KR101005659B1 - Composition comprising acrylated ester monomer and coating products using the same - Google Patents

Abstract

The present invention relates to a composition comprising an acrylate ester monomer and a coating agent using the same, an acrylate ester monomer (A) synthesized from a polyol (A1) and an acrylic monomer (A2) represented by the following [Formula 1]; An acrylic monomer (B) polymerized with the acrylic ester monomer (A); Inorganic oxides (C); And a silane coupling agent (D).

[Formula 1]

(In Formula 1, R is hydrogen or hydrocarbon.)

Acrylate esters, acrylics, inorganic oxides, coatings, coatings, antistatic

Description

COMPOSITION COMPRISING ACRYLATED ESTER MONOMER AND COATING PRODUCTS USING THE SAME}

The present invention relates to a composition comprising an acrylate ester monomer derived from vegetable oil and a coating agent using the same, and more particularly to synthesize the acrylate ester monomer using a polyol obtained from a vegetable oil (edible oil, etc.) By dispersing and formulating an inorganic oxide using a silane coupling agent in the monomer, a low cost environmentally friendly coating material having excellent mechanical properties, in particular a composition that can be usefully used for antistatic and the like (coating product) It is about.

In general, many commercial products, including optically functional products such as lenses, optical screens, optical filters, prism sheets, and the like, are made of thermoset or thermoplastic polymers. For example, polycarbonate, polymethacrylate, polyurethane, polyester, phenoxy, phenol resin, cellulose resin, polystyrene, styrene copolymer, epoxy and the like are produced. However, many of these thermosetting and thermoplastic polymers are excellent in dimensional stability, transparency, impact resistance, etc., but have poor wear resistance and solvent resistance, so that products made from the polymers are vulnerable to scratches and abrasion.

For this reason, the above resin products are subjected to a wear-resistant hard coating on the surface to protect from physical or mechanical damage. However, the hard coating agent used in the conventional plastic coating is generally impossible to mold due to the hard surface (cracks during molding), or the antistatic property is often the cause of failure during processing. In addition, a metal, carbon powder, conductive polymer, and the like using free electron charge transfer are mixed to provide antistatic properties. However, in this case, although antistatic property lasts for a long time, it has been investigated that the problem of chromaticity hinders the transparency of the substrate for use as an optical product. In addition, there is a disadvantage in that the unit price is expensive when using the metal powder, when using the carbon powder has a disadvantage in that the work is blown off the work process and the conductive carbon particles are relaxed on the surface after coating.

In addition, colloidal silica dispersion in which silica was added using a stabilizer such as N, N-dimethylacrylamide (DMA) or ACMO (Acryl Morpholine) was attempted, but it was toxic by DMA, ACMO, etc., and had hardness, curing resistance, There is a problem in that mechanical properties such as wear resistance and antiblocking properties are inferior.

The present invention is to solve the problems of the prior art as described above, to synthesize an acrylate ester monomer using a polyol obtained from vegetable oil (edible oil, etc.) as an environmentally friendly product, using a silane coupling agent in the monomer It is an object of the present invention to provide a low cost environmentally friendly coating material having excellent mechanical properties by dispersing and forming an inorganic oxide, in particular a composition which can be usefully used for antistatic and the like and a coating agent using the same.

The present invention to achieve the above object,

An acrylate ester monomer (A) synthesized from a polyol (A1) and an acrylic monomer (A2) represented by the following [Formula 1];

An acrylic monomer (B) polymerized with the acrylic ester monomer (A);

Inorganic oxides (C); And

Provided is a composition comprising a silane coupling agent (D).

[Formula 1]

(In Formula 1, R is hydrogen or hydrocarbon.)

At this time, the polyol (A1) represented by the formula (1) is obtained from vegetable oil, it is preferable that R in the formula (1) is (CH2) n-OH (n is an integer of 1 to 20). In addition, the composition according to the present invention preferably further comprises a conductive material (E) for improving the antistatic performance, the conductive material (E) may be used at least one selected from alkali metal salts and transition metal salts.

In addition, the present invention; And a coating layer formed on the substrate, wherein the coating layer provides a coating film formed by coating and curing the composition of the present invention. In this case, the coating layer may be formed by coating the composition on a substrate and curing by ultraviolet irradiation.

According to the present invention to form a coating film excellent in mechanical properties such as film hardness, adhesive strength, and has an effect that can be usefully used as an antistatic coating material with the conductivity. In addition, the polyol (A1) of the formula (1) is obtained from vegetable oil can be supplied at low cost, it is environmentally friendly. Accordingly, the present invention can supply a high value-added coating agent using the existing resources at a low price.

Hereinafter, the present invention will be described in detail.

The composition according to the present invention comprises an acrylate ester monomer (A); Acrylic monomers (B); Inorganic oxides (C); And a silane coupling agent (D). The composition according to the invention may optionally further comprise additional ingredients, depending on the purpose and use of the coated article. Preferably, the conductive material (E) is further included to improve the antistatic performance. In addition, the composition according to the present invention may be coated on the coated body in the presence of a polymerization initiator (photoinitiator), and then photocured by irradiation with ultraviolet (UV) or the like. The composition according to the invention is coated / cured on the coating to have excellent mechanical coating properties.

The said acrylate ester monomer (A) is synthesize | combined from the polyol (A1) and acryl-type monomer (A2) shown by following [Formula 1].

[Formula 1]

In this case, in Formula 1, R is hydrogen or a hydrocarbon. In Formula 1, R is a hydrocarbon, for example, (CH2) n-OH (n is an integer of 1 to 20); (CH2) n-SH (n is an integer from 1 to 20); Or allyl alcohol, vinyl alcohol, alkyl alcohol, alkenyl alcohol, alkynyl alcohol, aromatic alcohol and thiol containing C1 to C20 and containing 1 to 10 O, N and S in the molecule. Hydrocarbons selected from the group. R in the general formula (1) is preferably (CH2) n-OH (n is an integer of 1 to 20).

Polyol (A1) of Formula 1 is obtained by epoxidizing vegetable oil (edible oil, etc.). For example, vegetable oils used as edible oils such as soybean oil, corn oil or palm oil have triacylglycerol (glyceride) structure and have a glycerol structure as a main chain, and include various hydroxyl groups in various fatty acids derived from carboxylic acids. It has a side chain structure. Vegetable oil used in the synthesis of the polyol (A1) of Formula 1 has three fatty acids and glycerol ester bond. According to the present invention, the polyol (A1) synthesized from the above vegetable oil reacts with the acrylic monomer (A2) and the chemical structure is modified to have excellent mechanical properties such as elongation, hardness, adhesive strength, hydrophobic, etc. A tide ester monomer (A) is produced. In addition, the said acrylate ester monomer (A) has the outstanding photocuring characteristic in presence of a polymerization initiator (photoinitiator). At this time, the acrylic monomer (A2) used in the synthesis of the acrylic ester monomer (A) is at least one selected from methacryloyl chloride (methacryloyl chloride), acrylic acid (acrylate), acrylate (acrylate), etc. Preference is given to using (one or both selected). In the present invention 'acrylic' includes acrylate (acrylate) and acrylic (acrylic).

The polyol (A1) of Formula 1 may be obtained by, for example, preparing an epoxidized soy-bean oil (ESBO) and then reacting the ESBO with alcohols, glycols or thiols. At this time, the hydroxyl group of the obtained polyol (A1) reacts with acrylic monomers, such as methacryloyl chloride, and the acrylate ester monomer (A) which has a polyfunctional group is produced. The acrylate ester monomer (A) may be represented by, for example, the following formula (2).

[Formula 2]

In Formula 2, R 'may be allyl, vinyl, alkyl, alkenyl, alkynyl or aromatic hydrocarbon as a hydrocarbon. R 'in the formula (2), preferably has C1 to C20 carbon atoms, and contains 1 to 10 O, N and S in the molecule.

More specific acrylate ester monomer (A) may have a molecular structure shown in Scheme 1 below. Scheme 1 below illustrates a reaction mechanism in which multiple acrylate ester monomers (A) are synthesized using soy-bean oil as a starting material.

Scheme 1

The acrylate ester monomer (A) is preferably included in the range of 2.0 to 90.0% by weight based on the total weight of the composition. At this time, when the content of the acrylate ester monomer (A) is less than 2.0% by weight, the hardness of the coating film is particularly weak, and the coating is thin, so that it is difficult to obtain a desired resistance (antistatic property). In addition, when the content of the arc related ester monomer (A) exceeds 90.0% by weight, the hardness of the coating film is too high, so that the cracking of the coating film is high due to low flexibility, and the appearance is poor, which is not preferable. The acrylated monomer (A) is preferably contained in the composition at 5.0 to 60.0% by weight.

In addition, the composition according to the present invention comprises a polymerizable acrylic monomer (B) which is polymerized with the acrylic ester monomer (A) to improve physical properties such as elongation, hardness and flexibility of the coating film, such a polymerizable acrylic monomer (B) is preferably included in 5.0 to 70.0% by weight based on the total weight of the composition. In this case, when the content of the acrylic monomer (B) is less than 5.0% by weight, it is difficult to improve the physical properties such as hardness due to a drop in the degree of polymerization (fine-grain density), and when it exceeds 70.0% by weight, elongation may decrease.

As the acrylic monomer (B), a bifunctional to 15 functional monomer may be used, and specific examples thereof include di-propylene glycol diacrylate and poly (oxy-1,2-ethenediel) (poly (oxy-1,2). -ethanediyl), ditrimethylolpropane tetraacrylate, polyethyleneglycol diacrylate (PEGDA), bisphenol A-ethyleneglycol diacrylate (BPEGDA), 1 , 6-hexanediol-diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), ethoxylate pentaerythritol tetraacrylate (PPTTA), pentaeryth Lithol triacrylate (PETA), dipentaerythritol pentaacrylate (DPPA), dipentaerythritol hexaacrylate (DPHA), di-trimethylolpropane triacrylate (DI-TMPTA), Any one selected from the group consisting of tandiol diacrylate (BUDA), triethylene glycol diacrylate (TEGDA), neopentyl glycol diacrylate (NPGDA), polyethylene glycol diacrylate and urethane-acrylate Or a mixture of two or more).

The acrylic monomer (B) is preferably used by appropriately combining the above monomers according to the use and purpose of use of the product. Specifically, bifunctional monomers, such as di-propylene glycol diacrylate; 6 functional monomers, such as poly (oxy-1, 2-ethanediyl); It is preferable to include at least one monomer (property reinforcing monomer) selected from tetrafunctional monomers such as di-trimethylolpropane tetraacrylate in the composition. Such monomers (property reinforcing monomers) provide advantages such as elongation, hardness and flexibility of the coating film. At this time, the monomer (property reinforcing monomer) is preferably included in 10.0 ~ 30.0% by weight based on the total weight of the composition. At this time, when the content of the monomer (property reinforcing monomer) is less than 10.0% by weight, it is not possible to secure a crosslinking density that can give an appropriate hardness and flexibility in the coating film, and when it exceeds 30.0% by weight, the elongation may be reduced. In addition, bifunctional monomers (conductive reinforcing monomers) such as polyethyleneglycol diacrylate (PEGDA) and bisphenol A-ethyleneglycol diacrylate (BPEGDA) may be used to improve the charge ring performance. It is preferable to include at least in the inside, and they improve the conductivity of dissociated ions. Such a monomer (conductive reinforcing monomer) is preferably included in 10.0 ~ 50.0% by weight based on the total weight of the composition. At this time, if it is less than 10.0% by weight, it is difficult to improve the ion conductivity, and when it exceeds 50.0% by weight, the ion conductivity may be improved but the hardness of the coating film may be too low.

In addition, the composition according to the present invention includes an inorganic oxide (C) for coating film strength (such as wear resistance) and anti-curling charge resistance, the inorganic oxide (C) is silica (SiO 2), titanium dioxide (TiO 2) ), One or more selected from the group consisting of metal oxides such as alumina (Al 2 O 3), antimony oxide (SbO 2) and tin oxide (SnO 2) may be used, but is not limited thereto. The inorganic oxide (C) may be included in the powder form or colloidal form in the composition, the particle size is preferably 5nm ~ 1000nm. At this time, when the particle size of the inorganic oxide (C) is less than 5 nm is too fine to workability is bad, when it exceeds 100 nm it is difficult to disperse the particles in the composition to obtain an optically smooth and transparent surface. The inorganic oxide (C) preferably has a size of 5 nm to 100 nm. In addition, the oxide-free (C) is preferably a surface treatment (for example, a resin coating, etc.) so that the dispersibility in the composition is good.

In addition, the inorganic oxide (C) is preferably included in the composition in a colloidal form (sol) dispersed in a solution, such inorganic oxide colloid (sol) can be prepared by a method well known in the art, Commercially available products can also be used. For example, colloidal silica in which silica is dispersed in an aqueous solution may be commercially available under the trade name LUDOX (available from Aldrich Chemical Company of Milwaukee, Wisconsin, USA). Specific examples include LUDOX HS-40, HS-30, TM, SM, AM, LS, AS, CL-X, SK, TMA, PG, CL, CL-P, DM, FM and the like. In addition, it is possible to use domestic silicate lithium silicate (LS-L100, LS-H100), potassium metasilicate (PMS-60). The inorganic oxide (C) is preferably included in 2.0 to 60.0% by weight based on the total weight of the composition. At this time, when the content of the inorganic oxide (C) is less than 2.0% by weight, the effect of coating film strength (wear resistance, etc.), warpage improvement and antiblocking according to the content thereof is insignificant. This becomes rough and cracks may occur.

In addition, the composition according to the present invention includes a silane coupling agent (D) for enhancing the dispersibility and adhesion of the inorganic oxide particles, such a silane coupling agent (D) may be used a crosslinkable silane compound. The silane coupling agent (D) is preferably included in 0.2 to 30.0% by weight based on the total weight of the composition. At this time, when the content of the silane coupling agent (D) is less than 0.2% by weight, dispersibility and adhesion may be lowered, thereby causing problems in transparency or quality. When the content of the silane coupling agent (D) exceeds 30.0% by weight, the surface whitening phenomenon and curing rate may be slowed. Due to this, the physical properties may be reduced.

Any silane coupling agent (D) may be used as long as it contains a hydrolyzable silane moiety and / or a polymerizable moiety as a crosslinkable silane compound. For example, the silane coupling agent (D) may be selected from chlorosilanes, vinyl silanes, aminosilanes, hydroxy silanes, epoxy silanes, (meth) acryloxysilanes, carboxy silanes and silicones substituted with alkoxy functional groups. Specific examples of the silane coupling agent (D) include methyltrimethoxysilane, dimethylmethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, and 3-aminopropyltrimethoxysilane. , Vinyl tris (β-methoxy) silane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, acryloxyalkyl trimethoxysilane, meta Krilloxyalkyl trimethoxysilane, (meth) acryloxyalkyl triethoxysilane, (meth) acryloxyalkyl trichlorosilane, phenyl trichlorosilane, phenyl trimethoxysilane, phenyl triethoxysilane, vinyl trimethoxy Silane, vinyl triethoxysilane, vinyl trichlorosilane, methyl trimethoxysilane, methyltriethoxysilane, propyl trimethoxysilane, propyl triethoxysilane, glycidoxyalkyl trimethoxysilane, glycidoxyalkyl Triethoxysilane, Glee One or more selected from the group consisting of deoxyalkyl trichlorosilane, perfluoroalkyl trialkoxysilane, perfluoromethyl alkyl trialkoxysilane, perfluoroalkyl trichlorosilane and the like can be used. Can be.

In addition, according to the present invention, after the composition is coated on the coated body in the presence of a polymerization initiator, it is possible to form a coating film by thermal curing or photocuring. Preferably, after coating in the presence of a polymerization initiator (photoinitiator), it is photocured by irradiation with ultraviolet (UV) or the like.

At this time, the polymerization initiator may be used as long as it helps to cure, for example, organic peroxide, azo compound, quinone, nitroso compound, acyl halide, hydrazone, mercapto compound, pyrilium compound, imidazole, chlorotri Azine, benzoin, benzoin alkyl ether, diketone, phenone and mixtures thereof can be used. Moreover, benzoin ether, such as benzoin methyl ether and benzoin isopropyl ether; Substituted benzoin ether, such as anisole methyl ether; Substituted acetophenones such as 2,2-diethoxyacetophenone and 2,2-dimethoxy-2-phenylacetophenone; Substituted α-ketols such as 1-hydroxycyclohexyl-phenyl-ketone and 2-methyl-2-hydroxypropiophenone; Aromatic sulfonyl chlorides such as 2-naphthalenesulfonyl chloride; Optically active oximes such as 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime and the like can be used. In addition, the polymerization initiator may use a photoinitiator set forth in US Pat. No. 4,735,632. The polymerization initiator may be included in the composition at 0.1 to 10.0% by weight based on the total weight of the composition to sufficiently satisfy the internal and surface curing of the coating film. In this case, the polymerization initiator (photoinitiator) receives ultraviolet light (UV) to generate free radicals, and then the generated free radicals attack the double bonds of the acrylic monomer (B) having at least one acrylic functional group to double bonds. As it is broken, a crosslinking reaction occurs with the acrylate ester monomer (A), thereby forming a structure having a high density of crosslinking.

In addition, the composition according to the present invention may further optionally include additional components depending on the purpose and use of the product. Additional components include, for example, antioxidants, color pigments and the like.

The composition according to the present invention preferably further comprises a conductive material (E) so that the antistatic performance is improved. The conductive material (E) may be used that is commonly used in this field. The conductive material (E) is a conductive cation-ion conductive material, for example an alkali metal salt which induces an alkali metal cation; Transition metal salts which induce transition metal cations; And a cation conducting organic compound having a boiling point of 120 ° C. or higher having a lone pair electron such as oxygen, nitrogen, sulfur, phosphorus, etc., which can form a ligand for coordinating with them; One or more selected from inorganic salts such as lithium silicate and potassium metasilicate may be used. In this case, the alkali metal salt may be at least one selected from, for example, lithium salt (Li salt), sodium salt (Na salt) and potassium (K salt), and the transition metal salt may be, for example, Fe, Ni, Cu, or Zn. And salts. In addition, examples of the cationic conducting organic compound include carbonate, ketone, sulfone, amide, ether, polyol, nitrile, and nitrile. and organic compounds having nitrite, phosphonate, and acetate groups. These may be used in admixture with polyols such as ethylene glycol, diethylene glycol and the like.

The conductive material (E) may be used by mixing one or more salts selected from quaternary ammonium salts and metal salts with poly (3,4-ethylenedioxythiophene) (eg, Baytron PH, manufactured by Bayer Co.). In this case, the metal salt may be at least one selected from, for example, lithium salt (Li salt), sodium salt (Na salt), potassium (K salt), and the like.

The conductive material (E) is preferably included in 0.1 to 20.0% by weight based on the total weight of the composition. At this time, when the content of the conductive material (E) is less than 0.1% by weight, the antistatic performance improvement effect according to its content is insignificant, and when it exceeds 20.0% by weight, the relatively acrylated ester monomer (A) or acrylic monomer (B) Etc., the content of the coating may decrease, resulting in poor coating properties.

The composition according to the present invention described above is an environmentally friendly paint that can be used without the addition of an organic solvent when used in the form of a solvent, and may be coated on a substrate (coated body), and then formed by coating with heat or photocuring. . Preferably, it can be photocured by irradiating the amount of ultraviolet light of 350-2000mJ / cm <2> on a base material (coated body) in presence of a polymerization initiator (photoinitiator). In addition, if necessary, in consideration of viscosity, an organic solvent may be added and used. In this case, the organic solvent may be uniformly mixed with the organic solvent and then coated on a substrate. Specifically, the composition according to the present invention may further include an organic solvent. At this time, after coating the composition on the substrate, and heat-dried for 1 to 10 minutes at a temperature range of 40 ~ 70 ℃ completely remove the organic solvent in the mixed composition, and then irradiated with a UV light amount of 350 ~ 2000mJ / ㎠ on the substrate The coating coating layer may be formed.

The composition according to the invention from the group consisting of paper release agent, building water repellent agent, waterproof coating agent of fiber, ink, adhesive, anti-fog agent, hard coating agent, photocurable hard coating agent, antistatic coating agent, paint and packaging material (film) in its use. It may be used for the selected purpose, and may be preferably used as an antistatic coating agent.

On the other hand, the coating agent according to the invention the base material (coated body); And a coating layer formed on the substrate (coated body), wherein the coating layer is formed by coating and curing the composition according to the present invention as described above. In this case, the coating method may include, for example, gravure coating, curtain coating, silkscreen coating, roll coating, bar coating, dip coating, flow coating, spray coating, and the like, but is not limited thereto. The coating layer is preferably formed by coating the composition according to the present invention as described above in the presence of a polymerization initiator (photoinitiator) and then cured by ultraviolet irradiation.

In the present invention, the substrate (coated body) may include a plate-like plastic substrate, a glass substrate, but the material and shape thereof are not limited. The substrate (coated body) also includes semifinished and finished products. In addition, the base material (coated body) is a semi-finished product or a finished product, for example, a mobile phone case, a lens, a keypad, a liquid crystal display, a car headlight and a tail light, a display case, a ship's hull, a stereo cover, a furniture, a television screen, an instrument Gauge cover, optical screen, optical filter, reflective sheet keypad, mobile phone window, touch panel, article case, automotive dashboard exterior parts, building materials, soundproof walls, optical materials and cosmetic containers, etc. no.

As described above, according to the present invention, a commercially available acrylated ester monomer (A) is synthesized from the polyol (A1) of Formula 1, and the acrylic monomer (B) is polymerized to the monomer (A) to provide high crosslinking. The coating material which has the outstanding coating-film characteristic (film hardness, adhesive strength, etc.) is provided by synthesize | combining resin of density and disperse | distributing an inorganic oxide (C) through a silane coupling agent (D) here. In addition, the polyol (A1) of the formula (1) is obtained from vegetable oil, a high value-added new material obtained by using the existing resources, it is economical and biodegradable and environmentally friendly. In addition, since N, N-dimethylacrylamide (DMA) and formaldehyde, which are conventionally used, are not used at all, strong toxicity that is harmful to the human body can be eliminated, and the economical unit price can be lowered. Superior to existing products In addition, it has excellent transparency on plastic substrates, does not cause curling, and has antiblocking and dimensional stability. In addition, by further including an ion conductive material (E), the antistatic performance is further improved to obtain an effect of eliminating the sudden electrostatic discharge phenomenon from the insulating object.

Hereinafter, the manufacture example and the Example of this invention are illustrated. The following Preparation Examples and Examples are merely to aid the understanding of the present invention, whereby the technical scope of the present invention is not limited.

[ Production Example  One] - Amberlite ( Amberlite ) refine

100 g of Amberlite (Amberlite) was added to a 250 mL flask having three injection holes (Three-necked), filled with acetic acid (glacial acetic acid) sufficiently to be stirred, and stirred for about 4 to 5 hours. Next, acetic acid was filtered and the filtered amberlite was washed eight times (about 800 mL) with acetone. Thereafter, it was widely spread on a silver foil, followed by expanding the amber light on it and drying at room temperature for about 24 hours.

[ Production Example  2]-of soybean oil Epoxidation  ( Epoxidized Soy - bean Oil )

100 ml soybean oil (0.14 mol), acetic acid (glacial acetic acid, 0.42 mol) 25.2 g, 25 g of amberlite of Preparation Example 1 and 40 g of toluene (three-necked) 500 mL flask Put in. The mixtures were kept constant at 55 ° C. and then slowly added 69 g of 34.5 wt% hydrogen peroxide (H 2 O 2, 0.7 mol) using a dropping funnel and then held at 55 ° C. for 7 hours. After completion of the reaction, the crude product was filtered to remove amberlite and washed several times with distilled water until pH 7.0. The purified product was transferred to a separatory funnel to remove the aqueous layer and residual moisture was removed using sodium sulfate (Na 2 SO 4) in the oil layer. After filtering, toluene was removed in a rotary evaporator at 55 ° C. Yield was around 90%.

[ Production Example  3]- Polyol  synthesis

200g soybean oil (ESBO) epoxidized in Preparation Example 2, 200mL ethylene glycol (ethylene glycol), 20mL distilled water (water), 500mL isopropanol (isopropanol), 8g tetrafluoroboric acid (HBF4 (aq), 48% 8g) was added and maintained at 50 ° C for 1 hour. The hydroxyl group was controlled by the amount of tetrafluoroboric acid. After 1 hour, the reaction was terminated by dropping ammonia (ammonia, 30% in water). When the pH became neutral, no more ammonia was added. The product was then removed with isopropanol using a 50 ° C. rotary evaporator and transferred to a separatory funnel. Notice the two layers were separated, the water layer was removed and the oil layer was filtered out. Subsequently, toluene was added and dissolved in the oil layer, and then residual water was removed using sodium sulfate (Na 2 SO 4), and then toluene was removed using a rotary evaporator at 55 ° C. As a remaining yellow viscous oil, a polyol of Formula 1 was obtained.

[ Production Example  4] - Acrylated Ester Monomer  synthesis

After dissolving the polyol obtained in Preparation Example 3 in toluene, methacryloyl chloride and potassium carbonate were added in the same equivalent ratio as the polyol and reacted at a temperature of 80 ℃ for 20 hours. The reaction was filtered through celite to remove inorganics and then solvent to obtain multiple acrylated monomers.

[ Production Example  5]-photocurable composition

38% by weight of the multi-acrylate ester monomer obtained in Preparation Example 4, 21% by weight of polyethylene glycol diacrylate, 30% by weight of aqueous silica sol (AS-40, Grace. Co.) as an inorganic oxide , 3 wt% of lithium silica sol (LS-L100, Yeongilsung Co., Ltd.), 8 wt% of silane compound (3-methacrylocxa propyltrimethoxy silane, DOW Corning Co.) as a silane coupling agent The reaction was completed while removing water and methanol to prepare a photocurable hard coating composition.

[ Production Example  6]- Li Alkali  Manufacture of Antistatic Agent Using Metal Salt

In a reactor with a cooling device, 4 wt% of LiClO4 is added first, and then 30 wt% of poly (oxy-1,2-ethanediyl) and polyethylene glycol diacrylate 44 wt% polyethyleneglycol diacrylate), 12 wt% 2-Ethoxy ethanol and 10 wt% N-methyl pyrrolidone (NMP) were added, and then the reactor was kept at 70 DEG C for 24 hours. Stir while mixing. Thereafter, the mixture was cooled to 50 ° C. and vacuum-reduced for about 1 hour, followed by cooling at room temperature, thereby preparing a Li-antistatic hard coating solution of a colorless transparent liquid solution.

[ Production Example  7]- Na Alkali  Manufacture of Antistatic Agent Using Metal Salt

4 wt% NaClO4 is added first to the reactor with cooling device, and then 30 wt% poly (oxy-1,2-ethanediyl), polyethylene glycol diacrylate 44% by weight of polyethyleneglycol diacrylate), 12% by weight of 2-Ethoxy ethanol and 10% by weight of N-methyl pyrrolidone (NMP) were added, and then the reactor temperature was maintained at 70 ° C for 24 hours. Stir while mixing. Thereafter, the mixture was cooled to 50 ° C., and vacuum-reduced for about 1 hour, followed by cooling at room temperature, thereby preparing a Na-antistatic hard coating solution of a colorless transparent liquid solution.

[ Example  1]-Preparation of photocurable antistatic composition and specimen

20 wt% of the photocurable composition prepared in Preparation Example 5, 10 wt% of the Li-antistatic agent prepared in Preparation Example 6, 5 wt% of the photocuring agent (Igacure 184, Ciba Geigy Co.), an organic solvent (ethyl acetate 20 Wt%, 15% by weight of methyl cellosolve, 20% by weight of methyl isobutyl ketone, 10% by weight of isobutyl alcohol) was added to prepare a photocurable antistatic hard coating composition.

After coating the photocurable antistatic hard coating composition prepared as described above on a polycarbonate (PC) plastic substrate by flow coating method, and heat-dried at 60 ℃ for 2 minutes to remove the solvent in the coating composition, and then a high-pressure mercury lamp ( The antistatic coating sheet (sample) was manufactured by irradiating an ultraviolet-ray of 700 mJ / cm <3> light quantity using the litzen Co., Ltd. product).

The surface resistance of the antistatic sheet prepared in accordance with the present Example was measured at 60% RH, 25 ° C., and applied voltage of 500V according to ASTM D257. As a result, 3 × 10 ¹⁰ Ω / sq was obtained. , The film hardness was measured by pencil hardness method (ASTM D3502) HB, the light transmittance was 90.8% in the visible light (550nm) region using a UV photometer (Simazu Co.). And Haze didn't happen. The above results are shown in the following [Table 1].

[ Example  2]-Preparation of photocurable antistatic composition and specimen

20 wt% of the photocurable composition prepared in Preparation Example 5, 10 wt% of the Na-antistatic agent prepared in Preparation Example 7, 5 wt% of the photocuring agent (Igacure 184, Ciba Geigy Co.), organic solvent (ethyl acetate 20 Wt%, 15% by weight of methyl cellosolve, 20% by weight of methyl isobutyl ketone, 10% by weight of isobutyl alcohol) was added to prepare a photocurable antistatic hard coating composition.

After coating the photocurable antistatic hard coating composition prepared as described above on a polycarbonate (PC) plastic substrate by flow coating method, and heat-dried at 60 ℃ for 2 minutes to remove the solvent in the coating composition, and then a high-pressure mercury lamp ( The antistatic coating sheet (sample) was manufactured by irradiating an ultraviolet-ray of 700 mJ / cm <3> light quantity using the litzen Co., Ltd. product).

The surface resistance of the antistatic sheet prepared in accordance with the present Example was measured at 60% RH, 25 ° C., and applied voltage of 500V according to ASTM D257. As a result, it was 7 × 10 ¹⁰ Ω / sq. , The film hardness was measured by pencil hardness method (ASTM D3502) HB, the light transmittance was 90.1% in the visible light (550nm) region using a UV photometer (Simazu Co.). And some Haze occurred. The above results are shown in the following [Table 1].

[ Example  3]-photocurable antistatic composition and specimen preparation

30 wt% of the photocurable composition prepared in Preparation Example 5, 5 wt% of a photocuring agent (Igacure 184, Ciba Geigy Co.), an organic solvent (20 wt% of ethyl acetate, 15 wt% of methyl cellosolve, methyl isobutyl ketone 20 wt%, isobutyl alcohol 10 wt%) 65 wt% was added to prepare a photocurable antistatic hard coating composition.

After coating the photocurable antistatic hard coating composition prepared as described above on a polycarbonate (PC) plastic substrate by flow coating method, and heat-dried at 60 ℃ for 2 minutes to remove the solvent in the coating composition, and then a high-pressure mercury lamp ( The antistatic coating sheet (sample) was manufactured by irradiating an ultraviolet-ray of 700 mJ / cm <3> light quantity using the litzen Co., Ltd. product).

The surface resistance of the antistatic sheet prepared according to the present Example was measured under conditions of 60% RH, 25 ° C., and an applied voltage of 500 V based on the ASTM D257 measuring method, and showed 9 × 10 ¹¹ Ω / sq. Was measured by the pencil hardness method (ASTM D3502) H, the light transmittance was 91% in the visible light (550nm) region using a UV photometer (Simazu Co.). And Haze didn't happen. The above results are shown in the following [Table 1].

[ Example  4]-Preparation of photocurable antistatic composition and specimen

25 wt% of the photocurable composition prepared in Preparation Example 5 5 wt% of a photocuring agent (Igacure 184, Ciba Geigy Co.), water-soluble poly (3,4-ethylenedioxythiophene) (Baytron PH, Bayer Co.) 7 Weight%, organic solvent (ethanol 12.7%, methyl cellosolve 20%, isopropanol 30%) 62.7% by weight, other slip agent (DOWCORNING PA-57, PA-67) by adding 0.3% by weight Prominent photocurable antistatic hard coating compositions were prepared.

After coating the photocurable antistatic hard coating composition prepared as described above on a polycarbonate (PC) plastic substrate by flow coating method, and heat-dried at 60 ℃ for 2 minutes to remove the solvent in the coating composition, and then a high-pressure mercury lamp ( The antistatic coating sheet (sample) was manufactured by irradiating an ultraviolet-ray of 700 mJ / cm <3> light quantity using the litzen Co., Ltd. product).

The surface resistance of the antistatic sheet prepared in accordance with the present Example was measured at 60% RH, 25 ° C., and an applied voltage of 500V according to ASTM D257. As a result, it was 6 × 10 ⁷ Ω / sq. , The film hardness was measured by pencil hardness method (ASTM D3502) HB, the light transmittance was measured at 86.5% in the visible light (550nm) region using a UV photometer (Simazu Co.). And some Haze occurred. The above results are shown in the following [Table 1].

[ Comparative example  One] - Li  Antistatic Coating Specimen Preparation

The Li-antistatic agent hard coating solution prepared in Preparation Example 6 was coated on a polycarbonate (PC) plastic substrate by a flow coating method, and then thermally cured to prepare a Li-antistatic coating sheet (sample).

The surface resistance of the antistatic sheet prepared in accordance with the present comparative example was 5 x 10 ⁹ Ω / sq as measured by 60% RH, 25 ° C, and applied voltage 500V according to ASTM D257. , The film hardness was measured by pencil hardness method (ASTM D3502) B, the light transmittance was 88.7% in the visible light (550nm) region using a UV photometer (Simazu Co.). And some Haze occurred. The above results are shown in the following [Table 1].

 [ Comparative example  2] - Na  Antistatic Coating Specimen Preparation

The Na-antistatic agent hard coating solution prepared in Preparation Example 7 was coated on a polycarbonate (PC) plastic substrate by a flow coating method, and then thermally cured to prepare a Na-antistatic coating sheet (sample).

The surface resistance of the antistatic sheet (sample) prepared according to this comparative example was 6 x 10 ⁹ Ω / sq as measured by 60% RH, 25 ° C, and applied voltage 500V according to ASTM D257. The film hardness was measured by pencil hardness method (ASTM D3502) B, and the light transmittance was measured at 86.4% in the visible light (550 nm) region using a UV photometer (Simazu Co.). And some Haze occurred. The above results are shown in the following [Table 1].

< Experimental Example  1: Adhesion Strength Test>

Adhesive strength was tested for the Examples 1 to 4 and the antistatic coating sheets (samples) prepared according to Comparative Examples 1 and 2. Adhesive strength was measured using a cross-cut test method. After cutting the coating surface at 1 mm intervals, a 3M Scotch tape having a width of about 2 cm was attached to the coating surface. (I left it at some 90 degrees to the surface). After standing for 1 minute, the remaining portion was pulled vertically and the extent of the coating surface remained on the sheet was observed. The results are shown in the following [Table 1].

< Experimental Example  2 : Content  Test>

Examples 1 to 4 and the antistatic coating sheets (samples) prepared according to Comparative Examples 1 and 2 were respectively immersed in toluene, acetone, methyl ethyl ketone, methanol and isopropyl alcohol at room temperature for 48 hours. The physical properties of the coating film were evaluated. The results are shown in the following [Table 1].

Item
Example 1
Example 2
Example 3
Example 4
Comparative Example 1
Comparative Example 2
Light transmittance (T%)
90.8
90.1
91
86.5
88.7
86.4
Surface resistance
(Ω / sq)
3 x 10 ¹⁰
7 x 10 ¹⁰
9 x 10 ¹¹
6 x 10 ⁷
5 x 10 ⁹
6 x 10 ⁹
Haze
0.8
1.2
0.6
2.1
2.1
2.1
Pencil hardness
HB
HB
H
HB
B
B
Adhesive strength
100/100
100/100
100/100
100/100
100/98
100/98
Solvent resistance
clear
clear
clear
clear
clear
clear

As shown in Table 1, the photocurable composition (Preparation Example 5) according to the present invention was found to be excellently evaluated in mechanical properties (pencil hardness and adhesive strength), chemical resistance (solvent resistance) and light transmittance. . In particular, when used in combination with an antistatic agent containing a metal salt (Li salt, Na salt) as in Examples 1 and 2, it was possible to obtain a hard coating composition excellent in antistatic properties and excellent optical properties and excellent mechanical properties.

Claims (18)

An acrylate ester monomer (A) synthesized from a polyol (A1) and an acrylic monomer (A2) represented by the following [Formula 1]; An acrylic monomer (B) polymerized with the acrylic ester monomer (A); Inorganic oxides (C); And An antistatic coating composition comprising a silane coupling agent (D). [Formula 1]

(In Formula 1, R is hydrogen or (CH2) n-OH (n is an integer from 1 to 20); (CH2) n-SH (n is an integer from 1 to 20); Or allyl alcohol, vinyl alcohol, alkyl alcohol, alkenyl alcohol, alkynyl alcohol, aromatic alcohol and thiol containing C1 to C20 and containing 1 to 10 O, N and S in the molecule. Hydrocarbon selected from the group) The method of claim 1, Polyol (A1) represented by the formula (1) is an antistatic coating composition, characterized in that obtained from vegetable oil. delete The method of claim 1, The acrylic monomer (A2) for synthesizing the acrylic ester monomer (A) is at least one selected from methacryloyl chloride (methacryloyl chloride), acrylic acid (acrylic acid) and acrylate (acrylate) Prevention coating composition. The method of claim 1, The acrylic monomer (B) polymerized with the acrylic acid ester monomer (A) is di-propylene glycol diacrylate, poly (oxy-1,2-ethenediel) (poly (oxy-1,2-ethanediyl)) , Di-trimethylolpropane tetraacrylate, polyethyleneglycol diacrylate (PEGDA), bisphenol A-ethyleneglycol diacrylate (BPEGDA), 1,6-hexane Diol-diacrylate (HDDA), tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), ethoxylate pentaerythritol tetraacrylate (PPTTA), pentaerythritol triacrylate (PETA), dipentaerythritol pentaacrylate (DPPA), dipentaerythritol hexaacrylate (DPHA), di-trimethylolpropane triacrylate (DI-TMPTA), butanediol diacryl Antistatic coating, characterized in that any one selected from the group consisting of latex (BUDA), triethylene glycol diacrylate (TEGDA), neopentyl glycol diacrylate (NPGDA), polyethylene glycol diacrylate and urethane-acrylate Composition. The method of claim 1, The inorganic oxide (C) is an antistatic coating composition, characterized in that at least one selected from the group consisting of silica (SiO2), titanium dioxide (TiO2), alumina (Al2O3), antimony oxide (SbO2) and tin oxide (SnO2). The method of claim 1, The silane coupling agent (D) is methyltrimethoxysilane, dimethylmethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltrimethoxysilane, vinyltris (β) -Methoxy) silane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, acryloxyalkyl trimethoxysilane, methacryloxyalkyl trimeth Methoxysilane, (meth) acryloxyalkyl triethoxysilane, (meth) acryloxyalkyl trichlorosilane, phenyl trichlorosilane, phenyl trimethoxysilane, phenyl triethoxysilane, vinyl trimethoxysilane, vinyl trie Methoxysilane, vinyl trichlorosilane, methyl trimethoxysilane, methyltriethoxysilane, propyl trimethoxysilane, propyl triethoxysilane, glycidoxyalkyl trimethoxysilane, glycidoxyalkyltriethoxysilane, Glysidoxyalkyl Trickle A silane, perfluoro alkyl trialkoxysilane, perfluoroalkyl methyl alkyltrialkoxysilane and antistatic coating composition, characterized in that at least one selected from the group of silanes with alkyl trichloro perfluoroalkyl. The method of claim 1, The composition is 2.0 to 90.0% by weight of the acrylic ester monomer (A); 5.0-70.0 weight% of an acrylic monomer (B); Inorganic oxides (C) 2.0 to 60.0% by weight; And a silane coupling agent (D) of 0.2 to 30.0 wt%. The method of claim 1, The composition is an antistatic coating composition further comprises a conductive material (E) for improving the antistatic performance. The method of claim 8, The composition is an antistatic coating composition, characterized in that it further comprises 0.1 to 20.0% by weight of the conductive material (E) for improving the antistatic performance. 10. The method of claim 9, The conductive material (E) is an antistatic coating composition, characterized in that at least one selected from alkali metal salts and transition metal salts. The method of claim 11, The alkali metal salt is an antistatic coating composition, characterized in that at least one selected from Na salt, Li salt and K salt. 10. The method of claim 9, The conductive material (E) is an antistatic coating composition comprising at least one salt selected from quaternary ammonium salts and metal salts and poly (3,4-ethylenedioxythiophene). The method of claim 13, The metal salt is an antistatic coating composition, characterized in that at least one selected from Na salt, Li salt and K salt. materials; And a coating layer formed on the substrate, The coating layer is an antistatic coating agent, characterized in that formed by coating, curing the composition according to any one of claims 1, 2 and 4 to 14. The method of claim 15, The coating layer is an antistatic coating, characterized in that formed after the composition is coated on the substrate and cured by ultraviolet irradiation. The method of claim 16, The coating layer is an antistatic coating, characterized in that cured by irradiation of 350 ~ 2000mJ / ㎠ ultraviolet light. The method of claim 16, The coating layer is coated with a composition further comprising an organic solvent, and then heat-dried at 40 to 70 ° C. for 1 to 10 minutes to remove the organic solvent, and then cured by irradiation of 350 to 2000 mJ / cm 2 ultraviolet rays. An antistatic coating agent.