KR101293735B1 - Composition for preparing transparent film being capable of controlling curing temperature - Google Patents

Abstract

The present invention relates to a composition for forming a transparent film having a controlled curing temperature, and more particularly, to a composition for transparent insulating films or transparent protective films used in optical parts, liquid crystal displays, OLED displays, and touch panels. To the mixture, a thermal acid generator for generating a volatile strong acid or a thermal base generator for generating a volatile strong base, wherein the volatile strong acid or volatile strong base has a volatilization temperature of less than 250 ° C, and an acid generating temperature of the thermal acid generator is 50 ° C. The composition for transparent film formation which is above is provided.
According to the present invention as described above, by lowering the curing temperature required for film formation, it is possible to reduce the time, cost, etc. required in the process, and to expand the range of selection in relation to the heat resistance of the coating object, It is possible to minimize the deterioration of physical properties due to the heating of the object to be coated.

Description

Composition for preparing transparent film being capable of controlling curing temperature}

The present invention relates to a composition for forming a transparent film having a controlled curing temperature, and more particularly, to a composition for transparent insulating films or transparent protective films used in optical parts, liquid crystal displays, OLED displays, and touch panels. To, a thermal acid generator for generating a volatile strong acid or a thermal base generator for generating a volatile strong base, wherein the volatile strong acid or volatile strong base has a volatilization temperature of 20 ~ 250 ℃, the thermal acid generator or thermal base generator Provided is a transparent film-forming composition having an acid or base generation temperature of 50 to 250 ° C.

According to the present invention as described above, by lowering the curing temperature required for film formation, it is possible to reduce the time, cost, etc. required in the process, and to expand the range of selection in relation to the heat resistance of the coating object, It is possible to minimize the deterioration of physical properties due to heating of the object to be coated.

Optical components, electromagnetic components, flat panel display panels, etc. are used by coating a transparent insulating film or a transparent protective film used as a protective coating on the surface or the required portion. In general, the transparent protective film is intended to protect against mechanical trauma such as scratches on the surface of optical components and display panels, or to have chemical resistance, and to protect the human body from electromagnetic waves emitted when the device is used. Since the light transmittance does not decrease in spite of the coating, the transparent insulating film or the protective film contains various technical and know-how elements in the composition and coating method. do.

Conventionally, such a transparent insulating film or a protective film has been manufactured using urethane atryl, epoxy acrylate, novolac resin, and the like, and the materials have thermosetting or photosetting properties. However, in order to harden the coating-type transparent thin film made of organic resins or inorganic siloxanes to the commercialization level, a high temperature treatment of more than 250 ° C. is required, thus increasing the process cost and delaying the process in relation to the film forming process. And other problems may occur, while there is a problem in that the components to be formed are separately subjected to heat-resistant materials or subjected to heat treatment.

The present invention has been made to solve the above problems, the present invention is to reduce the manufacturing temperature of the transparent protective film or transparent insulating film applied to the optical component, display panel, etc., that is, lowering the curing temperature of the film, optical component, panel, etc. The purpose of this is to prevent the deterioration of physical properties caused by high temperature heating.

In addition, another object of the present invention is to provide a transparent coating composition which is more suitable for mass production systems by greatly reducing the process burden in terms of time and cost applied to the curing process by lowering the curing temperature during film formation.

In order to achieve the above object, the present invention comprises a hydrolyzed siloxane oligomer and a thermal acid generator for generating a volatile strong acid or a thermal base generator for generating a volatile strong base, wherein the volatile strong acid or volatile strong base is volatile. Provided is a composition for forming a transparent film having a temperature of 20 to 250 ° C and an acid or base generating temperature of a thermal acid generator or a heat base generator of 50 to 250 ° C.

The thermal acid generator or thermal base generator is preferably added to 0.01 to 10 parts by weight when the weight of the siloxane oligomer is 100 parts by weight.

The silane used in the formation of the siloxane oligomer is an alkyl-substituted trifunctional silane, a phenyl-substituted trifunctional silane, a silane bonded to a hydrocarbon group including one or more unsaturated bonds, a tetrafunctional silane, 3-mer Captopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxytriethoxysilane , Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, dimethylmethoxyacetoxysilane, dimethyl diisocyanate silane, dimethylmethoxy isocyanate silane, dimethyl screw (acetoxim) silane ( (CH ₃ ) ₂ Si [ONC (CH ₃ ) ₂ ]), methylvinyldimethoxysilane, methylphenyldimethoxysilane and diphenyldimethoxysilane are preferred.

The thermal acid generator is Bis (4-t-butylphenyliodonium) trifluoromethanesulfonate, triarylsulfonium hexafluoroandimonate, triarylsulfonium hexafluorophosphate, tetramethylammonium It is preferable that it is at least any one selected from trifluoromethanesulfonate and triethylamnefluorosulfonate.

The thermal base generator is tetramethylammonium acetate, tetramethylammonium octylate, tetrabutylammonium acetate, tetrabutylammonium octylate, trimethylbenzyl ammonium acetate, azabicycloundeceneformate, triethylamine p-toluenesulfo It is preferable that it is at least any one chosen from the nates.

It is preferable that (meth) acrylic acid ester is further added to the said composition.

It is preferable that the said acrylic acid ester is the (meth) acrylic acid ester of dihydric or more alcohol, or the (meth) acrylic acid ester oligomer of functional group number 2 or more.

It is preferable to further add an optical radical generating agent or a thermal radical generating agent to the said composition.

According to the present invention as described above, by lowering the manufacturing temperature, that is, the curing temperature of the transparent protective film or transparent insulating film applied to an optical component, a display panel, etc., a film generated by performing a curing process by a high curing temperature at the time of film formation. And physical property degradation due to high temperature heating of optical parts, panels and the like can be prevented.

In addition, the present invention can reduce the process cost and improve the process speed by lowering the curing temperature during film formation, and thus can be more suitably applied to mass production systems such as optical components, display panels.

In addition, by lowering the curing temperature of the coating, there is an effect that the coating can be formed even on a coating object that is vulnerable at high temperature such as plastic or polymer film.

In addition, by using a thermal acid generator or a thermal base generator in which strong acid, strong base generation temperature and volatilization temperature are controlled, the shelf life of the thermal acid generator and the thermal base generator is facilitated, and it does not remain in the film even after the formation of the film. In order to prevent volatilization, it is possible to prevent the physical properties of the film and the coated object from being lowered.

Hereinafter, the present invention will be described in more detail based on the preferred embodiments.

In the present invention, a siloxane oligomer having high hardness and high transparency and having excellent physical properties as a coating composition was used as the coating composition.

In more detail, a siloxane oligomer having a weight average molecular weight of 1,000 to 10,000 prepared by hydrolysis was used. By heating the siloxane oligomer at a temperature of 50 ° C. or higher, a strong acid generated in a range of 20 to 250 ° C. was generated. A thermal acid generator or a thermal base generator for generating a strong base volatilized in the range of 20 to 250 ° C is added. The thermal acid generator and thermal base generator generates a strong acid and a strong base in the temperature range of 50 ~ 250 ℃.

For example, tributylamine, which is generated by the reaction of (C4H9) 4NOCOCH3-> (C4H9) 3N + C4H9OCOCH3, is a strong base with a boiling point of 216 ° C. Trifluoromethanesulfonic acid, generated by the reaction of CF3SO3H, is a strong acid with a boiling point of 162 ° C.

Here, in view of the temperature at which the strong acid and the strong base are generated from the thermal acid generator and the thermal base generator, if a strong acid and a strong base are generated at a lower temperature than 50 ° C, it means that a strong acid and a strong base are generated at room temperature. It means that the shelf life of the generator and the heat base generator is not good, and if a strong acid or a strong base is generated at a high temperature of more than 250 ° C., the curing temperature is very high, which is not practical, and it is beyond the scope of the present invention. Thus, the temperature at which strong acids and strong bases occur is of critical significance in the above range.

On the other hand, in view of the generated strong acid and strong base volatilization temperature, the strong acid which volatilates at 250 ° C. or higher, the strong base may remain in the film even after curing, may adversely affect the applied device, and the strong acid volatilized at 20 ° C. or lower, The strong base has a problem that the time to stagnate in the film is too short and hardening does not proceed sufficiently. Therefore, the volatilization temperature of strong acid and strong base has its critical significance in the above range.

In curing by siloxane oligomer condensation polymerization, an acid or a base acts as a catalyst. Acids and bases have a catalytic effect only by adding them to the original composition batch, but when normal acids or bases are added regardless of heating, the solution becomes unstable and condensation hardens unnecessarily during storage.

Therefore, this invention is characterized by adding the compound which generate | occur | produces an acid or a base for the first time when heat is applied. In this way, when an acid or a base is generated by heating, the condensation is greatly promoted by a one-time reaction, so that the curing process can be efficiently performed. An important characteristic of such a thermal acid and thermal base generator is that acid or base is generated for the first time by heat at 50 ° C. On the other hand, in order to lower the curing temperature, acid or base must be surely generated at 250 ° C or lower. In the present invention, a material suitable for this is applied.

Examples of the silanes used in the present invention, for example, preferably alkyl substituted trifunctional silanes, especially methyl substituted trifunctional silane is more preferred, such methyl group substituted trifunctional silane Phosphorus includes methyltrimethoxysilane, methyltrichlorosilane, methylchlorodiethoxysilane, methyltriacetoxysilane, methylmethoxydiacetoxysilane, methyltriisocyanedosilane, methyltris ( Methyl ethyl methoxy mo) silane and the like.

As the silane, a phenyl group-substituted trifunctional silane can be preferably used. Examples of the phenyl group-substituted trifunctional silane include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, Phenyltriacetoxysilane, phenyltriisocyanatosilane, phenyltris (methylethylketoxymo) silane, and the like.

In addition, a silane may be used in combination with a hydrocarbon group including one or more unsaturated bonds. Particularly, a vinyl group-substituted trifunctional silane is preferably used, and such vinyl group-substituted trifunctional silane may be used. Ethoxysilane, vinyl trichlorosilane, vinyl triacetoxy silane, vinyl ethoxy diacetoxy silane, vinyl tris (menyl ethyl methoxy mo) silane and the like.

In addition, as the silane, tetrafunctional silane can be preferably used, and tetrafunctional silane is tetramethoxysilane, tetrachlorosilane, dimethoxydichlorosilane, tetraethoxysilane, tetraacetoxy Silane, tetraisocyanatosilane, tetrakis (methylethylketoxymo) silane, and the like.

Each of these silanes may be hydrolytically polymerized alone, or may be mixed and hydrolyzed.

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

In addition, examples of other silane compounds include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, dimethylmethoxyacetoxysilane, dimethyldiisocyanate silane, dimethylmethoxyisocyanate silane, and dimethyl screw. (Acetoxy) silane ((CH ₃ ) ₂ Si [ONC (CH ₃ ) ₂ ]), methylvinyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, and the like.

If the volatilization temperature of the thermal acid generator or thermal base generator is higher than 250 ° C., the strong acid or strong base generated after cure remains in the membrane, thereby significantly deteriorating the characteristics of the membrane.

Specific examples of the thermal acid generator include Bis (4-t-butylphenyl iodonium) trifluoromethanesulfonate (Bis (4-t-butylphenyl iodonium) trifluoromethanesulfonate)) and triarylsulfonium hexafluoroandimonate (Tririsulsulfoniumhexafluoroantimonate), triarylsulfonium hexafluorophosphate, tetramethylammonium trifluoromethanesulfonate, and triethylamnefluorosulfate, which is at least one selected from among Do.

The thermal acid generator is a heating condition of 50 ℃ or more, trifluoromethanesulfonic acid (Hexfluorophosphoric acid), fluorosulphonic acid (Fluorosulfonic acid) at a volatilization temperature of 250 ℃ or less Etc. It generates strong acid.

Specific examples of the thermal base generator include tetramethylammoniumacetate, tetramethylammoniu octylate, tetrabutylammonium acetate, tetrabutylammonium octylate, and trimethylbenzyl ammonium acetate. (Trimethylbenzylammoniumacetate), azabicycloundeceneformate (Azabicycloundeceneformate), triethylamine p-toluenesulfonate (Triethylamine p-toluenesulfonate) is preferably at least one selected from.

The thermal base generator generates strong bases such as trimethylamine, tributylamine, and azabiscycloundecene at a volatilization temperature of 250 ° C. or lower under heating conditions of 50 ° C. or higher.

When the addition amount is 100 parts by weight of the siloxane oligomer, the amount is preferably 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight. When the thermal acid generator or thermal base generator is added in less than 0.01 parts by weight, the effect of the addition is insignificant, and when it is added in excess of 10 parts by weight, the unreacted thermal acid generator or thermal base generator remains in the coating film. Can cause deterioration of the characteristics. Therefore, the amount of the thermal acid generator and the thermal base generator added has a critical significance in the above range.

The strong acid or strong base generated by heating is a catalyst for condensation of the OH group or the OR group at the end of the siloxane resin, and has a property of curing at a lower temperature than when it is not added.

On the other hand, in relation to the thermal acid generator or the thermal base generator, since the condensation is accelerated even when the Si-OH component is added to both the acid and the base, the effect of curing should be regarded as the same for the thermal acid generator and the thermal base generator.

Moreover, acrylic acid ester can be further added to the composition of this invention. The reason for adding the acrylate ester is to maintain the transparency of the formed film as much as possible, to give photosensitive or thermosetting properties to the coating composition, and to give flexibility to the film according to the selection of the type of acrylate ester, Or, in contrast, it is possible to impart toughness by increasing the hardness. In addition, it is possible to control the refractive index and the flame resistance of the film, and there is an advantage in that various properties can be changed in the design of the film properties. On the other hand, by applying the acrylic ester by heat or by promoting the curing together with an optical radical initiator or a thermal radical initiator, since the curing is promoted without increasing the curing temperature, there is an advantage that the curing temperature can be lowered.

Therefore, when a material which cannot be processed at a high temperature such as plastic or a film is used as a coated object, such an acrylate ester can be applied to form a film.

The specific kind of such acrylate ester is

Methyl methacrylate, Methyl acrylate, Ethyl acrylate, Ethyl methacrylate, Butyl methacrylate, Butyl acrylate , 2-ethylhexyl acrylate, 2-hydroxyhexyl acrylate, hydroxyethyl acrylate, benzyl acrylate, phenoxyethyl acrylate, tetrahydropulperyl acrylate Tetrahydrofurfulyl monofunctional (meth) acrylic acid esters such as acrylate, phenyl acrylate, naphtyl acrylate, and phenanthlyl acrylate;

Ethylene glycol diacrylate, propylene glycol diacrylate, diethyleneglycoldiacrylate, dipropylene glycol diacrylate, hexanediol diacrylate ( Hexane dioldiacrylate (HDDA), Polyethylene glycol diacrylate, Polypropylene glycol diacrylate, Bisphenol-A diacrylate, Bisphenol-A ethoxylated di Bifunctional (meth) acrylic acid esters such as bisphenol-A ethoxylated diacrylate, fluorene bisphenol diacrylate, and adamantyl bisphenol diacrylate;

Glycerin triacrylate, Trimethylol propane triacrylate (TMPTA), Trimethylol propane ethoxylated triacrylate, Pentaerythritol triacrylate (Penta) trifunctional (meth) acrylic acid esters such as erythritol triacrylate) and ditrimethylol propane triacrylate;

4 such as di trimethylol propane tetraacrylate, Di pentaerythritol hexaacrylate pentaacrylate (DTPA), dipentaerythritol hexaacrylate (DIPentaerythritolhexaacrylate, DPHA) The (meth) acrylic acid ester more than a functional is said, respectively.

Among these, it is more preferable to use a bifunctional or higher polyhydric alcohol (meth) acrylic acid ester than to use a monofunctional (meth) acrylic acid ester, which promotes hardening because more functional groups can increase crosslinking density. This is because there is an advantage in that the formed film can be formed.

In addition, an optical radical generating agent or a thermal radical generating agent may be further added to the composition of the present invention, and may be added to generate radicals by applying light or heat, and to promote curing by such radicals. Examples of the kind include oligomers having a molecular weight of 3,000 to 100,000 such as epoxy acrylate oligomer, urethane acrylate oligomer, polyester acrylate oligomer, silicone acrylate oligomer, and novolak resin acrylate.

The optical radical generating agent and the thermal radical generating agent are necessary for curing the acrylate ester, and are essentially used when the curing temperature is about 200 ° C. or less. However, when a curing temperature of 200 ° C. or more is applied, the acrylate ester may be cured only by heat, and thus, it is not necessary to use an optical radical generator and a thermal radical generator.

Here, if the molecular weight is less than 3,000 above, there is a problem that the thickness of the film is too thin because the optical radical generating agent or the heat radical generating agent is volatilized before the film is cured. If the molecular weight is larger than 100,000, the formation of the film is difficult. Range has its critical significance.

In addition, it is also possible to add a solvent, another organic resin, a crosslinking agent, a solvent, a silica, a surfactant, a dye, a viscosity modifier, an antifoamer, etc. as a component of a coating liquid by selection.

As the solvent, ketones such as alcohol, methyl ethyl ketone or acetone are used, such as ethanol or 2 propanol, and are used for improving coating properties or adjusting viscosity.

As the organic resin, solvent-soluble alkyd resins, acrylic resins, epoxy resins, urethane resins, and the like are used, and used to change the quality of the film.

As a crosslinking agent, polyacrylate monomer, isocyanuric acid crosslinked with acryl, etc. are used, and it is used in order to raise the hardness of a film | membrane.

Silica is used as a filler and is used to reduce thermal expansion or increase hardness.

Surfactants are used to improve the coating surface, and there is a wide range to choose from according to the purpose.

In addition, when color is required, dyes may be mixed and used, and for viscosity control, carboxymethyl cellulose (Carboxymethyl Cellulose), hydroxypropyl cellulose (Hydroxypropyl Cellulose) and fumed silica (Fumed Silica) are used.

An optional organic solvent is added for the purpose of dissolving and diluting the silane together with the thermal acid generator and the thermal base generator, and these solvents are mixed and used according to a drying rate or a coating performance. The purpose of dissolving and diluting the silane is used for the purpose of controlling the drying speed and the thickness of the film during coating, and the film can be thinly and uniformly formed.

The kind of solvent which can be selected is as follows.

Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, sec-butane, 1-pentanol, 2-methylbutanol, 3-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, methylpentyl acetate, - ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethyl propionate, n-butyl propionate, isoamyl propionate, Butyrolactate, n-pentyl lactate, methyl methoxy propionate, ethyl ethoxypropionate, ethyl lactate, ethyl lactate, ethyl lactate, diethyl oxalate, di- , Diethyl malonate, dimethyl phthalate, diethyl phthalate, diethyl carbonate, propylene carbonate 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-pentanediol , 2-methylpentane-2,4-diol, 2,5-hexanediol, 2,4-heptanediol, 2-ethylhexane-1,3-diol, diethylene glycol, dipropylene glycol, triethylene glycol Glycols such as tripropylene glycol and the like; 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- Dibutyl 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, 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. However, this example of mixing is also possible, as it is possible to select other solvents in different groups with different boiling points, which is only illustrative.

The mixing of the solvents is because the volatilization, viscosity, and coating properties of each of the coating films are to be considered, and it is preferable to mix the various solvents rather than one solvent to match the characteristics thereof.

In addition to the said essential component, the said coating composition has adhesion promoters, such as water, arbitrary organic solvents, organic amino compound, organic ammonium compound, reaction acceleration catalyst, such as a titanium and a tin compound, arbitrary surfactant, an antifoamer, a silane coupling agent, etc. Or the like may be added for a predetermined purpose.

≪ Example 1 >

Example 1 for producing a film-forming composition according to the present invention is as follows. However, this is only an embodiment, other embodiments are possible, and the present invention should not be construed as being limited thereto. The same is applied hereinafter.

(1) Preparation of the siloxane

According to Table 1, phenyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, and tetraethoxysilane were mixed in different compositions, and placed in a three-necked flask having a volume of about 2 liters, and a solvent. 1 liter (208.3 g) of butyl acetate was added to the flask, followed by vigorous stirring of the contents of the flask. The solution was then added dropwise for 30 minutes using a dropping funnel equipped with 2 ml of 1 molar concentration of nitric acid and 180 ml of pure water. It was. As a result, an exothermic reaction occurred in the flask contents and was initially a white cloudy solution, but stirring continued to give a colorless transparent solution.

A B Phenyltrimethoxysilane 193.8 g - Methyltrimethoxysilane - 136.2 g Vinyltrimethoxysilane 53.9 g 149.2 g Tetraethoxysilane 57.7 g 152.0 g

(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 siloxanes A and B thus obtained were mixed with additives as in the composition shown in Table 2 below, aged at 0 ° C. for 12 hours, and filtered through a 0.1 μm PTFE filter to prepare a coating composition.

One 2 3 4 5 6 Oligomer threshold A (100) A (100) A (100) B (100) B (100) B (100) Low temperature hardener none #One #2 none- #2 #2

# 1: Tetrabutylammonium acetate

# 2: DiazabicycloundeceneEthylhexanonic acid

As a result of applying the coating composition synthesized as above to the silicon wafer at a rotation speed of 1000 rpm, a transparent thin film having a thickness of 1.5 μm was formed. In the present embodiment, the coated object is a silicon wafer, but the coated object can be used in various ways without being limited to the form of glass, plastic or other materials.

(3) Property evaluation

The film thus formed was cured at a temperature of 80, 100, 120, 140, 160, 180, 200, and 220 ° C for 15 minutes, and then tested for pencil hardness and chemical resistance against propylene glycol monomethyl ether aectate (PGMEA). Table 3 shows.

Curing temperature (℃) Sample No 80 100 120 140 160 180 200 220 Pencil hardness One 1H 1H 1H 1H 2H 2H 2H 3H Chemical resistance (%) 0 0 0 0 50 80 90 98 Pencil hardness 2 1H 1H 2H 3H 4H 4H 4H 4H Chemical resistance 30 50 70 80 97 98 98 98 Pencil hardness 3 1H 1H 2H 3H 3H 4H 4H 4H Chemical resistance 20 30 60 80 92 97 98 98 Pencil hardness 4 1H 1H 3H 5H 7H 9H 9H 9H Chemical resistance 0 0 0 30 55 85 95 98 Pencil hardness 5 1H 3H 7H 9H 9H 9H 9H 9H Chemical resistance 30 60 92 98 98 98 98 98 Pencil hardness 6 1H 2H 6H 8H 9H 9H 9H 9H Chemical resistance 30 55 85 94 97 98 98 98

In general, the degree of curing of the coating can be confirmed by deriving the hardness of the coating and chemical resistance to the solvent. From the results, it can be seen that there is a significant difference between the addition and the addition of the low temperature curing agent. . In addition, the hardness and chemical resistance showed a slight difference depending on the composition of the monomer, but the role of the low temperature curing agent was clearly confirmed.

<Example 2>

In Example 2, the siloxane oligomer applied in the present invention together with the above-described coating composition of Example 1 was polymerized with an acrylic binder to confirm the properties of the coating composition.

(1) Preparation of the siloxane

As shown in Table 4, in Example 2, phenyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, tetraethoxysilane, dimethoxydemethylsilane, 3methacryl Roxypropyl trimethoxysilane and glycidoxy propyltrimethoxysilane were combined in different compositions and placed in a three-necked flask having a volume of about 2 liters, followed by adding 1 liter (208.3 g) of butyl acetate as a solvent. While the contents of the flask were vigorously stirred, a solution of 2 ml of 1 mol of nitric acid and 180 ml of pure water was added dropwise for 30 minutes using a dropping funnel installed in the flask.

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

The following glycidoxypropyltrimethoxysilane can be generally used to enhance the flexibility of the coating.

C D Phenyltrimethoxysilane 158.2 g 180.5 g Methyltrimethoxysilane 70.4 g - Vinyltrimethoxysilane - 20.5 g Tetraethoxysilane 80.1 g 28.5 g Dimethoxydimethylsilane 27.8 g 3 methacryloxypropyl trimethoxysilane 135.5 g 135.5 g Glycidoxypropyltrimethoxysilane 30.8 g 30.8 g

(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 siloxanes C and D thus obtained were mixed with additives as in the composition of Table 5 below, aged at 0 ° C. for 12 hours, and then filtered through a 0.1 μm PTFE filter to prepare a coating composition.

7 8 9 10 11 12 Oligomer threshold A (100) A (100) A (100) B (100) B (100) B (100) Acrylic crosslinking agent 20 20 20 20 20 20 Thermal radical initiator 2 2 2 2 2 2 Low temperature hardener none #One #2 none- #2 #2

# 1: Tetrabutylammonium acetate

# 2: DiazabicycloundeceneEthylhexanonic acid

As a result of applying the coating composition synthesized as above to the silicon wafer at a rotation speed of 1000 rpm, a transparent film having a thickness of 1.5 μm was formed. In the present embodiment, the coated object is a silicon wafer, but the coated object can be used in various ways without being limited to the form of glass, plastic or other materials.

Here, the thermal radical initiator may be replaced with an optical radical initiator.

And an acrylic crosslinking agent means a (meth) acrylic acid ester, and any of the acrylic acid esters enumerated above can be used. The acrylic crosslinking agent crosslinks the silane as a whole, but more particularly, crosslinking of 3methacryloxypropyltrimethoxysilane and glycidoxypropyltrimethoxysilane. This is because the 3methacryloxypropyltrimethoxysilane and glycidoxypropyltrimethoxysilane contain an acrylic component.

(3) Property evaluation

The film thus formed was cured at a temperature of 100, 120, 130, 140, 150, and 160 ° C for 10 minutes, and then tested for pencil hardness and resistance to Propylene Glycol Monomethyl ether Aectate (PGMEA). .

Curing temperature (℃) Sample No 100 120 130 140 150 160 Pencil hardness 7 1H 1H 1H 1H 2H 3H Chemical resistance (%) 0 0 0 25 35 55 Pencil hardness 8 1H 5H 6H 9H 9H 9H Chemical resistance 0 65 70 95 97 97 Pencil hardness 9 1H 4H 5H 7H 9H 9H Chemical resistance 0 55 65 85 93 97 Pencil hardness 10 1H 1H 1H 1H 2H 3H Chemical resistance 0 0 0 30 45 55 Pencil hardness 11 1H 5H 9H 9H 9H 9H Chemical resistance 35 70 92 95 95 95 Pencil hardness 12 1H 4H 7H 9H 9H 9H Chemical resistance 30 65 85 92 97 97

As in Example 1, the test was carried out, and when acrylic is included, UV curing or heat curing should be possible, and the field to be applied should be performed using a material that cannot be processed at high temperature such as plastic or film. Therefore, the temperature range was performed at a low temperature by applying an acrylate ester. Nevertheless, the effect of the low-temperature curing agent was confirmed through the present Example 2 because hardening was promoted.

Claims (8)

The hydrolyzed siloxane oligomer and the thermal acid generator for generating volatile strong acid or the thermal base generator for generating volatile strong base are mixed, and the volatile strong acid or volatile strong base has a volatilization temperature of 20 to 250 ° C. Or acid or base generation temperature of the heat base generator is 50 ~ 250 ℃,
The thermal acid generator is Bis (4-t-butylphenyliodonium) trifluoromethanesulfonate, triarylsulfonium hexafluoroandimonate, triarylsulfonium hexafluorophosphate, tetramethylammonium A composition for forming a transparent film, which is at least one selected from trifluoromethanesulfonate and triethylamnefluorosulfonate. The hydrolyzed siloxane oligomer and the thermal acid generator for generating volatile strong acid or the thermal base generator for generating volatile strong base are mixed, and the volatile strong acid or volatile strong base has a volatilization temperature of 20 to 250 ° C. Or acid or base generation temperature of the heat base generator is 50 ~ 250 ℃,
The thermal base generator is tetramethylammonium acetate, tetramethylammonium octylate, tetrabutylammonium acetate, tetrabutylammonium octylate, trimethylbenzyl ammonium acetate, azabicycloundeceneformate, triethylamine p-toluenesulfo A composition for forming a transparent film, wherein the composition is at least one selected from nates. 3. The method according to claim 1 or 2,
The thermal acid generator or thermal base generator is 0.01 to 10 parts by weight when added to 100 parts by weight of the siloxane oligomer composition for forming a transparent film. 3. The method according to claim 1 or 2,
The silane used in the formation of the siloxane oligomer is an alkyl-substituted trifunctional silane, a phenyl-substituted trifunctional silane, a silane bonded to a hydrocarbon group including one or more unsaturated bonds, a tetrafunctional silane, 3-mer Captopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrialkoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxytriethoxysilane , Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, dimethylmethoxyacetoxysilane, dimethyl diisocyanate silane, dimethylmethoxy isocyanate silane, dimethyl screw (acetoxim) silane ( _{(CH 3) 2 Si [ONC} (CH 3) 2]), to form a transparent coating, characterized in that any one of selected from the group consisting of methyl vinyl dimethoxy silane, phenyl dimethoxy silane, diphenyl-dimethoxy-silane Composition. delete 3. The method according to claim 1 or 2,
(Meth) acrylic acid ester is further added to the said composition, The composition for transparent film formation characterized by the above-mentioned. The method according to claim 6,
The acrylic acid ester is a (meth) acrylic acid ester of a dihydric or higher alcohol or a (meth) acrylic acid ester oligomer having 2 or more functional groups. A composition for forming a transparent film. The method according to claim 6,
The composition for forming a transparent film, further comprising an optical radical generating agent or a thermal radical generating agent added to the composition.