KR101631075B1 - Siloxane polymer composition - Google Patents

Abstract

The present invention relates to a siloxane polymer composition, a cured film formed from the composition, an interlayer insulating film, and an interlayer insulating film, which are suitable as materials for forming a cured film such as an interlayer insulating film of a display element such as a liquid crystal display element (LCD) Forming method.
According to the present invention, it is possible to provide a siloxane-based polymer composition which can be used as a material of an interlayer insulating film having improved heat resistance and transmittance while improving hardness, a cured film formed from the siloxane-based polymer composition, an interlayer insulating film, and a method of forming the interlayer insulating film . Therefore, the interlayer insulating film formed by the present invention can be suitably used for a display device, a protective film for a touch panel display device, and the like, which is useful.

Description

Siloxane polymer composition {SILOXANE POLYMER COMPOSITION}

The present invention relates to a siloxane polymer composition, a cured film formed from the composition, and an interlayer insulating film which are suitable as a material for forming a cured film such as an interlayer insulating film of a display element such as a liquid crystal display element (LCD) or an organic EL display element.

Color TFT liquid crystal display elements and the like are formed by overlapping a color filter substrate and a TFT array substrate. In the TFT array substrate, an interlayer insulating film is formed in order to insulate between wirings arranged in a generally layered form. As the material for forming the interlayer insulating film, a positive radiation-sensitive composition is widely used because it is preferable that the number of processes for obtaining a required pattern shape is small and furthermore, it is desired to have sufficient flatness.

Acrylic resin is mainly used as a component of the radiation-sensitive composition for forming an interlayer insulating film (see Japanese Unexamined Patent Publication (Kokai) No. 2001-354822). Recently, a polysiloxane-based material superior in heat resistance and transparency to acrylic resin (JP-A-2006-178436, JP-A-2006-276598, JP-A-2006-293337).

On the other hand, an input device for operating a device by pressing a display on a screen, such as a touch panel, a touch screen, or a touch screen, for an automatic cash dispenser such as a bank, a vending machine, a mobile phone, a portable information display terminal, have. Since the touch panel is normally pressed directly by a finger or the like, a protective film is provided. The protective film is required to have surface hardness such as adhesiveness to wiring of a touch panel element and scratch resistance as a protective film.

Accordingly, it is necessary to develop a polysiloxane positive photosensitive composition having high heat resistance, transparency, low dielectric constant, etching resistance, hardness, high voltage holding ratio and high compatibility with a photosensitizer.

Under these circumstances, the present inventors have made intensive efforts to develop a siloxane-based polymer composition that can be used as a material of an interlayer insulating film having improved surface hardness and excellent heat resistance and transmittance. As a result, It is possible to form an interlayer insulating film which can satisfactorily satisfy general requirements such as heat resistance and transmittance while improving the hardness when the siloxane polymer composition is used.

An object of the present invention is to provide a siloxane-based polymer composition which can be used as a material for an interlayer insulating film having improved heat resistance and transmittance while improving hardness, a cured film formed from the siloxane-based polymer composition, and a method for forming an interlayer insulating film and an interlayer insulating film.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.

In one aspect, the present invention provides a siloxane polymer obtained by hydrolysis and condensation of (A) a silane compound and (a2) benzyl alcohol or benzyl ether, wherein the silane compound (a1) a2) 70% to 97% by weight based on the total weight of the composition, (a2) the benzyl alcohol or the benzyl ether is used in an amount of 3% by weight to 30% by weight based on the total weight of the compound (a1) (B) a siloxane polymer composition containing a solvent

≪ Component (A): siloxane polymer >

The siloxane polymer of the component (A) is a compound having a siloxane bond obtained by hydrolysis and condensation of (a1) a silane compound and (a2) benzyl alcohol or benzyl ether.

The silane compound (a1) is preferably a hydrolyzable silane compound represented by the following formula (1).

[Chemical Formula 1]

(R ¹ ) _n -Si- (OR ² ) _4-n

R ¹ in the above formula (1) each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. Examples of the alkyl group include a methyl group, ethyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n-hexyl group and n-decyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group. However, some or all of hydrogen atoms of these alkyl groups and aryl groups may be substituted.

R ² in the above formula (1) independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the acyl group include an esyl group, a propionyl group and a butanoyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and the like. However, some or all of hydrogen atoms of these alkyl groups and aryl groups may be substituted.

N in the formula (1) represents an integer of 0 to 3. When n = 0, it is a tetrafunctional silane, when n = 1 it is a trifunctional silane, when n = 2 it is a bifunctional silane, and when n = 3 it is a monofunctional silane.

Examples of the hydrolyzable silane compound according to the present invention represented by Formula 1 include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, Propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyl But are not limited to, trimethoxysilane, n-hexyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane. From the viewpoint of hardness of the cured film among these hydrolyzable silane compounds, it is preferable to use trifunctional silane and tetrafunctional silane.

The (a2) benzyl alcohol or benzyl ether is preferably a compound represented by the following formula (2).

(2)

또는

or

Wherein R is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, R 'is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X is a hydrogen atom or an OH group, Y is a hydrogen atom, methyl or triple Lt; / RTI >

As the benzyl compound represented by the formula (2), R is one of a hydrogen atom, a methyl group, an ethyl group, a propyl group and an n-butyl group, and R 'is one of a hydrogen atom, methyl, ethyl and t-butyl. Benzene dimethanol, 1,4-benzene dimethanol, 2,6-bis (hydroxymethyl) -p-cresol, 1,4-bis (methoxymethyl) Benzyl compounds such as benzene, 4,4'-isopropylidenebis (2,6-dihydroxymethylphenol) and 4,4-isopropylidenebis (2,6-dimethoxymethylphenol) 3 to 30% by weight of the amount of the monomer used.

In the present invention, the term "hydrolyzable silane compound" refers to a compound capable of hydrolyzing to generate a silanol group by heating in the temperature range of room temperature (about 25 ° C.) to about 100 ° C. in the presence of a non- Or a group capable of forming a siloxane condensate.

Preferably, the siloxane monomer represented by the formula (1) and the benzyl alcohol or benzyl ether represented by the formula (2) can be produced by hydrolysis and condensation polymerization to produce the siloxane polymer (A) of the present invention. (A2) benzyl alcohol or benzyl ether is used in an amount of from 3% by weight to 30% by weight, based on the total weight of the compound (a1) and the compound (a2) Weight% of the siloxane polymer can be hydrolyzed and condensed and polymerized to produce "(A) siloxane polymer ".

As described above, it is possible to produce a siloxane polymer capable of producing an interlayer insulating film having excellent hardness and transparency by controlling the amounts of (a1) and (a2) used in the production of the siloxane polymer (A). In one embodiment of the present invention, (A) a siloxane polymer was prepared by varying the weight ratio of (a1) and / or (a2). As a result, when the amount of the benzylic compound (a2) is more than 30% by weight, the transparency of the interlayer insulating film to be produced deteriorates. When the amount of the benzylic compound is 3% by weight to 30% by weight, It was confirmed that the production was possible. Therefore, it is preferable to use 70% by weight to 97% by weight of the siloxane monomer (a1) compound and 3% by weight to 30% by weight of the benzylic compound (a2) in the production of the siloxane polymer (A).

The solvent which can be used for the hydrolysis polymerization is not particularly limited. Any solvent commonly used in the positive photosensitive composition can be used without limitation. Preferable examples of the ether solvents include tetrahydrofuran, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, As the ether acetates, ethers such as ethylene glycol monoalkyl ether acetate and propylene glycol monoalkyl ether acetate, ketones such as methyl ethyl ketone, and various esters can be used. Examples of the aromatic hydrocarbons include toluene and xylene.

As the water used for the hydrolysis and condensation, it is preferable to use water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment or distillation. By using such purified water, it is possible to suppress the side reaction and improve the reactivity of hydrolysis. The amount of water to be used is preferably 0.1 to 3 mol, more preferably 0.3 to 2 mol, and still more preferably 0.5 to 1.5 mol, relative to 1 mol of the total amount of the hydrolyzable groups of the hydrolyzable silane compound represented by the above formula It is a quantity. By using such an amount of water, the reaction rate of hydrolysis and condensation can be optimized.

The hydrolysis and condensation reaction of the (a1) silane compound and (a2) benzyl alcohol or benzyl ether for producing the siloxane polymer (A) according to the present invention can be carried out preferably under an acid catalyst. The catalyst can be used in the form of a Lewis acid. As the Lewis acid, all Lewis acids such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluorosulfonic acid, toluenesulfonic acid and phosphoric acid can be used.

The reaction temperature and the reaction time in the hydrolysis and condensation for producing the siloxane polymer (A) according to the present invention can be suitably set. For example, the following conditions may be employed. The reaction temperature is preferably 40 to 200 占 폚, more preferably 50 to 150 占 폚. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours. The hydrolysis and condensation reaction can be carried out efficiently at such reaction temperature and reaction time. In the hydrolysis and condensation, a hydrolyzable silane compound, water and a catalyst may be added to the reaction system at one time to carry out the reaction. Alternatively, the hydrolyzable silane compound, water and catalyst may be added in several reaction systems , And the hydrolysis and condensation reaction may be carried out in multiple steps. Further, after the hydrolysis and condensation reaction, water and the produced alcohol can be removed from the reaction system by adding a dehydrating agent and then adding to the condensation.

The molecular weight of the siloxane polymer (A), which is the hydrolyzate and condensate of the hydrolyzable silane compound according to the present invention, is determined by GPC (gel permeation chromatography) using tetrahydrofuran as the mobile phase, and the polystyrene reduced number average molecular weight . ≪ / RTI > The number average molecular weight of the hydrolysis-condensation product is preferably within a range of usually 1,000 to 40,000. When the value of the number average molecular weight of the hydrolyzed condensate is 1,000 or more, the film forming property of the positive-tone radiation-sensitive composition can be improved. On the other hand, when the value of the number average molecular weight of the hydrolysis-condensation product is 40,000 or less, deterioration of the radiation sensitivity of the positive-tone radiation-sensitive composition can be prevented.

≪ Component (B): Solvent >

The component (B) is a solvent. Although not particularly limited, it is particularly preferable to contain an alcoholic solvent which is a protonic solvent. By using an alcoholic solvent, it is possible to uniformly dissolve or disperse the respective components, thereby making it possible to improve the coating property of the composition solution on a large substrate, and also to improve the coating uniformity (streaks, pin marks, Etc.) can be suppressed and the film thickness uniformity can be further improved.

Examples of such alcohol solvents include long chain alkyl alcohols such as 1-hexanol, 1-octanol, 1-nonanol, 1-dodecanol, 1,6-hexanediol and 1,8-octanediol; Aromatic alcohols such as benzyl alcohol; Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether; Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; And dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and dipropylene glycol monobutyl ether. These alcoholic solvents may be used alone or in combination of two or more.

Among these alcoholic solvents, benzyl alcohol, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether are particularly preferable from the viewpoint of improvement in coating performance.

The component (B) may be used singly or in a mixture of two or more kinds.

The amount of the component (B) to be used is preferably 5 parts by mass to 300 parts by mass, more preferably 10 parts by mass to 200 parts by mass, per 100 parts by mass of the component (A). By making the amount of the component (B) fall within the above-mentioned range, it is possible to improve the coating property on a glass substrate or the like and to suppress the occurrence of uneven coating (uneven streaks, pin marks or fog stains) Can be further improved.

In the present invention, in addition to the alcohol solvent, other solvents such as ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ketones , Esters and the like.

As the solvent other than the alcoholic solvent, the following may be mentioned.

As the ethers, for example, tetrahydrofuran and the like; Examples of diethylene glycol alkyl ethers include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and the like; As the ethylene glycol alkyl ether acetates, for example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate and the like; Examples of the propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like; Examples of the propylene glycol monoalkyl ether propionate include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like ; As the aromatic hydrocarbon, for example, toluene, xylene and the like; Examples of the ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-

Carbon monoxide and the like; Examples of esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy- Hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, Propyl methoxyacetate, propyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate , Ethoxyacetic acid propyl acetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, Propoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, , Butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, and the like. These solvents may be used alone or in combination of two or more.

The polysiloxane composition of the present invention may further contain the following components.

≪ Component (C): Thermal acid generator or thermal base generator >

The thermal acid generators or thermal base generators may be used in the production of the siloxane polymer (A) according to the present invention by reacting an acidic active substance which acts as a catalyst in the hydrolytic condensation reaction of the compound (a1) and the compound (a2) Is defined as a compound capable of releasing a basic active substance. By using the compound of the component (C), the condensation reaction of the components in the heating step after the development of the positive-tone radiation-sensitive composition can be promoted, and an interlayer insulating film excellent in surface hardness and heat resistance can be formed. As the thermal acid generators or the heat base generators of the component (C), there may be used a pre-baking method at a relatively low temperature (for example, 70 to 120 ° C) in the step of forming a coating film of the positive- Does not emit an acidic active substance or a basic active substance but emits an acidic or basic active substance at post-baking at a relatively high temperature (for example, 120 to 250 占 폚) in a heating step after development .

(4) The thermal acid generator of component (C) includes an ionic compound and a nonionic compound. As the ionic compound, it is preferable not to contain a heavy metal or a halogen ion. Examples of the ionic thermosensitive acid generators include triphenylsulfonium, 1-dimethylthi naphthalene, 1-dimethylthio-4-hydroxynaphthalene, 1-dimethylthio-4,7-dihydroxynaphthalene, Benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2- Methanesulfonic acid salts such as benzoyloxyphenylmethylsulfonium, trifluoromethanesulfonic acid salts, camphorsulfonic acid salts, p-toluenesulfonic acid salts, and hexafluorophosphonic acid salts. Examples of the nonionic thermally sensitive acid generator include a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carbonic acid ester compound, a phosphoric acid ester compound, a sulfonimide compound, a sulfonbenzotriazole compound, have. Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound. Examples of preferred halogen-containing compounds are 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) Naphthyl-4,6-bis (trichloromethyl) -s-triazine, and the like. Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p- (2,4-xylylsulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, tilsulfonyl-p-toluenesulfonyldiazomethane,

(1,1-dimethylethylsulfonyl) diazomethane, ss (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane and the like. Examples of the sulfone compounds include? -Ketosulfone compounds,? -Sulfonyl sulfone compounds, diaryl sulfone compounds, and the like. Examples of preferable sulfone compounds include 4-trisphenacylsulfone, mesitylphenylacylsulfone, bis (phenylsulfonyl) methane, 4-chlorophenyl-4-methylphenyldisulfone compounds and the like. Alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, and iminosulfonates. Examples of preferable sulfonate ester compounds include benzoin tosylate, pyrogallol trimesilate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, and 2,6-dinitrobenzylbenzenesulfonate. Examples of the carbonic acid ester compound include carbonic acid o-nitrobenzyl ester.

 Examples of the thermal base generator of component (C) include transition metal complexes such as cobalt, orthonitrobenzyl carbamates,?,? -Dimethyl-3,5-dimethoxybenzylcarbamates, acyloxyiminos have. Examples of the transition metal complexes include bromopentaham ammonia cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexammonium cobalt perchlorate, hexamethylamine cobalt perchlorate, hexapropylamine cobalt perchlorate, Salts and the like. Examples of the acyloxyimines include propionyl acetophenone oxime, propionylbenzophenone oxime, propionylacetone oxime, butyryl acetophenone oxime, butyrylbenzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoyl benzo Acetoacetophenone oxime, acroylbenzophenone oxime, acroacetone oxime, and the like can be given. Other examples of thermosensitive base generators include 2-nitrobenzylcyclohexylcarbamate and O-carbamoylhydroxyamide.

However, the present invention is not limited thereto. As the thermal acid generators or the thermal base generators of the component (C), either an acid or a base may be used. One type may be used alone, or two or more types may be used in combination. When the component (C) is used, the amount is preferably 0.1 parts by mass to 10 parts by mass, more preferably 1 part by mass to 5 parts by mass, relative to 100 parts by mass of the component (A). By setting the amount of the component (C) to be 0.1 part by mass to 10 parts by mass, the radiation sensitivity of the positive-tone radiation-sensitive composition can be optimized, and an interlayer insulating film with high surface hardness can be formed while maintaining transparency.

≪ Formation of cured film &

In another aspect, the present invention provides a cured film formed from the polysiloxane composition of the present invention and a method of forming the cured film.

The cured film according to the present invention can be produced by the following process.

(1) a coating process for coating the substrate with the polysiloxane composition of the present invention to a desired thickness,

(2) a step of pre-baking the coated substrate applied in the step (1)

(3) a step of exposing and developing the coating film pre-baked in the step (2)

(4) A step of post-baking the developed coating film in the step (3).

As the material of the substrate usable in the present invention, glass, silicon, quartz, resin, or the like can be used. By pre-baking the coated substrate, the solvent is removed and a coating film is formed. In order to form a pattern on the coated film, the resist film is exposed through a photomask having a predetermined pattern. After exposure to light of a certain wavelength through a photomask, unnecessary portions are removed to form a pattern. As the developing solution used in the developing process, an aqueous alkali solution is preferable. Examples of the alkali to be used include sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like. After the development is completed, the patterned thin film is heated and cured. Such post-baking is usually carried out at a temperature of 120 to 250 degrees Celsius.

By forming a pattern by coating, pre-baking, exposure, development, and heating using a photosensitive composition, a display element interlayer insulating film having a fine pattern can be easily formed. Also, the interlayer insulating film formed in this way forms an interlayer insulating film having excellent hardness, heat resistance, and transparency.

In the present invention, the term "cured film" is a general term for thermosetting products formed using the siloxane polymer composition, and examples of the cured film of the display element include a protective film and an interlayer insulating film.

Since the siloxane polymer composition according to the present invention can form a cured film excellent in transparency and scratch resistance, such a cured film can be applied to technical applications requiring high scratch resistance or transparency, and for example, a liquid crystal display element or a touch A protective film of various devices such as a panel, an interlayer insulating film, and the like.

Cured film (protective film or interlayer insulating film)

As described above, the cured film formed from the polysiloxane composition of the present invention has excellent surface hardness, heat resistance, and transparency characteristics with respect to the substrate. Therefore, the cured film can be suitably used for a display element such as a touch panel of a liquid crystal display element.

According to the present invention, it is possible to provide a siloxane-based polymer composition which can be used as a material of an interlayer insulating film having improved heat resistance and transmittance while improving hardness, a cured film formed from the siloxane-based polymer composition, an interlayer insulating film, and a method of forming the interlayer insulating film . Therefore, the interlayer insulating film formed by the present invention can be suitably used for display devices, protective films for touch panel display devices, and the like.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these embodiments are merely examples for explaining the content and scope of the technical idea of the present invention, and thus the technical scope of the present invention is not limited or changed. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the technical idea of the present invention based on these examples.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples and Examples, but the present invention is not limited to the following Examples.

The weight average molecular weight (Mw) of the hydrolyzed condensate of the hydrolyzable silane compound obtained from each of the following synthesis examples was measured by gel permeation chromatography (GPC) according to the following specifications.

Device: GPC Waters e2695

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Showa Denko K.K.)

Mobile phase: tetrahydrofuran

Synthesis Example of Polysiloxane as Component [A]

Synthesis Example 1

25% by weight of phenyltriethoxysilane, 35% by weight of methyltriethoxysilane, 25% by weight of tetraethoxysilane and 15% by weight of 4,4'-isopropylidenebis (2,6-dihydroxymethylphenol) And 50 parts by weight of a tetrahydrofuran solvent were added to a reactor equipped with a reflux condenser and a solution prepared by adding 2 wt% of sulfuric acid to 20 wt% of ultrapure water with vigorous stirring was slowly added to the reactor. The reactor was refluxed for 12 hours and then cooled. The cooled reaction solution was diluted and subjected to GPC analysis. As a result, a polymer having a weight average molecular weight of 5,000 in terms of polystyrene was prepared.

Synthesis Example 2

35% by weight of phenyltriethoxysilane, 35% by weight of methyltriethoxysilane, 25% by weight of tetraethoxysilane and 5% by weight of 4,4'-isopropylidenebis (2,6-dihydroxymethylphenol) And 50 parts by weight of a tetrahydrofuran solvent were added to a reactor equipped with a reflux condenser and a solution prepared by adding 2 wt% of sulfuric acid to 20 wt% of ultrapure water with vigorous stirring was slowly added to the reactor. The reactor was refluxed for 12 hours and then cooled. The cooled reaction solution was diluted and subjected to GPC analysis. As a result, a polymer having a weight average molecular weight of 3,500 in terms of polystyrene was prepared.

Synthesis Example 3

35 parts by weight of phenyltriethoxysilane, 35 parts by weight of methyltriethoxysilane, 25 parts by weight of tetraethoxysilane and 5 parts by weight of 1,4-bis (methoxymethyl) benzene were added, and 50 parts by weight of a tetrahydrofuran solvent The solution was added to a reactor equipped with a reflux condenser and a solution prepared by adding 2 wt% of sulfuric acid to 20 wt% of ultrapure water with vigorous stirring was slowly added to the reactor. The reactor was refluxed for 12 hours and then cooled. The cooled reaction solution was diluted and subjected to GPC analysis. As a result, a polymer having a weight average molecular weight of 7,500 in terms of polystyrene was prepared.

Synthesis Example 4

30 parts by weight of phenyltriethoxysilane, 35 parts by weight of methyltriethoxysilane, 25 parts by weight of tetraethoxysilane and 10 parts by weight of 1,4-bis (methoxymethyl) benzene were added, and 50 parts by weight of a tetrahydrofuran solvent The solution was added to a reactor equipped with a reflux condenser and a solution prepared by adding 2 wt% of sulfuric acid to 20 wt% of ultrapure water with vigorous stirring was slowly added to the reactor. The reactor was refluxed for 12 hours and then cooled. The cooled reaction solution was diluted and subjected to GPC analysis. As a result, a polymer having a weight average molecular weight of 13,000 in terms of polystyrene was prepared.

Synthesis Example 5

25 parts by weight of phenyltriethoxysilane, 35 parts by weight of methyltriethoxysilane, 25 parts by weight of tetraethoxysilane and 15 parts by weight of 1,4-benzenedimethanol were placed and 50 parts by weight of a tetrahydrofuran solvent was charged into a reflux condenser A solution prepared by adding 20 wt% of sulfuric acid to 20 wt% of ultrapure water while stirring vigorously was added to the reactor slowly. The reactor was refluxed for 12 hours and then cooled. The cooled reaction solution was diluted and subjected to GPC analysis. As a result, a polymer having a weight average molecular weight of 5,900 in terms of polystyrene was prepared.

Synthesis Example 6

25% by weight of phenyltriethoxysilane, 35% by weight of methyltriethoxysilane, 25% by weight of tetraethoxysilane and 15% by weight of 2,6-bis (hydroxymethyl) -p-cresol were dissolved in a tetrahydrofuran solvent Were added to a reactor equipped with a reflux condenser and a solution prepared by adding 2 wt% sulfuric acid to 20 wt% of ultrapure water while vigorously stirring was slowly added to the reactor. The reactor was refluxed for 12 hours and cooled. The cooled reaction solution was diluted and subjected to GPC analysis. As a result, a polymer having a weight average molecular weight of 7,400 in terms of polystyrene was prepared.

Synthesis Example 7

25 parts by weight of phenyltriethoxysilane, 35 parts by weight of methyltriethoxysilane, 25 parts by weight of tetraethoxysilane and 15 parts by weight of 1,2-benzenedimethanol were placed and 50 parts by weight of a tetrahydrofuran solvent was charged into a reflux condenser A solution prepared by adding 20 wt% of sulfuric acid to 20 wt% of ultrapure water while stirring vigorously was added to the reactor slowly. The reactor was refluxed for 12 hours and cooled. The cooled reaction solution was diluted and subjected to GPC analysis. As a result, a polymer having a weight average molecular weight of 6,500 in terms of polystyrene was prepared.

Comparative Example 1

29 weight% of phenyltriethoxysilane, 42 weight% of methyltriethoxysilane, and 29 weight% of tetraethoxysilane were placed in a reactor equipped with a reflux condenser and 50 weight parts of a tetrahydrofuran solvent were added to 20 weight parts of ultrapure water A solution containing 2% by weight of sulfuric acid in an amount of 10% was added slowly to the reactor. The reactor was refluxed for 12 hours and then cooled. The cooled reaction solution was diluted and subjected to GPC analysis. As a result, a polymer having a weight average molecular weight of 6,100 in terms of polystyrene was prepared.

Comparative Example 2

25% by weight of phenyltriethoxysilane, 35% by weight of methyltriethoxysilane, 25% by weight of tetraethoxysilane and 2% by weight of 4,4'-isopropylidenebis (2,6-dihydroxymethylphenol) And 50 parts by weight of a tetrahydrofuran solvent were added to a reactor equipped with a reflux condenser and a solution prepared by adding 2 wt% of sulfuric acid to 20 wt% of ultrapure water with vigorous stirring was slowly added to the reactor. The reactor was refluxed for 12 hours and cooled. The cooled reaction solution was diluted and subjected to GPC analysis. As a result, a polymer having a weight average molecular weight of 6,300 in terms of polystyrene was prepared.

Comparative Example 3

25% by weight of phenyltriethoxysilane, 35% by weight of methyltriethoxysilane, 25% by weight of tetraethoxysilane and 45% by weight of 4,4'-isopropylidenebis (2,6-dihydroxymethylphenol) And 50 parts by weight of a tetrahydrofuran solvent were added to a reactor equipped with a reflux condenser and a solution prepared by adding 2 wt% of sulfuric acid to 20 wt% of ultrapure water with vigorous stirring was slowly added to the reactor. The reactor was refluxed for 12 hours and then cooled. The cooled reaction solution was diluted and subjected to GPC analysis. As a result, a polymer having a weight average molecular weight of 6,800 in terms of polystyrene was prepared.

Various physical properties of the interlayer insulating film formed by using the siloxane-based polymer composition of the present invention were evaluated.

[Pencil hardness measurement]

On the silicon substrate, the prepared siloxane-based polymers (Synthesis Examples 1 to 7 and Comparative Examples 1 to 3) were spin-coated and then pre-baked at 100 degrees for 3 minutes. After prebaking, the film thickness was about 4.0 microns. The thus obtained coating film was post-baked at 240 degrees for 1 hour. The pencil hardness of the cured film was measured using a pencil hardness meter. The measurement results are shown in Table 1.

[Heat resistance evaluation]

The thickness of the cured coating film was measured to determine the pencil hardness (T1), and the thickness (T2) obtained by further baking the coating at 230 DEG C for 1 hour was measured. [(T1-T2) / T2 x 100 (%) The thickness variation before and after the additional baking was calculated as a percentage. When the thickness deviation ratio is within 3%, it can be said that the heat resistance is excellent.

[Evaluation of transmittance]

The coated film was coated on a glass substrate and heated at 230 DEG C for 1 hour to obtain a cured film. The glass substrate having the cured film was measured at 400 nm using a spectrophotometer, and the results are shown in Table 1.

Synthetic example Comparative Example One 2 3 4 5 6 7 One 2 3 Hardness 5H 6H 5H 5H 6H 5H 5H 3H 3H 5H Heat resistance 1.5 1.6 1.4 1.4 1.5 1.3 1.3 2.1 1.9 1.3 Transmittance 95 96 95 95 96 96 95 96 95 93

From the above description, it will be understood by those skilled in the art that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. In this regard, it should be understood that the above-described embodiments are to be considered in all respects as illustrative and not restrictive. The scope of the present invention should be construed as being included in the scope of the present invention without departing from the scope of the present invention as defined by the appended claims.

Claims (6)

(A) a siloxane polymer obtained by hydrolysis and condensation of (a1) a silane compound and (a2) benzyl alcohol or benzyl ether, wherein the silane compound (a1) (A2) benzyl alcohol or benzyl ether is used in an amount of 3 to 30% by weight based on the total weight of the compound (a1) and the compound (a2), and
(B) Solvent
≪ / RTI > The method according to claim 1,
The siloxane polymer (A)
(a1) a silane compound represented by the following formula (1)
(a2) a siloxane polymer composition which is a hydrolysis condensation product of benzyl alcohol or benzyl ether represented by the following formula (2):
[Chemical Formula 1]
(R ¹ ) _n -Si- (OR ² ) _4-n
(Wherein R ¹ is each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; R ² each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, An alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms; and n is 0 to 3, provided that each of the alkyl group and aryl group is substituted or unsubstituted in part or all of the hydrogen atoms )
(2)

or

(Wherein R is an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, R 'is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, X is a hydrogen atom or an OH group, Y is a hydrogen atom, methyl or triple Methyl)
The siloxane polymer composition according to claim 1, further comprising (C) a thermal acid generator or a thermal base generator.
The siloxane polymer composition according to claim 1, wherein the siloxane polymer (A) has a weight average molecular weight in terms of polystyrene of 1,000 to 40,000.
A cured film formed from the siloxane polymer composition according to any one of claims 1 to 4.
The cured film according to claim 5, wherein the cured film is an interlayer insulating film of a display element.