JP6770779B2 - Siloxane resin composition - Google Patents

Description

The present invention relates to a siloxane resin composition having high transparency and excellent gas barrier properties.

Conventionally, polyvinylidene chloride (hereinafter abbreviated as "PVDC") has been used as a gas barrier membrane in many situations. In fact, PVDC exhibits excellent gas barrier properties and also exhibits high gas barrier properties even under high humidity conditions. However, when PVDC is incinerated, if it is not burned under appropriate conditions, there is a concern that substances harmful to the environment and the human body such as dioxin and chlorine gas will be generated. For these reasons, the development of gas barrier membranes that can be easily disposed of is being promoted, but there are many disadvantages such as low gas barrier properties and low transparency, and they have not been put into practical use.

Further, in the field of electronic materials, for example, organic EL and solar cells, a gas barrier film having a high gas barrier property is required in order to protect organic molecules which are organic light emitters. Gas barrier membranes generally used for electronic materials are formed by silica-film deposition, but the silica-film deposition equipment is large, the cost of machine introduction is high, and there is a big economic problem. For example, although there are reports that high gas barrier properties have been obtained by electron beam thermal thin-film deposition, a large amount of cost investment is required for equipment introduction (see, for example, Patent Documents 1 and 2).

On the other hand, in semiconductors and display materials, materials exhibiting high heat resistance are required due to an increase in current density and a shorter emission wavelength as the performance is improved. As such a material, a siloxane resin having high transparency and heat resistance has attracted attention and is widely used. Therefore, the inventors have stated that, as a resin composition having a gas barrier property when applied to a substrate or the like, a composition composed of a siloxane resin having an epoxy group, a specific amine compound and an alcohol has a high gas barrier property. Although it was found (see Patent Document 3), further improvement in barrier properties was required.

Japanese Unexamined Patent Publication No. 2011-102042 Japanese Unexamined Patent Publication No. 2013-52561 Japanese Unexamined Patent Publication No. 2016-27112

An object of the present invention is to provide a siloxane resin composition having good coatability on a substrate and excellent transparency and gas barrier property.

（式中、ｍ、ｎは、モル％を示し、ｍは９０〜６０モル％、ｎは１０〜４０モル％であり、ｍとｎの合計は１００モル％である。Ｒ¹はエポキシ基を含む炭化水素基、Ｘは水素原子またはケイ素原子を示す。）
ＧＰＣで測定される重量平均分子量が５００から１００，０００、分散度が１から２０、エポキシ当量が４００ｇ／ｅｑ以下であることを特徴とする。 The siloxane resin composition of the present invention is a siloxane resin composition composed of a siloxane resin, an aromatic polyamine compound and an alcohol solvent, and the siloxane resin is represented by the following general formula (1).

(In the formula, m and n represent mol%, m is 90 to 60 mol%, n is 10 to 40 mol%, and the total of m and n is 100 mol%. R ¹ is an epoxy group. A hydrocarbon group containing, X indicates a hydrogen atom or a silicon atom.)
It is characterized in that the weight average molecular weight measured by GPC is 500 to 100,000, the dispersity is 1 to 20, and the epoxy equivalent is 400 g / eq or less.

The siloxane resin composition of the present invention comprises a specific siloxane resin, an aromatic polyamine compound and an alcohol solvent, the siloxane resin has an epoxy group on the side chain, and the weight average molecular weight Mw is 500 to 100. Since the dispersion degree Mw / Mn was 1 to 20, the epoxy equivalent was 400 g / eq or less, the coatability was good in a solution state in which the siloxane resin and the aromatic polyamine compound were dissolved in an alcohol solvent. .. A thin film can be formed on a substrate by applying a solution of this siloxane resin composition to various substrates, and a thermosetting film can be produced on the substrate by applying heat. Since the thermosetting film thus formed has excellent properties of transparency and heat resistance, it can be used as a protective film for semiconductors and displays.

R ¹ described in the general formula (1) can be a 3-glycidoxypropyl group or a 2- (3,4-epoxycyclohexyl) ethyl group.
The aromatic polyamine-based compound can be p-xylene diamine. Further, the alcohol solvent can be methanol.
When applied to a substrate, the siloxane resin composition can be cured at a temperature of 100 ° C. or higher.

By applying the above-mentioned siloxane resin composition to a substrate and curing it at a temperature of 100 ° C. or higher, a cured film having excellent transparency and heat resistance can be produced.

The cured film obtained by this production method can have an oxygen permeability of less than 5.0 × 10 ^-12 mol · m ⁻² · S ^-1 · Pa ^-1 .
The moisture permeability of the cured film obtained by this production method can be less than 16.0 g / m ² · day (25 μm conversion).

Further, the siloxane resin composition of the present invention can be applied not only to the electronic field but also to a wide range of fields such as paints and adhesives.

（式中、ｍ、ｎは、モル％を示し、ｍは９０〜６０モル％、ｎは１０〜４０モル％であり、ｍとｎの合計は１００モル％である。Ｒ¹はエポキシ基を含む炭化水素基、Ｘは水素原子またはケイ素原子を示す。） The siloxane resin composition of the present invention comprises a siloxane resin, an aromatic polyamine-based compound, and an alcohol-based solvent. Of these, the siloxane resin is represented by the following general formula (1), and the weight average molecular weight measured by GPC is 500 to 100,000, the dispersity is 1 to 20, and the epoxy equivalent is 400 g / eq or less.

(In the formula, m and n represent mol%, m is 90 to 60 mol%, n is 10 to 40 mol%, and the total of m and n is 100 mol%. R ¹ is an epoxy group. A hydrocarbon group containing, X indicates a hydrogen atom or a silicon atom.)

In the siloxane resin represented by the general formula (1), R ¹ represents a hydrocarbon group containing an epoxy group. The number of carbon atoms of the hydrocarbon group including the epoxy group is preferably 4 to 10. Examples of R ¹ include glycidoxyalkyl groups such as 2-glycidoxyethyl group and 3-glycidoxypropyl group, and epoxycycloalkyl groups such as 3,4-epoxycyclopentyl group and 3,4-epoxycyclohexyl group. , 2- (3,4-epoxycyclopentyl) ethyl group, 2- (3,4-epoxycyclohexyl) ethyl group and other alkyl groups having an epoxycycloalkyl group. Among them, industrially available 3-glycidoxypropyl group and 2- (3,4-epoxycyclohexyl) ethyl group are particularly preferable.

In the general formula (1), m and n represent mol%, and the total of m and n is 100 mol%. m is 90 to 60 mol%, preferably 80 to 70 mol%, and n is 10 to 40 mol%, preferably 20 to 30 mol%. When m is 90 mol% or less and n is 10 mol% or more, the gas barrier property is enhanced. Further, when m is 60 mol% or more and n is 40 mol% or less, gelation of the siloxane resin is suppressed and stable production becomes possible. m and n can be increased or decreased by adjusting the monomer composition when polymerizing the siloxane resin.

In the general formula (1), X represents a hydrogen atom or a silicon atom. When X is a hydrogen atom, it indicates an acidic substituent called general silanol. On the other hand, when X is a silicon atom, it shows a siloxane bond of Si—O—Si.

（式中、Ｒはエポキシ基を含む炭化水素基を示す） The siloxane resin constituting the present invention has the structure of the following general formula (3) in which three oxygen atoms are bonded to a silicon atom, and is generally called silsesquioxane.

(In the formula, R indicates a hydrocarbon group containing an epoxy group)

（式中、Ｒはエポキシ基を含む炭化水素基を示す） The silsesquioxane may have a silanol group at the terminal as shown in the following general formula (4), for example.

(In the formula, R indicates a hydrocarbon group containing an epoxy group)

（式中、Ｒはエポキシ基を含む炭化水素基を示すし、ｎは一般的な重合度を示す整数を示す。） Further, silsesquioxane can also be represented by the following general formula (5).

(In the formula, R represents a hydrocarbon group containing an epoxy group, and n represents an integer indicating a general degree of polymerization.)

（式中、Ｒはエポキシ基を含む炭化水素基を、ｎは一般的な重合度を示す整数を示す。） Further, silsesquioxane may contain a ladder-type structure represented by the following general formula (6).

(In the formula, R is a hydrocarbon group containing an epoxy group, and n is an integer indicating a general degree of polymerization.)

Further, the siloxane resin constituting the present invention may include the following cage-shaped structure in the three-dimensional structure of the molecule. Typical cage-shaped structures include a T8 structure having eight silicon atoms represented by the following general formula (7), a T10 structure having ten silicon atoms represented by the following general formula (8), and the following general formula (9). ), A T12 structure having 12 silicon atoms can be mentioned.

（式中、Ｒはエポキシ基を含む炭化水素基を示す）

(In the formula, R indicates a hydrocarbon group containing an epoxy group)

（式中、Ｒはエポキシ基を含む炭化水素基を示す）

(In the formula, R indicates a hydrocarbon group containing an epoxy group)

（式中、Ｒはエポキシ基を含む炭化水素基を示す）

(In the formula, R indicates a hydrocarbon group containing an epoxy group)

（式中、Ｒはエポキシ基を含む炭化水素基を示す） These structures are not completely condensed, and may include a structure in which terminal Si—OH remains partially, for example, a structure represented by the following general formula (10). Further, not only in the cage type but also in the ladder type structure in which the ring is not closed, the terminal Si-OH may partially remain.

(In the formula, R indicates a hydrocarbon group containing an epoxy group)

The weight average molecular weight of the siloxane resin constituting the present invention measured by GPC is 500 to 100,000, preferably 1,000 to 100,000, more preferably 1,000 to 80,000, still more preferably. It is 1,500 to 50,000. When the weight average molecular weight is 500 or more, a dense coating film can be formed, and when it is 100,000 or less, it is soluble in an organic solvent, which is preferable.

The dispersity (Mw / Mn) obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn) is 1 to 20, preferably 1 to 5. By setting the dispersity (Mw / Mn) of the siloxane resin to 1 to 20, a dense coating film can be formed.

In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the Z average molecular weight (Mz) of the siloxane resin can be measured by gel permeation chromatography (GPC) and obtained by standard polystyrene conversion. You can.

Further, the epoxy equivalent of the siloxane resin is 400 g / eq or less, preferably 100 to 400 g / eq, and more preferably 150 to 400 g / eq. By setting the epoxy equivalent to 400 g / eq or less, cross-linking is formed with the cross-linking agent, and a dense coating film can be formed.
The siloxane resin constituting the present invention is preferably soluble in an alcohol solvent.

（式中、Ｒはエポキシ基を含む炭化水素基を、Ａは炭素数１から５のアルキル基を示す。） As a method for producing the above-mentioned siloxane resin, a production method in which a silicon monomer represented by the following general formula (11) is hydrolyzed and polycondensed using water in the presence of a basic catalyst is preferable.

(In the formula, R represents a hydrocarbon group containing an epoxy group, and A represents an alkyl group having 1 to 5 carbon atoms.)

The substituent R of the silicon monomer represented by the general formula (11) is a hydrocarbon group R ¹ containing an epoxy group described in the general formula (1). Further, A represents an alkyl group having 1 to 5 carbon atoms, and is an alkyl group such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-pentyl and iso-pentyl. Can be exemplified. Of these, methyl and ethyl, which are easily available as raw materials, are preferable.

Water is required to hydrolyze and polycondensate the silicon monomer of the general formula (11). The amount of water used is preferably 1.0 to 10.0 equivalents, more preferably 1.0 to 5.0 equivalents, relative to the number of moles of the silicon monomer. From the viewpoint of reaction stability, it is more preferable to use 1.0 to 3.0 equivalents of water.

Further, when hydrolyzing or polycondensing a silicon monomer, it is preferable to use a basic catalyst because the reaction proceeds faster. The amount of the basic catalyst used is preferably 0.004 to 1.0 equivalent with respect to the number of moles of the silicon monomer, and 0.004 to 0.5 from the viewpoint of high reaction reproducibility and ease of reaction control. Equivalents are more preferred.

As the conditions for hydrolysis and polycondensation, the reaction temperature is preferably 0 to 100 ° C., and more preferably 20 to 50 ° C. because the reaction easily proceeds by using a catalyst. When the temperature is 100 ° C. or lower, the siloxane does not polymerize, which is preferable.

The basic catalyst used for producing the siloxane resin constituting the present invention is preferably an inorganic basic catalyst, a quaternary ammonium salt, or amines, and examples of the inorganic basic catalyst are sodium hydroxide, potassium hydroxide, and the like. Can be mentioned. Examples of the quaternary ammonium salt include tetrabutylammonium fluoride, benzyltributylammonium chloride, benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetran-butylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, and benzyltrin-butyl. Ammonium bromide, benzyltriethylammonium bromide, benzyltrimethylammonium bromide, n-octyltrimethylammonium bromide, hexyltrimethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium bromide, tetradecyltrimethylammonium bromide, tetramethylammonium bromide, tetra n-propylammonium Bromide, Tetrabutylammonium Iodide, Tetraethylammonium Iodide, Tetramethylammonium Iodide, Tetran-propylammonium Iodide, trimethylphenylammonium Iodide, benzyltrimethylammonium hydroxide, Phenyltrimethylammonium hydroxide, Tetrabutylammonium hydroxide , Tetraethylammonium hydroxide, tetramethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydrogen sulfate, tetrabutylammonium tetrafluoroborate, tetramethylammonium thiocyanate, tetramethylammonium p-toluene sulfonate, etc. Be done. Examples of amines include trimethylamine, triethylamine, pyridine, N, N-dimethylaminopyridine and the like. In particular, tetramethylammonium hydroxide, which can control the hydrolysis rate of the monomer with a strong base, is more preferable.

In the polymerization reaction of the siloxane resin, the reaction can be carried out without a solvent, but from the viewpoint of viscosity and stability, it is preferable to use a polymerization solvent. As the polymerization solvent, an aproton solvent such as toluene and xylene, a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, an alcohol solvent such as methanol, ethanol and isopropanol, and a solvent such as an ether solvent such as diethyl ether and tetrahydrofuran are used. It can be used in a mixed system of one or more of them. When the obtained polysiloxane resin is dissolved in a high boiling solvent such as propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, or ethyl lactate, it may be used as it is as a reaction solvent. When an aprotic solvent is used, it is presumed that the hydrolysis reaction is slow because it is not mixed with water. In such a case, it is desirable to add a soluble alcohol solvent to the water to cause the hydrolysis reaction.

After completion of the reaction, the basic catalyst may be neutralized with a carboxylic acid or an inorganic acid. Then, a non-polar solvent is added to separate the reaction product from water, the reaction product dissolved in the polymerization solvent is recovered, washed with water, and then the solvent is distilled off to obtain the desired siloxane resin. it can.

The siloxane resin composition of the present invention comprises the siloxane resin synthesized above, an aromatic polyamine-based compound, and an alcohol-based solvent. The aromatic polyamine-based compound is a compound containing a plurality of amino groups and has an aromatic ring in the molecule. For example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, chloro-p-phenylenediamine, chloro-m-phenylenediamine, fluorophenylenediamine, dichlorophenylenediamine, methylphenylenediamine, dimethylphenylenediamine, o-xylylene. Phenylenediamines such as rangeamine, m-xylylenediamine, p-xylylenediamine, toluylenediamine, diphenylmethanes such as benzidine, o-tridin, dianisidedin, diaminodiphenylmethane, diaminodichlorodiphenylmethane, diaminodimethyldiphenylmethane, diaminodiethyldiphenylmethane , Naphthalenediamine, diaminobenzanilide, diaminodiphenyl ether, diaminostillylenedisulfonic acid, diaminophenol dihydrochloride, leucodiaminoanthraquinone, amino-N, N-diethylaminotruidine hydrochloride or amino-N-ethyl-N- (β-methanesulfone) Amidoethyl) -toluidine sulfate hydrate and the like. Among them, when o-xylylenediamine, m-xylylenediamine, and p-xylylenediamine are used, they are preferable because they have high gas barrier properties, and p-xylylenediamine is more preferable.

As the alcohol solvent, an alcohol having a low boiling point is preferable from the viewpoint that the siloxane resin composition can be applied to a substrate or the like and then distilled off with a slight heating, and the compatibility between the siloxane resin and the aromatic polyamine compound is particularly excellent. Methanol, ethanol, isopropanol, n-butanol, t-butanol, n-heptanol, n-hexanol and the like are preferable. Of these, methanol and ethanol, which are small molecules, are more preferable.

In the present invention, the content of the siloxane resin in the siloxane resin composition is preferably 5% by weight or more. More preferably, it is 5 to 50% by weight, and the film thickness of the gas barrier film can be changed by changing the resin content. If the content of the siloxane resin is high, the viscosity of the composition increases and the coatability decreases. Therefore, 5 to 30% by weight is more preferable, and 5 to 20% by weight is further preferable. Further, when the content of the siloxane resin is 5% by weight or more, the gas barrier property is high, which is preferable.

The content of the aromatic polyamine compound in the siloxane resin composition is preferably 5 to 50% by weight. Since the viscosity of the composition increases when the content of the aromatic polyamine compound is high, 5 to 30% by weight is more preferable, and 5 to 20% by weight is further preferable.

The content of the alcohol solvent in the siloxane resin composition is preferably 45 to 90% by weight, more preferably 55 to 90% by weight, and even more preferably 65 to 90% by weight.

A general method for producing a gas barrier film using a siloxane resin composition will be described below. To prepare a gas barrier film, a siloxane resin composition is applied onto a substrate to form a thin film, which is then heated to prepare a gas barrier film. Examples of the substrate include a glass substrate, a silicon wafer, and a film such as polypropylene (PP), polyethylene (PE), and polyethylene terephthalate (PET). These may be either a stretched film or a non-stretched film. Further, examples of the coating method include a spin coating method, a dip coating method, a gravure coating method, and a doctor blade method. In particular, the siloxane resin composition of the present invention has good spin coatability, has a uniform thickness, and can easily form a homogeneous thin film.

Next, the thin film formed on the substrate is placed in a hot plate or an oven and heated to remove the alcohol solvent, and the epoxy unit in the siloxane resin is reacted with the amine to prepare a thermosetting film. ..

Generally, in the production of a thermosetting film, it can be produced at preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and can be produced at a temperature suitable for an actual process. However, when it is applied on a film such as PE, it is preferably produced at 80 to 150 ° C., and more preferably 80 to 120 ° C.

The gas barrier film thus produced is formed from a cured product of a siloxane resin, and is a gas barrier film having excellent transparency and heat resistance. In the method for producing a cured film of the present invention, a gas barrier film can be easily produced simply by applying a siloxane resin composition on a glass substrate, a silicon wafer, or a film and heating at preferably 100 ° C. or higher. The obtained cured film is a gas barrier film having excellent oxygen barrier properties and transparency.

The oxygen permeability of the gas barrier membrane is preferably less than 5.0 × 10 ^-12 mol · m ⁻² · S ^-1 · Pa ^-1 , more preferably 4.0 × 10 ^-12 mol · m ⁻² · S ^{−. It} should be ¹ · Pa ^-1 or less. By setting the oxygen permeability of the gas barrier membrane to less than 5.0 × 10 ^-12 mol ・ m ^-2・ S ^-1・ Pa ^-1 , it is decided to prepare an excellent gas barrier membrane showing high oxygen barrier properties. Can be done.

The moisture permeability of the gas barrier membrane is preferably less than 20.0 g / m ² · day (25 μm conversion), more preferably 15.0 g / m ² · day (25 μm conversion) or less. By setting the moisture permeability of the gas barrier membrane to less than 20.0 g / m ² · day (25 μm conversion), it is possible to produce an excellent gas barrier membrane exhibiting high water vapor barrier properties.

Since the gas barrier film of the present invention can be easily produced as described above, it is not only applicable to gas barrier films such as semiconductors and displays, but also becomes an excellent gas barrier film having transparency and heat resistance.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, the following equipment is used for measurement, and general reagents purchased from reagent manufacturers (Tokyo Chemicals, Wako Pure Chemicals, Nacalai Tesque, Azmax, Shin-Etsu Chemical) are used as raw materials. There was.

<Measuring device and measuring method>
-IR measurement IR Prestige-21 manufactured by Shimadzu Corporation was used. A small amount of the synthesized compound was applied to the KBr plate, sandwiched between other KBr plates, and infrared light was transmitted to the measurement.

-GPC measurement Using the HLC-8220GPC system manufactured by Tosoh Corporation, TSKgel SuperHZ3000, TSKgel SuperHZ2000, and TSKgel SuperHZ1000 manufactured by Tosoh Corporation were connected in series for analysis. The detection was performed by RI (refractive index meter), and one TSKgelSuperH-RC was used as a reference column. Tetrahydrofuran manufactured by Wako Pure Chemical Industries, Ltd. was used as the developing solvent, and the flow rate between the column and the reference column was 0.35 mL / min. The measurement temperature was 40 ° C. for both the plunger pump and the column. The sample was prepared by diluting about 0.025 g of siloxane resin with 10 mL of tetrahydrofuran and pouring 1 μL into the sample. For molecular weight distribution calculation, Tosoh TSK standard polystyrene (A-500, A-1000, A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F -40, F-80) was used as a standard substance for calculation.

-Oxygen permeability measurement method Using a gas permeability measurement device by the pressure sensor method based on the plastic-film and sheet-gas permeability test method (JIS-K7126-1), the measurement temperature is 40 ° C and the relative humidity is 0%. And said.

-Humidity Permeability Measurement Method The moisture permeability was measured under Condition B in accordance with the moisture permeability test method (JIS-Z0208) for moisture-proof packaging materials.

-Evaluation of spin coatability when forming a gas barrier film Regarding the spin coatability when forming a gas barrier film from a siloxane resin composition, those that could be applied evenly to polypropylene film (CPP) are ○, and there is no problem in practical use. Those that could be applied in 1 were marked with Δ, and those that could not be applied successfully were marked with ×.

-Evaluation of the transparency of the gas barrier film The transparency of the obtained gas barrier film is evaluated visually by visually evaluating the cured film after heat curing, and the colorless and transparent one is ○, which is a level of transparency that does not cause any practical problems. Those having a property were designated as Δ, and those having a property were designated as ×.

Synthesis of siloxane resin Synthesis example 1
132.4 g (0.56 mol) of γ-glycidoxypropyltrimethoxysilane and 50.0 g (0.24 mol) of tetraethoxysilane in a 1 L 4-neck flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer. ), Methyl isobutyl ketone 364.7 g (2.0 weight times / monomer), and methanol 72.9 g (0.4 weight times / monomer) were charged. Then, 48.1 g (0.05 eq / methoxy group) of a 25% tetramethylammonium hyrodoxide aqueous solution was added dropwise from the dropping funnel at a temperature of 15 to 40 ° C. After completion of the dropping, the reaction solution was aged at 25 ° C. for 7 hours. After aging, it was neutralized with 209.0 g (1.05 eq / tetramethylammonium hydroxide) of a 13% aqueous citric acid solution. After the liquid separation, the water layer was removed and the obtained oil layer was washed twice. The obtained oil layer was concentrated under reduced pressure to obtain 92.1 g of a siloxane resin which is a colorless transparent viscous liquid. The weight average molecular weight (Mw) of the obtained polysiloxane resin was 2,480, the dispersity (Mw / Mn) was 1.26, and the epoxy equivalent was 250 g / eq.

Synthesis example 2
In a 500 mL four-necked flask, 25 mL of 2-propanol, 50 mL of toluene, 0.1 g (0.001 mol) of a 25% tetramethylammonium hydride aqueous solution and 5.88 g (0.326 mol) of water were charged, and then γ-glycidoxy. 50 g (0.211 mol) of propyltrimethoxysilane was added dropwise at 30-40 ° C., and the mixture was polymerized as it was for 2 hours. After completion of the reaction, the reaction was neutralized, washed, and the solvent was distilled off to obtain 35.4 g of a siloxane resin containing a γ-glycidoxypropyl group. The weight average molecular weight (Mw) of the obtained polysiloxane resin was 2,000, the dispersity (Mw / Mn) was 1.12, and the epoxy equivalent was 175 g / eq.

Fabrication of Gas Barrier Membrane Example 1
1 g of the polysiloxane resin obtained in Synthesis Example 1 and 0.6 g of p-xylene diamine were weighed, dissolved in 9 g of methanol, and stirred for 30 minutes to prepare a coating liquid. The prepared coating solution was spin-coated on a polypropylene film (CPP) as a base material at 1000 rpm for 30 seconds to form a thin film, and thermoset at 100 ° C. for 2 hours to prepare a gas barrier film. The oxygen permeability and humidity permeability of the prepared gas barrier membrane were measured and shown in Table 1. The oxygen permeability of the polypropylene film (CPP) used as the substrate was 1.7 × 10 ^-11 mol · m ⁻² · S ^-1 · Pa ^-1 .

Example 2
A gas barrier membrane was prepared by the same operation as in Example 1 except that the p-xylene diamine described in Example 1 was changed from 0.6 g to 0.8 g, and the oxygen permeability and moisture permeability were measured.

Example 3
A gas barrier membrane was prepared by the same operation as in Example 1 except that the p-xylene diamine described in Example 1 was changed from 0.6 g to 0.9 g, and the oxygen permeability and moisture permeability were measured.

Example 4
A gas barrier membrane was prepared by the same operation as in Example 1 except that the p-xylene diamine described in Example 1 was changed from 0.6 g to 1.0 g, and the oxygen permeability and moisture permeability were measured.

Comparative Example 1
1 g of the polysiloxane resin obtained in Synthesis Example 2 and 1 g of ethylenediamine were weighed, dissolved in 9 g of methanol, and stirred for 180 minutes to prepare a coating liquid. The prepared coating solution was spin-coated on a polypropylene film (CPP) as a base material at 1000 rpm for 30 seconds to form a thin film, and thermoset at 100 ° C. for 2 hours to prepare a gas barrier film. The oxygen permeability and humidity permeability of the prepared gas barrier membrane were measured and shown in Table 1.

Comparative Example 2
A gas barrier membrane was prepared by the same operation as in Comparative Example 1 except that 1 g of ethylenediamine described in Comparative Example 2 was changed to 1 g of polyethyleneimine (average molecular weight of about 10,000), and oxygen permeability and moisture permeability were measured. ..

The formulation and evaluation results of the siloxane resin compositions in Examples 1 to 4 and Comparative Examples 1 and 2 are summarized in the table below.

Claims (6)

A siloxane resin composition comprising a siloxane resin, an aromatic polyamine-based compound, and an alcohol-based solvent, wherein the siloxane resin is represented by the following general formula (1).

(In the formula, m and n represent mol%, m is 90 to 60 mol%, n is 10 to 40 mol%, and the total of m and n is 100 mol%. R ¹ is an epoxy group. A hydrocarbon group containing, X indicates a hydrogen atom or a silicon atom.)
A siloxane resin composition characterized by having a weight average molecular weight of 500 to 100,000 measured by GPC, a dispersity of 1 to 20, and an epoxy equivalent of 400 g / eq or less. The siloxane resin composition according to claim 1, wherein R ^{1 according} to the general formula (1) is a 3-glycidoxypropyl group or a 2- (3,4-epoxycyclohexyl) ethyl group. The siloxane resin composition according to claim 1 or 2, wherein the aromatic polyamine-based compound is p-xylene diamine. The siloxane resin composition according to any one of claims 1 to 3, wherein the alcohol solvent is methanol. The siloxane resin composition according to any one of claims 1 to 4, which can be cured at a temperature of 100 ° C. or higher when the siloxane resin composition is applied to a substrate. A method for producing a cured film, wherein the siloxane resin composition according to any one of claims 1 to 5 is applied to a substrate and cured at a temperature of 100 ° C. or higher.