JP2005290352A - Compound having basket-shaped silsesquioxane structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a material which is soluble to a solvent, has a good film-formability, and can give a high heat-resistance film easily by calcinating its formed film. <P>SOLUTION: In the subject silsesquioxane compound, at least two basket-shaped silsesquioxanes are bonded through at least one structure selected from the group consisting of an oxyalkylene, a siloxane, their polymer, and a structure of formula (1). (In formula (1), R<SB>1</SB>, R<SB>2</SB>, R<SB>1</SB>' and R<SB>2</SB>' are each hydrogen atom, chlorine atom, hydroxy group or a monovalent organic group. (j), (k) and (l) are each 1 or 0. At least one of (k) and (l) is 1). <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a compound having a cage silsesquioxane structure and excellent in heat resistance.

Polymer materials are used in various fields such as electronic materials, and the application fields requiring high heat resistance are increasing while having suitability according to each application.
For example, in recent years, a plasma display panel has attracted attention as a display with a high image quality and a large screen, and a dielectric is used in the AC drive type plasma display panel to protect electrodes. The plasma display panel is required to have high heat resistance because high temperature is applied in the manufacturing process. For this reason, conventionally, a lead-containing glass paste has been used as a dielectric material (Non-Patent Document 1). However, from the viewpoint of environmental protection, a dielectric material not containing lead is desired.
In order to realize such a dielectric material, various attempts have been made to realize a high heat-resistant film using a silsesquioxane material.

For example, Patent Document 1 describes that a compound obtained by polymerizing octakis (silsesquioxane) and a diyne compound exhibits high heat resistance. However, the film formed using the above materials has a problem that heat resistance in air is not sufficient, and a weight loss of about 40% is observed when heated to 1000 ° C. in an air atmosphere. This weight loss is caused by the decomposition of an organic structure (diyne compound) copolymerized with octakis (silsesquioxane) under high temperature conditions in air. Therefore, the film described in Patent Document 1 is difficult to use in applications where a high temperature is applied under air in the manufacturing process, represented by a plasma display, because contamination by decomposition products occurs.
In addition, by actively decomposing this organic structure, it is not easy to remove the organic structure derived from the diyne compound by calcination, even if an attempt is made to obtain a residue with high heat resistance. There was a problem of not becoming.

“2003 Electronics Film / Thin Film Market Outlook”, Fuji Keizai, 2003 Japanese Patent No. 2884073

  An object of the present invention is to provide a material that is soluble in a solvent, has good film formability, and can easily obtain a highly heat-resistant film by baking after film formation.

The present inventor has intensively studied to solve the above problems. As a result, if a compound in which a cage-like silsesquioxane structure with high heat resistance is combined with a structure that is easily thermally decomposed, the structure that is easily thermally decomposed by baking after film formation disappears, and the cage-like silsesquioxane structure is lost. It was found that a structure in which the suns were directly bonded was formed, and a highly heat-resistant film was obtained.
That is, in the present invention, at least two cage silsesquioxanes are bonded via at least one structure selected from oxyalkylene, siloxane, polymers thereof, and a structure represented by the following general formula (1). It is a silsesquioxane compound.

（Ｒ_１、Ｒ_２、Ｒ_１’、Ｒ_２’は水素原子、塩素原子、ヒドロキシル基または一価の有機基をあらわす。ｎは自然数をあらわす。Ｒ_３、Ｒ_４はアルキレン基をあらわす。ｊとｋとｌは１または０をあらわし、ｋ、ｌの少なくともひとつは１である。）

(R ₁ , R ₂ , R ₁ ′ and R ₂ ′ represent a hydrogen atom, a chlorine atom, a hydroxyl group or a monovalent organic group. N represents a natural number. R ₃ and R ₄ represent an alkylene group. J And k and l represent 1 or 0, and at least one of k and l is 1.)

  Since the cage silsesquioxane compound of the present invention is soluble in a solvent, a uniform film can be formed by coating. By baking this film, a highly heat-resistant film can be easily obtained. This material is suitably used as a dielectric forming material.

The cage-like silsesquioxane in the present invention refers to a caged siloxane structure. A specific structure is represented by the following general formula (2).
(RSiO _3/2 ) _y (R'SiO _3/2 ) _xy (2)
In the general formula (2), x represents an integer of 6 to 14. y is an integer from 1 to x. R is at least one structure selected from oxyalkylene, siloxane, a polymer thereof, and a structure represented by the general formula (1) linked to another cage silsesquioxane structure. R ′ is selected from a hydrogen atom, an alkoxyl group, an aryloxy group, a substituted or unsubstituted hydrocarbon group, and a silicon atom-containing group.

The specific structure of the cage silsesquioxane is a structure represented by the general formula (RSiO _3/2 ) _y (R′SiO _3/2 ) _6-y represented by the general formula (3), the general formula (RSiO _3/2 ) _y (R′SiO _3/2 ) _8-y structure represented by general formula (4), general formula (RSiO _3/2 ) _y (R′SiO _3/2 ) _10-y A structure represented by the general formula (5), a structure represented by the general formula (RSiO _3/2 ) _y (R′SiO _3/2 ) _12-y , (RSiO _3/2 ) _y (R′SiO _3/2 ) A structure such as the general formula (7) represented by the general formula of _14-y can be given.

However, in the general formulas (3) to (7), at least one of “R or R ′” or “R or R ′” is R.
Examples of when R ′ is an alkoxyl group include a methoxy group, ethoxy group, n-propyloxy group, n-butyloxy group, t-butyloxy group, n-hexyloxy group, cyclohexyloxy group and the like.
Examples of when R ′ is an aryloxy group include a phenoxy group and a 2,6-dimethylphenoxy group.

  Examples of when R ′ is a hydrocarbon group include methyl, ethyl, n-propyl, i-propyl, butyl (n-butyl, i-butyl, t-butyl, sec-butyl), pentyl (n-pentyl, i-pentyl, neopentyl, cyclopentyl, etc.), hexyl (n-hexyl, i-hexyl, cyclohexyl, etc.), heptyl (n-heptyl, i-heptyl, etc.), octyl (n-octyl, i-octyl, t-octyl, etc.) ), Nonyl (n-nonyl, i-nonyl etc.), decyl (n-decyl, i-decyl etc.), undecyl (n-undecyl, i-undecyl etc.), dodecyl (n-dodecyl, i-dodecyl etc.) etc. An acyclic or cyclic aliphatic hydrocarbon group, vinyl, propenyl, butenyl, pentenyl, hexenyl, cyclohexenyl, cyclohexenylethyl, Acyclic and cyclic alkenyl groups such as rubornenylethyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, styryl, etc., benzyl, phenethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, etc. Aralkyl groups such as aralkyl groups, PhCH═CH— groups, aryl groups such as phenyl groups, tolyl groups, or xylyl groups, 4-aminophenyl groups, 4-hydroxyphenyl groups, 4-methoxyphenyl groups, 4- Examples include substituted aryl groups such as vinylphenyl group.

A hydrogen atom or a part of the skeleton of the hydrocarbon group may be partially substituted with an organic group. Organic groups include ether bond, ester group (bond), hydroxyl group, carbonyl group, carboxylic anhydride bond, thiol group, thioether bond, sulfone group, aldehyde group, epoxy group, amino group, amide group (bond), urea Examples thereof include polar groups (polar bonds) such as groups (bonds), isocyanate groups, and cyano groups. The hydrogen atom of the hydrocarbon group may be substituted with a halogen. Examples thereof include a fluorine atom, a chlorine atom, and a bromine atom.
When R ′ is a silicon atom-containing group, for example, groups having the structures of the following general formula (8) and general formula (9) can be mentioned.

R ₅ , R ₆ , R ₇ , R ₈ and R ₉ in the general formulas (8) and (9) are a hydrogen atom, a hydroxyl group, an alkoxy group, a chlorine atom, or an organic group having 1 to 10 carbon atoms. . R _{5 to} R ₉ may be the same or different. A in general formula (8) and b in (9) represent natural numbers. The range of a is 1-1000, preferably 1-100. The range of b is 1-1000, preferably 1-100.
R _{10 in the} general formula (9) represents a divalent organic group, and examples thereof include an alkylene group of — (CH ₂ ) _m — (m is a natural number). The range of m is 1-100, preferably 1-10.
In the cage silsesquioxane compound of the present invention, at least two cage silsesquioxane structures are selected from oxyalkylene, siloxane, a polymer thereof, and a structure represented by the general formula (1). They are connected by a structure composed of at least one kind (hereinafter, this portion may be referred to as a pyrolysis structure).

  Since the cage-like silsesquioxane structure is linked via the thermal decomposition structure, the organic property of the compound is increased and the solubility in various solvents is improved. Is possible. Furthermore, when caged silsesquioxanes are bonded to each other by the above thermal decomposition structure, the thermal decomposition structure has a lower decomposition temperature than the caged silsesquioxane structure part, so that it can be easily removed by baking after film formation. Is done. When the above structure is decomposed and removed, a cage-like silsesquioxane monomer or a cage-like silsesquioxane is bonded to each other by a highly heat-resistant Si—Si bond or Si—O bond. Remains. Therefore, the thin film produced by firing has a very high heat resistance due to the combination of the heat resistance derived from the special cage structure of the cage silsesquioxane and the heat resistance of the binding site. Become.

An oxyalkylene structure forming a thermal decomposition structure and a polymer thereof-(R "O) _p- (R" is an alkylene group, p is a natural number) are oxymethylene group, oxyethylene group, oxypropylene group, polyoxymethylene , Polyoxyethylene, polyoxypropylene and the like. The above p is preferably 1 or more and 10000 or less, preferably 1 or more and 100 or less from the viewpoint of the solubility of the silsesquioxane compound of the present invention in a solvent and the content of the cage silsesquioxane structure in the coating solution. Is more preferable.
Examples of the siloxane and the polymer thereof that form a pyrolytic structure include structures represented by the following general formula (10).

Here, R ₁₁ and R ₁₂ represent a hydrogen atom, a chlorine atom, a hydroxyl group or a monovalent organic group. Examples of the monovalent organic group include an alkyl group, an alkoxy group, and a partially substituted product thereof. q is a natural number, and preferably 1 or more and 10,000 or less from the viewpoint of the solubility of the silsesquioxane compound of the present invention in a solvent and the content of the cage silsesquioxane structure in the coating solution. 100 or less is more preferable.
Examples of the alkyl group and partially substituted products thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, 2-cyclohexyl-ethyl group, octyl group, dodecyl group, etc. An aliphatic hydrocarbon group containing an unsaturated hydrocarbon bond such as a vinyl group or an allyl group; an aromatic hydrocarbon group such as a phenyl group, a benzyl group, or a phenethyl group; or CF ₃ CH ₂ CH ₂ — Examples thereof include polar group-substituted alkyl groups such as fluorine-containing alkyl groups and aminoalkyl groups.

Examples of the alkoxy group and partially substituted products thereof include a methoxy group, an ethoxy group, a butoxy group, or a group in which part or all of the hydrogen of the alkoxy group is substituted with a halogen (for example, a trifluoromethoxy group). .
R ₁₁ and R ₁₂ may be the same group or different.
Specific examples of the general formula (10) include dimethylsiloxane, diphenylsiloxane, methylphenylsiloxane, hydrogenmethylsiloxane, and the like.
The structure represented by the general formula (1) that forms the pyrolysis structure is as follows.

（Ｒ_１、Ｒ_２、Ｒ_１’、Ｒ_２’は水素原子、塩素原子、ヒドロキシル基または一価の有機基をあらわす。）

(R ₁ , R ₂ , R ₁ ′ and R ₂ ′ represent a hydrogen atom, a chlorine atom, a hydroxyl group or a monovalent organic group.)

Examples of the monovalent organic group include an alkyl group, an alkoxy group, and a partially substituted product thereof. n is a natural number, and preferably 1 or more and 10,000 or less from the viewpoint of the solubility of the silsesquioxane compound of the present invention in a solvent and the content of the cage silsesquioxane structure in the coating solution. 100 or less is more preferable.
Examples of the alkyl group and partially substituted products thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, 2-cyclohexyl-ethyl group, octyl group, dodecyl group, etc. An aliphatic hydrocarbon group containing an unsaturated hydrocarbon bond such as a vinyl group or an allyl group; an aromatic hydrocarbon group such as a phenyl group, a benzyl group, or a phenethyl group; or CF ₃ CH ₂ CH ₂ — Examples thereof include polar group-substituted alkyl groups such as fluorine-containing alkyl groups and aminoalkyl groups.

Examples of the alkoxy group and partially substituted products thereof include a methoxy group, an ethoxy group, a butoxy group, or a group in which part or all of the hydrogen of the alkoxy group is substituted with a halogen (for example, a trifluoromethoxy group). It is done.
R ₁ , R ₂ , R ₁ ′ and R ₂ ′ may be the same group or different.
Specific examples of the structure of the portion sandwiched between R ₃ and R ₄ in the general formula (1) include dimethylsiloxane, diphenylsiloxane, methylphenylsiloxane, and hydrogenmethylsiloxane.
R ₃ and R ₄ represent an alkylene group. Examples of the alkylene group include — (CH ₂ ) _t — (t is a natural number). Specific examples include methylene, ethylene, polyethylene structures and the like. The above t is preferably from 1 to 10 and more preferably from 1 to 5 in terms of the thermal decomposability of the structure (1) of the present invention and the content of the cage silsesquioxane structure in the coating liquid. .

j, k, and l represent 1 or 0, and at least one of k and l is 1.
In the structure represented by oxyalkylene, siloxane, a polymer thereof, and the general formula (1) that form a thermal decomposition structure, a hydrogen atom or a part of the skeleton may be partially substituted with an organic group. Examples of the organic group include ether bond, ester group (bond), hydroxyl group, carbonyl group, carboxylic anhydride bond, thiol group, thioether bond, sulfone group, aldehyde group, epoxy group, amino group, amide group (bond). And a polar group (polar bond) such as a urea group (bond), an isocyanate group and a cyano group, or a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom. It is more preferable that all the bonds are composed of single bonds because the bond energy is lower than that of the multiple bond, and the heat resistance of the pyrolysis structure is lowered.

The pyrolysis structure of the present invention may be a structure in which a plurality of the structures described above are combined. The following example is given as a combined form.
1) A plurality of pyrolytic structures are combined in one cage-like silsesquioxane structure. This pyrolysis structure may be the same type or a combination of different types.
2) A structure in which a plurality of different structures are connected in the pyrolysis structure itself.
3) A structure in which at least one of the plurality of pyrolysis structure parts of 1) has a structure in which a plurality of heterogeneous structures are connected as in 2).

The molecular weight of the silsesquioxane compound of the present invention is preferably from 800 to 1,000,000 in view of solubility and component concentration of the cage silsesquioxane structure when used as a coating solution. The molecular weight of the silsesquioxane compound of the present invention can be measured by GPC (gel permeation chromatography).
The composition of the cage silsesquioxane structure and the pyrolysis structure of the silsesquioxane compound of the present invention is preferably a molar ratio of 2: 1 to 1: 4 in terms of coating properties and film density. More preferably, it is 1: 1 to 1: 3. The molar ratio here refers to the ratio of the number of cage silsesquioxane structures present in the structure of the compound of the present invention to the number of pyrolytic structures in which the cage silsesquioxanes are bonded together. Say. For example, when two cage-like silsesquioxane structures are bonded by one pyrolysis structure, the molar ratio is 2: 1. If two caged silsesquioxanes are linked by two pyrolytic structures, the molar ratio is 2: 2 = 1: 1.

The silsesquioxane compound of the present invention can be produced by a known synthesis method. Synthesis examples are given below.
The cage silsesquioxane is commercially available or can be synthesized by the following method. For example, hydro-T8-silsesquioxane, which is a kind of cage silsesquioxane, can be obtained by reacting trichlorosilane in the presence of anhydrous iron chloride / hydrochloric acid. Further, by reacting tetramethylammonium hydroxide pentahydrate in a water / acetone solvent, octakis (tetramethylammonium) -T8-silsesquioxane, which is a kind of cage silsesquioxane, can be obtained. it can.

As a method for introducing a pyrolysis structure into a cage silsesquioxane, a pyrolysis structure (oxyalkylene, siloxane, a polymer thereof, and a structure represented by the general formula (1)) is synthesized in advance, There is a method of bonding to a cage siloxane by a reaction such as esterification, etherification, hydrosilylation or the like. For example, a book having a oxyalkylene group by forming a pyrolysis structure by hydrosilylation reaction between a caged silsesquioxane compound of the general formula (2) in which R is a hydrogen atom and a vinyl glycol of both terminal vinyl type. The silsesquioxane compound of the invention can be obtained.
When a polysiloxane having both terminals vinyl type is used instead of the both terminal vinyl type polyethylene glycol, the silsesquioxane compound of the present invention having a siloxane group as a thermal decomposition structure can be obtained.

There is a method in which a reactive functional group cage silsesquioxane is selected as R in the general formula (2), and this R is reacted with each other so that the reacted R itself has a pyrolytic structure. For example, a cage silsesquioxane compound in which R is —OSiMe ₂ H structure in the general formula (2), and a cage silsesquioxane compound in which R is —CH═CH ₂ structure in the general formula (2) Is subjected to a hydrosilylation reaction, whereby the silsesquioxane structure of the present invention having (—CH ₂ —CH ₂ —SiMe ₂ —O—) as a thermal decomposition structure can be obtained.
When cage-shaped hydrogen silsesquioxane is selected as a raw material and copolymerized with a thermal decomposition structure by hydrosilylation, some cage-shaped silsesquioxanes are bonded through oxygen atoms by side reaction. However, as long as the effects of the present invention are not inhibited, some cage silsesquioxanes of the silsesquioxane compound may be bonded to each other through an oxygen atom.

The structure of the silsesquioxane compound of the present invention can be confirmed by using ¹ H-NMR and ²⁹ Si-NMR.
Transparent film with low dielectric constant, high heat resistance, and low gas generation after film formation by applying the coating liquid containing the silsesquioxane compound of the present invention to the substrate according to the purpose and baking Can be obtained.
Hereinafter, a method of forming a film using the silsesquioxane compound of the present invention will be described.
First, a silsesquioxane compound is dissolved in a solvent to prepare a coating solution. As the solvent, a solvent in which the silsesquioxane compound of the present invention is dissolved can be used. For example, organic solvents typified by tetrahydrofuran, dichloromethane, chloroform, toluene, methyl alcohol, ethyl alcohol and the like are preferable because they are highly volatile and can be easily removed. Further, the reaction solution obtained by synthesizing the silsesquioxane compound may be used as a coating solution as it is or after being diluted.

The coating liquid of the present invention may contain components other than the silsesquioxane compound (for example, additives such as surfactants) as long as the effects of the present invention are not impaired.
Next, the coating solution is applied to the substrate. As a coating method, a known coating technique can be employed, and specifically, bar coating, roller coating, die coating, blade coating, dip coating, doctor knife, spray coating, flow coating, brush coating, etc. can be exemplified. . The substrate to be coated is selected from a material that is not damaged by baking in subsequent film formation. Examples thereof include metals, glass, ceramics, heat resistant resins and the like.
After coating, the solvent is dried by standing at room temperature or heating as necessary.

Next, the film can be obtained by firing at a temperature higher than the decomposition temperature of the pyrolysis structure. Although the firing temperature and time depend on the pyrolysis structure, for example, about 400 ° C. to 600 ° C. is a typical condition. As for the decomposition temperature of the pyrolysis structure, the weight loss when the silsesquioxane compound is heated using TGA is measured, and the inflection point (temperature showing significant weight loss) in the chart is defined as the pyrolysis temperature. .
When firing is performed in an air atmosphere, there is no coloring due to incomplete combustion or the like, which is preferable.
It is presumed that high heat resistance is obtained by decomposition and disappearance of the pyrolytic structure during the firing and recombination of the remaining caged silsesquioxane structure. The cage silsesquioxane has extremely high heat resistance due to its unique cage structure.

Films manufactured using the silsesquioxane compound of the present invention include dielectric films, semiconductor interlayer insulating films, circuit board photoresist films, heat resistant films for ceramic sensors, heat resistant paints, flame retardant / fire resistant paints, building materials coatings It can be used for an agent, a dielectric film for a plasma display panel and the like.
The transparent film obtained from the silsesquioxane compound of the present invention can be particularly suitably used as a dielectric film for a plasma display panel because of its low dielectric constant, low degassing, and high heat resistance.
FIG. 1 shows a conceptual diagram of a cell structure of a plasma display panel.
A transparent electrode 2 and a bus electrode 3 are formed on the front glass substrate 1. These electrodes are covered with a transparent dielectric layer 4, and a protective layer 5 is further formed thereon.

A data electrode 7 is formed on the rear glass substrate 6 and is covered with a reflective layer 8.
The rib 9 is formed between the front glass substrate 1 and the rear glass substrate 6 and divides the discharge gas space 10. A phosphor 11 is formed on the reflective layer 7 and the rib 9 in the discharge gas space.
The dielectric film of the plasma display panel according to the present invention includes the transparent dielectric layer 4, the reflective layer 8, and the rib 9. The film obtained from the silsesquioxane compound of the present invention can be used for any of them. It is.

Hereinafter, the present invention will be described specifically by way of examples.
In addition, Shodex KF-804L (made by Showa Denko) was used as a GPC column used in a present Example. Tetrahydrofuran (THF) was used as a developing solvent.
As the NMR measuring apparatus, JNM-LA400 (manufactured by JEOL Ltd.) was used. Deuterated tetrahydrofuran (THF-d8) was used as a solvent for NMR measurement. ^{In the} symbols used in the table showing the ²⁹ Si-NMR results, M, D, T and Q represent Si with one, two, three and four oxygens directly bonded, respectively. . However, M1 represents M in which adjacent Si (Si bonded through oxygen) is M. M4 represents M in which adjacent Si (Si bonded through oxygen) is Q.

As a vertical firing furnace, VF-1000 (manufactured by Koyo Lindberg) was used.
MIKASA COATER (manufactured by MIKASA) was used as the spin coater.
The film thickness was measured using a reflection spectral film thickness meter FE-3000 (manufactured by Otsuka Electronics Co., Ltd.).
TGA2950 (made by TA Instruments) was used for TGA measurement.
Infrared absorption spectrum was measured using Spectrum One (manufactured by PerkinElmer).

[Example 1]
(1) Synthesis of Silsesquioxane Compound Octakis (dimethylsiloxy) -T8-silsesquioxane (manufactured by Gelest) 0.5 g, 1,3-divinyltetramethyldisiloxane (manufactured by Gelest) 0.28 g, and 0.008 g of platinum catalyst (1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex 3% xylene solution, manufactured by Aldrich) was dissolved in 4 ml of dehydrated tetrahydrofuran (manufactured by Kanto Chemical). By reacting at 60 ° C. for 3 hours under nitrogen, a silsesquioxane compound was synthesized.
When the number average molecular weight of this polymer was measured by GPC, it was about 7300.
Table 1 shows the ¹ H-NMR and ²⁹ Si-NMR measurement results of this polymer.

(2) Film formation / firing The silsesquioxane compound reaction solution synthesized in (1) above was diluted 5-fold with tetrahydrofuran and then spin-coated on a silicon wafer at 1000 rpm. The silicon wafer on which this film was formed was dried at 140 ° C. for 1 hour, and then baked in a vertical furnace at 600 ° C. for 3 hours.
As a result, a transparent film formed on the silicon wafer was obtained. The film thickness of this transparent film was 390 nm.
When the TGA of this film was measured in an air atmosphere, 3% of moisture was desorbed by 110 ° C., and the weight loss from 110 ° C. to 1000 ° C. was 2.6%.
Moreover, when the infrared absorption spectrum of this transparent film was measured, since the peak (2960 cm < ^-1 >) of the methyl group derived from a thermal decomposition structure has disappeared, it was confirmed that the thermal decomposition structure disappeared.

[Example 2]
(1) Synthesis of Silsesquioxane Compound 1 g of octakis (dimethylsiloxy) -T8-silsesquioxane (manufactured by Gelest), 1.3 g of divinyltetraphenyldisiloxane (manufactured by Gelest), and platinum catalyst (1, 3) -0.016 g of divinyl-1,1,3,3-tetramethyldisiloxane platinum complex 3% xylene solution (manufactured by Aldrich) was dissolved in 12 ml of dehydrated tetrahydrofuran (manufactured by Kanto Kagaku) and dissolved at 60 ° C. under nitrogen for 6 hours. By reacting, a silsesquioxane compound was synthesized.
When the average degree of polymerization of this polymer was measured by GPC, it was about 5600.
Table 1 shows the ¹ H-NMR and ²⁹ Si-NMR measurement results of this polymer.

(2) Film formation / firing The silsesquioxane compound reaction solution synthesized in (1) above was diluted 5-fold with tetrahydrofuran and then spin-coated on a silicon wafer at 1000 rpm. The silicon wafer on which this film was formed was dried at 140 ° C. for 1 hour, and then baked in a vertical furnace at 600 ° C. for 3 hours in an air atmosphere.
As a result, a transparent film formed on the silicon wafer was obtained. The film thickness of this transparent film was 220 nm.
When the TGA of this film was measured in an air atmosphere, 3% moisture desorption was observed by 110 ° C., and the weight loss from 110 ° C. to 1000 ° C. was 4%.
When the infrared absorption spectrum of this transparent film was measured, it was confirmed that the pyrolysis structure disappeared because the peak (1600 cm ⁻¹ ) of the phenyl group derived from the pyrolysis structure disappeared.

[Example 3]
(1) Synthesis of silsesquioxane compound Octakis (dimethylsiloxy) -T8-silsesquioxane (manufactured by Gelest) 0.51 g, octavinyl-T8-silsesquioxane (manufactured by Gelest) 0.32 g, and platinum 0.062 g of the catalyst (1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex 3% xylene solution, manufactured by Aldrich) was dissolved in 4 ml of dehydrated tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) and dissolved at room temperature. A silsesquioxane compound was synthesized by reacting for a period of time.
When the average degree of polymerization of this polymer was measured by GPC, it was about 18,000.
Table 3 shows the ¹ H-NMR and ²⁹ Si-NMR measurement results of this polymer.

(2) Film formation / firing The silsesquioxane compound reaction solution synthesized in (1) above was diluted 5-fold with tetrahydrofuran and then spin-coated on a silicon wafer at 1000 rpm. The silicon wafer on which this film was formed was dried under conditions of 140 ° C. and 1 hr, and then baked in a vertical furnace under conditions of 600 ° C. and 1 hr in an air atmosphere.
As a result, a transparent film formed on the silicon wafer was obtained. The film thickness of this transparent film was 230 nm.
When the TGA of this film was measured in an air atmosphere, water desorption of 3.3% was observed by 100 ° C., and the weight loss from 110 ° C. to 1000 ° C. was 3.7%.
When the infrared absorption spectrum of this transparent film was measured, the C—H peak (2960 cm ⁻¹ ) derived from the pyrolysis structure disappeared, and it was confirmed that the pyrolysis structure disappeared.

[Example 4]
(1) Synthesis of Silsesquioxane Compound Octakis (dimethylsiloxy) -T8-silsesquioxane (manufactured by Gelest) 1.02 g, polyethylene glycol divinyl ether (molecular weight 240, Aldrich) 0.72 g, and platinum catalyst 0.016 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex 3% xylene solution (manufactured by Aldrich) was dissolved in 8.7 ml of dehydrated tetrahydrofuran (manufactured by Kanto Kagaku) and ice-cooled. The reaction was continued for 15 minutes to synthesize a silsesquioxane compound.
When the average degree of polymerization of this polymer was measured by GPC, it was about 16000.
Table 1 shows the ¹ H-NMR and ²⁹ Si-NMR measurement results of this polymer.

(2) Film formation / firing The silsesquioxane compound reaction solution synthesized in (1) above was diluted 5-fold with tetrahydrofuran and then spin-coated on a silicon wafer at 1000 rpm. The silicon wafer on which this film was formed was dried under conditions of 140 ° C. and 1 hour, and then baked in a vertical furnace under conditions of 600 ° C. and 3 hours in an air atmosphere.
As a result, a transparent film formed on the silicon wafer was obtained. The thickness of this transparent film is 230 nm.
When the TGA of this film was measured in an air atmosphere, 3.4% moisture desorption was observed by 100 ° C., and the weight loss from 110 ° C. to 1000 ° C. was 2.7%.
When the infrared absorption spectrum of this transparent film was measured, the C—H peak (2960 cm ⁻¹ ) derived from the pyrolysis structure disappeared, and it was confirmed that the pyrolysis structure disappeared.

  Films manufactured using the silsesquioxane compound of the present invention include dielectric films, semiconductor interlayer insulating films, circuit board photoresist films, heat resistant films for ceramic sensors, heat resistant paints, flame retardant / fire resistant paints, building materials coatings It can be used for an agent, a dielectric film for a plasma display panel, and the like.

The cell structure conceptual diagram of a plasma display panel.

Explanation of symbols

1. Front glass substrate Transparent electrode 3. Bus electrode 4. Transparent dielectric layer Protective layer 6. 6. Back glass substrate Data electrode 8. Reflective layer 9. Rib 10. 10. Discharge gas space Phosphor

Claims (1)

Silsesquioxane in which at least two cage-like silsesquioxanes are bonded via at least one structure selected from oxyalkylene, siloxane, polymers thereof, and a structure represented by the following general formula (1) Sun compound.

(R ₁ , R ₂ , R ₁ ′ and R ₂ ′ represent a hydrogen atom, a chlorine atom, a hydroxyl group or a monovalent organic group. N represents a natural number. R ₃ and R ₄ represent an alkylene group. J And k and l represent 1 or 0, and at least one of k and l is 1.)

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