Film forming materials

Abstract

To provide a film-forming material excellent in whitening resistance.SOLUTION: The film-forming material contains an epoxy compound, an amine compound, a phenol compound (1) having one specific substituent, and a phenol compound (2) having two or three specific substituents. The mixing ratio (weight ratio) of the phenol compound (1) to the phenol compound (2) is 50:50-99:1. The specific substituents of the phenol compound (1) and the phenol compound (2) are each a substituent having an unsaturated six-membered ring structure, a substituent having a saturated six-membered ring structure, or a C1-12 linear or branched alkyl group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a novel film-forming material which improves the whitening of coating films. [Background technology]

[0002] Epoxy-based film-forming materials containing epoxy compounds and amine compounds have been widely adopted in the field of coatings due to their excellent physical properties.

[0003] However, it has been pointed out that epoxy-based coating materials have a problem of whitening during coating formation, particularly in high humidity and low temperature environments, and various attempts to prevent such whitening have been proposed. For example, Patent Document 1 describes that an epoxy resin using a specific amine is effective for whitening.

[0004] However, even in the above-mentioned patent documents, it is sometimes difficult to prevent whitening, and there is a demand for a technique that can more reliably prevent whitening. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special publication 2014-532805 Summary of the Invention [Problem to be solved by the invention]

[0006] SUMMARY OF THE PRESENT EMBODIMENT In view of the above problems, an object of the present invention is to provide a film-forming material having excellent whitening resistance. [Means for solving the problem]

[0007] As a result of intensive research, the present inventors have found that a film-forming material having excellent whitening resistance can be obtained by containing a phenol compound (1) having one specific substituent and a phenol compound (2) having two or three specific substituents in a specific ratio together with an epoxy compound and an amine compound, and have thus completed the present invention.

[0008] That is, the present invention has the following features. 1. A film-forming material containing an epoxy compound, an amine compound, and a phenol compound, The composition comprises a base agent containing the epoxy compound and the phenol compound, and a curing agent containing the amine compound, The phenol compound is Consists of monophenylethylphenol A phenolic compound (1), Consists of diphenylethylphenol Contains a phenol compound (2), The mixing ratio (weight ratio) of the phenol compound (1) and the phenol compound (2) is 85 : 15 A coating material characterized in that the ratio is about 99:1. 2. The epoxy equivalent of the epoxy compound is 50 g / eq or more and 500 g / eq or less. To The coating material described herein. 3. The active hydrogen equivalent of the amine compound is 30 g / eq or more and 300 g / eq or less. OR 2 .A coating material as described above. Effect of the Invention

[0009] The film-forming material of the present invention has excellent whitening resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, an embodiment of the present invention will be described.

[0011] The coating material of the present invention contains an epoxy compound, an amine compound, and a phenol compound. The phenol compound contains a phenol compound (1) represented by formula (1) and a phenol compound (2) represented by formula (2), and the mixing ratio (weight ratio) of the phenol compound (1) to the phenol compound (2) is 50:50 to 99:1. Formula (1) TIFF0007636941000001.tif3992 formula (2) TIFF0007636941000002.tif4090 (m is 1, n is an integer of 2 or 3, and R1 may be the same or different and represents a substituent having an unsaturated 6-membered ring structure, a substituent having a saturated 6-membered ring structure, or a substituent having a linear or branched alkyl group having 1 to 12 carbon atoms.)

[0012] In the present invention, a film-forming material having excellent whitening resistance can be obtained by containing the phenol compound (1) and the phenol compound (2) in a mixing ratio (weight ratio) of 50:50 to 99:1, preferably 55:45 to 95:5, and more preferably 60:40 to 90:10. In the present invention, the whitening resistance is particularly excellent at low temperatures (10°C or less). If the mixing ratio (weight ratio) is outside the above range, no improvement in whitening resistance is observed. In addition, no improvement in whitening resistance is observed when either the phenol compound (1) or the phenol compound (2) is used alone.

[0013] The phenol compound (1) has one substituent (R1) on phenol, and examples of the substituent (R1) include substituents having an unsaturated 6-membered ring structure such as phenyl group, methylphenyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, diethylphenyl group, triethylphenyl group, phenylmethyl group, diphenylmethyl group, triphenylmethyl group, phenylethyl group, and methylphenylethyl group, substituents having a saturated 6-membered ring structure such as cyclohexyl group, methylcyclohexyl group, and ethylcyclohexyl group, and substituents having a linear or branched alkyl group having 1 to 12 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, i-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, and dodecyl group. The position of the substituent is not limited to ortho, para, meta, etc. As the phenol compound (1), it is particularly preferable to use one or more compounds selected from phenylphenol, methylphenylphenol, phenylmethylphenol, phenylethylphenol, t-butylphenol, dodecylphenol, cyclohexylphenol, and the like.

[0014] The phenol compound (2) has two or three substituents (R1) on the phenol, and the substituents (R1) may be, for example, those shown above, and the types of the substituents may be the same or different. The position of the substituents is not limited to ortho, para, meta, etc. As the phenol compound (2), it is particularly preferable to use one or more selected from diphenylphenol, triphenylphenol, di(methylphenyl)phenol, tri(methylphenyl)phenol, di(phenylmethyl)phenol, tri(phenylmethyl)phenol, di(phenylethyl)phenol, tri(phenylethyl)phenol, di-t-butylphenol, tri-t-butylphenol, didodecylphenol, tridodecylphenol, dicyclohexylphenol, tricyclohexylphenol, isopropylmethylphenol, dimethyl(phenylethyl)phenol, dimethylethyl(phenylethyl)phenol, and the like.

[0015] In addition to the above phenolic compound (1) and phenolic compound (2), phenolic compounds such as cardanol and salicylic acid, and naphthol compounds having the above-mentioned substituents may also be included to the extent that the effects of the present invention are not impaired.

[0016] Examples of the epoxy compound include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, phenol novolac type epoxy resins such as phenol novolac type bisphenol A epoxy resin and phenol novolac type bisphenol F epoxy resin, novolac type epoxy resins such as cresol novolac type epoxy resin and bisphenol A novolac type epoxy resin, copolymer type epoxy resin of bisphenol A type epoxy resin and phenol novolac resin, diglycidyl ether of dihydroxynaphthalene, polyglycidyl ether of mono(di)hydroxynaphthalene novolac, polyglycidyl ether of phenol-divinylbenzene crosslinked phenolic resin, polyglycidyl ether of bisphenol A-divinylbenzene crosslinked phenolic resin, polyglycidyl ether of mono(di)hydroxynaphthalene-divinylbenzene crosslinked phenolic resin, and the like. One or more of these may be used. In the present invention, the composition may be in any form, including water-soluble, water-dispersible, self-dispersible, solvent-soluble, solventless, or non-aqueous dispersible, but is preferably in the solventless form.

[0017] In the present invention, the epoxy equivalent (per solid content) of the epoxy compound is preferably 50 g / eq or more and 500 g / eq or less, more preferably 80 g / eq or more and 450 g / eq or less, and even more preferably 100 g / eq or more and 400 g / eq or less.

[0018] The mixing ratio of the epoxy compound and the phenol compound is not particularly limited, but it is preferable that the phenol compound is used in an amount of 10 parts by weight or more and 50 parts by weight or less, and more preferably 15 parts by weight or more and 40 parts by weight or less, per 100 parts by weight of the epoxy compound (solid content).

[0019] Examples of the amine compound include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, heterocyclic amines, aliphatic polyamides, alicyclic polyamides, aromatic polyamides, aliphatic polyamidoamines, alicyclic polyamidoamines, aromatic polyamidoamines, and the like. One or more of these can be used. In the present invention, the composition may be in any form, including water-soluble, water-dispersible, self-dispersible, solvent-soluble, solventless, or non-aqueous dispersible, but is preferably in the solventless form.

[0020] In the present invention, the active hydrogen equivalent (per solid content) of the amine compound is preferably 30 g / eq or more and 300 g / eq or less, more preferably 50 g / eq or more and 250 g / eq or less, and even more preferably 75 g / eq or more and 200 g / eq or less.

[0021] The mixing ratio of the epoxy compound and the amine compound is not particularly limited, but it is preferable that the ratio of (amount of epoxy compound / epoxy equivalent of epoxy compound) / (amount of amine compound / active hydrogen equivalent of amine compound) is within the range of 0.1 to 10, and more preferably 0.3 to 3.

[0022] The solvent used in the present invention can be appropriately selected depending on the type of epoxy compound, amine compound, etc., and examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as n-hexane, n-pentane, n-octane, n-nonane, n-decane, n-undecane, and n-dodecane, petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha, ketone solvents such as n-methylpyrrolidone, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone, ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, and isopropyl acetate, ethylene glycol, propane, and the like. Examples of the solvent that can be used include glycol-based solvents such as propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and dipropylene glycol monomethyl ether; alcohol-based solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and t-butyl alcohol; and water.

[0023] In addition to the above-mentioned components, for example, pigments, aggregates, silane coupling agents, thickeners, leveling agents, wetting agents, catalysts, plasticizers, preservatives, antifungal agents, anti-algae agents, antibacterial agents, antifreeze agents, pH adjusters, surfactants, dispersants, defoamers, adsorbents, fibers, crosslinking agents, ultraviolet absorbers, antioxidants, etc. can also be mixed, so long as the effects of the present invention are not impaired.

[0024] As the pigment, known pigments can be used, and examples thereof include titanium oxide, zinc oxide, carbon black, graphite, black iron oxide, copper chromium black, cobalt black, copper manganese iron black, red iron oxide, molybdate orange, permanent red, permanent carmine, anthraquinone red, perylene red, quinacridone red, yellow iron oxide, titanium yellow, fast yellow, benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine blue, Prussian blue, cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine violet, metal pigments, and pearl pigments.

[0025] As the aggregate, known aggregates can be used, such as heavy calcium carbonate, precipitated calcium carbonate, kaolin, talc, clay, china clay, barium sulfate, barium carbonate, silica powder, diatomaceous earth, as well as silica sand, river sand, mountain sand, crushed marble, crushed granite, crushed obsidian, crushed limestone, crushed ceramics, glass beads, crushed glass, and the like.

[0026] The present invention can be applied to a one-liquid type film-forming material in which an epoxy compound, an amine compound, and a phenol compound are mixed, or a two-liquid type film-forming material in which a base agent containing an epoxy compound, a curing agent containing an amine compound, a base agent and / or a curing agent containing a phenol compound are mixed, or a three-liquid type film-forming material consisting of a base agent containing an epoxy compound, a curing agent containing an amine compound, and an auxiliary agent containing a phenol compound, but in the present invention, it is particularly preferred to use it as a two-liquid type film-forming material consisting of an epoxy compound, a base agent containing a phenol compound, and a curing agent containing an amine compound. In particular, in the two-liquid type, the phenol compound can be mixed into the base agent containing an epoxy compound to improve the whitening resistance.

[0027] The film-forming material of the present invention can be applied mainly to buildings, civil engineering structures, etc., and can be applied to various substrates such as concrete, mortar, asphalt, siding boards, porcelain tiles, extrusion molded boards, gypsum boards, perlite boards, bricks, plastics, colored steel sheets, copper sheets, aluminum sheets, titanium sheets, stainless steel sheets, galvanized steel sheets, metals, steel frames (steel materials), wood, glass, etc. In particular, the present invention is preferably applied to indoor floor surfaces of architectural structures such as factories, warehouses, parking lots, athletic stadiums, hospitals, schools, etc., or outdoor floor surfaces such as general sidewalks, pedestrian bridges, parks, amusement parks, platforms, building rooftops, etc.

[0028] The method for applying the coating material is not particularly limited, but the coating material can be applied using tools such as a trowel, brush, roller, spray, or spray gun, and the coating can also be applied to a base that has already been coated with a primer. The amount of the coating material to be applied is not particularly limited, but is preferably 0.1 kg / m 2 More than 5kg / m 2 Below that, even 0.2kg / m 2 More than 3kg / m 2 The following coatings can be applied in one or multiple coats: EXAMPLES

[0029] The following examples and comparative examples will clarify the features of the present invention.

[0030] [Table 1]

[0031] [Table 2]

[0032] (Examples 1 to 7, Comparative Examples 1 to 3) Using the raw materials shown in Table 1 and the formulation shown in Table 2, a base material composed of a mixture of an epoxy compound, a phenol compound, a pigment, and an additive, and a curing agent composed of an amine compound were produced in a conventional manner. The obtained base resin and hardener were used to carry out the following tests.

[0033] (Whitening 1) A coating material consisting of a mixture of base agent and hardener was applied to a slate (400mm x 200mm x 6mm) that had previously been coated with epoxy primer, with a trowel at a coating weight of 1.5kg / m2 under conditions of 23°C temperature and 90% relative humidity. 2 The whitening was evaluated by observing the surface of the coating 24 hours after coating. The evaluation was done on a 5-point scale from 5: no abnormality was observed to 1: whitening of the coating was observed. The results are shown in Table 2. (Whitening 2) Except for the conditions of temperature 5°C and relative humidity 90%, bleaching property was evaluated in the same manner as in bleaching property 1. The results are shown in Table 2. (curable) A coating material consisting of a mixture of base agent and hardener was applied to a slate (400mm x 200mm x 6mm) that had previously been coated with epoxy primer, with a trowel at a coating weight of 1.5kg / m2 under conditions of 23°C temperature and 90% relative humidity. 2 The curing property was evaluated 24 hours after painting by measuring the pencil hardness in accordance with JIS K 5600-5-4 scratch hardness (pencil method). The evaluation results are as follows. The results are shown in Table 2. 4: HB or more 3:B or 2B 2:3B or 4B 1:5B or less

[0034] Example 8 In the formulation of Example 1 shown in Table 1, a base agent was prepared by mixing an epoxy compound, a pigment, and an additive, and a curing agent was prepared by mixing an amine compound and a phenol compound. Using the obtained base resin and hardener, we carried out Whitening Test 1 and Whitening Test 2. The results are shown in Table 2.

Claims

1. A film-forming material comprising an epoxy compound, an amine compound, and a phenol compound, The composition comprises a base agent containing the epoxy compound and the phenol compound, and a curing agent containing the amine compound, The phenol compound is The present invention comprises a phenolic compound (1) consisting of monophenylethylphenol and a phenolic compound (2) consisting of diphenylethylphenol, A coating material characterized in that the mixing ratio (weight ratio) of the phenol compound (1) to the phenol compound (2) is 85:15 to 99:

1.

2. 2. The coating material according to claim 1, wherein the epoxy equivalent of the epoxy compound is 50 g / eq or more and 500 g / eq or less.

3. 3. The film-forming material according to claim 1, wherein the active hydrogen equivalent of the amine compound is 30 g / eq or more and 300 g / eq or less.

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