KR101954135B1 - Organic/inorganic hybridized anticorrosive coating composition and preparation method thereof - Google Patents

Abstract

The present invention relates to a process for preparing an anticorrosive coating composition of organic / inorganic hybrid type, wherein a process for preparing a rust-inhibitive coating composition comprises the steps of: a) reacting an alcohol compound having an amino group with a silane compound having an epoxy group in a nitrogen atmosphere, A silane compound; And b) subjecting the prepared silane compound to a sol-gel reaction, or a) reacting an alcohol compound having an amino group with a silane compound having an epoxy group in a nitrogen atmosphere to prepare a silane compound having a hydroxy group step; b) reacting the prepared silane compound with a bisphenol epoxy compound to prepare an organic / inorganic hybrid precursor compound; And c) sol-gel-reacting the prepared precursor compound.

Description

[0001] The present invention relates to an organic / inorganic hybrid anticorrosive coating composition and an organic / inorganic hybrid anticorrosive coating composition and preparation method thereof,

The present invention relates to an anticorrosive coating composition for preventing corrosion of a metal surface such as aluminum, and more particularly to an anticorrosive coating composition for preventing corrosion of a metal surface such as aluminum. More specifically, the present invention relates to an anticorrosive coating composition for coating a metal surface with high hardness using an organic / inorganic hybrid compound as an active ingredient, , Acid resistance, salt water resistance, water resistance and the like, and a method for producing the same.

Demand for lightweight metals is rapidly increasing as interest in energy efficiency increases significantly. Representative light metals are aluminum and magnesium, and their usage is greatly increased in various fields such as construction, machinery parts, medical parts, transportation and aviation parts. Especially, the frame construction, which occupies a large portion in modern construction works, needs to be shortened economically and in terms of air. However, the construction using conventional formwork such as synthetic wood (for example, EURO-FORM) Aluminum form (AL-FORM) has been replaced. AL-FORM has many advantages compared to conventional formwork but it causes corrosion or discoloration very easily in alkali solution by contact with concrete and cement, resulting in durability, appearance and quality of drastically reduced. Various surface treatment processes and surface coating agents have been developed to prevent such corrosion and discoloration. However, all of these surface coating agents for metal rust prevention are in the form of a coating in which an acrylic resin or a polyurethane resin is dissolved in an aromatic organic solvent (40-45 wt%) AL-FORM In the surface coating process, a lot of harmful organic solvents volatilize and there is a great risk of environmental pollution and fire in the workplace. There is a great concern about worker avoidance and industrial accidents due to odor problem. The use of existing surface coatings is very likely to be limited.

Currently, the most commonly used corrosion protection technologies are (1) coating of organic materials such as polymers (polyvinyl butyral, acrylic resin, polyurethane, vinyl epoxy, phenolic resin, polyether imide), (2) (3) Electro-chemical anodizing, plating, (4) Plasma Electrolytic Oxidation (PEO) process, and (5) Sol-gel coating process. Since each process has advantages and disadvantages, processes to be used depend on products and processes. The most commonly used process, the chemical process and the electrochemical process, show very good surface treatment effect. However, since the use of a large amount of toxic chemicals, the environmental pollution problem and the risk of the workplace are high, alternative process development is urgently required . The sol-gel coating process, which has been developed as an alternative process, has lower toxicity (least harmful substances occur) and easier coating process than existing chemical and electrochemical processes, Some studies have been made to improve the disadvantages of the sol-gel coating process by using a mixture of organic alkoxysilane compounds and metal alkoxides, and there have been some commercially available products. However, at present, coating hardness, alkali resistance, There is no product satisfying the prevention function. In the case of these commercially available products, since the above-mentioned organic alkoxysilane compounds are mostly used, the alkyl groups (R) capable of forming a continuous phase are short and can not form a uniform and dense coating film. It does not satisfy the physical properties. Therefore, it is urgently required to develop a metal rust-preventive coating agent that is environment-friendly, has excellent durability (such as alkali resistance) and mechanical hardness.

The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a chromium-based heavy metal surface treatment agent, an expensive plating apparatus, and a toxic aromatic solvent, Which is excellent in various physical properties against rust prevention (method) such as water resistance, water resistance, water resistance, adhesion and the like.

In order to achieve the above object, the present invention provides a novel silane compound having various organic functional groups or a new type epoxy-based reactive organic / inorganic hybrid precursor, / Inorganic hybrid type rust-preventive coating composition.

The present invention provides a method for preparing a silane compound, comprising: a) reacting an alcohol compound having an amino group with a silane compound having an epoxy group in a nitrogen atmosphere to produce a silane compound having a hydroxy group; And b) subjecting the prepared silane compound to a sol-gel reaction. The present invention also provides a process for producing an organic / inorganic hybrid rust-preventive coating composition.

On the other hand, the present invention provides a method for producing a silane compound, comprising: a) reacting an alcohol compound having an amino group with a silane compound having an epoxy group in a nitrogen atmosphere to prepare a silane compound having a hydroxy group; b) reacting the prepared silane compound with a bisphenol epoxy compound to prepare an organic / inorganic hybrid precursor compound; And c) subjecting the prepared precursor compound to a sol-gel reaction. The present invention also provides a process for producing an organic / inorganic hybrid rust-preventive coating composition.

The alcohol compound having an amino group may be at least one selected from the group consisting of 2-amino-2-hydroxymethyl-1,3-propanediol, 3-amino-1-propanol, Amino-2-methyl-1-propanol, 1-amino-2-propanol and diethanolamine are preferable, and 2-amino- 1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, and the like.

The epoxy group-containing silane compound is preferably a 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, diethoxy (3-glycidyloxypropyl ) Methylsilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Of these, 3-glycidoxypropyltrimethoxysilane is more preferable.

The bisphenol epoxy compound is preferably selected from bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, and phenol novolak.

Meanwhile, in order to increase the hardness of the rust-preventive coating composition of the present invention, it is preferable to use at least one of gamma-methacryloxypropyltrimethoxysilane (PTMS), methyltrimethoxysilane (MTMS), titanium isopropoxide (TTiP ) And an alkoxide compound composed of zirconium butoxide, or a mixture thereof is further added and sol-gel-reacted.

In addition, the rust-preventive coating composition of the present invention may further comprise a curing agent (curing accelerator), preferably a polyether amine curing agent, and more preferably Jeffamine.

The rust-preventive coating composition according to the present invention is prepared through a simple sol-gel reaction using a novel silane compound having an organic functional group or an epoxy-based reactive organic / inorganic hybrid precursor as compared with the prior art, and is environmentally friendly , High hardness compared to the existing sol-gel method, excellent chemical resistance such as alkali resistance, acid resistance, and metal surface adhesion, and thus can be used as a metal corrosion inhibiting coating agent, especially a rust inhibitive coating agent for AL- Can be effectively used.

1 is a photograph of an organic / inorganic hybrid type antirust coating composition synthesized according to Examples 3, 10, 17, and 23 of the present invention.
2 is a photograph of a rust-coated aluminum plate according to an embodiment of the present invention.
FIG. 3 is a photograph of a rust-inhibiting coating composition according to Examples 20 to 22, in which tetraethyl orthosate (TEOS) was added to an alkoxysilane compound to perform sol-gel reaction.

The present invention relates to a process for synthesizing an organic alkoxysilane compound having a sufficiently long chain having a multifunctional hydroxy group capable of forming a continuous phase and cross-linking the silane compound through a sol-gel process to form an organic / inorganic hybrid anti- The method comprising:

The organic alkoxysilane compound having the polyfunctional hydroxy group of the present invention can be prepared by reacting an alcohol compound having an amino group (substance A) with a silane compound having an epoxy group (substance B). The amino group of the substance A provides a long chain capable of reacting with the epoxy group (glycidyl group) of the substance B to form a continuous phase, while the hydroxy group generated in the reaction is multifunctional with the hydroxy group of the substance A And has excellent cross-linking ability with alcoholic silane in sol-gel reaction.

The present invention also relates to a process for synthesizing a novel epoxy-based reactive organic / inorganic hybrid precursor using an organoalkoxysilane compound having a polyfunctional hydroxy group for better physical properties, and crosslinking the precursor through a sol- To provide a method for preparing an oil / inorganic hybrid rust-preventive coating composition. The epoxy-based reactive organic / inorganic hybrid precursor of the present invention can be prepared by further reacting a bisphenol-based epoxy compound (substance C) with the synthesized polyalkoxylated hydroxyalkanoylated organic alkoxysilane compound. In the present invention, the bisphenol-based epoxy compound is a diglycidyl ether compound in which one epoxy group reacts with an amine group of the substance A, and another epoxy remains. The epoxy-based reactive organic / inorganic hybrid precursor may be a structure of A-C or B-A-C, and the structure of A-C and B-A-C may be somewhat crosslinked.

Since the metal anticorrosive coating composition of the present invention is prepared through a typical sol-gel process, it is possible to form a hard inorganic layer on an aluminum plate (at a relatively low temperature, < 150 ° C) without electrochemical reaction or large- It has a feature that it can perform anti-rust function.

Representative materials of the materials A, B and C applicable to the present invention are shown in Tables 1 to 3 below.

A

2-amino-2-hydroxymethyl-1,3-propanediol, (trishydroxymethylaminomethane)

3-amino-1-propanol

3-amino-1,2-propanediol

2-amino-2-methyl-1,3-propanediol

2-Amino-2-methyl-1-propanol

1-amino-2-propanol

Diethanolamine

B

3-glycidoxypropyltrimethoxysilane

3-glycidoxypropyltriethoxysilane

5,6-epoxyhexyltriethoxysilane

Diethoxy (3-glycidyloxypropyl) methylsilane

2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

C

Bisphenol A diglycidyl ether (DGEBA)

Bisphenol A type
(Bisphenol A diglycidyl ether)

Bisphenol F type
(Bisphenol F diglycidyl ether)

Phenol novolac

Synthesis of a silane compound having an organic functional group and a novel type epoxy-based reactive organic / inorganic hybrid precursor used for preparing the rust-preventive coating composition of the present invention is performed through the following process.

Synthesis of silane compounds with multifunctional hydroxy groups

Under the nitrogen atmosphere, the substance A having the hydroxy group and the amino group simultaneously and the silane compound B having at least one epoxy group were stirred at 70 DEG C for 4 hours in an equivalent ratio of 1: 2 to 2: 1, preferably 1: . The amino group of the substance A bonds with the epoxy group of the substance B to form a long chain structure, and a hydroxyl group is generated according to an amino group and an epoxy group reaction, so that the amino group of the substance A is multifunctional together with the hydroxy group of the substance A. The synthesized polyfunctional hydroxy group-containing silane compound is crosslinked through a typical sol-gel reaction.

Epoxy-based organic / inorganic hybrid precursor synthesis

The epoxy-based organic / inorganic hybrid precursor according to the present invention can be produced through the first step and the second step as follows.

Step 1: A mixture of a substance A having a hydroxy group and an amino group at the same time and a silane compound B having at least one epoxy group in a reaction equivalent ratio of 1: 1 to 2: 1, preferably 2: 1, And stirred for 4 hours to synthesize a silane compound having a polyfunctional hydroxy group. At this time, not only the synthesized A-B compound but also unreacted material A may be present in the silane compound.

Step 2: Bisphenol-based epoxy compound C is added to the compound obtained in the first step and reacted to synthesize an A-C or B-A-C structure or a siloxane bond or cross-linked secondary reaction product of these compounds. The reaction mole ratio of the material C is reacted with the material A at various equivalence ratios to synthesize an epoxy-based organic / inorganic hybrid precursor.

Preparation of Oil / Inorganic Hybrid Rust Coating Composition

The organic / inorganic hybrid type rust-preventive coating composition according to the present invention is prepared through a typical sol-gel process using the synthesized polyfunctional hydroxy group-containing silane compound or the epoxy-based reactive organic / inorganic hybrid precursor, The metal anti-corrosive coating composition is not only transparent, but also exhibits excellent anti-corrosive properties and excellent hardness.

The physical properties of the organic / inorganic hybrid type anticorrosive coating composition prepared according to the present invention can be variously controlled depending on the type of alkoxysilane compound used and the type and content of the epoxy compound, and the process for producing the solution is as follows.

A novel type of silane compound or epoxy-based organic / inorganic hybrid precursor of the present invention is mixed with ethanol or tetrahydrofuran at a weight ratio of 1: 1 at 70 占 폚. An aqueous solution of hydrochloric acid in various concentrations was gradually added dropwise to the solution while vigorously stirring to prepare an aluminum anti-corrosion coating composition.

Hereinafter, the production method of the present invention will be described in detail through examples.

Synthesis of silane compounds with multifunctional hydroxy groups

Example 1

Amino-2-hydroxymethyl-1,3-propanediol (Substance A) and 3-glycidoxypropyltrimethoxysilane (Substance B) were mixed in a nitrogen atmosphere at a ratio of 1: For a period of time to synthesize a new type of silane compound 1-1.

Example 2

2-hydroxymethyl-1,3-propanediol and 3-glycidoxypropyltrimethoxysilane were reacted in the same manner as in Example 1 at a 2: 1 equivalent ratio to obtain a novel silane compound 1-2 were synthesized.

Example 3

Amino-2-methyl-1,3-propanediol and 3-glycidoxypropyltrimethoxysilane were reacted in the same manner as in Example 1 at a 1: 1 equivalent ratio to obtain a novel silane compound 2- 1 was synthesized.

Example 4

Amino-2-methyl-1,3-propanediol and 3-glycidoxypropyltrimethoxysilane were reacted in the same manner as in Example 1 at a 2: 1 equivalent ratio to obtain a novel silane compound 2- 2 were synthesized.

Example 5

2-methyl-1-propanol and 3-glycidoxypropyltrimethoxysilane were reacted in an equivalent ratio of 1: 1 to synthesize a new type of silane compound 3-1 Respectively.

Example 6

Amino-2-methyl-1-propanol and 3-glycidoxypropyltrimethoxysilane were reacted in a 2: 1 equivalent ratio to synthesize a novel silane compound 3-2 Respectively.

Example 7

The reaction was carried out in the same manner as in Example 1 except that diethanolamine and 3-glycidoxypropyltrimethoxysilane were reacted at an equivalent ratio of 1: 1 to synthesize a novel silane compound 4-1.

Example 8

The reaction was carried out in the same manner as in Example 1 except that diethanolamine and 3-glycidoxypropyltrimethoxysilane were reacted at an equivalent ratio of 2: 1 to synthesize a novel silane compound 4-2.

Epoxy-based organic / inorganic hybrid precursor synthesis

Example 9

An epoxy-based organic / inorganic hybrid precursor 1-D0 was synthesized by adding bisphenol A diglycidyl ether (DGEBA) at an equivalent ratio of 1: 1 to the compound 1-2 obtained in the same manner as in Example 2 .

Example 10

A bisphenol A type epoxy resin (bisphenol A diglycidyl ether) was added in an equivalent ratio of 1: 1 to the compound 1-2 obtained in the same manner as in Example 2, and the mixture was stirred to obtain an epoxy-based organic / inorganic hybrid precursor 1- A was synthesized.

Example 11

A bisphenol F type epoxy resin (bisphenol F diglycidyl ether) was added in an equivalent ratio of 1: 1 to the compound 1-2 obtained in the same manner as in Example 2, and the mixture was stirred to produce an epoxy-based organic / inorganic hybrid precursor 1- F was synthesized.

Example 12

A bisphenol A type epoxy resin (bisphenol A diglycidyl ether) was added in an equivalent ratio of 1: 1 to the compound 1-2 obtained in the same manner as in Example 4, and the mixture was stirred to produce an epoxy-based organic / inorganic hybrid precursor 4- A was synthesized.

Example 13

A bisphenol F type epoxy resin (bisphenol F diglycidyl ether) was added in an equivalent ratio of 1: 1 to the compound 1-2 obtained in the same manner as in Example 4 and stirred to obtain an epoxy-based organic / inorganic hybrid precursor 4- F was synthesized.

Example 14

Bisphenol A type epoxy resin (bisphenol A diglycidyl ether) was added at an equivalent ratio of 1: 1 to the compound 1-2 obtained in the same manner as in Example 6, and the mixture was stirred to produce an epoxy-based organic / inorganic hybrid precursor 6- A was synthesized.

Example 15

A bisphenol F type epoxy resin (bisphenol F diglycidyl ether) was added in an equivalent ratio of 1: 1 to the compound 1-2 obtained in the same manner as in Example 6, and the mixture was stirred to produce an epoxy-based organic / inorganic hybrid precursor 6- F was synthesized.

1 is a photograph of an organic / inorganic hybrid type antirust coating composition synthesized according to Examples 3, 10, 17, and 23 of the present invention.

Experimental Example 1: Alkali resistance test of Examples 1 to 15

The anticorrosive coating composition prepared in Example 1 to Example 19 was coated on an aluminum plate by dip coating to a thickness of 30 to 40 μm to form a coating film and then cured at 100 ° C. for about 12 hours to perform anti- .

2 is a photograph of a rust-coated aluminum plate according to an embodiment of the present invention.

The alkali resistance and the pencil hardness of the anti-rust coated aluminum sheet were measured by the method shown in Table 4, and the results are shown in Table 5.

Subject Assessment Methods Alkali resistance 5% KOH aqueous solution or saturated Ca (OH) ₂ solution, no swelling, cracking or dropping after 24 hours of immersion
Test specification; KS M ISO 2812-1: 2012 Pencil hardness Using Miss Bishi Pencil
Test specification; KS M ISO 15184: 2013

Example Compound name Transparency (%) Hardness (H) Alkali resistance Example 1 Silane compound 1-1 99.6% 2H X Example 2 Silane compounds 1-2 99.6% 1H X Example 3 Silane compound 2-1 99.5% 1H O Example 4 Silane compound 2-2 99.6% 1H X Example 5 Silane compound 3-1 99.6% 2H X Example 6 Silane compound 3-2 99.5% 1H X Example 7 Silane compound 4-1 99.6% 1H X Example 8 Silane compound 4-2 99.6% 1H X Example 9 Precursor 1-D0 99.8% 2H X Example 10 Precursor 1-A 99.8% 3H O Example 11 Precursor 1-F 99.4% 3H O Example 12 Precursor 4-A 99.4% 3H X Example 13 Precursor 4-F 99.5% 3H O Example 14 Precursor 6-A 99.4% 3H X Example 15 Precursor 6-F 99.3% 2H X

(Good: O, poor: X)

Preparation of crosslinked compounds by sol-gel reaction

In Example 1, a rust-inhibitive coating composition crosslinked through a sol-gel reaction was prepared on the silane compound (Example 3) having excellent alkali resistance and the precursors (Examples 10, 11 and 13) as described below.

Example 16

Under a nitrogen atmosphere, 1 part by weight of a silane compound of a novel type synthesized in Example 3 was mixed with 5 parts by weight of ethanol or tetrahydrofuran. An organic / inorganic hybrid anticorrosive coating composition was prepared by slowly stirring the aqueous solution with a 0.1 M hydrochloric acid solution and agitating the mixture at 70 to 80 ° C for 4 hours with stirring.

Example 17

Under nitrogen, 1 part by weight of the epoxy-based organic / inorganic hybrid precursor synthesized in Example 10 was mixed with 5 parts by weight of ethanol or tetrahydrofuran. An organic / inorganic hybrid anticorrosive coating composition was prepared by slowly stirring the aqueous solution with a 0.1 M hydrochloric acid solution and agitating the mixture at 70 to 80 ° C for 4 hours with stirring.

Example 18

Under nitrogen, 1 part by weight of the epoxy-based organic / inorganic hybrid precursor synthesized in Example 11 was mixed with 5 parts by weight of ethanol or tetrahydrofuran. An organic / inorganic hybrid anticorrosive coating composition was prepared by slowly stirring the aqueous solution with a 0.1 M hydrochloric acid solution and agitating the mixture at 70 to 80 ° C for 4 hours with stirring.

Example 19

Under nitrogen, 1 part by weight of the epoxy-based organic / inorganic hybrid precursor synthesized in Example 13 was mixed with 5 parts by weight of ethanol or tetrahydrofuran. An organic / inorganic hybrid anticorrosive coating composition was prepared by slowly stirring the aqueous solution with a 0.1 M hydrochloric acid solution and agitating the mixture at 70 to 80 ° C for 4 hours with stirring.

Experimental Example 2: Alkali resistance test of Examples 16 to 19

The rust-preventive coating compositions prepared in Examples 16 to 19 were dip-coated on an aluminum plate and coated to a thickness of 30 to 40 탆 to form a coated film. The coating was cured at a temperature of 100 캜 for about 12 hours to perform anti- The alkali resistance and pencil hardness of the plate were tested and the results are shown in Table 6.

Example Compound name Transparency (%) Hardness (H) Alkali resistance Example 16 SG-silane compound 2-1 99.6% 2H O Example 17 SG-Precursor 1-A 99.8% 3H O Example 18 SG-Precursor 1-F 99.5% 3H X Example 19 SG-precursor 4-F 99.5% 3H O

The rust-preventive coating composition through the sol-gel crosslinking reaction showed good hardness and excellent alkali resistance as in the above examples.

Preparation of rust-inhibiting coating composition by addition of alkoxysilane compound

Example 20

10 parts by weight of tetraethyl orthosate (TEOS) was added in the same manner as in Example 16, and the rust-preventive coating composition of the present invention was prepared through a sol-gel reaction.

Example 21

10 parts by weight of tetraethyl orthosate (TEOS) was added in the same manner as in Example 17, and the rust-preventive coating composition of the present invention was prepared through a sol-gel reaction.

Example 22

10 parts by weight of tetraethyl orthosate (TEOS) was added in the same manner as in Example 19, and the rust-preventive coating composition of the present invention was prepared through a sol-gel reaction.

Example 23

5 parts by weight of gamma-methacryloxypropyltrimethoxysilane (PTMS) and methyltrimethoxysilane (MTMS) were added in the same manner as in Example 17, Coating composition.

Example 24

5 parts by weight of gamma-methacryloxypropyltrimethoxysilane (PTMS) and methyltrimethoxysilane (MTMS) were added in the same manner as in Example 19, Coating composition.

Experimental Example 3: Alkali resistance test of Examples 20 to 24

FIG. 3 is a photograph of the rust-inhibiting coating composition according to Examples 20 to 22, wherein when the tetraethyl orthosate (TEOS) was added to the alkoxysilane compound to perform a sol-gel reaction, the solution precipitated precipitously.

The rust-preventive coating compositions prepared in Examples 20 to 24 were dip-coated on an aluminum plate and coated to a thickness of 30 to 40 탆 to form a coating film. The coated film was then cured at a temperature of 100 캜 for about 12 hours, The alkali resistance and the pencil hardness of the plate were tested and the results are shown in Table 7.

Compound name Alkoxysilane transparency Hardness Alkali resistance Example 20 SG-silane compound 2-4-T TEOS - 5H X Example 21 SG-Precursor 1-A-T TEOS - 5H X Example 22 SG-Precursor 4-F-T TEOS - 4H X Example 23 SG-Precursor 1-A-P-M PTMS, MTMS 99.8% 5H O Example 24 SG-Precursor 4-F-P-M PTMS, MTMS 99.6% 5H O

(Good: O, poor: X)

As shown in Table 7, when tetraethyl orthosate (TEOS) was added, the alkali resistance was poor, while gamma-methacryloxypropyltrimethoxysilane (PTMS) and methyltrimethoxysilane (MTMS) It is confirmed that not only the transparency but also the hardness are excellent and the alkali resistance is also excellent.

Preparation of rust-inhibiting coating composition according to kind of curing agent

Example 25

In order to improve the crosslinking density, triethylenetetramine (TETA), which is a typical amine-based aliphatic curing agent, was added to 10 parts by weight of the representative aluminum-based anti-corrosion coating composition in the same manner as in Example 3, A composition was prepared.

Example 26

In order to improve the crosslinking density, 10 parts by weight of triethylenetetramine (TETA), which is a typical amine-based aliphatic curing agent, was added to the aluminum corrosion inhibiting coating composition prepared in the same manner as in Example 10, A composition was prepared.

Example 27

In order to improve the crosslinking density, triethylenetetramine (TETA), which is a typical amine-based aliphatic curing agent, was added to 10 parts by weight of the representative aluminum-based anti-corrosive coating composition in the same manner as in Example 13, A composition was prepared.

Example 28

In order to improve the crosslinking density, triethylenetetramine (TETA), which is a typical amine-based aliphatic curing agent, was added to 10 parts by weight of the representative aluminum-based anti-corrosion coating composition and crosslinked to prepare the anti- A composition was prepared.

Example 29

In order to improve the crosslinking density, 10 parts by weight of triethylenetetramine (TETA), which is a typical amine-based aliphatic curing agent, was added to the aluminum anti-corrosion coating composition prepared in the same manner as in Example 24, A composition was prepared.

Example 30

The anti-corrosive coating composition of the present invention was prepared by adding 10 parts by weight of Zephamine, a representative polyether amine hardener, to the aluminum corrosion inhibiting coating composition prepared in the same manner as in Example 3 to improve the crosslinking density .

Example 31

The rust-preventive coating composition of the present invention was prepared by adding 10 parts by weight of Zephamine, a representative polyether amine hardener, to the aluminum corrosion inhibiting coating composition prepared in the same manner as in Example 10 to improve the crosslinking density .

Example 32

The anti-corrosive coating composition of the present invention was prepared by adding 10 parts by weight of Zephamine, a representative polyether amine hardener, to the aluminum corrosion inhibiting coating composition prepared in the same manner as in Example 13 to improve the crosslinking density .

Example 33

The anti-corrosive coating composition of the present invention was prepared by adding 10 parts by weight of Zephamine, a typical polyether amine hardener, to the aluminum corrosion inhibiting coating composition prepared in the same manner as in Example 23 to improve the crosslinking density .

Example 34

The anti-corrosive coating composition of the present invention was prepared by adding 10 parts by weight of Zephamine as a typical polyether amine hardening agent to the aluminum corrosion inhibiting coating composition prepared in the same manner as in Example 24 to improve the crosslinking density .

Experimental Example 4: The alkali resistance test of Examples 25 to 34

The rust-preventive coating compositions prepared in Examples 25 to 24 were dip-coated on an aluminum plate and coated to a thickness of 30 to 40 탆 to form a coating film. The coated film was then cured at a temperature of 100 캜 for about 12 hours, The alkali resistance and the pencil hardness of the plate were tested, and the results are shown in Table 8.

Compound name Curing agent transparency Hardness Alkali resistance Example 25 Silane compound 2-1-TT TETA 99.7% 4H X Example 26 Precursor 1-A-TT TETA 99.6% 5H O Example 27 The precursor 4-F-TT TETA 99.6% 4H X Example 28 SG-Precursor 1-A-P-M-TT TETA 99.5% 5H X Example 29 SG-Precursor 4-F-P-M-TT TETA 99.6% 4H X Example 30 Silane compound 2-1-JF JEFFAMINE 99.7% 3H O Example 31 Precursor 1-A-JF JEFFAMINE 99.8% 4H X Example 32 The precursor 4-F-JF JEFFAMINE 99.6% 4H X Example 33 SG-Precursor 1-A-P-M-JF JEFFAMINE 99.7% 4H O Example 34 SG-Precursor 4-F-P-M-JF JEFFAMINE 99.7% 4H X

(Good: O, poor: X)

As shown in Table 8, the aluminum anticorrosion coating compositions prepared according to the present invention were transparent with a transparency of 99.4% or more and had a pencil hardness of 4-5H. In the case of alkali resistance, the type of alkoxysilane compound used, the type and content of epoxy, and the kind of curing agent used varied.

Experimental Example 5: All properties test

Only the compositions exhibiting the excellent alkali resistance produced in the above Examples were selected and tested for their salt resistance, adhesive strength, acid resistance and water resistance by the evaluation method shown in Table 9, and the results are shown.

evaluation
object Assessment Methods Example 23 24 26 30 33 Salt water resistance (corrosion resistance) After 24 hours of immersion in 5% NaCl aqueous solution, there should be no white rust
Test specification; ASTM B117-11 (KS M2109) O O O O O Adhesion tape test (cross cut)
Test specification; ASTM D 3002, D3359 (ISO 2409) X X X X O Acid resistance No swelling, cracking or peeling after soaking in a 10% solution of hydrofluoric acid for 30 minutes O O X O O Water resistance No swelling, cracking, discoloration or adhesion after immersion in water at 40 ° C for 120 hours. O O O O O

(Good: O, poor: X)

As shown in Table 9, the coating compositions to which the curing agent was added exhibited superior alkali resistance, corrosion resistance (acid resistance), hardness, and adhesion than the coating compositions to which no curing agent was added. This is because, as the crosslink density increases, almost no pores such as pinholes are present on the surface. When polyphenamine, which is a polyester amine-based curing agent, is used rather than amine-based aliphatic curing agent triethylenetetramine, And the adhesion between the plate and the coating film is more excellent.

Claims (8)

delete a) preparing a silane compound having a hydroxy group by reacting 2-amino-2-hydroxymethyl-1,3-propanediol with 3-glycidoxypropyltrimethoxysilane in a nitrogen atmosphere;
b) reacting the prepared silane compound with bisphenol A diglycidyl ether to prepare an organic / inorganic hybrid precursor compound; And
c) sol-gel-reacting the prepared precursor compound with an alkoxide compound.
A method for preparing an organic / inorganic hybrid rust-preventive coating composition.
delete delete delete 3. The method of claim 2,
The alkoxide compound may be at least one selected from the group consisting of gamma-methacryloxypropyltrimethoxysilane (PTMS), methyltrimethoxysilane (MTMS), titanium isopropoxide (TTiP), and zirconium butoxide &Lt; / RTI &gt;
A method for preparing an organic / inorganic hybrid rust-preventive coating composition.
3. The method of claim 2,
Characterized in that Jeffamine is further added as a curing agent of the rust-preventive coating composition prepared by the sol-gel reaction.
A method for preparing an organic / inorganic hybrid rust-preventive coating composition.
a) In a nitrogen atmosphere, 2-amino-2-hydroxymethyl-1,3-propanediol and 3-glycidoxypropyltrimethoxysilane are reacted at an equivalent ratio of 1: 1 to 2: 1 to prepare a silane compound step;
b) reacting the prepared silane compound with bisphenol A diglycidyl ether to prepare an organic / inorganic hybrid precursor compound; And
c) adding to the prepared precursor compound gamma-methacryloxypropyltrimethoxysilane (PTMS), methyltrimethoxysilane (MTMS) or a mixture thereof and sol-gel reaction.
A method for preparing an organic / inorganic hybrid rust-preventive coating composition.

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