KR102594979B1 - solvent-free epoxy type paint composition and offshore structure comprising coating film of thereof - Google Patents

Abstract

The present invention relates to a solvent-free epoxy paint composition and a marine structure having a coating film thereof. The solvent-free epoxy paint composition includes an epoxy resin containing two or more epoxy groups in the molecule, a reactive diluent containing an epoxide group, a non-reactive diluent, and It is characterized by comprising a base agent containing acrylate as an amine blushing inhibitor, and a curing agent containing an aliphatic amine and an alicyclic amine.

Description

Solvent-free epoxy type paint composition and offshore structure comprising coating film of the same}

The present invention relates to a solvent-free epoxy paint composition and a marine structure having a coating film thereof.

The development and use of solvent-free epoxy paint compositions that can be applied to harsh corrosive environments such as ballast tanks of ships, crude oil tanks, and seawater immersion areas of marine structures are increasing.

Recently, research has been conducted on solvent-free epoxy anticorrosive paint compositions that do not contain solvents. In particular, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, which has at least two or more epoxy groups in the molecule, a base containing a reactive diluent with a mono epoxide, and an amine-type curing agent, have excellent coating film properties such as rust prevention and corrosion resistance. Paint compositions are being developed.

However, these solvent-free paint compositions have excellent rust prevention properties, but have poor drying properties at low temperatures (below 5°C), generate free amines, cause amine blushing, and have poor adhesion during subsequent painting. There is a problem of being inferior.

Methods for preventing such amine blushing include lowering the equivalence ratio of amine in the paint composition or speeding up the curing speed. However, if the equivalence ratio of the amine is lowered, the cross-linking density is lowered, resulting in inferior chemical resistance, and if the curing speed is accelerated, the pot life at high temperatures becomes too short.

Specifically, in U.S. Patent No. 5,442,035, calcium sulfonate or calcium hydrocarbonyl sulfate was introduced, and in U.S. Patent No. 6,465,597, sulfur element was introduced to speed up the curing speed, but there was a disadvantage in that adhesion performance was reduced.

US Patent No. 5,442,035 US Patent No. 6,465,597

The present invention was created to solve the problems of the prior art as described above, and the purpose of the present invention is to maintain excellent rust prevention and corrosion resistance when applied to ship paint, while maintaining drying performance at low temperature conditions of 5°C or less and adhesion of subsequent painting. The purpose is to provide this excellent solvent-free epoxy paint composition.

The solvent-free epoxy paint composition according to one aspect of the present invention includes an epoxy resin containing two or more epoxy groups in a molecule, a reactive diluent containing an epoxide group, a non-reactive diluent, and an acrylate as an amine blushing inhibitor. , and a curing agent containing an aliphatic amine and an alicyclic amine.

Specifically, the solvent-free epoxy paint composition may have a solid content of 90 parts by weight or more based on 100 parts by weight of the composition.

Specifically, the content of the acrylate may be 0.1 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the main agent.

Specifically, the acrylates include trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetraethylene glycol dimethacrylate, and ethylene glycol dimethacrylate. selected from the group consisting of acrylate, triethylene glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, 1,6-hexanediol diacrylate and 1,6-hexanediol dimethacrylate There may be one or more types.

The solvent-free epoxy paint composition according to the present invention can produce a coating film with excellent rust prevention and corrosion resistance.

The solvent-free epoxy paint composition according to the present invention can improve pattern workability of airless spray painting under low temperature conditions of 5°C or lower.

The solvent-free epoxy paint composition according to the present invention can improve recoatability by suppressing carbamate formation on the surface of the coating film due to amine blushing.

The effect of the present invention is not limited to the above-mentioned effect, and effects not mentioned will be clearly understood by those skilled in the art from the present specification and the attached drawings.

Throughout the specification of the present application, when a part is said to “include” a certain element, this means that it may further include other elements rather than excluding other elements, unless specifically stated to the contrary.

Throughout the specification herein, the unit “part by weight” may refer to the ratio of weight between each component.

The solvent-free epoxy paint composition according to the present invention is composed of a two-component type containing a base material and a hardener.

The subject matter includes an epoxy resin as a binder resin and a polyfunctional (meth)acrylate as an amine blushing inhibitor, and the curing agent includes an aliphatic amine and an alicyclic amine. The above base material and hardener are mixed before application.

The present inventors found that when a non-solvent type epoxy paint composition includes (meth)acrylate as an epoxy resin, a curing agent, and an amine blushing inhibitor, the formation of carbamate on the surface of the coating film due to amine blushing can be suppressed and recoatability can be improved.

Hereinafter, this specification will be described in more detail.

The main components of the epoxy paint composition according to the present invention include an epoxy resin containing two or more epoxy groups in the molecule, a reactive diluent containing an epoxide group, a non-reactive diluent, and an acrylate as an amine blushing inhibitor.

The epoxy resin according to an embodiment of the present invention may include a solvent-free epoxy resin with a solid content of 90% by weight or more and almost no content of volatile solvent. More preferably, the solid content may be 95% by weight or more. A paint composition containing an epoxy resin with a solid content of 95% by weight or more can produce a coating film with excellent physical properties such as corrosion resistance and seawater resistance.

The epoxy equivalent weight (EEW) of the epoxy resin may be 160 g/eq or more and 220 g/eq or less. Specifically, the epoxy equivalent weight of the epoxy resin may be 170 g/eq or more and 200 g/eq or less, or 175 g/eq or more and 190 g/eq or less. By adjusting the epoxy equivalent weight of the epoxy resin within the above-mentioned range, excessive increase in viscosity of the solvent-free epoxy paint composition can be suppressed, and the dispersibility of the paint and airless spray painting workability can be prevented from being reduced.

The epoxy resin may include at least one of bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, and a mixed epoxy resin thereof having two or more epoxy groups in the molecule. Specifically, the epoxy resin may include at least one of a bisphenol F-type epoxy resin or a bisphenol A-type epoxy resin, and a mixed resin of the bisphenol F-type epoxy resin and the bisphenol A-type epoxy resin. The content of the bisphenol F-type epoxy resin or bisphenol A-type epoxy resin used alone may be 15 parts by weight or more and 45 parts by weight or less, for example, 25 parts by weight or more and 35 parts by weight or less, based on 100 parts by weight of the main ingredient. there is. In addition, the mixed resin of the bisphenol F-type epoxy resin and the bisphenol A-type epoxy resin may be 1 part by weight or more and 20 parts by weight or less, for example, 5 parts by weight or more and 15 parts by weight or less, based on 100 parts by weight of the main ingredient.

The content of the epoxy resin may be 15 parts by weight or more and 65 parts by weight or less, for example, 30 parts by weight or more and 50 parts by weight or less, based on 100 parts by weight of the base material. If the content is less than 15 parts by weight, as the pigment content relatively increases, the viscosity of the paint becomes too high, lowering workability, and the appearance of the formed coating film may be poor. In addition, if the content exceeds 65 parts by weight, the pot life is shortened, and mechanical properties such as coating film hardness are deteriorated.

By adjusting the content of the epoxy resin to the above-mentioned range, it is possible to suppress the deterioration of workability and coating film appearance due to an increase in the viscosity of the coating composition as the pigment content increases, and to prevent the coating film physical properties such as rust prevention and seawater resistance from deteriorating. can be suppressed. In addition, when the content of the epoxy resin is within the above-mentioned range, the pot life of the solvent-free epoxy paint composition can be improved and the decrease in mechanical properties such as coating film hardness can be suppressed.

By including a reactive diluent, the solvent-free epoxy paint composition according to an embodiment of the present invention can overcome limitations in pigment application due to the high viscosity of the epoxy resin and maintain a viscosity that allows airless spray painting.

The reactive diluent included in the above subject contains an epoxide group and can participate in the reaction with the curing agent to form part of the cured paint film. The content of the reactive diluent according to an embodiment of the present invention may be 5 parts by weight or more and 25 parts by weight or less, for example, 10 parts by weight or more and 20 parts by weight or less, based on 100 parts by weight of the main agent. If the content is less than 5 parts by weight, the mechanical properties of the coating film may deteriorate as the amount of usable pigment decreases. In addition, if the content exceeds 25 parts by weight, the hardness and rust prevention of the coating film decreases and the drying time of the coating film is delayed.

When the content of the reactive diluent is within the above-mentioned range, it is possible to suppress the phenomenon of deterioration of mechanical properties and inferiority of airless spray painting workability as the content of usable pigment decreases. In addition, by adjusting the content of the reactive diluent to the above-mentioned range, the physical properties of the coating film, such as coating film hardness and rust prevention, can be improved, and the drying time of the coating film can be shortened.

The epoxy equivalent weight of the reactive diluent may be 150 g/eq or more and 600 g/eq or less, for example, 250 g/eq or more and 400 g/eq or less. Additionally, the reactive diluent may include an alkyl glycidyl ether having the above-described epoxy equivalent. By using the reaction diluent as described above, the painting workability of the solvent-free epoxy paint composition can be improved.

The reactive diluent may include a monoepoxide type compound containing one epoxide group. By using a reactive diluent containing a monoepoxide type compound, the viscosity of the solvent-free epoxy paint composition can be appropriately adjusted.

The solvent-free epoxy paint composition according to an embodiment of the present invention may include a non-reactive diluent, and the non-reactive diluent included in the main agent or hardener does not participate in the reaction, but remains in the coating film and may affect the physical properties of the coating film. You can.

As a non-reactive diluent, for example, one or more types selected from the group consisting of benzyl alcohol, dodecyl phenol, and phenol modified liquid hydrocarbon resin may be used.

The content of the non-reactive diluent according to an embodiment of the present invention may be 0.1 part by weight or more and 10 parts by weight or less, for example, 1 part by weight or more and 5 parts by weight or less, based on 100 parts by weight of the main ingredient. If the content is less than 0.1 part by weight, the mechanical properties of the coating film may deteriorate as the amount of usable pigment decreases. In addition, if the content exceeds 10 parts by weight, the hardness and rust prevention of the coating film decreases and the drying time of the coating film is delayed.

By adjusting the content of the non-reactive diluent within the above-mentioned range, airless spray painting workability can be improved and deterioration of physical properties such as hardness and rust prevention of the coating film can be suppressed.

The solvent-free epoxy paint composition according to an embodiment of the present invention may further include an extender pigment. The extender pigment has high hardness and can increase the hardness of the paint to create a coating film with excellent wear resistance. For example, feldspar, silica, calcium carbonate, talc, mica, glass flake, etc. can be used alone. It may be used, and two or more types may be used, and feldspar is preferred.

The feldspar has a low oil absorption and improves the degree of atomization of airless spraying under low temperature conditions of 5°C or lower, resulting in a good spray pattern. As thixotropic properties are provided, the feldspar has good flowability, making it a paint with improved airless spray painting workability in low temperature conditions. A composition may be provided.

The content of the extender pigment may be 15 parts by weight or more and 45 parts by weight or less, and 20 parts by weight or more and 40 parts by weight or less, based on 100 parts by weight of the main ingredient. If the content is less than 15 parts by weight, the mechanical properties of the coating film may deteriorate, and if the content exceeds 45 parts by weight, the rust prevention of the coating film may decrease and workability may be lowered.

By adjusting the content of the extender pigment within the above-mentioned range, airless spray painting workability of the solvent-free epoxy paint composition can be improved and deterioration of the mechanical properties of the coating film can be suppressed.

The subject matter according to an embodiment of the present invention may further include a colored pigment. Colored pigments are used to express color in the coating film of a solvent-free epoxy paint composition, and colored pigments used in the industry can be used without limitation. For example, TiO ₂ and the like can be used as a white pigment, and carbon black and the like can be used as a black pigment. The content of the colored pigment may be 1 part by weight or more and 10 parts by weight or less based on 100 parts by weight of the main ingredient.

The solvent-free epoxy paint composition according to an embodiment of the present invention further includes an anti-settling agent, thereby solving the problem of feldspar having poor paint storage stability. The anti-settling agent may be any conventional anti-settling agent known in the art without limitation. For example, a clay-type, wax-type, or urethane polymer type anti-settling agent may be used. Preferably, a clay-type anti-settling agent may be used. may further include. This clay-type anti-settling agent can compensate for the shortcomings of feldspar, which has poor paint storage stability, while improving the workability and film properties of the paint.

The content of the anti-settling agent may be 0.5 parts by weight or more and 5 parts by weight or less, based on 100 parts by weight of the subject matter. If the content is less than 0.5 parts by weight, leveling of the paint film is ensured, but workability of the paint becomes poor. Specifically, the workability of the paint (flowability when painting vertical surfaces) may be reduced. If the content exceeds 5 parts by weight, the physical properties of the coating film, such as poor workability and water resistance, may decrease due to an increase in viscosity.

When the content of the anti-settling agent is within the above-mentioned range, the coating film properties, storage stability, and workability of the solvent-free epoxy paint composition can be secured at the same time.

The paint composition according to an embodiment of the present invention may further include an additive including at least one of a dispersant, an antifoaming agent, and a functional additive.

The dispersing agent may adsorb to the surface of the pigment and maintain a constant distance between the pigments through electric repulsion or steric hindrance effect to prevent the pigments from re-agglomerating. The dispersant used in the art can be used without limitation, and examples include silicone-based dispersants or non-silicone-based dispersants (eg, polycarboxylic acid polyester type dispersants).

The antifoaming agent is used to prevent defects in the coating film, such as the generation of bubbles in the coating film. If these bubbles remain in the coating film, they may cause poor adhesion to the substrate or deterioration of physical properties. The defoaming agent may be used without limitation in the field, and examples include mineral oil-based, silicone-based, and non-silicone-based. In one embodiment of the present invention, a silicone-based defoaming agent is used in terms of maximizing the defoaming power. You can.

In addition, the functional additive can be used as an additive to prevent defoaming defects, prevent cratering, prevent color separation, remove air bubbles on the surface of the coating film, and provide smoothness to the coating film. Silicone additives such as polyethersiloxane and polyester siloxane can be used. It may be desirable to select a type that has both leveling performance and defoaming performance. In addition, in order to reduce the viscosity of the paint and improve its adhesion to the substrate, an adhesion enhancer may be further included. For example, a silane-based compound may be used.

The content of the additive may be 0.5 parts by weight or more and 10 parts by weight or less, for example, 2 parts by weight or more and 7 parts by weight or less, based on 100 parts by weight of the main ingredient.

The subject matter according to one embodiment of the present invention may include (meth)acrylate as an amine blushing inhibitor. (Meth)acrylate can inhibit amine blushing by reacting with free amine contained in the hardener. Amine blushing is when free amine in the paint film reacts with carbon dioxide and water in the air under low temperature and high humidity conditions to form carbamate on the surface of the paint film. Amine blushing is suppressed by reacting (meth)acrylate with free amine first. can do.

The (meth)acrylate is not limited to the type as long as it contains a (meth)acrylate group and can react with free amine. It may be a compound containing two or more acrylate groups or methacrylate groups as described above. The (meth)acrylates include, for example, trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetraethylene glycol dimethacrylate, Ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, 1,6-hexanediol diacrylate and 1,6-hexanediol dimethacrylate. It may be one or more types selected from the group consisting of, but is preferably trimethylolpropane triacrylate.

The content of the (meth)acrylate may be 0.1 part by weight or more and 10 parts by weight or less, and 1 part by weight or more and 7 parts by weight or less, based on 100 parts by weight of the main ingredient.

By adjusting the content of the (meth)acrylate to the above-mentioned range, amine blushing can be suppressed by first reacting the (meth)acrylate with the free amine, wherein the (meth)acrylate is contained in less than 0.1 part by weight. If it is used, it may be difficult to suppress blushing due to the presence of free amine, and if it exceeds 10 parts by weight, the pot life may be short and the paint film may be brittle.

The curing agent according to an embodiment of the present invention includes an aliphatic amine and an alicyclic amine curing agent, and includes active hydrogen-containing amines such as ketimines prepared by condensation reaction of amines and ketones, or polyamineamides and polyamines using these amines. It may further include modified resins such as midoamine, phenol-modified amine, and epoxy addition-type amine.

The aliphatic amine may include at least one of diethylenetriamine, triethylenetetraamine, and polyoxypropylenediamine, but the type of the aliphatic amine is not limited. Additionally, the alicyclic amine may include at least one alicyclic group selected from cyclohexyl, cycloheptyl, and cyclopentyl, but the type of alicyclic group is not limited.

The curing agent according to an embodiment of the present invention may have an aliphatic amine content of 70 parts by weight or more and 99 parts by weight or less, for example, 80 parts by weight or more and 95 parts by weight or less, based on 100 parts by weight of the curing agent.

Additionally, the content of the cycloaliphatic amine may be 1 part by weight or more and 30 parts by weight or less, for example, 5 parts by weight or more and 20 parts by weight or less, based on 100 parts by weight of the curing agent.

By adjusting the content of the aliphatic amine and the cycloaliphatic amine within the above-described range, rapid occurrence of the reaction can be suppressed under high temperature conditions of 35° C. or higher, thereby improving pot life. In addition, when the content of the aliphatic amine and the cycloaliphatic amine is within the above range, it is possible to prevent the coating film physical properties such as rust prevention and flowability from being deteriorated.

In addition, the solvent-free epoxy paint composition of the present invention contains the aliphatic amine and the cycloaliphatic amine in a weight ratio of 15 to 3:1 and 10 to 4:1, thereby improving painting workability and painting physical properties.

Meanwhile, according to one embodiment of the present invention, the curing agent may further include a non-reactive diluent, and may be the same as or different from the non-reactive diluent included in the above subject.

According to one embodiment of the present invention, the curing agent may further include a curing accelerator.

The curing accelerator content may be 1 part by weight or more and 10 parts by weight or less, based on 100 parts by weight of the curing agent. Specifically, based on 100 parts by weight of the curing agent, the content of the curing accelerator may be 1.5 parts by weight or more and 8 parts by weight or less, or 2.5 parts by weight or more and 5 parts by weight or less.

By adjusting the content of the curing accelerator within the above-mentioned range, the curing speed can be appropriately controlled. Through this, it is possible to suppress problems such as lower coating film hardness and brushing properties due to increased curing speed, lower pot life due to faster curing speed, and poor flow properties.

The curing accelerator may include at least one of tridimethyl amino methyl phenol, triphenyl phosphite, and amino ethyl piperazine.

In the solvent-free epoxy paint composition according to an embodiment of the present invention, the weight ratio of the main agent and the curing agent may be 75:25 to 85:15, 77.5:22.5 to 82.5:17.5, or 80:20 to 85:15. .

By adjusting the weight ratio of the base material and the hardener within the above-mentioned range, a solvent-free epoxy paint composition capable of producing a coating film with good airless spray painting workability and excellent physical properties can be provided.

The marine structure according to one aspect of the present invention is characterized by having a coating film of the solvent-free epoxy paint composition.

The coating film provided on the marine structure according to an embodiment of the present invention may include a cured product of the solvent-free epoxy paint composition.

As described above, the solvent-free epoxy paint composition according to an embodiment of the present invention is applicable to the harsh corrosive environment of ships or marine structures, and has a solid content of 90 parts by weight or more, for example, 95 parts by weight, based on 100 parts by weight of the composition. It can be more than 99 parts by weight or more, making it environmentally friendly and safe for construction.

In addition, the solvent-free epoxy paint composition, unlike existing solvent-free epoxy paints, can have the advantage of excellent workability due to good spray patterning during airless spray painting work under low temperature conditions of 5 ° C. or less.

Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of this specification are provided to more completely explain the present invention to those skilled in the art.

Preparation of solvent-free epoxy paint composition

Examples 1 to 9

The base material was prepared with the composition (unit: parts by weight) shown in Table 1 below.

Specifically, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-A/F type epoxy resin, epichlorhydrin reactive diluent, polycarboxylic acid polyester type dispersant, hydrocarbon-based defoaming agent, clay. Type anti-settling agent, silane-based adhesion enhancer, and trimethylolpropane triacrylate (TMPTA) were added and stirred to prepare a reaction solution. The extender pigment was slowly added to the reaction solution in the amount shown in Table 1 below and stirred, and then a white pigment (TiO ₂ ) as a colored pigment was slowly added and stirred. Afterwards, the reaction solution was dispersed using a High Speed Dissolver (HSD) until the particle size was 80㎛ or less to prepare the main product.

In addition, a curing agent was prepared with the composition (unit: parts by weight) shown in Table 1 below.

Specifically, 85 parts by weight of aliphatic amine resin and 15 parts by weight of cycloaliphatic amine resin were weighed and added to the reactor. The reactor was mixed with low-speed stirring to prepare a curing agent mixture.

Afterwards, the base material prepared above and the hardener were mixed at a weight ratio of 80:20 to prepare a solvent-free epoxy paint composition. The specific composition is as shown in Table 1 below.

division Example One 2 3 4 5 6 7 8 9 subject BPA Resin ⁽¹⁾ - - - - - - - - 30 BPF Resin ⁽²⁾ 35 30 30 28 25 30 40 20 - BPA/F Resin ⁽³⁾ 9 8 10 10 11 8 3 18 10 TMPTA ⁽⁴⁾ One 3 5 7 9 3 3 5 5 Reactive Diluent ⁽⁵⁾ 14 14 14 14 14 14 6 13 14 Non-reactive diluent ⁽⁶⁾ 2 One 2 2 2 One 3 5 2 Anti-settling agent 2 2 2 2 2 2 2 2 2 Constitutional pigment ⁽⁷⁾ 29 34 29 29 29 34 34 34 29 Colored pigment (TiO ₂ ) 5 5 5 5 5 5 6 5 additive dispersant One One One One One One One One One defoamer One One One One One One One One One Adhesion enhancer ⁽⁸⁾ One One One One One One One One One solvent - - - - - - - - - Sum 100 100 100 100 100 100 100 100 100 hardener Aliphatic Amines ⁽⁹⁾ 85 85 85 85 85 90 87 8 85 Alicyclic Amines ⁽¹⁰⁾ 15 15 15 15 15 10 13 20 15 Sum 100 100 100 100 100 100 100 100 100

Comparative Examples 1 to 5

An epoxy paint composition was prepared in the same manner as in the Example, except that TMPTA was not included in the main preparation, the content was different, a solvent was included, or an alicyclic amine was not included. The specific composition is as shown in Table 2 below.

division Comparative example One 2 3 4 5
subject BPA Resin ⁽¹⁾ - - - - - BPF Resin ⁽²⁾ 28 28 30 30 30 BPA/F Resin ⁽³⁾ 5 5 8 8 10 TMPTA ⁽⁴⁾ X One X 12 5 Reactive Diluent ⁽⁵⁾ 10 10 14 10 14 Non-reactive diluent ⁽⁶⁾ 2 One 4 0 2 Anti-settling agent 2 2 2 2 2 Constitutional pigment ⁽⁷⁾ 25 25 34 30 29 Colored pigment (TiO ₂ ) 5 5 5 5 5 additive dispersant One One One One - defoamer One One One One - Adhesion enhancer ⁽⁸⁾ One One One One - Solvent (xylene) 20 20 - - - Sum 100 100 100 100 100 hardener Aliphatic Amines ⁽⁹⁾ 90 90 90 90 100 Alicyclic Amines ⁽¹⁰⁾ 10 10 10 10 X Sum 100 100 100 100 100

(1) Bisphenol-A type epoxy resin (solids 100%, epoxy equivalent weight 189g/eq)

(2) Bisphenol-F type epoxy resin (solids 100%, epoxy equivalent weight 178g/eq)

(3) Bisphenol-A/F type epoxy resin (solids 100%, epoxy equivalent weight 175g/eq)

(4) TMPTA (Trimethylolpropane triacrylate) for free amine removal (weight average molecular weight 296g/mol)

(5) CASHEW, NUT SHELL LIQ.,POLYMER WITH EPICHLOROHYDRIN reactive diluent (epoxy equivalent weight 383g/eq)

(6) Benzyl alcohol

(7) Feldspar-group minerals (particle size 1 ~ 100㎛)

(8) Epoxy silane (Cas no. 2530-83-8)

(9) ANCAMIN 2432 (EVONIC)

(10) ANCAMIN 2280 (EVONIC)

In Table 1, the contents (parts by weight) of each resin, reactive diluent, dispersant, antifoaming agent, adhesion enhancer, TMPTA, anti-settling agent, colored pigment, extender pigment, and non-reactive diluent are based on a total of 100 parts by weight of the subject matter. In addition, in Tables 1 and 2, the content (parts by weight) of aliphatic amine and cycloaliphatic amine is based on a total of 100 parts by weight of the curing agent.

Evaluation of physical properties of solvent-free epoxy paint composition

The epoxy paint compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 5 were painted under the following conditions. First, rust, dust, moisture, oil, and other contaminants on the surface of the substrate were completely removed using fresh water or an appropriate solvent, and then blaster polished to a surface roughness of 25 ㎛ to 75 ㎛. Then, the prepared specimen was painted using an airless sprayer with a nozzle diameter of 0.019" to 0.025", a spray pressure of 3 bar to 5 bar, and a spray angle of 50°. Workability was evaluated through airless spraying, and the workability results are shown in Table 2. In the case of the physical property specimen, a dry film of 320㎛ was applied under horizontal conditions. Rust prevention, seawater resistance, and test specimens were produced by drawing a line with a tungsten pen until the surface was visible. Impact resistance specimens were tested in accordance with the test method of ASTM D2794, and bending resistance specimens were tested using a conical mandrel test device in accordance with ASTM D522. The test was conducted by bending the specimen. The obtained coating film properties were evaluated for rust prevention, seawater resistance, impact resistance, and bending resistance, and the results are shown in Tables 3 and 4 below.

The specific test method is as follows.

Rust prevention

According to ASTM B117, samples tested for 1500 hours in a SALTFOG device were evaluated for rust generation, surface blister generation, and film peeling distance, and the evaluation results are shown in Tables 3 and 4 below.

seawater resistance

Specimens immersed in a bath containing seawater for 3 months were evaluated for rust generation, surface blister generation, and coating film peeling distance, and the evaluation results are shown in Tables 3 and 4 below.

impact resistance

The degree of defect occurrence was evaluated after 160 lb.in impact on the front and back of the painted specimen using the method of ASTM D2794, and the evaluation results are shown in Tables 3 and 4 below.

bending resistance

The degree of defect occurrence was evaluated after the conical mandrel test on the painted specimen using the method of ASTM D522, and the evaluation results are shown in Tables 3 and 4 below.

Airless spray workability

Using an airless spray, set the nozzle diameter to 0.019" to 0.025", the spray pressure to 3 bar to 5 bar, and the spray angle to 50° before painting. Airless spray pattern under low temperature (5°C or lower) conditions. Maximum flow thickness, thin film dry film (less than 200㎛) leveling, and pot life under high temperature (over 20°C) conditions were measured, and the measurement results are shown in Tables 3 and 4 below.

division Example One 2 3 4 5 6 7 8 9 Rust prevention Blister ⁽¹⁾ No.8M No.8F No.8F No.8F No.8F No.8M No.8F No.8F No.8F Paint peeling distance 1mm 0.5mm 0.5mm 0.5mm 0.5mm 0.7mm 0.6mm 0.5mm 0.5mm seawater resistance Blister ⁽¹⁾ No.10 No.10 No.10 No.10 No.10 No.10 No.10 No.10 No.10 Cross-cut ⁽²⁾ 4B 4B 4B 4B 4B 4B 4B 4B 4B Impact resistance ⁽³⁾ Direct E E E E E E E E E Reverse E E E E E E E E E Flexibility ⁽³⁾ E G G G G G G G E Workability ⁽⁴⁾ Low temperature (5℃)
Dryness (time) 21 20 20 20 20 19 25 20 19 Sagging(㎛) 900 900 900 900 900 900 900 900 1000 Leveling ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ ◎ High temperature (20℃) pot life (minutes) 30 30 30 25 20 25 30 30 25 blushing Low temperature (5℃) Not occurred Not occurred Not occurred Not occurred Not occurred Not occurred Not occurred Not occurred Not occurred Recoating interval 15 days↑ 15 days↑ 15 days↑ 15 days↑ 15 days↑ 15 days↑ 15 days↑ 15 days↑ 15 days↑ Non-volatile content (%) ⁽⁵⁾ 98.2 98.5 98.6 98.8 98.8 98.2 98.5 98.5 99.2

division Comparative example One 2 3 4 5 Rust prevention Blister ⁽¹⁾ No.4M No.8M No.4M No.8F No.8M Paint peeling distance 2mm 1mm 2mm 0.5mm 2mm seawater resistance Blister ⁽¹⁾ No.10 No.10 No.10 No.10 No.10 Cross-cut ⁽²⁾ 3B 4B 3B 4B 3B Impact resistance ⁽³⁾ Direct G G G E G Reverse G G G E G Flexibility ⁽³⁾ E G E G G Workability ⁽⁴⁾ Low temperature (5℃)
Dryness (time) 27 24 25 20 19 Sagging(㎛) 600 600 800 900 900 Leveling ◎ ◎ ◎ ◎ ◎ High temperature (20℃) pot life (minutes) 40 35 30 15 15 blushing Low temperature (5℃) generation Not occurred generation Not occurred Not occurred Recoating interval 7 days 15 days↑ 7 days 15 days↑ 15th Non-volatile content (%) ⁽⁵⁾ 78.3 78.5 97.4 98.7 98.1

(1) Blister Size: No.2 > No.4 > No.6 > No.8 > No.10 (No Blister)

Blister Frequency: D=Dense, MD=Medium Dense, M=Medium, F=Few

(2) Cross-cut: ASTM D 3359

(3) Impact & Bending Resistance Performance: E > G > F > P > VP

E=Excellent, G=Good, F=Fair, P=Poor, VP=Very Poor

(4) Pattern & Leveling Evaluation: (Excellent) ◎ > ○ > △ > X (Poor)

Referring to Tables 1 and 2, the solvent-free epoxy paint compositions according to Examples 1 to 9 of the present invention had excellent workability, excellent appearance of the coating film, and physical properties of rust prevention, seawater resistance, impact resistance, and bending resistance. This excellence was confirmed. Additionally, it was confirmed that amine blushing did not occur in the formed coating film. In addition, since the solvent-free epoxy paint composition of the present invention does not contain a solvent, it has a high non-volatile content (low VOC emissions) and is confirmed to be environmentally friendly.

On the other hand, in the case of Comparative Examples 1 and 3 in which trimethylpropanol acrylate was not used as an amine blushing inhibitor, it was confirmed that the impact resistance of the coating film was relatively poor, drying properties at low temperatures were poor, and amine blushing occurred.

In the case of Comparative Example 4, in which more trimethylpropanol acrylate was used than the upper limit, amine blushing did not occur, but the pot life was drastically reduced by half at high temperatures, confirming that workability was inferior.

In the case of Comparative Example 2 including trimethylpropanol acrylate and solvent, it was confirmed that non-volatile matter was low (VOC emissions were high).

In addition, in the case of Comparative Example 5, which did not contain an alicyclic amine, it was confirmed that rust prevention and seawater resistance were lowered compared to the Examples.

Therefore, it can be seen that the solvent-free epoxy paint composition according to an embodiment of the present invention has excellent airless spray painting workability and pot life, and can implement a coating film with excellent physical properties without amine blushing.

The present invention is not limited to the embodiments described above, and of course may include a combination of the above embodiments or a combination of at least one of the above embodiments with known techniques as another embodiment.

Although the present invention has been described in detail through specific examples, this is for the purpose of specifically explaining the present invention, and the present invention is not limited thereto, and can be understood by those skilled in the art within the technical spirit of the present invention. It would be clear that modifications and improvements are possible.

All simple modifications or changes of the present invention fall within the scope of the present invention, and the specific scope of protection of the present invention will be made clear by the appended claims.

Claims (4)

Subjects including epoxy resins containing two or more epoxy groups in the molecule, reactive diluents containing epoxide groups, non-reactive diluents, and acrylates as amine blushing inhibitors; and
Curing agents containing aliphatic amines and cycloaliphatic amines;
Including,
The aliphatic amine is in an amount of 70 parts by weight or more and less than 90 parts by weight based on 100 parts by weight of the curing agent,
A solvent-free epoxy paint composition comprising the aliphatic amine and the cycloaliphatic amine in a weight ratio of 15 to 3:1. According to claim 1,
The solvent-free epoxy paint composition is:
A solvent-free epoxy paint composition, characterized in that the solid content is 90 parts by weight or more based on 100 parts by weight of the composition. The method of claim 1, wherein the subject matter is:
A solvent-free epoxy paint composition, characterized in that the content of the acrylate is 0.1 parts by weight or more and 10 parts by weight or less, based on 100 parts by weight of the base material. The method of claim 1, wherein the acrylate is trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetraethylene glycol dimethacrylate, ethylene. Consists of glycol dimethacrylate, triethylene glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, 1,6-hexanediol diacrylate and 1,6-hexanediol dimethacrylate. A solvent-free epoxy paint composition comprising at least one selected from the group.