KR101110843B1 - Block copolymer resin having anti-fogging property and composition comprising the same for anti-fogging coating with excellent weatherability - Google Patents

Abstract

The present invention relates to a block copolymer resin having an antifogging property and a composition for antifogging coating having excellent weather resistance, and more particularly, to a complex monomer and a reaction process by polymerizing a macromonomer together with a hydrophilic monomer and a hydrophobic monomer. It can be easily prepared as a block copolymer by a common acrylic polymerization method, and when applied to a transparent material such as glass, plastic, spectacle lens, vinyl, satisfies the general physical properties such as water resistance, adhesion, curability and strength and sudden temperature difference The present invention relates to a block copolymer resin which continuously expresses a function of not forming fine water droplets on a surface even when contacted with moisture and also exhibits excellent weather resistance even after long-term exposure to ultraviolet rays, and particularly, a composition for antifogging coating having excellent weather resistance.

Anti-fog, Block Copolymer Resin, Weather Resistance, Coating, Composition

Description

Block copolymer resin having anti-fogging property and composition for the anti-fogging coating having excellent weather resistance {{Block copolymer resin having anti-fogging property and composition comprising the same for anti-fogging coating with excellent weatherability}

The present invention relates to a block copolymer resin having an antifogging property and a composition for antifogging coating having excellent weather resistance, and more particularly, to a complex monomer and a reaction process by polymerizing a macromonomer together with a hydrophilic monomer and a hydrophobic monomer. It can be easily prepared as a block copolymer by a common acrylic polymerization method, and when applied to a transparent material such as glass, plastic, spectacle lens, vinyl, satisfies the general physical properties such as water resistance, adhesion, curability and strength and sudden temperature difference The present invention relates to a block copolymer resin which continuously expresses a function of not forming fine water droplets on a surface even when contacted with moisture and also exhibits excellent weather resistance even after long-term exposure to ultraviolet rays, and particularly, a composition for antifogging coating having excellent weather resistance.

The number and type of polymer materials are diversified according to the technological development in the chemical field, and the polymer materials and polymers are suitable for the required characteristics of application fields such as engineering plastics, automotive plastics, textiles, electronic materials, rubber fields, coating agents, adhesives Related technologies are also developing. One of the fields relates to a polymer coating material. In particular, in recent years, development of a functional coating material that requires a special function of forming a thin water film without forming fine water droplets even during long-term moisture contact is required.

In general, water droplets form or form a thin film of water, which is caused by moisture in contact with the surface tension of the substrate in automobile glass or plastic, bathroom mirror, glass, spectacle lens, optical lens, packaging vinyl, or vinyl house vinyl. This is caused by the difference between the surface tension and the difference in temperature and humidity inside and outside of the substrate, water condensation due to vapor pressure or saturated vapor pressure, and a combination of various contaminants.

In the case of vinyl applied to the plastic house packaging, condensation occurs in the vinyl house due to crossover or temperature difference between the inside of the vinyl house and the outside air, causing water droplets to be scattered. There has been a problem of not being able to receive even sunlight. In addition, in the case of polycarbonate (PC) lenses for headlamps, UV hard coating was only applied to the outer surface of the PC lens, but recently, due to the high-end automotive specifications, By providing a function to prevent fine water droplets, car headlights are being further enhanced by improving reflector damage caused by condensation in headlights and deterioration of light distribution sharpness. The provision of such a function has usually been made by surface coating with a surfactant-containing composition, surface water-repellent coating with a silicon-based or matrix-free system, or plasma surface treatment. However, these conventional methods have the following problems.

First, when the surfactant is introduced into the coating to lower the surface tension of the substrate to express the physical properties, it is difficult to maintain it for a long time because the surfactant component is eluted with time.

Second, in the case of coating the surface of the substrate by using a silicon or inorganic material having a lower surface tension than water, it is difficult to obtain a sufficient level of water droplet prevention effect.

Third, the plasma treatment to impart an effect by giving a hydrophilic radical to the surface of the substrate is difficult to commercialize because the treatment cost is very expensive.

In addition, in general, the process for producing a block copolymer or a graft copolymer requires a difficult polymerization condition such as vacuum or reduced pressure, unlike a general acrylic resin manufacturing method, and thus has a limited range of use, and uses a highly reactive organic anion as a medium. Water must be removed 100%, there is a limitation in the type of monomer that can be used due to restrictions on the reactor, the reaction temperature is low and the reaction time is relatively long, it is difficult to use commercially directly.

On the other hand, paints that have been used to prevent condensation inside the PC lens have a problem of remarkably inferiority, lack of water resistance, melting the coating film, and poor transparency. Therefore, a variety of technologies related to coating materials or coating compositions having anti-condensation functions have been developed, which are disclosed in, for example, the following prior documents.

Japanese Patent Laid-Open Nos. 63-066250 and 57-003832, European Patent 399441 and US Patent 4,080,476 use a composition composed of a hydrophilic acrylic resin, a photocrosslinkable acrylate, and a surfactant to cure abrasion resistance to a substrate surface. A technique for obtaining the effect by forming a film is disclosed. However, this technique has a disadvantage in that the hydrophilic function and the wear resistance are inversely proportional to each other.

Korean Patent Publication Nos. 1997-8987 and 52-47754 disclose a method of forming a film on the surface of a transparent material using a random copolymer containing a hydrophilic polymer and a hydrophobic polymer portion, or a combination of a hydrophilic polymer and a surfactant. Is disclosed. However, such a film is excellent in strength and adhesion but has a disadvantage in that water droplets are prevented from forming.

Korean Patent Publication No. 199595-14730, Japanese Patent Application Laid-Open No. 56-62865 and the like disclose a method of forming a mixture film composed of a random copolymer composed of hydrophilic and hydrophobic moieties and a surfactant on the surface of a transparent material. In the case of this method, however, the initial function is expressed, but the function decreases with time, and the use of a large amount of the surfactant has a problem in that the strength and the adhesion decrease.

Japanese Patent Application Laid-Open No. 57-8236 and International Patent Application No. PCT / EP95 / 3736 describe a method of preparing a film by blending a hydrophilic surfactant or a hydrophilic polymer when the film is formed. Although the required physical properties are satisfied, after one year or more, since the surfactant or the hydrophilic polymer is eluted to the surface, the function of preventing the formation of water droplets gradually decreases.

In addition, a composition comprising an inorganic filler in a polyolefin resin or an inorganic colloid and a hydrophobic thermoplastic resin as a main component is known (Japanese Patent Application No. 11-141348, Japanese Patent Application No. 11-273972), in which case it is stored for a long time. There is a disadvantage of poor stability.

In short, the conventional anti-dropping functional resin and coating composition is applied to the interior of the automotive PC lens and PET film made of a material such as polycarbonate to polymethyl methacrylate, the coating film strength is poor, the whitening phenomenon due to lack of water resistance Occurs due to this, there is a problem in poor transparency, chemical resistance, weather resistance and yellowing resistance.

The present invention is to solve the problems of the prior art as described above, the present invention, the general physical properties such as water resistance, heat resistance, adhesion, curing and strength when applied to a transparent material such as glass, plastic, spectacle lenses, vinyl In addition, the block copolymer resin and the antifogging coating containing the same, which continuously express a special function that does not form fine water droplets on the surface even when sudden temperature difference or moisture contact, and also exhibits excellent weather resistance even after long-term UV exposure. It is a technical subject to provide a composition.

The present invention to solve the above technical problem, (i) a macromonomer-derived polymer unit having a polymerizable functional group at the end of the molecular chain, (ii) at least one hydrophilic monomer-derived polymer unit and (iii) at least one hydrophobic monomer It provides an antifogging block copolymer resin comprising a derived polymer unit, characterized in that the content of the macromonomer-derived polymer unit is 5 to 25% by weight based on 100% by weight of the total monomer-derived polymer unit.

According to another aspect of the present invention, there is provided an antifogging coating composition comprising the antifogging block copolymer resin, a curing agent, and a dilution solvent, wherein the block copolymer resin content is 20 to 60% by weight.

Hereinafter, the technical configuration of the present invention will be described in detail.

The macromonomer (i) included in the antifogging block copolymer resin of the present invention as a polymer unit is a relatively long linear molecule having a polymerizable functional group at the molecular chain terminal, for example, an unsaturated group such as a carbon-carbon double bond. In the molecular chain of the coalescence many branches are derived from the long linear molecules of this macromonomer. The macromonomer is in oligomeric form, and its number average molecular weight is preferably 1000 to 30000, more preferably 6000 to 9000. The macro monomer preferably has a polymer unit of at least one monomer selected from the group consisting of methyl methacrylate, styrene, butyl acrylate and isobutyl methacrylate as the main chain segment, and a polymerizable functional group at the terminal of the molecular chain. It may have acryloyl group, methacryloyl group and the like, in terms of ease of copolymerization methacryloyl group is preferred.

The ratio of the macromonomer-derived polymerized unit included in the block copolymer resin of the present invention is 5 to 25% by weight based on 100% by weight of the total monomer-derived polymerized units used. When the ratio of the macromonomer-derived polymer unit is less than 5% by weight of the total monomer polymerized unit amount, the amount of the macromonomer-derived polymer unit is small, so that the desired block copolymer structure cannot be properly obtained, and when it exceeds 25% by weight, the macromonomer itself is a hydrophobic monomer. The hydrophobic structure is excessively high in the physical property rather deteriorates.

When the copolymer is prepared using macro monomers and hydrophilic monomers, the hydrophilic monomers react with the polymerizable functional groups attached to the macro monomer terminals to form hydrophilic chains, and since the macro monomers themselves have long hydrophobic chains, Block copolymers having chains at the same time can be prepared. In general, to prepare a block copolymer requires a difficult manufacturing process and equipment, there are restrictions on the monomers, initiators, etc. that can be used, but using macro monomers, it is possible to apply a variety of commonly used monomers and initiators without complex manufacturing process The block copolymer can be easily obtained by the acrylic polymerization method which is commercially available.

As (ii) at least one hydrophilic monomer contained in the antifogging block copolymer resin of the present invention as a polymer unit, a hydrophilic monomer having a solubility constant of 12 or more is preferable, and specifically N-vinyl caprolactone, N, N- It is more preferable to use at least one selected from the group consisting of dimethyl acrylamide, butoxy acrylate, acrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate and N-methylol acrylamide.

It is preferable that the ratio of the said hydrophilic monomer derived polymer unit contained in the block copolymer resin of this invention is 15 to 45 weight% based on 100 weight% of all the monomer derived polymer units used. When the ratio of the hydrophilic monomer-derived polymer unit is less than 15% by weight of the total monomer polymerized unit, antifogging function is not easily expressed, and when it exceeds 45% by weight, the water resistance of the coating film is remarkably reduced, and the wrinkles of the coating film in contact with moisture or moisture The back may be damaged or the coating may peel off.

(Iii) At least one hydrophobic monomer contained in the antifogging block copolymer resin of the present invention as a polymer unit is for imparting strength to the coating film, and a (meth) acrylic monomer is preferable, and methyl (meth) acrylate, ethyl ( Meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-ethyl Such as C1-C20 alkyl (meth) acrylates, benzyl (meth) acrylates and phenyl (meth) acrylates such as hexyl (meth) acrylate, tridecyl (meth) acrylate and stearyl (meth) acrylate Aminoalkyl (meth) acrylates such as C6-C12 aryl (meth) acrylate, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate More preferably at least one member selected from the group true.

It is preferable that the ratio of the said hydrophobic monomer derived polymer unit contained in the block copolymer resin of this invention is 30 to 60 weight% based on 100 weight% of all the monomer derived polymer units used. When the ratio of the hydrophobic monomer-derived polymer unit is less than 30% by weight of the total monomer polymerized unit, the strength of the coating film may be lowered. When the hydrophobic monomer-derived polymer unit ratio exceeds 60% by weight, the hydrophobic property may be so strong that it may not properly function to prevent water droplet formation. .

The glass transition temperature (T _g ) of the antifogging block copolymer resin of the present invention can be easily adjusted as necessary by adjusting the ratio of the hydrophobic monomer and the hydrophilic monomer content in the monomer mixture, preferably 50 to 70 ° C. However, it is not necessarily limited thereto.

The polymerization initiator which can be used for the polymerization of the antifogging block copolymer resin of the present invention is not particularly limited, and radicals are formed by a water-soluble and oil-soluble initiator or an oxidation-reduction reaction in which radicals are formed by thermal dissociation at high temperatures. All initiators can be used without limitation. Exemplary polymerization initiators include azobisisobutyronitrile, 2,2-azobis-2,4-dimethylvaleronitrile, 2,2-azobismethylbutyronitrile and 1,1-azobiscyclo Azo initiators such as hexanecarbonitrile; Peroxide-based initiators such as benzoyl peroxide, cumene hydroperoxide, t-butylperoxide, t-butylperbenzoate and methyl ethyl ketone peroxide; Persulfate-based initiators such as ammonium persulfate, t-butyl hydrogen peroxide potassium persulfate, ammonium persulfate and potassium persulfate; Persulfates; And peroxides, such as hydrogen peroxide and peracetic acid, etc. can be mentioned, It can be used individually or in combination of 2 or more types. Preferably, azo initiators (such as the VAZO series sold by I. DuPont de Nemoas and Company) can be used.

The amount of the initiator is preferably 1 to 5 parts by weight based on 100 parts by weight of the total amount of monomers. If the amount of the initiator is less than 1 part by weight per 100 parts by weight of the total monomer, the molecular weight of the polymer to be polymerized becomes excessively large, the reaction conversion rate decreases, and the rate of polymerization is slowed, so that unreacted monomers remain. It may cause a decrease in physical properties. On the other hand, when the amount of the initiator is more than 5 parts by weight, the molecular weight of the resin is reduced, thereby affecting the water resistance of the coating film. If necessary, the molecular weight of the resin produced by applying a molecular weight regulator in addition to the initiator may be adjusted.

On the other hand, as the solvent usable for synthesizing the antifogging block copolymer resin of the present invention, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, methoxypropanol and diacetone alcohol are not particularly limited. ; Alcohol ether solvents such as methyl carbitol, ethyl carbitol and butyl carbitol can be used, and in view of long-term durability, it is preferable to use an alcohol solvent. In addition, since physical properties such as adhesion may be inhibited due to the solvent remaining during drying or curing of the coating film, it is preferable to use a solvent having a boiling point of less than 150 ° C. In consideration of physical properties and workability, the solvent is preferably used in an amount such that the nonvolatile content is 20 to 50% by weight based on the total weight of the mixture as a result of the polymerization.

Unlike the general acrylic resin manufacturing method, the block copolymer manufacturing method requires a difficult polymerization condition such as vacuum or reduced pressure, and thus has a limited use range. Therefore, 100% of moisture must be removed because the organic anion is used as a medium. Restrictions on the reactor limit the types of monomers that can be used. In addition, the reaction temperature is low and the reaction time is relatively long, there is a disadvantage that it is difficult to use commercially directly. However, the antifogging block copolymer resin of the present invention has an advantage that it can be easily synthesized without restriction under general acrylic polymerization conditions by applying a macro monomer.

On the other hand, according to another aspect of the present invention, the antifogging coating comprising an antifogging block copolymer resin, a curing agent and a diluent of the present invention as described above, characterized in that the block copolymer resin content is 20 to 60% by weight A composition for use is provided.

The anti-fogging coating composition of the present invention includes 20 to 60% by weight of the block copolymer resin of the present invention. If the content is less than 20% by weight, the antifogging effect of the coating is lowered, and if it exceeds 60% by weight, There is a problem that the appearance and leveling are lowered.

The curing agent included in the antifogging coating composition of the present invention increases the reactivity of the crosslinking functional group of the copolymer resin to enable low temperature and short curing time, and preferably includes one or more acid catalysts. It is more preferable to contain 1 or more types. Examples of sulfonic acid based acid catalysts include naphthalene sulfonic acid-formaldehyde condensates, alkyl naphthalene sulfonic acids, dinonylnaphthalene disulfonic acids, dodecyl benzene sulfonic acids and para toluene sulfonic acids. The curing agent is preferably 0.5 to 5% by weight in the antifogging coating composition of the present invention, if the content is less than 0.5% by weight is likely to decrease the curability and coating film strength, when the content exceeds 5% by weight of the paint storage There is a fear that this will be poor.

Diluent solvent included in the antifogging coating composition of the present invention is used to improve the coating properties of the composition by adjusting the viscosity of the composition, methanol, ethanol, n-propanol, isopropanol, n-butanol and diacetone alcohol and Same alcohol solvents; Alcohol ether solvents such as methyl carbitol, ethyl carbitol and butyl carbitol; Cellosolve solvents such as cellosolve acetate; Isophorone; And it is preferable to use one or more selected from the group consisting of alkoxy alcohol solvents such as 3-methoxy-3-methyl-1-butanol and methoxy propanol, but is not necessarily limited thereto. The amount of the dilution solvent used may vary depending on the viscosity of the desired composition, preferably 40 to 80% by weight is included in the coating composition of the present invention, if the content is less than 40% by weight workability due to insufficient dilution The appearance may be degraded due to defects, and if it exceeds 80% by weight, the curability, adhesion, scratch resistance, and the like may decrease.

On the other hand, the antifogging coating composition of the present invention may further include a surfactant to improve antifogging durability. It is preferable to use at least 1 type of nonionic surfactant as a surfactant from the viewpoint of preventing the occurrence of cloudiness after the water contact of the coating film and improving the coating film strength. Specifically, the surfactant may be polyethylene oxide alkyl ether, polyethylene oxide alkyl phenyl ether, sorbitan fatty acid ester, polyoxyethylene fatty acid amide, N, N-bis-2-hydroxy alkyl amine, glycerin Preference is given to using at least one member selected from the group consisting of fatty acid mono esters, methyl ester ethoxylates and pentathiol fatty acid ester surfactants. The surfactant is preferably included in 10 parts by weight or less, such as 1 to 10 parts by weight with respect to 100 parts by weight of the coating composition of the present invention. have.

In addition, the antifogging coating composition of the present invention may further include an additive for controlling the surface to improve the slip (slip) and leveling (leveling) of the coating film. As the surface-control additive, a silicon diacrylate-based compound or a silicone-modified polyacrylate compound is preferably used. In order not to lower the physical properties of the coating film while obtaining the effect of addition, 2 wt% or less of the total weight of the composition, for example It is preferable to use it at 0.1-2 weight%.

In addition, the antifogging coating composition of the present invention may further include a light stabilizer to prevent the physical properties of the coating film due to light exposure over a long period of time. As the light stabilizer, it is particularly preferable to use a triadine-based ultraviolet stabilizer. In order not to reduce the antifogging function of a coating film, while obtaining a light stabilizing effect, it is preferable to contain 2 weight part or less, for example, 0.1-2 weight part of light stabilizers per 100 weight part of coating compositions.

In addition to the above components, the antifogging coating composition of the present invention may further include additives that are conventionally added to the antifogging coating composition within a range capable of achieving the object of the present invention.

There is no particular limitation on the method for preparing the antifogging coating composition of the present invention, for example, the above-mentioned essential ingredients and optional ingredients are added to a mixing equipment such as a dissolver, a stirrer, etc. It may be prepared according to the method.

According to the present invention, the coating is excellent in physical properties such as water resistance, adhesion, curability, heat resistance and weather resistance, and can exhibit an excellent anti-fogging function in which fine water droplets are not formed on the surface even when a large amount of moisture is contacted. A particularly effective antifogging composition can be obtained for coating transparent materials such as plastics and lenses. In addition, the water resistance, moisture resistance and the bubble (bubble) is improved, and has the advantage of minimizing the white turbidity commonly seen in conventional anti-fog coating composition. In particular, macro monomers can be applied to easily block copolymers using common acrylic polymerization methods without complex equipment and reaction processes, and the initial physical properties compared to resins and coating compositions composed of conventional random copolymers through blocked copolymers This is good and has the advantage of being able to express physical properties over a long period of time.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are only to aid the understanding of the present invention, and the present invention is not limited thereto.

(1) copolymer resin production

Example 1

Into a four-necked flask equipped with a nitrogen inlet, a thermometer sensor, a dropping funnel, and a stirrer, 1,260 g of propanol was added as a solvent for polymerization, and the temperature of the reaction section was increased to 90 ° C. 30 g of methacryloxy methyl methacrylate (AA-6, Toagosei Co., Ltd.) and 35 g of methacrylic acid-styrene-modified macromonomer (AS-6, Toagosei Co.) as macromonomers; 90 g of N, N-dimethylacrylamide, 50 g of N-methylol acrylamide and 34 g of hydroxyethyl acrylate as hydrophilic monomers; 200 g of methyl methacrylate and 60 g of butyl methacrylate as hydrophobic monomers; And 14 g of 2,2-azobis 2-methylbutyronitrile as an initiator were added dropwise for about 4 hours. At the time of dropping, the temperature was maintained at 80 ± 10 ° C. After the addition of the reactants, the polymerization was carried out by maintaining the temperature at 90 ± 1 ° C. for about 1.5 hours, and then cooling the resultant mixture to prepare a copolymer resin.

Example 2

Into a four-necked flask equipped with a nitrogen inlet, a thermometer sensor, a dropping funnel, and a stirrer, 1,260 g of propanol was added as a solvent for polymerization, and the temperature of the reaction section was raised to 90 ° C. 10 g of AA-6 and 15 g of AS-6; 90 g of N, N-dimethylacrylamide, 50 g of N-methylol acrylamide and 55 g of hydroxyethyl acrylate as hydrophilic monomers; 200 g of methyl methacrylate and 80 g of butyl methacrylate as hydrophobic monomers; And 14 g of 2,2-azobis 2-methylbutyronitrile as an initiator were added dropwise for about 4 hours. At the time of dropping, the temperature was maintained at 80 ± 10 ° C. After the addition of the reactants, the polymerization was carried out by maintaining the temperature at 90 ± 1 ° C. for about 1.5 hours, and then cooling the resultant mixture to prepare a copolymer resin.

Example 3

Into a four-necked flask equipped with a nitrogen inlet, a thermometer sensor, a dropping funnel, and a stirrer, 1,260 g of propanol was added as a solvent for polymerization, and the temperature of the reaction section was increased to 90 ° C. Here, as macro monomers, 60 g of AA-6 and 65 g of AS-6 from Toagosei Co., Ltd .; 80 g of N, N-dimethylacrylamide, 50 g of N-methylol acrylamide and 40 g of hydroxyethyl acrylate as hydrophilic monomers; 175 g of methyl methacrylate and 30 g of butyl methacrylate as hydrophobic monomers; And 14 g of 2,2-azobis 2-methylbutyronitrile as an initiator were added dropwise for about 4 hours. At the time of dropping, the temperature was maintained at 80 ± 10 ° C. After the addition of the reactants, the polymerization was carried out by maintaining the temperature at 90 ± 1 ° C. for about 1.5 hours, and then cooling the resultant mixture to prepare a copolymer resin.

Comparative Example 1

In a four-necked flask equipped with a nitrogen inlet, a thermometer sensor, a dropping funnel, and a stirrer, 1,250 g of propanol was added as a solvent for polymerization, and the temperature of the reaction portion was raised to 90 ° C. As a hydrophilic monomer, 100 g of N, N- dimethyl acrylamide, 50 g of N-methylol acrylamides, and 50 g of hydroxyethyl acrylate; 200 g of methyl methacrylate and 100 g of butyl methacrylate as hydrophobic monomers; And 16 g of 2,2-azobis 2-methylbutyronitrile as an initiator were added dropwise for about 4 hours. At the time of dropping, the temperature was maintained at 80 ± 10 ° C. After the addition of the reactants, the polymerization was carried out by maintaining the temperature at 90 ± 1 ° C. for about 1.5 hours, and then cooling the resultant mixture to prepare a copolymer resin.

Comparative Example 2

Into a four-necked flask equipped with a nitrogen inlet, a thermometer sensor, a dropping funnel, and a stirrer, 1,260 g of propanol was added as a solvent for polymerization, and the temperature of the reaction section was increased to 90 ° C. 10 g of AA-6 and 5 g of AS-6; 90 g of N, N-dimethylacrylamide, 50 g of N-methylol acrylamide and 45 g of hydroxyethyl acrylate as hydrophilic monomers; 200 g of methyl methacrylate and 90 g of butyl methacrylate as hydrophobic monomers; And 17 g of 2,2-azobis 2-methylbutyronitrile as an initiator were mixed and added dropwise for about 4 hours. At the time of dropping, the temperature was maintained at 80 ± 10 ° C. After the addition of the reactants, the polymerization was carried out by maintaining the temperature at 90 ± 1 ° C. for about 1.5 hours, and then cooling the resultant mixture to prepare a copolymer resin.

Comparative Example 3

In a four-necked flask equipped with a nitrogen inlet, a thermometer sensor, a dropping funnel, and a stirrer, 1,200 g of propanol was added as a polymerization solvent, and the temperature of the reaction section was increased to 90 ° C. 100 g of AA-6 and AS-6 of Toagosei Inc. as macromonomers; 80 g of N, N-dimethylacrylamide, 50 g of N-methylol acrylamide and 40 g of hydroxyethyl acrylate as hydrophilic monomers; 170 g of methyl methacrylate and 30 g of butyl methacrylate as hydrophobic monomers; And 17 g of 2,2-azobis 2-methylbutyronitrile as an initiator were mixed and added dropwise for about 3 hours. At the time of dropping, the temperature was maintained at 80 ± 10 ° C. After the addition of the reactants, the polymerization was carried out by maintaining the temperature at 90 ± 1 ° C. for about 1.5 hours, and then cooling the resultant mixture to prepare a copolymer resin.

(2) Preparation of antifogging functional coating composition

Examples 4-6, Comparative Examples 4-6

Using each of the copolymer resins prepared above, the antifogging coating compositions of Examples 4 to 6 and Comparative Examples 4 to 6 were prepared with compositions as shown in Table 1 below.

The antifogging coating compositions of Examples 4 to 6 and Comparative Examples 4 to 6 prepared above were spray-coated with a thickness of about 4 microns on a transparent polycarbonate specimen (Lexan resin), and then heated at a temperature of 120 ° C. for about 30 minutes. The antifogging coating specimens formed by curing were evaluated for the following items, and the results are shown in Table 2 below.

1) Adhesion: evaluated by cross cut tape test according to ASTM D3359

2) Moisture test: After spraying moisture on anti-fog coated surface for 3 seconds at room temperature, observe the state of the coated surface visually.

3) Heat resistance: After leaving the specimen at 130 ℃ for one hour, visually observe whether yellowing, whitening, crack, and rainbow phenomenon occur on the surface of the coated surface.

4) Acid resistance: Apply 0.2 ml of 0.1N sulfuric acid solution on the coated surface of the specimen and leave it for 24 hours, wash the specimen with water and leave it for another hour, then delete the crack, discoloration, wrinkle, peeling and swelling on the coated surface. Visually observe if abnormalities occur

5) Alkali resistance: Apply 0.2 ml of 0.1N sodium hydroxide solution on the coated surface of the specimen and leave it for 24 hours, wash the specimen with water and leave it for another hour, then crack, discoloration, wrinkle, peeling and swelling Visually observe whether harmful abnormalities occur

6) Moisture resistance: After leaving the specimen in a constant temperature and humidity chamber at 50 ° C and 98% relative humidity for 240 hours, observe the naked eye for yellowing, cracks, wrinkles, whitening and rainbow on the coated surface.

7) Cold-resistant cycle: The specimen is left for 2 hours at -40 ° C, and it is then repeated 10 times at 80 ° C for 2 hours, and then yellowing, whitening, cracks, wrinkles and rainbows on the coated surface. Visually observe if this occurs

8) Water resistance: After immersing the specimen in water at 40 ℃ for 240 hours and drying for 1 hour, visually observe if any harmful abnormalities such as cracks, discoloration, peeling, wrinkles and swelling occur on the coated surface.

9) UV weather resistance: A accelerated weather resistance tester using a xenon light source was tested for 100 hours at a panel temperature of 80 ° C. for 100 hours to observe yellowing.

Examples 7-9, Comparative Examples 7-10

Using the copolymer resin of Example 1, antifogging coating compositions (Examples 7 to 9 and Comparative Examples 7 to 8) of the composition as shown in Table 3 were prepared in the same manner as in Example 1, Anti-fogging coating specimens were prepared in the same manner as in Examples 4-6.

Meanwhile, antifogging coating specimens were prepared in the same manner as in Examples 4 to 6 using the currently commercially available antifogging coating compositions (Comparative Example 9: Japan Oil, Inc., Comparative Example 10: Fujikura Kasei, Inc.). The physical properties of the prepared antifogging specimens were evaluated in the same manner as in Examples 4 to 6, and the results are shown in Table 4 below.

Claims (9)

Antifogging block copolymer resins, curing agents and diluents, The antifogging block copolymer resin (i) a macromonomer-derived polymerized unit having a polymerizable functional group at the terminal of the molecular chain, (ii) at least one hydrophilic monomer-derived polymerized unit, and (iii) at least one hydrophobic monomer-derived polymerized unit Including, The macro monomer-derived polymer unit content is 5 to 25% by weight based on 100% by weight of the total monomer-derived polymer unit, The antifogging block copolymer resin content is 20 to 60% by weight composition for antifogging coating, characterized in that. The antifogging coating composition according to claim 1, wherein the macromonomer is in an oligomer form having a number average molecular weight of 1000 to 30000. The antifogging coating composition according to claim 1, wherein the terminal polymerizable functional group of the macromonomer is a methacryloyl group. The hydrophilic monomer of claim 1, wherein the hydrophilic monomer is N-vinylcaprolactone, N, N-dimethylacrylamide, butoxy acrylate, acrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate and N-methylol acrylamide. Anti-fog coating composition, characterized in that at least one selected from the group consisting of. The method of claim 1, wherein the hydrophobic monomer is at least one member selected from the group consisting of 1 to 20 alkyl (meth) acrylates, 6 to 12 aryl (meth) acrylates and aminoalkyl (meth) acrylates Antifog coating composition. The antifogging coating composition according to claim 1, further comprising a surfactant. The antifogging coating composition according to claim 1, further comprising a light stabilizer. The antifogging coating composition according to claim 7, wherein the light stabilizer is a triadine-based ultraviolet stabilizer. delete