KR101153893B1 - Thermally fast-curable coating materials for surface treatment of steel and surface treated steel using the same - Google Patents

Abstract

The present invention relates to a composition for treating high-speed thermosetting metal surface and to a surface-treated steel sheet, and more particularly to a composition for treating a metal surface which reduces the drying or curing time of the coating film to be applied to a continuous production line in a thermosetting type. On the basis of the corrosion resistance, chemical resistance, coating adhesion, low temperature drying properties and to a transparent environmentally friendly surface treated steel sheet.

Description

Thermally fast-curable coating materials for surface treatment of steel and surface treated steel using the same}

The present invention relates to a composition for high speed thermosetting metal surface treatment and a surface treated steel sheet.

In order to add corrosion resistance and special functions to the steel sheet, zinc and various metals are plated to manufacture zinc and various plated steel sheets. However, in such a galvanized steel sheet and various coated steel sheets, as metal components such as zinc are exposed to a corrosive environment for a long time, rust such as white rust occurs. Therefore, surface treatment using pretreatment agents, such as a chromate system, has been performed in order to prevent the occurrence of white rust, such as a plated steel plate.

The chromated steel sheet is dense and solid, which has good corrosion resistance, stable in air and low cost, and also has excellent hardness, abrasion resistance, lubricity, mold releasability, decoration, etc. As the severity of the severity and the demands on environmental regulations have increased, the restrictions on the use of harmful ingredients are increasing. Hexavalent chromium of chromic acid used in chromate treatment can cause lung cancer and the like due to strong oxidizing power, and wastewater generated in the treatment process causes serious water pollution, and thus, wastewater treatment costs are excessively generated. As a result, global and domestic regulations on hexavalent chromium in water quality and workplaces are being enforced, and most steel companies are working to develop alternative technologies for chromate treatment.

The most representative alternative to chromate treatment is the use of trivalent chromium instead of hexavalent chromium. In addition, electroplating of inorganic materials such as bisulfate, silicate, Zr and V compounds, Mo, and W is performed. In addition, a technique for forming a film by depositing permanganate (permanganate) may be developed, which may be a problem in the actual production process because the deposition time is long and the temperature must be controlled. In the case of using organic ginseng salts, excellent corrosion resistance is shown, but an alternative technology that satisfies all the various characteristics has not been developed yet, and there is little expectation that it will be developed in the near future. The inorganic coating technology has a problem in that the difference in physical properties according to drying conditions and the drying temperature is very high, and the treatment time of the treatment agent must be deposited for a long time.

Recently, a hybrid coating technique is being applied to supplement the advantages and disadvantages of inorganic and organic coating techniques. Currently, the application of a concept of increasing inorganic corrosion resistance by dispersing inorganic colloidal coatings in organic coating resins is widely used.

As described above, in the case of the organic-inorganic composite (hybrid) coating, the coating properties including the solution, the working properties, and the corrosion resistance have relatively good results. Thus, organic-inorganic composite coating technology is applied as an alternative technology for chromate treatment currently used in industry. As a result, physical properties such as corrosion resistance and coating adhesion can be satisfied, but due to long drying or curing, It is somewhat difficult to apply to production lines that have to be dried within tens of seconds.

Accordingly, in order to solve the problems of the prior art as described above, the present inventors use an organic siloxane resin prepared by using a sol-gel process and an appropriate organic resin in place of the conventional method, and are environmentally friendly, high corrosion resistance, and coating adhesion. The present invention has been completed by producing a composition for metal surface treatment which is excellent in low temperature drying property and transparency and which can be hardened quickly.

Accordingly, the present invention provides at least one binder resin selected from the group consisting of a compound comprising a siloxane repeating unit having at least one amine functional group, and a compound comprising a siloxane repeating unit having at least one epoxy functional group; And an at least one curing agent selected from the group consisting of an amine compound and an epoxy resin.

In addition, the present invention has another object to provide a steel sheet comprising a coating layer using the composition for treating the metal surface and a method for producing the same.

In order to achieve the above object, the present invention

At least one binder resin selected from the group consisting of a compound comprising a siloxane repeating unit having at least one amine functional group, and a compound comprising a siloxane repeating unit having at least one epoxy functional group; And

It is characterized by a composition for treating a metal surface comprising at least one curing agent selected from the group consisting of an amine compound and an epoxy resin.

In addition, the present invention is characterized in that the steel sheet including the coating layer using the composition for treating the metal surface and a method for producing the same.

The composition for treating a metal surface according to the present invention is environmentally friendly by using an organic siloxane resin and an appropriate organic resin, and is excellent in corrosion resistance, coating adhesion, low temperature drying, transparency, and fast curing. Therefore, the steel sheet including the composition as a coating layer is applicable to steel surface treatment coating applications that can be produced in-line.

1 shows a GI steel sheet surface (top), a steel sheet surface (middle) coated with the metal surface treatment composition of Comparative Example 1, and a steel sheet surface (bottom) coated with the metal surface treatment composition of Example 1. FIG.
Figure 2 shows the change of the steel sheet coated with the composition for treating the metal surface of Example 3 immersed in 10% sulfuric acid solution.
Figure 3 shows the change of the steel sheet coated with the composition for treating the metal surface of Example 3 immersed in a 10% solution of sodium hydroxide.
Figure 4 is a result of the corrosion resistance test by cutting the steel plate coated with the composition for treating the metal surface of Example 1.

Hereinafter, the present invention will be described in detail.

One or more binder resins selected from the group consisting of compounds comprising siloxane repeating units having at least one amine functional group, and compounds comprising siloxane repeating units having at least one epoxy functional group; And it relates to a metal surface treatment composition comprising at least one curing agent selected from the group consisting of an amine compound and an epoxy resin, and a surface-treated steel sheet prepared therefrom.

The binder resin according to the present invention is included in the resin composition for steel sheet surface treatment and coated on a plated or unplated steel sheet to produce a high speed thermosetting metal steel sheet with excellent corrosion resistance, coating adhesion, and the like. Preference is given to using at least one selected from the group consisting of a compound comprising a siloxane repeating unit having at least one amine functional group, and a compound comprising a siloxane repeating unit having at least one epoxy functional group.

The compound having the siloxane repeating unit refers to an oligomer or polymer siloxane resin in which an epoxy group or an amine group is prepared by a condensation reaction of a silane compound of epoxyalkoxysilane or aminealkoxysilane and water or silanol, and in particular, a siloxane repeating unit Oligomers having 1 to 100 are more preferred.

In particular, when a compound having at least one epoxy functional group and siloxane repeating unit is used as the binder resin, an amine compound is included as a curing agent, and when a compound having at least one amine functional group and a siloxane repeating unit is used as the binder resin, an epoxy resin is used as the curing agent. It is more preferable to include.

It is preferable that the compound including the siloxane repeating unit having one or more amine functional groups is derived from the compound represented by Formula 1 below;

[Formula 1]

R ₁ Si (R ₂ ) _a (R ₃ ) _b

In Chemical Formula 1,

R ₁ is substituted with one or more substituents selected from the group consisting of -NH ₂ , -NH (R ₄ ), -N (R ₅ ) (R ₆ ), pyridyl, pyrrole, imidazole, ureido, and acetamide C _{1 - 20} alkyl, C _2-20 alkenyl, C _{2 - 20} alkynyl, C _{3 - 8} cycloalkyl, C _{6 - 20} aryl, or C _{7 -} represents a ₂₀ aralkyl,

R ₂ is C _{1 - 20} alkyl or C _{6 - 20} aryl group refers to,

R ₃ is C _{1 - 20} alkoxy or C _{6 - 20} represents an aryloxy group,

Wherein, R _4, R ₅ and R ₆ are each independently C _{1 - 20} alkyl, C _{2 - 20} alkenyl, C _{2 - 20} alkynyl, C _3-8 cycloalkyl, or C _{6 - 20} aryl group refers to,

a represents an integer of 0 to 2,

b represents an integer of 1 to 3,

The sum of a and b is 3.

In Chemical Formula 1,

R ₁ is _{-NH 2, -NH (R 4)} , and -N (R ₅₎ with (R ₆₎ substituted with one or more substituents selected from the group consisting of C _{1 - 12} alkyl, or C _{6 - 12} aryl ,

R ₃ is C _{1 - 12} represents alkyl,

Wherein, R _4, R ₅ and R ₆ are each independently C _{1 - 12} represents a alkyl,

More preferably, a is 0 and b is derived from a compound of 3.

In particular, the compound comprising a siloxane repeating unit having one or more amine functional groups is 3-aminopropyltrimethoxysilane, 3-aminopropylethoxysilane, 4-aminobutyltriethoxysilane, m-aminophenyltrimethoxy Silane, p-aminophenyltrimethoxysilane, aminophenyltrimethoxysilane, 3-aminopropyltri (methoxyethoxyethoxy) silane, 11-aminoundecyltriethoxysilane, 2- (4-pyridyl Ethyl) triethoxysilane, 2- (trimethoxysilylethyl) pyridine, N- (3-trimethoxynisylpropyl) pyrrole, 3- (m-aminophenoxy) propyltrimethoxysilane, aminopropylsilanetri All, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldiisopropylethoxysilane, 3-aminopropyldimethylethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane , N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- (6-aminohexyl) aminometh Triethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane , N-3-[(amino (polypropylenoxy)] aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylsilanetriol, N- (2-aminoethyl) -3- Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane, (aminoethylamino) -3-isobutyldimethylmethoxysilane, (3-trimethoxy Silylpropyl) diethylenetriamine, n-butylaminopropyltrimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3 -(N-allylamino) propyltrimethoxysilane, (cyclohexylaminomethyl) triethoxysilane, N-cyclohexylaminopropyltrimethoxy Silane, N-ethylaminoisobutylmethyldiethoxysilane, (phenylaminomethyl) methyldimethoxysilane, N-phenylaminomethyltriethoxysilane, N-methylaminopropylmethyldimethoxysilane, ureidopropyl tree It may be an amine functional group-containing siloxane compound produced by a sol-gel reaction using at least one silane compound selected from the group consisting of ethoxysilane, acetamidopropyltrimethoxysilane and ureidopropyltrimethoxysilane. The alkoxy group can be prepared by making hydroxy using water or by directly reacting with silanol, silandiol or silanetriol.

In addition, the compound including the siloxane repeating unit having one or more amine functional groups preferably has an active hydrogen equivalent of 50 to 600 g / eq.

It is preferable that the compound including the siloxane repeating unit having one or more epoxy functional groups is derived from the compound represented by Formula 2 below;

[Formula 2]

R ₇ Si (R ₈ ) _a (R ₉ ) _b

In Chemical Formula 2,

R ₇ is C ₁ having an epoxide _ring-20 alkyl, C _{3 - 8} cycloalkyl, or C _{1 -} represents a ₂₀ alkoxy,

R ₈ is C _{1 - 20} alkyl or C _{6 - 20} aryl group refers to,

R ₉ is C _{1 - 20} alkoxy or C _{6 - 20} represents an aryloxy group,

a represents an integer of 0 to 2,

b represents an integer of 1 to 3,

The sum of a and b is 3.

In Chemical Formula 2

R ₇ represents epoxycyclohexyl, glycidoxy, or epoxyhexyl,

R ₉ is C _{1 - 12} represents alkyl,

More preferably, a is 0 and b is derived from a compound of 3.

Compounds comprising siloxane repeating units having one or more epoxy functional groups include 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ( 3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) trimethoxysilane, 5,6-epoxyhexyltriethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, Epoxy functional group-containing siloxane made by sol-gel reaction using at least one silane compound selected from the group consisting of (3-glycidoxypropyl) methyldimethoxysilane and (3-glycidoxypropyl) dimethylmethoxysilane The compound may be an alkoxy group of silane, which may be prepared by making hydroxy using water or by directly reacting with silanol, silandiol or silantriol.

In addition, the compound comprising a siloxane repeating unit having one or more epoxy functional groups preferably has an epoxy equivalent of 50 to 600 g / eq.

In the present invention, the curing agent is preferably an epoxy resin when a compound containing a siloxane repeating unit having at least one amine functional group is used as the binder resin, and an amine type when a compound containing a siloxane repeating unit having at least one epoxy functional group is used. Compounds are suitable.

The epoxy resin used as said hardening | curing agent is formed by reacting polyphenols, such as bisphenol A, bisphenol F, and a novolak-type phenol, with epihalohydrin, such as epichlorohydrin, and introducing a glycidyl group, or this glyc Aromatic epoxy resin which makes a molecular weight increase by further making polyphenols react with a cylyl group introduction reaction product; Furthermore, an aliphatic epoxy resin, an alicyclic epoxy resin, etc. are mentioned, These 1 type can be used individually or in mixture of 2 or more types. Especially when these epoxy resins require film formability in low temperature, it is suitable that a number average molecular weight is 1500 or more (preferably 1500-10000).

The epoxy resin also includes a resin obtained by reacting various modifiers with an epoxy group or a hydroxyl group in the epoxy resin, and includes, for example, an epoxy ester resin reacted with dry oil and fat dispersion; Epoxy acrylate resin modified with a polymerizable unsaturated monomer component containing acrylic acid or methacrylic acid; The urethane modified epoxy resin etc. which made the isocyanate compound react are mentioned.

Moreover, as an epoxy resin, the unsaturated monomer which has an epoxy group, and the polymerizable unsaturated monomer component which consists of acrylic ester or methacrylic acid ester are copolymerized with the epoxy group containing monomer synthesize | combined by solution polymerization method, emulsion polymerization method, suspension polymerization method, etc. And one acrylic copolymer resin. Examples of the polymerizable unsaturated monomer component include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-, iso- or tert-butyl. (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate such as acrylic acid or methacrylic acid of the C _{1 -24} Alkyl esters; Acrylic acid, methacrylic acid, styrene, vinyltoluene, acrylamide, acrylonitrile, N- methylol (meth) acrylamide, N- methylol (meth) C _{1 -4} alkyl ether compound of acrylamide; N, N-diethylaminoethyl methacrylate, etc. are mentioned. Moreover, as an unsaturated monomer which has an epoxy group, especially if it has an epoxy group and polymerizable unsaturated groups, such as glycidyl methacrylate, glycidyl acrylate, and 3, 4- epoxycyclohexyl-1-methyl (meth) acrylate, It is not limited.

As the epoxy monomer resin, butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, para-t-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, parac Silyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexate, glycidyl benzoate, and the like. Examples of the polyvalent epoxy compound include bisphenol A, bisphenol F, bisphenol AD, and bisphenol S. , An epoxy resin glycidylated with a dihydric phenol such as bisphenol-type epoxy resin obtained by glycidylating bisphenols such as tetramethylbisphenol A, tetramethylbisphenol AD, tetramethylbisphenol S, biphenol, dihydroxy naphthalene, 1 Epoxy resin which glycidylated trisphenols, such as 1,1,-tris (4-hydroxyphenyl) methane, the epoxy resin which glycidylated tetrakisphenol, phenol novolak, cresol novolak, etc. Aliphatic ether type epoxy resin which glycidylated polyhydric alcohols, such as an epoxy resin which glycidated novolak, glycerin, and polyethyleneglycol, and ether ester type epoxy which glycidylated hydroxycarboxylic acids, such as p-oxybenzoic acid The ester type epoxy resin which glycidylated polycarboxylic acid, such as resin, a phthalic acid, a terephthalic acid, an alicyclic epoxide, etc. is mentioned, It is not limited to this.

In addition, the amine compound used as the curing agent is at least one primary amine and / or secondary amine compound, for example methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, Primary amines which do not have tertiary amino groups, such as diethylenetriamine, and secondary amines which do not have tertiary amino groups, such as dimethylamine, dicyclohexylamine, piperidine, and phenylethylamine, are mentioned. In addition, tertiary amines having at least one tertiary amino group and at least one active hydrogen group can be used, for example, amino alcohols such as 2-dimethylaminoethanol and triethanolamine, aminophenols, imidazoles, and imida. Sleepiness, aminocarboxylic acids, aminohydrazide, and the like, and the like, and the amine compound is not limited thereto.

In particular, the binder resin and the curing agent in the composition for treating the metal surface according to the present invention are preferably such that the active hydrogen equivalent of the binder resin and the epoxy equivalent of the curing agent are 1: 1. Outside the above range there is a problem that the curing rate of the coating film is slowed.

The metal surface treatment composition according to the present invention may be used with a solvent in addition to the binder resin and the curing agent, but such solvent is not particularly limited as long as it is a solvent commonly used in the art as a component excluding solids in the metal surface treatment composition. It is preferable to use alkylene glycol monoalkyl ether acetate and / or water, and the amount thereof is preferably 0 to 300 parts by weight based on 100 parts by weight of the binder resin. If it exceeds 300 parts by weight, the viscosity of the solution is reduced too much, there is a problem of poor coating properties.

At this time, the solvent may further add a separate alcohol solvent and an alkaline aqueous solution in order to improve the properties such as wettability, dispersibility of the metal surface treatment composition. Ethanol, methanol, propanol, isopropanol, glycerol, and the like may be used as the alcohol solvent, and as the alkaline aqueous solution, an amine compound, N-methylpyrrolidone, sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium hydroxide, or the like may be used. Can be.

In addition, the composition for treating the metal surface of the present invention may further include one or more additives such as a wetting agent, a crosslinking agent, a lubricant, and an antifoaming agent. The wetting agent is effective in streaking and adhesion, the crosslinking agent in corrosion resistance and alkali resistance, the lubricant in friction coefficient and processability, and the antifoaming agent in further improving workability.

These additives are preferably used in an amount of 10 to 200 parts by weight, more preferably 50 to 150 parts by weight, based on 100 parts by weight of the binder resin. If the content of the additive is less than 10 parts by weight, there is no use effect of the additives such as corrosion resistance, alkali resistance, etc., if it exceeds 200 parts by weight, the effect is saturated, and further addition is not meaningful and there is a problem of reducing solution stability.

The wetting agent includes a deagglomerated wet dispersant, a polymer wet dispersant, and the like. Examples of the wetting agent include a wet dispersant commercially available from EFKA and Tego, and the like. EFKA 3580 (Ciba) and BW-W500 (Bumwoo Chemical) Or WET500 (Ciba).

Examples of the crosslinking agent include vinylsilane, methoxysilane, acrylicsilane, epoxysilane, chlorosilane, alkoxysilane, silazane, silylating agent, melamine, melamine resin, alkylmelamine, alkylmelamine resin, fluorinated melamine and fluorinated melamine resin, and polyamine type. , Alkylated aromatic polyamine-based, polyamide-based or acid-anhydride-based curing agents and the like can be used.

The lubricant includes silicone wax, polyethylene wax, polypropylene wax, amide wax, polytetrafluoroethylene (PTFE) wax, paraffin wax, and the like.

The antifoaming agent may be an oil type, a modified type, a solution type, a powder type, or an emulsion type silicone antifoaming agent.

The present invention also relates to a steel sheet comprising a coating layer using the composition for treating the metal surface.

The metal surface treatment composition of the present invention as a coating layer may be applied to a steel sheet and dried to treat the steel sheet.

The steel sheet to which the composition for treating the metal surface according to the present invention may be applied as a coating layer is not particularly limited thereto. As the meaning of the metal, any steel plate commonly used in the art for this purpose may be any, but preferably cold-rolled steel sheet; Zinc-based electroplating steel sheets such as galvanized steel sheet, zinc nickel plated steel sheet, galvanized steel sheet, zinc titanium plated steel sheet, zinc magnesium plated steel sheet, zinc manganese plated steel sheet and zinc aluminum plated steel sheet; Hot-dip galvanized steel sheet; Aluminum plated steel sheet; Further, plated steel sheets containing, as the dissimilar metals or impurities in these plating layers, for example, cobalt, molybdenum, tungsten, nickel, titanium, aluminum, manganese, iron, magnesium, tin, copper, and the like; Further, plated steel sheet in which inorganic materials such as silica and alumina are dispersed in these plating layers; Or an aluminum alloy plate containing silicon, copper, magnesium, iron, manganese, titanium, zinc or the like; Or galvanized steel sheet coated with phosphate; Alternatively, a hot rolled steel sheet may be used, and a multilayer plated sheet obtained by sequentially treating two or more kinds during the plating may be used as necessary.

The method for treating the steel sheet using the composition of the present invention may be carried out after washing the surface of the steel sheet by a method generally known in the art in order to remove oil and stains attached to the steel sheet, if necessary. Although washing | cleaning is not limited to this, It can carry out using an alkali degreasing agent, an acidic degreasing agent, high temperature water, or a solvent. After cleaning, surface adjustment can be performed using acid or alkali.

It is preferable to wash with water after washing so that the cleaning agent does not remain on the surface of the steel sheet as much as possible when cleaning the surface of the steel sheet. Although not limited to this, As an example, it is preferable to surface-treat with the metal surface treatment composition of this invention after wash | cleaning, water washing, and surface adjustment of the raw material metal (steel plate) surface as mentioned above.

In treating the metal surface by the method according to the present invention, the composition for treating the metal surface may be applied as a coating layer on the surface of the steel sheet by any coating method generally known in the art. The coating method used in the application is not particularly limited, and known coating methods such as bar coating, dip coating, roll coating, curtain coating, spray coating, slit coating, gravure coating, and the like can be used. At this time, the coating temperature is not particularly limited. The thickness of the coating layer is preferably 1.0 ~ 7.0 ㎛.

Thus, the surface pretreated steel sheet may be prepared by curing the metal surface treatment composition on the surface of the base steel sheet at 100 to 300 ° C. within 5 minutes (1 second to 5 minutes).

As described above, the composition for treating the metal surface according to the present invention can be quickly cured by mixing and using an organic siloxane resin and an appropriate organic resin, and is environmentally friendly, and has high corrosion resistance, coating adhesion, low temperature drying property, and transparency.

Hereinafter, the present invention will be described in more detail by way of examples. It should be noted, however, that the following examples are illustrative of the invention and are not intended to limit the scope of the invention.

[ Manufacturing example Binder Resin Manufacturing

Manufacturing example  1: having an epoxy functional group Siloxane  Compounds containing repeating units ( HEOS / 170)

3-glycidoxypropyltrimethoxysilane (GPTS, Aldrich) was used as a starting material of the compound (HEOS / 170) including a siloxane repeating unit having an epoxy functional group. For hydrolysis, 1.5 mol of water (H ₂ O) was used in comparison to 1 mol of GPTS, and Amberlite IRA-400 chloride type (Aldrich) ion exchange resin was used as a catalyst for promoting the condensation reaction. In addition, it was synthesized using a solvent propylene glycol monomethyl ether acetate (PGMEA, Aldrich) to prevent phase separation due to insolubility of alkoxysilane and water in the initial stage. All starting materials were mixed and then reacted at 80 ° C. for 24 hours in reflux.

HEOS / 170 has 8 to 13 epoxy groups per molecule modified after the particles are formed, and this is represented by the molecular weight attached to one epoxy (epoxy equivalent, epoxy equivalent), and the epoxy equivalent of HEOS / 170 is 170 g / mol to be.

Manufacturing example  2: having amine functionality Siloxane  Compounds containing repeating units ( AOS / 130)

As a starting material of the compound (AOS / 130) containing a siloxane repeating unit having an amine functional group, 3-aminopropyltrimethoxysilane (APTS, Aldrich) and diphenylsilanediol (DPSD, Gelest) were used. Barium hydroxide monohydrate (Ba (OH) ₂ .H ₂ O, Aldrich) was used as the catalyst. The amount of Ba (OH) ₂ .H ₂ O was 0.1 mol% of the total silane used, and the reaction was carried out at high temperature using a magnetic stirrer and a silicone oil batch in a flask. It was fixed at 80 ° C. to evaporate. After a total of 3 hours of reaction, a final product of the resin form was obtained after filtration using a 0.45 μm filter to remove the catalyst. The amount of APTS and DPSD was made by reacting 2: 1 in mol ratio.

After the particles were produced, AOS / 130 averaged two to three amine groups per molecule, and the equivalents were calculated based on active hydrogen (two hydrogens present in the amine group). Is 130 g / eq.

Manufacturing example  3: having amine functionality Siloxane  Compounds containing repeating units ( AOS / 210)

As a starting material of the compound (AOS / 210) containing a siloxane repeating unit having an amine functional group, 3-aminopropyltrimethoxysilane (APTS, Aldrich) and diphenylsilanediol (DPSD, Gelest) were used. Barium hydroxide monohydrate (Ba (OH) ₂ .H ₂ O, Aldrich) was used as the catalyst. The amount of Ba (OH) ₂ .H ₂ O was 0.1 mol% of the total silane used, and the reaction was carried out at high temperature using a magnetic stirrer and a silicone oil batch in a flask. It was fixed at 80 ° C. to evaporate. After a total of 3 hours of reaction, a final product of the resin form was obtained after filtration using a 0.45 μm filter to remove the catalyst. The amount of APTS and DPSD was made by reacting 1: 1 in mol ratio.

AOS / 210 has two to three amine groups per molecule modified after particles are produced, and the equivalents are calculated based on active hydrogen (two hydrogens present in the amine groups). 210 g / eq.

[ Reference Example : Using curing agent]

Reference Example  1: epoxy Monomer  Suzy

Bisphenol A diglycidyl ether (YD-128, Kukdo Chemical Co., Ltd.) having an epoxy equivalent of 185 was used as the epoxy resin.

Reference Example  2: epoxy Dimer  Suzy

Bisphenol A diglycidyl ether (YD-172, Kukdo Chemical Co., Ltd.) having an epoxy equivalent of 650 was used as an epoxy resin.

Reference Example  3: amine compound

Ethylenediamine (EDA, Sigma Aldrich) having an active hydrogen equivalent of 15 was used as the amine compound.

[ Example  1 to 5 and Comparative example  1: Preparation of Composition for Metal Surface Treatment]

Example  One

Next, as shown in Table 1, a compound (AOS / 130) including an epoxy monomer resin (YD-128) as a curing agent and a siloxane repeating unit having an amine functional group as a binder resin was mixed and stirred for 10 minutes to prepare a composition for metal surface treatment. . In this case, propylene glycol monomethyl ether acetate (PGMEA, Aldrich) was used as the solvent.

The mixing ratio of YD-128 and AOS / 130 was composed of the epoxy equivalent and the active hydrogen equivalent of 1: 1 and the weight ratio of 185: 130, respectively.

Example  2

Next, as shown in Table 1, a compound (AOS / 210) containing an epoxy monomer resin (YD-128) as a curing agent and a siloxane repeating unit having an amine functional group as a binder resin was mixed and stirred for 10 minutes to prepare a metal surface treatment composition. . In this case, propylene glycol monomethyl ether acetate (PGMEA, Aldrich) was used as the solvent.

The compounding ratio of YD-128 and AOS / 210 was composed of the epoxy and active hydrogen equivalents of 1: 1 and 185: 210 by weight.

Example  3

Next, as shown in Table 1, a compound (AOS / 130) containing an epoxy dimer resin (YD-172) as a curing agent and a siloxane repeating unit having an amine functional group as a binder resin was mixed and stirred for 10 minutes to prepare a composition for metal surface treatment. . In this case, propylene glycol monomethyl ether acetate (PGMEA, Aldrich) was used as the solvent.

The compounding ratio of YD-172 and AOS / 130 was composed of the epoxy equivalent and the active hydrogen equivalent of 1: 1 and the weight ratio of 650: 130, respectively.

Example  4

Next, as shown in Table 1, a compound (AOS / 210) containing an epoxy dimer resin (YD-172) as a curing agent and a siloxane repeating unit having an amine functional group as a binder resin (AOS / 210) was mixed and stirred for 10 minutes to prepare a composition for metal surface treatment. . In this case, propylene glycol monomethyl ether acetate (PGMEA, Aldrich) was used as the solvent.

The blending ratio of YD-172 and AOS / 210 consisted of a weight ratio of 1: 1 and 650: 210 of epoxy equivalent and active hydrogen equivalent, respectively.

Example  5

Next, mixing and stirring the epoxy monomer resin (YD-128), the epoxy dimer resin (YD-172), and the siloxane repeating unit having an amine functional group as the binder resin (AOS / 210) for 10 minutes as shown in Table 1 To prepare a composition for treating a metal surface. In this case, propylene glycol monomethyl ether acetate (PGMEA, Aldrich) was used as the solvent.

The blending ratio of the curing agent (YD-128 and YD-172) and AOS / 210 was composed of the epoxy equivalent and the active hydrogen equivalent of 1: 1 and the weight ratio of 835: 210, respectively.

Example  6

Next, as shown in Table 1, a compound (HEOS / 170) including an amine compound (EDA) and a siloxane repeating unit having an epoxy functional group was mixed and stirred for 10 minutes to prepare a metal surface treatment composition. In this case, propylene glycol monomethyl ether acetate (PGMEA, Aldrich) was used as the solvent.

The mixing ratio of EDA and HEOS / 170 consisted of 1: 1 and 15: 170 weight ratios of epoxy equivalent and active hydrogen equivalent, respectively.

Comparative example  One

As shown in Table 1, a composition for treating a metal surface is prepared by combining a compound including a siloxane repeating unit having an epoxy functional group as a binder resin (HEOS / 170) and a compound including a siloxane repeating unit having an amine functional group (AOS / 130). Prepared. In this case, propylene glycol monomethyl ether acetate (PGMEA, Aldrich) was used as the solvent.

The blending ratio of HEOS / 170 and AOS / 130 consisted of a weight ratio of 170: 130 of 1: 1 epoxy equivalent and active hydrogen equivalent, respectively.

Division (weight part) Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 bookbinder
Suzy Epoxy group
contain
Siloxane compound HEOS
/ 170 170 - - - - - 170 Amine group containing
Siloxane
compound AOS
/ 130 130 130 - 130 - - - AOS
/ 210 - - 210 - 210 210 - Hardener Epoxy
Suzy YD
-128 - 185 185 - - 185 - YD
-172 - - - 650 650 650 - Amine compound EDA - - - - - - 15 solvent PGMEA 130 115 115 350 350 465 130 total 430 430 510 1130 1210 1510 315

Experimental Example  1: check physical properties

Bar coating on the metal surface treatment compositions of Examples 1 to 6 and Comparative Example 1 using a coil bar so that the adhesion of the dry coating film to the GI mark (Immersing galvanized steel sheet), which is a hot dip galvanized steel sheet, may be 5 to 10 mg / m 2. At this time, the thickness of the substrate was 0.55 ~ 0.6 mm. Subsequently, it was placed on a conveyor belt moving at 220 ° C. at 220 ° C. in an electric induction heater and cured to prepare a surface-treated steel sheet, which was used as a specimen in a physical property test [coating layer thickness: 3 to 5 μm].

1 shows a GI steel sheet surface (top), a steel sheet surface (middle) coated with the metal surface treatment composition of Comparative Example 1, and a steel sheet surface (bottom) coated with the metal surface treatment composition of Example 1. FIG. The rough GI steel plate surface (top) was coated with the smooth steel plate surface (bottom) through the metal surface treatment of Example 1. In the steel plate surface (middle) coated with the composition for metal surface treatment of the comparative example 1, the rough coating surface is shown.

Steel sheets coated with the metal surface treatment compositions of Examples 1 to 6 and Comparative Example 1 were evaluated as follows, and the evaluation results are shown in Table 2 below.

1) fast curing

It was placed on a conveyor belt moving at a speed of 2 meters per minute at 220 ° C. in an electric induction heater, and the curing was carried out.

All compositions of Examples 1 to 6 and Comparative Example 1 were cured.

2) chemical resistance

The surface change was evaluated when the hardened steel sheet was rubbed with methyl ethyl ketone (MEK).

[Judge criteria]

○: No surface change after rubbing 100 times

△: within 100% of surface change rate after rubbing 100 times

×: 100% or more of surface change rate after rubbing 100 times

3) Adhesive / Processable

In order to test the change of adhesion due to the deformation of the coating film, the cross-cut specimen using diamond knife is made by bending using circular beads, and then the tape is attached to the entire bending surface and the adhesion test is performed. In detail, it is as follows.

If you cross-cut a coated steel sheet to make 10 x 10 isolated coated surfaces and make bends in the cross-cut area using the Erichsen machine, then 100 tapes are removed if the tape is securely attached to the cross-cut area. You can evaluate how much the coated surface sticks to the tape. When the flexibility of the material is good and the adhesion of the coating is good, less sticking out of the steel sheet due to sticking to the tape occurs, and when the adhesiveness between the material and the steel sheet is bad, the coating adheres to the tape.

[Judge criteria]

○: no coating dropout rate

▲: coating rejection rate 1 to 5%

(Triangle | delta): 5-20% of coating | column dropping ratios

×: 20% or more coating dropout rate

4) Chemical resistance

After making 10% sulfuric acid and 10% sodium hydroxide, respectively, the coated sample was immersed in the solution to confirm the change trend.

[Judge criteria]

○: within 5% of coating film change after 72 hours

△: coating film change after 72 hours 5 to 20%

×: 20% or more of coating film change after 72 hours

5) corrosion resistance

After hardening, the steel sheet was cut out, and both the cut steel sheet and the uncoated steel sheet were placed in a salt spray tank continuously spraying 5% saline solution at 35 ° C. and 95% humidity, and the degree of rusting over time was confirmed.

[Judge criteria]

○: no after 500 hours

▲: 1 to 5% incineration rate after 500 hours

(Triangle | delta): 5 to 20% of a coating ratio after 500 hours

×: after 500 hours incineration rate 20% or more

division result Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Fast curing 2 mpm curing at 220 ℃ electric induction heater Chemical resistance × ○ ○ ○ ○ ○ ○ Adhesive / Processable × △ △ △ ▲ ○ △ Chemical resistance Sulfuric acid × △ △ ○ △ ○ △ NaOH × ○ ○ ○ △ △ △ Corrosion resistance × ○ △ ▲ △ △ △

Figure 2 shows the change of the steel sheet coated with the composition for treating the metal surface of Example 3 immersed in 10% sulfuric acid solution, there was no change in the coating film and the steel sheet until 72 hours.

Figure 3 shows the change of the steel sheet coated with the composition for treating the metal surface of Example 3 immersed in a 10% solution of sodium hydroxide, there was no change in the coating film and the steel sheet until 72 hours.

Figure 4 shows the corrosion resistance test by cutting the steel plate coated with the composition for treating the metal surface of Example 1, the red blue began to appear after 58 days.

Claims (15)

A binder resin comprising a compound comprising a siloxane repeating unit having at least one amine functional group, and an epoxy resin as a curing agent,
The compound comprising a siloxane repeating unit having one or more amine functional groups has an active hydrogen equivalent of 50 to 600 g / eq, a composition for high-speed thermosetting metal surface treatment, characterized in that derived from the compound of formula
[Formula 1]
R ₁ Si (R ₂ ) _a (R ₃ ) _b
In Chemical Formula 1,
R ₁ is substituted with one or more substituents selected from the group consisting of -NH ₂ , -NH (R ₄ ), -N (R ₅ ) (R ₆ ), pyridyl, pyrrole, imidazole, ureido, and acetamide C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _3-8 cycloalkyl, C _6-20 aryl, or C _7-20 aralkyl,
R ₂ represents C _1-20 alkyl or C _6-20 aryl,
R ₃ represents C _1-20 alkoxy or C _6-20 aryloxy,
Wherein R ₄ , R ₅ and R ₆ each independently represent C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _3-8 cycloalkyl, or C _6-20 aryl,
a represents an integer of 0 to 2,
b represents an integer of 1 to 3,
The sum of a and b is 3.
The method of claim 1,
The compound having a siloxane repeating unit is prepared by a condensation reaction of an amine alkoxysilane and water or silanol.
delete delete delete The method of claim 1,
R ₁ represents C _1-12 alkyl substituted with one or more substituents selected from the group consisting of —NH ₂ , —NH (R ₄ ), and —N (R ₅ ) (R ₆ ), or C _6-12 aryl ,
R ₃ represents C _1-12 alkoxy,
Wherein R ₄ , R ₅ and R ₆ each independently represent C _1-12 alkyl,
a is 0, b is 3, The composition for high-speed thermosetting metal surface treatment.
delete delete delete delete delete The method of claim 1,
The epoxy resin is at least one selected from the group consisting of aromatic epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, epoxy ester resins, epoxy acrylate resins and urethane-modified epoxy resin composition for a high-speed thermosetting metal surface treatment.
The method of claim 1,
The binder resin and the curing agent comprises a 1: 1 active hydrogen equivalent of the binder resin and epoxy equivalent of the curing agent in a high speed thermosetting metal surface treatment composition.
The method of claim 1,
A composition for high speed thermosetting metal surface treatment further comprising at least one additive selected from the group consisting of a crosslinking agent, a wetting agent, a lubricant and an antifoaming agent.
Base steel sheet; And
The steel sheet according to claim 1, wherein the composition for treating the high-speed thermosetting metal surface is cured to include a coating layer formed on one or both surfaces of the base steel sheet.

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