq to 150 g / eq.
In the epoxy resin and amine curing agent according to the present invention, the active hydrogen equivalent of the amine curing agent and the epoxy equivalent of the epoxy resin are less than 0.4 in terms of [active hydrogen equivalent of the amine curing agent / epoxy equivalent of the epoxy resin]. Preferably, each material is set to be used in a combination of 0.01 to 0.3, more preferably 0.03 to 0.25, and even more preferably 0.05 to 0.2. It is characterized by.

  The epoxy equivalent is a value obtained by dividing the molecular weight of the epoxy resin by the number of epoxy groups. The active hydrogen equivalent is a value obtained by dividing the molecular weight of the amine curing agent by the number of hydrogen atoms in the amino group.

In general, the mixing of the epoxy resin and the amine curing agent is based on the epoxy equivalent of the epoxy resin, and the active hydrogen equivalent of the amine curing agent is often combined with about 0.5 to 2 times the epoxy equivalent, The equivalent ratio is usually set to about 1.
However, in the present invention, a specific epoxy resin having an epoxy equivalent of 500 g / eq or more and 2000 g / eq or less and a specific amine curing agent having an active hydrogen equivalent of 50 g / eq or more and 200 g / eq or less are selected as [active hydrogen of amine curing agent]. Equivalent / Epoxy equivalent of epoxy resin] is selected to be less than 0.4, and by combining these, it has been found for the first time that it exhibits excellent adhesion to a wide range of substrates and coating surfaces. is there. In particular, excellent adhesion can be exhibited even on coating surfaces having high functions such as high durability and antifouling properties, which are frequently employed recently.
Although the details of such a mechanism are unknown, it is thought to be due to the balance between the molecular weight balance of the epoxy resin and the amine curing agent and the strong cross-linked structure of the epoxy-amine.

When [active hydrogen equivalent of amine curing agent / epoxy equivalent of epoxy resin] is 0.4 or more, it becomes difficult to exhibit excellent adhesion to a wide range of substrates and coating surfaces.
Moreover, when the epoxy equivalent of an epoxy resin and the active hydrogen equivalent of an amine hardening | curing agent are too larger than the said range, or too small, there exists a possibility that it may be inferior to adhesiveness.

  Further, the blending ratio of the epoxy resin and the amine curing agent is not particularly limited, but [(the blending amount of the amine curing agent / the active hydrogen equivalent of the amine curing agent) / (the blending amount of the epoxy resin / epoxy equivalent of the epoxy resin)] And preferably 0.1 or more and 10 or less, more preferably 0.3 or more and 2 or less, and still more preferably 0.6 or more and 1.2 or less.

The epoxy resin is not particularly limited as long as it satisfies the above conditions. For example, bisphenol type epoxy resin such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, phenol novolac type bisphenol A epoxy resin, and phenol novolac type bisphenol. Phenolic novolac type epoxy resin such as F epoxy resin, cresol novolac type epoxy resin, novolac type epoxy resin such as bisphenol A novolac type epoxy resin, copolymer type epoxy resin of bisphenol A type epoxy resin and phenol novolac resin, dihydroxynaphthalene Of diglycidyl ether, mono (di) hydroxynaphthalene novolac polyglycidyl ether, phenol-divinylbenzene cross-linked phenolic resin Li glycidyl ethers, bisphenol A- divinylbenzene crosslinked phenolic resins polyglycidyl ether, mono (di) hydroxy naphthalene - polyglycidyl ethers of divinylbenzene crosslinked phenolic resins.
In the present invention, in particular, one or more phenol novolac type epoxy resins selected from a phenol novolac type bisphenol A epoxy resin and a phenol novolac type bisphenol F epoxy resin can be suitably used.

The amine curing agent is not particularly limited as long as the above conditions are satisfied. For example, aliphatic polyamine, alicyclic polyamine, aromatic polyamine, heterocyclic amine, aliphatic polyamide, alicyclic polyamide, aromatic polyamide, aliphatic Polyamide amine, alicyclic polyamidoamine, aromatic polyamidoamine and the like can be mentioned.
In the present invention, in particular, one or more aliphatic amine curing agents selected from aliphatic polyamines, aliphatic polyamides, and aliphatic polyamidoamines can be suitably used.

The film forming material of the present invention preferably contains a silane compound.
As the silane compound, for example,
Tetrafunctional alkoxysilane compounds such as tetraethoxysilane, tetramethoxysilane, tetrabutoxysilane,
Methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, Trifunctional alkoxysilane compounds such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxy Bifunctional alkoxysilane compounds such as silane, diphenyldibutoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane,
Chlorosilane compounds such as tetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane,
Acetoxysilane compounds such as tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, diphenyldiacetoxysilane,
γ-glycidoxypropyltrimexisilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriisopropenyl Contains epoxy groups such as oxysilane, γ-glycidoxypropyltriiminooxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, adduct of γ-isocyanatopropyltriisopropenyloxysilane and glycidol Silane compounds,
N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. A silane compound containing an amino group of
γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, etc. And silane compounds containing a (meth) acryloxy group.
By including these silane compounds, the adhesion can be further improved.
In the present invention, in particular, one or more selected from a silane compound containing an epoxy group and a silane compound containing an amino group can be suitably used.

The mixing ratio of the silane compound is not particularly limited, but is 0.1 parts by weight or more and 30 parts by weight or less (more preferably 0.3 parts by weight or more and 10 parts by weight or less, based on 100 parts by weight of the epoxy resin (solid content), 0.5 parts by weight or more and 3 parts by weight or less) is preferable.
By being in such a range, the adhesiveness can be further improved, and not only when coating immediately after mixing of the epoxy resin and the amine curing agent, but also when mixing after mixing and elapses, it is excellent. Adhesion can be shown.

Moreover, it does not specifically limit as a solvent used with the film forming material of this invention, For example, toluene, xylene, n-hexane, n-pentane, n-octane, n-nonane, n-decane, n-undecane, n -Hydrocarbon solvents such as dodecane, terpin oil, mineral spirits, sorbeso,
Ethanol, propanol, butanol, hexanol, octanol, 2-ethyl-1-hexanol, decanol, benzyl alcohol, ethylene glycol mono-2-ethylhexyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, tri Alcohol solvents such as propylene glycol mono-n-butyl ether, propylene glycol mono-2-ethylhexyl ether, propylene glycol monophenyl ether,
Ester solvents such as n-butyl acetate, isobutyl acetate, isoamyl acetate, methyl amyl acetate, ethylene glycol monobutyl ether acetate,
Examples include ketone solvents such as methyl isobutyl ketone, cyclohexanone, ethyl n-amyl ketone, and diisobutyl ketone.

In this invention, it is preferable that a hydrocarbon solvent and an alcohol solvent are included as a solvent. In particular, an alcohol solvent having a solubility parameter (SP value) of 10 to 15 (preferably 12 to 14) is preferably used as the alcohol solvent. By using such a solvent, excellent performance can be exhibited even in a low temperature environment of 10 ° C. or lower. Moreover, it is preferable to use an alcohol solvent having a boiling point of 70 ° C. or higher and 260 ° C. or lower (further 150 ° C. or higher and 230 ° C. or lower). By using such a solvent, it is excellent even in a low temperature environment such as 10 ° C. or lower. Performance can be demonstrated. In particular, better adhesion to the substrate and the coating surface can be exhibited.
As such an alcohol solvent, isopropyl alcohol (SP value 11.5, boiling point 82 ° C.), n-butyl alcohol (SP value 11.4, boiling point 117 ° C.), hexanol (SP value 10.1, boiling point 158 ° C.) Octanol (SP value 10.3, boiling point 195 ° C.), ethyl alcohol (SP value 12.7, boiling point 78 ° C.), benzyl alcohol (SP value 12.1, boiling point 205 ° C.), etc. are preferably used. .

  The solubility parameter (SP value) is a value that serves as an index of solubility. Polymer Handbook Fourth Edition (Polymer Handbook Fourth Edition, written by J. Brand, published in Wiley, 1998) The values described on pages VII-675 to VII-711 were employed.

As the film forming material of the present invention, in addition to the above-mentioned components, if necessary, a color pigment, an extender pigment, a rust preventive pigment, a plasticizer, an antiseptic, an antifungal agent, an antialgae, an antifoaming agent, a leveling agent, a pigment A dispersant, an anti-settling agent, an anti-sagging agent, a matting agent, a catalyst, a curing accelerator and the like can be mixed within a range in which the effect of the present invention is not inhibited.
In addition, the film forming material can be produced by uniformly stirring and mixing the above components by a conventional method. The form of the film-forming material is preferably a two-part form consisting of a main agent containing an epoxy resin and a curing agent containing an amine curing agent during distribution, and these are desirably mixed and used during painting.

The film forming material of the present invention can be preferably applied to a base material or an old coating film as a primer.
Examples of the base material include concrete, mortar, slate plate, calcium silicate plate, ALC plate, extruded plate, slate tile, cement tile, new roof tile, porcelain tile, siding board, metal, glass, wood, plywood and the like. It is done.

  Moreover, as an old coating film, it is a coating film coated on the said base material, for example, a weather-resistant top coat paint for construction (JISK5658: 2010), a weatherproof paint for steel structures (JISK5659: 2008), Shiny synthetic resin emulsion paint (JISK5660: 2008), fire protection paint for construction (JISK5661: 1970), synthetic resin emulsion paint (JISK5663: 2008), road marking paint (JISK5665: 2011), multicolored paint (JISK5667: 2003) , Synthetic resin emulsion pattern paint (JISK5668: 2010), acrylic resin-based non-aqueous dispersion paint (JISK5670: 2008), lead / chromium-free rust preventive paint (JISK5674: 2008), high solar reflectance paint for roofs (JISK5675: 011), building floor paint (JISK5970: 2008), architectural coatings waterproof material (JISA6021: 2011), architectural finish coating material (JISA6909: 2014) coating film and the like formed by the like. In particular, the present invention can be applied to a fluororesin coating film, a silicon resin coating film, and the like.

In the coating of the film forming material, various methods such as brush coating, roller coating, and spray coating can be employed. Moreover, when painting in a factory, it can also paint using a roll coater, a flow coater, etc.
The coating amount of the film forming material is preferably about 0.05 to 0.5 kg / m2, more preferably about 0.07 to 0.3 kg / m2.
The number of times the coating film forming material is applied may be appropriately set depending on the surface condition of the substrate, and is preferably 1 to 2 times. With the film forming material of the present invention, a coating film having excellent sealing properties can be formed even with such a small number of coatings.
The drying time of the film forming material is preferably 1 hour or more and 1 week or less. The drying temperature is preferably −10 ° C. or more and 50 ° C. or less, more preferably −5 ° C. or more and 40 ° C. or less. In the present invention, excellent performance is exhibited even in a low-temperature environment of 10 ° C. or lower.

  In the present invention, a top coating material can be further applied on the surface of the film forming material. With the top coating material, the finished surface can be protected or the aesthetics can be improved.

The top coating material is not particularly limited, but preferably contains a binder.
Examples of the binder include acrylic resin, urethane resin, vinyl acetate resin, vinyl chloride resin, epoxy resin, urethane resin, silicon resin, fluorine resin, acrylic vinyl acetate resin, acrylic urethane resin, acrylic silicon resin, and the like. These 1 type (s) or 2 or more types can be used.

In addition to the binder, the top coat material may contain colored particles to impart aesthetics.
Examples of the colored particles include pigments, colored aggregates, colored resin particles, and colored gel particles.

In addition to the above-mentioned components, the top coating material contains a thickener, a film-forming aid, a leveling agent, a wetting agent, a plasticizer, an antifreezing agent, a pH adjuster, an extender pigment, an antiseptic, an anti-corrosion agent. In the range where the effect of the present invention is not inhibited, such as glaze, anti-algae, antibacterial agent, dispersant, antifoaming agent, adsorbent, fiber, cross-linking agent, ultraviolet absorber, antioxidant, catalyst, solvent, water, etc. Can be mixed in.
Further, the top coating material can be produced by uniformly stirring and mixing the above-described components by a conventional method.

  The top coating material can be applied using, for example, a known coating instrument such as a brush, a trowel, a roller, or a spray.

  Examples and comparative examples are shown below to clarify the features of the present invention.

○ Manufacture of main agent (main agent 1)
Epoxy resin A {mineral spirit solution of phenol novolac type bisphenol A epoxy resin, solid content 50% by weight, epoxy equivalent (solid content) 950 g / eq} 200 parts by weight, hydrocarbon solvent (mixture of mineral spirit and aromatic hydrocarbon) 45 parts by weight and 5 parts by weight of additives (thickener, antifoaming agent, etc.) were uniformly mixed by a conventional method to produce the main agent 1.

(Main agent 2)
Epoxy resin B {mineral spirit solution of phenol novolac-type bisphenol A epoxy resin, solid content 50% by weight, epoxy equivalent (solid content) 730 g / eq} 200 parts by weight, hydrocarbon solvent (mixture of mineral spirit and aromatic hydrocarbon) 45 parts by weight and 5 parts by weight of additives (thickener, antifoaming agent, etc.) were uniformly mixed by a conventional method to produce the main agent 2.

(Main agent 3)
Epoxy resin C {mineral spirit solution of phenol novolac type bisphenol A epoxy resin, solid content 50% by weight, epoxy equivalent (solid content) 550 g / eq} 200 parts by weight, hydrocarbon solvent (mixture of mineral spirit and aromatic hydrocarbon) 45 parts by weight and 5 parts by weight of additives (thickener, antifoaming agent, etc.) were uniformly mixed by a conventional method to produce the main agent 3.

(Main agent 4)
Epoxy resin D {Phenol novolac-type bisphenol A epoxy resin mineral spirit solution, solid content 50% by weight, epoxy equivalent (solid content) 1600 g / eq} 200 parts by weight, hydrocarbon solvent (mixture of mineral spirit and aromatic hydrocarbon) 45 parts by weight and 5 parts by weight of additives (thickener, antifoaming agent, etc.) were uniformly mixed by a conventional method to produce the main agent 4.

(Main agent 5)
Epoxy resin E {bisphenol A epoxy resin solution, solid content 50% by weight, epoxy equivalent (solid content) 240 g / eq} 200 parts by weight, hydrocarbon solvent (mixture of mineral spirit and aromatic hydrocarbon) 45 parts by weight, additive 5 parts by weight (thickener, antifoaming agent, etc.) were uniformly mixed by a conventional method to produce the base 5

○ Production of curing agent (curing agent 1)
Amine curing agent A {aliphatic polyamidoamine, solid content 100% by weight, active hydrogen equivalent (solid content) 80 g / eq} 8 parts by weight, hydrocarbon solvent (mixture of mineral spirit and aromatic hydrocarbon) 42 parts by weight The curing agent 1 was produced by mixing uniformly by the method.

(Curing agent 2)
Amine curing agent A {aliphatic polyamidoamine, solid content 100% by weight, active hydrogen equivalent (solid content) 80 g / eq} 6 parts by weight, hydrocarbon solvent (mixture of mineral spirit and aromatic hydrocarbon) 42 parts by weight, silane 2 parts by weight of the compound {N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane} was uniformly mixed by a conventional method to produce a curing agent 2.

(Curing agent 3)
Amine curing agent A {aliphatic polyamidoamine, solid content 100% by weight, active hydrogen equivalent (solid content) 80 g / eq} 6 parts by weight, hydrocarbon solvent (mixture of mineral spirit and aromatic hydrocarbon) 30 parts by weight, alcohol 12 parts by weight of a solvent (isopropyl alcohol, SP value 11.5, boiling point 82 ° C.) and 2 parts by weight of a silane compound {N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane} are uniformly mixed by a conventional method. Thus, a curing agent 3 was produced.

(Curing agent 4)
Amine curing agent A {aliphatic polyamidoamine, solid content 100% by weight, active hydrogen equivalent (solid content) 80 g / eq} 6 parts by weight, hydrocarbon solvent (mixture of mineral spirit and aromatic hydrocarbon) 30 parts by weight, alcohol 12 parts by weight of a solvent (n-butyl alcohol, SP value 11.4, boiling point 117 ° C.) and 2 parts by weight of a silane compound {N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane} are uniformly obtained by a conventional method. The curing agent 4 was produced.

(Curing agent 5)
Amine curing agent A {aliphatic polyamidoamine, solid content 100% by weight, active hydrogen equivalent (solid content) 80 g / eq} 6 parts by weight, hydrocarbon solvent (mixture of mineral spirit and aromatic hydrocarbon) 30 parts by weight, alcohol 12 parts by weight of a solvent (benzyl alcohol, SP value 12.1, boiling point 205 ° C.) and 2 parts by weight of a silane compound {N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane} are uniformly mixed by a conventional method. Then, a curing agent 5 was produced.

(Curing agent 6)
Amine curing agent B {aliphatic polyamidoamine, solid content 100% by weight, active hydrogen equivalent (solid content) 230 g / eq} 23 parts by weight, hydrocarbon solvent (mixture of mineral spirit and aromatic hydrocarbon) 27 parts by weight The curing agent 6 was produced by uniformly mixing by the method.

(Curing agent 7)
Amine curing agent A {aliphatic polyamidoamine, solid content 100% by weight, active hydrogen equivalent (solid content) 80 g / eq} 6 parts by weight, hydrocarbon solvent (mixture of mineral spirit and aromatic hydrocarbon) 40 parts by weight, silane 4 parts by weight of the compound {N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane} was uniformly mixed by a conventional method to produce a curing agent 7.

(Curing agent 8)
Amine curing agent C {aliphatic polyamine, solid content 100% by weight, active hydrogen equivalent (solid content) 20 g / eq} 8 parts by weight, hydrocarbon solvent (mixture of mineral spirit and aromatic hydrocarbon) 42 parts by weight Were mixed uniformly to produce a curing agent 1.

Example 1
The base material 1 (250 parts by weight) and the curing agent 1 (50 parts by weight) were uniformly mixed to prepare a film forming material of Example 1. The obtained film forming material was subjected to the following test.

○ Test 1
The obtained film forming material was spray-coated at a coating amount of 0.15 kg / m 2 on each of the following substrates, and then dried for 72 hours to prepare a test plate. The coating and drying were performed in a standard state (temperature 23 ° C., relative humidity 50% RH). After the test plate obtained by the above method was immersed in water for 14 days, the adhesion was evaluated by a cross-cut tape method according to JIS K 5600-5-6. The results are shown in Table 1. The evaluation criteria are as follows.
5: No defect part 4: The area of the defect part is less than 10% 3: The area of the defect part is 10% or more and less than 25% 2: The area of the defect part is 25% or more and less than 40% 1: The area of the defect part is 40% that's all

・ Base material A: Painted siding board (old paint film: acrylic resin paint film)
・ Base material B: Painted siding board (former coating film: fluororesin coating film)
・ Substrate C: Painted siding board (old paint film: silicone resin paint film)

(Examples 2-9, Comparative Examples 1-4)
A film-forming material was produced and tested in the same manner as in Example 1 except that those shown in Table 1 were used as the main agent and curing agent. The results are shown in Table 1.

○ Test 2
The following tests were conducted on the film forming materials of Examples 3 to 6 and 8.
After spray-coating the film forming material at a coating amount of 0.15 kg / m ² on the base material C and drying for 72 hours, an acrylic resin emulsion paint was further applied thereon, and the coating amount was 0.3 kg / m. ^{After 2} roller painting, it was dried for 24 hours to obtain a test specimen. The coating and drying were performed in a standard state (temperature 23 ° C., relative humidity 50% RH).
After the test plate obtained by the above method was immersed in water for 14 days, adhesion was evaluated by a cross-cut tape method according to JIS K 5600-5-6 (evaluation criteria are the same as in Test 1 above).
The evaluation results were “5” for Examples 3 to 6 and “4” for Example 8.

○ Test 3
The following tests were conducted on the film forming materials of Examples 3 to 6 and 8.
A test body was obtained in the same manner as in Test 1 except that the above-mentioned base material C was used as the base material, and a film forming material after 5 hours had elapsed after mixing the main agent and the curing agent as the film forming material. The adhesion was evaluated by the method.
The evaluation results were “5” for Examples 3 to 6 and “4” for Example 8.

○ Test 4
The following tests were conducted on the film forming materials of Examples 3 to 6.
A test plate was prepared by spraying the base material C with a film-forming material at a coating amount of 0.15 kg / m ² and drying for 72 hours. In addition, painting and drying were performed in 5 degreeC atmosphere. After the test plate obtained by the above method was immersed in water for 14 days, adhesion was evaluated by a cross-cut tape method according to JIS K 5600-5-6 (evaluation criteria are the same as in Test 1 above).
The evaluation results were “3” for Example 3, “4” for Example 4 and Example 5, and “5” for Example 6.

Claims (6)

A two-component film-forming material containing a main agent containing an epoxy resin and a curing agent containing an amine curing agent,
The epoxy equivalent of the epoxy resin is 500 g / eq or more and 2000 g / eq or less,
The active hydrogen equivalent of the amine curing agent is 50 g / eq or more and 200 g / eq or less,
The epoxy equivalent of the active hydrogen equivalent to the epoxy resin in the amine curing agent state, and are less than 0.4 in the epoxy equivalent of the active hydrogen equivalent / epoxy amine curing agent,
The base resin and / or hardener two-film-forming material which is characterized that you containing silane compound.   The two-component film-forming material according to claim 1, wherein the silane compound contains an amino group and is contained only in the curing agent.   The silane compound is N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-amino. 3. The two-component film-forming material according to claim 2, which is at least one selected from the group consisting of propyltriethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane.   The two-component film-forming material according to any one of claims 1 to 3, wherein the epoxy resin contains a phenol novolac type epoxy resin.   The two-component film-forming material according to any one of claims 1 to 4, wherein the main agent and / or the curing agent contains benzyl alcohol as a solvent.   The two-component film-forming material according to any one of claims 1 to 5, wherein the two-component film-forming material is applied to a base material and / or an old coating film as an undercoat material.