KR100518623B1 - Coating-Composition and Manufacturing Method Thereof - Google Patents

Abstract

The present invention relates to an abrasion resistant coating composition having improved stability and a method for manufacturing the same, and more particularly, to improve dispersibility by surface modification of a metal oxide nanoparticle or its hydrolysis-condensate, thereby improving storage and work stability and abrasion resistance. It relates to an improved siloxane coating composition.

The present invention solves the disadvantage that the organic groups of the alkoxysilanes are made of polyoxyethylene for the surface modification, so that the dispersibility caused by the use of the organic groups of the alkoxysilane in the form of a single molecule in the prior art is insufficient. .

According to the present invention, since polyoxyethylene, which is a polymer, functions as a surfactant, it is possible to realize more effective dispersibility and to significantly increase the work stability due to storage stability and humidity change, and the hydrolysis-part of the alkoxysilane. It can be mixed with the condensate to significantly enhance the wear resistance of the coating composition.

Description

Abrasion-resistant coating composition with improved stability and manufacturing method thereof {Coating-Composition and Manufacturing Method Thereof}

The present invention relates to an abrasion resistant coating composition having improved stability and a method of manufacturing the same, and more particularly, to improve dispersibility by surface modification of a metal oxide nanoparticle or a hydrolysis-condensation compound to improve storage and work stability and wear resistance. It relates to a siloxane-based coating composition.

Transparent plastic materials have been in the spotlight as an alternative material in many fields that have been using glass due to advantages such as high transparency, impact resistance, light weight, and convenience of molding.

In recent years, due to the rapid development of information and communication, it is also used for transparent display windows such as mobile phones and thin film transistor liquid crystal display devices, and automotive parts such as headlamp lenses, taillight lenses and sunroofs, optical materials such as eyeglass lenses and cameras, and highways. Many transparent plastic materials are used for soundproof walls and buildings.

Such transparent plastic materials include polycarbonate resin (PC), polymethyl methacrylate resin (PMMA), polyethylene terephthalate resin (PET), diethylene glycol bisaryl carbonate resin (CR-39), polystyrene resin (PS), Polyolefin resins;

Since the synthetic resin molded article of the above material is insufficient in the wear resistance of the surface, it is susceptible to damage to the surface during the contaminants, dust, or cleaning process. In addition, damage to the surface deteriorates light transmittance and other performance, thereby damaging the merchandise value of the molded article.

Various attempts have been made to solve the above disadvantages of transparent plastics and to improve wear resistance. Korean Patent Application No. 89-2892 and British Patent Application No. 2044787A disclose a colorable wear resistant siloxane based coating composition.

However, this coating composition has a disadvantage in that discoloration occurs upon curing, storage stability is poor, and thus it is impossible to use it for a long time, and wear resistance and peeling phenomenon of the coating layer occur due to changes over time.

Japanese Patent Application Nos. 57-2735, 62-9266, and 53-30361 also disclose coating compositions similar to the above, but discoloration during curing, discoloration of the coating solution itself with time-dependent change, and wear resistance of the coating. And problems such as poor weather resistance have been exposed.

Abrasion resistant coating compositions are also disclosed in Korean patent applications 96-20734, 98-38432, 98-30203, etc., but since colloidal silica is used to increase the wear resistance without surface modification, the storage stability of the colloidal silica is poor. Due to rapid cohesion, defects are easily formed on the surface of the coating film, and thus, there is a disadvantage in that work stability is poor when humidity changes.

In addition, U.S. Patent Nos. 3,708,225, 3,986,997, 3,976,497, 4,027,073, 4,159,206, 4,177,315, and Korean Patent Application No. 2000-43249 include inorganic oxide nanoparticles such as colloidal silica, silica gel or composite oxides such as alcohol and water. Scratch-resistant coating compositions formed by combining with a hydrolyzable silane in a hydrolysis medium are known.

However, since the organic group of the hydrolyzable silane is present in the form of a single molecule, the storage stability is inferior as in the above-mentioned invention, and defects are easily formed on the surface of the coating film due to the rapid aggregation of colloidal silica when coating in a humid environment. There is a disadvantage that the work stability is poor when changing.

The present invention has been made to solve the above-mentioned problems of the prior art, by using a metal oxide or a hydrolysis-part condensate thereof modified surface using alkoxysilane in the polymer form as a dispersion solution, storage stability, humidity An object of the present invention is to provide a coating composition having improved work stability and abrasion resistance according to a change and a method of manufacturing the same.

The present invention to achieve the above object,

(A) 1 part by weight of a hydrolysis-part condensate of an alkoxysilane having a polyoxyethylene chain structure represented by the following general formula (1-1) or (1-2) and a metal oxide represented by the general formula (2) Or dispersion solution by mixing reaction of 5 to 70 parts by weight of silicon oxide nanoparticles; (B) 8 to 75 parts by weight of an alkoxysilane represented by the following General Formula (3); (C) an adhesive comprising 0.6 to 5.5 parts by weight of a urethane or epoxy (meth) acrylate oligomer and 0.015 to 0.14 parts by weight of an acryl curing catalyst; And (D) 1 to 10 parts by weight of the siloxane curing catalyst of the alkoxysilane; provides improved stability of the wear-resistant coating composition comprising a.

General formula (1-1)

General formula (1-2)

MxAy general formula (2)

R7cSi (OR8) 4-c general formula (3)

[a, b are integers of 0-2, c is an integer of 0-3; R1, R2, R4, R5 and R7 are alkyl groups, ketone groups, acrylic groups, allyl groups, aromatic groups, halogen groups, amine groups, amino groups, mercapto groups, ether groups, ester groups, or epoxy functional groups alone or two or more C1-10 having linear, branched or cyclic form; R3, R6, R8 are hydrogen or a C1-6 material having an alkyl group, an alkoxy group, a ketone group alone or in combination of two or more thereof; x, y is an integer; M is metal or silicon; A is an oxygen group, a chlorine group, a hydroxyl group or an alkoxy group]

In the present invention, the term "hydrolysis-part condensate" means that the oxide is hydrolyzed to a compound having a hydroxy group (or a compound having a hydroxy group), and a partial condensation reaction is carried out between the compounds having a hydroxy group. It refers to a linear, network or colloidal subcondensate formed.

The present invention will be described in more detail based on the ingredients to be added and the manufacturing process.

(1) The materials of the general formulas (1-1) and (1-2) are complexes of metal alkoxides, metal chlorides, metals with β-diketones or β-ketoesters in alkoxysilanes having epoxy functional groups as basic resins. As a catalyst (P. Innocenzi, A. Sassi, G. Brutusin and 5 others; A Novel Synthesis of Sol-Gel Hybrid Materials by a Nonhydrolytic Reaction of (3-Glycidoxypropyl) trimethoxyslane with TiCl 4; Chem. Mater. 2001, Vol 13, pp 3635 ~ 3643).

The process of obtaining the compound of the general formula (1-1) or the general formula (1-2) from the alkoxysilane having the epoxy functional group is shown in the following reaction formula (1) or reaction formula (2).

Examples of the alkoxysilane containing the epoxy functional group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxy Propylmethyldiethoxysilane, 3-glycidoxypropyltris (methoxyethoxy) silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Triethoxysilane, 3-glycidoxy propylphenyl diethoxysilane, etc. are mentioned. In the present invention, the alkoxysilane may be used in combination with one or two or more.

As the catalyst, alkoxides, chlorides, ketones and the like consisting of titanium, zirconium, aluminum, chromium and tin may be used. Specific examples of the titanium metal include titanium ethoxide, titanium propoxide, titanium butoxide and titanium chloride. And titanium acetylacetonate can be used.

(2) A metal oxide or a silicon oxide, which is a substance of the general formula (2), is a metal (or silicon) oxide, a metal (or silicon) chloride, or a metal (or silicon) that can form a hydroxyl group on the surface by hydrolysis. Refers to a partial condensation product of a metal (or silicon) hydroxide formed by partial condensation reaction of silicon) hydroxide or metal (or silicon) alkoxide or ② metal (or silicon) hydroxide. As will be described later, the materials of ① are changed to the hydrolysis-part condensate of the material of ②, ie, metal (or silicon) oxide nanoparticles in the reaction process according to the present invention.

The metal (or silicon) oxide may be a single metal (or silicon) oxide, or may be a complex metal (or silicon) oxide involving two or more metals (or silicon). Examples of the metal oxide include silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, cerium oxide, indium oxide, tin oxide, antimony oxide, iron oxide and the like.

Hereinafter, metal oxides or silicon oxides are simply referred to as "metal oxides". Therefore, hereinafter, metal oxide is used as a concept containing silicon oxide.

(3) The dispersion solution is prepared by mixing the substance of formula (1-1) or (1-2) with the substance of formula (2), stirring it uniformly, and then adding water (H 2 O). .

The alkoxy group of the general formula (1-1) or (1-2) substance is hydrolyzed by water (H2O), and the metal oxide nano fine particles represented by the general formula (2) or the hydrolyzate or partial condensate of the metal oxide thereof. The surface-modified metal oxide nanoparticles can be obtained by condensation reaction with an alkoxy group or a hydroxyl group on the surface (see Scheme (3)).

The dispersion is 1 part by weight of the alkoxysilane of the general formula (1-1) or (1-2) and ② the hydrolysis-partial condensate of the metal oxide nano fine particles represented by the general formula (2) or a metal oxide thereof. 70 parts by weight, preferably 10 to 35 parts by weight. In order to catalyze the hydrolysis and condensation reaction of the above compounds, (3) H ₂ O may be added at a rate of 0.5 to 2 mol, preferably 0.7 to 1.3 mol, per mol of the alkoxy group.

If necessary, in order to promote hydrolysis of the alkoxysilane, an appropriate acid or base catalyst may be used depending on the type of the metal oxide. The acid or base catalyst added at this time is preferably 0.001 to 2% by weight based on the solids of the dispersion. Acid catalysts include acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid, chlorosulfonic acid, para-toluic acid, trichloroacetic acid, polyphosphoric acid, pyrophosphoric acid, iodic acid, tartaric acid, or perchloric acid; base catalysts are caustic soda, ammonia, hydroxide Potassium, n-butylamine, di-n-butylamine, tri-n-butylamine, imidazole or ammonium perchlorate and the like can be used.

The dispersion solution production reaction (= surface modification reaction) can be carried out under various temperature conditions, such as 0 ~ 50 ℃ or more.

(4) The said dispersion solution is mixed with the hydrolysis-partial condensate of the alkoxysilane represented by General formula (3) which is a basic matrix of the coating composition of this invention.

Examples of the alkoxysilane represented by the general formula (3) include methyltrimethoxysilane, methyltriethoxysilane, methyltrippooxysilane, propylethyltrimethoxysilane, ethyltriethoxysilane, and vinyltrimethoxysilane. , Vinyltriethoxysilane, vinyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, phenyltrimethoxysilane, diphenylethoxyvinylsilane, tetramethoxy Methoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetraacetoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxy Silane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltripropoxysilane, 3-acryloxypropyldimethylmethoxysilane, 3-acrylic Oxypropyldimethylethoxysilane, 3-acryloxypropyldimethylpropoxysilane, 3-acryloxypropylmethylbis (trimethylsiloxy) silane, 3-acryloxy propyltrimethoxysilane, 3-acryloxy propyltriethoxysilane , 3-acryloxy propyltripropoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane or 3- (meth) acryloxypropyltripropoxysilane, N- (2-aminoethyl-3-aminopropyl) -trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) -triethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, Chloropropyltrimethoxysilane, Chloropropyltriethoxysilane, Trimethoxysilylpropyldiethylenetriamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Silane, 3-glycidoxypropylmethyldimethoxysil , 3-glycidoxypropylmethyldiethoxysilane, beta (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltris (methoxyethoxy) silane, 2- (3,4- Epoxycyclohexyl) ethyltriethoxysilane, 3-glycidoxypropylphenyldiethoxysilane, heptadecafluorodecyltrimethoxysilane, and the like, and the alkoxysilane may be used by mixing one or more than two.

The hydrolysis-partial condensate of the alkoxysilane is obtained by dissolving 8 to 75 parts by weight, preferably 15 to 38 parts by weight of alkoxysilane, in an solvent such as alcohol, based on 1 part by weight of the alkoxysilane containing the polyoxyethylene functional group. It is then obtained by adding water and stirring to induce (partial) hydrolysis and (partial) condensation reactions. If the amount of the alkoxysilane addition is 8 parts by weight or less, the dispersion solution is used a lot of economical efficiency and there is a problem that cracks on the surface of the coating when applying the final product, when the addition amount is 75 parts by weight or more difficult to implement excellent wear resistance.

Water used as a catalyst is suitable to be used at a rate of 0.5 to 2 mol, preferably 0.7 to 1.3 mol, per mol of hydrolyzable groups such as methoxy group, ethoxy group or propoxy group, but the amount of water used itself has a great effect on the reaction. It does not mean that.

In order to promote the hydrolysis and condensation reaction, an acid or a base catalyst is used as in the aforementioned dispersion solution preparation. The amount of acid or base catalyst added is preferably used in the range of 0.005 to 1% by weight based on the alkoxysilane solid content. The reaction can be carried out at various temperature conditions such as 0 ~ 50 ℃ or more.

Meanwhile, in order to increase the siloxane reaction of the alkoxy silane in the thermosetting process after the coating composition according to the present invention is coated, a siloxane curing catalyst of the alkoxy silane, which is a kind of heat curing type curing catalyst, is required. Such siloxane curing catalysts of alkoxy silanes may be added at any of the stages of preparing the coating composition. However, it is usually preferred to add it in the last step.

(5) In the present invention, in order to increase adhesion to various coating substrates and dyeing properties of the coating film, and to improve adhesion to the deposition film when various metal films or metal oxide films are deposited on the plastic substrate coated with the product according to the present invention. (Meth) acrylate oligomers, such as urethane (meth) acrylate or epoxy (meth) acrylate, are added.

That is, 30 minutes to 2 minutes after adding the surface-modified metal oxide nanoparticles or the hydrolysis-partial condensate dispersion solution of metal oxides thereof to the hydrolysis-partial condensate of the alkoxysilane obtained through the process (4). After stirring for about an hour, a urethane or epoxy (meth) acrylate oligomer and an acrylic curing catalyst are added, followed by mixing and stirring to complete a wear resistant coating composition having improved stability according to the present invention.

At this time, the urethane or epoxy (meth) acrylate oligomer is 0.6 to 5.5 parts by weight (preferably 1.2 to 2.8 parts by weight) with respect to 1 part by weight of the alkoxysilane containing the polyoxyethylene functional group, the acrylic curing catalyst is 0.015 ˜0.14 parts by weight (preferably 0.03 to 0.07 parts by weight) is added.

When the urethane or epoxy (meth) acrylate oligomer is added in an amount of 0.6 parts by weight or less, it is easy to peel off the coating film due to insufficient adhesive strength with the coating material, and when used in an amount of 5.5 parts by weight or more, the light transmittance of the coating film is reduced due to phase separation. The wear resistance of the coating film is lowered.

The acrylic curing catalyst may not exhibit an effective curing property when used in less than 0.015 parts by weight, when used in more than 0.14 parts by weight may act as a defect on the coating surface due to local agglomeration, etc., and economical efficiency is low.

The urethane (meth) acrylate and epoxy (meth) acrylate may be used alone or in combination of two or more depending on the coating material.

1) Urethane (meth) acrylate oligomer

The urethane (meth) acrylate oligomer is a (1-1) polyol or polyol copolymer, (1-2) diisocyanate, (1-3) hydroxy (meth) acrylate, (1-4) urethane reaction catalyst, (1-5) It is preferable to be manufactured from the urethane (meth) acrylate oligomer composition containing a polymerization inhibitor.

1-1) The polyol or polyol copolymer preferably has a molecular weight of about 50 to 1,000, polyester polyol, polyether polyol, polycarbonate polyol, polycaprolactone polyol, ring-opening tetrahydrofuran propylene oxide copolymer, polybutadiene die Ol, polydimethylsiloxane diol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, 1., 4-cyclohexane It is preferable that it is selected from the group which consists of diols, such as dimethanol, bisphenol-A, hydrogenated bisphenol-A, these copolymers, or a mixture thereof.

1-2) diisocyanate is 2,4-toluene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, 1,5-naphthalene diisocyanate, 1,6-hexane diisocyanate, isophorone di It is preferably selected from the group consisting of isocyanates and mixtures thereof.

1-3) Hydroxy (meth) acrylate is a compound containing one or more (meth) acrylates and hydroxy functional groups, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylic Rate, 1-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, neopintyl glycol mono (meth) acrylate, 4-hydroxycyclohexyl (meth) Acrylate, 1,6-hexanediol mono (meth) acrylate, pentaerythritol penta (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2-methacryloxyethyl2-hydroxypropyl phthalate, Selected from the group consisting of glycerin di (meth) acrylate, 2-hydroxy-3-acroyloxypropyl (meth) acrylate, polycaprolactone polyol mono (meth) acrylate, and mixtures thereof Is recommended.

1-4) The urethane reaction catalyst is added in a small amount during the reaction, copper naphthenate, cobalt naphthenate, zinc naphthenate, n-butyltinlaurate, tristilamine, 2-methyltriethylene diamide and mixtures thereof It is preferable to select from the group which consists of.

1-5) The polymerization inhibitor is preferably selected from the group consisting of hydroquinone, hydroquinone monomethyl ether, parabenzoquinone, phenothiazine and mixtures thereof.

5 to 60 parts by weight of the (1-1) polyol or polyol copolymer, 10 to 50 parts by weight of the (1-2) diisocyanate, and 5 to 50 of the (1-3) hydroxy (meth) acrylate By weight, the (1-4) urethane reaction catalyst is added in an amount of 0.01 to 1 part by weight, and the (1-5) polymerization inhibitor is added in an amount of 0.01 to 1 part by weight.

The urethane (meth) acrylate may be prepared by the following process.

The polyol or polyol copolymer is placed in a reactor and then depressurized to remove moisture to remove side reactions between water and the isocyanate described below. After maintaining the mixture from which the water is removed at 40-65 ° C., isocyanate is added and stirred at 200-300 rpm to add 1/3 of the catalyst used (exothermic reaction occurs). After the end of exotherm, the reactant is maintained at 50 to 75 ° C. for about 2 to 3 hours, and after completion of the reaction, hydroxy (meth) acrylate and a polymerization inhibitor are added (exothermic reaction occurs). After the end of exotherm, the reactant was heated to 80 ° C. and the remaining catalyst was added to obtain a urethane (meth) acrylate oligomer.

When the average molecular weight of the urethane (meth) acrylate oligomer is 50,000 or more, there is a disadvantage in that the light transmittance of the coating film is lowered due to phase separation due to poor compatibility with the rest of the composition, and when the molecular weight is 1,000 or less, the coating film is reduced in the implementation of adhesion. Because of the disadvantages, the average molecular weight of the oligomer is preferably from 1,000 to 50,000.

2) Epoxy (meth) acrylate oligomer

The epoxy (meth) acrylate oligomer is a (2-1) polyol or phenol-based diol, (2-2) glycidyl (meth) acrylate or glycidyl ether, (2-3) amine catalyst, ( 2-4) It is preferable that it is made of the epoxy (meth) acrylate oligomer composition containing a polymerization inhibitor.

2-1) The polyol or phenolic diol preferably has a molecular weight of 50 to 1,000, and a polyether polyol, polycarbonate polyol, polycaprolactone polyol, polydimethylsiloxane diol, ethylene glycol, propylene glycol, 1,4- Butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentylglycol, 1., 4-cyclohexanedimethanol, bisphenol-A, fluorinated bisphenol-A type diols or noses thereof It is preferably selected from the group consisting of polymers or mixtures thereof.

2-2) Glycidyl (meth) acrylate or glycidyl ether is allyl glycidyl ether, 1,2-butyl glycidyl ether, isopropyl glycidyl ether, phenyl glycidyl ether, 4-t -Butylphenyl glycidyl ether, 2-ethylhexyl glycidyl ether, diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, dodecanediol diglyci Cydyl ether, 1-4 cyclohexanemethanol diglycidyl ether, pentane ethyl triol polyglycidyl ether, lesocin diglycidyl ether, polypropylglycol diglycidyl ether, 0-cresyl glycidyl ether , Neopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, trimethylol propane polyglycidyl ether, diethyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether , Diglycerol ether, polyglycerol polyglycol Is used to select such sidil ether, it can be used as a mixture of two or more kinds.

2-3) The amine catalyst is selected by using trimethylbenzyl ammonium chloride, trimethylbenzyl ammonium bromide or quaternary ammonium series such as trimethylamine or trimethylamine.

2-4) The polymerization inhibitor is the same as that used for urethane (meth) acrylate.

It is preferable that 0.01-1 weight part and said polymerization inhibitor use 0.01-1 weight part of said amine catalysts.

The epoxy (meth) acrylate is a reaction of heating the polyol or phenol-based diol, glycidyl methacrylate, amine, and polymerization agent with toluene in a reactor and heating at 40-120 ° C. for 4-10 hours. Obtained.

When the average molecular weight of the epoxy (meth) acrylate oligomer is 30,000 or more, there is a disadvantage in that the light transmittance of the coating film is lowered due to phase separation due to poor compatibility with the rest of the composition, and when the molecular weight is 300 or less, the implementation of the adhesion is reduced. And a disadvantage that the dyeability and adhesion to the metal deposition film is poor, the average molecular weight of the oligomer is preferably 300 to 30,000.

3) Curing Catalyst

3-1) Thermosetting Acrylic Curing Catalyst

Examples of the thermosetting acrylic curing catalyst include 2,5-bis- (tert-butyl-peroxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethyl-hexanoate, benzoyl peroxide, Peroxides of methyl ethyl ketone peroxide, 2,2-azo-bis-isobutylonitrile or 2,2-azo-bis- (2,4-dimethylvaleronitrile), t-butyl peroxy benzoate.

The amount of the curing catalyst used is 0.1 to 10 parts by weight of the epoxy or urethane (meth) acrylate oligomer composition, but preferably 1 to 5 parts by weight. If the catalyst is used at 0.1 parts by weight or less, the polymerization of the radical film does not occur effectively, so that the properties of the coating film is very poor, and when used at 10 parts by weight or more, there is a disadvantage in terms of economics, although there is no degradation in properties.

3-2) Curing Catalyst to Promote Siloxane Bonding

Examples of the curing catalyst for promoting siloxane bonding include (2-1) metal acetylacetonate, (2-2) diamide, (2-3) imidazole, (2-4) amines, and (2-5) eutechonic acid. And amine salts thereof and alkali metal salts of carboxylic acids (2-6).

The 2-1) metal acetylacetonate includes a compound such as metal acetylacetonate such as aluminum, zirconium, zinc, iron, cobalt, titanium, chromium or tin, and 2-2) diamide is dicyandiamide. And 2-3) imidazoles include compounds such as 2-methylimidazole, 2-ethyl-4methylimidazole and 1-cyanoethyl-2-propylimidazole. Are compounds such as benzyldimethylamine and 1,2-diaminocyclohexane, and 2-5) euphonic acid and amine salts thereof are compounds such as trifluoromethanesulfonic acid, and 2-6) alkalis of carboxylic acids. Metal salts include compounds such as sodium acetate.

The curing catalyst may be used one or two or more mixtures in consideration of the concentration, pH of the coating composition.

(6) In the present invention, it is possible to add a diluent solvent such as ketones, alcohols, cellosolves, etc. in consideration of viscosity, pH, stability of solution, concentration of solid content and the like.

The solvent is methanol, ethanol, propanol, butanol, pentanol, diacetone alcohol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve acetate, acetylacetone, acetone, methyl ethyl ketone, Methyl isobutyl ketone, 2,4-hexanedione, cyclohexanone, and the like, and such a dilution organic solvent may be used by mixing one or two or more in consideration of the characteristics of the solution.

When adding a diluent, the content is 7-60 weight part, Preferably it is 14-30 weight part with respect to 1 weight part of alkoxysilanes which have a polyoxy ethylene chain structure.

The preparation method of the wear-resistant coating composition according to the present invention up to this step is as follows.

First, hydrolysis-partial condensates of alkoxysilanes having a polyoxy ethylene chain structure represented by general formula (1-1) or (1-2), and metal oxide or silicon oxide nano represented by general formula (2) Mixing and stirring the fine particles to prepare a dispersion solution of the surface-modified nanoparticles ((a) step; dispersion solution production step).

Subsequently, the alkoxysilane represented by the general formula (3) is mixed and stirred to prepare an alkoxysilane hydrolysis-part condensate ((b) step; alkoxysilane condensate production step). Next, the dispersion solution of the nanoparticles obtained in step (a) and the alkoxysilane hydrolysis-part condensate obtained in step (b) are mixed and stirred ((c) step; mixing step). Next, a urethane or epoxy (meth) acrylate oligomer and an acrylic curing catalyst are added to the reaction solution obtained in the step (c) and mixed and stirred ((d) step; adhesive addition step). Before and after any of the above steps, a siloxane curing catalyst of alkoxy silane is added and mixed and stirred ((e) step; curing catalyst addition step).

If necessary, a step ((bar); dilution step) of adding a diluent to the reaction solution may be added before or after the optional step.

(7) Others In the present invention, an appropriate amount of a surfactant, a ultraviolet absorber, etc. may be added for the additional performance of the product.

In order to impart coatability, anti-foaming property, wettability and surface slip property of the coating film according to the product of the present invention, a surfactant made of a fluorine-based or copolymer of dimethylsiloxane and polyoxyethylene may be added.

 In addition, the ultraviolet absorbent may be added in an amount that does not lower the physical properties of the composition of the present invention for improving weather resistance.

(8) The coating composition according to the present invention can be applied to coatings in various ways.

Depending on the form of the coating substrate, the plastic substrate may be formed by using a flow coating method, spin coating method, dip coating method, bar coating method, or roll coating method. It is possible to obtain a protective film of high hardness by applying to a heat treatment. In order to increase adhesion between coating substrates, in the case of a general polymer substrate, an etching process using an acid or a base, and a pretreatment process such as corona or plasma discharge may be used.

Since there is a difference in thickness depending on each coating method, when the thickness is thin, it is appropriate to apply the coating several times so that the thickness of the coating film is about 1 to 20 μm, and more preferably, about 3 to 10 μm. To form a coating film. When the coating film thickness is 1 μm or less, the wear resistance of the coating film is decreased, and when the coating film thickness is 20 μm or more, there is a risk of cracking during drying of the coating film.

Post-coating curing conditions of the coating composition is somewhat different depending on the blending ratio and components, but in general, a protective film of the desired hardness can be obtained by curing for 30 minutes to 4 hours at a temperature below the softening point of the substrate. .

Hereinafter, the embodiment of the present invention will be described in detail. The following examples are only examples of the manufacturing method of the present invention, and thus the scope of the present invention is not limited or changed.

Example

(1) Preparation of Alkoxysilanes Having Polyoxyethylene Chain Structure

3-glycidoxy propyltrimethoxysilane was dissolved in solvent methylene chloride and titanium chloride was used as the catalyst for Chem. An alkoxysilane having a polyoxy ethylene chain structure was prepared according to the method described in Mater. 2001, Vol 13, 3635-3643.

The reaction product was obtained by distillation under reduced pressure, which was then diluted to 50% by weight in isopropanol and used (reactant A).

(2) Preparation of urethane (meth) acrylate

In a 2 L flask, 12.62 g of ring-opened 1,4-cyclohexanedimethanol, 26.50 g of polycaprolactone polyol, and 22.20 g of isophorone diisocyanate (IPDI) were mixed, and the temperature was raised to 40 ° C. to n-butyltinlaurate 0.1 The reaction was added by adding g. After the exothermic reaction was maintained at 70 ℃ for 1 hour, 0.13 g of hydroquinone monomethyl ether, 13.50 g of 2-hydroxypropyl acrylate, 0.1 g of n-butyl tin laurate was added.

After the exothermic reaction was completed, the temperature was maintained while maintaining the reaction for about 30 minutes, and then cooled to room temperature to obtain a urethane acrylate oligomer (Reactant B).

(3) Preparation of epoxy (meth) acrylate

In a 500 ml flask, 30 g of bisphenol-A, 38.30 g of glycidyl methacrylate, 0.01 g of hydroquinone, and 0.1 ml of triethylamine were added to 100 ml of toluene and stirred at 90 ° C. for 4 hours.

After the reaction was completed, distillation under reduced pressure using a vacuum aspirator to remove toluene to obtain an epoxy (meth) acrylate (reactant C).

Example 1

As a metal (or silicon) oxide, 150 g of methanol-dispersed colloidal silica sol (30% by weight) manufactured by a conventional method (manufactured by Gamatek) and 9 g of the reactant A were mixed and stirred. After 30 minutes, 1 g of water and 0.1 g of acetic acid were added, followed by further stirring for 3 hours to obtain a methanol-dispersed colloidal silica sol (nanoparticle dispersion) with a modified surface (dispersion preparation step).

225 g of 3-glycidoxypropyltrimethoxysilane and 43.8 g of ethanol were mixed and stirred for 30 minutes, and then an aqueous 14.4% acetic acid solution was added dropwise at room temperature and reacted for 3 hours to prepare an alkoxysilane hydrolysis-part condensate ( Alkoxysilane condensate production step).

The surface-modified methanol dispersed colloidal silica sol and the alkoxysilane hydrolysis-part condensate were mixed and stirred (mixing step), followed by adding 100 g of acetylacetone, 30 g of methyl cellosolve and 50 g of isopropanol as a diluent and stirring for about 2 hours. (Dilution addition step).

Thereafter, 11 g of the reactant B and 5 g of the reactant C, 0.4 g of the benzoyl peroxide, and 7 g of aluminum acetylacetonate, a curing catalyst for siloxane bonding of the alkoxy silane, were added and stirred for 2 hours (adding the adhesive and curing catalyst). The final coating composition was obtained.

Example 2-Changes to Alkoxysilanes

Instead of 3-glycidoxypropyltrimethoxysilane in Example 1, 175 g of 3-glycidoxypropyltrimethoxysilane and 60 g of methyltriethoxysilane were used, and the rest of the process was carried out in the same manner as in Example 1 for the final coating. A composition was obtained.

Example 3 Change to Silicon Oxide

Instead of methanol dispersed colloidal silica sol (manufactured by Gamatek) in Example 1, except that Snowtex-O manufactured by Nissan Chemical Co., Ltd. was used as a dispersion colloidal silica sol, it was prepared in the same manner as in Example 1.

Example 4 Changes to Alkoxysilanes and Silicon Oxides

It was prepared in the same manner as in Example 2 except that Snowtex-O manufactured by Nissan Chemical Co., Ltd., a water-dispersible colloidal silica sol, was used instead of the methanol dispersed colloidal silica sol (manufactured by Gamatek) in Example 2.

Example 5 Changes to Silicon Oxide

20 g of water-dispersed alumina sol (AS-520) manufactured by Nissan Chemical Co., Ltd., 100 g of methanol-dispersed colloidal silica sol (manufactured by Gamatech, 30% solids), and 12 g of the reactant A were mixed and stirred for about 30 minutes. Subsequently, 1.5 g of water and 2 g of acetic acid were added and stirred for 3 hours to prepare a surface-modified inorganic nanoparticle mixed solution.

Thereafter, a final coating composition was obtained in the same manner as in Example 1.

Example 6 Changes to Alkoxysilanes and Silicon Oxides

20 g of water-dispersed alumina sol (AS-520) manufactured by Nissan Chemical Co., Ltd., 100 g of methanol-dispersed colloidal silica sol (manufactured by Gamatech, 30% solids), and 12 g of the reactant A were mixed and stirred for about 30 minutes. Subsequently, 1.5 g of water and 2 g of acetic acid were added and stirred for 3 hours to prepare a surface-modified inorganic nanoparticle mixed solution.

Thereafter, the final coating composition was obtained in the same manner as in Example 2.

Example 7-Changes in Silicon Oxide

Instead of using only methanol dispersed silica sol (manufactured by Gamatek), Example 1 was used except that 30 g of HIT-30M (SnO2-TiO2-ZrO2) manufactured by Nissan Chemical Co., Ltd. was mixed with 120 g of methanol dispersed silica sol (manufactured by Gamatek). In the same manner as in the final coating composition was obtained.

Example 8 Changes to Alkoxysilanes and Silicon Oxides

A final coating composition was obtained in the same manner as in Example 2, except that 30 g of HIT-30M (SnO 2 -TiO 2 -ZrO 2) manufactured by Nissan Chemical Co., Ltd. and 120 g of methanol-dispersed silica sol (manufactured by Gamatek) were used.

Example 9-Change in the amount of alkoxy silanes

After 21.9 g of ethanol was mixed with 122.5 g of 3-glycidoxypropyltrimethoxysilane and stirred for 30 minutes, 30 g of an aqueous 14.4% acetic acid solution was added dropwise at room temperature and reacted for 3 hours. Subsequently, the surface-modified methanol dispersed colloidal silica sol was added in the same manner as in Example 1, followed by addition of 100 g of acetylacetone, 30 g of methyl cellosolve, and 50 g of isopropanol, followed by stirring for about 2 hours.

Thereafter, 11 g of reactant B and 5 g of reactant C were added, and 0.4 g of benzoyl peroxide and 7 g of aluminum acetylacetonate were added thereto, followed by stirring for 2 hours to obtain a final coating composition.

Example 10 Changes in Amount and Type of Alkoxy Silanes

Final coating composition in the same manner as in Example 9, except that 87.5 g of 3-glycidoxypropyltrimethoxysilane was mixed with 30 g of methyltrimethoxysilane instead of 3-glycidoxypropyltrimethoxysilane. Was prepared.

Comparative Examples 1 to 10-Replacement of Alkoxysilanes with Polyoxyethylene Structures with Regular Alkoxysilanes

Comparative Example 1

A final coating composition was prepared in the same manner as in Example 1 except that 3-glycidoxypropyltrimethoxysilane was used instead of Reactant A.

Comparative Example 2

Instead of 3-glycidoxypropyltrimethoxysilane, 175 g of 3-glycidoxypropyltrimethoxysilane and 60 g of methyltriethoxysilane were used, and the remaining process was carried out in the same manner as in Comparative Example 1 to obtain a final coating composition.

Comparative Example 3

Example 1 except that 3-glycidoxypropyltrimethoxysilane was used instead of reactant A and Snowtex-O manufactured by Nissan Chemical Co., Ltd., which is a water-soluble colloidal silica sol instead of methanol dispersed colloidal silica sol (manufactured by Gamatek) In the same manner as in the final coating composition was prepared.

Comparative Example 4

Using 3-glycidoxypropyltrimethoxysilane instead of reactant A, using Snowtex-O manufactured by Nissan Chemical Co., Ltd., which is a water-soluble colloidal silica sol instead of methanol dispersed colloidal silica sol (manufactured by Gamatek) and in Example 1 A final coating composition was obtained in the same manner as in Example 1 except that 175 g of 3-glycidoxypropyltrimethoxysilane and 60 g of methyltriethoxysilane were used instead of 3-glycidoxypropyltrimethoxysilane. .

Comparative Example 5

A final coating composition was obtained in the same manner as in Example 5 except that 3-glycidoxypropyltrimethoxysilane was used instead of Reactant A.

Comparative Example 6

A final coating composition was obtained in the same manner as in Example 6 except that 3-glycidoxypropyltrimethoxysilane was used instead of Reactant A.

Comparative Example 7

A final coating composition was obtained in the same manner as in Example 7 except that 3-glycidoxypropyltrimethoxysilane was used instead of the reactant A.

Comparative Example 8

A final coating composition was obtained in the same manner as in Example 2 except that 3-glycidoxypropyltrimethoxysilane was used instead of Reactant A.

Comparative Example 9

A final coating composition was obtained in the same manner as in Example 9 except that 3-glycidoxypropyltrimethoxysilane was used instead of Reactant A.

Comparative Example 10

A final coating composition was obtained in the same manner as in Example 10 except that 3-glycidoxypropyltrimethoxysilane was used instead of Reactant A.

Comparative Examples 11 and 12-Excluding Adhesive

Comparative Example 11

A final coating composition was prepared in the same manner as in Example 1, except that three components such as reactant B, reactant C, and benzoyl peroxide were not added.

Comparative Example 12

A final coating composition was prepared in the same manner as in Example 2, except that three components, such as reactant B, reactant C, and benzoyl peroxide, were not added.

Application and evaluation

(1) Application (Coating Method)

The final coating composition prepared by each of the above Examples and Comparative Examples was coated on a general medium refractive lens by dip coating, and dried at 120 ° C. for 1 hour and 30 minutes. The average coating thickness was 4 μm.

(2) evaluation method

A) Taber wear test

Taber wear of the coating composition applied to the substrate was performed according to ASTM D1044. Haze was measured by observing the worn specimens with Haze gard plus (BYK gardner Co.) at room temperature for 500 g with a CS-10F wheel under 500 g weight.

B) adhesion

According to ASTM D 3359, 100 cells were made on the film at intervals of 1 mm in width and length, and 5 times of peel tests were performed using Nippon Nishiban Co., Ltd. cellophane tape to determine the number of cells attached without peeling.

C) pencil hardness

The coating composition was cured and measured using a pencil hardness tester.

D) storage safety

The change in viscosity when stored for 3 months at 25 ° C. was observed.

E) appearance

Change the relative humidity to 30 ~ 60% in a 10,000 Class clean room (ambient temperature 20 ℃, coating bath temperature 10 ℃) while immersing the substrate in the coating composition and curing it to observe the appearance to observe the appearance of surface defects. It was.

F) water resistance

The coated substrate was immersed in water at 70 ° C. for 7 days, followed by visual inspection and adhesion test.

Each coating composition was immersed in polymethyl methacrylate material, first dried at 80 ° C. for 20 minutes, and cured at 100 ° C. for 2 hours to form a coating film. It was.

The above mentioned evaluation items evaluated the performance of the coating film after drying by changing the relative humidity to 35%, 45%, 55%, and d) the storage stability, which is a general laboratory condition without fixing relative humidity. Stored for 3 months at room temperature, humidity 40 ~ 70% and evaluated by observing the change in viscosity.

(3) Evaluation result

In the present invention, the performance evaluation of the coating composition was tested in the same manner as described above, and the items that can be evaluated by specific values were evaluated using numerical values. Insufficient steps are marked with □.

A) Storage stability of coating solution

As can be seen in Table 1, in the wear-resistant coating composition according to the present invention, all showed excellent storage stability within various composition ranges. On the other hand, instead of the hydrolysis-partial condensates of the alkoxysilanes having a polyoxy ethylene chain structure, it can be seen that when the general alkoxy silane is used (Comparative Examples 1 to 10), the stability is relatively low.

B) Characteristics of coating film

As can be seen from Tables 2 to 4, when coated under various humidity conditions, when coated with the coating composition according to the present invention, almost no change in taper wear, adhesion, pencil strength, appearance, and water resistance regardless of humidity conditions Showed excellent and stable performance.

On the other hand, instead of the hydrolysis-partial condensates of the alkoxysilanes having a polyoxyethylene chain structure, in Comparative Examples 1 to 10 using general alkoxy silanes, it can be seen that the taper wear and pencil strengths were changed according to the humidity conditions to be coated. , Adhesion, appearance, and water resistance can also be seen that the higher the humidity, the lower the performance.

As described in detail above, the present invention is to provide a coating composition excellent in surface stability of the inorganic nano oxide fine particles by the storage stability, work stability according to the humidity change and wear resistance.

The present invention has a disadvantage that the organic group of the alkoxysilane has a polymer form of polyoxyethylene, so that the organic group of the alkoxysilane used for surface modification has a monomolecular form and thus does not effectively improve dispersibility. Solved.

In addition, since the polyoxyethylene can even act as a surfactant, it is possible to realize more effective dispersibility and significantly increase the work stability due to storage stability and humidity change, and is mixed with the hydrolyzate or partial condensate of the alkoxysilane. Abrasion resistance of the coating composition can be significantly enhanced.

In particular, the cured protective film exhibited high hardness, high wear resistance and water resistance, and showed excellent adhesion, such as polymethyl methacrylate resin (PMMA), polycarbonate resin (PC), polyethylene terephthalate resin (PET), di It is applicable to ethylene glycol bis aryl carbonate resin (CR-39), polystyrene resin (PS), polyolefin resin and the like, and when applied to plastic spectacle lenses, it is possible to provide a coating composition that enhances the wear resistance of the substrate.

Claims (11)

(A) 1 part by weight of a hydrolysis-part condensate of an alkoxysilane having a polyoxyethylene chain structure represented by the following general formula (1-1) or (1-2) and a metal oxide represented by the general formula (2) Or dispersion solution by mixing reaction of 5 to 70 parts by weight of silicon oxide nanoparticles; (B) 8 to 75 parts by weight of an alkoxysilane represented by the following General Formula (3); (C) an adhesive comprising 0.6 to 5.5 parts by weight of a urethane or epoxy (meth) acrylate oligomer and 0.015 to 0.14 parts by weight of an acryl curing catalyst; And (D) 1 to 10 parts by weight of a siloxane curing catalyst of the alkoxysilane; improved abrasion resistance coating composition characterized in that it comprises a. General formula (1-1) General formula (1-2) MxAy general formula (2) R7cSi (OR8) 4-c general formula (3) [a, b are integers of 0-2, c is an integer of 0-3; R1, R2, R4, R5 and R7 are alkyl groups, ketone groups, acrylic groups, allyl groups, aromatic groups, halogen groups, amine groups, amino groups, mercapto groups, ether groups, ester groups, or epoxy functional groups alone or two or more C _1-10 having a linear, branched or cyclic form; R3, R6, R8 are hydrogen or a C _1-6 material having an alkyl group, an alkoxy group, a ketone group alone or in combination of two or more thereof; x, y is an integer; M is metal or silicon; A is an oxygen group, a chlorine group, a hydroxyl group or an alkoxy group] The method of claim 1, (A) 1 part by weight of a hydrolysis-partial condensate of an alkoxysilane having a polyoxy ethylene chain structure represented by formula (1-1) or (1-2) and a metal oxide represented by formula (2), or Dispersion solution by mixing reaction of 10 to 35 parts by weight of silicon oxide nanoparticles; (B) 15 to 38 parts by weight of alkoxysilane represented by the general formula (3); (C) 1.2 to 2.8 parts by weight of an urethane or epoxy (meth) acrylate oligomer and 0.03 to 0.07 parts by weight of an acrylic curing catalyst; And (D) 2 to 5 parts by weight of a siloxane curing catalyst of alkoxysilane; improved abrasion resistance coating composition characterized in that it comprises a. The method according to claim 1 or 2, The alkoxysilane which has the polyoxy ethylene chain structure represented by said general formula (1-1) or (1-2), 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxy propylmethyldiethoxysilane, 3-glycidoxypropyl Tris (methoxyethoxy) silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and 3-glycidoxypropylphenyl Wear-resistant coating composition with improved stability, characterized in that one or more mixtures selected from the group consisting of diethoxysilane. The method according to claim 1 or 2, The metal oxide or silicon oxide represented by the general formula (2), An abrasion resistant coating composition having improved stability, characterized in that an oxygen group, a chlorine group, a hydroxyl group or an alkoxy group is formed or is a mixture of two or more kinds of metal oxides or silicon oxides which can be formed. The method according to claim 1 or 2, The alkoxysilane represented by the said General formula (3), Methyltrimethoxysilane, Methyltriethoxysilane, Methyltripropoxysilane, Propylethyltrimethoxysilane, Ethyltriethoxysilane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Vinyltripropoxysilane, Dimethyl Dimethoxysilane, dimethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, phenyltrimethoxysilane, diphenylethoxyvinylsilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetra Butoxysilane, Tetraphenoxysilane, Tetraacetoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltripropoxysilane, 3-acryloxypropyldimethylmethoxysilane, 3-acryloxy Propyldimethylethoxysilane, 3-acryloxypro Dimethylpropoxysilane, 3-acryloxypropylmethylbis (trimethylsiloxy) silane, 3-acryloxy propyltrimethoxysilane, 3-acryloxy propyltriethoxysilane, 3-acryloxy propyltripropoxysilane, 3 -(Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane or 3- (meth) acryloxypropyltripropoxysilane, N- (2-aminoethyl-3-aminopropyl ) -Trimethoxysilane, N- (2-aminoethyl-3-aminopropyl) -triethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, chloropropyltrimethoxysilane , Chloropropyltriethoxysilane, trimethoxysilylpropyldiethylenetriamine, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropylmethyldiethoxysilane, beta (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltris (methoxyethoxy) silane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3-glycidoxypropylphenyl The wear-resistant coating composition with improved stability, characterized in that one or two or more mixtures selected from the group consisting of diethoxysilane and heptadecafluorodecyltrimethoxysilane. The method according to claim 1 or 2, The siloxane curing catalyst, (i) metal compounds such as aluminum, zirconium, zinc, iron, cobalt, titanium, chromium or tin acetylacetonate, (ii) dicyandiamide, (iii) 2-methylimidazole, 2-ethyl-4methyl Imidazoles, such as imidazole or 1-cyanoethyl-2-propylimidazole, (iv) benzyldimethylamine or 1,2-diaminocyclohexane, (v) eutechonic acid, such as trifluoromethanesulfonic acid, or Abrasion-resistant coating composition with improved stability, characterized in that one or more mixtures selected from the group consisting of amine salts thereof and (vi) alkali metal salts of carboxylic acids such as sodium acetate. The method according to claim 1 or 2, The acrylic curing catalyst, 2,5-bis- (tert-butyl-peroxy) -2,5-dimethylhexane, tert-butylperoxy-2-ethyl-hexanoate, benzoyl peroxide, methyl ethyl ketone peroxide, 2, One or two or more mixtures selected from the group consisting of 2-azo-bis-isobutylonitrile, 2,2-azo-bis- (2,4-dimethylvaleronitrile) and t-butyl peroxy benzoate Abrasion resistant coating composition with improved stability. The method according to claim 1 or 2, (D) Wear-resistant coating composition with improved stability, characterized in that it further comprises 7 to 60 parts by weight of a diluent. The method of claim 8, The diluent, Wear-resistant coating composition with improved stability, characterized in that one or two or more mixed solvents selected from the group consisting of ketones, alcohols and cellosolves. In the production method of the wear-resistant coating composition according to claim 1, (A) Hydrolysis-partial condensates of alkoxysilanes having a polyoxy ethylene chain structure represented by general formula (1-1) or (1-2), and metal oxides or silicon oxides represented by general formula (2) Preparing a dispersion solution of the surface-modified nanoparticles by mixing and stirring the nanoparticles; (B) mixing and stirring the alkoxysilane represented by the general formula (3) to prepare an alkoxysilane hydrolysis-partial condensate; (C) mixing and stirring the dispersion solution of the nanoparticles obtained in step (a) and the alkoxysilane hydrolysis-part condensate obtained in step (b); (D) adding a urethane or epoxy (meth) acrylate oligomer and an acryl curing catalyst to the reaction solution obtained in the step (c), followed by mixing and stirring; And (E) adding a siloxane curing catalyst of the alkoxy silane before and after any of the above steps; a method of producing a stable wear-resistant coating composition characterized in that it comprises a. The method of claim 10, (F) The method of producing a wear-resistant coating composition with improved stability, further comprising the step of adding a diluent to the reaction solution before and after the optional step.