KR101368223B1 - UV curable coating composition for LCD tempered glass - Google Patents

Abstract

The present invention relates to an ultraviolet curable coating liquid composition for LCD tempered glass, comprising a binder resin, a polymerizable compound, a photoinitiator, and a solvent, and has a technical feature. The curing time can be shortened compared to a thermal curing method, and adhesive strength is increased. It is excellent in that it is not easily separated from the glass during waterjet cutting, is not pushed by the water pressure by brittle, there is an advantage that it is easy to peel off from the glass after waterjet cutting.

Description

UV curable coating composition for LCD tempered glass

The present invention relates to a UV-curable coating liquid composition for LCD tempered glass, and more particularly, UV-curable coating liquid for urethane acrylic LCD tempered glass that is not only easy to remove after processing the LCD glass but also excellent in adhesion during processing. It relates to a composition.

The use of glass for LCD manufacture requires a very clean glass surface that is substantially dust free and free of other organic or inorganic contaminants. Upon exposure to the environment, the glass surface is very quickly contaminated with dust and inorganic or organic air pollutants, which are observed in several hours.

Small pieces of glass are often created in current processes used to cut and grind glass surfaces and edges. These pieces range in size from about 1 to 100 microns. Some of these particles adhere to irreversibly clean glass surfaces, making glass used in many applications obsolete. This is a serious problem for the LCD glass surface.

LCD glass is manufactured in a melt draw process that creates a flat and smooth glass surface. The glass sheet is cut to an appropriate size and then the edges are ground. If water is actively included between the glass piece and the surface produced during the cutting and grinding step, permanent chemical bonding occurs, causing the glass piece to irreversibly adhere to the surface.

As a method of protecting the LCD glass sheet surface, preliminary polymer films are applied to all major glass surfaces to protect the glass during scoring, breaking and beveling processes. In a conventional method, one major surface has a polymer film attached with an adhesive and the other major surface has a film attached statically. The first film is removed when the edge finish of the sheet is completed, while the second film is removed before the finishing process. Although the adhesively attached film can protect the surface from scratching by the work tool, it presents another problem. The problem with this film is that adhesive residue remains on the glass surface. Another problem with these films is that the glass breaks while peeling off the film from the glass surface, especially large and thin glass sheets.

Many polymer coatings, such as polyvinyl alcohol, provide particle protection and scratch resistance. However, only a few of these can be completely removed with the wash solution at temperatures below 40 ° C. during conventional manufacturing processes. In particular, a method for temporary protection of a glass surface, such as an LCD glass surface, may be achieved by applying an aqueous polysaccharide solution to the glass surface, removing water from the solution to form a polysaccharide protective coating on the glass surface, and revealing the protective surface. When the aqueous solution is used to substantially remove the polysaccharide-containing coating from the glass surface. However, the method is defective due to the high water solubility of polysaccharides, especially starch. Prior to the cleaning step, the glass sheet is generally subjected to finishing steps such as cutting and edge grinding, where water may be used as the coolant. Therefore, due to their high water solubility, the polysaccharide coating can be reduced during this same step, and particle protection and scratch resistance are reduced.

A suitable property for temporary protective coatings for the surface of LCD glass is removable. LCD manufacturers use glass as a starting point for complex manufacturing processes for forming semiconductors, for example thin film transistors, on glass substrates. In order not to adversely affect this process, all protective coatings on the glass surface must be easily removed prior to the start of the LCD manufacturing process without substantially changing the chemical and physical properties of the glass surface.

Thus, there is a need for an improved method that can temporarily protect glass surfaces for LCD manufacturing from air pollutants, contaminants generated during glass processing or scratching using coating systems. The coating system should be easy to remove and there should be no residue present on the glass surface upon removal, and should be able to be restored to a substantially clean, uncoated surface for subsequent use of the glass, such as in LCD manufacturing.

Republic of Korea Patent Publication No. 10-2002-0085841 (2002.11.16.) Discloses a removable coating for LCD glass.

The coating has an advantage that it is easy to remove after processing the LCD glass, but there is a problem that the adhesion to the glass is insufficient to separate from the glass during processing.

Accordingly, the present inventors have developed a UV curable coating liquid composition for urethane acrylic LCD tempered glass that is not only easy to remove after processing the LCD glass but also excellent in adhesion during processing.

KR 10-2002-0085841 A 2002.11.16.

It is an object of the present invention to provide a UV curable coating liquid composition for urethane acrylic LCD tempered glass that is not only easy to remove after processing the LCD glass but also excellent in adhesion during processing.

In order to achieve the above object, the present invention provides the following means.

The present invention is characterized in that it comprises 15 to 40 mol% of monomers containing acid groups, 15 to 25 mol% of monomers containing hydroxy groups, 20 to 30 mol% of aromatic vinyl monomers and 20 to 30 wt% of aliphatic vinyl monomers. Provide binder resin.

The monomer containing an acid group is a compound selected from the group consisting of (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmalinic acid, isoprenesulfonic acid, styrenesulfonic acid and 5-norbornene-2-carboxylic acid It is characterized by that.

Monomers containing the hydroxy group include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, and 4-hydroxybutyl (meth). ) Acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylic It is characterized in that the compound selected from the group consisting of latex and butyl α-hydroxymethyl acrylate.

The aromatic vinyl monomer is characterized in that the compound selected from the group consisting of styrene, chlorostyrene, α-methyl styrene, vinyl toluene.

The aliphatic vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydroperpril ( Meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , Acyl octyloxy 02-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylic Late, methock Triethylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonyl phenoxy polyethylene glycol (meth) Acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octa It is characterized in that the compound selected from the group consisting of fluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, and tribromophenyl (meth) acrylate.

The weight average molecular weight of the binder resin is 5,000 ~ 100,000, characterized in that the acid value is 70 ~ 140 KOHmg / g.

In addition, the present invention comprises the steps of reacting a monomer having a hydroxy group and a diisocyanate compound to prepare a monomer having a urethane and an isocyanate group at the same time; It provides a binder resin comprising a; and copolymerizing by adding a monomer containing an acid group and an aliphatic or aromatic vinyl monomer to the monomer having a urethane group and an isocyanate group at the same time.

Monomers having the hydroxy group include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, and 4-hydroxybutyl (meth). Acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylate And it is characterized in that the compound selected from the group consisting of butyl α-hydroxymethyl acrylate.

The diisocyanate compound is 2,6-toylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1 , 3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, w, w'-diisocyanate-1.3-dimethylbenzene, w, w'-diisocyanate-1,4- Dimethylbenzene, w, w'-diisocyanate-1.3-diethylbenzene, 1.4-tetramethyl xylene diisocyanate, 1.3-tetramethyl xylene diisocyanate, isophorone diisocyanate, 1.3-cyclopentane diisocyanate, 1.3-cyclohexanedi Isocyanates, 1.4-cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexane diisocyanate Consisting of soocyanate, 4,4'-methylene bis isocyanate methylcyclohexane, 2,5-isocyanatemethyl bicyclo [2,2,2] heptane and 2,6-isocyanatemethyl bicyclo [2,2,1] heptane It is characterized by one or more selected from the group.

The monomer containing an acid group is 1 selected from the group consisting of (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmalinic acid, isoprenesulfonic acid, styrenesulfonic acid and 5-norbornene-2-carboxylic acid. It is characterized by more than one species.

The aromatic vinyl monomer is characterized in that the compound selected from the group consisting of styrene, chlorostyrene, α-methyl styrene, vinyl toluene.

The aliphatic vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydroperpril ( Meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , Acyl octyloxy 02-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylic Late, methock Triethylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonyl phenoxy polyethylene glycol (meth) Acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octa It is characterized in that the compound selected from the group consisting of fluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, and tribromophenyl (meth) acrylate.

The reaction is characterized in that it is carried out by radical polymerization.

In addition, the present invention, 83% by weight binder resin, 13% by weight polymerizable compound, 2% by weight photopolymerization initiator, 0.25% by weight silane epoxy compound, 0.25% by weight thermal polymerization inhibitor, 0.5% by weight leveling agent and 1% by weight solvent It provides a UV curable coating liquid composition for LCD tempered glass comprising a.

The polymerizable compound may be polyethylene glycol mono (meth) acrylate, polypropylrel glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylglycol (meth) acrylate, polypropylene glycol (meth) acryl Rate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol (meth) acrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol penta At least one member selected from the group consisting of acrylate and dipentaerythritol hexaacrylate.

The photopolymerization initiator is a triazine compound; Biimidazole compounds; Acetophenone compounds; O-acyl oxime compound; Benzophenone compounds; Fluorenone compounds; Thioxanthone type compounds; Xanthone compounds; Anthraquinone compounds; Acridine-based compounds; Dicarbonyl compounds; Phosphine oxide compounds; Amine synergy; Coumarin compound; Chalcone compound; It is characterized by one or more selected from the group consisting of 2-benzoylmethylene and 3-methyl-β-naphthothiazoline.

The solvent is acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethyl glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether , Propylene glycol diethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1, -trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloroethane , 1,2,3-trichloropropane, hexane, heptane, octane, cyclopentane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, propylene glycol monomethyl ether, propyl Reel glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol monomethyl ether, methyl carbitol , Ethyl carbitol, propyl carbitol, butyl carbitol, cyclopentanone, cyclohexanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol methyl ether propionate, 3-methoxybutyl acetate, 3- At least one member selected from the group consisting of methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propyl acetate and ethyl acetate.

The UV curable coating liquid composition for LCD tempered glass according to the present invention can shorten the curing time compared to the thermosetting method, has excellent adhesion and is not easily separated from the glass during waterjet cutting, brittle and not pushed by water pressure, waterjet cutting There is an advantage that it is easy to peel off from the glass after.

Hereinafter, the present invention will be described in detail.

The LCD glass processing process consists of laminating 10 or more sheets of glass to be used for LCD, cutting the laminated glass to a desired size and shape by a water jet method, and reinforcing the cut glass through a strengthening process.

Polymer coatings are used to protect the glass from cross-cutting during the lamination process for 10 or more sheets of glass to be cut to the desired size, cracking of the edges during the cutting process, and surface damage caused by broken glass fragments.

Conventionally, thermosetting resin is used as a polymer coating for LCD glass protection. The thermosetting method takes a few minutes to several ten minutes to apply heat after application of a coating solution. Curing is possible within 1 minute.

The important physical properties of the coating liquid used to temporarily protect the LCD glass are excellent adhesion and should not be easily separated from the glass during processing, and should be easily removed from the glass after processing.

The present invention is characterized by providing a UV-curable coating solution that can be easily removed from the glass after the processing is not easily separated from the glass because of excellent adhesion during the LCD glass processing.

The UV curable coating liquid composition for LCD tempered glass according to the present invention comprises 75 to 90% by weight of the binder resin, 5 to 25% by weight of the polymerizable compound, 0.5 to 4% by weight of the photopolymerization initiator and 0.1 to 1% by weight of the solvent.

First, the manufacturing method of binder resin is demonstrated.

Method for producing a binder resin of the present invention comprises the steps of reacting a monomer having a hydroxy group and a diisocyanate compound to prepare a monomer having a urethane and an isocyanate group at the same time; And copolymerizing the monomer including an acid group and an aliphatic or aromatic vinyl monomer to the monomer having the urethane group and the isocyanate group at the same time.

The monomer containing a hydroxy group used in the first step is hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl It is preferable to use one or more compounds selected from the group consisting of α-hydroxymethyl acrylate and butyl α-hydroxymethyl acrylate, but is not limited thereto.

In addition, specific examples of the diisocyanate compound include 2,6-toylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3 -Butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate, w, w'- diisocyanate-1.3-dimethylbenzene, w, w'-di Isocyanate-1,4-dimethylbenzene, w, w'-diisocyanate-1.3-diethylbenzene, 1.4-tetramethyl xylene diisocyanate, 1.3-tetramethyl xylene diisocyanate, isophorone diisocyanate, 1.3-cyclopentane diisocyanate , 1.3-cyclohexanediisocyanate, 1.4-cyclohexanediisocyanate, methyl-2,4-cyclohexanediisocyanate, methy -2,6-cyclohexane diisocyanate, 4,4'-methylene bis isocyanate methylcyclohexane, 2,5-isocyanatemethyl bicyclo [2,2,2] heptane and 2,6-isocyanatemethyl bicyclo [2, 2,1] heptane, but is not limited thereto.

In the first step, when the monomer including the hydroxy group and the diisocyanate compound are reacted for 1 to 5 hours at a temperature of 24 to 60 ° C. under an organic solvent, a monomer containing a urethane and an isocyanate group can be obtained at the same time.

It is preferable that the reaction equivalent ratio of the monomer containing the said hydroxyl group and a diisocyanate compound is 1.0: 1.0-1.0: 1.2.

Next, the second step is prepared by adding a monomer containing an acid functioal group, a monomer containing hydroxy, and a solution copolymerizing aliphatic or aromatic vinyl monomers to the monomer containing the urethane and isocyanate groups simultaneously. do.

Specifically, a copolymer solution is prepared by mixing and reacting a monomer containing an acid group, a monomer containing a hydroxyl group, and an aliphatic or aromatic vinyl monomer under a thermal initiator, and then simultaneously containing the urethane and isocyanate groups. The monomer is added and then reacted until the isocyanate group disappears completely.

The monomer containing an acid group is selected from the group consisting of (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmalinic acid, isoprenesulfonic acid, styrenesulfonic acid and 5-norbornene-2-carboxylic acid. Compound.

Moreover, as a monomer containing a hydroxyl group, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3- chloropropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxy Compound selected from the group consisting of methyl acrylate and butyl α-hydroxymethyl acrylate.

In addition, the aromatic vinyl monomers are compounds selected from the group consisting of styrene, chlorostyrene, α-methyl styrene and vinyltoluene.

In addition, examples of the aliphatic vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and isobutyl (Meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate , Tetrahydroperpril (meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxy Butyl (meth) acrylate, acyl octyloxy 02-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydi Ethylene Glycol (Meta) Acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxy Polyethylene glycol (meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth ) Acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, and tribromophenyl (meth) acrylate.

The reaction may be prepared by any one of a variety of polymerization methods known in the art, such as radical polymerization, cationic polymerization, anionic polymerization, condensation polymerization, etc., but it is most preferable to use radical polymerization in view of ease of production and economical efficiency. desirable.

For example, the monomer may be prepared by mixing with a polymerization solvent and heating to an appropriate temperature, followed by removal of oxygen through nitrogen purging. Further, it can be prepared preferably by adding a radical polymerization initiator and a chain transfer agent as necessary and maintaining the polymerization temperature. In the above method, the polymerization temperature and the polymerization time can be determined in consideration of the half life period of the polymerization initiator to be used depending on the temperature.

For example, since the half life of 2,2'- azobisisobutyronitrile (AIBN) at 70 ° C is 4.8 hours, the polymerization time when using this is preferably 6 hours or more. In general, the polymerization temperature is preferably between 50 and 150 ° C, and the polymerization time is preferably between 30 minutes and 48 hours.

The said binder resin can be used individually or in mixture of 2 or more types.

The chain tranfer agent is for controlling the weight average molecular weight, specific examples are n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid , 3-mercaptopropionic acid, a-methylstyrene dimer, and the like, but are not limited thereto, and those known in the art may be used.

The present invention also provides a UV curable coating liquid composition for LCD tempered glass containing the binder resin, a polymerizable compound, a photopolymerization initiator and a solvent.

The binder resin used in the composition of the present invention has an acid value of about 70 ~ 140KOH mg / g, preferably a weight average molecular weight of 5,000 ~ 100,000, more preferably in the range of 8,000 ~ 50,000.

The binder resin may be used alone or in combination of two or more, the content is preferably 75 to 90% by weight of the total coating liquid composition. If it is less than 75% by weight, the adhesion of the formed film is inferior, and if it exceeds 90% by weight, there is a disadvantage in that peeling is difficult in a later step.

The functional monomer which has the said ethylenically unsaturated double bond can be used individually or in mixture of 2 or more types.

Specific examples of the functional monomer having an ethylenically unsaturated bond include polyethylene glycol mono (meth) acrylate, polypropylrel glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, and polyethyl glycol (meth). Acrylate, polypropylene glycol (meth) acrylate, trimethylol ethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol (meth) acrylate, pentaerythritol tetraacrylate, pentaeryte At least one selected from the group consisting of lititol triacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.

More specifically, the functional monomers in which caprolactone is introduced include KAYARAD DPCA-20, KAYARAD DPCA-3, and KAYARAD DPCA-12- in the form of dipentaerythritol, and are introduced into tetrahydrofurfuryl acrylate. KAYARAD TC-110S, KAYARAD HX-220 and KAYARAD HK-620 introduced in neopentylglycol hydroxypivalate.

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The solvent used in the composition of the present invention is to dissolve other components in order to provide coating properties to the coating liquid composition, the viscosity can be adjusted according to the amount used. Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethyl glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl Ether, propylene glycol diethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1, -trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloro Ten, 1,2,3-trichloropropane, hexane, heptane, octane, cyclopentane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, propylene glycol monomethyl ether, Propyl glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol monomethyl ether, methyl carby Tol, ethyl carbitol, propyl carbitol, butyl carbitol, cyclopentanone, cyclohexanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol methyl ether propionate, 3-methoxybutyl acetate, 3 Single or two or more selected from the group consisting of -methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propyl acetate and ethyl acetate Can be mixed and used.

The photopolymerization initiator used in the coating liquid composition of the present invention is a compound capable of generating a photopolymerization reaction by absorbing light upon irradiation of light such as UV and generating radical active species by a photochemical reaction.

Examples of photopolymerization initiators include 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine, 2 , 4-trichloromethyl- (pipelonyl) -6-triazine, 2,4-trichloromethyl- (3 ', 4'-dimethoxyphenyl) -6-triazine and 3- {4- [2 Triazine compound selected from the group consisting of, 4-bis (trichloromethyl) -s-triazin-6-yl] phenylthio} propanoic acid; 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl biimidazole, and 2,2'-bis (2,3-dichlorophenyl) -4,4', Biimidazole compounds selected from the group consisting of 5,5'-tetraphenylbiimidazole; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxy Methoxy) -phenyl (2-hydroxy) propyl ketone, 1-hydroxycyclohexylphenyl ketone, benzoinmethyl ether, benzoinethyl ether, benzoin isobutyl ether, benzoinbutyl ether, 2,2-dimethoxy- 2-phenyl acetophenone, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one, and 2-benzyl-2-dimethylamino-1- (4-morpholino Acetophenone compounds selected from the group consisting of phenyl) -butan-1-one; O-acyl oxime compounds selected from the group consisting of Irgacure OXE 01 and Irgacure OXE 02 from Ciba Geigy; Benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2,4,6-trimethylamino benzophenone, methyl-o-benzoylbezoate, 3 Benzophenone compounds selected from the group consisting of, 3'-dimethyl-4-methoxybenzophenone and 3,3 ', 4,4'-tetra (t-butylpooxycarbonyl) benzophenone; Fluorenone compounds selected from the group consisting of 9- fluorenone, 2-chloro-9- fluorenone and 2-methyl-9- fluorenone; Thioxanthone, 2,4-diethyl thioxanthone, 2-chloro thioxanthone, 1-chloro-4-propyloxy thioxanthone, isopropyl thioxanthone and diisopropyl thioxanthone Thioxanthone type compounds; Xanthone compounds such as xanthone or 2-methylxanthone; Anthraquinone compounds selected from the group consisting of anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, t-butyl anthraquinone, and 2,6-dichloro-9,10-anthraquinone; Consisting of 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) pentane and 1,3-bis (9-acridinyl) propane Acridine-based compounds selected from the group; Dicarbonyl compounds selected from the group consisting of benzyl, 1,7,7-trimethyl-bisclo [2,2,1] heptan-2,3-dione and 9,10-phenanthrenquinone; 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4, -trimethylpentyl phosphine oxide, and bis (2,6-dichlorobenzoyl) propyl force Phosphine oxide compounds selected from the group consisting of pin oxides; Methyl 4- (dimethylamino) benzoate, ethyl-4 (dimethylamino) benzoate, 2-n-butoxyethyl 4- (dimethylamino) benzoate, 2,5-bis (4-diethylaminobenzal) cyclo Amine synergists selected from the group consisting of pentanone, 2,6-bis (4-diethylaminobenzal) cyclohexanone and 2,6-bis (4-diethylaminobenzal) -4-methyl-cyclohexanone ; 3,3'-carbonylvinyl-7- (diethylamino) coumarin, 3- (2-benzothiazolyl) -7- (diethylamino) coumarin, 3-benzoyl-7- (diethylamino) coumarin, 3-benzoyl-7-methoxy-coumarin and 10,10'-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H-Cl] Coumarin-based compounds selected from the group consisting of -benzopyrano [6,7,8-ij] -quinolizin-11-one; Chalcone compounds, such as 4-diethylaminochalcone and 4-azidebenzalacetophenone; One or more kinds selected from the group consisting of 2-benzoylmethylene and 3-methyl-β-naphthothiazoline may be used, but photopolymerization initiators known in the art may be used without being limited thereto.

The amount of the photopolymerization initiator used in the coating liquid composition of the present invention is preferably 0.5 to 4% by weight in the total coating liquid composition. If the amount is less than 0.5% by weight it takes a long time to cure, if it exceeds 4% by weight is difficult to control the thickness of the pattern.

The solvent used in the composition of the present invention is to dissolve other components in order to provide coating properties to the coating liquid composition, the viscosity can be adjusted according to the amount used. Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethyl glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl Ether, propylene glycol diethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1, -trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloro Ten, 1,2,3-trichloropropane, hexane, heptane, octane, cyclopentane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, propylene glycol monomethyl ether, Propyl glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol monomethyl ether, methyl carby Tol, ethyl carbitol, propyl carbitol, butyl carbitol, cyclopentanone, cyclohexanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol methyl ether propionate, 3-methoxybutyl acetate, 3 Single or two or more selected from the group consisting of -methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propyl acetate and ethyl acetate Can be mixed and used. In consideration of viscosity control, the amount of the solvent is preferably 0.1 to 1% by weight of the total coating solution composition.

The coating liquid composition of the present invention may be hydroquinone, 4-methoxy phenol, quinone, pyrocatechol, t-butyl catechol, phenothiazine, etc. Thermal polymerization inhibitors; Plasticizers; A silicone-based adhesion promoter; Other additives commonly used in fillers or coatings.

UV-curable coating liquid composition for LCD tempered glass of the present invention can shorten the curing time compared to the thermal curing method, and excellent adhesion, not easily separated from the glass during waterjet cutting, brittle not pushed by water pressure, after waterjet cutting There is an advantage that peeling from glass is easy.

Hereinafter, the constitution and effects of the present invention will be described in more detail through examples. These embodiments are only for illustrating the present invention, and the scope of the present invention is not limited by these embodiments.

1-1. Synthesis of Monomer Containing Urethane and Isocyanate Group

106.9 g of hydroxyethyl methacrylate and 143.1 g of 2,6-toylene diisocyanate were added to the reactor, and 250 g of hexane solvent was added thereto, followed by reaction for 2 hours while maintaining the temperature at 50 ° C. After the reaction was terminated, the precipitated white solid was filtered, washed several times with hexane and dried to obtain 210 g of a monomer containing urethane and isocyanate groups simultaneously.

1-2. Preparation of Binder Resin 1

3 parts by weight of a thermal initiator was dissolved in a reaction vessel, and hydroxyethyl acrylate / benzyl methacrylate / styrene / methacrylic acid was added at a molar ratio of 20/25/25/30, and then maintained at 60 ° C. in a nitrogen atmosphere. The reaction was time.

The copolymer solution obtained above was put into a flask with a stirrer. A monomer containing the urethane and isocyanate groups prepared in 1-1 at the same time was added and reacted until the isocyanate group disappeared completely to prepare a copolymer. The acid value of the prepared binder resin was 95 KOH mg / g, the weight average molecular weight was 13,500.

1-3. Preparation of Coating Liquid Composition

83 wt% of the binder resin prepared in the above 1-2, 13 wt% of the polyfunctional monomer (dipentaerythritol hexaacrylate), a photoinitiator (trade name: OXE-02) 2.0 in a reaction mixing tank equipped with an ultraviolet ray shield and a stirrer. Weight%, 0.25 weight% of silane epoxy compound (brand name: KBM503), 0.25 weight% of thermal polymerization inhibitors (4-methoxyphenol), 0.5 weight% of leveling agents (brand name: BYK 331), and 1 weight% of propylene glycol methyl ether acetate Were added sequentially to prepare a coating solution composition and then stirred.

2-1. Preparation of Binder Resin 2

3 parts by weight of a thermal initiator was dissolved in a reaction vessel, and then hydroxyethyl acrylate / benzyl methacrylate / styrene / dicyclopentanyl methacrylate / methacrylic acid was added at a molar ratio of 20/20/20/10/30. The reaction was carried out for 12 hours while maintaining at 60 ° C. in a nitrogen atmosphere.

The copolymer solution obtained above was put into a flask with a stirrer. A monomer containing the urethane and isocyanate groups prepared in 1-1 at the same time was added and reacted until the isocyanate group disappeared completely to prepare a copolymer. The acid value of the prepared binder resin was 90 KOH mg / g, the weight average molecular weight was 12,300.

2-2. Preparation of Coating Liquid Composition

Except for using the binder resin 2 prepared in Example 2-1 instead of the binder resin 1, a coating solution composition was prepared in the same manner as in Example 1-3.

Claims (18)

delete delete delete delete delete delete delete delete delete delete delete delete delete delete 83 wt% binder resin, 13 wt% polymerizable compound, 2 wt% photopolymerization initiator, 0.25 wt% silane epoxy compound, 0.25 wt% thermal polymerization inhibitor, 0.5 wt% leveling agent and 1 wt% solvent,
The binder resin includes 15 to 40 mol% of monomers including acid groups, 15 to 25 mol% of monomers including hydroxy groups, 20 to 30 mol% of aromatic vinyl monomers, and 20 to 30 wt% of aliphatic vinyl monomers.
The monomer containing an acid group is a compound selected from the group consisting of (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmalinic acid, isoprenesulfonic acid, styrenesulfonic acid and 5-norbornene-2-carboxylic acid ego,
Monomers containing the hydroxy group include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, and 4-hydroxybutyl (meth). ) Acrylate, acyloctyloxy-2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate methyl α-hydroxymethyl acrylate, ethyl α-hydroxymethyl acrylate, propyl α-hydroxymethyl acrylic Compound selected from the group consisting of latex and butyl a-hydroxymethyl acrylate,
The aromatic vinyl monomer is a compound selected from the group consisting of styrene, chlorostyrene, α-methyl styrene, vinyl toluene,
The aliphatic vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, tetrahydroperpril ( Meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate , Acyl octyloxy 02-hydroxypropyl (meth) acrylate, ethylhexyl acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylic Late, methock Triethylene glycol (meth) acrylate, methoxy tripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonyl phenoxy polyethylene glycol (meth) Acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octa An ultraviolet curable coating liquid composition for LCD tempered glass, which is a compound selected from the group consisting of fluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, and tribromophenyl (meth) acrylate.
16. The method of claim 15,
The polymerizable compound may be polyethylene glycol mono (meth) acrylate, polypropylrel glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylglycol (meth) acrylate, polypropylene glycol (meth) acryl Rate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol (meth) acrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, dipentaerythritol penta UV-curable coating liquid composition for LCD tempered glass, characterized in that at least one member selected from the group consisting of acrylate and dipentaerythritol hexaacrylate.
16. The method of claim 15,
The photopolymerization initiator is a triazine compound; Biimidazole compounds; Acetophenone compounds; O-acyl oxime compound; Benzophenone compounds; Fluorenone compounds; Thioxanthone type compounds; Xanthone compounds; Anthraquinone compounds; Acridine-based compounds; Dicarbonyl compounds; Phosphine oxide compounds; Amine synergy; Coumarin compound; Chalcone compound; UV curable coating liquid composition for LCD tempered glass, characterized in that at least one member selected from the group consisting of 2-benzoylmethylene and 3-methyl-β-naphthothiazoline.
16. The method of claim 15,
The solvent is acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, ethyl glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether , Propylene glycol diethyl ether, chloroform, methylene chloride, 1,2-dichloroethane, 1,1,1, -trichloroethane, 1,1,2-trichloroethane, 1,1,2-trichloroethane , 1,2,3-trichloropropane, hexane, heptane, octane, cyclopentane, cyclohexane, benzene, toluene, xylene, methanol, ethanol, isopropanol, propanol, butanol, t-butanol, propylene glycol monomethyl ether, propyl Reel glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol monomethyl ether, methyl carbitol , Ethyl carbitol, propyl carbitol, butyl carbitol, cyclopentanone, cyclohexanone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol methyl ether propionate, 3-methoxybutyl acetate, 3- LCD, characterized in that at least one member selected from the group consisting of methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, ethyl cellosolve acetate, methyl cellosolve acetate, butyl acetate, propyl acetate and ethyl acetate UV curable coating liquid composition for tempered glass.