KR102112628B1 - Resin comprising cardol, abietic acid and synthetic resin, electromagnetic interference shielding paint composition, and method for manufacturing of the same - Google Patents

Abstract

The present invention relates to a resin comprising cardol, abietic acid and a synthetic resin, a paint composition comprising the same, and a method for manufacturing the same. More particularly, a resin according to the present invention may include a repeating unit derived from cardol, a repeating unit derived from abietic acid, and a repeating unit derived from a synthetic resin. The paint composition according to the present invention can form a paint film having significantly improved weather resistance, corrosion resistance, anti-microbial properties, insect repellency, anti-fouling properties and peeling resistance, and thus can store a substrate to be coated excellently for a long period of time, and provide a carrier having electromagnetic shielding properties to improve electromagnetic shielding properties.

Description

Resin, electromagnetic shielding coating composition, and manufacturing method thereof including cardol, abietic acid, and synthetic resins {RESIN COMPRISING CARDOL, ABIETIC ACID AND SYNTHETIC RESIN, ELECTROMAGNETIC INTERFERENCE SHIELDING PAINT COMPOSITION, AND METHOD FOR MANUFACTURING OF THE SAME}

The present invention relates to a resin and coating composition comprising kardol, abietic acid, and synthetic resins, and more particularly, to form a coating film having significantly improved weather resistance, corrosion resistance, anti-fogging property, anti-fouling property and peeling resistance. The present invention relates to a resin comprising kardol, abietic acid, and a synthetic resin, an electromagnetic shielding coating composition comprising the same, and a method for manufacturing the same.

The paint refers to a flowable material that paints on the surface of a solid substrate to form a solid film to protect and beautify the surface.

Conventional paints are made of a solvent and a solvent, and are largely divided into natural resin paints, synthetic resin paints, water-based paints, and oil-based paints depending on the components of the above-mentioned subject.

Synthetic resin paints are provided in a wide variety, such as wax, varnish, and urethane varnish, and are used in many industries because of their ease of use and low cost. However, since it is provided with raw materials from petroleum, it has a peculiar smell and toxicity, which has big problems from simple allergies to severe cancer.

In addition, in the case of natural resin coatings, there are problems such as getting on clothes or the body even after application and drying, and it is difficult to work, as well as weathering, electromagnetic shielding, and corrosion resistance to electric vehicles, iron materials, plastics, wood, and construction materials. , There was a problem that can not sufficiently provide performance such as anti-fog, insect-resistant, anti-fouling and peeling resistance.

In particular, in the case of using electric vehicles, iron, plastics, wood, and construction materials as the base material to be coated, the purpose and frequency of use is very high due to its own color, unique characteristics, etc. It becomes a habitat for mold and various fungi, which makes steel, plastic, wood, and construction materials decay, corrode, or discoloration, making them unusable, or cracking and cracking, and stretching and shrinking deformations are repeated. There is also a case where the base material is damaged, and it was not possible to store such electric vehicles, iron materials, plastics, wood, and construction materials for a long time with natural resin paints of the prior art. In addition, an electromagnetic wave is an electromagnetic wave composed of two types of waves, an electric field and a magnetic field, and is a kind of electromagnetic energy generated in the flow of electricity and magnetism.

Recently, as various electronic devices are indispensable all over the human living environment, the level of exposure to electromagnetic waves is gradually changing, which can affect the human body beyond the level that electromagnetic waves adversely affect other electronic devices. As it reaches to a certain level, various technologies for shielding electromagnetic waves are required.

Accordingly, various shielding technologies such as selection, placement, adjustment, isolation, grounding, and filter of components have been developed for shielding electromagnetic waves, and in particular, discharge light display (ELD), vacuum fluorescent display (VFD), liquid crystal display (LCD) In the case of various display devices such as a surface conduction type electron emitting device display (SED), a separate transparent electromagnetic wave shielding film is configured outside the housing of the display device or inside the circuit board as optical problems such as transmittance of output light are linked. It has been designed in addition to.

As a result, it is related to the weight and size of the entire device, but there is a problem that the structural complexity of the overall configuration of the device may also increase, and the electromagnetic shielding in terms of materials that can be integrated with parts and perform the electromagnetic shielding function Research on technology is in demand.

In this regard, prior art documents related to the prior art provided to form a coating film for electromagnetic shielding using metal particles and metal oxides to improve shielding efficiency are described in Korean Patent Registration No. 10-0737634 "Coating Composition for Electromagnetic Shielding" (hereinafter , 'Conventional technology').

However, the conventional electromagnetic shielding materials, including the prior art, use metal particles such as copper and nickel, resulting in a problem of high workability in the coating process due to precipitation and oxidation of particles and high non-uniformity of the coating film. , There was a problem that a lot of restrictions on the shape and weight of the entire product.

 In addition, in order to solve the above-described problem, when preparing a conductive filler by using a silver filler that provides a low electrical resistance and a high attenuation rate to prepare an electromagnetic wave shielding material, manufacturing cost is excessive when using expensive silver particles. By being generated, there has been a problem in that many restrictions are generated on the practical use and productization of the product.

Therefore, surface pollutants that occur only on the surface of electric vehicles, steel materials, plastics, woods, and construction materials due to incomplete fungus and electric vehicles, steel materials, plastics, etc., caused by mold during the post-process of electric vehicles, iron materials, plastics, wood and construction materials, Discoloration, corrosion, and decay damage of wood and building materials has become the mainstream, and existing electromagnetic shielding materials use metal particles such as copper and nickel, and the workability in the coating process is reduced due to precipitation and oxidation of particles. There is a problem in that the production cost is excessively generated in the use of expensive silver particles and the non-uniformity of the coating film causes many restrictions on the practical use and productization of the product.

Korean Patent Publication No. 10-0737634 Korean Patent Publication No. 10-2016-0139705

An object of the present invention is to provide a resin having excellent weather resistance, corrosion resistance, anti-fogging, and peeling resistance, an electromagnetic shielding coating composition comprising the same, and a method for manufacturing the same.

According to a preferred embodiment of the present invention, a repeating unit derived from cardol represented by the following Chemical Formula 1, a repeating unit derived from abietic acid represented by the following Chemical Formula 2, and a repeating unit derived from a synthetic resin Resin can be provided.

[Formula 1]

[Formula 2]

The resin is greater than 0% by weight to less than 15% by weight of repeating units derived from the cardol, greater than 0% by weight to less than 15% by weight of repeating units derived from abietic acid, and repeating units derived from the synthetic resin 60 To 90% by weight.

The synthetic resin may be any one selected from the group consisting of styrene acrylic resin, acrylic resin, urethane resin, epoxy resin, latex type acrylic resin, mixtures thereof, and copolymers thereof.

The resin may further include a portion forming a complex with a metal derived from one or more metal oxides selected from cobalt oxide and manganese oxide.

According to another preferred embodiment of the present invention, it is possible to provide an electromagnetic shielding coating composition comprising the resin.

The coating composition may further include an electromagnetic shielding agent, and the electromagnetic shielding agent may be any component selected from graphite, carbon black, graphene, carbon nanotubes, fullerene, and mixtures thereof. In addition, the coating composition may further include a porous carrier. In addition, in the coating composition, the electromagnetic shielding agent may be supported on the porous carrier.

[Formula 3]

According to another preferred embodiment of the present invention, the coating composition comprising the step of preparing a resin by reacting a cardol represented by the following formula 1, abietic acid represented by the following formula 2, and a synthetic resin It can provide a manufacturing method.

[Formula 1]

[Formula 2]

The synthetic resin may react with the cardol and abietic acid in a solid and liquid form.

The step of preparing the resin may be reacted after adding more than 0% to 5% by weight of cobalt oxide, more than 0% to 5% by weight of manganese oxide, and 0.05 to 15% by weight of free radical initiator.

The step of preparing the resin may be performed at 150 to 230 ° C. for 1 to 50 atm for 12 to 48 hours.

Since the resin according to the present invention and the coating composition comprising the same are resins capable of forming a coating film having significantly improved weather resistance, corrosion resistance, anti-fog resistance, insect resistance, anti-fouling property and peeling resistance, the substrate to be coated is stored for a long time and electromagnetic By providing a carrier having shielding properties, it is possible to improve electromagnetic shielding properties.

1 is a graph comparing the electrical conductivity of the sample after coating the coating composition according to the content of the functional additive (B) in Experimental Example 2.
2 is a graph comparing the electromagnetic shielding properties after coating the coating composition according to the content of the functional additive (B) in Experimental Example 2.
3 is a graph comparing the thermal conductivity after coating the coating composition according to the content of the functional additive (B) in Experimental Example 2.
Figure 4 is a photograph comparing the particle size after coating the coating composition according to the content of the functional additive (B) in Experimental Example 2.

Hereinafter, embodiments of the present invention will be described in more detail so that those skilled in the art to which the present invention pertains can easily practice. However, the present invention may be implemented in various different forms, and is not limited to the embodiments described herein.

Terms used in the specification of the present invention are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as 'comprises' or 'have' are intended to designate the existence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, and one or more other. It should be understood that features or numbers, steps, operations, components, parts or combinations thereof are not excluded in advance.

1. Coating composition

(1) Resin

A resin excellent in weather resistance, corrosion resistance, anti-microbial properties, insect repellency, antifouling property, and peeling resistance according to an embodiment of the present invention is a repeating unit derived from kardol represented by the following Chemical Formula 1, and abiet represented by the following Chemical Formula 2 Repeating units derived from an acid, and repeating units derived from a synthetic resin.

[Formula 1]

[Formula 2]

More specifically, the resin is greater than 0% by weight to 15% by weight of repeating units derived from the cardol, greater than 0% by weight to 15% by weight of repeating units derived from abietic acid, and derived from the synthetic resin It may contain 60 to 90% by weight of the repeating unit.

The cardol of the present invention is also referred to as 5-pentadecyl resorcinol, and is a polyvalent phenol widely distributed in various plants, and can be prepared by collecting and heating the sap.

The unit derived from the cardol may be included in an amount of more than 0% by weight to 15% by weight or less, more preferably 1 to 5% by weight. When the content of the repeating unit derived from the cardol is 0% by weight or less, the viscosity of the resin composition is too low, a problem of insufficient substrate integrity of the coating composition may occur, and when it exceeds 15% by weight, the viscosity of the resin composition Is too high, and there may be a problem that gelation is likely to occur.

The unit derived from the abietic acid of the present invention is separated from the rosin of the pine tree, and forms a majority of the rosin, which is a solid part of the oleoresin of conifers, and collectively refers to the abietic acid substance exhibiting antioxidant and anti-microbial effects. Can be configured. The unit derived from abietic acid has an average molecular weight of 100 to 20,000 g / mol, and has a polyphenol structure as a basic skeleton. Normally, when abietic acid and cardol are heated, a useful abietic oligomer is produced.

The unit derived from the abietic acid may be included in an amount of more than 0% by weight to 15% by weight or less, and more preferably 1 to 10% by weight. When the content of the abietic acid is 0% by weight or less, there is a problem that the viscosity of the resin composition is too low and the substrate preservability of the coating composition is insufficient, and when it exceeds 15% by weight, the viscosity of the resin composition is too high and gelation occurs. Easier problems may occur.

The synthetic resin may be a styrene acrylic resin, an acrylic resin, a urethane resin, an epoxy resin, a latex type acrylic resin, a mixture of one or more of them, or a copolymer of one or more of them.

The synthetic resin may be contained in 60 to 90% by weight, preferably 60 to 70% by weight. When the synthetic resin is included in less than 60% by weight, the performance of the coating film such as flexibility and elasticity may be deteriorated, and when it exceeds 90% by weight, the coating film may not dry well.

The synthetic resin according to an embodiment of the present invention may include a compound containing a repeating unit represented by the following formula (3).

[Formula 3]

In Formula 3, R ₁ is hydrogen, a substituted or unsubstituted alkyl group of C _1-10 , aryl group, alkenyl group, cyano group, amino group, nitro group, alkoxy group, cycloalkyl group, halogenated alkyl group, and combinations thereof And R ₂ and R ₃ are each independently selected from the group consisting of C _1-10 substituted or unsubstituted alkyl group, aryl group, alkenyl group, halogenated alkyl group, and combinations thereof. R ₄ is selected from the group consisting of C _1-10 substituted or unsubstituted alkyl group, C _3-30 carbocyclic aromatic compound, C _3-30 heteroaromatic compound, and combinations thereof. It may be one, preferably a phenyl group.

The a to d is a molar ratio of each repeating unit, the a to d are each a real number of 0 to 1 independently, satisfies the condition of a + b + c + d = 1.

The resin of the present invention may have an average molecular weight of 3,000 to 260,000 g / mol, preferably 80,000 to 200,000 g / mol.

In addition, the resin may be in the form of a complex with a metal, preferably cobalt and / or manganese.

The resin according to one embodiment of the present invention further comprises any one selected from the group consisting of a metal oxide catalyst, a free radical initiator, and mixtures thereof, together with the cardol, the abietic acid, and the synthetic resin Can be produced by manufacturing. Accordingly, the resin of the present invention may further include a portion forming a complex with a metal derived from the metal oxide.

As the metal of the metal oxide catalyst, cobalt and / or manganese may be used, and more specifically, a catalytic reaction may be induced using the cobalt and / or manganese oxide form. The metal oxide catalyst may be used in an amount of more than 0% by weight to 10% by weight or less, and accordingly, when using cobalt and manganese oxide, the metal oxide may be used in an amount of more than 0% by weight to 5% by weight or less, respectively. have.

The free radical initiator is benzoyl peroxide, t-butyl peroxyacetate, di-t-butylperoxide, t-butylperoxy pivalate, t-butylperoxy-2-ethyl hexanoate, t-butylperoxy Neodecanoate, t-butylperoxyisobutyrate, t-butylperoxy benzoate, t-amylperoxy neodecanoate, t-amylperoxy pimalate, t-amylperoxy-2-ethyl hexanoate Eight, 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile and 2,2'-azobis-2-methylpropionamidine and mixtures thereof. It is any one, and can be used by including 0.05 to 15% by weight, more preferably 0.05 to 10% by weight.

In addition, according to another preferred embodiment of the present invention, it is possible to provide a coating composition comprising the resin.

(2) Functional additive

Meanwhile, the coating composition of the present invention may further contain one or more functional additives.

The functional additive may include a porous carrier. The porous carrier included in the functional additive is not particularly limited as long as it can elute gradually by supporting components such as electromagnetic shielding agents.

Preferably, the porous carrier may be selected from diatomaceous earth, zeolite, and activated carbon, and more preferably, zeolite, in particular, in the form of a powder having a size of 5 to 10 μm in diameter.

The functional additive may include an electromagnetic shielding agent. The electromagnetic shielding agent included in the functional additive may include one or more selected from graphite, carbon black, graphene, carbon nanotubes, and fullerenes, and any conventional ones that can be used in the coating composition may be used. For example, the electromagnetic shielding agent may be graphite, carbon black, graphene, carbon nanotubes, or fullerene compounds. The functional additive is preferably added to the coating composition in a state supported on a porous carrier.

The functional additive may further include one or more components selected from antiseptics, insect repellents and antifouling agents. The anti-fog agent, insect repellent, and anti-fouling agent are not particularly limited and may be selected from conventional ones that can be used in the coating composition.

For example, the repellents are pyrethrin, allethrin, phenothrin, permethin, empentrin, benfuracarb, fipronil (fipronil), ethofenprox, furathiocarb, carbosulfan, or imidacloprid.

For example, the antifouling agent is an inorganic compound such as zinc sulfate, zinc oxide, nickel sulfate and copper-nickel alloys, auxin copper, copper nonylphenol sulfonate, copper bis (ethylene-diamine) bis (dodecylbenzenesulfonate) Organocopper compounds such as copper acetate, copper naphthenate and copper bis (pentachlorophenolate), organonickel compounds such as nickel acetate and nickel dimethyldithiocarbamate, zinc acetate, zinc carbamate, zinc dimethyldithiocarba Organic zinc compounds such as mate, zinc pyrithione and zinc methylenebis (dithiocarbamate) or N-trichloromethylthiophthalimide, N- (2,4,6-trichlorophenyl) maleimide, dithiocy Anomethane, tetramethylthiuram disulfide, 2,3,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, 2-methylthio-4-t-butylamino-6-cyclop Peel amino may be a -S- triazine and 4,6-dichloro -2-n- octyl-4-isothiazolin-3-one containing a metal such as a light organic compound.

The functional additive may preferably be included in the coating composition in an amount of 0.02 to 7 parts by weight based on 100 parts by weight of the resin component.

(3) Other ingredients

On the other hand, the coating composition of the present invention may further contain other conventional additives and solvents used in the manufacture of the coating composition.

Examples of the other additives include pigments, matting agents, dispersants, antifoaming agents and antioxidants.

Specifically, the pigment is a rutile (Rutile) R- sugar, titanium dioxide (TiO ₂ ), iron oxide (Fe ₂ O ₃ ), lead carbonate (PbCO ₃ ), zinc oxide (ZnO), copper sulfide (CuS), Coloring pigments such as zinc sulfide (ZnS) and chromium oxide, and extender pigments such as talc, clay, mica, calcium carbonate (CaCO ₃ ), magnesium carbonate (MgCO ₃ ), barium sulfate, silicic acid, silicate, aluminum oxide hydrate and potassium sulfate It may be any one or more selected from the like.

The matting agent may be silica or alpha-alumina, and more specifically, white silica.

The dispersing agent such as 2-amino-2-methyl-1-propanol (AMP), dimethyl amino ethanol (DMAE), potassium tripolyphosphate (KTPP), trisodium polyphosphate (TSPP), citric acid, carboxylic acid and polycarboxylic acid-based polymer It can be a nonionic, anionic or cationic dispersant.

The anti-foaming agent may be a silicone-based antifoaming agent or a mineral oil-based antifoaming agent such as a polysiloxane compound and an organic modified polysiloxane compound.

The antioxidant may be a phenol-based antioxidant, an organic sulfur-based antioxidant or a phosphite-based antioxidant, for example, 2,6-di-t-butyl-1-hydroxy-4-methylbenzene.

The solvent may be vegetable oils such as terpene oil and orange oil.

The coating composition of the present invention can be used to paint various substrates including paper, fiber, plastic, wood, metal, especially alloy substrates such as electric vehicles, iron materials, plastics, or construction materials.

The coating composition of the present invention can be coated by a known coating method such as roller coating, spray coating, immersion coating, and the like.

2. Preparation method of coating composition

Method for producing a coating composition according to another embodiment of the present invention, (a-1) kardol, (a-2) abietic acid, and (a-3) reacting a synthetic resin to prepare a resin ( A) may be included.

More specifically, the method for producing the coating composition includes (a-1) cardol, (a-2) abietic acid, (a-3) synthetic resin, (a-4) metal oxide catalyst, and (a-5) The free radical initiator, and (a-6) may include a step (A) of preparing a resin for condensation reaction by mixing a solvent.

In addition, the method for preparing the coating composition of the present invention may further include the step (B) of mixing the resin and the functional additive prepared in step (A), specifically, step (B) is (b-1 ) It may be a preparation step (B) of a functional additive mixing one or more components selected from a porous carrier, (b-2) electromagnetic shielding agent and (b-3) binder.

In addition, the method for preparing the coating composition of the present invention may further include a step (C) of mixing the resin prepared in step (A) and the functional additive prepared in step (B). Step (C) may be mixed by further adding other additives and solvents, if necessary.

(1) Resin production step (A)

In step (A) of the present invention, the (a-1) cardol is preferably included in an amount of more than 0% by weight to 15% by weight or less. If the content is 0% by weight or less, the viscosity of the resin is too low, there is a problem that the substrate preservability of the coating composition is insufficient, and when it exceeds 15% by weight, the viscosity of the resin is too high, and a problem that gelation is likely to occur may occur. have.

The (a-2) abietic acid may preferably contain more than 0% by weight to 15% by weight or less. If the content is 0% by weight or less, the viscosity of the resin is too low, there is a problem that the substrate preservability of the coating composition is insufficient, and when it exceeds 15% by weight, the viscosity of the resin is too high, and a problem that gelation is likely to occur may occur. have.

The (a-1) kardol and (a-2) abietic acid are used in the form of flakes or granular powder, and other specifics for the (a-1) kardol and (a-2) abietic acid are It is the same as described above with respect to the coating composition.

The (a-3) synthetic resin may be preferably mixed in an amount of 60 to 90% by weight, more preferably in an amount of 60 to 70% by weight. When the synthetic resin component is included in less than 60% by weight, the performance of the coating film such as flexibility and elasticity may deteriorate, and when it exceeds 90% by weight, the coating film may not dry well.

The synthetic resin (a-3) may be a styrene acrylic resin, an acrylic resin, a urethane resin, an epoxy resin, a latex type acrylic resin, a mixture of one or more of them, or a copolymer of one or more of them. In addition, the synthetic resin component may be provided in an emulsion form to react with the cardol and abietic acid.

The (a-4) metal oxide catalyst may be mixed in an amount of more than 0% by weight to 10% by weight or less. Preferably, the metal oxide catalyst may be any one or more selected from cobalt oxide and manganese oxide, more preferably, the cobalt oxide catalyst is greater than 0% by weight to 5% by weight and the manganese oxide catalyst is greater than 0% by weight to 5% by weight % Or less.

The (a-5) free radical initiator may be mixed in an amount of 0.05 to 15% by weight, preferably 0.05 to 10% by weight. Preferably, the free radical initiator is benzoyl peroxide, t-butyl peroxyacetate, di-t-butylperoxide, t-butylperoxy pivalate, t-butylperoxy-2-ethyl hexanoate, t-butyl Peroxyneodecanoate, t-butylperoxyisobutyrate, t-butylperoxy benzoate, t-amylperoxy neodecanoate, t-amylperoxy pimalate, t-amylperoxy-2-ethyl In the group consisting of hexanoate, 2,2'-azobisisobutyronitrile, 1,1'-azobiscyclohexanecarbonitrile and 2,2'-azobis-2-methylpropionamidine and mixtures thereof Any one selected, more preferably benzoyl peroxide.

The (a-6) solvent is preferably mixed in an amount of 5 to 15% by weight, more preferably 5 to 10% by weight. Preferably, it is at least one selected from the group consisting of terepine oil and orange oil, and more preferably, may be terepine oil.

The step (A) preferably mixes (a-1) to (a-3), specifically (a-1) to (a-6), and vacuum-presses the impregnator ( vacuum & pressure impregnation), and the resin can be prepared by hydrogenating at 150 to 230 ° C. for 1 to 50 atm for 12 to 48 hours.

The specific reaction temperature and reaction pressure can be easily understood and carried out by a person skilled in the art according to the specific type of the component used, etc., and easily changed by a person skilled in the art within a range in which the reaction rate and yield are lowered or a side reaction occurs and productivity does not decrease. It is possible.

More preferably, the manufacturing process of the resin may be represented by the following formula (4).

[Formula 4]

In Formula 4, R ₁ is hydrogen, a substituted or unsubstituted alkyl group of C _1-10 , aryl group, alkenyl group, cyano group, amino group, nitro group, alkoxy group, cycloalkyl group, halogenated alkyl group, and combinations thereof And R ₂ and R ₃ are each independently selected from the group consisting of C _1-10 substituted or unsubstituted alkyl group, aryl group, alkenyl group, halogenated alkyl group, and combinations thereof. R ₄ is selected from the group consisting of C _1-10 substituted or unsubstituted alkyl group, C _3-30 carbocyclic aromatic compound, C _3-30 heteroaromatic compound, and combinations thereof. It may be one, preferably a phenyl group.

The a to d is a molar ratio of each repeating unit, the a to d are each a real number of 0 to 1 independently, satisfies the condition of a + b + c + d = 1.

The m and n are independently real numbers of 0 <m≤1 and 0 <n≤1, respectively.

The resin component may have an average molecular weight of 3,000 to 260,000 g / mol, preferably 80,000 to 200,000 g / mol.

In addition, the resin may be in the form of a complex with a metal, preferably cobalt and / or manganese.

(2) Preparation step of functional additive (B)

In step (B) of the present invention, the porous carrier (b-1) is mixed in an amount of 10 to 70% by weight. When the porous carrier is less than 10% by weight, the functional additive is not uniformly dispersed in the coating film, and thus the electromagnetic shielding, insect repellent, and antifouling effects are poor, and when it exceeds 70% by weight, the adhesion of the coating film to the coated substrate is poor. The porous carrier is not particularly limited as long as it can be slowly eluted by supporting components such as an electromagnetic shielding agent, and is preferably selected from diatomaceous earth, zeolite and activated carbon, and more preferably 5 to 10 μm in size. Zeolites in powder form can be used.

The (b-2) electromagnetic shielding agent is mixed in an amount of 1 to 50% by weight, preferably 5 to 30% by weight. If necessary, in addition to the (b-2) electromagnetic shielding agent, one or more additional functional additives selected from insect repellents, antifouling agents, and antimicrobial agents may be further mixed, wherein the (b-2) electromagnetic shielding agent and The total amount of the additional functional additive may be an amount of 1 to 50% by weight, preferably 5 to 30% by weight as described above. Other specifics for the electromagnetic shielding agent, antiseptic, insect repellent and antifouling agent components are the same as described above with respect to the coating composition.

The (b-3) binder is mixed in an amount of 1 to 40% by weight, preferably 10 to 35% by weight. The binder used is not particularly limited as long as it can combine the porous carrier and the electromagnetic shielding agent. For example, vinyl resin, polyamide resin, polyester hot melt resin, aqueous polyurethane resin, acrylic resin, epoxy Resin, melamine resin, styrene resin, acrylic urethane resin, silicone resin, liquid sodium silicate, liquid potassium silicate, liquid lithium silicate, and ethyl silicate.

If necessary, the solvent (b-4) in step (B) of the present invention may be further mixed. The (b-4) solvent is mixed in an amount of more than 0 to 20% by weight, preferably more than 0 to 15% by weight. As the solvent used, it is compatible with the above-mentioned components, but any known solvent that does not react with them can be used. For example, polypropylene glycol may be preferred from the viewpoint of solubility of the resin component.

(3) Mixing step of the resin and functional additive (C)

In step (C) of the present invention, the resin prepared in step (A) is mixed in an amount of 20 to 50% by weight, and the functional additive prepared in step (B) in an amount of 5 to 20% by weight.

In addition, other additives and solvents may be used conventionally used in the production of coating compositions. For example, the other additives may include pigments, matting agents, dispersing agents, anti-foaming agents and antioxidants, pigments in an amount of 0.25 to 18% by weight, matting agents in an amount of 8 to 18% by weight, and dispersing agents in 0.1 In an amount of 5 to 5% by weight, the anti-foaming agent may be mixed in an amount of 0.1 to 1% by weight, and an antioxidant in an amount of 0.1 to 1% by weight.

Further, the solvent is preferably a vegetable oil such as terepine oil and orange oil, and is mixed in an amount of 20 to 60% by weight, preferably 20 to 40% by weight. For further details of the other additives and solvents, refer to the above-mentioned with respect to the coating composition.

The step (C) may be preferably performed at 30 to 60 ℃.

Hereinafter, preferred embodiments are presented to help understanding of the invention. However, the following examples are only for illustrating the invention, the present invention is not limited to these.

[Production Example 1]

After mixing 5 g of kardol, 5 g of abietic acid, 70 g of styrene acrylic resin as a synthetic resin component, 8 g of benzoyl peroxide, 1 g of cobalt oxide (Co ₂ O ₅ ) and 1 g of manganese oxide (MnO ₄ ) , The mixture was put in a vacuum pressure impregnation machine and reacted at 150 to 230 ° C. for 1 to 50 atm for 24 hours, and as a result, about 65 g of transparent resin (A) (Abietic Oligomer) was obtained.

30 g of the resin (A), 27 g of terpine oil as a solvent, 10 g of Rutile type titanium dioxide (TiO ₂ ) and 1 g of zinc oxide (ZnO) as a coloring pigment, 5 g of calcium carbonate (CaCO ₃ ) as a constitutional pigment, and talc 2 g, 18 g of white silica as a matting agent, 5 g of a polycarboxylic acid-based polymer as a dispersing agent, 1 g of an organic modified polysiloxane as an antifoaming agent, 2,6-di-t-butyl-1-hydroxy-4-methylbenzene 1 as an antioxidant It mixed with g and stirred at 40 degreeC, and obtained the coating composition.

[Production Example 2]

Functional additive (B) was prepared by mixing 90 g of zeolite powder with a size of 5 to 10 μm in diameter as a porous carrier and 30 g of graphene and 80 g of aerosol as an electromagnetic shielding agent.

Reducing 15 wt% based on the total weight of the functional additive (B) prepared above, 30 g of the resin (A) prepared in Preparation Example 1, 10 g of Rutile type titanium dioxide (TiO ₂ ) and zinc oxide ( ZnO) 1 g, 5 g potassium carbonate (CaCO ₃ ) and 2 g talc as extender pigment, 18 g white silica as matting agent, 5 g polycarboxylic acid polymer as dispersing agent, 1 g organic modified polysiloxane as antifoaming agent, 2 as antioxidant It was mixed with 1 g of 6-di-t-butyl-1-hydroxy-4-methylbenzene and stirred at 40 ° C. to obtain a coating composition.

[Experimental Example 1]

In order to evaluate the properties of the coating film formed from the coating composition according to the present invention, physical property evaluation experiments were performed using the following examples and comparative examples, and the results are shown in Table 1 below.

[Example 1]

After coating the test piece of 150 x 70 x 3 mm made of steel using the coating composition prepared in Preparation Example 1, corrosion resistance evaluation through KS D 9502 test method, KS J 3201, ASTM G21, ISO 846 test method Table 1 shows the evaluation of the antimicrobial properties.

[Example 2]

After the coating was performed under the same conditions as in Example 1, except that the coating composition prepared in Preparation Example 2 was used, a property evaluation experiment was performed.

[Comparative Example 1]

Physical property evaluation experiments were performed under the same conditions as in Example 1, except that the conventional lacquer coating composition was used.

[Comparative Example 2]

After coating under the same conditions as in Example 1 using a coating composition prepared using a styrene acrylic resin without using the resin and the functional additive of the present invention, a physical property evaluation experiment was performed.

[Comparative Example 3]

After coating under the same conditions as in Example 1, except that a coating composition obtained by mixing graphene and aerosol with the coating composition prepared using the styrene acrylic resin of Comparative Example 2 was performed. Did.

Corrosion resistance ¹⁾ Flammability ²⁾ Coating thickness ³⁾ Example 1

No more than 240 hours

Grade 0

65㎛ Example 2 No more than 240 hours

Grade 0

62㎛ Comparative Example 1 72 hours hearing

Level 4

65㎛ Comparative Example 2 160 hours listening

Level 3

67㎛ Comparative example
3 200 hours of hearing

Level 2

65㎛ 1) Corrosion resistance test method; KS D 9502
2) Test method for anti-fog properties; KS J 3201, ASTM G21, ISO 846
Strain used; Asperfillus niger ATCC 9642 , Chaetomium globosum ATCC 6205, Penioillium pinophilum ATCC 11797, Gliooledium virens ATCC 9645, Aureobasidium pullulans ATCC 15233
Rating table; Grade 0-Strains cannot grow
Grade 1-Up to 10% on the specimen
Grade 2-10 to 30% on specimens
Grade 3-30-60% above specimen
Level 4-Over 60% on the specimen
3) Test method for coating film thickness measurement; KS M ISO 2808

As shown in Table 1, Examples 1 to 2 using the coating composition containing the resin and / or functional additive of the present invention include corrosion resistance and anti-fogging properties compared to Comparative Examples not using the coating composition of the present invention. The preservability was remarkably excellent, and the peeling resistance also showed a remarkable effect compared to the comparative examples.

[Production Example 3]

A functional additive (B) was prepared by mixing 30 g of a zeolite powder having a size of 5 to 10 μm in diameter as a porous carrier and 50 g of graphene as an electromagnetic shielding agent and 20 g of aerosol.

Based on the total weight of the functional additive (B) prepared by removing 15% by weight, 10% by weight, 5% by weight, 30 g of the resin (A) prepared in Preparation Example 1, Rutile type titanium dioxide as a coloring pigment ( TiO ₂ ) 10 g and zinc oxide (ZnO) 1 g, 5 g potassium carbonate (CaCO ₃ ) and 2 g talc as extender pigment, 18 g white silica as matting agent, 5 g polycarboxylic acid polymer as dispersing agent, organic modification as antifoaming agent It was mixed with 1 g of polysiloxane and 1 g of 2,6-di-t-butyl-1-hydroxy-4-methylbenzene as an antioxidant and stirred at 40 ° C. to obtain a coating composition.

[Experimental Example 2]

Electromagnetic shielding evaluation through the ASTM D 4935-89 test method for samples coated on the surface of a specimen of 150 x 70 x 3 mm made of plastic (PA66) from the coating compositions of Preparation Examples 1 and 3 according to the present invention And KS M ISO 6297 by conducting physical property evaluation experiments such as electrical conductivity evaluation, and the results are shown in Table 2 and FIGS. 1 to 4.

As shown in Table 2, the coatings of Preparation Example 1 and Preparation Example 3 using the coating composition containing the resin and / or functional additive of the present invention are the same as those shown in Table 2 and FIGS. 1 to 4 for the present invention. Likewise, in the case of PA66 + Abietic Oligomer + functional additive 15%, it can be seen that the electromagnetic wave shielding property is high at low frequency compared to the same PA66 + Abietic Oligomer + functional additive 10%. When the filler was added in the same volume, 15% of the functional additive contained better properties in the low-frequency region than that of the PA66 + Abietic Oligomer + 5% functional additive, and the thermal conductivity was remarkably excellent.

The preferred embodiments of the present invention have been described in detail above, but the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concept of the present invention defined in the claims are also provided. It belongs to the scope of rights.

Claims (15)

A repeating unit derived from cardol represented by the following Chemical Formula 1,
A repeating unit derived from abietic acid represented by Formula 2 below,
Repeating units derived from synthetic resins, and
It consists of a part forming a complex with a metal derived from at least one metal oxide selected from cobalt oxide and manganese oxide,
The synthetic resin is any one selected from the group consisting of styrene acrylic resin, acrylic resin, urethane resin, latex type acrylic resin, mixtures thereof, and copolymers thereof.
[Formula 1]

[Formula 2]

According to claim 1,
The resin is greater than 0% by weight to less than 15% by weight of repeating units derived from the cardol, greater than 0% by weight to less than 15% by weight of repeating units derived from abietic acid, and repeating units derived from the synthetic resin 60 To 90% by weight of the resin. delete delete A coating composition comprising the resin of claim 1. The method of claim 5,
The coating composition further comprises an electromagnetic shielding agent. The method of claim 6,
The electromagnetic shielding agent is a coating composition that is at least one selected from graphite, carbon black, graphene, carbon nanotubes, and fullerene. The method of claim 6,
The electromagnetic shielding agent is a coating composition that is supported on a porous carrier. (A) preparing a resin by reacting a cardol represented by Chemical Formula 1, at least one metal oxide selected from abietic acid represented by Chemical Formula 2, synthetic resin, cobalt oxide, and manganese oxide, and a free radical initiator Including,
The synthetic resin is any one selected from the group consisting of styrene acrylic resin, acrylic resin, urethane resin, latex type acrylic resin, mixtures thereof, and copolymers thereof, a method for producing a coating composition.
[Formula 1]

[Formula 2]

The method of claim 9,
The synthetic resin is a method for producing a coating composition that is condensed with the cardol and abietic acid in a solid and liquid form. The method of claim 9,
The step (A) of preparing the resin includes the cobalt oxide, the manganese oxide, and the free radical initiator of more than 0% by weight to 5% by weight, more than 0% by weight to 5% by weight, and 0.05 to 15% by weight, respectively. A method for producing a coating composition that is reacted in an amount. The method of claim 9,
Step (A) for preparing the resin is a method for producing a coating composition that is performed for 12 to 48 hours at 150 to 230 ° C. and 1 to 50 atm conditions. The method of claim 9,
A method for producing a coating composition further comprising the step (B) of mixing the resin and the functional additive prepared in step (A). The method of claim 13,
The functional additive is one or more electromagnetic shielding agents selected from graphite, carbon black, graphene, carbon nanotubes, and fullerene, the method of manufacturing a coating composition. The method of claim 14,
The electromagnetic shielding agent is supported on a porous carrier, a method for producing a coating composition.

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