WO2011013921A2 - Composition for forming a coating and coating applied with the composition - Google Patents

Abstract

The present invention relates to a composition for forming a coating and to a coating applied with the composition, and more particularly, to a composition for forming a coating and to a coating applied with the composition, which significantly increase in coating hardness to ultimately enhance the durability of materials such as substrates on which the coating is applied, wherein the composition consists of: 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 SiX”₄ (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, to significantly improve the hardness of the coating by means of a Si-(C-)nSi structure (where n is a natural number from 2 to 4), particularly by enabling heating during the polymerization of a siloxane oligomer as a starting material to produce up to 4 C bonds in an Si-C-Si bond.

Description

Composition for film formation and film to which the composition is applied

The present invention relates to a composition for forming a film and a film to which the composition is applied, and more particularly, a trifunctional silane represented by the general formula R ₁ SiX ₃ and a trifunctional represented by the general formula R ₂ SiX ' ₃ . Oligomers obtained by simultaneous or sequential polymerization of silanes, tetrafunctional silanes represented by the general formula SiX '' ₄ , wherein R ₁ is at least one selected from alkyl groups or phenyl groups, R ₂ is one or more unsaturated The hydrocarbon group containing the bond, X, X 'and X "are the same or different from each other, a hydrolyzable group); a radical initiator; and a solvent in which the oligomer and radical initiator are dissolved. In particular, Si- (C-) nSi (n is 2 or more) by producing up to four C-bonds of Si-C-Si bonds by heating during polymerization of the starting material siloxane oligomer. The natural hardness of 4 or less) provides a coating film having a coating composition and a composition for forming a coating which can greatly improve the hardness of the coating, and ultimately improve the durability of the coating material such as a substrate.

Glass has physical properties characterized by reflection performance, transparency, and the like, and thus, it is applied to automobile glass, window glass, or the like, because the mirror is manufactured or translucent. However, the glass has a disadvantage in that the resistance to impact is so small that it is easily broken even though it is under pressure when instantaneously applied.

Therefore, recently, in the application field, synthetic resins, that is, plastics having excellent impact resistance than glass have been manufactured and used. Plastics are widely replacing glass applied areas of public transportation such as trains, buses, taxis, and passenger cars, and are expanding their application areas to beakers, flasks, laboratory equipment, glasses, telescopes, and cameras.

In particular, such plastics have a smaller weight per unit volume than glass, and in particular, when the plastic is applied to a vehicle such as a vehicle, fuel consumption or battery consumption of the vehicle may be reduced.

However, since plastics have a very low hardness compared to glass, it is easy to cause scratches, and thus, the transparency of the plastics is degraded, and as a result, the entire product to which the plastic is applied looks old or worn out despite its short lifespan. There was a problem of unreasonably shortening the life of the product by advancing the replacement time of the product by the user who is dissatisfied with the appearance.

Therefore, while continuously applying this by acknowledging the superiority of plastics, there is an urgent need to develop a technology that can reinforce the weaknesses of these plastics.

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. However, in order to improve the hardness and durability of the plastic itself, investment in related technologies should be made. Due to the nature of new material development, it takes a long time to develop the technology, and in terms of processing technology such as shape processing technology of the developed high hardness and high durability plastic There is a problem that technology development is not simple, such as a new condition must be presented. Therefore, a method of applying a release material can be considered as a simpler method.

As described above, the Republic of Korea Patent Publication No. 1997-42864 discloses a technique related to a non-metallic surface coating composition with respect to a technology of improving the overall durability of a plastic product by applying a release material to a 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, an object of the present invention is to polymerize a plurality of silanes, and then to add a radical initiator from the beginning in the polymerization of the film-forming composition By thermal curing it to form a Si-C-Si bond from the composition, the number of carbon (C) to be bonded by up to four, by the inter-carbon bond is a surface coating agent with superior surface hardness than the conventional surface coating agent It is to make the ultimate effect to improve the mechanical properties, such as resistance to the scratch of the coating object.

The present invention, in order to achieve the object as described above, trifunctional silane represented by the general formula R ₁ SiX ₃ , trifunctional silane represented by the general formula R ₂ SiX ' ₃ , general formula SiX'' ₄ Oligomers obtained by polymerizing a tetrafunctional silane simultaneously or sequentially represented by (wherein R ₁ is at least one selected from an alkyl group or a phenyl group, R ₂ is a hydrocarbon group containing at least one unsaturated bond, X, X 'And X' are the same or different hydrolyzable groups), a radical initiator, and a solvent for dissolving the oligomer and the radical initiator; and provide a film-forming composition in which these components are formed by polymerization.

The silane is a methyl group substituted trifunctional silane represented by the general formula CH ₃ SiX ₃ in the case of an alkyl group substituted trifunctional silane in the trifunctional silane represented by the general formula R ₁ SiX ₃ , and R ₂ SiX "in the case of a trifunctional silane represented by the general formula ₃ C ₂ H ₃ SiX 'is preferably a vinyl group substituted with a trifunctional silane represented by _3.

The hydrolyzable group (X, X ', X' ') is preferably at least any one selected from a halogen element, hydrogen, or a carbon compound containing 1 to 4 carbons.

The carbon compound containing 1 to 4 carbons includes a halogen group, an alkylamino group, an alkoxy group, an acyloxy group, and an oxime group, and preferably at least one of them.

The halogen group is an isocyanate, the alkoxy group is at least one selected from methoxy or ethoxy, the acyloxy group is acetoxy, the oxime group is methyl ethyl methoxy.

The radical initiator is preferably 0.001 to 1% by weight when the total weight of all the silanes is 100.

The polymerization reaction for obtaining the oligomer is carried out in the 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 to use any one selected.

The radical initiator is at least one of ketone peroxides, peroxy ketals, hydroperoxides, dialkal peroxides, diacryl peroxides, peroxycarbonates, peroxyacid esters, and peroxyalkyl compounds. It is preferable that it is an organic peroxide containing.

In addition, the present invention provides a composition for forming a film in which the structure of the main chain is a siloxane oligomer of the formula (1), the side chain is crosslinked by heating to generate the structure of the formula (2).

Formula (1):-(Si-O-) n n is a natural number of 20 or more

Formula 2: Si- (C-) nSi n is a natural number of 2 or more and 4 or less

It is preferable that the said film forming composition is apply | coated on a board | substrate.

In addition, the present invention provides a film formed by applying the film-forming composition on a substrate in order to achieve the above object.

As can be seen from the above, according to the present invention, the bond structure by carbon (C) of the film formed from the film-forming composition is strengthened, and the surface hardness and abrasion resistance of the film are remarkably increased, in particular, surface scratching is prevented. The effect is expected to be.

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 anticipated.

In addition, especially when the thermal initiator is used, since the entire curing of the film can be made quickly, an effect that can shorten the process time is expected.

In addition, especially in the case of using a radical initiator, since the heat source is inexpensive in terms of the cost of the equipment compared to 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 trifunctional silane represented by the general formula R ₁ SiX ₃ , a trifunctional silane represented by the general formula R ₂ SiX ' _3, and a tetrafunctional represented by the general formula SiX'' ₄ . Oligomers obtained by polymerization of silanes simultaneously or sequentially (wherein R ₁ is at least one selected from alkyl or phenyl groups, R ₂ is a hydrocarbon group comprising one or more unsaturated bonds, X, X 'and X " Hydrolyzable groups identical or different from each other), a radical initiator, and a solvent for dissolving the oligomer and the radical initiator.

R ₁ is at least one selected from an alkyl group or a phenyl group, R ₂ is a hydrocarbon group including one or more unsaturated bonds, and specific examples thereof will be described later.

In addition, X, X ', X' 'is a hydrolyzable group,

(1) halogen elements

(2) hydrogen

(3) carbon compounds containing 1 to 4 carbons

At least any one of, in particular the carbon compound,

(3-1) halogen groups such as cyanide, cyanate, isocyanate and thiocyanate;

(3-2) alkylamino groups such as amino, methylamino, ethylamino, propylamino, butylamino, anilino, phenylmethylamino, dimethylamino, diethylamino, dipropylamino, N-phenyl-N-methylamino and the like;

(3-3) alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secbutoxy, t-butoxy, benzyl;

(3-4) acyloxy groups such as acetoxy, propioxy, pivaloxy, octyloxy and benzoxoxy;

(3-5) Methylethylketoxymo, acetoaldoximo, acetoxymo, butyl adoximo, hexanoneoxymo, 4-pentene-2oxymo, cyclopentaoxymo, cyclohexaoxymo, 2-methylcyclo Oxime groups such as pentaoxime, benzal doxime, acetophenoxime, benzophenoxime and benzyl ethyl methoxymox;

Etc. can be mentioned.

Here, X, X ', X' 'may be the same as or different from each other.

Also, among the carbon compounds containing 1 to 4 carbons above, at least one of isocyanate in the halogen group, methoxy or ethoxy in the alkoxy group, acetoxy in the acyloxy group and methyl ethyl methoxy in the oxime group It is better to use the back. 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.

On the other hand, a hydrolysis reaction using hydrogen and a halogen element as a hydrolyzable group is as follows.

Si-H + H ₂ O = Si-OH + H ₂ (reacts under conditions of high temperature or high pH)

Si-Cl + H ₂ O = Si-OH + HCl (very fast reaction rate)

Here, when the hydrogen is hydrolyzed as a hydrolyzable group, the reaction occurs under conditions of high temperature or high pH, and when hydrolyzed with a halogen element (here, chlorine) as a hydrolyzable group, the reaction rate is very fast. There is this.

The silanes form a copolymer by a cross copolymerization reaction.

Representatively, the main chain is composed of a siloxane oligomer having a main chain structure of-(Si-O-) n (n is a natural number of 20 or more), and when such a siloxane oligomer is heated, side chains are crosslinked by heating to form Si- The present invention relates to a film-forming composition that generates (C-) nSi (n is a natural number of 2 or more and 4 or less).

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 radical initiator, and these bonds form a network. Is 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 (hydrolysis polycondensation reaction of monomer)

(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 film formed therefrom by forming bonds and polymerizing them becomes very high.

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.

Examples of the catalyst for hydrolysis include inorganic acids such as hydrochloric acid, hydrofluoric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid, and silicic acid fluoride (H ₂ SiF ₆ ); Organic acids such as formic acid, acetic acid, lactic acid, oxalic acid, succinic acid, citric acid, toluenesulfonic acid, trifluoroacetic acid and trifluoromethanesulfonic acid; Solid acids such as weakly acidic ion exchange resin, strongly acidic ion exchange resin, and activated aluminum oxide; Ammonia, methylamine, dimethylamine, trimethylamine, triethylamine, isopropylamine, butylamine, tributylamine, cyclohexylamine, benzylamine, ethylenediamine, diethylenetriamine, piperazine, polyethylene imine, etc. Amines; Organic alkalis such as tetramethylammonium hydroxide, tetrabutylammonium hydroxide, butyltrimethylammonium hydroxide and triphenylphosphonium hydroxide; Metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide; Alkali alkoxides such as sodium methoxide and sodium ethoxide; Lewis acids such as aluminum chloride, triphenylphosphine and boron trifluoric acid; Titanium chloride (IV), titanium sulfate, titanium nitrate, titanium tetraisofuroxide, titanium tetra-n-butoxide, titanium tetrastearate, bisacetylacetonite diisopuropoxytitanium, tetrakisacylacetonato Titanium compounds such as titanium; Aluminum compounds such as aluminum sulfate, aluminum nitrate, aluminum acetate, aluminum triisopuroxide, aluminum second butoxide, acetacetonatodiisopuroxy aluminum, trisacetacetonato aluminum, etc .; Back is 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 polycondensation step is a 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 condenses, 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.

In addition, the above three kinds of silanes may be polymerized simultaneously or sequentially polymerized in various orders.

Examples of the silanes include alkyl group-substituted trifunctional silanes, and in particular, methyl group-substituted trifunctional silanes are preferably used. Such methyl group-substituted trifunctional silanes are preferably methyltrimethoxysilane. , Methyltrichlorosilane, methylchlorodiethoxysilane, methyltriacetoxysilane, methylmethoxydiacetoxysilane, methyltriisocyanedosilane, methyltris (methylethylmethoxymethoxy) silane, etc. have.

In addition, a phenyl group-substituted trifunctional silane may be used as the silane, and such a phenyl group-substituted trifunctional silane may be phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, or phenyltriacene. Methoxysilane, phenyltriisocyanatosilane, phenyltris (methylethylketoxymo) silane, and the like.

In addition, as the silane, a hydrocarbon group containing at least one unsaturated bond may be used, and in particular, a vinyl-substituted trifunctional silane is preferably used. As such a vinyl-substituted trifunctional silane, vinyltriethoxysilane is used. Phosphorus, vinyl trichlorosilane, vinyl triacetoxy silane, vinyl ethoxy diacetoxy silane, vinyl tris (menylethyl methoxy moth) silane and the like.

As the silane, the tetrafunctional silane is tetramethoxysilane, tetrachlorosilane, dimethoxydichlorosilane, tetraethoxysilane, tetraacetoxysilane, tetraisocyanatosilane, tetrakis (methyl Ethyl ketoxy) 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 in order to form a 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 to greatly improve the hardness of the film. It is.

As mentioned above, it is preferable that methyl silane and vinyl silane contribute to the radical polymerization, and each is polymerized by the same reaction as follows. 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, when the total weight of the silane is assumed to be 100, 0.001 to 1% by weight of a radical initiator is added thereto, and the polymerization is carried out by stirring during heating.

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, an azo compound, an azo-amide compound, a peroxide, diphenylalkaine, a benzophenone derivative, or the like may be used. Organic peroxides which are characterized by solubility and high stability and are 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-butyperoxy)- 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- dialkyl peroxides 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-tetramailbutylperoxy-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 melcaptopropionate ester, dibutoxyhydroxytoluene, and a melcaptobenzothiazole.

An arbitrary organic solvent is added for the purpose of dissolving and diluting the thermal initiator and the silane, and these solvents are mixed and used according to the drying rate or coating performance. 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, 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 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.

The overall reaction time takes about 1 to 12 hours.

In addition, the said hydrolysis-condensation polymerization and radical polymerization can also be advanced simultaneously by adding water, a catalyst, and a radical initiator simultaneously.

The order may be determined in the direction of hydrolysis condensation polymerization followed by radical polymerization or in the direction of hydrolysis condensation polymerization after radical 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.

<Example 1>

Example 1 for producing a coating composition according to the present 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 are placed in a three-necked flask having a capacity of about 2 liters, and the contents of the flask are vigorously stirred The solution which mixed 2 ml of nitric acid and 180 ml of pure waters of the density | concentration of 1 mol / liter, 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 as in the composition of Table 1, aged at 0 ° C. for 12 hours, and filtered with a 0.1 μm PTFE filter to prepare a coating composition.

Table 1

	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
Oligomer threshold	100	100	100	100	100	100
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	6H
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

PGMEA: Propylene Glycol Monomethyl Ether Acetate

IPA: Isoprophyl Alcohol

PGME: Propylene Glycol Monomethyl Ether

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.

In the present embodiment, the coated object is made of glass, but the coated object can be used in various ways without being limited to the form of plastic or other materials thereof introduced in the background art.

(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 a conventional 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 became high, which can be seen from the above chemical equation.

Therefore, as can be seen from Table 1, the coating composition prepared according to the present invention can be seen that the hardness value measured more than four times higher than the coating composition prepared by excluding the conventional radical initiator, in the case of insulation breakdown voltage Edo was three times higher. However, no difference was observed between the two compositions as the light transmittance was not a factor that depends on the radical initiator.

<Example 2>

(1) Preparation of the siloxane

According to Table 2, 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 vigorously stirring the contents of the flask, using a dropping funnel in which 2 ml of 1 mol / liter of nitric acid and 180 ml of pure water were added to the flask. It was dripped for a while.

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.

TABLE 2

	A	B	C
Phenyltrimethoxysilane	193.8 g	-	99.1 g
Methyltrimethoxysilane	-	136.2 g	68.1 g
Vinyltrimethoxysilane	149.2 g	149.2 g	149.2 g
Tetraethoxysilane	63.5 g	52.0 g	41.7 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-C thus obtained were mixed with additives as in the composition shown in Table 3 below, aged at 0 ° C. for 12 hours, and filtered through a 0.1 μm PTFE filter to prepare a coating composition.

TABLE 3

	One	2	3	4	5	6
Oligomer threshold	A (100)	A (100)	B (100)	B (100)	C (100)	C (100)
Radical initiator	#One	#2	# 3	#One	#2	-
menstruum	PGMEA	PGMEA	IPA	IPA	PGME	PGMEA
Light transmittance	> 98%	> 98%	> 98%	> 98%	> 98%	> 98%
Limit film thickness	> 3 μm	> 3 μm	> 1 μm	> 1 μm	> 2 μm	> 2 μm
Pencil hardness	9H	9H	9H	9H	9H	6H
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

PGMEA: Propylene Glycol Monomethyl Ether Acetate

IPA: Isoprophyl Alcohol

PGME: Propylene Glycol Monomethyl Ether

As a result of applying the coating composition synthesized as described above to an alkali-free glass at a rotational speed of 1000 rpm, a transparent thin film having a thickness of 700 nm was applied at 600 rpm to form a transparent thin film having a thickness of 1 μm.

The above crack limit film thicknesses expressed at 2 and 3 μm correspond to those applied at less than 600 rpm.

In the present embodiment, the coated object is made of glass, but the coated object can be used in various ways without being limited to the form of plastic or other materials thereof introduced in the background art.

(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.

In the measurement of the crack limit film thickness, the number of rotations during application was reduced to make the film thicker, and the presence or absence of cracks after curing was visually observed.

Unlike the coating composition which does not use a conventional 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 became high, which can be seen from the above chemical equation.

Therefore, as can be seen from Table 3, the coating composition prepared according to the present invention can be seen that the hardness value measured more than four times higher than the coating composition prepared by excluding the conventional radical initiator, in the case of dielectric breakdown voltage Edo was three times higher. However, no difference was observed between the two compositions as the light transmittance is not a factor that depends on the radical initiator.

<Example 3>

In this example, the coating compositions prepared by polymerizing the above-described coating compositions of Examples 1 and 2 and other oligomers other than the oligomers applied in the present invention together with the radical initiator were compared to demonstrate the superiority of the present invention.

(1) Preparation of the siloxane

According to Table 4, 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 vigorously stirring the contents of the flask, using a dropping funnel in which 2 ml of 1 mol / liter of nitric acid and 180 ml of pure water were added to the flask. It was dripped for a while.

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.

Table 4

	A	B	C (comparative example)	D (Comparative Example)
Phenyltrimethoxysilane	147.7 g	147.7 g	105.5 g	105.5 g
Methyltrimethoxysilane	54.0 g		45.0 g	144.1 g
Vinyltrimethoxysilane	149.2 g	149.2 g	-	149.2 g
Tetraethoxysilane	63.5 g	63.5 g	52.0 g	-

Here, the present invention is at least one selected from phenyl trimethoxy silane and methyl trimethoxy silane, trifunctional silane having a vinyl trimethoxy silane, tetraethoxy silane as an embodiment, Since the tetrafunctional silane is an essential component of the polymer, C and D polymerized by removing vinyltrimethoxysilane as the vinyl-substituted trifunctional silane or tetraethoxysilane as the tetrafunctional silane. Becomes a comparative example.

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

Table 5

	One	2	3	4
Oligomer threshold	A (100)	B (100)	C (100)	D (100)
Radical initiator	-	-	-	-
menstruum	PGMEA	PGMEA	PGMEA	PGMEA
Light transmittance	> 98%	> 98%	> 98%	> 98%
Limit film thickness	> 2 μm	> 2 μm	> 1.5 μm	> 1 μm
Pencil hardness	6H	4H	H	H
Insulation	> 3.0MV / cm	> 3.0MV / cm	> 3.0MV / cm	> 3.0MV / cm

PGMEA: Propylene Glycol Monomethyl Ether Acetate

As a result of applying the coating composition synthesized as described above to an alkali-free glass at a rotational speed of 1000 rpm, a transparent thin film having a thickness of 700 nm was applied at 600 rpm to form a transparent thin film having a thickness of 1 μm.

The above crack limit film thicknesses expressed in 2, 1.5, and 1 μm correspond to those applied at less than 600 rpm.

In the present embodiment, the coated object is made of glass, but the coated object can be used in various ways without being limited to the form of plastic or other materials thereof introduced in the background art.

(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.

In the measurement of the crack limit film thickness, the number of rotations during application was reduced to make the film thicker, and the presence or absence of cracks after curing was visually observed.

The composition according to the present invention prepared as described above did not apply all of the vinyl-substituted trifunctional silane and tetrafunctional silane, it was found that the hardness value was measured 2 to 4 times higher than the composition of the comparative example selectively applied one by one Could.

This is considered to be because more oligomers having 2 or more and 4 or less carbon atoms are produced when a polymer containing a vinyl group-substituted trifunctional silane and a tetrafunctional silane is used.

<Example 4>

In this example, by replacing the vinyl-substituted trifunctional silane corresponding to R ₂ among the silanes applied in the present invention to another hydrocarbon group within the scope of the present invention, comparing the radical initiator with or without using the radical initiator An attempt was made to demonstrate the superiority of the present invention using radical initiators.

(1) Preparation of the siloxane

Phenyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, tetraethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-glycidoxypropyl, according to the following Table 6 Triethoxysilanes were mixed 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, and then stirring the contents of the flask vigorously, 1 mol / A solution of 2 ml 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.

Table 6

	A	B	E
Phenyltrimethoxysilane	105.5 g	-	-
Methyltrimethoxysilane	-	90.1 g	90.1 g
Tetraethoxysilane	105.2 g	105.2 g	105.2 g
3-methacryloxypropyltrimethoxysilane	124.2 g	124.2 g	62.7 g
3-glycidoxypropyltrimethoxysilane	-	-	59.7 g

In the present invention, at least one selected from phenyltrimethoxysilane and methyltrimethoxysilane, a trifunctional silane and a tetrafunctional silane each having tetraethoxysilane as an embodiment are polymers. It is an essential component of and replaces vinyltrimethoxysilane with other carbon-based materials (3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane) for equal efficacy. It was confirmed.

(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 to E thus obtained were mixed with additives as in the composition shown in Table 7 below, aged at 0 ° C. for 12 hours, and filtered through a 0.1 μm PTFE filter to prepare a coating composition.

TABLE 7

	EXAMPLE	EXAMPLE	EXAMPLE	Comparative example
Oligomer threshold	A	B	E	E
	100	100	100	100
Radical initiator	#2	#2	#2	-
menstruum	PGME	PGME	PGME	PGME
Light transmittance	> 98%	> 98%	> 95%	> 98%
Limit film thickness	> 5 μm	> 3 μm	> 4 μm	> 4 μm
Pencil hardness	9H	9H	8H	6H
Insulation	> 3.0MV / cm	> 3.0MV / cm	> 3.0MV / cm	> 2.0MV / cm

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

PGME: Propylene Glycol Monomethyl Ether

As a result of applying the coating composition synthesized as above to an alkali-free glass at a rotation speed of 1000 rpm, a transparent thin film having a thickness of 1 μm was formed.

The above crack limit film thicknesses expressed in 3, 4, and 5 μm correspond to those applied at less than 600 rpm.

In the present embodiment, the coated object is made of glass, but the coated object can be used in various ways without being limited to the form of plastic or other materials thereof introduced in the background art.

(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.

In the measurement of the crack limit film thickness, the number of rotations during application was reduced to make the film thicker, and the presence or absence of cracks after curing was visually observed.

The composition according to the present invention prepared as described above was prepared by applying a substance containing another hydrocarbon group instead of the vinyl-substituted trifunctional silane, and exhibited similar properties to those of the vinyl-substituted trifunctional silane when the radical initiator was used. However, in the case of the epoxy group (3-glycidoxypropyltrimethoxysilane) having a long carbon-to-carbon coupling distance and flexible characteristics, the pencil hardness was relatively low in view of its physical properties. The difference was not significant.

In addition, from the difference between using and not using a radical initiator, as described above, the use of a radical initiator produces a Si- (C-) nSi (n is a natural number of 2 or more and 4 or less) bonds in addition to the Si-O bond. As a result, the bond strength was relatively high.

Claims (11)

1. The trifunctional silane represented by general formula R ₁ SiX ₃ , the trifunctional silane represented by general formula R ₂ SiX ' _3, and the tetrafunctional silane represented by general formula SiX'' ₄ , simultaneously or sequentially Oligomers obtained by polymerization (wherein R ₁ is at least one selected from an alkyl group or a phenyl group, R ₂ is a hydrocarbon group comprising one or more unsaturated bonds, X, X ′ and X ″ are the same or different hydrolysable groups from each other) Wow;

   Radical initiators; And

   A solvent for dissolving the oligomer and radical initiator;

   A composition for forming a film comprising a, wherein these components are formed by polymerization.
2. The method of claim 1,

   The silane is a methyl group substituted trifunctional silane represented by the general formula CH ₃ SiX ₃ in the case of an alkyl group substituted trifunctional silane in the trifunctional silane represented by the general formula R ₁ SiX ₃ , and R ₂ SiX "in the case of a trifunctional silane represented by formula ₃ H ₂ C ₃ SiX, a vinyl group represented by the _{3-substituted} trifunctional silane of the composition for film formation as claimed.
3. The method of claim 1,

   The hydrolyzable group (X, X ', X' ') is a film-forming composition, characterized in that at least any one selected from halogen elements, hydrogen or a carbon compound containing 1 to 4 carbons.
4. The method of claim 3, wherein

   The carbon compound containing 1 to 4 carbons includes a halogen group, an alkylamino group, an alkoxy group, an acyloxy group, an oxime group, and at least any one of them.
5. The method of claim 4, wherein

   The halogen group is an isocyanate, the alkoxy group is at least one selected from methoxy or ethoxy, the acyloxy group is acetoxy, the oxime group is methyl ethyl ketoxy.
6. The method of claim 1,

   The radical initiator is a composition for forming a film, characterized in that when the total weight of all the silane is 100, 0.001 to 1% by weight.
7. 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. Formation composition.
8. The method of claim 1,

   The radical initiator is at least any one of ketone peroxides, peroxy ketals, hydroperoxides, dialkyl peroxides, diacryl peroxides, peroxycarbonates, peroxyacid esters, and peroxyalkyl compounds. Composition for forming a film, characterized in that the organic peroxide containing one.
9. A structure for forming a film, wherein the main chain is a siloxane oligomer having the formula (1), wherein the side chain is crosslinked by heating to generate the structure of the formula (2).

   Formula (1):-(Si-O-) n n is a natural number of 20 or more

   Formula 2: Si- (C-) nSi n is a natural number of 2 or more and 4 or less
10. The method according to any one of claims 1 to 9,

    The film-forming composition is a film-forming composition, characterized in that the coating on the substrate.
11. The film | membrane formed by apply | coating the film forming composition of any one of Claims 1-9 on a board | substrate.