JP5610379B2 - Siloxane polymer, siloxane-based crosslinkable composition, and silicone film - Google Patents

Description

  The present invention relates to a siloxane polymer, a siloxane-based crosslinkable composition, and a silicone film obtained from the crosslinkable composition.

A polymer containing a silsesquioxane skeleton has been attracting attention from various fields because it has a unique structure and is expected to have a unique effect. As such a polymer containing a silsesquioxane skeleton, a silicon-based polymer having a silsesquioxane skeleton in the main chain is known (for example, see Patent Document 1). This silicon-based polymer can be used for films, sheets, and molded articles having excellent transparency, film-forming properties, and the like. However, since the silicon-based polymer has thermoplasticity, application to a field requiring heat resistance of the molded body is limited. As described above, the silicon-based polymer still has room for examination in terms of heat resistance of the molded body.
JP 2006-22207 A

  The present invention provides a technique for providing a silicone film having a silsesquioxane skeleton in the main chain of a silicon-based polymer and excellent in heat resistance.

  The present invention provides a siloxane polymer obtained by reacting a hydroxyl group at a terminal of a specific silicon compound having a silsesquioxane skeleton in the main chain with a tetrafunctional or higher functional crosslinkable silicon compound having a binding property to the hydroxyl group, A crosslinkable composition containing a compound and a silicone film formed from the siloxane polymer are provided.

Further, the present invention provides a siloxane polymer obtained by introducing a crosslinkable silicon compound that is crosslinked by moisture at the terminal of a silicon-based polymer having a silsesquioxane skeleton in the main chain, and the terminal of the siloxane polymer is crosslinked. Providing a silicone film, all formed of a siloxane polymer.
That is, the present invention provides the inventions represented by the following [1] to [11].

[1] and the silicon compound represented by the following formula (1), a siloxane polymer obtained from the crosslinkable silicon compound having groups or atoms 4 or reacts with the hydroxyl group of the silicon compound.

In formula (1), m independently represents an integer of 0 to 30; n represents an integer of 1 to 1,000; R ⁰ independently represents an aryl or carbon having 6 to 20 carbon atoms. Represents cycloalkyl having 5 or 6; R ¹ and R ² independently represent alkyl having 1 to 40 carbons, aryl having 6 to 40 carbons, or arylalkyl having 7 to 40 carbons;
In the aryl, the cycloalkyl, and the aryl in the arylalkyl, any hydrogen may be independently replaced with a halogen or an alkyl having 1 to 20 carbons; the alkyl having 1 to 40 carbons is Any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced with —O— or a cycloalkylene having 5 to 20 carbon atoms; , The carbon number thereof is 1 to 10, and any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—, —CH═CH— or a carbon number of 5 in it may be replaced 20 cycloalkylene; alkyl having 1 to 20 carbon atoms may be replaced by fluorine independent arbitrary hydrogen, any -CH ₂ - Independently -O-, it may be replaced by cycloalkylene of 5 to 20 carbon atoms, or phenylene.

[2] A crosslinkable silicon compound having four or more groups or atoms that react with a hydroxyl group in the silicon compound represented by the formula (1) is tetraethoxysilane, an oligomer thereof, bis (3- (triethoxysilyl) propyl. [1] Description, which is selected from disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine Siloxane polymer.

[3] A silicon compound represented by the formula (1) and a crosslinkable silicon compound having 4 or more groups or atoms that react with a hydroxyl group in the silicon compound are tetraethoxysilane, an oligomer thereof, and a methyltrimethoxylane oligomer. The siloxane polymer according to [2], which is selected from the group consisting of:

[4] The siloxane polymer according to any one of [1] to [3], wherein R ^{0 to} R ² are each independently methyl or phenyl.

[5] The siloxane polymer according to [4], wherein R ⁰ is phenyl and R ¹ and R ² are methyl.

[6] The (1) and a silicon compound represented by the crosslinkable composition comprising a crosslinkable silicon compound having a group or atom which reacts with the hydroxyl group of the silicon compound in 4 above.

[7] A crosslinkable silicon compound having four or more groups or atoms that react with a hydroxyl group in the silicon compound represented by the formula (1) is tetraethoxysilane, an oligomer thereof, bis (3- (triethoxysilyl) propyl. [6] Description, characterized in that it is selected from disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine. Crosslinkable composition.

[8] A silicon compound represented by the formula (1) and a crosslinkable silicon compound having four or more groups or atoms that react with a hydroxyl group in the silicon compound are tetraethoxysilane, an oligomer thereof, and a methyltrimethoxylane oligomer. The crosslinkable composition according to [7], which is selected from the group consisting of:

[9] The crosslinkable composition according to any one of [6] to [8], wherein R ^{0 to} R ² are each independently methyl or phenyl.

[10] The crosslinkable composition according to [9], wherein R ⁰ is phenyl and R ¹ and R ² are methyl.

[11] A silicone film obtained by curing a film of the crosslinkable composition according to any one of [6] to [10].

  In the present invention, in a crosslinkable composition containing the silicon compound represented by the formula (1) and the crosslinkable silicon compound, the silicon compound and the crosslinkable silicon compound are combined to form a film-like siloxane. Since a polymer can be obtained, it is possible to provide a silicone film having a silsesquioxane skeleton in the main chain of the silicon-based polymer and excellent in heat resistance.

  Moreover, in this invention, since a comparatively hard self-supporting film | membrane is obtained by using the crosslinkable silicon compound which has 4 or more bondable groups, the application to a film etc. can be anticipated and it can become a useful material.

  The siloxane polymer of the present invention is obtained from a silicon compound represented by the following formula (1) and a crosslinkable silicon compound bonded to the silicon compound. The silicon compound may be one type or two or more types.

In the formula (1), R ⁰ independently represents aryl or cycloalkyl having 6 to 20 carbon atoms. In the aryl and cycloalkyl of R ⁰ , any hydrogen may be independently replaced by halogen or alkyl having 1 to 20 carbons.

In the formula (1), R ¹ and R ² independently represent alkyl having 1 to 40 carbon atoms, aryl having 6 to 40 carbon atoms, or arylalkyl having 7 to 40 carbon atoms. In the alkyl group having 1 to 40 carbon atoms in R ¹ and R ² , any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently —O— or C 5-20. It may be replaced with cycloalkylene.

In the aryl group having 6 to 40 carbon atoms in R ¹ and R ² , any hydrogen may be independently replaced with halogen or alkyl having 1 to 20 carbon atoms. In the arylalkyl having 7 to 40 carbon atoms in R ¹ and R ² , any hydrogen in the aryl may be independently replaced with halogen or alkyl having 1 to 20 carbon atoms.

As for the alkyl having 1 to 20 carbon atoms which is a substituent of aryl having 6 to 40 carbon atoms and arylalkyl having 7 to 40 carbon atoms in R ¹ and R ² , any hydrogen may be independently replaced by fluorine. Any —CH ₂ — may be independently replaced with —O—, C 5-20 cycloalkylene or phenylene. Further, the alkylene of the arylalkyl having 1 to 40 carbon atoms in R ¹ and R ² has 1 to 10 carbon atoms, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced by —O—, —CH═CH—, or cycloalkylene having 5 to 20 carbon atoms.

R ⁰ to R ² may be the all the same, may be the same in each of the R ⁰ to R ^2, may be different in each of R ⁰ ~R ^2, R ⁰ ~ All of R ² may be different. Specifically, R ^{0 to} R ² include methyl and phenyl. R ^{0 to} R ² are preferably R ⁰ is phenyl and R ¹ and R ² are methyl from the viewpoints of obtaining various characteristics such as optical characteristics and the ease of synthesis.

  In said formula (1), m represents the integer of 0-30 independently, and n represents the integer of 1-1000. m is preferably from 0 to 9, more preferably from 0 to 5, and even more preferably from 1 to 3, from the viewpoints of ease of synthesis, physical properties of the resulting silicone film, and the like. N is preferably 1 to 1,000, more preferably 3 to 200, and still more preferably 5 to 30 from the viewpoints of ease of synthesis, physical properties of the resulting silicone film, and the like. When m is too large, when the silicon compound represented by the formula (1) is synthesized, it may not be synthesized in one step. If m is too large, the characteristics of the siloxane may be too strong in the characteristics of the silicon compound represented by the formula (1) as compared with the characteristics of silsesquioxane.

  The weight average molecular weight of the silicon compound represented by the formula (1) is preferably 4,000 to 200,000, more preferably 7,000 to 50,000.

  As described in Patent Document 1, the silicon compound comprises a silsesquioxane represented by the following formula (5) and a chain siloxane represented by the following formula (6) in a base such as triethylamine. It is obtained by reacting in the presence. M in the formula (1) can be determined by the type of the chain siloxane. N in the formula (1) is adjusted according to the reaction conditions (temperature, the concentration of the chain siloxane represented by the formula (6), etc.).

  The silsesquioxane represented by the formula (5) is also a compound represented by the following formula (7) and a compound represented by the following formula (8), as described in Patent Document 1. It is obtained by reacting and hydrolyzing. Here, X represents halogen or hydrogen. The compound represented by the following formula (7) is also hydrolyzed and condensed from the compound represented by the following formula (9) in the presence of sodium hydroxide and water, as described in Patent Document 1. Obtained by polymerization. The reaction at this time may be in the presence or absence of an organic solvent.

The crosslinkable silicon compound Ru der those having the hydroxyl group-reactive radicals or atoms of the silicon compound in (hereinafter also referred to as "crosslinkable functional group") 4 or more. The crosslinkable silicon compound may be one kind or two or more kinds. Examples of the crosslinkable silicon compound include silicon compounds having four or more crosslinkable functional groups, oligomers thereof, and oligomers of silicon compounds, and oligomers having four or more crosslinkable functional groups.

Examples of the crosslinkable silicon compound having four or more groups or atoms that react with the hydroxyl group in the silicon compound represented by the formula (1) include tetraethoxysilane, its oligomer, and bis (3- (triethoxysilyl) propyl. ) Disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine.

  From the viewpoint of availability, the oligomer as the crosslinkable silicon compound preferably has 2 to 20 repeating units (degree of polymerization), more preferably 2 to 15 and more preferably 4 to More preferably, it is 10. Examples of the oligomer include methyl silicate 51 (tetramethoxysilane tetramer), methyl silicate 53 (tetramethoxysilane heptamer), ethyl silicate 40 (tetraethoxysilane pentamer), ethyl, manufactured by Colcoat Co., Ltd. Examples thereof include silicate 48 (tetraethoxysilane decamer). The oligomer of a crosslinkable silicon compound can also be obtained from Tama Chemical Co., Ltd.

In particular, the crosslinkable silicon compound, tetraethoxy silane, oligomers thereof, that is one or more selected from methyltrimethoxysilane oligomer chromatography or Ranaru group, in the case of using ease of availability, and as crosslinking agent It is preferable from the viewpoint of effect.

The crosslinkable silicon compound may further have other groups as long as it has four or more of the crosslinkable functional groups. Other groups may be one kind or two or more kinds. Examples of such other groups include alkyl such as methyl, ethyl and propyl, and aryl such as phenyl.

Crosslinking between the silicon compound represented by the formula (1) and the crosslinkable silicon compound is a crosslinkable functional group that the crosslinkable silicon compound has and reacts with a hydroxyl group in the silicon compound represented by the formula (1). Based on the kind of the above, it is carried out by allowing both silicon compounds to coexist under appropriate conditions. Regarding the crosslinking between the silicon compound represented by the formula (1) and the crosslinkable silicon compound, R ⁰ in the silicon compound represented by the formula (1) is phenyl, R ¹ and R ² are methyl, The case where m is 2 and the crosslinkable silicon compound is vinyltrimethoxysilane will be further described as an example.

  As shown in the chemical formula, the siloxane polymer of the present invention is a condensation polymer in which the hydroxyl group of the silicon compound represented by the formula (1) and the crosslinkable silicon compound are condensed, and the terminal silicon has two methoxy groups. Along with this, methanol, which is a condensate of hydrogen and methoxy group of the hydroxyl group, is also produced.

  When the silicon compound represented by the formula (1) and the crosslinkable silicon compound are brought into contact with an atmosphere containing moisture such as air, the methoxy group in the crosslinkable silicon compound is hydrolyzed by moisture in the atmosphere. Thus, the siloxane polymer 1 in which the crosslinkable silicon compound is bonded to the terminal silicon of the silicon compound represented by the formula (1) and methanol are formed. Further, the methoxy group located at the end of the siloxane polymer 1 is similarly hydrolyzed by moisture in the air, and siloxane polymer 2 having a hydroxyl group introduced at the end and methanol are produced.

In this hydrolysis process, there are at least two of a siloxane polymer having a hydroxyl group at the terminal, a siloxane polymer having a methoxy group at the terminal, and a siloxane polymer having a hydroxyl group and a methoxy group at the terminal. The crosslinkable siloxane polymer is crosslinked by further condensation with methoxy groups of other siloxane polymers while producing methanol.

  When a sufficient amount of the crosslinkable silicon compound is subjected to condensation with respect to the silicon compound represented by the formula (1), the crosslinkable silicon compound is condensed at both ends of the silicon compound as shown in the following chemical formula. The crosslinked siloxane polymer is formed and crosslinked through the process described above.

  Further, as shown in the following chemical formula, when the crosslinkable silicon compound has four or more alkoxy groups such as tetraethoxysilane, both of the silicon compounds represented by the formula (1) as described above. A siloxane polymer in which the crosslinkable silicon compound is condensed at the terminal is formed, and crosslinks through the process described above.

  In the chemical formula, a siloxane in which the silicon compound represented by the formula (1) and the crosslinkable silicon compound are regularly reacted in an equal amount or double amount, and hydrolysis with water is also regularly performed. Although one form of polymer has been shown, the siloxane polymer of the present invention is not limited to this form. For example, the siloxane polymer of the present invention may include this form, or a form in which two or three silicon compounds represented by the formula (1) are bonded to one crosslinkable silicon compound. May be included.

  The reaction between the silicon compound and the crosslinkable silicon compound can be performed in the presence of a catalyst, if necessary. Examples of the catalyst include acid catalysts such as acetic acid and hydrochloric acid, and organotin catalysts. The type and amount of the catalyst can be determined according to the type of the crosslinkable functional group. For example, when the crosslinkable functional group is ethoxy, for example, dibutyltin laurate is used as the catalyst, and 100 weight of the crosslinkable silicon compound. Used in an amount of 0.01 to 5 parts by weight with respect to parts.

  The siloxane polymer of the present invention can be confirmed by a change in heat resistance and solubility in a solvent when produced from the silicon compound represented by the formula (1) and the crosslinkable silicon compound. For example, the formation of the siloxane polymer of the present invention can be confirmed by not melting when heated to 120 ° C., or by the product being insoluble in acetone.

  The crosslinkable composition of the present invention contains the silicon compound and the crosslinkable silicon compound. The content of the crosslinkable silicon compound in the crosslinkable composition is 0.1 to 50 parts by weight with respect to 100 parts by weight of the silicon compound from the viewpoint of improving the hardness, heat resistance, and the like of the cured product. The amount is preferably 1 to 20 parts by weight, more preferably 5 to 10 parts by weight.

  The crosslinkable composition may further contain components other than the silicon compound and the crosslinkable silicon compound as long as the effects of the present invention are obtained. Examples of such other components include solvents, catalysts, polymers other than the siloxane polymer of the present invention, and various additives. As the catalyst, the catalyst described above in the description of the siloxane polymer of the present invention can be used.

  The solvent is preferably a solvent that dissolves a component containing the silicon compound and the crosslinkable silicon compound, and is preferably a solvent that is not reactive with the component. The solvent may be one type or two or more types. Examples of such solvents include hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and ether solvents such as diethyl ether, tetrahydrofuran (THF), and dioxane. , Halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride, and ester solvents such as ethyl acetate.

  The other polymer can be appropriately selected from known polymers according to desired properties of the silicone film formed from the crosslinkable composition. One kind or two or more kinds of other polymers may be used. Other polymers may have a group capable of reacting with the crosslinkable functional group. The other polymer preferably has a group capable of reacting with the crosslinkable functional group from the viewpoint of improving the mechanical properties of the silicone film. Examples of the other polymer include an alkoxysilyl group-containing polymer, a vinyl group-containing polymer, and a hydrosilyl group-containing polymer.

As the additive, various known additives can be used from the viewpoint of imparting or improving desired properties to the crosslinkable composition or the silicone film. Examples of such additives include surfactants, fillers such as silica and mica, and the like.

  The content of the solvent in the crosslinkable composition is 10 to 90% by weight in the crosslinkable composition, since the content of the solid component blended in the crosslinkable composition is from the viewpoint of improving the coatability of the crosslinkable composition. %, More preferably 30 to 70% by weight, even more preferably 40 to 60% by weight.

  In general, the content of the catalyst in the crosslinkable composition is preferably 0.1 to 10 parts by weight and more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the crosslinkable silicon compound. Preferably, it is 0.5 to 2 parts by weight.

  The content of the other polymer in the crosslinkable composition can be arbitrarily determined from the viewpoint of improving the properties of the silicone film by the addition of the polymer.

  The content of the additive in the crosslinkable composition is preferably from 0.1 to 40% by weight, more preferably from 0.5 to 20% by weight, from the viewpoint of obtaining an effect by addition of the additive. Preferably, it is 1 to 10% by weight.

  Any component of the other components may be added to the crosslinkable composition without being mixed with the crosslinkable composition. For example, the crosslinkable composition of the present invention does not contain the above-mentioned optional components, and the amount of the crosslinkable composition contained in the container and the amount of the crosslinkable composition contained in the container and the composition, The form which consists of the said arbitrary component accommodated in the other container may be sufficient.

  The silicone film of the present invention can be obtained by curing the film of the crosslinkable composition.

  The film of the crosslinkable composition can be formed by applying the crosslinkable composition to a substrate or a film. As a method for applying such a crosslinkable composition, a known method such as a dipping method, a method using a bar coater or an applicator can be used.

  Curing of the film of the crosslinkable composition is carried out by subjecting the film of the crosslinkable composition to standing in a water-containing gas atmosphere, heating, light irradiation or the like according to the type of the crosslinkable functional group. This can be done by processing based on the above-described conditions for generating. For example, the film of the crosslinkable composition is cured by hydrolysis with moisture in the air by leaving it in normal air with a humidity of about 50%. The rate of cure is increased by the incorporation of the catalyst into the crosslinkable composition and can also be increased by heating the membrane. Furthermore, in such a heat treatment, for example, when a crosslinkable silicon compound having a vinyl group or a methacryl group is used, radical polymerization due to vinyl group or methacryl group polymerization may also occur. Secondary crosslinking is also expected.

  The silicone film of the present invention is a crosslinked main chain formed mainly from silanol in which siloxane chains and silsesquioxanes are alternately arranged via a crosslinkable silicon compound and are crosslinked by a crosslinkable silicon compound. Composed of things. The silicone film of the present invention has characteristics such as solubility, heat resistance, and flame retardancy unique to silicon compounds, gas permeability, light permeability, low dielectric constant, and other characteristics unique to silsesquioxane and crosslinking. It is expected to be excellent in properties such as mechanical strength depending on the structure. The silicone film of such an invention is expected to be used for a wide range of applications. Applications of the silicone film of the present invention include, for example, substrate coating agents such as metal elution preventing films, gas barrier films, and antireflection films, liquid sealants, interlayer insulating films, antifouling coating agents, microlenses, and light guide plates. Applications to electrical and electronic materials such as optical elements such as optical waveguide materials, display substrates and printed wiring boards.

[Synthesis Example 1] Synthesis of Siloxane Polymer In the above formula (1), R ⁰ is phenyl and R ¹ is methyl. 15.00 g (12.65 mmol) of silsesquioxane represented by the following structural formula is transferred to a reaction vessel. The reaction vessel was stored and vacuum-heated to remove water, the reaction vessel was cooled to 0 ° C. in a nitrogen atmosphere, 100 mL of dehydrated toluene and 31.80 mL (228.00 mmol) of triethylamine were added to the reaction vessel, and the colorless and transparent A solution was obtained. 3.63 mL (12.65 mmol) of 1,5-dichlorohexamethyltrisiloxane was added to the resulting solution, and the reaction was started at 0 ° C. After 2 hours, the reaction temperature was raised to 40 ° C., and the reaction was stopped after stirring for 4 days. This reaction gave a viscous milky white solution.

  The obtained solution was washed by liquid separation until the aqueous phase became neutral using ultrapure water, the obtained oil phase was concentrated under reduced pressure with an evaporator, and the obtained concentrate was dissolved in acetone. Hexane was added dropwise to this solution to obtain a white oily precipitate. The obtained precipitate was dissolved in toluene, applied to a fluororesin plate, and the coated product was gradually dried to obtain a siloxane polymer represented by the following formula as a translucent flexible film. When the obtained siloxane polymer was measured by GPC, the weight average molecular weight Mw was 10,000. Further, the ratio Mw / Mn of the weight average molecular weight to the number average molecular weight Mn was 2.1, and the degree of polymerization Dp was 7.

The measurement conditions for GPC measurement are shown below.
<Measurement conditions>
Column: Shodex KF-806M 300 × 8.0 mm
Mobile phase: THF
Flow rate: 1.0 ml / min
Temperature: 35 ° C
Detector: UV (256 nm)
Molecular weight standard sample: polystyrene with known molecular weight

  Furthermore, the thermal characteristics of the obtained siloxane polymer were evaluated. The thermal properties of the siloxane polymer were evaluated by TG-DTA (thermogravimetric-differential thermal analysis). The 5% weight loss amount temperature of the siloxane polymer was 443 ° C., and the weight loss at 800 ° C. was 32.0% by weight.

The conditions for TG-DTA measurement are shown below.
<Measurement conditions>
Measuring device: simultaneous differential thermothermal weight measuring device EXSTAR6000 TG / DTA6300 (manufactured by Seiko Instruments Inc.)
Bread: Pt
Standard sample: Aluminum oxide (10 mg)
Sample mass: about 10mg
Temperature program: 25-800 ° C
Temperature increase rate: 10 ° C / min
Atmosphere: Nitrogen

[Example 1]
In a nitrogen atmosphere, 5 g of the siloxane polymer obtained in Synthesis Example 1 is dissolved in 5 g of toluene in a screw tube, and 0.25 g of tetraethoxysilane (TEOS) is added to and mixed with the resulting solution to form a crosslinkable composition. 1 was obtained.

  To the obtained prepolymer 1 solution, 0.1 g of dibutyltin laurate was added as a catalyst. After stirring and defoaming for 15 minutes, the obtained crosslinkable composition 1 was applied to a release agent-coated film, and the obtained coating film was air-dried for 10 minutes. The coating film was heated in an oven at 80 ° C. for 1 hour and further cured by heating at 120 ° C. for 2 hours, and the resulting cured film was peeled off from the release agent-coated film, resulting in a thickness of about 100 μm. A transparent silicone film 1 was obtained. The thickness of the silicone film 1 was measured with a film thickness meter (EL-30, manufactured by Sanko Electronics Laboratory).

  Furthermore, the mechanical strength of the obtained silicone film 1 was evaluated. The mechanical strength of the silicone film 1 was evaluated by pencil hardness. The pencil hardness of the silicone film 1 was measured by the method defined in JIS K 5600-4. As a result, the pencil hardness of the silicone film 1 was B. Further, as in Synthesis Example 1, the thermal characteristics of the obtained silicone film 1 were evaluated. As a result, the 5% weight loss amount temperature of the silicone film 1 was 514 ° C., and the weight loss at 800 ° C. was 14.3% by weight.

[Example 2]
In Example 1, except that a tetraethoxysilane oligomer (TEOS oligomer, average 10-mer) was used instead of tetraethoxysilane, the same operation as in Example 1 was performed to obtain a crosslinkable composition 2, A transparent silicone film 2 having a thickness of about 100 μm was obtained. The resulting silicone film 2 had a pencil hardness of HB.

[Example 3]
Example 1 Example 1 was carried out except that 0.5 g of methyltrimethoxysilane oligomer methanol and toluene solution (SS-101 manufactured by Colcoat Co., Ltd., concentration: 50% by weight) was used instead of tetraethoxysilane as a crosslinking agent. The same operation as in Example 1 was carried out to obtain a crosslinkable composition 3
A transparent silicone film 3 having a thickness of about 100 μm was obtained. The resulting silicone film 3 had a pencil hardness of B.

[ Reference Example 4]
In Example 1, the same procedure as in Example 1 was performed, except that vinyltrimethoxysilane (Silaace (registered trademark) S210 manufactured by Chisso Corporation) was used instead of tetraethoxysilane as a crosslinking agent. Material 4 was obtained, and a transparent silicone film 4 having a thickness of about 100 μm was obtained. The resulting silicone film 4 had a pencil hardness of 2B. Further, as in Synthesis Example 1, the thermal characteristics of the obtained silicone film 4 were evaluated. As a result, the 5% weight loss amount temperature of the silicone film 4 was 540 ° C., and the weight loss at 800 ° C. was 13.2% by weight.

[ Reference Example 5]
In Example 1, the same operation as in Example 1 was carried out except that 3-glycidoxypropyltrimethoxysilane (Silas Ace (registered trademark) S510, manufactured by Chisso Corporation) was used instead of tetraethoxysilane as the crosslinking agent. Then, a crosslinkable composition 5 was obtained, and a transparent silicone film 5 having a thickness of about 100 μm was obtained.

[ Reference Example 6]
In Example 1, operation was performed in the same manner as in Example 1 except that 3-methacryloxypropyltrimethoxysilane (Syraace (registered trademark) S710 manufactured by Chisso Corporation) was used instead of tetraethoxysilane as a crosslinking agent. Then, a crosslinkable composition 6 was obtained, and a transparent silicone film 6 having a thickness of about 100 μm was obtained.

[Reference Example 1]
In Example 1, except that ethyltrimethoxysilane was used instead of tetraethoxysilane as a crosslinking agent, the same operation as in Example 1 was performed to obtain a crosslinkable composition 7, and a transparent film having a thickness of about 100 μm was obtained. A silicone film 7 was obtained. The resulting silicone film 7 had a pencil hardness of 4B.

[Reference Example 2]
In Example 1, except that phenyltrimethoxysilane was used instead of tetraethoxysilane as a crosslinking agent, the same operation as in Example 1 was performed to obtain a crosslinkable composition 8, and a transparent film having a thickness of about 100 μm was obtained. A silicone film 8 was obtained. The resulting silicone film 8 had a pencil hardness of B. Further, the thermal characteristics of the obtained silicone film 8 were evaluated in the same manner as in Example 2. As a result, the 5% weight loss amount temperature of the silicone film 8 was 395 ° C., and the weight loss at 800 ° C. was 27.7% by weight.

  As described above, by reacting the siloxane polymer with a silicon compound having four or more groups that react with a hydroxyl group bonded to silicon in the presence of dibutyltin laurate, a transparent material having high hardness and high heat resistance is obtained. It has been found that a film can be obtained.

  As described above, in the presence of dibutyltin laurate, the siloxane polymer can be subjected to a reaction such as crosslinking in addition to a group that causes a condensation reaction with a hydroxyl group bonded to silicon necessary for crosslinking or three atoms. It was found that a transparent film having high hardness and high heat resistance can be obtained by reacting one or more silicon compounds having

According to the present invention, a silicone film having high light transmittance in addition to high hardness and heat resistance can be obtained by a simple method of applying a liquid composition and curing thereof. Further, according to the present invention, the siloxane polymer of the present invention can be obtained by curing the liquid composition. Therefore, the siloxane polymer of the present invention having various shapes can be formed by using an appropriate mold. Therefore, it can be applied to optical materials such as lenses, etc., as well as electric and electronic materials for forming various layers in various display elements, and can be used in various other technical fields.

Claims (11)

And a silicon compound represented by the following formula (1), a siloxane polymer obtained from the crosslinkable silicon compound having groups or atoms 4 or reacts with the hydroxyl group of the silicon compound.

(In formula (1), m independently represents an integer of 0 to 30; n represents an integer of 1 to 1,000; R ⁰ is independently aryl having 6 to 20 carbon atoms; Represents cycloalkyl having 5 or 6 carbon atoms; R ¹ and R ² independently represent alkyl having 1 to 40 carbon atoms, aryl having 6 to 40 carbon atoms, or arylalkyl having 7 to 40 carbon atoms;
In the aryl, the cycloalkyl, and the aryl in the arylalkyl, any hydrogen may be independently replaced with a halogen or an alkyl having 1 to 20 carbons; the alkyl having 1 to 40 carbons is Any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced with —O— or a cycloalkylene having 5 to 20 carbon atoms; , The carbon number thereof is 1 to 10, and any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—, —CH═CH— or a carbon number of 5 in it may be replaced 20 cycloalkylene; alkyl having 1 to 20 carbon atoms may be replaced by fluorine independent arbitrary hydrogen, any -CH ₂ - Independently -O-, it may be replaced by cycloalkylene of 5 to 20 carbon atoms, or phenylene. ) A crosslinkable silicon compound having four or more groups or atoms that react with a hydroxyl group in the silicon compound represented by the formula (1) is tetraethoxysilane, an oligomer thereof, bis (3- (triethoxysilyl) propyl) disulfide, The siloxane polymer according to claim 1, wherein the siloxane polymer is selected from bis (3- (triethoxysilyl) propyl) tetrasulfide and N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine. . The silicon compound represented by the formula (1) and the crosslinkable silicon compound having 4 or more groups or atoms that react with a hydroxyl group in the silicon compound are selected from tetraethoxysilane, an oligomer thereof, and a methyltrimethoxylane oligomer. siloxane polymer according to claim 2, characterized in that. The siloxane polymer according to any one of claims 1 to 3, wherein each of R ^{0 to} R ² is independently methyl or phenyl. The siloxane polymer according to claim 4, wherein R ⁰ is phenyl and R ¹ and R ² are methyl. The silicon compound represented by the following formula (1) and the crosslinkable composition comprising a crosslinkable silicon compound having groups or atoms 4 or reacts with the hydroxyl group of the silicon compound.

(In formula (1), m independently represents an integer of 0 to 30; n represents an integer of 1 to 1,000; R ⁰ is independently aryl having 6 to 20 carbon atoms; Represents cycloalkyl having 5 or 6 carbon atoms; R ¹ and R ² independently represent alkyl having 1 to 40 carbon atoms, aryl having 6 to 40 carbon atoms, or arylalkyl having 7 to 40 carbon atoms;
In the aryl, the cycloalkyl, and the aryl in the arylalkyl, any hydrogen may be independently replaced with a halogen or an alkyl having 1 to 20 carbons; the alkyl having 1 to 40 carbons is Any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced with —O— or a cycloalkylene having 5 to 20 carbon atoms; The carbon number is 1
Any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced with —O—, —CH═CH— or C 5-20 cycloalkylene. The alkyl having 1 to 20 carbon atoms may be optionally substituted with any hydrogen independently with fluorine, and any —CH ₂ — may independently be —O—, cyclohexane having 5 to 20 carbon atoms; Alkylene or phenylene may be substituted. ) A crosslinkable silicon compound having four or more groups or atoms that react with a hydroxyl group in the silicon compound represented by the formula (1) is tetraethoxysilane, an oligomer thereof, bis (3- (triethoxysilyl) propyl) disulfide, 7. Crosslinkability according to claim 6, characterized in that it is selected from bis (3- (triethoxysilyl) propyl) tetrasulfide and N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine. Composition. The silicon compound represented by the formula (1) and the crosslinkable silicon compound having 4 or more groups or atoms that react with a hydroxyl group in the silicon compound are selected from tetraethoxysilane, an oligomer thereof, and a methyltrimethoxylane oligomer. and characterized in that, according to claim 7 crosslinkable composition. The crosslinkable composition according to any one of claims 6 to 8, wherein R ^{0 to} R ² are each independently methyl or phenyl. Wherein R ⁰ is phenyl, wherein R ¹ and R ² are crosslinkable composition of claim 9 wherein the methyl.   The silicone film | membrane formed by hardening | curing the film | membrane of the crosslinkable composition as described in any one of Claims 6-10.