KR101761181B1 - Photosensitive siloxane composition, cured film formed form same, and element having cured film - Google Patents

Abstract

(b) a quinone diazide compound, (c) a solvent, and (d) a polysiloxane represented by the general formula (2), wherein the polysiloxane is at least one compound selected from the group consisting of: (a) a polysiloxane synthesized by reacting at least one organosilane represented by the general formula A photosensitive siloxane composition containing a silicate compound.

[In the formula (1), R ¹ represents any ^one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ^{1 s} may be the same or different . R ² represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and the plurality of R ^{2 s} may be the same or different. n represents an integer of 0 to 3]

[In the formula (2), R ³ to R ⁶ each independently represent any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms. and p represents an integer of 2 to 10) to provide a photosensitive siloxane composition capable of obtaining a cured film having heat resistance and high transparency and having excellent chemical resistance.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive siloxane composition, a cured film formed therefrom, and a device having the cured film. BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a planarizing film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a photosensitive film for forming a protective film or insulating film of a touch panel, an interlayer insulating film of a semiconductor element, Siloxane compositions, cured films formed therefrom, and devices having the cured films.

In recent years, it has been required to realize a new fixed resolution and high resolution in a liquid crystal monitor, an organic EL display, and the like.

Recently, a touch panel has been actively used in a liquid crystal display or the like, and in particular, a touch panel of a capacitive type has been attracting attention.

(Patent Literature)

For example, Patent Document 1 discloses a method of increasing the aperture ratio of a display device as a method of realizing a new fixed definition and high resolution in a liquid crystal monitor, an organic EL display, and the like. This is a method of increasing the aperture ratio as compared with the prior art by making it possible to overlap the data line and the pixel electrode by forming a transparent planarization film as a protective film on the TFT substrate.

As a material for the TFT substrate flattening film, it is necessary to form a hole pattern having a thickness of several micrometers to 50 micrometers in order to connect the TFT substrate electrode and the ITO electrode with high heat resistance and high transparency. Generally, Materials are used.

Patent Documents 2 and 3 describe a material in which a quinone diazide compound is combined with an acrylic resin as typical examples of a positive photosensitive material.

On the other hand, a polysiloxane is known as a material having high heat resistance and high transparency. In Patent Documents 4, 5 and 6, a material in which a quinone diazide compound is combined to impart a positive photosensitivity thereto is described. The heat resistance is high and defects such as cracks do not occur even by the high temperature treatment, and a highly transparent cured film can be obtained.

(Patent Document 1) Japanese Patent Application Laid-Open No. 9-152625 (Claim 1)

(Patent Document 2) Japanese Patent Application Laid-Open No. 2001-281853 (Claim 1)

(Patent Document 3) Japanese Patent Laid-Open No. 2001-281861 (Claim 1)

(Patent Document 4) Japanese Patent Laid-Open Publication No. 2006-178436 (Claim 1)

(Patent Document 5) JP-A-2009-211033 (Claim 1)

(Patent Document 6) Japanese Patent Laid-Open No. 2010-33005 (Claim 1)

However, since the transparent planarizing film of Patent Document 1 uses an acrylic resin material, heat resistance is insufficient.

In addition, the materials described in Patent Documents 2 and 3 have insufficient heat resistance, so that the cured film is colored by the high temperature treatment of the substrate, and transparency is lowered. In addition, due to the improvement in the performance of the touch panel, high transparency and high degree of transparency due to the high-temperature film formation of ITO, which is a transparent electrode member, have been investigated and therefore heat resistance is required for a material used as a protective film or an insulating film. However, So that a highly transparent ITO having high conductivity can not be formed.

The materials described in Patent Documents 4, 5, and 6 are insufficient in resistance to a chemical solution such as an ITO etchant, and improvement in chemical resistance is demanded.

It is an object of the present invention to provide a photosensitive siloxane composition which has been made on the basis of the above-described circumstances, and which can obtain a cured film having high heat resistance and high transparency and having good chemical resistance. Another object of the present invention is to provide a device such as a flattening film for a TFT substrate, a cured film such as an insulating film for a touch panel, and a liquid crystal display element having the cured film formed from the above photosensitive siloxane composition.

(B) a quinone diazide compound, (c) a solvent, and (d) a compound represented by the general formula (1): wherein R 1 and R 2 are independently selected from the group consisting of 2). ≪ / RTI >

(Wherein R ¹ represents any ^one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ^{1 s} may be the same or different.) R ² Represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and aryl having 6 to 15 carbon atoms, the plurality of R ^{2 s} may be the same or different, and n is an integer of 0 to 3 )

(Wherein R ³ to R ⁶ each independently represent any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and p is an integer of 2 to 10 Lt; / RTI >

(Effects of the Invention)

According to the photosensitive siloxane composition of the present invention, a cured film having high heat resistance, high transparency, and excellent chemical resistance can be obtained. The obtained cured film can be preferably used as a flattening film for a TFT substrate or an insulating film for a touch panel.

The photosensitive siloxane composition of the present invention is a photosensitive siloxane composition containing (a) a polysiloxane, (b) a quinone diazide compound, (c) a solvent, and (d) a silicate compound.

The photosensitive siloxane composition of the present invention contains (a) a polysiloxane. The polysiloxane used in the present invention is a polysiloxane synthesized by reacting at least one organosilane represented by the general formula (1).

(Wherein R ¹ represents any ^one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ^{1 s} may be the same or different.) R ² Represents an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms, the plurality of R ^{2 s} may be the same or different, and n is an integer of 0 to 3, )

In the organosilane represented by the general formula ⁽¹⁾ R 1 is hydrogen, represents any one of 1 to 10 carbon atoms in an alkyl group, having 2 to 10 alkenyl group, having 6 to 15 aryl group, a plurality of R ¹ May be the same or different. The alkyl group, alkenyl group and aryl group of these may all be either unsubstituted or substituted, and may be selected depending on the characteristics of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, (3-ethyl-3-oxetanyl) methoxy] propyl group, a 3-aminopropyl group, a 3-ethylhexyloxy group, -Mercaptopropyl group, and 3-isocyanatepropyl group. Specific examples of the alkenyl group include a vinyl group, a 3-acryloxypropyl group and a 3-methacryloxypropyl group. Specific examples of the aryl group include a phenyl group, a thryl group, a p-hydroxyphenyl group, a 1- (p-hydroxyphenyl) ethyl group, a 2- (p- Phenylcarbonyloxy) pentyl group, and naphthyl group.

R ² in the general formula (1) represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and the plurality of R ^{2 s} may be the same or different. These alkyl groups, acyl groups and aryl groups may all be either unsubstituted or substituted, and may be selected depending on the characteristics of the composition. Specific examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group. A specific example of the acyl group includes an acetyl group. Specific examples of the aryl group include a phenyl group.

N in the general 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 x = 3, it is a monofunctional silane.

Specific examples of the organosilane represented by the general formula (1) include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane and tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxy Silane, methyltriisopropoxysilane, methyltri n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri n-butoxysilane, n-propyltrimethoxy Silane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriethoxysilane, phenyltriethoxysilane, Ethoxy silane, p-hydroxyphenyltrimethoxysilane, 1- (p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane , Trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclo [(3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] propyltriethoxysilane, Trifunctional silane such as 3-mercaptopropyltrimethoxysilane and 3-trimethoxysilylpropylsuccinic acid, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, di-n-butyl Bifunctional silanes such as trimethylmethoxysilane, diphenyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane and (3-glycidoxypropyl) methyldiethoxysilane, trimethylmethoxysilane, tri (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, etc. These organosilanes may be used alone or in combination of two or more of them. Two or more types may be used in combination. Of these organosilanes, trifunctional silanes are preferably used in view of crack resistance and hardness of the cured film.

In the polysiloxane used in the present invention, a polysiloxane synthesized by reacting a silicate compound (d) described later together with at least one organosilane represented by the general formula (1) may be used. The pattern resolution is improved by reacting the silicate compound. This is believed to be because the glass transition temperature of the film is increased by introducing a polyfunctional silicate compound into the polysiloxane so as to inhibit pattern sensitization during thermal curing.

The mixing ratio in the case of using a silicate compound is not particularly limited, but is preferably 50% or less with respect to the number of moles of Si atoms in the polymer as a whole. When the silicate compound is in this range, the compatibility of the polysiloxane and the quinone diazide compound is improved and the transparency of the cured film is maintained. The Si atom molar ratio of the silicate compound with respect to the number of moles of Si atoms in the entire polymer can be obtained from the ratio of the peak derived from the Si-C bond and the peak derived from the Si-O bond in IR. When superposition of peaks is not required much, the structure of the monomers other than the silicate compound is determined by 1 H-NMR, 13 C-NMR, IR, TOF-MS and the like, and the gas generated in the elemental analysis and the remaining ash ) (All are assumed to be SiO ₂ ).

For the purpose of improving the compatibility with the quinone diazide compound (b) to be described later in the polysiloxane used in the present invention and forming a uniformly cured film without phase separation, the content of phenyl groups in the polysiloxane is preferably Is preferably 30 mol% or more, and more preferably 40 mol% or more. When the content of the phenyl group is within the preferable range, since the polysiloxane and the quinone diazide compound are difficult to cause phase separation during coating, drying and thermosetting, the film is not cloudy and the transparency of the cured film is maintained. The upper limit of the content of the phenyl group is preferably 70 mol% or less based on Si atoms. When the content of the phenyl group is within the preferable range, crosslinking at the time of thermal curing is sufficiently caused and the chemical resistance of the cured film is excellent. The content of the phenyl group can be determined, for example, from the ratio of the peak area of the Si bonded to the phenyl group to the peak area of the Si bonded to the phenyl group measured by 29Si-NMR of the polysiloxane.

The weight average molecular weight (Mw) of the polysiloxane used in the present invention is not particularly limited, but is preferably 1,000 to 100,000, more preferably 2,000 to 50,000 in terms of polystyrene measured by GPC (gel permeation chromatography). When the Mw is within this preferable range, the coating film is good and the solubility in the developer at the time of pattern formation becomes good.

The polysiloxane used in the present invention is synthesized by hydrolysis and partial condensation of monomers such as organosilane represented by the general formula (1). General methods can be used for hydrolysis and partial condensation. For example, a solvent, water and, if necessary, a catalyst are added to the mixture and the mixture is heated and stirred at 50 to 150 ° C for 0.5 to 100 hours. The hydrolysis by-products (alcohol such as methanol) and condensation by-products (water) may be distilled by distillation as necessary during stirring.

The reaction solvent is not particularly limited, but usually the same solvent as the solvent (c) described below is used. The amount of the solvent to be added is preferably 10 to 1000 parts by mass based on 100 parts by mass of the monomer such as organosilane. The amount of water to be used for the hydrolysis reaction is preferably 0.5 to 2 moles relative to 1 mole of the hydrolyzable group.

The catalyst to be added as needed is not particularly limited, but an acid catalyst or a base catalyst is preferably used. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or an anhydride thereof and ion exchange resins. Specific examples of the base catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, sodium hydroxide, An alkoxysilane having an amino group, and an ion exchange resin. The addition amount of the catalyst is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the monomer such as organosilane.

From the viewpoint of the storage stability of the composition, it is preferable that the polysiloxane solution after hydrolysis and partial condensation does not contain a catalyst, and the catalyst can be removed if necessary. The removal method is not particularly limited, but preferably includes washing with water and / or treatment with an ion exchange resin. The water rinsing is a method of diluting a polysiloxane solution with an appropriate hydrophobic solvent, washing it several times with water, and concentrating the obtained organic layer with an evaporator. Treatment with an ion exchange resin is a method of bringing a polysiloxane solution into contact with an appropriate ion exchange resin.

The photosensitive siloxane composition of the present invention contains (b) a quinone diazide compound. By containing a quinone diazide compound, a positive type in which an exposed portion is removed by a developer can be formed. The quinone diazide compound to be used is not particularly limited, but a compound in which a naphthoquinone diazide sulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group, and the ortho and para positions of the phenolic hydroxyl group of the compound are each independently hydrogen, And a substituent represented by the following formula (3) are preferably used.

(Wherein R ⁷ , R ⁸ and R ⁹ each independently represent any one of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, and a substituted phenyl group, or may form a ring with R ⁷ , R ⁸ and R ⁹ )

In the substituent represented by the general formula (3), R ⁷ , R ⁸ , and R ⁹ each independently represent any one of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, and a substituted phenyl group. The alkyl group may be either non-substituted or substituted, and may be selected depending on the characteristics of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, A trifluoromethyl group, and a 2-carboxyethyl group. The substituent substituted on the phenyl group may be a hydroxyl group. Further, R ⁷ , R ⁸ and R ⁹ may form a ring, and specific examples thereof include cyclopentane rings, cyclohexane rings, adamantane rings, and fluorene rings.

When the ortho position and the para position of the phenolic hydroxyl group are each independently any one of hydrogen and the substituent represented by the general formula (3) as described above, oxidation decomposition does not occur even by thermosetting, so that a quinoid structure The representative conjugated system compound is not formed, and the cured film is not colored so that colorless transparency is maintained.

These quinone diazide compounds can also be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinone diazidesulfonyl chloride.

Specific examples of the compound having a phenolic hydroxyl group include the following compounds (all manufactured by Honshu Kagaku Kogyo Co., Ltd.).

Another preferred form of the quinone diazide compound is a compound in which a naphthoquinone diazide sulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group represented by the general formula (7).

(Wherein R ²⁴ and R ²⁵ each independently represent any one of hydrogen, an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 15 carbon atoms, R ²⁶ and R ²⁷ each independently represent a hydrogen atom, represents any one of the 8 alkyl group, an alkoxyl group, a carboxyl group, an ester group, multiple R ^26, R ²⁷ may be the same or different. a, b represents an integer of 0 ~ 4, c, d is 1 to 5 A + c and b + d are integers of 1 to 5, c? D and c + d? 3,

The quinone diazide compound in which the naphthoquinone diazidesulfonic acid is ester-bonded to the compound having a phenolic hydroxyl group represented by the general formula (7) has a low molecular weight and an asymmetric structure, so that (a) a polysiloxane or (d) a silicate compound And the amount of the quinone diazide compound is increased, the film does not become cloudy. When the quinone diazide compound is added in a large amount, the dissolution contrast between the exposed portion and the unexposed portion is improved and pattern formation at a high sensitivity can be realized by suppressing the reduction of the developed film in the unexposed portion.

Specific examples of the compound having a phenolic hydroxyl group represented by the general formula (7) include the following compounds.

As naphthoquinonediazidesulfonic acid, 4-naphthoquinonediazidesulfonic acid or 5-naphthoquinonediazidesulfonic acid can be used. The 4-naphthoquinone diazidesulfonic acid ester compound is suitable for i-line exposure because it absorbs in the i-line (wavelength 365 nm) region. The 5-naphthoquinone diazidesulfonic acid ester compound is also suitable for exposure to a wide range of wavelengths because absorption is present in a wide range of wavelengths. It is preferable to select a 4-naphthoquinone diazide sulfonic acid ester compound and a 5-naphthoquinone diazide sulfonic acid ester compound by the wavelength to be exposed. A 4-naphthoquinone diazidesulfonic acid ester compound and a 5-naphthoquinone diazidesulfonic acid ester compound may be mixed and used.

The amount of the quinone diazide compound to be added is not particularly limited, but is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, per 100 parts by mass of the polysiloxane. When the added amount of the quinone diazide compound is within the preferable range, the dissolution contrast between the exposed portion and the unexposed portion is not excessively low, so that it has realistic photosensitivity. On the other hand, since the compatibility of the polysiloxane and the quinone diazide compound is maintained well, whitening of the coating film does not occur and coloring due to decomposition of the quinone diazide compound during thermal curing can be suppressed, so that the colorless transparency of the cured film is maintained .

The photosensitive siloxane composition of the present invention contains (c) a solvent. The solvent to be used is not particularly limited, but a compound having an alcoholic hydroxyl group is preferably used. When these solvents are used, the polysiloxane and the quinone diazide compound dissolve uniformly, and even when the composition is coated, the film is not whitened and high transparency can be achieved.

The compound having an alcoholic hydroxyl group is not particularly limited, but is preferably a compound having a boiling point at atmospheric pressure of 110 to 250 ° C. When the boiling point is within this preferable range, the amount of the residual solvent in the film is small, and film shrinkage at the time of curing can be suppressed, and good flatness can be obtained. On the other hand, since the drying time of the coating film is not too fast, the film surface is excellent and the film surface is not rough.

Specific examples of the compound having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy- 4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n- Butyl ether, propylene glycol mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 3-methoxy- Methyl-3-methoxy-1-butanol, and the like. These alcoholic hydroxyl group-containing compounds may be used alone or in combination of two or more.

The photosensitive siloxane composition of the present invention may contain other solvent as long as the effect of the present invention is not impaired. Examples of the other solvent include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1 -butylacetate, Butyl acetate, and ethyl acetoacetate; ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone and acetylacetone; ketones such as diethyl ether, diisopropyl ether, di-n-butyl ether, Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether; ethers such as? -Butyrolactone,? -Valerolactone,? -Valerolactone, propylene carbonate, N -Methylpyrrolidone, cyclopentanone, cyclohexanone, cycloheptanone, and the like.

The amount of the solvent to be added is not particularly limited, but is preferably in the range of 100 to 1000 parts by mass based on 100 parts by mass of the polysiloxane.

The photosensitive siloxane composition of the present invention (d) contains a silicate compound represented by the general formula (2).

(Wherein R ³ to R ⁶ each independently represent any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and p is an integer of 2 to 10 Lt; / RTI &

Specific examples of the silicate compound represented by the general formula (2) include methyl silicate 51 (manufactured by FUSO KAGAKU CO., LTD.), M silicate 51, silicate 40, silicate 45 (manufactured by Tama Kagakukogyo K.K.), methyl silicate 51 , Methyl silicate 53A, ethyl silicate 40, ethyl silicate 48 (manufactured by Korukoto), and the like.

Of these, from the viewpoint of reactivity with the polysiloxane at the time of thermosetting, compounds in which R ³ to R ⁶ are methyl groups are preferable, and specifically, methyl silicate 51 (manufactured by Fusokagakuko Kogyo Co., Ltd.), M silicate 51 Ltd.), methyl silicate 51, and methyl silicate 53A (manufactured by Korukoto K.K.) are preferable. Specific examples thereof include methyl silicate 51 (manufactured by FUSO Kagaku Kogyo Co., Ltd.), M silicate 51 (manufactured by Tamakagakuko Kogyo Co., Ltd.), methyl (meth) acrylate Silicate 51 (manufactured by Korukoto K.K.) is preferred.

The silicate compound is a compound having high heat resistance and high transparency, and is similar in structure to polysiloxane. Since the silicate compound has many Si-OR groups in one molecule, it reacts with the silanol group in the polysiloxane at the time of thermosetting, so that the degree of crosslinking of the cured film increases and the chemical resistance is improved.

The amount of the silicate compound to be added is not particularly limited, but is preferably 3 to 20 parts by mass based on 100 parts by mass of the polysiloxane. More preferably 3 to 10 parts by mass. When the addition amount of the silicate compound is within this preferable range, the effect of improving the chemical resistance is great. On the other hand, since the reduction amount of the developing film in the unexposed portion is small, the uniformity of the film thickness becomes good.

Further, the photosensitive resin composition of the present invention may contain (e) a metal chelate compound represented by the following general formula (6).

In the metal chelate compound represented by the general formula (6), M is a metal atom. The plurality of R ^{21 s} may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, and a substituent thereof.

The plurality of R ²² and R ²³ may be the same or different and each represents hydrogen, an alkyl group, an aryl group, an alkenyl group, an alkoxy group, and a substituent thereof. j represents an atomic valence of a metal atom M, and k represents an integer of 0 or more and j or less.

The incorporation of the metal chelate compound improves the developing adhesion and improves the chemical resistance of the resulting cured film.

In the general formula (6), M is a metal atom and is not particularly limited. From the viewpoint of transparency, metal atoms such as titanium, zirconium, aluminum, zinc, cobalt, molybdenum, lanthanum, barium, strontium, have. Among them, zirconium or aluminum is preferable from the viewpoints of developing adhesion and chemical resistance of the cured film.

R ²¹ is a group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decanyl group, A vinyl group, an allyl group, and an oleyl group. Among them, from the standpoint of stability of the compound, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n- A decyl group, and a phenyl group are preferable. R ²² and R ²³ are each independently selected from the group consisting of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, N-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n- An octadecyl group, and a benzyloxy group. Of these, a methyl group, a t-butyl group, a phenyl group, a methoxy group, an ethoxy group and an n-octadecyl group are preferable in that the synthesis is easy and the compound is stable.

Examples of the compound represented by the general formula (6) include zirconium tetra n-propoxide, zirconium tetra n-butoxide, zirconium tetra sec-butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, (2,2,6,6-tetramethyl-3,5-heptanedionate), zirconium tetramethylacetoacetate, zirconium tetraethylacetoacetate, zirconium tetramethylmalonate, zirconium tetraethylmalonate, zirconium tetrabenzoyl acetone (Acetylacetonate), zirconium mono-n-butoxytris (acetyl acetonate), zirconium mono-n-butoxyethylacetoacetate bis Acetonate), zirconium mono-n-butoxytris (acetic acid Zirconium di (n-butoxy) bis (ethyl acetoacetate), zirconium di (n-butoxy) bis (acetylacetonate) Di (n-butoxy) bis (benzoyl acetonate), and zirconium di (n-butoxy) bis (dibenzoylmethanate).

Examples of the aluminum compound include aluminum tris isopropoxide, aluminum tris n-propoxide, aluminum tris sec-butoxide, aluminum tris n-butoxide, aluminum trisphenoxide, aluminum trisacetylacetonate, aluminum tris , 6,6-tetramethyl-3,5-heptanedionate), aluminum tris ethyl acetoacetate, aluminum tris methylacetoacetate, aluminum trismethyl malonate, aluminum tris ethyl malonate, aluminum ethyl acetate di (isopropoxide ), Aluminum acetylacetonate di (isopropoxide), aluminum methyl acetoacetate di (isopropoxide), aluminum octadecyl acetoacetate di (isopropylate), aluminum monoacetylacetonate bis (ethylacetoacetate) And the like.

Examples of the titanium compound include titanium tetra n-propoxide, titanium tetra n-butoxide, titanium tetra-sec-butoxide, titanium tetraphenoxide, titanium tetraacetylacetonate, titanium tetra (2,2,6,6- 3,5-heptanedionate), titanium tetramethylacetoacetate, titanium tetraethyl acetoacetate, titanium tetramethyl malonate, titanium tetraethyl malonate, titanium tetrabenzoyl acetonate, titanium tetradibenzoyl methanate, titanium mono n- Butoxyethylacetonate bis (ethylacetoacetate), titanium mono n-butoxyethylacetoacetate bis (acetylacetonate), titanium mono n-butoxytris (acetylacetonate), titanium mono-n-butoxytris (N-butoxy) bis (acetoacetate), titanium di (n-butoxy) bis (acetylacetonate) (N-butoxy) bis (dibenzoylmethanate), titanium tetra-2-ethylhexyloxide and the like can be used. .

Among them, zirconium tetra n-butoxide, zirconium tetra-n-butoxide, zirconium tetraphenoxide, zirconium tetraacetylacetonate, zirconium tetra (2,2,6,6-tetra Methyl-3,5-heptanedionate), zirconium tetramethylmalonate, zirconium tetraethyl malonate, zirconium tetraethylacetoacetate, zirconium dinormalbutoxybis (ethylacetoacetate), zirconium mononuclear butoxyacetylacetonate bis (Ethyl acetoacetate), aluminum tris acetylacetonate, aluminum tris (2,2,6,6-tetramethyl-3,5-heptanedionate), aluminum tris ethyl acetoacetate, aluminum tris methylacetoacetate , Aluminum trismethyl malonate, aluminum (Isopropoxide), aluminum methyl acetoacetate di (isopropoxide), aluminum octadecyl acetoacetate di (isopropyl myristate), aluminum ethyl acetoacetate di (isopropoxide), aluminum acetylacetonate) (Aluminum acetate), and aluminum monoacetylacetonate bis (ethylacetoacetate), titanium compounds such as titanium tetra n-butoxide, titanium tetra n-butoxide, titanium tetra phenoxide, titanium tetraacetylacetonate, titanium tetra 6,6-tetramethyl-3,5-heptanedionate), titanium tetramethyl malonate, titanium tetraethyl malonate, titanium tetraethyl acetoacetate, titanium dinormal butoxybis (ethylacetoacetate) (Ethylacetoacetate), and the like are preferable, and a titanium compound such as The metal complex system is preferably used.

The amount of the metal chelate compound to be added is not particularly limited, but is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the polysiloxane. And more preferably from 0.3 to 4 parts by weight. With the above range, the developing adhesion and the chemical resistance of the cured film can be made compatible at a high level.

The photosensitive siloxane composition of the present invention may contain additives such as a silane coupling agent, a crosslinking agent, a crosslinking accelerator, a sensitizer, a heat radical generator, a dissolution accelerator, a dissolution inhibiting agent, a surfactant, a stabilizer and a defoaming agent.

The photosensitive siloxane composition of the present invention may contain a silane coupling agent. The incorporation of the silane coupling agent improves the adhesion to the substrate.

Specific examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n- Propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, vinyltrimethoxy Silane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-1,3-dimethyl- Amine, N-phenyl-3-aminopropyltrimethoxysilane, 3-gly 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- ( (3-ethyl-3-oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl) methoxy] Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxy Silyl propyl succinic acid, and Nt-butyl-3- (3-trimethoxysilylpropyl) succinic acid imide.

The amount of the silane coupling agent to be added is not particularly limited, but is preferably in the range of 0.1 to 10 parts by mass based on 100 parts by mass of the polysiloxane. When the addition amount is within this preferable range, the effect of improving the adhesion is sufficient, and on the other hand, the condensation reaction of the silane coupling agents during storage is difficult to occur, so that the silane coupling agent does not cause the residue to be dissolved in the development.

The photosensitive siloxane composition of the present invention may contain a crosslinking agent. The crosslinking agent is a compound which is crosslinked in the polysiloxane at the time of thermosetting and is put into the resin, and the crosslinking degree of the cured film is increased by inclusion thereof. As a result, the chemical resistance of the cured film is improved, and deterioration of the pattern resolution due to pattern deterioration upon thermal curing is suppressed.

The crosslinking agent is not particularly limited, but preferably includes a compound having two or more groups represented by the general formula (4).

R ¹⁰ represents any one of hydrogen and an alkyl group having 1 to 10 carbon atoms. The plurality of R < ¹⁰ > in the compound may be the same or different.

In the compound having two or more groups represented by the general formula (4), R ¹⁰ represents any one of hydrogen and an alkyl group having 1 to 10 carbon atoms. The plurality of R < ¹⁰ > in the compound may be the same or different. Specific examples of the alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group and n-decyl group.

Specific examples of the compound having two or more groups represented by the general formula (4) include the following melamine derivatives and urea derivatives (trade name, manufactured by Sanwa Chemical Co., Ltd.).

These crosslinking agents may be used alone or in combination of two or more.

The amount of the crosslinking agent to be added is not particularly limited, but is preferably in the range of 0.1 to 10 parts by mass based on 100 parts by mass of the polysiloxane. When the addition amount of the crosslinking agent is within the preferable range, crosslinking of the resin becomes sufficient. On the other hand, the colorless transparency of the cured film is maintained and the storage stability of the composition is excellent.

The photosensitive siloxane composition of the present invention may contain a crosslinking accelerator. The crosslinking accelerator is a compound that promotes crosslinking of the polysiloxane at the time of thermal curing. A thermal acid generator that generates acid upon thermal curing or a photo acid generator that generates acid upon bleaching exposure before thermal curing is used. The presence of an acid in the film during thermal curing accelerates the condensation reaction of the unreacted silanol groups in the polysiloxane to increase the degree of crosslinking of the cured film. As a result, the chemical resistance of the cured film is improved, and deterioration of the pattern resolution due to pattern deterioration upon thermal curing is suppressed.

The thermal acid generator used in the present invention is a compound which generates an acid upon thermal curing, and it is preferable that no acid is generated or only a small amount is generated during prebaking after application of the composition. Therefore, the compound is preferably a compound which generates an acid at a temperature higher than the prebake temperature, for example, 100 占 폚 or higher. If an acid is generated at a temperature lower than the prebake temperature, the polysiloxane tends to be crosslinked at the time of prebaking, resulting in lowering of the sensitivity or remaining in the melt at the time of development.

Specific examples of the thermal acid generators which are preferably used are SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI- 4-hydroxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-hydroxy-4-hydroxyphenylsulfonium trifluoromethanesulfonate (trade name, Phenylmethylsulfonium trifluoromethanesulfonate, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium trifluoromethanesulfonate, 4-acetoxyphenyldimethylsulfonium trifluoromethanesulfonate, 4-acetoxy Phenylbenzylmethylsulfonium trifluoromethanesulfonate, 4-methoxycarbonyloxyphenyldimethylsulfonium trifluoromethanesulfonate, benzyl-4-methoxycarbonyloxyphenylmethylsulfonium trifluoromethanesulfonate ( (Manufactured by Otsuka Chemical Co., Ltd.) and the like. These compounds may be used alone or in combination of two or more.

The photoacid generator used in the present invention is a compound which generates an acid at the time of bleaching exposure and is an acid at an exposure wavelength of 365 nm (i line), 405 nm (h line), 436 nm (g line) . Therefore, even in the case of pattern exposure using the same light source, there is a possibility of generating an acid, but the pattern exposure does not cause a problem because only a small amount of acid occurs because the amount of exposure is small as compared with the bleaching exposure. The acid to be generated is preferably a strong acid such as perfluoroalkylsulfonic acid or p-toluenesulfonic acid, and the quinone diazide compound in which a carboxylic acid is generated does not have the function of the photoacid generator mentioned above, It is different from accelerator.

Specific examples of the photoacid generator that is preferably used include SI-100, SI-101, SI-105, SI-106, SI-109, PI-105, PI-106, PI-109, NAI- NAI-1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-101, NDI-105, NDI-106, NDI-109, PAI- 106, PAI-1001 manufactured by Midori Kagaku Co., Ltd., SP-077, SP-082 (manufactured by ADEKA), TPS-PFBS (manufactured by Toyo Kosase Kogyo Co., ), CGI-MDT, CGI-NIT (manufactured by Chiba Japan), WPAG-281, WPAG-336, WPAG-339, WPAG-342, WPAG-344, WPAG- -372, WPAG-449, WPAG-469, WPAG-505 and WPAG-506 (all trade names, manufactured by Wako Pure Chemical Industries, Ltd.). These compounds may be used alone or in combination of two or more.

It is also possible to use the thermal acid generator and the photo acid generator described above as a crosslinking accelerator in combination. The amount of the crosslinking accelerator to be added is not particularly limited, but is preferably in the range of 0.01 to 5 parts by mass based on 100 parts by mass of the polysiloxane. When the addition amount of the crosslinking accelerator is within the preferable range, the effect is sufficient, and the crosslinking of the polysiloxane does not occur at the time of prebaking or pattern exposure.

The photosensitive siloxane composition of the present invention may contain a sensitizer. The addition of a sensitizer accelerates the reaction of the naphthoquinone diazide compound, which is a photosensitizer, thereby enhancing the sensitivity. In addition, when a photoacid generator is contained as a crosslinking accelerator, the reaction at the time of bleaching exposure is promoted to improve the chemical resistance and pattern resolution .

The sensitizer used in the present invention is not particularly limited, but preferably a sensitizer which is vaporized by heat treatment and / or is faded by light irradiation is used. This sensitizer needs to have absorption for 365 nm (i line), 405 nm (h line), and 436 nm (g line), which are the wavelengths of the light source in pattern exposure or bleaching exposure, The colorless transparency is lowered. Thus, the sensitizer used for preventing the deterioration of the colorless transparency due to the sensitizer may be a compound which is vaporized by heat treatment such as heat curing (sensitizer) and / or a compound which is faded by light irradiation such as bleaching exposure ) Is preferable.

Specific examples of the sensitizer that is vaporized by the heat treatment and discolored by light irradiation include coumarin such as 3,3'-carbonylbis (diethylaminocoumarin), anthraquinone such as 9,10-anthraquinone, Aromatic ketones such as phenol, 4,4'-dimethoxybenzophenone, acetophenone, 4-methoxyacetophenone and benzaldehyde, aromatic ketones such as biphenyl, 1,4-dimethylnaphthalene, 9-fluorenone, fluorene, phenanthrene, tri (4-methoxyphenyl) anthracene, 9,10-bis (triphenylsilyl) silane, 9,10-diphenylanthracene, Anthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, And condensed aromatic groups such as 9,10-dibutoxyanthracene and 9,10-bis (trimethylsilylethynyl) anthracene.

Among these sensitizers, the sensitizer which is vaporized by the heat treatment is preferably a sensitizer that sublimates, evaporates, or sublimates or pyrolyses pyrolysis products by thermal treatment. The vaporization temperature of the sensitizer is preferably 130 ° C to 400 ° C, more preferably 150 ° C to 250 ° C. If the vaporization temperature of the sensitizer is in the above preferable range, the sensitizer is difficult to vaporize during the pre-baking, so that the sensitizer is not present during the exposure process and the sensitivity can be kept high. On the other hand, since the sensitizer is vaporized at the time of thermal curing, it does not remain in the cured film and colorless transparency can be maintained. Further, in order to completely vaporize during thermal curing, the vaporization temperature of the sensitizer is preferably 250 ° C or lower.

On the other hand, the sensitizer which is faded by light irradiation is preferably a sensitizer whose absorption in the visible light region is discolored by light irradiation from the viewpoint of transparency. Further, a more preferable compound that is discolored by light irradiation is a compound which is dimerized by light irradiation. By diminution by light irradiation, the molecular weight is increased to insolubilize, so that the effect of improving chemical resistance, heat resistance, and reducing the extract from the transparent cured film can be obtained.

An anthracene-based compound is preferable because the sensitizer can attain a high sensitivity, is diminished by dimming by light irradiation, and the anthracene-based compound having 9,10 position hydrogen is unstable in heat, so 9,10-2 Substituted anthracene-based compound. From the viewpoint of improvement of the solubility of the sensitizer and reactivity of the dimerization reaction, the compound is preferably a 9,10-dialkoxy anthracene compound represented by the general formula (5).

R ¹¹ to R ¹⁸ in the general formula (5) each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an aryl group, an acyl group, and an organic group substituted therewith. Specific examples of the alkyl group include a methyl group, an ethyl group and an n-propyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentyloxy group. Specific examples of the alkenyl group include a vinyl group, an acryloxypropyl group and a methacryloxypropyl group. Specific examples of the aryl group include a phenyl group, a trityl group and a naphthyl group. A specific example of the acyl group includes an acetyl group. From the viewpoint of the vaporization property of the compound and the reactivity of dimerization, it is preferable that R ¹¹ to R ¹⁸ are hydrogen or an organic group having 1 to 6 carbon atoms. More preferably, R ¹¹ , R ¹⁴ , R ¹⁵ and R ¹⁸ are preferably hydrogen.

R ¹⁹ and R ²⁰ in the general formula (5) represent an alkoxy group having 1 to 20 carbon atoms, and an organic group substituted therewith. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a pentyloxy group, but a propoxy group and a butoxy group are preferable from the viewpoint of the solubility of the compound and the fading reaction by dimerization.

The amount of the sensitizer to be added is not particularly limited, but is preferably added in the range of 0.01 to 5 parts by mass based on 100 parts by mass of the polysiloxane. When the addition amount of the sensitizer is within the preferable range, the transparency is not lowered and the sensitivity is not lowered.

A method of forming a cured film using the photosensitive siloxane composition of the present invention will be described. The composition of the present invention is coated on a base substrate by a known method such as a spinner or a slit, and is prebaked in a heating apparatus such as a hot plate or an oven. The prebaking is preferably performed at a temperature in the range of 50 to 150 DEG C for 30 seconds to 30 minutes, and the film thickness after prebaking is preferably 0.1 to 15 mu m.

A pre-baked stepper, a mirror projection mask aligner (MPA), and a ferroalite mask mask aligner (PLA), and then exposed to a dose of about 10 to 4000 J / m 2 (corresponding to a wavelength of 365 nm) Pattern exposure.

The exposed portion is dissolved by development after exposure to obtain a positive pattern. As a developing method, it is preferable to immerse the developing solution for 5 seconds to 10 minutes by a method such as a shower, a dip or a paddle. As the developer, a known alkali developer can be used.

Specific examples thereof include inorganic alkalis such as hydroxides, carbonates, phosphates, silicates and borates of alkali metals, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and choline, And aqueous solutions containing two or more species. It is also preferable to rinse with water after development, and if necessary, dehydration and drying baking may be carried out in a heating apparatus such as a hot plate or oven at 50 to 150 캜.

It is preferable to carry out bleaching exposure. By performing bleaching exposure, the unreacted quinonediazide compound remaining in the film is photolyzed to further improve the light transparency of the film. As a method of bleaching exposure, an ultraviolet visible light exposure apparatus such as PLA is used to expose the entire surface to about 100 to 20000 J / m 2 (corresponding to a wavelength of 365 nm in terms of exposure dose).

If a bleached exposure film is required, it is soft baked in a heating apparatus such as a hot plate or oven for 30 seconds to 30 minutes at a temperature of 50 to 150 ° C, and then heated in a heating apparatus such as a hot plate or oven at a temperature of 150 A curing film made of a flattening film for a TFT in a display element, a protective film or an insulating film of a touch panel, an interlayer insulating film in a semiconductor element, or a core or clad material in an optical waveguide is formed.

The cured film produced using the photosensitive siloxane composition of the present invention has a light transmittance of 90% or more, more preferably 92% or more, per 3 m of the film thickness at 400 nm. When the light transmittance of the cured film is within the preferable range, no color change occurs when the backlight passes through when used as a flattening film for a TFT substrate of a liquid crystal display element, and there is no case where the white display is yellowish.

The transmittance per 3 m of the film thickness at the wavelength of 400 nm is obtained by the following method. The composition was spin-coated on a Tampax glass plate with a spin coater at an arbitrary number of revolutions and pre-baked at 100 占 폚 for 2 minutes using a hot plate. Thereafter, an ultrahigh-pressure mercury lamp was exposed on the entire surface of the film using PLA as a bleaching exposure, and the film was thermally cured in air at 220 DEG C for 1 hour using an oven to produce a cured film having a film thickness of 3 mu m do. The ultraviolet visible absorption spectrum of the obtained cured film is measured using "MultiSpec" -1500 manufactured by Shimadzu Corporation, and the transmittance at a wavelength of 400 nm is obtained.

This cured film is preferably used for a flattening film for a TFT substrate such as a liquid crystal display element, a protective film or an insulating film of a touch panel, an interlayer insulating film of a semiconductor element, or a core or clad material of an optical waveguide.

The element in the present invention refers to a liquid crystal display element, an organic EL display element, a touch panel, a semiconductor element, or an optical waveguide material having a cured film as described above, and particularly relates to a liquid crystal display element as a flattening film for a TFT substrate, As shown in Fig.

(Example)

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples. The abbreviations of the used compounds are shown below.

DAA: diacetone alcohol

PGMEA: Propylene glycol monomethyl ether acetate

PGME: Propylene glycol monomethyl ether

The polysiloxane solution, the solid content concentration of the acrylic resin solution, and the weight average molecular weight (Mw) of the polysiloxane and acrylic resin were determined as follows.

(1) Solid concentration

1 g of a polysiloxane (acrylic resin) solution was cast into an aluminum cup and heated at 250 DEG C for 30 minutes using a hot plate to evaporate the liquid components. The solid content remaining in the heated aluminum cup was weighed to determine the solid content concentration of the polysiloxane (acrylic resin) solution.

(2) Weight average molecular weight

The weight average molecular weight was determined by GPC (Waters 996 type detector, developing solvent: tetrahydrofuran) in terms of polystyrene.

Synthesis Example 1: Synthesis of polysiloxane solution (a)

In a 500 ml three-necked flask, 54.48 g (0.4 mol) of methyltrimethoxysilane, 99.15 g (0.5 mol) of phenyltrimethoxysilane and 24.64 g (0.5 mol) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 163.35 g of diacetone alcohol (hereinafter, abbreviated as DAA) was added thereto, and while stirring at room temperature, an aqueous solution of phosphoric acid in which 0.535 g of phosphoric acid (0.3 mass% based on the charged monomers) was dissolved in 54 g of water was stirred for 10 minutes Lt; / RTI > Thereafter, the flask was immersed in an oil bath at 40 DEG C and stirred for 30 minutes, and then the oil bath was heated to 115 DEG C over 30 minutes. After 1 hour from the start of raising the temperature, the inner temperature of the solution reached 100 占 폚, and the mixture was heated and stirred for 2 hours (100 占 폚 to 110 占 폚 inside temperature) to obtain the polysiloxane solution (a). In addition, 0.05 l (liter) / min of nitrogen was passed through the heating and stirring. During the reaction, a total of 120 g of methanol and water as by-products were distilled.

The solid content concentration of the obtained polysiloxane solution (a) was 40% by mass, and the weight average molecular weight of the polysiloxane was 6500. The phenyl group content in the polysiloxane was 50 mol% based on the Si atoms.

Synthesis Example 2: Synthesis of polysiloxane solution (b)

(0.3 mol) of methyltrimethoxysilane, 99.15 g (0.5 mol) of phenyltrimethoxysilane and 12.32 g (0.5 mol) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added to a 500- and 153.66 g of propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMEA) (17.63 g (0.15 mol in terms of the number of moles of silane atom)) of M silicate 51 (manufactured by Tamakagakuko Kogyo Co., Ltd.) While stirring at room temperature, an aqueous solution of phosphoric acid in which 0.51 g of phosphoric acid (0.3 mass% based on the charged monomer) had been dissolved was added over a period of 10 minutes to 53.55 g of water. Then, the flask was immersed in an oil bath at 40 캜 and stirred for 30 minutes The oil bath was heated to 115 占 폚 over 30 minutes. After 1 hour from the start of the temperature rise, the inner temperature of the solution reached 100 占 폚, and the mixture was heated and stirred for 2 hours (100 占 폚 to 110 占 폚 inner temperature) to obtain a polysiloxane solution (b) I spent a minute. During the reaction, a total of 120 g of methanol and water as by-products were distilled.

The solid content concentration of the obtained polysiloxane solution (b) was 40% by mass, and the weight average molecular weight of the polysiloxane was 10,000. The phenyl group content in the polysiloxane was 50 mol% based on the Si atoms.

Synthesis Example 3: Synthesis of polysiloxane solution (c)

(0.65 mol) of methyltrimethoxysilane, 49.58 g (0.25 mol) of phenyltrimethoxysilane, and 24.64 g of 2,4- (3,4-epoxycyclohexyl) ethyltrimethoxysilane were added to a 500- g (0.1 mol) of DAA and 144.83 g of DAA, and while stirring at room temperature, an aqueous phosphoric acid solution in which 0.081 g of phosphoric acid (0.05 mass% based on the charged monomers) was dissolved in 54 g of water was added over 10 minutes. Thereafter, the flask was immersed in an oil bath at 40 DEG C and stirred for 30 minutes, and then the oil bath was heated to 115 DEG C over 30 minutes. After 1 hour from the start of raising the temperature, the inner temperature of the solution reached 100 캜, and the mixture was heated and stirred for 2 hours (100 캜 to 110 캜 ambient temperature) to obtain a polysiloxane solution (c). In addition, 0.05 l (liter) / min of nitrogen was passed through the heating and stirring. During the reaction, a total of 120 g of methanol and water as by-products were distilled.

The solid content concentration of the obtained polysiloxane solution (c) was 40 mass%, and the weight average molecular weight of the polysiloxane was 9,000. The phenyl group content in the polysiloxane was 25 mol% based on the Si atoms.

Synthesis Example 4: Synthesis of polysiloxane solution (d)

In a 500 ml three-necked flask, 20.43 g (0.15 mol) of methyltrimethoxysilane, 158.64 g (0.8 mol) of phenyltrimethoxysilane, and 12.32 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane g (0.05 mol) of DAA and 179.54 g of DAA, and while stirring at room temperature, an aqueous solution of phosphoric acid in which 0.383 g of phosphoric acid (0.2 mass% based on the charged monomer) was dissolved in 54 g of water was added over 10 minutes. Thereafter, the flask was immersed in an oil bath at 40 DEG C and stirred for 30 minutes, and then the oil bath was heated to 115 DEG C over 30 minutes. After 1 hour from the start of raising the temperature, the inner temperature of the solution reached 100 占 폚, and the mixture was heated and stirred for 3 hours (100 占 폚 to 110 占 폚 inner temperature) to obtain a polysiloxane solution (d). In addition, 0.05 l (liter) / min of nitrogen was passed through the heating and stirring. During the reaction, a total of 120 g of methanol and water as by-products were distilled.

The solid content concentration of the obtained polysiloxane solution (d) was 40% by mass, and the weight average molecular weight of the polysiloxane was 7,000. The phenyl group content in the polysiloxane was 80 mol% based on the Si atoms.

Synthesis Example 5: Synthesis of acrylic resin solution (a)

5 g of 2,2'-azobis (isobutyronitrile) and 150 g of PGMEA were placed in a 500 ml flask. Thereafter, 27 g of methacrylic acid, 38 g of benzylmethacrylate, and 35 g of tricyclo [5.2.1.02,6] decan-8-yl methacrylate were added, stirred at room temperature for a while, Lt; 0 > C for 5 hours. Then, 15 g of glycidyl methacrylate, 1 g of dimethylbenzylamine and 0.2 g of p-methoxyphenol were added to the obtained solution, and the mixture was heated and stirred at 90 DEG C for 4 hours to obtain an acrylic resin solution (a).

The solid content concentration of the obtained acrylic resin solution (a) was 43 mass%, and the weight average molecular weight of the acrylic resin was 31,400.

Synthesis Example 6: Synthesis of quinone diazide compound (a)

21.23 g (0.05 mol) of a dry nitrogen stream Hartlis P-PA (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.) and 37.62 g (0.14 mol) of 5-naphthoquinonediazide sulfonyl chloride were added to 1,4- And dissolved in 450 g of oxalic acid to room temperature. 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature was not higher than 35 ° C. After dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered off and the filtrate was poured into water. After that, precipitate precipitated was collected by filtration. This precipitate was dried in a vacuum drier to obtain a quinone diazide compound (a) having the following structure.

Synthesis Example 7: Synthesis of quinone diazide compound (b)

(0.1 mol) of 5-naphthoquinonediazidosulfonyl chloride was added to a dry nitrogen stream of 15.32 g (0.05 mol) of Hottris P-HAP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.) And dissolved in 450 g of oxalic acid to room temperature. Here, 11.13 g (0.11 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature could not exceed 35 ° C. After dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered off and the filtrate was poured into water. After that, precipitate precipitated was collected by filtration. This precipitate was dried in a vacuum drier to obtain a quinone diazide compound (b) having the following structure.

Synthesis Example 8: Synthesis of quinone diazide compound (c)

15.32 g (0.05 mol) of PH-cc-AP-MF (trade name, manufactured by Honshu Kagaku Kogyo K.K.) and 37.62 g (0.14 mol) of 5-naphthoquinonediazidosulfonyl chloride were added to a 1, Was dissolved in 450 g of 4-dioxane to room temperature. 15.58 g (0.154 mol) of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature was not higher than 35 ° C. After dropwise addition, the mixture was stirred at 30 ° C for 2 hours. The triethylamine salt was filtered off and the filtrate was poured into water. After that, precipitate precipitated was collected by filtration. This precipitate was dried in a vacuum drier to obtain a quinonediazide compound (c) having the following structure.

(Example 1)

25.51 g of the polysiloxane solution (a) obtained in Synthesis Example 1, 0.92 g of the quinone diazide compound (c) obtained in Synthesis Example 8, 1.02 g of M silicate 51 (trade name, manufactured by Tamakagakukogyo K.K.) as a silicate compound, 0.20 g of KBM303 (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a coupling agent and 0.20 g of CGI-MDT (trade name, 0.05 g of DPA (9,10-dipropoxyanthracene, trade name, manufactured by Kawasaki Kasei Kogyo Co., Ltd.) as a sensitizer, 3.44 g of DAA as a solvent and 18.75 g of PGMEA were mixed and stirred in a yellow color, Solution and filtered through a 0.2 탆 filter to prepare Composition 1. Table 1 shows the composition. M silicate 51 used as a silicate compound and CGI-MDT used as a crosslinking accelerator are compounds having the structures shown below.

The composition 1 was spin-coated at an arbitrary number of revolutions using a silicon wafer and an OA-10 glass plate (manufactured by Nihon Denk Shou Co., Ltd.) using a spin coater (1H-360S manufactured by Mikasa) (SCW-636, manufactured by Nihon Screen Seizo Co., Ltd.) for 2 minutes at 100 占 폚 to prepare a film having a thickness of 3 占 퐉. The film thus formed was subjected to pattern exposure through a gray scale mask for sensitivity measurement using a ferrite sheet mask aligner (PLA-501F manufactured by Canon Inc.) (hereinafter referred to as PLA-501F) (Manufactured by Mitsubishi Gas Chemical Company, Ltd.) as a 2.38 mass% tetramethylammonium hydroxide aqueous solution (manufactured by Mitsubishi Gas Chemical Company) using AD-2000 manufactured by Takikazawa Sangyo Co., Ltd., followed by rinsing with water for 30 seconds . Thereafter, an ultrahigh-pressure mercury lamp was exposed to the entire surface of the film using PLA (PLA-501F, manufactured by Canon Inc.) as a bleaching exposure to expose the film to 3000 J / m 2 (wavelength 365 nm in terms of exposure dose). Thereafter, the substrate was soft baked at 110 DEG C for 2 minutes using a hot plate, and then cured in air at 220 DEG C for 1 hour by using an oven (IHPS-222 manufactured by Tavispeak Co., Ltd.) to produce a cured film.

Table 2 shows the evaluation results of the photosensitive characteristics and the cured film characteristics. The evaluation in the table was carried out by the following method. Evaluation of the following (3) to (6) was performed on a silicon wafer substrate, and evaluation of (8) and (9) was performed using OA-10 glass plate.

(3) Measurement of film thickness

Measurement was conducted at a refractive index of 1.50 using " Lambda Ace " STM-602 (trade name, manufactured by Dainippon Screen).

(4) Calculation of the residual film ratio

The residual film ratio was calculated according to the following formula.

Remaining film ratio (%) = unexposed film thickness after development / film thickness after prebaking 占 100

(5) Calculation of sensitivity

The exposure amount (hereinafter referred to as the optimum exposure amount) formed at a width of 1 mu m and a line-and-space pattern of 10 mu m after exposure and development was set as sensitivity.

(6) Calculation of resolution

The minimum pattern size after development in the optimum exposure amount was set as the post-development resolution, and the minimum pattern size after curing was set as the post-cure resolution.

(7) Measurement of mass reduction rate

Approximately 100 mg of the composition was placed in an aluminum cell and heated to 300 캜 at a heating rate of 10 캜 / min in a nitrogen atmosphere using a thermal mass measuring device (TGA-50, manufactured by Shimadzu Corporation) And then the temperature was raised from 400 ° C to 400 ° C at a heating rate of 10 ° C / min. When the temperature reached 300 DEG C, the mass was measured. When the temperature reached 400 DEG C, the mass was measured, and the difference from the mass at 300 DEG C was determined. The reduced mass was obtained as the mass reduction rate.

(8) Measurement of light transmittance

"Multi Spec" -1500 (trade name, manufactured by Shimadzu Corporation) was used, and only the OA-10 glass plate was measured, and the ultraviolet visible absorption spectrum thereof was set as a reference. Then, a cured film of the composition was formed on the OA-10 glass plate (pattern exposure was not performed), and this sample was measured with a single beam, and the light transmittance at a wavelength of 400 nm per 3 m was determined. .

(9) Evaluation of Chemical Resistance

A cured film of the composition was formed on the OA-10 glass plate (pattern exposure was not performed), and a square of 10 x 10 was formed on the cured film with a cutter knife at intervals of 1 mm. Subsequently, the substrate was immersed in an ITO etchant (hydrochloric acid / potassium chloride / water = 6/8/84 (mass ratio)) at 50 占 폚 for 300 seconds. A, 5% or less: B, 5% to 35%: C or more and 35% or more: F was determined by the peeling rate of the cured film on the square when the cellophane tape was attached on the square and peeled off.

(Examples 2 to 13 and Comparative Examples 1 to 4)

Composition 2 to 17 were prepared in the same manner as Composition 1 according to the composition shown in Table 1. In addition, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48 (trade name, manufactured by Korukoto K.K.), silane coupling agent NIKARAK MX-270 and NIKARAK MW-30HM (trade names, manufactured by Sanwa Chemical Co., Ltd.) used as a crosslinking agent were KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)

Using each composition thus obtained, the respective compositions were evaluated in the same manner as in Example 1. In the evaluation of Comparative Example 2, the development was carried out for 80 seconds with a 0.4 mass% aqueous solution of tetramethylammonium hydroxide (ELM-D diluted with water). The results are shown in Table 2. Comparative Examples 1, 2, and 4 do not contain the silicate compound represented by the general formula (2), and thus the chemical resistance of the cured film characteristics deteriorates. In Comparative Example 3, since the resin is an acrylic resin, the light transmittance of the cured film characteristic deteriorates.

The present invention relates to a planarizing film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a photosensitive film for forming a protective film or insulating film of a touch panel, an interlayer insulating film of a semiconductor element, Can be preferably used for the siloxane composition.

Claims (6)

(a) a polysiloxane synthesized by reacting at least one organosilane represented by the general formula (1), (b) a quinone diazide compound, (c) a solvent, and (d) a silicate represented by the general formula (2) ≪ RTI ID = 0.0 > 1, < / RTI >

Wherein R ¹ represents any ^one of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and a plurality of R ^{1 s} may be the same or different. R ² represents any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms, and the plurality of R ^{2 s} may be the same or different. n represents an integer of 0 to 3]

[In the formula, R ³ to R ⁶ each independently represent any one of hydrogen, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms. and p represents an integer of 2 to 10; The method according to claim 1,
The photosensitive siloxane composition according to the above (d), wherein R ³ to R ⁶ in the silicate compound represented by the general formula (2) is a methyl group. The method according to claim 1,
(e) a metal chelate compound represented by the general formula (6).

Wherein M is a metal atom. The plural R < ²¹ > s may be the same or different, and are each hydrogen; An alkyl group; An aryl group; An alkenyl group; Or a substituent of a group selected from the group consisting of an alkyl group, an aryl group and an alkenyl group. R ²² and R ^{23, which} may be the same or different, are each hydrogen; An alkyl group; An aryl group; An alkenyl group; An alkoxy group; Or a substituent of a group selected from the group consisting of an alkyl group, an aryl group, an alkenyl group and an alkoxy group. j is a valence of the metal atom M, and k is an integer of 1 or more and j or less. The method according to claim 1,
Wherein the quinonediazide compound (b) is a compound having an ester-bonded naphthoquinone diazidesulfonic acid to a compound having a phenolic hydroxyl group represented by the general formula (7).

Wherein R ²⁴ and R ²⁵ each independently represent any one of hydrogen, an alkyl group having 1 to 10 carbon atoms, and an aryl group having 6 to 15 carbon atoms. R ²⁶ and R ²⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group, a carboxyl group or an ester group, and a plurality of R ^{26 s} and R ^{27 s} may be the same or different. a and b each represent an integer of 0 to 4; c and d represent an integer of 1 to 5; Provided that a + c and b + d are integers of 1 to 5, c? D and c + d? 3, A cured film formed from the photosensitive siloxane composition according to claim 1,
Wherein the light transmittance per 3 m of the film thickness at 400 nm is 90% or more. An element comprising the cured film according to claim 5.