KR101136598B1 - Water-soluble polymer composition and paint composition containing them for coating flexible cables - Google Patents

Abstract

The present invention is 10-20% by weight polyester polyol, 0.5-2.0% by weight diol, 5-20% by weight isocyanate, 1-2% by weight ionic emulsifier, 0.1-2% by weight epoxy silane, 0.001-0.01 tin-based metal catalyst Water soluble polymer for braiding comprising: wt%, neutralizer 0.1-2 wt%, chain extender 0.1-2 wt%, defoamer 0.01-0.1 wt%, ion-exchanged water 45-70 wt%, and ketone solvent 2-8 wt% As a composition and a water-soluble coating composition for braiding comprising the same, according to the present invention, it is excellent in terms of dryness, flexibility, peel-adhesiveness, UV stability, salt water corrosion resistance, etc., which are environmentally friendly and conditions to be used for braided application compositions for ships. A coating composition can be provided.

Braided, Polyester Polyol, Environmentally Friendly

Description

WATER-SOLUBLE POLYMER COMPOSITION AND PAINT COMPOSITION CONTAINING THEM FOR COATING FLEXIBLE CABLES}

The present invention relates to a braided coating composition for use in ships and the like.

Currently, the physical condition that the braided coating composition used in ships has to be considered is drying property, flexibility, peeling adhesiveness, UV stability, salt water corrosion resistance, and the like. The composition of the oil-based braiding paint is a pigment and an organic solvent including an acrylic polyol polymer or a vinyl polymer, and a quick-drying solvent such as an aromatic organic solvent, a ketone organic solvent, an alcoholic organic solvent, and various additives (rust-preventing agent, antifoaming agent). , Thickeners, dispersants, and the like). In particular, the thickness of the coating film of the composition constituting the braid is so thin that the composition of the composition must include a large number of organic solvents.

Since the conventional braided coating composition has a problem of environmentally harmful volatile organic compounds, the development of an alternative paint to overcome the problem of air pollution is a key.

In order to solve the above problems, an object of the present invention is to provide a coating composition that is excellent in drying, flexibility, peel-off adhesiveness, UV stability, salt protection, and the like as a condition that an environment-friendly and braided application composition for ships should have. It is done.

The water-soluble polymer composition for braiding according to the present invention comprises 10 to 20% by weight of polyester polyol, 0.5 to 2.0% by weight of diol, 5 to 20% by weight of isocyanate, 1 to 2% by weight of ionic emulsifier, 0.1 to 2% by weight of epoxy silane, 0.001 to 0.01 wt% tin metal catalyst, 0.1 to 2 wt% neutralizing agent, 0.1 to 2 wt% chain extender, 0.01 to 0.1 wt% defoaming agent, 45 to 70 wt% ion-exchanged water, and 2 to 8 wt% ketone solvent Characterized in that it comprises a,

The polyester polyol contains 59.4 to 69.5 weight percent dimer fatty acid, 30.4 to 40.5 weight percent 1,6 hexanediol and 0.01 to 0.1 weight percent dibutyl tin oxide,

The diol is at least one member selected from the group consisting of monomers having two hydroxyl groups, such as ethylene glycol, butane diol, hexane diol, nonane diol, dicaine diol, propylene glycol, neopentyl glycol ,

The isocyanate is one or more selected from the group consisting of hexamethylene diisocyanate, trimethyl hexane diisocyanate, diphenylmethane diisocyanate and xylene diisocyanate.

And the water-soluble coating composition for braiding which concerns on this invention is 65-85 weight% of braided water-soluble polymer compositions, 5-20 weight% of pigments, 0.5-1.50 weight% of a dispersing agent, 0.05-2 weight% of antifoamers, leveling agents 1-3 It is characterized by comprising a weight percent, alcohol solvent 3-10% by weight, thickener 0.1-3% by weight and water 5-20% by weight.

According to the coating composition of the present invention, it is possible to provide a water-soluble coating composition excellent in environment-friendly, drying conditions, flexibility, peeling adhesiveness, UV stability, salt water corrosion resistance, etc. as conditions that the braided coating composition for ships should have, It can be used environmentally for braiding in ships.

Hereinafter will be described a water-soluble polymer composition and a water-soluble coating composition comprising the same.

Specifically, the water-soluble polymer of the present invention is 10-20% by weight polyester polyol, 0.5-2.0% by weight ethylene glycol, 5-20% by weight isocyanate, 1-2% by weight ionic emulsifier, 0.1-2% by weight epoxy silane, tin 0.001% to 0.01% by weight of metal catalyst, 0.1 to 2% by weight of neutralizer, 0.1 to 2% by weight of chain extender, 0.01 to 0.1% by weight of defoamer, 45 to 70% by weight of ion-exchanged water, and 2 to 8% by weight of ketone solvent It consists of a composition.

The raw material of the polyester polyol used in the present invention includes 59.4 ~ 69.5% by weight of dimer fatty acid, 30.4 ~ 40.5% by weight of 1,6 hexanediol, 0.01 ~ 0.1% by weight of dibutyl tin oxide, by the reaction of 220 ℃ Obtained. Dimer fatty acids used in polyester polyols are made by several oligomer reactions of unsaturated fatty acids. Various polymers composed of these dimer fatty acids have increased flexibility, improved hydrolytic stability, and resistance to oxidation and UV degradation due to the long hydrocarbon chains between the carboxylic acid groups in the dimer composition. Because of this, the composition containing the polymer containing the dimer fatty acid is characterized by long film life, high gloss and retention, high solids content and low cracking. The polyester polyol is a precursor for synthesizing the resin, and has a viscosity of 0.95 when the specific gravity is 25 ° C., a solid content of 99% or more, and a viscosity (Gardner viscosity) of 25 ° C. and a Z6-Z7, and an acid value of 1 or less. It is preferable to use 10-20 weight% of polyester polyols.

In the present invention, the diol may include monomers having two hydroxyl groups, such as ethylene glycol, butane diol, hexane diol, nonane diol, dicaine diol, propylene glycol, and neopentyl glycol. It is preferable to use 0.5-2.0 weight% of diol.

Isocyanate in the present invention may include hexamethylene diisocyanate, trimethylhexane diisocyanate, isopron diisocyanate, dicyclohexy diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate. Due to the high reactivity of the isocyanates with the low miscibility of water, there are many problems in the preparation in the water medium. Therefore, in the first step, diols and polyols are reacted with the diisocyanate, synthesized and dispersed in water in the next step. do. Polymers dispersed in water have isocyanates in their terminal groups, so highly reactive isocyanates such as aromatic isocyanates are limited in use. Relatively less reactive aliphatic isocyanates are introduced. In particular, the polymer may be introduced by selecting one from the group consisting of hexamethylene diisocyanate and isopron diisocyanate. It is preferable to use 5-20 weight% of isocyanates.

Reaction is performed at 60-110 degreeC temperature conditions using the said raw material. It is preferable to react within 10 to 20 weight% of polyester polyol, and diol to 0.5 to 2.0 weight% and 5 to 20 weight% of isocyanate. The solvent is a ketone solvent, and the ketone solvent may include methyl ethyl ketone, methyl isobutyl ketone, acetone, dipropyl ketone, diethyl ketone. The polymer may be introduced by selecting one from the group of ketone solvents. Ketone solvents are used within the range of 2 to 8% by weight.

In the present invention, in order to disperse the polymer in water, which is a highly polar solvent, a hydrophilic group in the polymer skeleton should be introduced. In general, techniques are introduced that physically mix a surfactant or emulsifier with hydrophilic and hydrophobic groups in one molecular structure to keep the polyurethane particles stable in the water medium. However, since the low molecular weight external emulsifier introduced into the urethane water dispersion system is not removed during the coating film formation process, it has a disadvantage of negatively affecting the physical properties of the final urethane coating film. Therefore, nonionic and ionic groups with hydrophilic groups are introduced. Since ionic groups have lower hydrophilicity and less water dispersion stability than ionic groups, ionic groups are introduced. The ionic groups are anionic groups such as carboxyl group, sulfonic acid group and sulfuric acid ester group. , An emulsifier having a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium base, which is a phosphate ester group and a cationic group, can be introduced. The polymer was used by selecting one from the group consisting of dimethylol butanoic acid and dimethylol propionic acid having a carboxyl group. The higher the content of the emulsifier having a carboxyl group which is a hydrophilic group, the smaller the number average particle size of the polymer and the narrower the particle size distribution. It is preferable to use 1 to 2 weight% of anionic emulsifiers.

In the present invention, silane was introduced to increase adhesion with the material. The silanes may include ester silanes, vinyl silanes, methacryloxy silanes, epoxy silanes, sulfo silanes, amino silanes, ureido silanes. In particular, the epoxy silane is selected from the group consisting of gamma-glycidoxypropyltrimethoxy silane, beta-epoxy cyclohexylethyltrimethoxy silane and shows high adhesion to the material. It is preferable to use 0.1 to 2 weight% of epoxy silanes.

Reaction is performed at 60-110 degreeC temperature conditions using the said raw material. It is preferable that anionic emulsifier reacts in 1-2 weight%, and an epoxy silane in the range of 0.1-2 weight%. The dibutyl tin dilaurate is preferably used in 0.001 ~ 0.01% by weight of a tin-based metal catalyst. The solvent is a ketone solvent, and the ketone solvent may include methyl ethyl ketone, methyl isobutyl ketone, acetone, dipropyl ketone, diethyl ketone. The polymer may be introduced by selecting one from the group of ketone solvents. Ketone solvents are used within the range of 2 to 8% by weight. This reaction should be maintained for at least 5 hours at a temperature of 60-110 ° C.

The resulting reactant is cooled to 70 ° C. or lower and the ketone solvent is added within the range of 1 to 4% by weight, and the resulting reactant is added to a neutralizing agent at 55 ° C. or lower and held for 20 minutes. The neutralizing agent neutralizes the carboxyl group of the emulsifier and the neutralizing agent may include diethanolamine, triethanolami, dimethylaminoethanol, triethylamine. The reaction is used by selecting one from the group of neutralizers. It is preferable to use 0.1 to 2 weight% of neutralizing agents.

The resulting reactant is cooled to 40 ° C. or lower, and ion-exchanged water is added dropwise for 3 to 5 minutes while stirring. It is preferable to use 35-50 weight% of ion-exchange water.

The chain extender dissolved in ion-exchanged water was added dropwise to the resultant reactant for 2 minutes and held for 30 minutes. It is preferable to use 0.1 to 2% by weight of ion-exchanged water, and the chain extender may include ethylenediamine, butanediamine, hexamethylenediamine, diaminepropane, trimethylhexanediamine, and isophoronediamine. The reaction is used by selecting one from the group of chain extenders. It is preferable to use 0.1-2 weight% of chain extenders.

The antifoaming agent is added to the resultant reactant, and the ketone solvent is vacuumed and ion exchanged water is added. It is preferable to use 0.01 to 0.1 weight% of antifoamers, and it is preferable to use 10-20 weight% of ion-exchange water.

The polymer of the present invention has a viscosity between A1 and A2 when the specific gravity is 25 ° C, 1.02, the solid content is 30 ± 2%, and the viscosity (Gardner viscosity) is 25 ° C.

In addition, the water-soluble coating composition according to the present invention comprises a pigment, a dispersant, an antifoaming agent, a leveling agent, an alcoholic solvent, a thickener, and water in the above-mentioned water-soluble polymer composition.

Hereinafter, the present invention will be described in more detail with reference to Examples. The following examples are provided to more specifically describe the contents of the present invention, but the scope of the present invention is not limited thereto.

Example - polyester Polyol  Produce

A four-necked flask equipped with a stirrer, a thermometer, a thermostat, a nitrogen inlet tube, and a condenser was mixed with 63.83 wt% of dimer fatty acid, 36.16 wt% of 1,6 hexanediol, and 0.01 wt% of dibutyltin oxide to react at 220 ° C. Obtained. The polyester polyol is a precursor for synthesizing the resin, and has a viscosity of 0.95 when the specific gravity is 25 ° C., a solid content of 99% or more, and a viscosity (Gardner viscosity) of 25 ° C., and a acid value of 1 or less.

Example  1-soluble Polymer  Preparation of the composition

In a four-necked flask equipped with a stirrer, a thermometer, a thermostat, a nitrogen inlet tube and a condenser, 13.13% by weight of polyester polyol, 1.32% by weight of ethylene glycol, 9.77% by weight of isopron diisocyanate, and 5.26% by weight of methyl ethyl ketone were stirred. It heated up to 85. 1.31% by weight of dimethylolbutanoic acid, 0.53% by weight of gamma-glycidoxypropyltrimethoxy silane, 1.84% by weight of methyl ethyl ketone, and 0.01% by weight of dibutyltin dilaurate were added and maintained at 85 ° C for at least 5 hours. do. 4.73 weight% of acetone is dripped after cooling to 70 degreeC. After cooling to 55 ° C., 0.72% by weight of triethylamine was added dropwise and the reaction was carried out for 20 minutes. 41.01% by weight of ion-exchanged water is added dropwise for 3 to 5 minutes while stirring at 40 ° C or lower. One minute after the dropwise addition, 0.71% by weight of isophorone diamine dissolved in 3.15% by weight of ion-exchanged water was added dropwise to the reaction mixture and maintained for 30 minutes. After holding for 30 minutes, 3.94% by weight of N-methyl-2-pyrrolidone and 0.04% by weight of antifoam are added. After vacuum recovery of the solvent, 12.51% by weight of ion-exchanged water is added to obtain a polymer. The polymer of the present invention has a viscosity between A2 and A2 when the specific gravity is 25 ° C, 1.02, the solid content is 30 ± 2%, and the viscosity (Gardner viscosity) is 25 ° C.

Example  2- water soluble Polymer  Preparation of the composition

Into a four-necked flask equipped with a stirrer, a thermometer, a thermostat, a nitrogen inlet tube, and a condenser, 10.74% by weight of polyester polyol, 1.42% by weight of ethylene glycol, 9.91% by weight of isopron diisocyanate, and 5.37% by weight of methyl ethyl ketone were stirred. It heated up at 85 degreeC, being. 1.34 weight% of dimethylol butanoic acid, 2.69 weight% of methyl ethyl ketone, and 0.01 weight% of dibutyl tin dilaurates are dripped, and it carries out 85 degreeC reaction for 5 hours or more. 2.69 weight% of 1, 6- hexamethylene diisocyanate trimers are dripped here. 5.37 weight% of acetone is dripped after cooling to 70 degreeC. After cooling to 55 ° C, 0.92% by weight of triethylamine was added dropwise and the reaction was carried out for 20 minutes. 54.25 weight% of ion-exchange water is dripped for 3 to 5 minutes, stirring at 40 degrees C or less. One minute after the dropwise addition, 0.71% by weight of ethylene diamine dissolved in 3.22% by weight of ion-exchanged water was added dropwise to the reaction mixture and maintained for 30 minutes. After holding for 30 minutes, 1.34% by weight of N-methyl-2-pyrrolidone and 0.03% by weight of an antifoam are added. The solvent is evacuated to obtain a polymer. The polymer of the present invention has a viscosity between D-J when the specific gravity is 25 ° C, 1.03, the solid content is 32 ± 2%, and the viscosity (Gardner viscosity) is 25 ° C.

Example  3- water soluble Polymer  Preparation of the composition

Into a four-necked flask equipped with a stirrer, a thermometer, a thermostat, a nitrogen inlet tube, and a condenser, 13.75 wt% of polyester polyol, 1.37 wt% of ethylene glycol, and 10.19 wt% of isopron diisocyanate were heated to 85 ° C. while stirring. 1.38 weight% of dimethylol butanoic acid, 8.25 weight% of methyl ethyl ketone, and 0.01 weight% of dibutyl tin dilaurate are dripped, and it carries out 85 degreeC reaction for 5 hours or more. 5.50 weight% of N-methyl- 2-pyrrolidone is dripped after cooling to 70 degreeC. After cooling to 60 ° C., 0.94% by weight of triethylamine was added dropwise and the reaction was carried out for 20 minutes. 54.47% by weight of ion-exchanged water is added dropwise for 3 to 5 minutes while stirring at 40 ° C or lower. One minute after the dropwise addition, 0.82% by weight of isophoronediamine dissolved in 3.30% by weight of ion-exchanged water was added dropwise to the reaction mixture and maintained for 30 minutes. After holding for 30 minutes, 0.01% by weight of antifoaming agent is added. The polymer is obtained by adding 0.02% by weight of an antifoaming agent under vacuum at 55 to 60 ° C. The polymer of the present invention has a viscosity between 1.02 when the specific gravity is 25 ° C, 30 ± 2% solids, and the viscosity (Gardner viscosity) at 25 ° C.

Example  Preparation of 4, 5, 6-Water-Soluble Coating Compositions

A water-soluble coating composition was prepared with the ingredients and contents shown in Table 1.

Paint Composition Example 4 Example 5 Example 6 combination
Furtherance
(weight%) Water soluble polymer 75 75 75 Dispersant One One One Thickener-1 0.5 0.5 0.5 Thickener-2 0.3 0.3 0.3 White Pigment 11 11 11 Antifoam 0.3 0.3 0.3 Leveling agent 0.2 0.2 0.2 Methanol 4 4 4 2-dimethyl
Aminoethanol 0.3 0.3 0.3 water 6.9 6.9 6.9 Rust preventive 0.5 0.5 0.5

Comparative example  Preparation of 1, 2-water-soluble paint composition

Coating compositions were prepared with the ingredients and contents shown in Table 2.

The polymer of Comparative Example 1 prepared an application composition using vinyl chlorides, and the polymer of Comparative Example 2 prepared an application composition using an acrylic polyol.

Paint Composition Comparative Example 1 Comparative Example 1 combination
Furtherance
(weight%) Polymer 75 75 Dispersant One One Thickener-1 0.5 0.5 Thickener-2 0.3 0.3 White Pigment 11 11 Antifoam 0.3 0.3 Leveling agent 0.2 0.2 Methanol 4 4 2-dimethyl
Aminoethanol 0.3 0.3 water 6.9 6.9 Rust preventive 0.5 0.5

Examples 4, 5, 6 and Comparative Examples 1, 2 with the application composition prepared according to the content and the content was measured under the following conditions for the measurement of physical properties.

The film evaluation test first removes rust, oil, dust, etc. from the surface of the galvanized braid using an appropriate solvent. Next, the zinc-plated braided wire was sufficiently dipped into the application composition, removed, and then set for 10 minutes at 20 to 30 ° C., and then dried in a 60 to 80 ° C. drying furnace for 10 to 20 minutes to obtain a coating film for evaluation test.

Water resistance rating

Film evaluation test The test specimen was exposed to water for 240 hours to evaluate the peeling of the coating film.

Salt Spray Resistance

Film evaluation test The test specimens were exposed to 5% salt solution for 1000 hours to evaluate the peeling of the coating film.

Adhesion  evaluation

① Dry adhesion

Film evaluation test After holding the specimen at both sides of the specimen at 18-27 ° C and bending and releasing it, it is evaluated for peeling.

② Moisture adhesion

Film evaluation test specimens are soaked in distilled or deionized water at 38 ° C for 12 hours. Wipe and dry the specimen. Within 5 minutes, the test is repeated as described for dry adhesion.

③ Boiling water adhesion

Film evaluation test specimens are soaked in boiling distilled or deionized water at 99 ~ 100 ℃ for 10 minutes. Wipe and dry the specimen. Within 5 minutes, the test is repeated as described for dry adhesion.

UV stability

Film evaluation test specimens were exposed to QUV UVA-340 lamps for 300 hours to assess color index aberrations.

Dryness and flowability are visually confirmed and evaluated.

Test Items Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Water resistance ○ ○ ○ △ △ Salt Spray Resistance ○ ○ ○ △ △ Flow △ △ ○ ○ △ Adhesion dry ○ ○ ○ ○ ○ humidity ○ ○ ○ △ △ Boiling water ○ △ △ × △ UV-rays
stability ○ ○ ○ △ ○ Dryness ○ ○ ○ ○ ○

(Good: ○ Medium: △ Bad: ×)

According to the coating composition according to the present invention from the results of Table 3, it can be seen that the drying property, flexibility, peeling adhesiveness, UV stability, and saline corrosion resistance are improved.

As described above, the detailed description of the present invention has been made by the embodiments with reference to the accompanying drawings. However, since the above-described embodiments have only been described with reference to preferred embodiments of the present invention, the present invention is limited to the above embodiments. It should not be understood that the scope of the present invention is to be understood by the claims and equivalent concepts described below.

Claims (5)

10-20 wt% polyester polyol; Diol 0.5-2.0 wt%; 5-20 wt% of isocyanates; 1-2 wt% of the ionic emulsifier; 0.1 to 2 wt% epoxy silane; 0.001-0.01 wt% tin-based metal catalyst; 0.1 to 2 wt% neutralizing agent; 0.1-2% by weight of chain extension agent; Antifoaming agent 0.01-0.1 wt%; 45-70 wt% of ion-exchanged water; And Ketone solvent 2-8% by weight; Water-soluble polymer composition for braiding comprising a The method of claim 1, The polyester polyol, 59.4 to 67.5 weight percent of dimer fatty acid; 10.4 hexanediol 30.4-40.5 wt%; And 0.01-0.1 wt% dibutyl tin oxide; Water-soluble polymer composition for braiding comprising a The method of claim 1, The diol is at least one member selected from the group consisting of monomers having two hydroxyl groups, such as ethylene glycol, butane diol, hexane diol, nonane diol, dicaine diol, propylene glycol, neopentyl glycol Braided water-soluble polymer composition The method of claim 1, The isocyanate is at least one selected from the group consisting of hexamethylene diisocyanate, trimethyl hexane diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate, wherein the water-soluble polymer composition for braiding delete