JP7636941B2 - Film forming material - Google Patents

Description

The present invention relates to a new film-forming material that improves the whitening of coating films.

Epoxy-based film-forming materials, which contain epoxy compounds and amine compounds, are widely used in the coating field due to their excellent physical properties.

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 in whitening.

However, even in the above patent documents, it can be difficult to prevent whitening, and there is a demand for technology that can more reliably prevent whitening.

Special table 2014-532805 publication

The object of the present invention is to provide a film-forming material with excellent whitening resistance, in consideration of the problems described above.

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

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
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 a mixing ratio (weight ratio) of the phenol compound (1) and the phenol compound (2) is 85:15 to 99 :1.
2. The film-forming material according to 1., characterized in that the epoxy equivalent of the epoxy compound is 50 g/eq or more and 500 g/eq or less.
3. The film-forming material according to 1. or 2. , wherein the active hydrogen equivalent of the amine compound is 30 g/eq or more and 300 g/eq or less.

The film-forming material of the present invention has excellent resistance to whitening.

The following describes how to implement the present invention.

式（２）

（ｍは１、ｎは２または３の整数、Ｒ１は同じでも異なっていてもよく、不飽和６員環構造を有する置換基、飽和６員環構造を有する置換基、または、炭素数１～１２の直鎖状あるいは分岐状アルキル基を有する置換基を示す。） The film-forming 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)

Equation (2)

(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.)

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 film-forming material has excellent whitening resistance at low temperatures (10° C. or lower), in particular.
When the mixing ratio (weight ratio) is deviated from the above range, no improvement in whitening resistance is observed. In addition, when either the phenol compound (1) or the phenol compound (2) is used alone, no improvement in whitening resistance is observed.

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

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.

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 substituents can also be included to the extent that the effects of the present invention are not impaired.

Examples of the epoxy compound include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, phenol novolac type epoxy resins such as phenol novolac type bisphenol A epoxy resins and phenol novolac type bisphenol F epoxy resins, novolac type epoxy resins such as cresol novolac type epoxy resins and bisphenol A novolac type epoxy resins, copolymer type epoxy resins of bisphenol A type epoxy resins and phenol novolac resins, 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 type may be water-soluble, water-dispersible, self-dispersible, solvent-soluble, solventless, or non-aqueous dispersible, but is not particularly limited thereto. In particular, it is preferable to use a solventless type.

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.

The mixing ratio of the epoxy compound and the phenol compound is not particularly limited, but it is preferable that the phenol compound is 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).

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. Among these, one or more kinds can be used.
In the present invention, the type may be water-soluble, water-dispersible, self-dispersible, solvent-soluble, solventless, or non-aqueous dispersible, but is not particularly limited thereto. In particular, it is preferable to use a solventless type.

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.

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.

The solvent used in the present invention can be appropriately set depending on the type of epoxy compound, amine compound, etc., but 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, Examples of solvents 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.

In addition to the above components, other additives such as 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, crosslinkers, UV absorbers, and antioxidants can also be mixed in as long as they do not impair the effects of the present invention.

As the pigment, known pigments can be used, such as titanium oxide, zinc oxide, carbon black, graphite, black iron oxide, copper chrome 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, pearl pigments, etc.

As the aggregate, known aggregates can be used, such as ground calcium carbonate, precipitated calcium carbonate, kaolin, talc, clay, china 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, etc.

The present invention can be applied to a one-liquid type film-forming material that is a mixture of an epoxy compound, an amine compound, and a phenol compound, or a two-liquid type film-forming material that contains a base agent that contains an epoxy compound, a hardener that contains an amine compound, and a phenol compound in the base agent and/or hardener, or a three-liquid type film-forming material that is a base agent that contains an epoxy compound, a hardener that contains an amine compound, and an auxiliary that contains a phenol compound. In particular, the present invention is preferably used as a two-liquid type film-forming material that is a base agent that contains an epoxy compound, a phenol compound, and a hardener that contains an amine compound. In particular, in the two-liquid type, the phenol compound can be mixed into the base agent that contains an epoxy compound to improve whitening resistance.

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, and glass. In particular, the present invention is preferably applied to indoor floor surfaces of architectural structures such as factories, warehouses, parking lots, athletic stadiums, hospitals, and schools, or outdoor floor surfaces such as general sidewalks, pedestrian bridges, parks, amusement parks, platforms, and building rooftops.

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 material 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 may be about 0.1 kg/m2 or ^more and 5 kg/m2 or ^less , and further about 0.2 kg/m2 or ^more and 3 kg/ ^m2 or less, and may be applied in one or more applications.

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

(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 by a conventional method.
The obtained base resin and hardener were used to carry out the following tests.

(Bleaching 1)
A film-forming material consisting of a mixture of base agent and hardener was applied to a slate (400 mm x 200 mm x 6 mm) that had previously been coated with an epoxy primer, at an air temperature of 23°C and a relative humidity of 90%, with a coating weight of 1.5 kg/ ^m2 , using a trowel. The whitening property was evaluated by observing the coating surface 24 hours after application. Evaluation was made 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.
(Bleaching 2)
The bleaching property was evaluated in the same manner as in bleaching property 1, except that the temperature was 5° C. and the relative humidity was 90%. The results are shown in Table 2.
(Curing property)
A film-forming material consisting of a mixture of a base agent and a hardener was applied to a slate (400 mm x 200 mm x 6 mm) that had previously been coated with an epoxy primer, at an air temperature of 23°C and a relative humidity of 90%, with a coating weight of 1.5 kg/ ^m2 , using a trowel. The hardening properties were evaluated 24 hours after application by pencil hardness according to the scratch hardness (pencil method) of JIS K 5600-5-4. The evaluation results are as follows. The results are shown in Table 2.
4: HB or above 3: B or 2B
2: 3B or 4B
1:5B or less

(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, whitening test 1 and whitening test 2 were carried out. The results are shown in Table 2.

Claims (3)

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 a mixing ratio (weight ratio) of the phenol compound (1) and the phenol compound (2) is 85:15 to 99 :1. 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. 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.