KR101809513B1 - Precomposition for preparing waterborne polyurethane, and waterborne polyurethane prepared therefrom - Google Patents

Abstract

More particularly, the present invention relates to a water-dispersible polyurethane composition having corrosion resistance, which comprises a diol compound having corrosion resistance in a recurring unit and forming a corrosion-resistant coating film on a surface of a highly corrosive metal, The present invention relates to a composition of a corrosion-resistant water-dispersible polyurethane which can effectively slow down the corrosion resistance.

Description

[0001] The present invention relates to a water-dispersible polyurethane precursor composition and a water-dispersible polyurethane prepared therefrom,

The present invention relates to a composition for the production of a water-dispersible polyurethane excellent in corrosion resistance, and to an aqueous dispersion polyurethane produced therefrom, and more particularly to an aqueous dispersion polyurethane which effectively inhibits the corrosion rate of a metal by forming a corrosion- And a water-dispersible polyurethane produced therefrom, and a water-dispersible polyurethane. The present invention also relates to a water-dispersible polyurethane composition comprising the water-dispersible polyurethane and the water-dispersible polyurethane.

Generally, the water tank, food processing tank, livestock liquid storage tank and sedimentation aeration tank of the sewage treatment plant are formed of reinforced concrete and concrete structures. However, the steel structure such as the water tank or the food processing tank of the apartment has a problem of contamination of the water or food stored in the corrosion of the reinforcing steel, and the structure such as the sewer pipe has a problem in that the sewage sulfur compound, And the inner surface of the structure is easily corroded by the generated sulfuric acid or the like.

In order to solve the above problems, conventionally, a coating layer, which is a mixture of FRP resin and mortar, was applied to the inner surfaces of reinforcing bars and concrete structures. However, since FRP resin has toxicity due to glass fiber and environmental hormone of coating agent, . Also, when applied to a sewer pipe, there is a disadvantage that a coating layer which is simply applied can not be expected to have a lasting effect because it is easily worn out due to interference generated in the continuous passage of sewage. In recent years, a technique of preventing corrosion by installing a separate sheet on the inner surface of the structure has been applied.

However, in order to join a member such as a sheet to the inner circumference of the structure as described above, it is required to be coupled with the formation of the structure at the same time, which complicates the fabrication process and is not applicable to general reinforcing bars and concrete structures. In addition, when the present invention is applied to a continuous structure such as a sewer pipe because the sheet is complicated due to the complicated structure of the sheet, mutual bonding of the sheets does not occur and a gap is generated, so that a complete toxicity and corrosion prevention effect can not be expected have.

Accordingly, researches have been actively conducted on techniques for preventing corrosion by applying polyurethane resin widely used for paints, adhesives, binders, coating agents and the like due to their physical properties such as abrasion resistance, adhesiveness, non-stickiness and elasticity. Korean Patent Laid-Open Publication No. 2013-0097943 discloses a method for manufacturing an inner surface lining centrifugal reinforced concrete pipe using a resin composition for a polyurethane-based structure system. However, according to the resin composition for a system proposed in the above-mentioned technique, It is difficult to solve the problems such as cracks generated in the lining and thus the durability is deteriorated and the corrosion resistance is insufficient. There is a problem in that the improvement of the roughness coefficient of the lining is not expected to be expected, Complexity and inefficiency.

In order to solve the problems of the prior art, studies have been made on a water-dispersible polyurethane coating used as a coating material for a surface-treated steel sheet by mixing and spraying and curing a water-dispersible polyurethane composition. International patent application WO 2006-055038 by Hontek Corporation discloses a corrosion resistant polyurethane coating made from an isocyanate prepolymer with polyaspartate. However, these coatings are also unsuitable for practical use due to the short duration of corrosion resistance to be used in industry.

Korean Patent Publication No. 2013-0097943 International Publication No. WO 2006-055038

Disclosure of the Invention In order to solve the above problems, the present invention provides an aqueous dispersion type polyurethane precursor composition capable of effectively slowing corrosion rate of metal by forming a corrosion-resistant coating film on a surface of a highly corrosive metal and exhibiting high corrosion resistance for a long time, Corrosion-resistant polyurethane which has the same effect as that of the water-dispersible polyurethane, and a water-dispersible polyurethane.

The present invention relates to an aqueous dispersion type polyurethane precursor composition comprising a diol compound represented by the following formula (1).

[Chemical Formula 1]

및

로 표시되는 작용기에서 선택되되, 상기 T₁ 내지 T₈ 중 최소 2개 이상은 서로 독립적으로

및

로 표시되는 작용기에서 선택되며; R₁ 및 R₄는 서로 독립적으로 치환 또는 비치환된 (C1-C20)알킬렌기, 치환 또는 비치환된 (C3-C20)시클로알킬렌기, 치환 또는 비치환된 (C2-C20)알케닐렌기, 치환 또는 비치환된 (C6-C30)아릴렌기 및 치환 또는 비치환된 (C3-C30)헤테로아릴렌기에서 선택되는 어느 하나이고; R₂ 내지 R₃는 서로 독립적으로 수소, 치환 또는 비치환된 (C1-C20)알킬기, 치환 또는 비치환된 (C3-C20)시클로알킬기, 치환 또는 비치환된 (C2-C20)알케닐기, 치환 또는 비치환된 (C6-C30)아릴기 및 치환 또는 비치환된 (C3-C30)헤테로아릴기에서 선택되는 어느 하나이며; R₅ 내지 R₆는 서로 독립적으로 -OH, -NCO 및 -NH₂에서 선택되는 어느 하나의 작용기일 수 있다.In Formula _1, T 1 to T ₈ are independently hydrogen, (C1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkynyl, (C2-C30) alkoxy, (C3- each other C20) cycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl,

And

, Wherein at least two of T ₁ to T ₈ are independently selected from the group consisting of

And

≪ / RTI > R ₁ and R ₄ independently represent a substituted or unsubstituted (C 1 -C 20) alkylene group, a substituted or unsubstituted (C 3 -C 20) cycloalkylene group, a substituted or unsubstituted (C 2 -C 20) alkenylene group, A substituted or unsubstituted (C6-C30) arylene group and a substituted or unsubstituted (C3-C30) heteroarylene group; R ₂ to R ₃ independently represent hydrogen, a substituted or unsubstituted (C 1 -C 20) alkyl group, a substituted or unsubstituted (C 3 -C 20) cycloalkyl group, a substituted or unsubstituted (C 2 -C 20) Or an unsubstituted (C6-C30) aryl group and a substituted or unsubstituted (C3-C30) heteroaryl group; R ₅ to R ₆ independently of each other may be any functional group selected from -OH, -NCO, and -NH ₂ .

In the present invention, the diol compound represented by Formula 1 may be a compound represented by Formula 2 below.

(2)

In Formula 2, R ₁ and R ₄ are each independently a substituted or unsubstituted (C 1 -C 4) alkylene group; R ₂ to R ₃ independently of each other may be any one selected from a methyl group, an ethyl group and a propyl group.

In the present invention, the aqueous dispersion type polyurethane precursor composition may further comprise a polyol compound, a polyisocyanate compound and an ionic functional group-introducing compound.

In the present invention, the polyol compound may be at least one polyol selected from the group consisting of a polyether polyol, a polycarbonate polyol and a polyester polyol; And a substituted or unsubstituted (C3-C30) alkylpolyol, a substituted or unsubstituted (C3-C30) cycloalkylpolyol, a substituted or unsubstituted (C6- ) Heteroaryl polyols. ≪ / RTI >

In the present invention, the ionic functional group-introducing compound may be any one selected from the group consisting of an anionic functional group-introducing compound and a cationic functional group-introducing compound.

In the present invention, the anionic functional group-introducing compound may be a compound containing at least one anionic functional group selected from a carboxyl group, a sulfonic acid group and a phosphoric acid group.

In the present invention, the cationic functional group-introducing compound may be a compound containing at least one cationic functional group selected from a secondary amine group, a tertiary amine group and a quaternary amine group.

Another embodiment of the present invention relates to an aqueous polyurethane produced from the aqueous dispersion type polyurethane precursor composition.

Another aspect of the present invention relates to a corrosion-inhibiting polyurethane coating composition comprising the water-dispersible polyurethane.

In the present invention, the aqueous polyurethane can be added in an amount of 0.1 to 30% by weight based on the total weight of the coating composition.

The aqueous dispersion type polyurethane precursor composition of the present invention comprises a polyol compound and a polyisocyanate compound which are dispersed in water to form a polyurethane and a diol compound capable of imparting high corrosion resistance, And a polyisocyanate compound to form a corrosion resistant polyurethane coating layer capable of effectively slowing the corrosion rate of the metal through a process of coating and curing the metal on a surface of a highly corrosive metal and exhibiting high corrosion resistance for a long time The effect can be obtained.

Fig. 1 shows the results of observing the specimen surface of Example 24 and Comparative Example 4 of the present invention in which Experiment 1 of the present invention was conducted for 96 hours.
2 shows the result of observing the surface of a specimen of Example 24 of the present invention in which Experiment 1 of the present invention was conducted for 432 hours.

Hereinafter, the water dispersible polyurethane precursor composition of the present invention will be described in detail. The following embodiments are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. It will be apparent to those skilled in the art that, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, And a description of the known function and configuration will be omitted.

In the entire specification, "water-dispersed polyurethane" is used as a word having the same meaning as "water-dispersible polyurethane", and "substituted" means that in the structure constituting the compound or compound, the hydrogen element bonded to the carbon element Substituted with at least one substituent selected from the group consisting of a nitro group, a C1-C7 alkyl group, a C3-C10 cycloalkyl group, a C1-C7 alkoxy group, a C6-C30 aryl group, a C3-C30 heteroaryl group, , &Quot; Corrosion-resistant diol compound " is used as the term " Diol compound represented by formula (1) "

Further, throughout the specification, " alkyl group " includes both straight chain alkyl groups and branched alkyl groups, and includes primary alkyl groups, secondary alkyl groups and tertiary alkyl groups unless otherwise specified.

The present invention relates to a precursor composition capable of producing a corrosion-resistant water-dispersible polyurethane capable of producing a coating film capable of effectively slowing corrosion rate of a metal by being coated and cured on a metal surface and exhibiting high corrosion resistance for a long time, To a water dispersible polyurethane precursor composition comprising a diol compound represented by the following formula (1) having high corrosion resistance.

[Chemical Formula 1]

및

로 표시되는 작용기에서 선택되되, 상기 T₁ 내지 T₈ 중 최소 2개 이상은 서로 독립적으로

및

로 표시되는 작용기에서 선택되며; 상기 R₁ 및 R₄는 서로 독립적으로 치환 또는 비치환된 (C1-C20)알킬렌기, 치환 또는 비치환된 (C3-C20)시클로알킬렌기, 치환 또는 비치환된 (C2-C20)알케닐렌기, 치환 또는 비치환된 (C6-C30)아릴렌기 및 치환 또는 비치환된 (C3-C30)헤테로아릴렌기에서 선택되는 어느 하나이고, R₂ 내지 R₃는 서로 독립적으로 수소, 치환 또는 비치환된 (C1-C20)알킬기, 치환 또는 비치환된 (C3-C20)시클로알킬기, 치환 또는 비치환된 (C2-C20)알케닐기, 치환 또는 비치환된 (C6-C30)아릴기 및 치환 또는 비치환된 (C3-C30)헤테로아릴기에서 선택되는 어느 하나이며, R₅ 내지 R₆는 서로 독립적으로 -OH, -NCO 및 -NH₂에서 선택되는 어느 하나의 작용기일 수 있으나, 이에 특별히 제한되는 것은 아니다. 상기 작용기의, “

” 은 결합부위를 의미하는 표식이며, 상기 R₅ 및 R₆ 관능기를 통하여, 폴리우레탄 중합반응 중 상기 화학식 1로 표시되는 내부식성 디올 화합물이 본 발명의 폴리우레탄의 반복단위에 포함될 수 있다.In Formula _1, T 1 to T ₈ are independently hydrogen, (C1-C20) alkyl, (C2-C20) alkenyl, (C2-C20) alkynyl, (C2-C30) alkoxy, (C3- each other C20) cycloalkyl, (C6-C30) aryl, (C3-C30) heteroaryl,

And

, Wherein at least two of T ₁ to T ₈ are independently selected from the group consisting of

And

≪ / RTI > Wherein R ₁ and R ₄ independently represent a substituted or unsubstituted (C 1 -C 20) alkylene group, a substituted or unsubstituted (C 3 -C 20) cycloalkylene group, a substituted or unsubstituted (C 2 -C 20) alkenylene group , A substituted or unsubstituted (C6-C30) arylene group and a substituted or unsubstituted (C3-C30) heteroarylene group, and R ₂ to R ₃ are each independently selected from hydrogen, substituted or unsubstituted (C 1 -C 20) alkyl group, a substituted or unsubstituted (C 3 -C 20) cycloalkyl group, a substituted or unsubstituted (C 2 -C 20) alkenyl group, a substituted or unsubstituted a (C3-C30) and one selected from a heteroaryl group, R ₅ to R ₆ include, but are each independently -OH, -NCO and date, but may any of the action is selected from -NH _2, in particular limitation no. The "

Refers to a binding site. Through the R ₅ and R ₆ functional groups, the corrosion-resistant diol compound represented by Formula 1 may be included in the polyurethane recurring unit of the present invention during the polyurethane polymerization reaction.

Thus, by adding the diol compound represented by the formula (1) to the precursor composition, it is possible to produce a corrosion-resistant, water-dispersible polyurethane having excellent water-dispersibility and improved corrosion resistance. Specifically, by adding the corrosion-resistant aqueous dispersion type polyurethane prepared by adding the diol compound represented by the formula (1) to the coating composition, as described in the following examples, when the corrosion resistance of the coating film is evaluated, An area of 5% of the area can be corroded for more than 120 hours.

In the present invention, the diol compound represented by the formula (1) is preferably a compound represented by the following formula (2), but is not particularly limited thereto.

(2)

In Formula 2, R ₁ and R ₄ are independently a substituted or unsubstituted (C 1 -C 4) alkylene group, and R ₂ to R ₃ are each independently selected from a methyl group, an ethyl group, and a propyl group have.

By using a diol compound satisfying this requirement, the corrosion resistance of the coating film can be further improved. Concretely, when evaluating the corrosion resistance of the coating film, the time of 5% of the total area of the specimen was eroded for 168 hours or more. At this time, the upper limit of the time when the area of 5% of the total area of the specimen is corroded is not particularly limited, and may be 1000 hours or less in a non-limiting specific example.

The aqueous dispersion type polyurethane precursor composition of the present invention may further comprise a polyol compound, a polyisocyanate compound and an ionic functional group-introducing compound in addition to the diol compound.

In the present invention, the polyol compound may be at least one high molecular weight polyol selected from the group consisting of a polyether polyol, a polycarbonate polyol and a polyester polyol; And a substituted or unsubstituted (C3-C30) alkylpolyol, a substituted or unsubstituted (C3-C30) cycloalkylpolyol, a substituted or unsubstituted (C6- ) Heteroaryl polyols, and the like; And the high molecular weight polyol may be a compound having a number average molecular weight of 400 to 5,000 g / mol, preferably 500 to 3,000 g / mol, and the low molecular weight polyol may have a number average molecular weight of 50 Lt; / RTI > to 400 g / mol. The number average molecular weight of the polyol is not particularly limited. However, when the above range is satisfied, the characteristics of the soft segment of the polyurethane produced are maximized and the softness and elasticity are maximized, so that the possibility of occurrence of defects such as cracks So that it can be minimized. In the present invention, the polyol compound may preferably be a di- to tetra-functional polyhydric alcohol having high dispersibility with respect to water, and more specifically, a polyether diol containing at least one diol selected from an aliphatic diol and an alicyclic diol, High molecular weight diols such as polycarbonate diol and polyester diol; 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol and 1,9- Chain aliphatic diols; Branched aliphatic diols such as 2-methyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol and 2-methyl-1,9-nonanediol; Tri- to tetra-functional aliphatic polyhydric alcohols such as trimethylolpropane and pentaerythritol; 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, 2,5- Methyl) -1,4-dioxane, 2,7-norbornanediol, tetrahydrofurandimethanol and 1,4-bis (hydroxyethoxy) cyclohexane; Aromatic diols such as 1,4-benzene dimethanol, 1,3-benzene dimethanol, 1,2-benzene dimethanol, 4,4'-naphthalene dimethanol and 3,4'-naphthalene dimethanol; And the like, and preferably 1,6-hexanediol, or 1,6-hexanediol and 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, Heptanediol, 1,8-octanediol, and 1,9-nonanediol, but is not particularly limited thereto.

In the present invention, the polyisocyanate compound may include at least one compound selected from the group consisting of aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate.

Examples of the aromatic polyisocyanate usable as the polyisocyanate compound in the present invention include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6- Isocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl- 4,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, m-iso Cyanatophenylsulfonyl isocyanate and p-isocyanatophenylsulfonyl isocyanate. The aliphatic polyisocyanate is specifically exemplified by ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate Iso 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) isocyanurate, Fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and the alicyclic polyisocyanate is specifically exemplified by isophorone di (Hydrogenated TDI), bis (2-isocyanatoethyl) - isocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate Dicyclohexene-1,2-dicarboxylate, 2,5-norbornanediisocyanate, 2,6-norbornadiisocyanate, and the like, but are not particularly limited thereto.

In the present invention, the polyisocyanate compound is preferably a diisocyanate having two isocyanate groups per molecule, and more preferably, the isophorone diisocyanate (IPDI) and 4,4'-dicyclohexylmethane diisocyanate Can be used as the diisocyanate. The polyisocyanate compound used in the present invention is not particularly limited, but when the compound is used, it is possible to produce polyurethane having high hardness and high durability. In addition, tri- to tetra-functional polyvalent isocyanates such as triphenylmethane triisocyanate may be used as the polyisocyanate compound in the present invention, as long as gelation does not occur in the polyurethane resin produced from the present invention.

The content of the polyisocyanate compound in the present invention is preferably such that the diol compound represented by the formula (1) used in the polyurethane precursor composition of the present invention and the mole number of the isocyanate group of the polyisocyanate compound To be 1.0 to 2.5, preferably 1.1 to 1.5. The content range of the polyisocyanate compound in the present invention is not particularly limited. However, when the above range is satisfied, the synthesis reaction of the water-dispersible polyurethane of the present invention can be performed at a high rate, Can be minimized, and the effect of maximizing polyurethane synthesis efficiency can be obtained.

The ionic functional group-introducing compound contained in the present invention as a repeating unit does not exhibit ionicity as a compound itself, but is used as a repeating unit in the polyurethane polymerization reaction of the present invention, and exhibits ionicity in the polyurethane polymer chain to be produced A functional group-introducing compound, an anionic functional group-introducing compound, and a cationic functional group-introducing compound. When an anionic functional group-introducing compound is used as the ionic functional group-introducing compound in the present invention, the polyurethane composition of the present invention may further contain an anionic functional neutralizer, and the ionic functional group- A cationic functional group neutralizing agent may be further contained in the polyurethane precursor composition of the present invention. In the present invention, by further including the anionic functional neutralizing agent and the cationic functional neutralizing agent as the polyurethane precursor composition, the ionic functional group introduced into the polymer chain by the ionic functional group introducing compound of the present invention is neutralized to obtain the polyurethane polymer Water-dispersibility can be imparted to the water-soluble polymer.

In the present invention, the anionic functional group-introducing compound may be a compound containing at least one anionic functional group selected from a carboxyl group, a sulfonic acid group and a phosphoric acid group, preferably dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolactic acid, , 1,4-butanediol-2-sulfonic acid, N, N-bishydroxyethylglycine, N, N-bishydroxyethylalanine, 3,4-dihydroxybutane sulfonic acid and 3,6-dihydroxy 2-toluenesulfonic acid, and the like, but is not limited thereto. In the present invention, the anionic functional neutralizing agent may be any compound capable of neutralizing the anionic functional groups present in the polymer chain by the anionic functional group introducing compound, and specifically, a tertiary amine compound and / Inorganic basic compounds and the like, and preferably at least one compound selected from the group consisting of trialkylamines, N, N-dialkylalkanolamines, N-alkyl-N, N-dialkanolamines, trialkanolamines , Ammonia and metal hydroxides, and more preferably at least one compound selected from trimethylamine, triethylamine, ammonia, sodium hydroxide, potassium hydroxide and lithium hydroxide, but is particularly limited thereto It is not.

In the present invention, the cationic functional group-introducing compound may be a compound containing at least one cationic functional group selected from a secondary amine group, a tertiary amine group and a quaternary amine group, and preferably N, N-dialkylalka N-alkyl-N, N-dialkanolamines, trialkanolamines, and the like, and more preferably N-methyl-N, N-diethanolamine and N-butyl-N , N-diethanolamine, and the like, but is not limited thereto. In the present invention, the cationic functional group neutralizing agent may be any compound capable of neutralizing the cationic functional group present in the polymer chain by the cationic functional group introducing compound, and specifically, a carboxylic acid, a sulfonic acid, Inorganic acid and preferably at least one compound selected from formic acid, acetic acid, lactic acid, succinic acid, glutaric acid, citric acid, sulfonic acid, p-toluenesulfonic acid, alkyl sulfonic acid, hydrochloric acid and phosphoric acid May be one or more compounds, but are not particularly limited thereto.

In the present invention, the ionic functional group-introducing compound may be contained in an amount of 1 to 1000 mol%, preferably 10 to 500 mol%, based on the total amount of the polyol compound including the diol compound represented by the formula (1) of the present invention. In the present invention, the content of the ionic functional group-introducing compound is not particularly limited. However, when the above range is satisfied, dispersion stability of the water dispersible polyurethane precursor composition produced when the above range is satisfied is maximized and poly The storage stability and film formability exhibited by the urethane dispersion can be obtained, and an aqueous dispersion type polyurethane excellent in durability, water resistance and transparency can be obtained from the polyurethane precursor composition of the present invention, A coating film or the like can be efficiently obtained.

The present invention also provides an aqueous dispersion polyurethane prepared from the aqueous dispersion type polyurethane precursor composition.

In one example of the present invention, the method for producing the water-dispersible polyurethane is not particularly limited, but it is preferable to mix the aqueous dispersion type polyurethane precursor composition of the present invention in a solvent which is hydrophilic and does not affect the urethane polymerization reaction To synthesize a prepolymer, and then dispersing the prepolymer in water to prepare a water-dispersible polyurethane through a prepolymer process. Examples of the solvent which is hydrophilic and does not affect the urethane polymerization reaction in the preparation of the prepolymer include at least one compound selected from acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, N-methyl-2-pyrrolidone, Acetone is preferably used, but it is not particularly limited.

The present invention also provides a polyurethane coating composition for preventing corrosion, which comprises the aqueous dispersion type polyurethane.

In one example of the present invention, the water dispersible polyurethane can be added in an amount of 0.1 to 30 wt%, more preferably 0.2 to 10 wt%, and more preferably 0.5 to 3 wt% based on the total weight of the coating composition have. The effect of improving the corrosion resistance is excellent in the above range, and the mechanical properties such as water resistance, strength and elongation of the coating film are not deteriorated.

The water dispersible polyurethane coating composition of the present invention may further contain additives such as crosslinking agents, emulsifiers, surface treatment agents, pigments, dyes, curing agents, external crosslinking agents, viscosity adjusting agents, leveling agents, defoamers, , At least one material selected from the group consisting of a dispersant, a stabilizer, a light stabilizer, an antioxidant, an ultraviolet absorber, a heat stabilizer, a filler, a plasticizer, a lubricant, an antistatic agent, a reinforcing agent, a catalyst, a thixotropic agent, an antimicrobial agent, It can be further included as an additive.

As the crosslinking agent that can be used as an additive in the water-dispersible polyurethane coating composition of the present invention, a crosslinking agent that is usually used in the production of a crosslinked polymer may be used, and preferably, a crosslinking agent such as melamine, monomethylol melamine, dimethylol melamine, At least one compound selected from the group consisting of melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, methylated methylol melamine, butylated methylol melamine and melamine resin may be used, but is not limited thereto no. In the present invention, the crosslinking agent is preferably used in an amount such that the isocyanate group of the crosslinking agent is 0.001 to 0.2 mol based on 1 mol of the isocyanate group contained in the polyisocyanate compound. However, the crosslinking agent is not particularly limited.

As the emulsifier that can be used as an additive in the present invention, an anionic surfactant, a nonionic surfactant, a cationic surfactant, and a polymeric surfactant, which are used in conventional chemical reactions, can be used, A surfactant, and a nonionic surfactant may be used, but the present invention is not limited thereto. In the present invention, the emulsifier may be contained in an amount of 1 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the polyurethane produced from the present invention. The content of the emulsifier is, Is not particularly limited within a range that does not cause deterioration of mechanical properties such as water resistance, strength, elongation and the like of a coating film or the like.

The water-dispersible polyurethane coating composition of the present invention can be used as a coating material, an adhesive, a binder, and a formed body such as a coating film. More specifically, the water-dispersible polyurethane coating composition can be used as a thermal paper coating agent, Inorganic coating materials, wood coating materials, textile treating agents, textile coating agents, electronic material parts coating agents, sponges, puffs and gloves.

When the aqueous dispersion type polyurethane coating composition of the present invention is used as a coating material, it is possible to use the water-dispersible polyurethane coating composition of the present invention by a method such as brush coating, roller coating, spray coating, reverse roll coating, curtain roll coating, dip coating, rod coating, bar coating and doctor blade coating The water dispersible polyurethane composition can be applied to the substrate.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, it is to be understood that the present invention is not limited to the disclosed embodiments, but various modifications and alterations may be made therein without departing from the spirit and scope of the invention.

First, the experimental method performed in the present invention is presented.

Experiment 1) Evaluation of corrosion resistance of coating film

In the spray chamber equipped with the condition of KSD9502, spraying apparatus (LYW-015, manufactured by Neuron Fusa) containing 5 wt% sodium chloride solution (pH 6.5 to 7.2) 7 was sprayed with the above sodium chloride solution (hereinafter, brine). At this time, the salt water tank temperature of the atomizing apparatus is maintained at 35 ± 2 ° C., the atomizing pressure of the atomizing apparatus is maintained at 0.075 ± 0.010 MPa, and the saline water is sprayed so as to fall freely to the specimen, .

The degree of corrosion of the specimen through spraying of the brine was checked at intervals of 24 hours and the time at which the specimen area was corroded by 5% or more was measured.

[ Synthetic example  1 to 3] Corrosion resistance Dior  Preparation of compounds

Methylaminoethanol, 3-ethylaminoethanol and 4-propylaminoethanol (Sigma Aldrich, USA) were added to three flasks containing 100 ml of pyridine and 5 g (18 mmol) of 1,5-dichloroanthraquinone , USA) were added at a rate of 4.13 ml (51.4 mmol) to prepare a mixed solution, and the three mixed solutions were subjected to a reflux reaction at 130 ° C for 24 hours. After completion of the reflux reaction, the three residues obtained by removing the pyridine present in each mixed solution were purified by column chromatography using a developing solvent of hexane: ethyl acetate = 1: 2 by volume, respectively, to obtain a corrosion resistant diol compound (AAQ1, AAQ3 and AAQ5).

^{AAQ1: 1 H NMR (400MHz,} CDCl 3) δ 2.88 (s, 6H), 3.62 (t, 4H), 3.80 (q, 4H), 3.85 (t, 2H), 7.42 (d, 2H), 7.56 (t , ≪ / RTI > 2H), 7.79 (d, 2H).

^{AAQ3: 1 H NMR (400 mHz} , DMSO) δ 1.15 (t, 6H), 3.41 (q, 4H), 3.73 (t, 4H), 4.20 (t, 4H), 4.34 (t, 2H), 7.56 (d , ≪ / RTI > 2H), 7.83 (d, 2H), 8.08 (t,

^{AAQ5: 1 H NMR (400 mHz} , DMSO) δ 0.80 (t, 6H), 1.51 (m, 4H), 3.34 (m, 8H), 3.52 (t, 4H), 4.44 (t, 2H), 7.58 (d , ≪ / RTI > 2H), 7.85 (d, 2H), 8.12 (t,

[Example 1] Synthesis of corrosion-resistant water-dispersed polyurethane

이며, x, y 및 z는 각 반복단위의 몰비로 x : y : z는 1 : 1 : 3이며, 각각의 반복단위는 랜덤하게 연결될 수 있다.)(In the above scheme,

And x, y and z are the molar ratios of the respective repeating units, x: y: z is 1: 1: 3, and each repeating unit can be randomly connected.

(0.47 g, 3.5 mmol, DMPA) and 1 mmol of the corrosion-inhibiting diol compound (AAQ1) of Synthesis Example 1 were added to a solution of polytetrahydrofuran (2 g, 1 mmol, PTHF-Mn 650, Mn 650 g / mol) The flask was charged with 25 ml of acetone and stirred at 50 ° C to prepare a mixed solution. Isophorone diisocyanate (1.45 mL, 6.5 mmol, IPDI) was added dropwise to the mixed solution prepared above, followed by reaction at 90 ° C for 3 hours. After the reaction mixture was stirred at room temperature for 12 hours, 0.97 ml (0.97 ml, 7 mmol) of triethylamine was added and the mixture was stirred for 1 hour. Thereafter, acetone was removed from the mixed solution after the stirring to obtain a residue. Distilled water was added to the residue to prepare a corrosion-resistant water-dispersible polyurethane having a solid content of 16 wt% and a number average molecular weight of 14,600 g / mol.

[Example 2]

(Hereinafter referred to as PTHF-Mn2000) having a number average molecular weight of 2,000 g / mol was used instead of polytetrahydrofuran (PTHF-Mn650) having a number average molecular weight of 650 g / mol in Example 1, A corrosion-resistant water-dispersed polyurethane was synthesized in the same manner as in Synthesis Example 1, except that 0.5 mmol of the corrosion-resistant diol compound (AAQ1) was used.

[Example 3]

Except that polytetrahydrofuran (PTHF-Mn2000) having a number average molecular weight of 2,000 g / mol was used instead of polytetrahydrofuran (PTHF-Mn650) having a number average molecular weight of 650 g / mol in Example 1 The remainder were synthesized by the same method as the water-dispersible polyurethane.

[Example 4]

The corrosion-resistant water-dispersed polyurethane was synthesized in the same manner as in Example 3, except that the corrosion-resistant diol compound (AAQ3) was used instead of the corrosion-resistant diol compound (AAQ1).

[Example 5]

The corrosion-resistant water-dispersed polyurethane was synthesized in the same manner as in Example 3, except that the corrosion-resistant diol compound (AAQ5) was used instead of the corrosion-resistant diol compound (AAQ1).

[Example 6]

A corrosion-resistant water-dispersible polyurethane was synthesized in the same manner as in Example 3 except that 2.8 mmol of dimethylol propionic acid (DMPA) was used and 5.8 mmol of isophorone diisocyanate (IPDI) was used.

[Example 7]

Except that a polycarbonate diol (hereinafter referred to as PCD-Mn800) having a number average molecular weight of 800 was used in place of the polytetrahydrofuran (PTHF-Mn650) having a number average molecular weight of 650 in Example 1, A corrosion - resistant water - dispersed polyurethane was synthesized.

[Example 8]

Except that polycarbonate diol (hereinafter referred to as PCD-Mn1000) having a number average molecular weight of 1,000 g / mol was used instead of polytetrahydrofuran (PTHF-Mn650) having a number average molecular weight of 650 g / mol in Example 1 And the remainder were synthesized in the same manner as the corrosion - resistant water - dispersed polyurethane.

[Example 9]

(Hereinafter referred to as PCD-Mn2000) having a number average molecular weight of 2,000 g / mol was used instead of polytetrahydrofuran (hereinafter referred to as PTHF-Mn2000) having a number average molecular weight of 2,000 g / mol in Example 2 Except that the remainder was used in the same manner to synthesize a corrosion resistant water dispersed polyurethane.

[Example 10]

Except that polycarbonate diol (PCD-Mn2000) having a number average molecular weight of 2,000 g / mol was used instead of polytetrahydrofuran (PTHF-Mn650) having a number average molecular weight of 650 g / mol in Example 1, Was prepared by the same method as described above.

[Example 11]

Except that polycarbonate diol (PCD-Mn2000) having a number average molecular weight of 2,000 g / mol was used instead of polytetrahydrofuran (PTHF-Mn2000) having a number average molecular weight of 2,000 g / mol in Example 4, Was prepared by the same method as described above.

[Example 12]

Except that polycarbonate diol (PCD-Mn2000) having a number average molecular weight of 2,000 g / mol was used instead of polytetrahydrofuran (PTHF-Mn2000) having a number average molecular weight of 2,000 g / mol in Example 5, Was prepared by the same method as described above.

[Comparative Example 1]

A corrosion-resistant water-dispersible polyurethane was synthesized in the same manner as in Example 10, except that the diol compound (ME1) was used as a corrosion-resistant diol compound instead of the corrosion-resistant diol compound (AAQ1) .

[Comparative Example 2]

The corrosion-resistant water-dispersed polyurethane was synthesized in the same manner as in Example 3, except that the corrosion-resistant diol compound (AAQ1) of Production Example 1 was not used.

[Comparative Example 3]

The corrosion-resistant water-dispersed polyurethane was synthesized in the same manner as in Example 10, except that the corrosion-resistant diol compound (AAQ1) of Preparation Example 1 was not used.

[Examples 13 to 29 and Comparative Examples 4 to 7]

The corrosion-resistant water-dispersed polyurethane synthesized from Examples 1 to 12 and Comparative Examples 1 to 3 were each mixed with the surface treatment agent in the composition shown in Table 2 below to prepare a coating solution. Thereafter, a 150 mm x 70 mm x 0.45 mm substrate (Galvanized steel sheet, Sail Steel Co., Ltd.) surface-treated with a degreasing solution was bar coated using the coating solution, and the bar- The specimens were thermally cured at 80 ℃ to form coating films on the surface.

For ease of understanding, the compositions of the corrosion-resistant water-dispersible polyurethane compositions used in Examples 1 to 12 and Comparative Examples 1 to 3 of the present invention are shown in the following Table 1, and Examples 13 to 29 and Comparative Examples The compositions of the coating liquid compositions prepared in Examples 4 to 7 are shown in Table 2 below.

The corrosion resistance of the corrosion-resistant water-dispersed polyurethane coating films existing on the surfaces of the respective specimens prepared through Examples 13 to 29 and Comparative Examples 4 to 7 is shown in Table 2 and FIG.

division Polyurethane precursor composition
(Content [mmol]) Corrosion-resistant diol compound Polyol compound DMPA IPDI Example 1 AAQ1
(One) PTHF-Mn650
(One) (3.5) (6.5) Example 2 AAQ1
(0.5) PTHF-Mn2000
(One) (3.5) (6.5) Example 3 AAQ1
(One) PTHF-Mn2000
(One) (3.5) (6.5) Example 4 AAQ3
(One) PTHF-Mn2000
(One) (3.5) (6.5) Example 5 AAQ5
(One) PTHF-Mn2000
(One) (3.5) (6.5) Example 6 AAQ1
(One) PTHF-Mn2000
(One) (2.8) (5.8) Example 7 AAQ1
(One) PCD-Mn800
(One) (3.5) (6.5) Example 8 AAQ1
(One) PCD-Mn1000
(One) (3.5) (6.5) Example 9 AAQ1
(0.5) PCD-Mn2000
(One) (3.5) (6.5) Example 10 AAQ1
(One) PCD-Mn2000
(One) (3.5) (6.5) Example 11 AAQ3
(One) PCD-Mn2000
(One) (3.5) (6.5) Example 12 AAQ5
(One) PCD-Mn2000
(One) (3.5) (6.5) Comparative Example 1 ME1
(One) PCD-Mn2000
(One) (3.5) (6.5) Comparative Example 2 - PTHF-Mn2000
(One) (3.5) (6.5) Comparative Example 3 - PCD-Mn2000
(One) (3.5) (6.5)

division Coating composition
(wt%) Physical Properties of Coating Film Corrosion-resistant water-dispersible polyurethane Surface treatment agent 5% corrosion time
(time) Example 13 Example 1 (0.6) (99.4) 168 Example 14 Example 1 (One) (99) 168 Example 15 Example 2 (0.6) (99.4) 168 Example 16 Example 3 (0.6) (99.4) 168 Example 17 Example 4 (0.6) (99.4) 168 Example 18 Example 5 (0.6) (99.4) 192 Example 19 Example 6 (0.6) (99.4) 168 Example 20 Example 6 (One) (99) 168 Example 21 Example 7 (0.6) (99.4) 288 Example 22 Example 7 (One) (99) 240 Example 23 Example 8 (0.6) (99.4) 264 Example 24 Example 8 (One) (99) 552 Example 25 Example 9 (One) (99) 528 Example 26 Example 10 (0.6) (99.4) 480 Example 27 Example 10 (One) (99) 504 Example 28 Example 11 (0.6) (99.4) 456 Example 29 Example 12 (0.6) (99.4) 432 Comparative Example 4 - (100) 96 Comparative Example 5 Comparative Example 1 (0.6) (99.4) 120 Comparative Example 6 Comparative Example 2 (One) (99) 72 Comparative Example 7 Comparative Example 3 (One) (99) 72

1 and 2, the test piece of Comparative Example 4 coated with the coating composition without the addition of the corrosion-resistant water-dispersed polyurethane showed a surface corrosion of not less than 5% at the elapse of 96 hours after the salt spray test However, in the case of the test piece having the coating film of Example 24 prepared with the corrosion-resistant diol compound of the present invention, white rust did not occur on the surface of the test piece after 96 hours of the salt water spray test, At 432 hours under certain experimental conditions, a slight amount of white rust appeared on the surface of the specimen, but it did not account for more than 5% of the total area of the specimen.

As can be seen from Table 2, in the case of the specimens having the corrosion-resistant polyurethane coating films of Examples 13 to 29 prepared with the corrosion-resistant diol compound of the present invention, the surface area of the specimen was 5% The time required for corrosion is 168 to 552 hours, indicating that the corrosion progression rate is slow. Furthermore, when compared with the specimens of Comparative Examples 4 to 7 in which the time required for 5% of the surface of the specimen to corrode was 72 to 120 hours, the specimens prepared through Examples 13 to 29 of the present invention exhibited corrosion It can be seen that the progress speed is remarkably slow.

From the above results, it can be seen that by including the corrosion-resistant diol compound of the present invention in the production of polyurethane, the corrosion rate of the metal can be effectively retarded, and the water dispersion which is remarkably improved in corrosion resistance in comparison with the polyurethane used for corrosion prevention It can be seen that the production of polyurethane is possible.

Claims (10)

1. A water dispersible polyurethane precursor composition comprising a diol compound represented by the following formula (1).
[Chemical Formula 1]

(In the formula 1,
T ₁ to T ₈ independently represent hydrogen, a (C 1 -C 20) alkyl group, a (C 2 -C 20) alkenyl group, a (C 2 -C 20) alkynyl group, a (C 2 -C 30) alkoxy group, (C6-C30) aryl group, (C3-C30) heteroaryl group,

And

, Wherein at least two of T ₁ to T ₈ are independently selected from the group consisting of

And

≪ / RTI >
Wherein R ₁ and R ₄ independently represent a substituted or unsubstituted (C 1 -C 20) alkylene group, a substituted or unsubstituted (C 3 -C 20) cycloalkylene group, a substituted or unsubstituted (C 2 -C 20) alkenylene group , A substituted or unsubstituted (C6-C30) arylene group and a substituted or unsubstituted (C3-C30) heteroarylene group;
R ₂ to R ₃ independently represent hydrogen, a substituted or unsubstituted (C 1 -C 20) alkyl group, a substituted or unsubstituted (C 3 -C 20) cycloalkyl group, a substituted or unsubstituted (C 2 -C 20) Or an unsubstituted (C6-C30) aryl group and a substituted or unsubstituted (C3-C30) heteroaryl group;
R ₅ to R ₆ are -OH.)
The method according to claim 1,
Wherein the diol compound represented by the formula (1) is a compound represented by the following formula (2).
(2)

(In the formula (2)
R ₁ and R ₄ are each independently a substituted or unsubstituted (C 1 -C 4) alkylene group;
R ₂ to R ₃ are each independently selected from a methyl group, an ethyl group and a propyl group.)
The method according to claim 1,
Wherein the aqueous dispersion type polyurethane precursor composition further comprises a polyol compound, a polyisocyanate compound, and an ionic functional group-introducing compound.
The method of claim 3,
The polyol compound
At least one polyol selected from the group consisting of polyether polyols, polycarbonate polyols and polyester polyols; And
A substituted or unsubstituted (C3-C30) alkylpolyol, a substituted or unsubstituted (C3-C30) cycloalkylpolyol, a substituted or unsubstituted (C6-C30) arylpolyol and a substituted or unsubstituted (C3- At least one polyol selected from the group consisting of heteroaryl polyols;
≪ / RTI > wherein the polyurethane precursor composition comprises at least one compound selected from the group consisting of polyurethane prepolymer and polyurethane prepolymer.
The method of claim 3,
Wherein the ionic functional group-introducing compound is any one selected from the group consisting of an anionic functional group-introducing compound and a cationic functional group-introducing compound.
6. The method of claim 5,
Wherein the anionic functional group-introducing compound is a compound containing at least one anionic functional group selected from a carboxyl group, a sulfonic acid group and a phosphoric acid group.
6. The method of claim 5,
Wherein the cationic functional group-introducing compound contains at least one cationic functional group selected from a secondary amine group, a tertiary amine group and a quaternary amine group.
A water dispersible polyurethane produced from the water dispersible polyurethane precursor composition according to any one of claims 1 to 7.
9. A corrosion inhibiting polyurethane coating composition comprising the water dispersible polyurethane of claim 8.
10. The method of claim 9,
Wherein the aqueous polyurethane is added in an amount of 0.1 to 30% by weight based on the total weight of the coating composition.

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