WO2015190873A1 - Siloxane polymer composition - Google Patents

Abstract

The present invention relates to: a siloxane polymer composition, which is suitable as a material for forming a hardened layer, such as an interlayer insulating film of a display device, such as a liquid crystal display (LCD) or organic EL display device; a hardened film formed of the composition; an interlayer insulating film; and a method for forming the interlayer insulating film. The present invention can provide: a siloxane-based polymer composition, which is usable as a material for an interlayer insulating film having improved hardness and excellent heat resistance and transmittance; a hardened film formed of the siloxane-based polymer composition; an interlayer insulating film; and a method for forming the interlayer insulating film. Therefore, the interlayer insulating film formed by the present invention is useful since the interlayer insulating film can be also appropriately used as a protective film of a display device or a touch panel display device, or the like.

Description

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 device such as a liquid crystal display device (LCD) or an organic EL display device.

A color TFT liquid crystal display element or the like is created by overlapping a color filter substrate and a TFT array substrate. In a TFT array substrate, an interlayer insulating film is formed in order to insulate between wirings generally arranged in a layer shape. As the material for forming the interlayer insulating film, a positive radiation-sensitive composition is widely used in that there are few processes for obtaining the required pattern shape, and it is preferable to have sufficient flatness.

Although an acrylic resin is mainly used as a component of the radiation sensitive composition for forming an interlayer insulating film (see Japanese Patent Laid-Open No. 2001-354822), recently, a polysiloxane material having better heat resistance and transparency than an acrylic resin is selected from the radiation-sensitive composition. Attempts have been made to use it as a component (see Japanese Patent Laid-Open No. 2006-178436, Japanese Patent Laid-Open No. 2006-276598 and Japanese Patent Laid-Open No. 2006-293337).

On the other hand, an input device for operating the device by pressing an on-screen display called a touch panel, a touch screen or a touch screen is used for an automatic teller machine such as a bank, a vending machine, a mobile phone, a portable information display terminal, or a digital audio player have. Since the touch panel is usually pressed directly with a finger or the like, a protective film is provided. The protective film requires surface hardness such as adhesion to the wiring of the touch panel element and scratch resistance as a protective film.

Accordingly, there is a need for the development of a polysiloxane-based positive photosensitive composition having high heat resistance, transparency and low dielectric constant, etch resistance, hardness, and high voltage retention and having high compatibility with a photosensitive agent.

Under these circumstances, the present inventors have made efforts to develop a siloxane-based polymer composition which can be used as a material of an interlayer insulating film having excellent heat resistance and transmittance while improving surface hardness. When the siloxane polymer composition is used, the present inventors have found that it is possible to form an interlayer insulating film capable of balancing the general required properties of heat resistance and transmittance while improving hardness, and completed the present invention.

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

Unless defined otherwise, 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 hydrolytically condensing (A) (a1) a silane compound with (a2) benzyl alcohol or benzyl ether; (a1) The silane compound is a compound (a1) and a compound ( a2) 70% to 97% by weight of the total weight, (a2) benzyl alcohol or benzyl ether, wherein the siloxane polymer uses from 3% to 30% by weight of the total weight of compound (a1) and compound (a2), and (B) Provides the siloxane polymer composition containing a solvent.

<(A) component: A siloxane polymer>

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

It is preferable that the said (a1) silane compound is a hydrolysable silane compound represented by following General formula (1).

[Formula 1]

(R ¹ ) _n -Si- (OR ² ) _4-n

R ¹ in 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 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 phenyl group, tolyl group, naphthyl group and the like. However, some or all of the hydrogen atoms of these alkyl groups and aryl groups may be substituted.

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

N in the said Formula (1) represents the integer of 0-3. When n = 0, it is a tetrafunctional silane, when n = 1, a trifunctional silane, when n = 2, 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 Chemical Formula 1 include tetramethoxy silane, tetraethoxy silane, tetraacetoxy silane, tetra phenoxy silane, methyl trimethoxy silane, methyl triethoxy silane, Ethyl tri-i-propoxy silane, methyl tributoxy silane, n-propyl trimethoxy silane, n-propyl triethoxy silane, n-butyl trimethoxy silane, n-butyl triethoxy silane, n-hexyl Trimethoxy silane, n-hexyl triethoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane and the like. It is preferable to use trifunctional silane and tetrafunctional silane from a hardness viewpoint of a cured film among these hydrolyzable silane compounds.

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

[Formula 2]

또는

or

[R in Formula 2 is an alkyl group or hydrogen atom having 1 to 4 carbon atoms, 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 Orormethyl.]

As the benzyl compound represented by the formula (2), R is one of a hydrogen atom, methyl, ethyl, propyl, and n-butyl group, and R 'is one of a hydrogen atom, methyl, ethyl and t-butyl. 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 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), and are used altogether It is 3-30 weight% of monomer usage.

As used herein, the term “hydrolyzable silane compound” is usually hydrolyzed to produce a silanol group by heating in a temperature range of room temperature (about 25 ° C.) to about 100 ° C. in the absence of a catalyst and excess water. It refers to a compound having an existing group or a group capable of forming a siloxane condensate.

Preferably, the siloxane monomer represented by Formula 1 and the benzyl alcohol or benzyl ether represented by Formula 2 may produce the (A) siloxane polymer of the present invention by hydrolysis and condensation polymerization, preferably (a1) silane 70 wt% to 97 wt% of the total weight of the compound (a1) and the compound (a2), and (a2) benzyl alcohol or benzyl ether, 3 wt% to 30 wt.% Of the total weight of the compound (a1) and the compound (a2). By weight hydrolysis and condensation polymerization can be made "(A) siloxane polymer".

As described above, by adjusting the amounts of (a1) and (a2) used in the production of the (A) siloxane polymer, a siloxane polymer capable of producing an interlayer insulating film having excellent hardness and transparency can be produced. In one embodiment of the present invention (A) siloxane polymer was prepared by varying the weight ratio of (a1) and / or (a2). As a result, when the amount of the (a2) benzyl compound to be used exceeds 30% by weight, the transparency of the interlayer insulating film to be produced decreases, and when it is 3% by weight to 30% by weight, the interlayer insulating film having excellent hardness and transparency It was confirmed that manufacturing is possible. Therefore, it is preferable to use 70 to 97 weight% of siloxane monomer (a1) compounds, and 3 to 30 weight% of benzyl compounds (a2) at the time of preparation of (A) siloxane polymer.

The solvent which can be used for the said hydrolysis polymerization is not specifically limited. Usually, as long as it is a solvent used for a positive photosensitive composition, it can use without a restriction. Preferably, etheryuno is tetrahydrofuran, diethylene glycol is diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethylmethyl 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. Moreover, toluene, xylene, etc. can be used as aromatic hydrocarbons.

As water used for the hydrolysis condensation, it is preferable to use water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment, distillation or the like. By using such purified water, a side reaction can be suppressed and the reactivity of hydrolysis can be improved. The amount of water to be used is preferably 0.1 to 3 moles, more preferably 0.3 to 2 moles, even more preferably 0.5 to 1.5 moles with respect to 1 mole of the total amount of the hydrolyzable groups of the hydrolyzable silane compound represented by the formula (1). Amount. By using this amount of water, the reaction rate of hydrolysis-condensation can be optimized.

The hydrolysis and condensation reaction of the (a) silane compound and the (a2) benzyl alcohol or benzyl ether for preparing the (A) siloxane polymer according to the present invention may be preferably performed under an acid catalyst. As long as the said catalyst is a Lewis acid, all can be used. As the Lewis acid, any Lewis acid such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoro acetic acid, trifluoro sulfonic acid, toluene sulfonic acid, phosphoric acid and the like can be used.

The reaction temperature and reaction time in hydrolysis condensation for production of the (A) siloxane polymer according to the present invention can be appropriately set. For example, the following conditions can be adopted. Reaction temperature becomes like this. Preferably it is 40-200 degreeC, More preferably, it is 50-150 degreeC. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours. Hydrolysis condensation reaction can be performed efficiently under such reaction temperature and reaction time. In this hydrolysis condensation, the hydrolyzable silane compound, water, and catalyst may be added to the reaction system at one time, and the reaction may be performed in one step. The hydrolyzable silane compound, water, and catalyst may be added in several times in the reaction system. The hydrolysis condensation reaction may be carried out in multiple stages. After the hydrolytic condensation reaction, water and the resulting alcohol can be removed from the reaction system by adding a dehydrating agent and then adding to the evaporation.

The molecular weight of the (A) siloxane polymer which is the hydrolysis-condensation product of the hydrolyzable silane compound which concerns on this invention is the number average molecular weight of polystyrene conversion using GPC (gel permeation chromatography) which used tetrahydrofuran for the mobile phase. It can be measured as. And it is preferable to make the number average molecular weight of a hydrolysis-condensation product into the value within the range of 1,000-40,000 normally. When the value of the number average molecular weight of a hydrolysis-condensation product is 1,000 or more, the film-forming property of the coating film of a positive radiation sensitive composition can be improved. On the other hand, by making the value of the number average molecular weight of a hydrolysis-condensation product into 40,000 or less, the radiation-sensitive fall of a positive radiation sensitive composition can be prevented.

<(B) component: A solvent>

(B) component is a solvent. Although it does not specifically limit, It is preferable to contain the alcohol solvent which is especially a protic solvent. By using an alcoholic solvent, each component can be dissolved or dispersed uniformly, thereby making it possible to improve the coatability of the composition solution to a large substrate, and also to apply coating stains (stripe-shaped stains, pin trace stains, mist stains). 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; Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, and the like. These alcohol solvents can be used individually or in combination of 2 or more types.

Among these alcohol 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 improving coating properties.

(B) A component may be used individually by 1 type and may mix and use 2 or more types.

The usage-amount of (B) component becomes like this. Preferably it is 5 mass parts-300 mass parts, More preferably, it is 10 mass parts-200 mass parts with respect to 100 mass parts of (A) component. By making the usage-amount of (B) component into the said range, coating property improvement with respect to a glass substrate etc. is attained, the generation | occurrence | production of application | coating stain (stripe-shaped stain, pin trace stain, fog stain, etc.) is suppressed, and film thickness uniformity Can be further improved.

In the present invention, along with the alcohol solvent, other solvents, for example, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatic hydrocarbons, ketones And esters.

As a solvent other than the alcohol solvent, the following may be mentioned.

As ethers, For example, tetrahydrofuran etc .; As diethylene glycol alkyl ether, For example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .; As ethylene glycol alkyl ether acetates, For example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc .; As propylene glycol monoalkyl ether acetates, For example, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, a propylene glycol monopropyl ether acetate, a propylene glycol monobutyl ether acetate, etc .; As propylene glycol monoalkyl ether propionates, a propylene glycol monomethyl ether propionate, a propylene glycol monoethyl ether propionate, a propylene glycol monopropyl ether propionate, a propylene glycol monobutyl ether propionate, etc. are mentioned, for example. ; As aromatic hydrocarbons, For example, toluene, xylene, etc .; As ketones, for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-phene

Tan temperature and the like; As esters, for example, methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2- Ethyl methyl propionate, methyl hydroxyacetic acid, ethyl hydroxyacetic acid, hydroxyacetic acid butyl, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionic acid methyl, 3-hydroxypropionic acid, 3-hydroxypropionic acid Propyl, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoic acid, methyl methoxyacetic acid, ethyl methoxyacetic acid, methoxyacetic acid propyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl Propyl ethoxyacetic acid, butyl ethoxyacetic acid, methyl propoxyacetate, ethyl propoxyacetate, Lopoxyacetic acid propyl, butyl propoxyacetic acid, methyl butoxyacetic acid, ethyl butoxyacetate, butoxyacetic acid propyl, butyl butoxyacetic acid, 2-methoxypropionate methyl, 2-methoxypropionic acid propyl, 2-methoxypropionic acid propyl And butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, and the like. These solvents can be used individually or in mixture of 2 or more types.

The polysiloxane composition of this invention can contain the following component further.

<(C) component: A thermal acid generator or a thermal base generator>

The thermal acid generator or the thermal base generator is an acidic active substance which acts as a catalyst in the hydrolytic condensation-curing reaction of the compound (a1) and the compound (a2) in preparing the (A) siloxane polymer according to the present invention. It is defined as a compound capable of releasing basic active substances. By using the compound of (C) component, the condensation reaction of the component in the heating process after image development of a positive radiation sensitive composition can be accelerated | stimulated, and the interlayer insulation film excellent in surface hardness and heat resistance can be formed. In addition, as a thermal acid generator or a thermal base generator of (C) component, at the time of prebaking at comparatively low temperature (for example, 70-120 degreeC) in the coating film formation process of a positive radiation sensitive composition. Does not release the acidic active substance or the basic active substance, but releases the acidic active substance or the basic active substance upon post-baking at a relatively high temperature (for example, 120 to 250 ° C.) in a heating step after development. It is preferable to have the property to make.

An ionic compound and a nonionic compound are contained in the thermal acid generator of (C) component. As an ionic compound, it is preferable that heavy metal and no halogen ion are included. Examples of the ionic thermosensitive acid generator include triphenylsulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, 1-dimethylthio-4,7-dihydroxynaphthalene and 4-hydroxy Phenyldimethylsulfonium, benzyl 4-hydroxyphenylmethylsulfonium, 2-methylbenzyl 4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl-4 Methane sulfonate, trifluoromethane sulfonate, camphor sulfonate, p-toluene sulfonate, hexafluoro phosphonate, etc., such as benzoyloxyphenyl methyl sulfonium, are mentioned. Examples of the nonionic thermosensitive acid generator include halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, phosphate ester compounds, sulfonimide compounds, sulfone benzotriazole compounds, and the like. have. As an example of a halogen containing compound, a haloalkyl group containing hydrocarbon compound, a haloalkyl group containing heterocyclic compound, etc. are mentioned. Examples of preferred halogen-containing compounds include 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2 -Naphthyl-4,6-bis (trichloromethyl) -s-triazine, etc. are mentioned. Examples of diazomethane compounds include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane and bis (p-tolylsulfonyl) dia Crude methane, bis (2,4-xyrylsulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, tilsulfonyl-p-toluenesulfonyldiazomethane,

Cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, s (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane, and the like. As an example of a sulfone compound, the (beta) -keto sulfone compound, the (beta) -sulfonyl sulfone compound, a diaryl disulfone compound, etc. are mentioned. As an example of a preferable sulfone compound, 4-trisphenacyl sulfone, mesityl penacyl sulfone, bis (phenylsulfonyl) methane, 4-chlorophenyl- 4-methylphenyl disulfone compound, etc. are mentioned. As an example of a sulfonic acid ester compound, an alkyl sulfonic acid ester, a haloalkyl sulfonic acid ester, an aryl sulfonic acid ester, an imino sulfonate, etc. are mentioned. Examples of the preferable sulfonic acid ester compound include benzointosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, 2,6-dinitrobenzylbenzenesulfonate, and the like. As an example of a carboxylic acid ester compound, carboxylic acid o-nitrobenzyl ester is mentioned.

 Examples of the thermal base generator of component (C) include transition metal complexes such as cobalt, orthonitrobenzylcarbamates, α, α-dimethyl-3,5-dimethoxybenzylcarbamates, acyloxyiminos, and the like. have. Examples of the transition metal complex include bromopentaammonium cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonia cobalt perchlorate, hexamethylamine cobalt perchlorate, hexapropylamine cobalt perchlorate Salts; and the like. Examples of acyloxyiminos include propionylacetophenone oxime, propionylbenzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoylbenzo Phenone oxime, adipoyl acetone oxime, acroyl acetophenone oxime, acroyl benzophenone oxime, acroyl acetone oxime and the like. Other examples of the thermosensitive base generator include 2-nitrobenzylcyclohexyl carbamate and O-carbamoylhydroxyamide.

However, the present invention is not limited thereto, and either the acid or the base may be used as the thermal acid generator or the thermal base generator of the component (C), one type may be used alone, or two or more types may be mixed and used. The quantity in the case of using (C) component becomes like this. Preferably it is 0.1 mass part-10 mass parts, More preferably, it is 1 mass part-5 mass parts with respect to 100 mass parts of (A) component. By setting the usage-amount of (C) component to 0.1 mass part-10 mass parts, the interlayer insulation film with high surface hardness can be formed, optimizing the radiation sensitivity of a positive radiation sensitive composition, and maintaining transparency.

<Formation of Curing Film>

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

The cured film which concerns on this invention can be manufactured including the following process.

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

(2) a step of prebaking the coated substrate applied in step (1),

(3) Process of exposing and developing coating coating film prebaked in process (2),

(4) The process of post-baking the coating film developed by process (3).

As a material of the substrate which can be used in the present invention, glass, silicon, quartz, resin, and the like can be used. By prebaking the applied substrate, the solvent is removed and a coating film is formed. In order to pattern a coating film, it exposes through the photomask which has a predetermined pattern. After exposure to light of a certain wavelength through the photomask, unnecessary portions are removed to form a pattern. As a developing solution used for a developing process, aqueous alkali solution is preferable. Examples of the alkali used may include sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide and the like. After the development is completed, the patterned thin film is heated to cure. Such postbaking is usually conducted for a certain time at 120 degrees or more and 250 degrees or less.

By using a photosensitive composition, by forming a pattern by coating, prebaking, exposure, development, and heating, an interlayer insulating film for display elements having a fine pattern can be easily formed. In addition, the interlayer insulation film thus formed is formed with an interlayer insulation film excellent in hardness, heat resistance, and transparency.

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

Since the siloxane polymer composition which concerns on this invention can form the cured film excellent in transparency and scratch resistance, such a cured film can be applied to the technical use which requires high scratch resistance, etc. transparency, For example, a liquid crystal display element or a touch It can use suitably as a protective film, an interlayer insulation film, etc. of various devices, such as a panel.

Cured film (protective film or interlayer insulation film)

As mentioned above, the cured film formed from the polysiloxane composition of this invention is excellent in the surface hardness, heat resistance, and transparency characteristic with respect to a board | substrate, as also apparent from the following Example. Therefore, the said cured film can be used suitably for display elements, 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 hardness and excellent heat resistance and transmittance, 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 insulation film formed by this invention can be used suitably also for uses, such as a display film and a protective film of a touchscreen display element.

Hereinafter, the present invention will be described in more detail with reference to the accompanying examples. However, such an embodiment is only an example for easily describing the content and scope of the technical idea of the present invention, whereby the technical scope of the present invention is not limited or changed. In addition, it will be apparent to those skilled in the art that various modifications and changes can be made within the scope of the present invention based on these examples.

(Example)

Although a synthesis example and an Example are shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

The weight average molecular weight (Mw) of the hydrolysis-condensation product of the hydrolyzable silane compound obtained from each synthesis example below was measured by the gel permeation chromatography (GPC) according to the following specification.

Device: GPC Waters e2695

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

Mobile phase: tetrahydrofuran

Synthesis Example of Polysiloxane as Component [A]

Synthesis Example 1

25% by weight of phenyltriethoxy silane, 35% by weight of methyltriethoxysilane, 25% by weight of tetraethoxysilane, 15% by weight of 4,4'-isopropylidenebis (2,6-dihydroxymethylphenol) 50 parts by weight of a tetrahydrofuran solvent was added to a reactor equipped with a reflux condenser, and vigorously stirred, a solution in which 2% by weight of sulfuric acid was added to 20 parts by weight of ultrapure water was slowly added to the reactor. The reactor was refluxed for 12 hours and then cooled. After diluting the cooled reaction solution, a polymer having a polystyrene reduced weight average molecular weight of 5,000 was prepared.

Synthesis Example 2

35 wt% of phenyltriethoxy silane, 35 wt% of methyltriethoxysilane, 25 wt% of tetraethoxysilane, and 5 wt% of 4,4'-isopropylidenebis (2,6-dihydroxymethylphenol) 50 parts by weight of a tetrahydrofuran solvent was added to a reactor equipped with a reflux condenser, and vigorously stirred, a solution in which 2% by weight of sulfuric acid was added to 20 parts by weight of ultrapure water was slowly added to the reactor. The reactor was refluxed for 12 hours and then cooled. After diluting the cooled reaction solution, GPC analysis was conducted to prepare a polymer having a polystyrene reduced weight average molecular weight of 3,500.

Synthesis Example 3

Add 35 wt% of phenyltriethoxy silane, 35 wt% of methyltriethoxysilane, 25 wt% of tetraethoxysilane, 5 wt% of 1,4-bis (methoxymethyl) benzene, and 50 wt parts of a tetrahydrofuran solvent. Into a reactor equipped with a reflux condenser, while vigorously stirring, a solution in which 2% by weight of sulfuric acid was added to 20 parts by weight of ultrapure water was slowly added to the reactor. The reactor was refluxed for 12 hours and then cooled. After diluting the cooled reaction solution, a polymer having a polystyrene reduced weight average molecular weight of 7,500 was prepared.

Synthesis Example 4

30 wt% of phenyltriethoxy silane, 35 wt% of methyltriethoxysilane, 25 wt% of tetraethoxysilane, 10 wt% of 1,4-bis (methoxymethyl) benzene, and 50 wt parts of a tetrahydrofuran solvent Into a reactor equipped with a reflux condenser, while vigorously stirring, a solution in which 2% by weight of sulfuric acid was added to 20 parts by weight of ultrapure water was slowly added to the reactor. The reactor was refluxed for 12 hours and then cooled. The cooled reaction solution was diluted to perform GPC analysis to prepare a polymer having a polystyrene reduced weight average molecular weight of 13,000.

Synthesis Example 5

25% by weight of phenyltriethoxy silane, 35% by weight of methyltriethoxysilane, 25% by weight of tetraethoxysilane, 15% by weight of 1,4-benzenedimethanol and 50 parts by weight of a tetrahydrofuran solvent were installed with a reflux condenser. Into the reactor, while vigorously stirring, a solution in which 2% by weight of sulfuric acid was added to 20 parts by weight of ultrapure water was slowly added to the reactor. The reactor was refluxed for 12 hours and then cooled. After diluting the cooled reaction solution, a polymer having a polystyrene reduced weight average molecular weight of 5,900 was prepared.

Synthesis Example 6

25% by weight of phenyltriethoxy silane, 35% by weight of methyltriethoxysilane, 25% by weight of tetraethoxysilane, 15% by weight of 2,6-bis (hydroxymethyl) -p-cresol, followed by a tetrahydrofuran solvent 50 parts by weight of the reactor was installed with a reflux condenser, while stirring vigorously, a solution in which 2% by weight of sulfuric acid was added to 20 parts by weight of ultrapure water was slowly added to the reactor. The reactor was refluxed for 12 hours and then cooled. After diluting the cooled reaction solution, a polymer having a polystyrene reduced weight average molecular weight of 7,400 was prepared.

Synthesis Example 7

25% by weight of phenyltriethoxy silane, 35% by weight of methyltriethoxysilane, 25% by weight of tetraethoxysilane and 15% by weight of 1,2-benzenedimethanol were added and 50 parts by weight of a tetrahydrofuran solvent was installed with a reflux condenser. Into the reactor, while vigorously stirring, a solution in which 2% by weight of sulfuric acid was added to 20 parts by weight of ultrapure water was slowly added to the reactor. The reactor was refluxed for 12 hours and then cooled. After diluting the cooled reaction solution, a polymer having a polystyrene reduced weight average molecular weight of 6, 500 was prepared.

Comparative Example 1

Add 29 wt% of phenyltriethoxy silane, 42 wt% of methyltriethoxysilane, 29 wt% of tetraethoxysilane, and add 50 wt parts of a tetrahydrofuran solvent to a reactor equipped with a reflux condenser and stir vigorously, 20 wt% of ultrapure water. A solution of 2% by weight sulfuric acid was added slowly to the reactor. The reactor was refluxed for 12 hours and then cooled. After diluting the cooled reaction solution, a polymer having a polystyrene reduced weight average molecular weight of 6,100 was prepared.

Comparative Example 2

25% by weight of phenyltriethoxy silane, 35% by weight of methyltriethoxysilane, 25% by weight of tetraethoxysilane, 2% by weight of 4,4'-isopropylidenebis (2,6-dihydroxymethylphenol) 50 parts by weight of a tetrahydrofuran solvent was added to a reactor equipped with a reflux condenser, and vigorously stirred, a solution in which 2% by weight of sulfuric acid was added to 20 parts by weight of ultrapure water was slowly added to the reactor. The reactor was refluxed for 12 hours and then cooled. After diluting the cooled reaction solution, GPC analysis was conducted to prepare a polymer having a polystyrene reduced weight average molecular weight of 6,300.

Comparative Example 3

25% by weight of phenyltriethoxy silane, 35% by weight of methyltriethoxysilane, 25% by weight of tetraethoxysilane, 45% by weight of 4,4'-isopropylidenebis (2,6-dihydroxymethylphenol) 50 parts by weight of a tetrahydrofuran solvent was added to a reactor equipped with a reflux condenser, and vigorously stirred, a solution in which 2% by weight of sulfuric acid was added to 20 parts by weight of ultrapure water 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 to prepare a polymer having a polystyrene reduced weight average molecular weight of 6,800.

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

[Pencil hardness measurement]

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

[Heat resistance evaluation]

In order to measure the pencil hardness, the cured coating film thickness was measured (T1) and the thickness (T2) obtained by further baking the coating film at 230 degrees for 1 hour was measured. [(T1-T2) / T2 x 100 (%) The thickness deviation before and after further baking was calculated as a percentage. When the thickness variation ratio is 3% or less, it can be said that heat resistance is excellent, and it is as shown in Table 1.

[Transmittance Evaluation]

After coating on a glass substrate to form a coating film, the cured film was obtained by heating at 230 degree | times for 1 hour. The glass substrate which has this cured film was measured at 400 nm using the spectrophotometer, and the result is shown in Table 1.

Table 1 Synthesis 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, those skilled in the art will appreciate that the present invention can be implemented in other specific forms without changing the technical spirit or essential features. In this regard, the embodiments described above are to be understood in all respects as illustrative and not restrictive. The scope of the present invention should be construed that all changes or modifications derived from the meaning and scope of the following claims and equivalent concepts rather than the detailed description are included in the scope of the present invention.

Claims (6)

A siloxane polymer obtained by hydrolytically condensing (A) (a1) a silane compound with (a2) benzyl alcohol or benzyl ether, wherein the (a1) silane compound is 70% by weight of the total weight of compound (a1) and compound (a2) % To 97% by weight, (a2) benzyl alcohol or benzyl ether, wherein the siloxane polymer uses from 3% to 30% by weight relative to the total weight of compound (a1) and compound (a2), and (B) solvent A siloxane polymer composition containing. The method of claim 1, (A) siloxane polymer, (a1) a silane compound represented by the following formula (1), (a2) A siloxane polymer composition which is a hydrolysis condensate of benzyl alcohol or benzyl ether represented by the following formula (2): [Formula 1] (R ¹ ) _n -Si- (OR ² ) _4-n (In formula, R <^1> respectively independently represents a hydrogen atom, a C1-C10 alkyl group, or a C6-C20 aryl group; R <^2> respectively independently represents a hydrogen atom and a C1-C6 alkyl group, Which represents an acyl group having 1 to 6 carbon atoms or an aryl group having 6 to 15 carbon atoms; n represents a case where 0 to 3. However, some or all of the hydrogen atoms of these alkyl groups and aryl groups may be substituted).  [Formula 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, and Y is a hydrogen atom, methyl or trifluoro) Represents methyl) The siloxane polymer composition according to claim 1 or 2, further comprising (C) a thermal acid generator or a thermal base generator. The siloxane polymer composition according to claim 1 or 2, wherein the (A) siloxane polymer has a polystyrene reduced weight average molecular weight of 1,000 or more and 40,000 or less. The cured film formed from the siloxane polymer composition of any one of Claims 1-4. The cured film of claim 5, wherein the cured film is an interlayer insulating film of a display element.