JP6363257B2 - Film forming composition - Google Patents

Description

  The present invention relates to a composition for producing a coating film having high gas barrier performance, which can be used for production of display devices and semiconductor elements.

  Silicone films are relatively high in hardness and hermeticity, and are therefore used in various applications in the field of manufacturing semiconductor devices. Specifically, hard coat films such as substrates and circuits, gas barrier films, substrates It is used for applications such as a material strength improving film. Various types of silicon films have been studied.

Among these, a method for forming a film having particularly excellent gas barrier performance has been studied. In these methods, polysilazane is generally used as a film forming material. For example, Patent Document 1 discloses a method of manufacturing a gas barrier film by laminating a plurality of gas barrier films, and Patent Document 2 discloses a gas barrier film in which an ultraviolet cut layer and a gas barrier film are formed on both surfaces of a substrate. Discloses a gas barrier film including a bleed-out preventing layer, a layer having UV cut property, and a fluororesin layer as required, all of which are polysilazane materials as part of the material of the gas barrier film. Is used.
Patent Document 4 discloses a method of forming a gas barrier film by irradiating a polysilazane film containing a catalyst with vacuum ultraviolet rays (wavelength 230 nm or less) and ultraviolet rays (wavelength 230 to 300 nm) in the presence of water vapor. Patent Document 5 discloses a method of forming a gas barrier film by irradiating a coating film formed from a polysilazane composition containing a transition metal with vacuum ultraviolet rays (wavelength of 230 nm or less) in a nitrogen atmosphere.
However, according to the study by the present inventors, a film formed from a film-forming material containing polysilazane as a main component often has insufficient gas barrier performance, and a film with improved gas barrier performance can be formed. A film forming composition and a film forming method have been desired.

JP 2011-173057 A JP 2011-194766 A JP 2012-006154 A Special table 2009-503157 JP 2012-148416 A US Pat. No. 6,329,487

  In view of the above-described problems, the present invention intends to provide a film-forming composition capable of forming a film with better gas barrier performance.

｛式中、Ｒ^１１はそれぞれ独立に、水素原子、アルキル基、アルケニル基、シクロアルキル基、アリール基、アルコキシ基、アミノ基、およびアルキルシリル基からなる群から選択される基であり、Ｒ^１１が水素原子以外の基であるとき、１またはそれ以上の、ハロゲン原子、アルキル基、アルコキシ基、アミノ基、シリル基、およびアルキルシリル基からなる群から選択される基により置換されていてもよく、式中のすべてのＲ^１１に含まれるアミノ基、およびアルコキシ基の総数が、Ｒ^１１の総数の５％以下であり、Ｒ^１２は、それぞれ独立に、炭素数１〜８の炭化水素基、または−Ｒ^１３−Ｎ−Ｒ^１４ _２（ここで、Ｒ^１３は炭素数１〜５の炭化水素基であり、Ｒ^１４はそれぞれ独立に水素または炭素数１〜３の炭化水素基である）である｝
であらわされるポリシロキサンと、ポリシラザンと、有機溶剤とを含んでなり、
前記ポリシロキサンのポリスチレン換算重量平均分子量が１，０００〜５０，０００の範囲にあることを特徴とするものである。 The film-forming composition according to the present invention has the following general formula (1):

{Wherein, R ¹¹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an amino group, and a group selected from the group consisting of alkyl silyl group, R ¹¹ Is a group other than a hydrogen atom, it may be substituted with one or more groups selected from the group consisting of halogen atoms, alkyl groups, alkoxy groups, amino groups, silyl groups, and alkylsilyl groups. In addition, the total number of amino groups and alkoxy groups included in all R ¹¹ in the formula is 5% or less of the total number of R ¹¹ , and each R ¹² is independently a hydrocarbon group having 1 to 8 carbon atoms, or ^-R 13 ^{-N-R 14} ₂ ^{(wherein, R 13} is a hydrocarbon group of 1 to 5 carbon ^{atoms, R 14} is a hydrocarbon group der hydrogen or 1 to 3 carbon atoms each independently ) Is a}
Comprising polysiloxane, polysilazane, and an organic solvent,
The polysiloxane has a polystyrene-equivalent weight average molecular weight in the range of 1,000 to 50,000.

  According to the present invention, it is possible to form a film having excellent gas barrier performance and having both high density and thermal stability.

  Hereinafter, embodiments of the present invention will be described in detail.

Film-forming composition The film-forming composition according to the present invention comprises polysiloxane, polysilazane, and an organic solvent as essential components, and may contain other additives as necessary. Each of these components will be described as follows.

Ｒ^１１はそれぞれ独立に、水素原子、アルキル基、アルケニル基、シクロアルキル基、アリール基、アルコキシ基、アミノ基、およびアルキルシリル基からなる群から選択される基である。これらの基は、１またはそれ以上の、ハロゲン原子、アルキル基、アルコキシ基、アミノ基、シリル基、およびアルキルシリル基からなる群から選択される基により置換されていてもよい。これらのＲ^１１は、ポリシロキサンの側鎖を形成するものであるが、不要な反応を防ぐために反応性の高い置換基を含まないことが好ましい。このため、アルキル基が好ましく、炭素数１〜３のアルキル基が好ましく、メチル基がもっとも好ましい。式中のＲ^１１は、それぞれ異なった基であってもよいが、すべてがアルキル基、特にメチル基であることが好ましい。 Polysiloxane In the present invention, polysiloxane having a specific structure is used. When the coating film formed from the film-forming composition according to the present invention is exposed, this polysiloxane reacts with polysilazane described later to form a cured film. This polysiloxane is represented by the following general formula (I).

R ¹¹ is each independently a group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an amino group, and an alkylsilyl group. These groups may be substituted with one or more groups selected from the group consisting of halogen atoms, alkyl groups, alkoxy groups, amino groups, silyl groups, and alkylsilyl groups. These R ¹¹ form a side chain of polysiloxane, but preferably do not contain a highly reactive substituent in order to prevent unnecessary reaction. For this reason, an alkyl group is preferable, a C1-C3 alkyl group is preferable, and a methyl group is the most preferable. R ¹¹ in the formula may be a different group, but all are preferably alkyl groups, particularly methyl groups.

R ¹¹ may contain a small amount of a reactive group as long as the effects of the present invention are not impaired. Specifically, the effects of the present invention can be exhibited if the total number of amino groups and alkoxy groups contained in all R ¹¹ is 5% or less, preferably 3% or less, of the total number of R ¹¹ . On the other hand, when R ¹¹ contains a hydroxyl group, a carboxyl group, or the like, a highly hydratable hydroxyl group remains in the film, and thus it is difficult to improve the gas barrier performance. Therefore, it is preferred that R ¹¹ does not contain a hydroxyl group or a carboxyl group.

R ¹² is a terminal group bonded to a silicon atom at the terminal of the polysiloxane main chain. Although the reaction mechanism when the film-forming composition according to the present invention cures has not been fully elucidated, this end group part binds to polysilazane described later, stabilizes nitrogen atoms in polysilazane, and has high gas barrier performance. It is estimated that Then, in order to proceed properly the reaction of the polysiloxane and polysilazane, R ¹² is required to be certain things.

Typically, R ¹² is a hydrocarbon group having 1 to 8 carbon atoms. Moreover, a part of carbon contained in such a hydrocarbon group may be substituted with nitrogen. Examples of the nitrogen-substituted hydrocarbon group include —R ¹³ —N—R ¹⁴ ₂ . Here, R ¹³ is a hydrocarbon group having 1 to 5 carbon atoms, and R ¹⁴ is independently hydrogen or a hydrocarbon group having 1 to 3 carbon atoms. As described above, R ¹² is selected to have an appropriate reactivity. Specifically, methyl group, ethyl group, propyl group, aminomethyl group, aminoethyl group, aminopropyl group, or N-ethylamino group is selected. A group selected from the group consisting of -2-methylpropyl groups is preferred. A plurality of R ¹² are contained in the polysiloxane represented by the formula (1), but they may be the same or different.

  Although the molecular weight of the polysiloxane used in the present invention is not particularly limited, for example, those having a polystyrene-equivalent weight average molecular weight in the range of 500 to 100,000 are preferred, and those having the molecular weight in the range of 1,000 to 50,000 are more preferred.

Ｒ^２１は、それぞれ独立に水素原子、アルキル基、アルケニル基、シクロアルキル基、アリール基、アルコキシ基、アミノ基、およびシリル基からなる群から選択される基である。Ｒ^２１が水素原子以外の基であるとき、１またはそれ以上の、ハロゲン原子、アルキル基、アルコキシ基、アミノ基、シリル基、およびアルキルシリル基からなる群から選択される基により置換されていてもよい。そのような置換基を有するＲ^２１の具体例としては、フルオロアルキル基、ペルフルオロアルキル基、シリルアルキル基、トリシリルアルキル基、アルキルシリルアルキル基、トリアルキルシリル基、アルコキシシリルアルキル基、フルオロアルコキシ基、シリルアルコキシ基、アルキルアミノ基、ジアルキルアミノ基、アルキルアミノアルキル基、アルキルシリル基、ジアルキルシリル基、アルコキシシリル基、ジアルコキシシリル基、およびトリアルコキシシリル基からなる群から選択される基を挙げることができる。これらのうち、前記Ｒ^２１は、それぞれ独立に、（ａ）水素、（ｂ）メチル基、エチル基、またはプロピル基などのアルキル基、（ｃ）ビニル基またはアリル基などのアルケニル基、（ｄ）フェニル基などのアリール基、（ｅ）トリメチルシリル基などのアルキルシリル基、および（ｆ）トリエトキシシリルプロピル基などのアルコキシシリルアルキル基からなる群から選択される基であることが好ましい。 Polysilazane The polysilazane used in the film-forming composition according to the present invention is not particularly limited, but typically has a structural unit represented by the following general formula (2).

R ²¹ is independently a group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an amino group, and a silyl group. When R ²¹ is a group other than a hydrogen atom, it is substituted with one or more groups selected from the group consisting of halogen atoms, alkyl groups, alkoxy groups, amino groups, silyl groups, and alkylsilyl groups. Also good. Specific examples of R ²¹ having such a substituent include a fluoroalkyl group, a perfluoroalkyl group, a silylalkyl group, a trisilylalkyl group, an alkylsilylalkyl group, a trialkylsilyl group, an alkoxysilylalkyl group, and a fluoroalkoxy group. , A group selected from the group consisting of a silylalkoxy group, an alkylamino group, a dialkylamino group, an alkylaminoalkyl group, an alkylsilyl group, a dialkylsilyl group, an alkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group be able to. Of these, each R ²¹ independently represents (a) hydrogen, (b) an alkyl group such as a methyl group, an ethyl group, or a propyl group, (c) an alkenyl group such as a vinyl group or an allyl group, (d It is preferably a group selected from the group consisting of: an aryl group such as a phenyl group, (e) an alkylsilyl group such as a trimethylsilyl group, and (f) an alkoxysilylalkyl group such as a triethoxysilylpropyl group.

The polysilazane mainly containing the structural unit represented by the general formula (2) has a linear structure. However, in the present invention, polysilazane having other structures, that is, a branched chain structure or a cyclic structure can also be used. Such polysilazane includes a structure of the following formula:

The polysilazanes represented by these formulas can be broadly classified into organopolysilazanes containing an organic group in R ²¹ and perhydropolysilazanes in which all of R ²¹ are hydrogen. These polysilazanes can be produced by any conventionally known method.

  Further, metallopolysilazanes in which some of these polysilazanes are modified with a metal compound, borosilazanes containing boron, polysiloxazanes containing a silicone structure, and the like can also be used. In the present invention, these polysilazane modified products are also referred to as polysilazane for convenience. In the present invention, two or more of these polysilazanes can be used in combination.

  Although the molecular weight of the polysilazane used in the present invention is not particularly limited, for example, those having a polystyrene-equivalent weight average molecular weight in the range of 500 to 20,000 are preferred, and those in the range of 1,000 to 10,000 are more preferred.

Organic Solvent The film-forming composition according to the present invention comprises a solvent capable of dissolving the polysiloxane and the polysilazane. Such a solvent is not particularly limited as long as it can dissolve the components to be used. Specific examples of preferable solvents include the following:
(A) aromatic hydrocarbon compounds such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, tetrahydronaphthalene, etc.
(B) saturated hydrocarbon compounds such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, n-octane, i-octane, n-nonane, i-nonane, n -Decane, i-decane, etc.
(C) Alicyclic hydrocarbon compounds such as ethylcyclohexane, methylcyclohexane, cyclohexane, cyclohexene, p-menthane, decahydronaphthalene, dipentene, limonene, etc.
(D) alkyl ethers such as dipropyl ether, dibutyl ether, diethyl ether, dipentyl ether, dihexyl ether, methyl tertiary butyl ether (hereinafter referred to as MTBE), anisole and the like, and (e) ketones such as methyl isobutyl ketone ( Hereinafter referred to as MIBK).
Of these, (a) aromatic hydrocarbon compounds, (b) saturated hydrocarbon compounds, (c) alicyclic hydrocarbon compounds, and (d) alkyl ethers are preferred, and xylene and dibutyl ether are particularly preferred.

  These solvents may be used in the form of a mixture of two or more as appropriate in order to adjust the evaporation rate of the solvent, to reduce the harmfulness to the human body, or to adjust the solubility of each component.

A commercially available solvent can also be used as such a solvent. For example, Pegasol 3040, Exol D30, Exol D40, Exol D80, Solvesso 100, Solvesso 150, Isopar H, Isopar L (trade name: manufactured by Exxon Mobil Corporation), New Solvent A, Cactus Fine SF-01, Cactus Fine SF-02 (Trade name: manufactured by JX Nippon Oil & Energy Corporation), Shellsol MC311, Shellsol MC811, Sol Eight Deluxe, New Shell Bright Sol (trade name: Shell Chemicals Japan Co., Ltd.) and the like are commercially available. Can also be used.
When a solvent mixture is used, the content of the aromatic hydrocarbon compound is preferably 30% by weight or less with respect to the total weight of the solvent mixture from the viewpoint of reducing the harmfulness to the human body.

Other Components In the present invention, the film-forming composition can also contain an amine compound or a metal complex compound. These compounds function as a catalyst when the composition applied on the substrate undergoes a curing reaction.

  Any amine compound can be used. For example, an aliphatic amine, an aromatic amine, or a heterocyclic amine can be preferably used. The aliphatic amine or aromatic amine may be a primary amine, secondary amine, or tertiary amine. These may have any number of nitrogen atoms, such as monoamine, diamine, or triamine. Examples of the heterocyclic amine include compounds containing a pyrrole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazole ring, and the like. These amine compounds may be substituted with any substituent, for example, a group selected from the group consisting of an alkoxy group, an alkylene group, a silyl group, and an alkylsilyl group.

  Specific examples of preferred amine compounds include dipropylamine, diisopropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, isobutylamine, diisobutylamine, tert-butylamine, pentylamine, tripentylamine hexylamine, N-methyl Hexylamine, N, N-dimethylhexylamine, N, N-dimethyl-2-ethylhexylamine, heptylamine, octylamine, di-n-octylamine N-methyl di-n-octylamine, tri-n-octylamine, N, N, N ′, N′-tetramethyldiaminomethane, N, N′-dimethylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1, 3-propanediamine, N N, N ′, N′-tetramethyl-1,4-butanediamine, N, N-ditert-butylethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′ , N′-tetramethyl-1,8-octanediamine, allylamine, diallylamine, triallylamine, N-methyldiallylamine, N, N-dimethylallylamine, benzylamine, dibenzylamine, N-methylbenzylamine, N, N— Dimethylbenzylamine, pyrrole, pyrroline, pyridine, picoline, lutidine, pyrazine, aminopyridine, aminomethylpyridine, phenylpyridine, vinylpyridine, aminopyrazine, 2-methoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3 -Propoxypropylamino , 3-isopropoxypropylamine, 3-butoxypropylamine, bis (2-aminoethyl ether), bis (3-aminopropyl ether), 3- (2-dimethylaminoethoxy) propylamine, hexamethyldisilazane, Examples include tetramethyldisilazane and heptamethyldisilazane.

  As the amine compound, any compound can be selected as long as it does not impair the effects of the present invention. However, when alcohol amine or some N-heterocyclic amine is used, Si is used for curing the coating. Care must be taken because -O bonds may increase.

  Any metal complex compound can be used as long as it can accelerate the curing reaction of the film. Specifically, the metal is preferably selected from the group consisting of nickel, titanium, platinum, rhodium, cobalt, iron, iridium, aluminum, ruthenium, palladium, rhenium, and tungsten. Moreover, what contains the ligand selected from the group which consists of an acetylacetonato group, a carbonyl group, and a carboxylate group is preferable. Here, the carboxylate group is a residue of a carboxylic acid selected from formic acid, acetic acid, propionic acid, butyric acid, octanoic acid, lauric acid, stearic acid, oleic acid, lactic acid, succinic acid, and citric acid Is preferred.

  Specific examples of preferred metal complex compounds include tris (acetylacetonato) aluminum, tris (acetylacetonato) iron, tris (acetylacetonato) rhodium, tris (acetylacetonato) cobalt, tris (acetylacetonato) ruthenium, Bis (acetylacetonato) palladium, hexacarbonyltungsten, dodecacarbonyltriruthenium, dodecacarbonyldirenium, palladium acetate, palladium propionate, nickel benzoate, nickel octoate, nickel oleate, iron formate, cobalt benzoate, citrus Examples include cobalt acid, cobalt formate, rhodium triacetate, dirhodium tetraacetate, titanium oleate, aluminum gluconate, aluminum benzoate, and aluminum butyrate.

  The film-forming composition according to the present invention may contain other additive components as necessary. Examples of such components include viscosity modifiers and crosslinking accelerators. In addition, a phosphorus compound such as tris (trimethylsilyl) phosphate may be contained for the purpose of obtaining a sodium gettering effect when used in a semiconductor device.

Film-forming composition The film-forming composition according to the present invention is obtained by dissolving or dispersing the polysiloxane, the polysilazane, and, if necessary, other additives in the organic solvent. Here, the order in which each component is dissolved in the organic solvent is not particularly limited. In addition, the solvent can be replaced after the components are reacted.

Moreover, content of each said component changes with uses of the target composition. The compounding ratio of polysiloxane and polysilazane can be appropriately adjusted according to the purpose. Generally, it is preferable that the compounding ratio of polysiloxane is large because the gas barrier property tends to be high.
For this reason, it is preferable that the compounding quantity of polysiloxane with respect to 100 weight part of polysilazane is 0.01 polymerization part or more, and it is more preferable that it is 0.1 weight part or more. Moreover, in order to accelerate | stimulate progress of a film formation reaction, the one where the compounding ratio of polysiloxane is smaller is preferable. For this reason, it is preferable that the compounding quantity of the polysiloxane with respect to 100 weight part of polysilazane is 25 polymerization parts or less, and it is more preferable that it is 8 weight parts or less.

  In the present invention, the content of the polymer component comprising polysiloxane and polysilazane is preferably 0.1 to 40% by weight based on the total weight of the composition in order to form a film having a sufficient film thickness. 0.1 to 30% by weight is more preferable. When the composition contains an amine compound, it is preferably a certain amount or more in order to sufficiently accelerate the curing reaction, and from the viewpoint of storage stability of the film forming composition, it may be a certain amount or less. preferable. For this reason, the content of the amine compound is preferably 0.005 to 1.00 mmol, more preferably 0.01 to 0.60 mmol, with respect to 1 g of the polymer. Further, when the composition contains a metal complex compound, it is preferably a certain amount or more in order to sufficiently accelerate the curing reaction, and from the viewpoint of storage stability of the film-forming composition, it is a certain amount or less. Is preferred. For this reason, it is preferable that it is 0.005-0.50 mmol with respect to 1 g of polymers, and, as for content of a metal complex compound, it is more preferable to set it as 0.01-0.20 mmol.

Film Forming Method The film forming method according to the present invention includes:
(1) The coating composition is applied to the substrate to form a coating film, and (2) an exposure process for irradiating the coating film with light.

  The substrate to which the film forming composition is applied is not particularly limited, and is selected from any materials such as organic materials, inorganic materials, and metals. Since the film formed by the present invention is characterized by high gas barrier performance, it is preferable to form a film on the surface of a substrate made of an organic material because a film material having high gas barrier performance can be obtained. As such an organic material, a plastic film such as polyethylene naphthalate, polyethylene terephthalate, polystyrene, polypropylene, polyethylene, polyimide, polyamide, cellulose acetate, acrylic, polycarbonate, and vinyl chloride is preferable. Among these, polyethylene naphthalate or polyethylene terephthalate is particularly preferable from the viewpoints of heat resistance and transparency.

  The coating can be formed not only on one side of the substrate but also on both sides of the substrate as required. In that case, it is necessary to select a substrate suitable for the purpose.

  In the coating step (1), the above-described film forming composition is applied to the surface of the substrate. In the film forming method according to the present invention, the film forming composition is applied to one or both of the substrate surfaces.

  As a method for applying the film-forming composition to the substrate surface, a conventionally known method can be used. Examples thereof include spin coating, dip coating, spraying, roll coating, transfer, slit coating, and bar coating. The thickness of the coated film after application is preferably thick so that the formed film can exhibit sufficient gas barrier performance. Specifically, it is preferably 10 nm or more, and more preferably 50 nm or more. Moreover, it is preferable to set appropriately the thickness of the coating film after application | coating so that it can harden | cure efficiently in the exposure process mentioned later. Specifically, it is preferably 900 nm or less, and more preferably 500 nm or less. In addition, when forming a film on both surfaces of a board | substrate, you may apply | coat sequentially about each surface, and may apply | coat both surfaces simultaneously.

  The coating film formed on the substrate surface is dried as necessary to remove excess organic solvent. In particular, since light having a relatively short wavelength is used in the exposure step described later, it is preferable to remove as much as possible the organic solvent that tends to absorb light in the short wavelength region. At this time, drying can be performed more efficiently by being performed at a relatively high temperature.

  Drying can also be performed under reduced pressure. That is, by applying a negative pressure to the substrate after coating with a vacuum pump, a rotary pump, or the like, evaporation of the solvent in the coating film is accelerated, and drying can be promoted.

  If necessary, an inert gas such as nitrogen can be sprayed onto the coating film from which excess solvent has been removed by drying. By such treatment, the deposits on the surface of the coating film can be removed to increase the efficiency of light irradiation. Furthermore, the solvent etc. adhering to the surface can also be removed by irradiating infrared rays.

  The coating film thus obtained is subsequently subjected to an exposure step. The light irradiation conditions in the exposure step are appropriately selected according to the thickness, composition, hardness and the like of the coating film to be formed.

  The light irradiated in the exposure step preferably has a maximum peak wavelength of 161 to 248 nm, and preferably 165 to 180 nm. Any light source can be used as long as it can emit light of the above-mentioned wavelength, but a xenon excimer laser is typically used. In addition, by using a lamp that emits light in a wide wavelength range, only necessary irradiation light can be used for irradiation by a filter or a spectroscope.

  In the film forming method according to the present invention, it is considered that the film having excellent gas barrier performance is formed by the reaction of the terminal group portion of the polysiloxane and the polysilazane by this exposure step. In addition, since the part where hardening is accelerated | stimulated in the depth direction in a coating film changes with wavelengths of the light to irradiate, the wavelength of the light to irradiate can be selected according to the objective. That is, by irradiating light with a long wavelength, curing of a deeper part of the coating film can be promoted, and by irradiating with light with a shorter wavelength, curing of a shallower part of the coating film can be further promoted. You can also.

  The atmosphere in which the exposure is performed is arbitrarily selected depending on the composition of the target film, but it is preferable to perform the light irradiation in an atmosphere in which oxygen does not penetrate into the film, that is, an atmosphere with little oxygen. Specifically, the oxygen content in the atmosphere is preferably 1000 ppm or less, and more preferably 100 ppm or less. In order to satisfy such conditions, light irradiation can be performed in a vacuum or under reduced pressure, or in an inert gas atmosphere. It is also effective to perform light irradiation after introducing an inert gas after reducing the atmosphere. Here, as the inert gas, nitrogen, argon, helium, a mixed gas thereof, or the like is used. In this case, nitrogen is preferably used from the viewpoint of handleability. At this time, the nitrogen gas is inactive and is not taken into the film and does not increase the composition ratio of nitrogen. Further, the light irradiation can be performed not only in a sealed container but also in an inert gas flow. In addition, for example, ultraviolet irradiation can be performed in a mixed gas of ammonia, dinitrogen monoxide, and an inert gas thereof. At this time, ammonia or dinitrogen monoxide can serve as a nitrogen source when forming a coating having a high Si-N content. Therefore, by using these, the Si-N content in the coating can be increased, and gas barrier performance can be further improved. Can be improved.

  In the exposure step, the coating film can be heated simultaneously with the light irradiation. Such heating can further accelerate the curing reaction. Further, after the exposure step, the curing reaction can be advanced by additional heating. The heating method is not particularly limited, and any method such as a method of heating a stage or the like on which a substrate is placed, a method of heating an atmospheric gas, or the like can be selected. However, when an organic material is used as the substrate, the heating temperature is preferably low because the substrate may be damaged if the heating temperature is too high. Specifically, the temperature until the coating film is cured and the coating film is formed is preferably 200 ° C. or less.

  The film formed in this way has excellent gas barrier performance, as well as excellent thermal stability and transparency. This film can be used for a gas barrier film such as a display device or a semiconductor device, and can also be used for a protective film or an insulating film.

  The present invention will be described below with examples.

Preparation of Coating Composition A polysiloxane represented by formulas (1A) to (1G) and a polysilazane represented by formulas (2A) to (2C) were prepared. Polysilazane was synthesized according to the method described in Patent Document 6 using dichlorosilane, methyldichlorosilane, or the like as a raw material.

  A glass beaker having a capacity of 500 ml was charged with 20 g of polysilazane and 60 g of dibutyl ether and mixed to obtain a polysilazane solution. Separately, a predetermined amount of polysiloxane and dibutyl ether were mixed in a glass beaker having a capacity of 50 ml to prepare a total solution of 20 g. The resulting polysiloxane solution is added to the polysilazane solution and bubbled and stirred by feeding dry nitrogen for 3 minutes to prepare a film-forming composition and dibutyl ether so as to obtain a desired film thickness. Dilution was performed.

Formation of Gas Barrier Film The prepared film forming composition was applied to a 125 μm thick polyethylene naphthalate film using a spin coater. Subsequently, the coated film was placed in an exposure apparatus, nitrogen was introduced into the apparatus to reduce the oxygen concentration to 100 ppm or less, and exposure treatment was performed for 30 minutes using a light source having a maximum peak wavelength of 172 nm to obtain a coating film. At this time, the illuminance of light was 8 mW / cm ² . The illuminance was measured using an ultraviolet integrated light meter UIT-250 and a light receiver VUV-S172 (both trade names, manufactured by USHIO INC.).

Using a DELTAPERRM-UH gas permeation measuring device (manufactured by Technolox), the water vapor permeability at 40 ° C. and 90% relative humidity of the film with the coating obtained by the above method was measured. Was measured. The moisture permeability of the film before coating was 1 g / m ² / day. Moreover, the film thickness of the film obtained by the ellipsometer was measured. All film thicknesses were 200 nm. The obtained results were as shown in Table 1.

Claims (6)

The following general formula (1):

{Where
R ¹¹ is each independently a group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an amino group, and an alkylsilyl group, and R ¹¹ is other than a hydrogen atom And may be substituted by one or more groups selected from the group consisting of halogen atoms, alkyl groups, alkoxy groups, amino groups, silyl groups, and alkylsilyl groups,
The total number of amino groups and alkoxy groups contained in all R ¹¹ in the formula is 5% or less of the total number of R ¹¹ ;
R ¹² is each independently a hydrocarbon group having 1 to 8 carbon atoms, or —R ¹³ —N—R ¹⁴ ₂ (wherein R ¹³ is a hydrocarbon group having 1 to 5 carbon atoms, and R ¹⁴ is Each independently hydrogen or a hydrocarbon group having 1 to 3 carbon atoms)}
Comprising polysiloxane, polysilazane, and an organic solvent,
The polystyrene-reduced weight average molecular weight of the polysiloxane Ri range near the 1000 to 50,000, and
A film-forming composition comprising 0.01 to 25 parts by weight of the polysiloxane with respect to 100 parts by weight of the polysilazane . The film forming composition according to claim 1, wherein R ¹¹ is an alkyl group having 1 to 3 carbon atoms. The R ¹² is a group selected from the group consisting of a methyl group, an ethyl group, a propyl group, an aminomethyl group, an aminoethyl group, an aminopropyl group, and an N-ethylamino-2-methylpropyl group. The composition for forming a film according to 1 or 2. The polysilazane is represented by the following general formula (2):

(Where
R ²¹ is each independently a group selected from the group consisting of a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an amino group, and a silyl group, and at least one of R ^{21 in} the formula One is a hydrogen atom, and a group other than a hydrogen atom is substituted with one or more groups selected from the group consisting of a halogen atom, an alkyl group, an alkoxy group, an amino group, a silyl group, and an alkylsilyl group May be)
The composition for film formation of any one of Claims 1-3 which has a structural unit represented by these. 5. The film forming composition according to claim 4, wherein each R ²¹ is independently a group selected from the group consisting of hydrogen, an alkyl group, an alkenyl group, an aryl group, an alkylsilyl group, and an alkoxysilylalkyl group. . The film formation according to any one of claims 1 to 5 , wherein the organic solvent comprises one or more solvents which are an aromatic hydrocarbon, a saturated hydrocarbon compound, an alicyclic hydrocarbon compound or an alkyl ether. Composition.