KR20110013148A - Coating composition for forming film on the surface and film - Google Patents

Abstract

PURPOSE: A coating composition for forming a film on the surface is provided to significantly increase in coating hardness to ultimately enhance the durability of materials such as substrates on which the coating is applied. CONSTITUTION: A coating composition for forming a film on the surface comprises: an oligomer obtained by simultaneously or sequentially polymerizing a 3-functional silane represented by the general formula R1SiX3, a 3-functional silane represented by the general formula R2SiX'3, and a 4-functional silane represented by the general formula SiX4 (where R1 is either an alkyl group or a phenyl group, R2 is a hydrocarbon group which includes one or more unsaturated bonds, and X, X', and X are mutually identical or different hydrolyzable groups); a radical initiator; and a solvent which dissolves the oligomer and the radical initiator.

Description

Coating composition for film formation and the film to which the composition is applied {Coating Composition for forming film on the surface and film}

The present invention relates to a coating composition for forming a film and a film to which the composition is applied. More specifically, the methyl group-substituted trifunctional silane represented by the general formula CH ₃ SiX ₃ (X is a hydrolyzable group), and general formula A vinyl-substituted trifunctional silane represented by C ₂ H ₄ SiX ' ₃ (X' is a hydrolyzable group), and a tetrafunctional silane represented by general formula SiX '' ₄ (X 'is a hydrolyzable group). An oligomer obtained by polymerization; Thermal radical initiators; And a solvent in which the oligomer and the thermal radical initiator are dissolved. The hardness of the film is further improved, and in particular, the C bond of the Si-C-Si bond is heated by heating in the polymerization process of the starting material siloxane oligomer. By producing up to four-Si- (C-) nSi (n is a natural number of 2 or more and 4 or less)-The hardness of the film is greatly improved by the above structure, thus ultimately improving the durability of the coating material such as the substrate The coating composition for film formation which can be provided, and the film to which the composition is apply | coated are provided.

Glass has physical properties based on reflection performance, transparency, and the like, and is manufactured as a mirror or applied to automobile glass, window glass, and the like based on light transmittance. However, the glass has a disadvantage that the resistance to impact is so small that it is easily broken by an instantaneous impact despite less pressure than expected.

In recent years, synthetic resins, that is, plastics having excellent impact resistance due to impact than glass have been manufactured and used in response to the weak physical properties of glass. Such plastics are widely used in place of glass in public transportation means such as trains, buses, taxis, and passenger cars. Furthermore, plastics are also used in laboratory instruments such as beakers and optical instruments such as glasses.

In particular, since the plastic has a lower weight than the glass, it has an important feature that can reduce the consumption of fuel, electricity, etc. when applied to a vehicle, such as a vehicle.

However, plastics have a very low hardness compared to glass, so that much more scratches can be generated on the surface for large and small external impacts, resulting in poor transparency and the application of the product as it looks. Apart from the mechanical strength of the structure, the service life was shortened.

Therefore, there is a need for technology development to improve the surface strength of such plastics more.

To this end, methods that can be taken include a method of improving the hardness and durability of the plastic itself, and a method of applying a release material having a hardness greater than that of plastic to the surface of the plastic.

In particular, the Republic of Korea Patent Publication No. 1997-42864 discloses a technique for the non-metallic surface coating composition with respect to the technology for improving the overall durability of the plastic product by applying a release material on the plastic surface. More specifically, 5 to 40% by weight of the polysiloxane macromer inorganic resin compound, 0.5 to 8% by weight of the silane coupling agent, 20 to 80% by weight of the acrylic copolymer, 2 to 45% by weight of the crosslinking agent and 10 to 50% by weight of the solvent. A nonmetallic surface coating agent composition is disclosed.

In particular, in order to bond the composition to the glass surface more firmly, a silane coupling agent and an acrylic copolymer were used, and a CC-based bond was formed by a copolymerization reaction, from which a Si-O bond was formed through a thermosetting reaction. The surface strength is improved by generating.

However, the Si-O bond forming the glass surface is weak in its hardness and still has a weak resistance to scratches and the like, and it is urgent to develop a surface coating material having a higher hardness.

Accordingly, the present invention has been made to solve the problems of the prior art as described above, the object of the present invention is a polymer of methyl-substituted trifunctional silane, vinyl-substituted trifunctional silane, tetrafunctional silane After adding a thermal radical initiator from the beginning and physically bonding them, the composition is thermally cured to form Si-C-Si bonds therein, such that the number of bonded Cs is up to 4 such carbon-to-carbon bonds. By producing a surface coating agent having a superior surface hardness than the conventional surface coating agent by the chain to ultimately improve the overall mechanical properties of the object to be coated.

The present invention, in order to achieve the above object, a methyl group substituted trifunctional silane represented by the general formula CH ₃ SiX ₃ (X is a hydrolyzable group), general formula C ₂ H ₄ SiX ' ₃ (X' is a hydrolyzable group An oligomer obtained by polymerizing a vinyl-substituted trifunctional silane represented by) and a tetrafunctional silane represented by the general formula SiX '' ₄ (X 'is a hydrolyzable group); Thermal radical initiators; It provides a coating composition for forming a film comprising a; and a solvent for dissolving the oligomer and the thermal radical initiator.

It is preferable that the said hydrolyzable group (X, X ', X ") is a substance containing 1-4 carbon atoms.

The material containing 1 to 4 carbon atoms preferably contains an alkoxy group, acetoxy, isocyanate, chloride, oxime.

The polymerization reaction for obtaining the oligomer is selected from radical polymerization, hydrolysis polycondensation, sequential reaction of radical polymerization and hydrolysis polycondensation, sequential reaction of hydrolysis polycondensation and radical polymerization, and simultaneous reaction of radical polymerization and hydrolysis polycondensation. It is preferable that it is either.

It is preferable to make the said coating composition for film formation apply | coat on a board | substrate.

By the polymerization reaction, a Si- (C-) nSi (n is a natural number of 2 or more and 4 or less) bond is formed from an oligomer having-(Si-O-) n (n is a natural number of 20 or more) as the main chain.

The present invention also provides a coating to which the composition is applied.

As can be seen from the above, according to the present invention, the surface hardness and abrasion resistance of the coating are remarkably increased by a large number of C conjugates, and in particular, the effect of preventing surface scratching is expected.

Moreover, the effect with which the adhesiveness with a to-be-coated object is improved and peeling or a crack of a film is reduced is expected.

In addition, especially when the thermal initiator is used, since the overall curing of the coating can be made quickly, an effect that can form a more robust coating in a short process time is expected.

In addition, especially in the case of using a thermal initiator, since the heat source is cheaper in terms of the cost of the equipment than the light source, it is expected that the effect of reducing the cost of the process.

In addition, it is expected that the coating applied to the substrate or the like has a higher hardness and dielectric breakdown voltage characteristics than the coating prepared by the conventional method or composed of the conventional components so that the substrate can be strengthened as a whole.

EMBODIMENT OF THE INVENTION Hereinafter, the preferable Example of the film forming agent which concerns on this invention which has a structure as mentioned above is demonstrated in detail.

The coating composition according to the present invention is a methyl group-substituted trifunctional silane represented by general formula CH ₃ SiX ₃ (X is a hydrolyzable group), general formula C ₂ H ₄ SiX ' ₃ (X' is a hydrolyzable group). An oligomer obtained by polymerizing a vinyl-substituted trifunctional silane represented by the general formula, and a tetrafunctional silane represented by the general formula SiX '' ₄ (X '' represents a hydrolyzable group); Thermal radical initiators; And a solvent in which the oligomer and the thermal radical initiator are dissolved.

Wherein X, X ', and X' 'represent a halogen element as a hydrolyzable group; Halogen groups such as cyanide, cyanate, isocyanate and thiocyanate; Amino groups such as amino, methylamino, ethylamino, propylamino, butylamino, anilino, phenylmethylamino, dimethylamino, diethylamino, dipropylamino, N-phenyl-N-methylamino and the like; Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secbutoxy, t-butoxy and benzyl; Acyloxy groups such as acetoxy, propioxy, pivaloxy, octyloxy and benzoxoxy; Methylethylketoxymo, acetoaldoximo, acetoxymo, butylaldoximo, hexanononeoxymo, 4-pentene-2oxymo, cyclopentaoxymo, cyclohexaoxymo, 2-methylcyclopentaoxime, benzaldoxime Oximes such as acetophenoxime, benzophenoxime and benzyl ethyl methoxymox; Hydrogen etc. are mentioned, X, X ', X "may mutually be same, and may differ from each other.

It is preferable here to use substances such as alkoxy groups, acetoxy, isocyanates, chlorides, oximes, preferably containing 1 to 4 carbons (C1 to C4). This is because in the case of the hydrolyzable group having a carbon number in the above range, the hydrolysis reaction rate is high and the degree of hydrolysis completeness is high.

The silanes form a copolymer by a cross copolymerization reaction.

The copolymers are basically a mixture of Si-OH bonds and Si-CH = CH 2 bonds. Each of the bonds forms Si-O-Si bonds, Si-CC-Si, Si-CCC-Si, and Si-CCCC-Si bonds by thermal curing with the participation of a thermal radical initiator, and these bonds form a network structure. Will be achieved.

Among them, the Si-CC-Si, Si-CCC-Si and Si-CCCC-Si bond structures represented by Si- (C-) nSi (n is a natural number of 2 or more and 4 or less) make the two siloxane chains very firm. Due to the bonding has a very high hardness compared to the Si-O bonding structure, this bonding structure plays a crucial role to improve the mechanical properties of the coating and the coated object. In particular, the greater the number of C included in the C-chain chain, the greater the hardness, and thus the present invention is characterized by the production of a C-chain chain including such a large number of C.

The present invention introduces a thermal initiator into the initial composition and reacts with the copolymer at the same time during the thermal curing to draw Si- (C-) nSi bond (n is a natural number of 2 or more and 4 or less) to improve the density and hardness of the film It will be noted that there is a feature, and it should be noted that this makes a significant difference from the prior art.

The reaction for generating a bond in the form of Si-O-Si and Si- (C-) nSi (n is a natural number of 2 or more and 4 or less) is expressed as follows.

(1) 2Si-OH → Si-O-Si + H ₂ O

(2) 2Si-CH ₃ + [O] → Si-CH ₂ -CH ₂ -Si + H ₂ O

(3) Si-CH ₃ + CH ₂ = CH-Si- + [O] → Si-CH ₂ -CH ₂ -CH (OH) -Si

(4) n-Si-CH = CH ₂ → [-CH (-Si) -CH ₂ -CH (Si-)-CH _2- ] n

That is, the Si-O-Si binder is reacted by the reaction of (1) during thermosetting, and Si- (C-) nSi (n is a natural number of 2 or more and 4 or less) by the reaction of (2) to (4). It can be said that the surface hardness of the coating is very high by forming bonds and forming them into a polymer.

A more specific polymerization method is as follows, and the three types of silanes mentioned above form an oligomer by superposing | polymerizing by the method mentioned later.

(1) hydrolysis axial polymerization method

After mixing each of the silane monomers (three types) in the raw state, water and a catalyst are added to hydrolyze to generate silanol groups (SiOH), and the silanol groups are reacted with each other to perform axial polymerization. In this case, the silane monomers in the raw state may be hydrolyzed independently of each other to produce silanol groups, and then mixed and induced to react and condensation polymerization.

Since hydrolysis and axial polymerization are mutually different reactions, it is common to proceed sequentially. However, such hydrolysis and axial polymerization may be performed simultaneously. In addition, the catalyst of hydrolysis and the catalyst of axial polymerization may mutually be same or different.

In addition, the silane monomer may be dissolved in any organic solvent such as alcohol, ketone, ester, ether, hydrocarbon, and the like before use. At this time, the solvent used for dilution of the silane monomer is preferably compatible with the silane monomer or water for the uniform progress of the reaction, but this compatibility is not essential and may be somewhat insufficient.

The amount of water used for hydrolysis is added in an amount of 0.5 to 10 equivalents to 1 equivalent of the hydrolyzable group contained in the silane.

If the equivalent of water is less than 0.5 equivalent, the molecular weight of the polymer does not increase sufficiently, and if it exceeds 10 equivalent, the concentration of the silane monomer relative to the relative reaction system decreases, or water phase separation is undesirable. More preferably, the water equivalent is in the range of 1.0 to 5.0 equivalents.

As a catalyst for hydrolysis, hydrochloric acid, hydrofluoric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, inorganic acids such as hydrofluoric acid (H2SiF6), formic acid, acetic acid, lactic acid, oxalic acid, succinic acid, citric acid, toluenesulfonic acid, trifluoroacetic acid, tri Organic acids such as fluoromethanesulfonic acid, weakly acidic ion exchange resins, strongly acidic ion exchange resins, solid acids such as activated aluminum oxide, ammonia, methylamine, dimethylamine, trimethylamine, triethylamine, isopropylamine, butylamine, tributyl Amines such as amines, cyclohexylamines, benzylamines, ethylenediamines, diethylenetriamines, piperadines, polyethylene imines, tetramethylamine hydroxides, tetrabutylamine hydroxides, butyltrimethylamine hydroxides, tetramethylammonium hydroxides, Organic alkalis such as triphenylphosphonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide Alkali alkoxides, such as a quick hydroxide, sodium methoxide, and sodium ethoxide, Lewis acids, such as aluminum chloride, a triphenylphosphine, and boron trifluoride, titanium chloride IV), titanyl sulfate, titanium nitrate, and titanium Titanium compounds such as tetraisopuroxide, titanium tetra-n-butoxide, titanium tetrastearate, bisacetylacetonite diisopuropoxytitanium, tetrakisacetacecetonatotitanium, aluminum sulfate, aluminum nitrate, and isotonic acid Aluminum compounds, such as aluminum, aluminum triisopuroxide, an aluminum second butoxide, acecylacetonato diisopuroxy aluminum, and a trisacetylacetonato aluminum, are used.

Among them, volatile acids such as nitric acid, hydrochloric acid, formic acid, acetic acid, trifluoroacetic acid, etc., in which the reaction proceeds relatively gently and do not take long separation, are very suitable as catalysts.

Although the addition amount of a hydrolysis catalyst changes with kinds of catalyst, 0.0001-1 molar equivalent is used with respect to a silane.

When an acid is used as a catalyst, a relatively high concentration of 0.001 to 0.1 molar equivalents, and when a base is used, 0.0001 to 0.01 molar equivalents are preferable.

If the catalyst concentration is less than 0.0001 molar equivalent, the reaction rate is drastically lowered and is not suitable for practical application. If the catalyst concentration is higher than 1 molar equivalent, the reaction rate is greatly increased, making it difficult to control the catalyst separation process. It is not desirable to proceed separately.

The temperature range of the hydrolysis and condensation polymerization step is in the range of low temperature to reflux temperature of about 0 ° C., depending on the blending ratio of the monomer, the catalyst, the dilution solvent and the amount thereof, and the time range is 0.1 hour to 30 hours. It is preferable to set it as the range of work. Where The reflux temperature is more preferably between 35 and 180 ° C.

The reflux temperature is determined by the type of solvent used, and in the case of 0 ° C. or lower, water used as a catalyst solidifies, which is not preferable.

For example, when 0.01 mol equivalent of an organic acid is used as a catalyst and the monomer is diluted with ethanol in a ratio of 1: 1, it is made to react at reflux for 2 to 8 hours.

In carrying out such a copolymerization reaction, an OH group, an isocyanate, an epoxy compound, or the like copolymerizable with silanol may be copolymerized with the silane monomer.

Examples of the silanes include the methyl group-substituted trifunctional silanes such as methyltrimethoxysilane, methyltrichlorosilane, methylchlorodiethoxysilane, methyltriacetoxysilane, and methylmethoxydiacetoxysilane. Phosphorus, methyltriisocyanedosilane, methyltris (methylethylketoxymo) silane, and the like. Examples of the vinyl-substituted trifunctional silane include vinyltriethoxysilane, vinyltrichlorosilane, and vinyltriacene. Methoxy silane, vinyl ethoxy diacetoxy silane, vinyl tris (menylethyl methoxymo) silane, etc., tetrafunctional silane, tetramethoxy silane, tetrachloro silane, dimethoxy dichloro silane , Tetraethoxysilane, tetraacetoxysilane, tetraisocyanatosilane, tetrakis (methylethylketoxymo) silane, and the like. Each of these silanes may be hydrolyzed and polymerized alone, or may be mixed and hydrolyzed.

Other silanes may also be used, such as 3-mercaptopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-acryloxypropyltriethoxy Silane, 3-methacryloxytriethoxysilane, and the like.

It is also possible to copolymerize hydrolyzable compounds containing elements other than silicon, such as boron, phosphorus, aluminum, titanium, zirconium, and the like.

(2) radical polymerization method

After mixing each of the silane monomers (three types) in the raw state, a radical initiator is added to polymerize the monomers.

This is different from the method of curing using a thermal initiator after hydrolysis, and forms Si- (C-) nSi (n is a natural number of 2 or more and 4 or less) bond in advance to obtain higher reaction efficiency and greatly improve the hardness of the film. I would like to.

As mentioned above, it is vinyl silane and methyl silane which contribute to radical polymerization, respectively, and superpose | polymerize by the same reaction below. This radical reaction forms silane-free oligomers.

(1) Si-CH ₃ + CH ₃ -Si → SiCH ₂ -CH ₂ Si (dehydration reaction)

(2) Si-CH ₃ + CH ₂ = CH-Si → Si-CH (OH) -CH ₂ CH ₂ -Si

(3) Si-CH = CH ₂ + CH ₂ = CH-Si → Si-CH = CH-CH ₂ CH ₂ -Si

However, although the reaction of (3) proceeds with a general radical initiator, the reaction of (1) and (2) may proceed by radically reacting with an organic peroxide (peroxide).

Specifically, 0.001 to 1% by weight of a radical initiator is added to the silane, followed by stirring while heating to polymerize.

If the radical initiator is 1% by weight or more, the molecular weight tends to be very small, and if it is 0.001% by weight or less, the polymerization reaction does not occur, the radical initiator has a critical significance in the above range.

As the radical initiator, any substance which generates free radicals by heating may be used, but preferably, azo compounds, azo-amide compounds, peroxides, diphenyl alkanes, benzophenone derivatives, and the like may be used. It is characterized by solubility and high stability, and organic peroxides capable of high-efficiency polymerization at low temperatures are preferred. Si- (C-) nSi (n is a natural number of 2 or more and 4 or less) bonds occur only when the reaction occurs at a lower temperature than at a high temperature.

Examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide and acetylacetone peroxide; 1,1-bis (t-hexyl peroxide-3, 3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy)- 2-methylcyclohexane, 1,1-bis (t-butyperoxy) cyclohexane, 2,2-bis (t-butyperoxy) butane, 3,3-bis (t-butyperoxy) butylpentano Peroxy ketals such as 8, 2,2-bis (4,4-bis (t-butyperoxy) cyclohexyl) propane; p-mentane hydroperoxide, diisopropyl benzenehydroperoxide, 1,1, Hydroperoxides such as 3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, bis (2-t-butylperoxyisopropyl) benzene, dicumylperoxide, 2,3- Imethyl-2,5-bis (t-butylperoxy) hexane, t-butyl cumyl peroxide, di-t-hexyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5- dialkalperoxides such as bis (t-butylperoxy) hexane-3, di-isobutyl peroxide, bis (3,5,5-trimethylhex Diacryl peroxides such as noyl) peroxide, dilauroxyl peroxide, disuccinic acid peroxide, bis (3-methylbenzoyl) peroxide, dibenzoyl peroxide, bis (4-methylbenzoyl) peroxide; n-propyl peroxydicarbonate, di-isopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, bis (2-ethylhexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate Oxycarbonates: cumyl peroxy neodicanoate, 1,1,3,3-tetramethylbutyl peroxy neodiganoate, t-hexyl peroxy pivalate, t-butyl peroxy pavalate, 1,1, 3,3-tetramail butylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) helic acid, t-hexylperoxy-2-ethylhexano T-butylperoxy-2-ethylhexanoate, t-hexyl peroxy isopropyl monocarbonate, t-butyl peroxy malic acid, t-butyl perox -3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate Peroxy acid esters such as 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy acetate, t-butylperoxy-3-methylbenzoate and t-butylperoxybenzoate Ryu; peroxyalkyl compounds such as t-butylperoxyallyl monocarbonate and 3,3'4,4'-tetrakis (t-butylperoxycarbonyl) benzophenone.

Moreover, in order to control molecular weight, you may add arbitrary chain reaction additives, such as a mercapto propionic acid ester, dibutoxy hydroxytoluene, and a melcapto benzothiazole.

Any organic solvent is added for the purpose of dissolving and diluting the thermal initiator and silane. Solvent is used by mixing according to drying speed or coating performance. The kind of solvent which can be selected is as follows.

Methanol, ethanol, 2-propanol, 1-propanol, 1-butanol, 2-butanol, sec-butan, 1-pentanol, 3-methylbutanol, 2-methylbutanol, 2-pentanol, 4-methyl-2- Alcohols such as pentanol, cyclohexanol, methylcyclohexanol, n-hexanol, perfuryl alcohol, perfuryl methanol, tetrahydrofurfuryl alcohol, benzyl alcohol; Acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, methyl t-butyl ketone, methyl n-pentyl ketone, methyl n-hexyl ketone, diethyl ketone, diisopropyl ketone, diisobutyl ketone, cyclo Ketones such as pentanone, cyclohexanone, methylcyclohexanone, cycloheptanone, cyclooctanone, 2,4-pentanedione, 2,5-hexadione and acetophenone; n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, octane, isooctane, 2,2,4-triethylpentane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, tri Hydrocarbons such as ethylbenzene, ethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, pentylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene and diisopropylbenzene; Tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, di-n-propyl ether, di-isopropyl ether, di-n-butyl ether, diisobutyl ether, di-n-hexyl ether, anisole, Phentol, diphenyl ether, ethyl benzyl ether, bis (2-ethylhexyl) ether, propylene oxide, 1,2-propylene oxide, 1,4-dioxane, 4-methyldioxoleine, dimethyldioxoleine, Ethers such as gresyl methyl ether, dibenzyl ether, buty phenyl ether; Methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2 Ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethyl propionate, n-butyl propionate, isoamyl propionate, methylpyru Bate, ethylpyruvate, diethyl oxalate, di-n-butyloxalate, methyl lactate, ethyl lactate, butyl lactate, n-pentyl lactate, methyl methoxy propionate, ethyl ethoxy propionate , Diethyl malonate, dimethyl phthalate, diethyl phthalate, diethyl carbonate, propylene carbonate, etc. Esters; Lactones such as gamma-butyrolactone, gamma-valerolactone and delta-valerolactone; Nitriles such as acetonitrile, propiononitrile, acrylonitrile, ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2-pentanecediol, 2,4-pentane Diol, 2-methylpentane-2,4-diol, 2,5-hexanediol, 2,4-heptanediol, 2-ethylhexane-1,3-diol, diethylene glycol, dipropylene glycol, triethylene Glycols such as glycol and tripropylene glycol; Hydroxyacetone (acetol), 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy Hydroxy ketones such as -4-methyl-2-pentanone; As glycol ethers, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol mono n-butyric ether, ethylene glycol mono n-pentyl ether, ethylene glycol mono n-hexyl ether, ethylene Ethylene glycol monoethers such as glycol mono2-ethylbutyl ether, ethylene glycol mono2-ethylhexyl ether, and ethylene glycol monophenyl ether; Ethylene glycol diethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol methyl ethyl ether, and ethylene glycol dibutyl ether; Ethylene glycol acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol moto n-butyl ether acetate, and ethylene glycol diacetate; Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, such as propylene glycol monoether, propylene glycol dimethyl ether, propylene glycol di Propylene glycol diethers such as ethyl ether and propylene glycol methyl ethyl ether; Propylene glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono n-propyl ether acetate, propylene glycol mono n-butyl ether acetate, and propylene glycol diacetate; 3-methoxy-1-butanol, 3-methoxybutylacetate, 3-methyl-3-methoxy-1-butanol, 3-methoxy-1-butylacetate, 3-methyl-3-methoxy-1- Diethyl glycol, such as butylene glycol derivatives, such as butyl acetate, diethyl glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol mono n-butyl ether, and diethylene glycol mono n-hexyl ether Monoethers; Diethylene glycol diethers such as diethylene glycol dimethyl ether, diethylene glycol methylethyl ether and diethylene glycol diethyl ether; Diethylene glycol acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol mono n-butyl ether acetate; Dipropylene glycol monoethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monopropyl ether; Dipropylene glycol diethers such as dipropylene glycol dimethyl ether; Dipropylene glycol such as dipropylene glycol monomethyl ether, triethylene glycol monoethyl ether, triylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether, tripropylene glycol monomethyl ether acetate, tetraethylene glycol di-n-butyl ether Acetates; As a heterogeneous compound, N-methylpyrrolidinone, N, N-dimethylimide azolidinone, formimide, N-methylformamide, N-ethylformamide, N, N-dimethylformamide, N, N -Diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methylpropionamide, N, N-dimethylsulfoxide, sulfolane, 1, 3-propanesultone and the like.

Preferably, a solvent having a boiling point of 100 ° C. or lower is preferably mixed with a solvent having a boiling point of 120 ° C. to 160 ° C., for example, a group consisting of ethanol, 2-propanol, cetbutyl alcohol and propylene glycol monomethyl A group consisting of ether, propylene glycol monomethyl ether acetate, methyl isobutyl ketone and n-propyl acetate is mixed with each other.

The overall reaction time takes about 1 to 12 hours.

Moreover, the said hydrolysis axial polymerization and radical polymerization can also advance simultaneously by adding water, a catalyst, and a thermal radical initiator simultaneously.

In addition, the hydrolysis axial polymerization may be followed by radical polymerization, or after the radical polymerization, the order may be determined in the direction of hydrolysis axial polymerization.

In addition to the said essential component, the said coating composition adhere | attaches water, arbitrary organic solvents, organic amino compound, organic ammonium compound, reaction promotion catalysts, such as a titanium and a tin compound, arbitrary surfactant, a defoaming agent, a silane coupling agent, etc. An accelerator or the like may also be added for a predetermined purpose.

Moreover, the adhesion promoter and surfactant based on the alkoxy silane can also be copolymerized previously with a silane compound.

<Examples>

The manufacture example for manufacturing the coating composition by this invention is as follows.

(1) Preparation of the siloxane

190.3 g of vinyltriethoxysilane, 178.3 g of methyltriethoxysilane, 208.3 g of tetraethoxysilane, and 1 liter of butyl acetate were placed in a three-necked flask having a capacity of about 2 liters, and the contents of the flask were vigorously stirred. The solution which mixed 2 ml of nitric acid of molar / liter concentration and 180 ml of pure waters was dripped for 30 minutes using the dropping funnel installed in the flask.

As a result, an exothermic reaction occurred in the flask contents, and initially a white cloudy solution, but stirring continued to give a colorless transparent solution.

(2) Preparation of Coating Composition

Thereafter, after the temperature of the contents became 50 ° C. or less, a reflux condenser was installed, and the mixture was heated under normal pressure to reflux for 3 hours.

The siloxane thus obtained was mixed with additives in the ratio shown in Table 1, aged at 0 ° C. for 12 hours, and then filtered through a 0.1 μm PTFE filter to prepare a coating composition.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Oligomer threshold 100 100 100 100 100 100 Thermal radical initiator #One #2 # 3 #One #2 - menstruum PGMEA PGMEA IPA IPA PGME PGMEA Light transmittance > 98% > 98% > 98% > 98% > 98% > 98% Pencil hardness 9H 9H 9H 9H 9H 2H Insulation > 3.0MV / cm > 3.0MV / cm > 3.0MV / cm > 3.0MV / cm > 3.0MV / cm 1.0 MV / cm

# 1: Bis (3-methylbenzoyl) peroxide

# 2: Bis (2-t-butylperoxyisopropyl) benzene

# 3: Bis (2-ethylhexyl) peroxydicarbonate

The coating solution prepared as described above was applied to alkali-free glass at a rotational speed of 1000 rpm to form a 500 nm transparent thin film.

(3) Property evaluation

The thin film thus formed was prebaked at a temperature of 100 ° C. for 15 minutes, and then cured at a temperature of 250 ° C. for 15 minutes, followed by visible light transmittance, pencil hardness test, and dielectric breakdown voltage test.

Unlike the coating composition which does not use the conventional thermal radical initiator, the composition prepared as described above generates Si- (C-) nSi (n is a natural number of 2 or more and 4 or less) bonds in addition to Si-O bonds, so that the bond strength is relatively high. It was found to be high, which can be seen from the above chemical equation.

Therefore, as can be seen from Table 1, it can be seen that the coating composition prepared by the present invention was measured at least four times higher than the coating composition prepared by excluding the conventional thermal radical initiator, and even in the case of dielectric breakdown voltage 3 It was found to be twice as high. However, no difference was observed between the two compositions as the light transmittance was not an element that depends on the thermal radical initiator.

Claims (9)

Methyl group substituted trifunctional silane represented by general formula CH ₃ SiX ₃ (X is a hydrolyzable group), vinyl group substituted trifunctional represented by general formula C ₂ H ₄ SiX ' ₃ (X' is a hydrolyzable group) An oligomer obtained by polymerization of a silane, a tetrafunctional silane represented by the general formula SiX '' ₄ (X '' is a hydrolyzable group) with a catalyst; Thermal radical initiators; And A solvent for dissolving the oligomer and thermal radical initiator; It is configured to include, these coating components for forming a coating, characterized in that the components are formed by polymerization. The method of claim 1, The hydrolyzable group (X, X ', X' ') is a coating composition for forming a film, characterized in that the material containing 1 to 4 carbon atoms. The method of claim 2, The material containing the carbon number of 1 to 4 is a composition for forming a film, characterized in that it contains an alkoxy group, acetoxy, isocyanate, chloride, oxime. The method of claim 1, The thermal radical initiator is a film forming composition, characterized in that 0.001 ~ 1% by weight relative to the total weight of the silane. The method of claim 1, The polymerization reaction to obtain the oligomer The film is any one selected from radical polymerization, hydrolysis polycondensation, sequential reaction of radical polymerization and hydrolysis polycondensation, sequential reaction of hydrolysis polycondensation and radical polymerization, and simultaneous reaction of radical polymerization and hydrolysis polycondensation. Coating composition for formation. The method of claim 1, The thermal radical initiator includes ketone peroxides, peroxy ketals, hydroperoxides, dialkal peroxides, diacryl peroxides, peroxycarbonates, peroxyacid esters, and peroxyalkyl compounds. It is an organic peroxide, The coating composition for film formation characterized by the above-mentioned. The method of claim 1, The coating composition for forming a film is a coating composition for forming a film, characterized in that the coating on the substrate. The method of claim 1, Si- (C-) nSi (n is a natural number of 2 or more and 4 or less) bonds are formed from the oligomer having-(Si-O-) n (n is a natural number of 20 or more) as a main chain by the polymerization reaction. Coating composition for film formation to say. The film of Claim 1 is apply | coated.