KR101992594B1 - Negative-type photosensitive siloxane composition - Google Patents

Abstract

[PROBLEMS] To provide a photosensitive siloxane composition having high resolution, high heat resistance and high transparency, and having high sensitivity and a high stickiness film ratio, in which thermal deflection easily occurs during thermal curing without increasing the molecular weight of the crosslinking agent or siloxane compound. (I) (Ia) (Ia) a polysiloxane having a solubility in a 5 wt% tetramethylammonium hydroxide aqueous solution and a dissolution rate of 3,000 Å / sec or less, and (Ib) a film after pre- , A polysiloxane-containing polysiloxane mixture having a dissolution rate of not less than 150 angstroms per second in a 2.38 wt% tetramethylammonium hydroxide aqueous solution, (II) a curing aid, and (III) a solvent. Polysiloxane composition.

Description

NEGATIVE-TYPE PHOTOSENSITIVE SILOXANE COMPOSITION [0002]

The present invention relates to a negative-working photosensitive siloxane composition. The present invention also relates to a method for producing a cured film using the same, a cured film formed therefrom, and an element having the cured film.

2. Description of the Related Art In recent years, various proposals have been made for optical devices such as displays, light emitting diodes, and solar cells for the purpose of improving light utilization efficiency and energy saving. For example, in a liquid crystal display, a method is known in which a transparent flattening film is formed over a thin film transistor (hereinafter, also referred to as TFT) element and a pixel electrode is formed on the flattening film to increase the aperture ratio of the display device Patent Document 1). A configuration of an organic electroluminescent element (hereinafter, also referred to as an organic EL element), a method of forming a light emitting layer on a transparent pixel electrode formed on a substrate and extracting the light emitted from the substrate side (bottom emission) There has been proposed a method of improving the aperture ratio like a liquid crystal display by making the transparent pixel electrode on the flattening film covered on the element and the light emitted from the light emitting layer thereon taken out to the side opposite to the TFT element (top emission) (See Patent Document 2).

In addition, the need for higher resolution, larger size, and higher image quality of the display increases, and with the introduction of new technologies such as 3D display, signal delay on wiring becomes a problem. The input time of the signal to the TFT is shortened due to the increase of the rewriting speed (frame frequency) of the image information. However, in order to improve the response speed by lowering the wiring resistance by extending the wiring width, there is a limit to the extension of the wiring width due to the demand for high resolution and the like. Therefore, it has been proposed to solve the problem of signal delay by increasing the wiring thickness (see Non-Patent Document 1).

As one of such planarizing film materials for a TFT substrate, there is known a negative photosensitive material mainly comprising a polysiloxane compound and a curing assistant. Such a polysiloxane compound is obtained by polymerizing a silane compound having a bifunctional functional group, for example, a dialkyldialkoxysilane in the presence of a catalyst. However, when such a polysiloxane compound is used, degassing may occur during the film formation process. The gas generated here is a decomposition product originating from an organic material generated at a high temperature and adversely affects the luminous efficiency and lifetime of the organic EL device, and therefore is not an optimal material for use. In addition, the resulting decomposition product may increase the dielectric constant and increase the parasitic capacitance due to the insulating film, resulting in increased power consumption, resulting in a delay of the liquid crystal element driving signal, and the like, which may cause a problem in the quality of image quality. Even if an insulating material having a large dielectric constant is used, for example, the capacitance can be reduced by increasing the film thickness. However, it is generally difficult to form a uniformly thick film and the amount of material used is also increased.

A negative photosensitive composition containing an amorphous polysiloxane compound obtained by polymerizing a silane compound containing two to four functionalities, for example, a silane compound containing 2 to 4 alkoxy groups, Since the width is too large, the residual film ratio after film formation is insufficient and the curing rate of the film progresses slowly, so that a large amount of exposure may be required. In addition, since more acid generator is required to maintain the pattern shape after firing, the transmittance tends to be greatly decreased (see Patent Document 4).

Japanese Patent Publication No. 2933879 Japanese Patent Application Laid-Open No. 2006-236839 Japanese Patent Application Laid-Open No. 2009-276777 Japanese Laid-Open Patent Publication No. 2006-18249 Japanese Patent Publication No. 2006-073021 Japanese Laid-Open Patent Publication No. 2011-190333

 IMID / IDMC / ASIA DISPLAY 2008 Digest (pages 9-12)

Disclosure of the Invention The present invention has been made based on the above-described circumstances, and has as its object to provide a high-resolution, high heat resistance, high transparency, Which is liable to occur during thermal curing and is suppressed in heat deflection and has a high sensitivity and a high stickiness ratio. Another object of the present invention is to provide a method for manufacturing a negative type photosensitive siloxane composition, which comprises the steps of: forming a planarizing film for a TFT substrate, a cured film such as an interlayer insulating film and the like, A filter, a high-luminance light emitting diode, a touch panel, a solar cell, an optical waveguide, and the like.

The negative-working photosensitive siloxane composition according to the present invention comprises

(I) (Ia) a polysiloxane obtained by hydrolyzing and condensing a silane compound (ia) selected from the group consisting of trialkoxysilane and tetraalkoxysilane in the presence of a basic catalyst, wherein the film after prebaking contains 5 wt% A polysiloxane soluble in an aqueous tetramethylammonium hydroxide solution and having a dissolution rate of 3,000 A / sec or less, and

(Ib) a polysiloxane obtained by hydrolysis / condensation of a silane compound (ib) selected from the group consisting of trialkoxysilane and tetraalkoxysilane in the presence of an acidic or basic catalyst, wherein 2.38% by weight of tetramethyl Lt; RTI ID = 0.0 > / sec < / RTI > to an aqueous solution of ammonium hydroxide,

, ≪ / RTI >

(II) a curing aid capable of generating an acid or base with heat or radiation, and

(III) Solvent

And the like.

The method for producing a cured film according to the present invention comprises coating a substrate with the above negative-type photosensitive siloxane composition to form a coating film, exposing the coating film to light, and heating.

Further, the cured film according to the present invention is characterized by being formed of the above-mentioned negative-type photosensitive siloxane composition.

Further, the element according to the present invention is characterized by being provided with the cured film.

The negative-working photosensitive siloxane composition of the present invention has high sensitivity and high resolution, and the obtained cured film is excellent in heat resistance, chemical resistance, environmental resistance, transparency, and residual film ratio, and does not decrease in resolution due to thermal deflection. In addition, since it is excellent in planarity and electrical insulation properties, it can be used as a flattening film for a thin film transistor (TFT) substrate used for a backplane of a display such as a liquid crystal display element or an organic EL display element, Various film forming materials such as an insulating film and a transparent protective film in an antireflection film, an antireflection plate, an optical filter, a high-luminance light emitting diode, a touch panel, a solar cell, and the like and also as an optical element such as an optical waveguide.

1 is an optical microphotograph of contact hole patterns of 3 mu m, 5 mu m, and 10 mu m after baking and curing at 250 DEG C obtained in Example 3. Fig.
2 is an optical microscope photograph of contact hole patterns of 3 mu m, 5 mu m, and 10 mu m after baking and curing at 250 DEG C obtained in Comparative Example 1. Fig.
3 is an optical microscope photograph showing the state of heat deflection which is a deformation of a pattern by heating.

Negative  Photosensitive Polysiloxane  Composition

The negative-working photosensitive siloxane composition of the present invention is a composition comprising a mixture of a polysiloxane having a specific dissolution rate, an acid or base capable of generating an acid or a base by heat or radiation, a tetramethylammonium hydroxide aqueous solution (hereinafter referred to as a TMAH aqueous solution) A curing aid, and a solvent. Hereinafter, the specific polysiloxane used in the negative-type photosensitive siloxane composition of the present invention, the curing agent capable of generating acid or base by heat or radiation, and the solvent will be described in detail in sequence.

(I) Polysiloxane  mixture

First, the characteristics of the polysiloxane mixture (I) used in the present invention will be described.

The polysiloxane mixture used in the present invention contains two kinds of polysiloxanes (Ia) and (Ib) which will be described later.

In general, when a pattern is to be formed using a negative-type photosensitive siloxane composition containing a polysiloxane compound, a curing aid, and a solvent, it is necessary that the dissolution rate of the coating formed by the composition is moderate. Specifically, when the dissolution rate of the formed film into the 2.38% TMAH aqueous solution is 50 Å / second or more, it is possible to form a negative pattern by exposure-development. However, when curing of the coating film is promoted by adding a large amount of curing assistant to adjust the solubility of the coating film using the highly soluble polysiloxane, the pattern shape obtained is deformed, and a decrease in the residual film ratio and a decrease in transmittance occur have.

It has been proposed to prevent the deformation of the pattern shape, the decrease of the residual film ratio, and the decrease of the transmittance by using a polysiloxane having a low dissolution rate (for example, Patent Document 4). However, when a composition mainly composed of an amorphous random polysiloxane synthesized using an acid catalyst described in Patent Document 4 is used, excessive heat deflow, reduction of the residual film ratio, decrease in transmittance can be prevented by controlling the dissolution rate It is difficult to completely prevent thermal deflection, which may cause problems such as lowered resolution and lower sensitivity (low sensitivity). The heat deflection is a phenomenon in which the pattern is deformed when the pattern is heated as shown in Fig. 3, for example, a pattern in which the cross section is rectangular and the ridgeline is clear, the ridge portion is rounded after heating, And the side surface of the rectangular shape is inclined.

On the other hand, the inventors of the present invention have found that the polysiloxane synthesized using a base catalyst can start to harden rapidly when a temperature of 150 ° C or higher is applied, and maintain a neat shape without causing thermal deflection even after firing. It has been found by the present inventors that the above problems can be solved at the same time by using a polysiloxane mixture containing such a specific polysiloxane.

That is, the negative-working photosensitive polysiloxane composition used in the present invention contains at least two kinds of polysiloxane.

(a) a first polysiloxane

The first polysiloxane,

(Ia) a polysiloxane obtained by hydrolyzing and condensing a silane compound (ia) selected from the group consisting of trialkoxysilane and tetraalkoxysilane in the presence of a basic catalyst, wherein the membrane after prebaking comprises 5 wt% tetramethylammonium Is a polysiloxane which is soluble in an aqueous solution of a hydroxide and has a dissolution rate of 3,000 Å / sec or less, preferably 2,000 Å / sec or less, which alone is poorly soluble in an aqueous solution of 2.38% TMAH.

This first polysiloxane is obtained by hydrolyzing and condensing a silane compound (ia) selected from the group consisting of trialkoxysilane and tetraalkoxysilane in the presence of a basic catalyst.

The silane compound (ia) selected from the group consisting of trialkoxysilane and tetraalkoxysilane used as a raw material may be any arbitrary one, and for example, those represented by the following formula (i) may be used.

(I)

R ¹ _n Si (OR ² ) _4-n

In the above formula (i)

R ¹ is a linear, branched or cyclic alkyl group of 1 to 20 carbon atoms in which arbitrary methylene may be substituted with oxygen or an aryl group of 6 to 20 carbon atoms in which arbitrary hydrogen may be substituted by fluorine,

n is 0 or 1,

R ² is an alkyl group having 1 to 5 carbon atoms.

In formula (i), examples of R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, an n- -Trifluoroethyl group, 3,3,3-trifluoropropyl group, cyclohexyl group, phenyl group, tolyl group, and naphthyl group. Particularly, a compound in which R ¹ is a methyl group is preferable because it is easy to obtain a starting material, has a high film hardness after curing, and has high drug resistance. Further, the phenyl group is preferable because the solubility of the polysiloxane in the solvent is increased and the cured film is hardly cracked.

On the other hand, in the formula (i), examples of R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. In the formula (i), a plurality of R ² is contained, but each R ² may be the same or different.

Specific examples of the trialkoxysilane compound represented by the above formula (i) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri n-butoxysilane, ethyltrimethoxysilane , Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n- Hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, naphtyltrimethoxysilane, naphthyltriethoxysilane, naphthyltrimethoxysilane, Naphthyltriisopropoxysilane, naphthyltri n-butoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc. . Of these, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane and phenyltriethoxysilane are preferable compounds because they are easily available.

Specific examples of the tetraalkoxysilane compound represented by the above formula (i) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. Of these, Ethoxysilane, tetraethoxysilane and the like are preferable because of their high reactivity.

The silane compound (ia) used in the production of the polysiloxane (Ia) may be used singly or in combination of two or more. Here, when tetraalkoxysilane is used as the silane compound (ia), thermal deflection tends to be reduced. This is considered to be because the crosslinking density of the polysiloxane is increased. However, if the blend ratio of the tetraalkoxysilane is excessively high, there is a possibility that the sensitivity is lowered. Therefore, when tetraalkoxysilane is used as a raw material of the polysiloxane (Ia), the blending ratio thereof is preferably 0.1 to 40 mol%, more preferably 1 to 20 mol%, based on the total molar amount of the trialkoxysilane and the tetraalkoxysilane, Is more preferable. Further, if the blending ratio of tetraalkoxysilane is decreased, thermal deflection increases, but such characteristics can be effectively utilized. For example, in the case of forming an insulating film for covering an element or the like formed on the surface of a substrate, a material having a large thermal deflection can be effectively used.

The polysiloxane (Ia) used in the present invention is prepared by hydrolyzing and condensing the above silane compound in the presence of a basic catalyst.

For example, a silane compound or a mixture of silane compounds is added dropwise to a reaction solvent composed of an organic solvent, a basic catalyst and water, subjected to a hydrolysis and condensation reaction, and if necessary, purified or concentrated by neutralization or washing , And replacing the reaction solvent with the desired organic solvent, if necessary.

Examples of the organic solvent used in the reaction solvent include hydrocarbon solvents such as hexane, toluene, xylene and benzene, ether solvents such as diethyl ether and tetrahydrofuran, ethyl acetate, propyleneglycol monomethylethylacetate and the like Ester solvents, alcohol solvents such as methanol, ethanol, isopropanol, butanol and 1,3-dipropanol, and ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone. These organic solvents may be used alone or in combination of two or more thereof. The amount of the organic solvent to be used is generally 0.1 to 10 times by weight, preferably 0.5 to 2 times by weight, of the mixed solution of the silane compound.

The reaction temperature for carrying out the hydrolysis and condensation reaction is generally 0 to 200 ° C, preferably 10 to 60 ° C. At this time, the temperature of the silane compound to be dropped and the temperature of the reaction solvent may be the same or different. The reaction time varies depending on the kind of the silane compound and the like, but is usually from several tens minutes to several tens hours, preferably at least 30 minutes. The various conditions in the hydrolysis and condensation reaction can be determined by setting the basic catalyst amount, the reaction temperature, the reaction time and the like in consideration of the reaction scale, the size and shape of the reaction vessel, Can be obtained.

Examples of the basic catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, alkoxysilane having an amino group Organic bases, inorganic bases such as sodium hydroxide and potassium hydroxide, quaternary ammonium salts such as anion-exchange resin, tetrabutylammonium hydroxide, tetraethylammonium hydroxide and tetramethylammonium hydroxide. The amount of the catalyst is preferably 0.0001 to 10 moles per mole of the mixture of the silane compound.

The degree of hydrolysis can be controlled by the amount of water added to the reaction solvent. Generally, the hydrolyzable alkoxy group of the silane compound is preferably reacted at a rate of 0.01 to 10 moles, preferably 0.1 to 5 moles, of water. If the addition amount of water is excessively smaller than the above range, the degree of hydrolysis is lowered to make it difficult to form a coating film of the composition. On the other hand, if it is too much, gelation tends to occur and storage stability tends to deteriorate. The water to be used is preferably ion-exchanged water or distilled water.

After completion of the reaction, the reaction solution may be neutral or weakly acidic using an acidic compound as a neutralizing agent. Examples of the acidic compound include inorganic acids such as phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid, polyvalent carboxylic acids and their anhydrides such as acetic acid, trifluoroacetic acid, formic acid, lactic acid, acrylic acid, oxalic acid, maleic acid, p-toluenesulfonic acid, or sulfonic acid such as methanesulfonic acid. It may also be neutralized using a cation exchange resin.

The amount of the neutralizing agent is appropriately selected according to the pH of the reaction solution after the reaction, but is preferably 0.5 to 1.5 moles, more preferably 1 to 1.1 moles per one mole of the basic catalyst. When a cation exchange resin is used, it is preferable that the number of ion groups contained in the cation exchange resin is within the above range.

The reaction solution after neutralization may be washed and purified as necessary. The cleaning method is not particularly limited. For example, a hydrophobic organic solvent and, if necessary, water are added to the reaction solution after neutralization, and the organic solvent is contacted with the polysiloxane with stirring to dissolve at least the polysiloxane (Ia) on the hydrophobic organic solvent . At this time, as the hydrophobic organic solvent, a compound which dissolves the polysiloxane (Ia) and is immiscible with water is used. When it is not miscible with water, it means that the water and the hydrophobic organic solvent are thoroughly mixed and then left to separate into water phase and organic phase.

Preferred examples of the hydrophobic organic solvent include ether solvents such as diethyl ether and the like, ester solvents such as ethyl acetate, alcohol solvents such as butanol, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, aromatic solvents such as toluene and xylene Based solvent and the like. The hydrophobic organic solvent used for washing may be the same as or different from the organic solvent used as the reaction solvent, or two or more kinds of them may be mixed and used. By this cleaning, most of the basic catalyst, neutralizing agent, and salts produced by neutralization, as well as alcohol or water, which is a by-product of the reaction, are contained in the aqueous layer and substantially excluded from the organic layer. The number of rinses can be changed as needed.

The temperature at the time of washing is not particularly limited, but is preferably 0 to 70 占 폚, more preferably 10 to 60 占 폚. The temperature at which the water phase and the organic phase are separated is not particularly limited, but is preferably 0 to 70 캜, more preferably 10 to 60 캜, from the viewpoint of shortening the liquid separation time.

By carrying out such cleaning, the coating property and storage stability of the composition may be improved.

The washed solution can be transferred to the composition according to the present invention as it is. However, if necessary, the solvent or the by-product of the remaining reaction, such as alcohol or water, may be removed by concentration to change the concentration, It may be substituted with another solvent. Concentration can be carried out under normal pressure (atmospheric pressure) or reduced pressure, and the degree of concentration can be arbitrarily changed by controlling the flow rate. The temperature at the time of concentration is generally 30 to 150 ° C, preferably 40 to 100 ° C. The solvent may also be replaced by adding the desired solvent in a timely manner to obtain the desired solvent composition and further concentrating the solvent.

The polysiloxane (Ia) used in the siloxane resin composition of the present invention can be produced by the above method.

(b) a second polysiloxane

The second polysiloxane,

(Ib) a polysiloxane obtained by hydrolyzing and condensing a silane compound (ib) selected from the group consisting of trialkoxy silane and tetraalkoxy silane in the presence of an acidic catalyst or a basic catalyst, Which is soluble in an aqueous solution of tetramethylammonium hydroxide and whose dissolution rate is not lower than 150 A / sec, preferably not lower than 500 A /

to be.

The polysiloxane (Ib) is prepared by hydrolyzing and condensing a silane compound (ib) selected from the group consisting of trialkoxysilane and tetraalkoxysilane in the presence of an acidic or basic catalyst.

Here, as the conditions of this production method, the same method as the production method of the polysiloxane (Ia) can be used. However, in addition to the basic catalyst, an acidic catalyst may be used as the reaction catalyst. Further, in order to attain the target dissolution rate, the conditions such as the amount of reaction solvent, in particular, the amount of water, the reaction time, and the reaction temperature are suitably adjusted.

The silane compound (ib) may be the same as or different from the silane compound (ia) used as the raw material of the polysiloxane (Ia). Here, when tetraalkoxysilane is used as the silane compound (ib), thermal deflection tends to be reduced.

When a relatively large amount of tetraalkoxysilane is used as a raw material of the first polysiloxane (Ia), the blending ratio of tetraalkoxysilane as a raw material of the second polysiloxane (Ib) is preferably low. This is because if the compounding ratio of the tetraalkoxysilane as a whole is high, precipitation of the silane compound occurs or sensitivity of the formed film is lowered. Therefore, the blending ratio of tetraalkoxysilane is preferably 1 to 40 mol%, more preferably 1 to 20 mol%, relative to the total number of moles of the silane compounds (ia) and (ib) as raw materials of the polysiloxanes (Ia) % Is more preferable.

In the production of the polysiloxane (Ib), an acidic catalyst may be used as the catalyst. Examples of the acidic catalyst that can be used include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acid or anhydrides thereof. The amount of the catalyst to be added is preferably 0.0001 to 10 moles per mole of the mixture of the silane compound depending on the strength of the acid.

When an acid catalyst is used for the production of the polysiloxane (Ib), the reaction solution may be neutralized after completion of the reaction, as in the case of using a basic catalyst. In this case, a basic compound is used as a neutralizing agent. Examples of the basic compound used for neutralization include organic compounds such as triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine or diethanolamine An inorganic base such as a base, sodium hydroxide or potassium hydroxide; a quaternary ammonium salt such as tetrabutylammonium hydroxide, tetraethylammonium hydroxide or tetramethylammonium hydroxide; and the like. Anion exchange resin may also be used. The amount of the neutralizing agent may be the same as in the case of using a basic catalyst. Is appropriately selected depending on the pH of the reaction solution after the reaction, but is preferably 0.5 to 1.5 molar equivalents, more preferably 1 to 1.1 molar equivalents, relative to the acidic catalyst.

Thus, the polysiloxane (Ib) used in the siloxane resin composition of the present invention can be produced.

The dissolution rate of the polysiloxane (Ib) in a 2.38% TMAH aqueous solution is required to be 150 Å / second or more as described later, and is preferably 500 Å / second or more. If the dissolution rate of the polysiloxane (Ib) to the aqueous 2.38% TMAH solution is less than 150 Å / second, the dissolution rate of the mixture of polysiloxane (Ia) and (Ib) to the aqueous solution of 2.38% TMAH should be 50 to 3,000 Å / It is necessary to reduce the content of the polysiloxane (Ia) as much as possible. When the content of the polysiloxane (Ia) is small, it is difficult to prevent thermal deformation of the pattern.

(c) Polysiloxane mixture (I)

The polysiloxane mixture (I) used in the present invention contains the above polysiloxane (Ia) and polysiloxane (Ib). The weight ratio of the polysiloxane (Ia) / polysiloxane (Ib) contained in the polysiloxane mixture (I) is preferably from 1/99 to 80/20, more preferably from 20/80 to 50/50 More preferable.

In the composition according to the present invention, it is not essential to use a basic catalyst, which is thought to be effective for improving heat deflection prevention, and tetraalkoxysilane as a raw material in the production of the polysiloxane (Ib). However, by using them, the effect of the present invention can be obtained even when the compounding amount of the polysiloxane (Ia) is reduced, and in some cases, it is preferable in terms of residualness and sensitivity. On the other hand, by increasing the blending amount of the tetraalkoxysilane used as the raw material of the polysiloxane (Ia), the effect of the present invention can be achieved without using tetraalkoxysilane as the raw material of the polysiloxane (Ib). However, if the blending amount of tetraalkoxysilane as the raw material of the polysiloxane (Ia) is increased, there is a possibility that a problem of deterioration of sensitivity and the like may occur even if the thermal deflection improvement effect is obtained. For this reason, it is preferable to use tetraalkoxysilane as a raw material for each of the polysiloxane (Ia) and the polysiloxane (Ib).

The weight average molecular weight (Mw) of the polysiloxane mixture (I) is preferably 5,000 or less, more preferably 1,000 to 4,000. If the weight average molecular weight is less than 1,000, the effect of preventing heat sagging is small. On the other hand, if the weight average molecular weight exceeds 5,000, the resin does not dissolve during development, and sufficient resolution is not obtained and sensitivity is lowered. Here, the weight average molecular weight refers to a value measured by gel permeation chromatography (GPC) using polystyrene as a standard.

When the dissolution rate of the polysiloxane (Ia) in the 5% aqueous solution of TMAH is 3,000 Å / sec or less and the dissolution rate of the polysiloxane (Ib) in the aqueous solution of 2.38% TMAH is 150 Å / sec or more, The dissolution rate of the polysiloxane mixture (I) in the 2.38% TMAH aqueous solution can be appropriately set according to the thickness of the cured film formed by the negative photosensitive silicone composition of the present invention, the developing time, and the like. The dissolution rate of the polysiloxane mixture (I) can be adjusted by changing the mixing ratio of the polysiloxanes (Ia) and (Ib), and varies depending on the type and amount of the photosensitizer contained in the negative-type photosensitive siloxane composition. When the film thickness is 0.1 to 10 mu m (1,000 to 100,000 ANGSTROM), the dissolution rate to the aqueous solution of 2.38% TMAH is preferably 50 to 3,000 A / sec.

(d) Alkali dissolution rate to aqueous TMAH solution

In the present invention, the polysiloxanes (Ia) and (Ib) each have a specific dissolution rate with respect to aqueous TMAH solution. The dissolution rate of the polysiloxane in the TMAH aqueous solution is measured as follows. The polysiloxane was diluted with propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) to 35% by weight and dissolved with stirring at room temperature for 1 hour with a stirrer. The prepared polysiloxane solution was dripped onto the center portion of a 1cc silicon wafer using a pipette on a silicon wafer of 4 inches and a thickness of 525 탆 in a clean room at a temperature of 23.0 占 0.5 占 폚 and a humidity of 50 占 5.0% And the solvent is then removed by heating on a hot plate at 100 DEG C for 90 seconds. The film thickness of the coating film is measured with a spectroscopic ellipsometer (manufactured by J. A. Woollam).

Next, the silicon wafer having this film was immersed in a glass shaker having a diameter of 6 inches, in which 100 ml of a predetermined concentration of TMAH aqueous solution had been adjusted to 23.0 占 폚 to 0.1 占 폚, and then allowed to stand until the time until the film was lost Respectively. The dissolution rate is obtained by dividing the time until the film in the inner portion of 10 mm from the end of the wafer disappears. When the dissolution rate is remarkably low, the wafer is immersed in a TMAH aqueous solution for a predetermined time and then heated on a hot plate at 200 DEG C for 5 minutes to remove moisture contained in the film during measurement of the dissolution rate, Is determined by dividing the amount of change in the film thickness by the immersion time to calculate the dissolution rate. The measurement is carried out five times, and the average of the obtained values is taken as the dissolution rate of the polysiloxane.

(II) Hardening aid

The negative-type photosensitive polysiloxane composition according to the present invention comprises a curing aid. The curing assistant includes a curing assistant which generates an acid or a base by radiation and a curing assistant which generates an acid or a base by heat.

The curing assistant can improve the resolution by enhancing the shape of the pattern or increasing the contrast of development. Examples of the curing assistant used in the present invention include a photoacid generator that releases an acid which is decomposed upon exposure to radiation to actively cure the composition, a photobase generator that releases a base, and an activator that decomposes by heat to thermally cure the composition A thermal acid generator that releases acid as a substance, and a thermal base generator that releases a base. Here, examples of the radiation include visible light, ultraviolet ray, infrared ray, X-ray, electron ray,? -Ray,? -Ray and the like.

The amount of the curing assistant to be added varies depending on the kind of the active material generated due to the decomposition of the curing aid, the amount of the generated curing agent, the required sensitivity, and the dissolution contrast of the exposed and unexposed portions. Preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight. When the addition amount is less than 0.001 part by weight, the dissolution contrast between the exposed portion and the unexposed portion is excessively low, and the addition effect may not be obtained. On the other hand, when the addition amount of the curing assistant is more than 10 parts by weight, cracks may be generated in the formed film or coloration due to decomposition of the curing assistant may become remarkable, so that the colorless transparency of the film may be lowered. Further, if the addition amount is increased, the electric insulation of the cured product is deteriorated by thermal decomposition and the gas is released, which may cause a problem in a post-process. In addition, the resistance of the coating film to a photoresist stripping liquid based on a monoethanolamine or the like may be lowered.

Examples of the photoacid generator include diazomethane compounds, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, ammonium salts, phosphonium salts, sulfonimide compounds and the like. The structure of these photoacid generators may be represented by the formula (A).

(A)

R ⁺ X ^-

In formula (A), R ⁺ is an organic ion selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an acyl group, and an alkoxyl group, which is modified with hydrogen, a carbon atom or other heteroatom such as diphenyl iodide And a triphenylsulfonium ion.

Also, it is preferable that X < ^- > is a counter ion represented by any one of the following formulas.

(In the above formula,

Y is a halogen atom,

R ^a is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, which is substituted with a substituent selected from ^a fluorine, a nitro group and a cyano group,

R ^b is hydrogen or an alkyl group having 1 to 8 carbon atoms,

p is a number from 0 to 6,

and q is a number of 0 to 4)

A specific ion ^{_{BF 4 -, (C 6 F}} 5) 4 B -, ((CF 3) 2 C 6 H 3) 4 B -, PF 6 -, (CF 3 CF 2) 3 PF 3 -, SbF 6 _{^{-, (C 6 F 5)}} 4 Ga -, ((CF 3) 2 C 6 H 3) 4 Ga -, SCN-, (CF 3 SO 2) 3 C-, (CF 3 SO 2) 2 N -, Those selected from the group consisting of formic acid ion, acetic acid ion, trifluoromethanesulfonic acid, nonafluorobutanesulfonic acid, methanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, .

Among the photoacid generators used in the present invention, it is particularly preferable to generate sulfonic acids, for example, triphenylsulfonium trifluoromethanesulfonic acid, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetra (purple 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonic acid, 1- (4-methoxyphenyl) 1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonic acid, diphenyl iodonium tetra (perfluorophenyl) borate, diphenyl iodonium trifluoromethanesulfonic acid, diphenyl iodide Hexafluoroarsenate, and the like.

Examples of the thermal acid generators include various aliphatic carboxylic acids and their salts with various fatty acid sulfonic acids and their salts, various carboxylic acids such as citric acid, acetic acid and maleic acid, salts with various aromatic carboxylic acids such as benzoic acid and phthalic acid, aromatic sulfonic acids and their ammonium salts, , An aromatic diazonium salt, a phosphonic acid and a salt thereof, and salts and esters which generate an organic acid. Among the thermal acid generators used in the present invention, salts of organic acids and organic bases are preferred, and salts of sulfonic acids and organic bases are more preferred.

Examples of preferred sulfonic acid-containing thermal acid generators include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, and methanesulfonic acid. These acid generators can be used alone or in combination.

Examples of the photo-base generator include a polysubstituted amide compound having an amide group, a lactam, an imide compound, or a compound containing such a structure.

Examples of the thermal base generator include N- (2-nitrobenzyloxycarbonyl) imidazole, N- (3-nitrobenzyloxycarbonyl) imidazole, N- Imidazole derivatives such as N- (5-methyl-2-nitrobenzyloxycarbonyl) imidazole and N- (4-chloro-2-nitrobenzyloxycarbonyl) imidazole, 1,8-diazabicyclo [ , 4,0 undecene-7, tertiary amines, quaternary ammonium salts, and mixtures thereof. These base generators can be used alone or in combination as in the case of the acid generators.

(III) Solvent

The negative-working photosensitive siloxane composition according to the present invention comprises a solvent. This solvent is not particularly limited as long as it uniformly dissolves or disperses the polysiloxane mixture (I), the curing auxiliary agent and the additive agent added as required. Examples of the solvent usable in the present invention include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene Diethylene glycol dialkyl ethers such as diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, Propylene glycol alkyl ether acetates such as monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate, aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone , Methyl isobu Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, ethyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like And cyclic esters such as esters and? -Butyrolactone. Of these, propylene glycol alkyl ether acetates and esters are preferably used from the viewpoints of availability, ease of handling, and solubility of the polymer. These solvents may be used alone or in combination of two or more kinds. The amount of the solvent to be used differs depending on the application method and the requirement of the film thickness after coating.

The solvent content of the negative-working photosensitive siloxane composition can be arbitrarily adjusted depending on the method of applying the composition and the like. For example, when the composition is applied by spray coating, the ratio of the solvent in the negative-type photosensitive siloxane composition may be 90 wt% or more. In addition, in the slit coating used in the coating of a large substrate, it is usually not less than 60% by weight, preferably not less than 70% by weight. The characteristics of the negative-working photosensitive siloxane composition of the present invention do not change greatly depending on the amount of the solvent.

(IV) Additive

The negative-type photosensitive siloxane composition according to the present invention may contain other additives, if necessary. Examples of such additives include a developer dissolution accelerator, a scum removing agent, a adhesion enhancer, a polymerization inhibitor, a defoaming agent, a surfactant, and a sensitizer.

The developer dissolution promoter or scum removing agent has an action of adjusting the solubility of a coating film to be formed in a developing solution and preventing scum from remaining on the substrate after development. As such an additive, a crown ether can be used. As the crown ether, those having the simplest structure are represented by the formula (-CH ₂ -CH ₂ -O-) _n . Among them, n is preferably 4 to 7 in the present invention. The crown ether may be referred to as x-crown-y-ether in which the total number of atoms constituting the ring is x and the number of oxygen atoms contained therein is y. In the present invention, it is preferable to select from the group consisting of crown ethers having x = 12, 15, 18 or 21, y = x / 3, and benzo condensates and cyclohexyl condensates thereof. Specific examples of the more preferred crown ethers are 21-crown-7-ether, 18-crown-6-ether, 15-crown- Crown-6-ether, dibenzo-15-crown-5-ether, dibenzo-12-crown-4-ether, dicyclohexyl-21-crown-7-ether, dicyclohexyl Crown-6-ether, dicyclohexyl-15-crown-5-ether, and dicyclohexyl-12-crown-4-ether. Among them, 18-crown-6-ether and 15-crown-5-ether are most preferred in the present invention. The addition amount thereof is preferably from 0.05 to 15 parts by weight, more preferably from 0.1 to 10 parts by weight, per 100 parts by weight of the polysiloxane mixture (I).

The adhesion enhancer has an effect of preventing the pattern from being peeled off by the pressure applied after firing, when the cured film is formed using the negative-working photosensitive siloxane composition of the present invention. As the adhesion enhancer, imidazoles and silane coupling agents are preferable. In the imidazoles, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole , 2-mercaptoimidazole and 2-aminoimidazole are preferable, and 2-hydroxybenzoimidazole, benzimidazole, 2-hydroxyimidazole and imidazole are particularly preferably used.

Examples of the silane coupling agent include epoxy silane coupling agents, aminosilane coupling agents and mercaptosilane coupling agents, and specific examples thereof include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, etc. . These may be used alone or in combination of two or more, and the amount thereof is preferably 0.05 to 15 parts by weight based on 100 parts by weight of the polysiloxane mixture (I).

As the silane coupling agent, a silane compound having an acid group, a siloxane compound or the like may also be used. Examples of the acid group include a carboxyl group, an acid anhydride group, and a phenolic hydroxyl group. In the case of containing a monobasic acid group such as a carboxyl group or a phenolic hydroxyl group, it is preferable that a single silicon-containing compound has a plurality of acid groups.

As specific examples of such silane coupling agents,

[Chemical Formula B]

X _n Si (OR ³ ) _4-n

, Or a polymer comprising the same as a polymerization unit. At this time, a plurality of polymerization units in which X or R ³ are different from each other may be used in combination.

In the above formula (B), examples of R ³ include hydrocarbon groups such as alkyl groups such as methyl, ethyl, n-propyl, isopropyl and n-butyl groups. In the formula (A), a plurality of R ³ is contained, but each R ³ may be the same or different.

Examples of X include those having an acid group such as a thiol, a phosphonium, a borate, a carboxyl, a phenol, a peroxide, a nitro, a cyano, a sulfo and an alcohol group and a group having such an acid group as acetyl, aryl, amyl, benzyl, methoxymethyl , Those protected with mesyl, tolyl, trimethoxysilyl, triethoxysilyl, triisopropylsilyl, or trityl groups, and acid anhydride groups.

Among them, methyl having R ³ and carboxylic acid anhydride group as X, for example, silicon containing an acid anhydride group is preferable. More specifically, a compound represented by the following formula (B-1) (X-12-967C (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)) or a structure corresponding to the structure is bonded to the terminal or side chain of a silicon- Is preferred. Also preferred are compounds in which an acid group such as thiol, phosphonium, borate, carboxyl, phenol, peroxide, nitro, cyano, and sulfo group is added to the terminal of dimethyl silicone. Examples of such a compound include compounds represented by the following formulas (B-2) and (B-3) (X-22-2290AS and X-22-1821 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.)).

[Formula B-1]

[Formula B-2]

[Formula B-3]

In the case where the silane coupling agent contains a silicon structure, if the molecular weight is too large, the compatibility with the polysiloxane contained in the composition is insufficient and the solubility in the developer is not improved, or the reactive group remains in the film, There is a possibility that adverse effects such as the inability to maintain the drug solution resistance are possible. Therefore, the weight average molecular weight of the silicon-containing compound is preferably 5,000 or less, more preferably 4,000 or less. The polymer corresponding to the formula (B-1) is preferably a relatively small weight average molecular weight of 1,000 or less, but in the case of a polymer containing a silicon structure in other repeating units, the weight average molecular weight is preferably 1,000 or more. When an silane compound having an acid group, a siloxane compound or the like is used as the silane coupling agent, the addition amount thereof is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the polysiloxane mixture (I).

As the polymerization inhibitor, a nitrone derivative, a nitroxide radical derivative, and a hydroquinone derivative such as hydroquinone, methylhydroquinone, and butylhydroquinone can be added. These may be used singly or in combination of two or more. The amount thereof is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the polysiloxane mixture (I).

Examples of the defoaming agent include alcohols (C ₁ to C ₁₈ ), higher fatty acids such as oleic acid and stearic acid, higher fatty acid esters such as glycerin monolaurate, polyethylene glycol (PEG) (Mn 200 to 10,000), polypropylene glycol Mn 200 to 10,000), silicone compounds such as dimethyl silicone oil, alkyl-modified silicone oil and fluorosilicone oil, and organosiloxane-based surfactants described in detail below. These may be used alone or in combination of two or more, and the amount thereof is preferably 0.1 to 3 parts by weight based on 100 parts by weight of the total of the polysiloxane mixture (I).

In addition, the negative-working photosensitive siloxane composition of the present invention may contain a surfactant if necessary. The surfactant is added for the purpose of improving the application properties, developability and the like. Examples of the surfactant usable in the present invention include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether and polyoxyethylene cetyl ether; and polyoxyethylene alkyl ethers such as polyoxyethylene alkyl ether, Acetylene glycol, acetylene glycol, acetylene glycol derivatives such as polyethoxylate of acetylene alcohol, polyethoxylate of acetylene glycol, and the like, acetylene glycol derivatives such as polyoxyethylene fatty acid monoester, polyoxyethylene polyoxypropylene block polymer, Surfactants such as Fluoride (trade name, manufactured by Sumitomo 3M Ltd.), Megapak (trade name, manufactured by DIC Corporation), Sulfuron (trade name, manufactured by Asahi Kasei Kogyo Co.) An activator such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) And the like. Examples of the acetylene glycol include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6- , 9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyn- Dimethyl-2,5-hexanediol, and the like.

Examples of the anionic surfactant include ammonium salts or organic amine salts of alkyl diphenyl ether disulfonic acid, ammonium salts or organic amine salts of alkyl diphenyl ether sulfonic acid, ammonium salts or organic amine salts of alkyl benzene sulfonic acids, polyoxyethylene alkyl ether sulfuric acid Ammonium salts or organic amine salts of alkylsulfuric acid, ammonium salts or organic amine salts of alkylsulfuric acid, and the like.

Examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauryl acid amide propyl hydroxyphosphate betaine and the like.

These surfactants may be used alone or in combination of two or more. The amount thereof is usually 50 to 2,000 ppm, preferably 100 to 1,000 ppm, relative to the negative-working photosensitive siloxane composition of the present invention.

Further, a sensitizer may be added to the negative-working photosensitive siloxane composition of the present invention, if necessary. Specific examples of the sensitizer used in the negative-working photosensitive siloxane composition of the present invention include coumarins, ketocoumarins and their derivatives, thiopyrylium salts and acetophenones, specifically, p-bis (o-methylstyryl ) Benzene, 7-dimethylamino-4-methylquinolone-2,7-amino-4-methylcoumarin, 4,6-dimethyl- Iodide, 7-diethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 2,3,5,6-1H, 4H-tetrahydro-8-methylquinolinodino- gh> coumarin, 7-diethylamino-4-trifluoromethylcoumarin, 7-dimethylamino-4-trifluoromethylcoumarin, 7-amino-4-trifluoromethylcoumarin, -1H, 4H-tetrahydroquinolinodino- <9,9a, 1-gh> coumarin, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, 7-ethylamino- Coumarin, 2,3,5,6-1H, 4H-tetrahydro-9- (2'-N-methylbenzimidazolyl) -7-N, N-diethylaminocoumarin, N-methyl-4-trifluoro Benzimidazolylethyl iodide, 3- (2'-benzimidazolyl) -7-N, N (N-dimethylaminostyryl) -Diethylaminocoumarin, 3- (2'-benzothiazolyl) -7-N, N-diethylaminocoumarin, and a sensitizing dye such as pyrylium salt and thiopyrylium salt represented by the following formula. The addition of the sensitizing dye enables patterning using an inexpensive light source such as a high-pressure mercury lamp (360 to 430 mm). The addition amount thereof is preferably from 0.05 to 15 parts by weight, more preferably from 0.1 to 10 parts by weight, per 100 parts by weight of the polysiloxane mixture (I).

As the sensitizer, an anthracene skeleton-containing compound may also be used. Specifically, there may be mentioned a compound represented by the following formula (C).

&Lt; RTI ID = 0.0 &

In formula (C) above,

R ³¹ is each independently a substituent selected from the group consisting of an alkyl group, an aralkyl group, an allyl group, a hydroxyalkyl group, an alkoxyalkyl group, a glycidyl group, and a halogenated alkyl group,

R ³² each independently represents a substituent selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, a hydroxyl group, an amino group and a carboalkoxy group,

k is an integer independently selected from 0, 1 to 4;

Such a sensitizer having an anthracene skeleton is also disclosed in Patent Document 5 or 6. When such a sensitizer having an anthracene skeleton is used, the amount thereof is preferably 0.01 to 5 parts by weight per 100 parts by weight of the polysiloxane mixture (I).

In the negative-type photosensitive siloxane composition according to the present invention, a stabilizer may be added if necessary. As the stabilizer, any of the commonly used stabilizer can be selected and used. In the composition according to the present invention, the aromatic amine is preferable because the effect of stabilization is high. Of these aromatic amines, pyridine derivatives are preferred, and particularly those having relatively bulky substituents at the 2-position and 6-position. Specifically, the following may be mentioned.

Method of forming a cured film

The method for forming a cured film according to the present invention comprises coating the above-mentioned negative-type polysiloxane photosensitive composition on the surface of a substrate, and curing the resultant by heating. The method of forming the cured film is described below in the order of steps.

(1) Coating process

First, the above negative-type photosensitive polysiloxane composition is applied to a substrate. Formation of the coating film of the photosensitive polysiloxane composition in the present invention can be carried out by any method known as a coating method of the photosensitive composition. Specifically, it can be arbitrarily selected from immersion coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, and slit coating. As the substrate to which the composition is applied, a suitable substrate such as a silicon substrate, a glass substrate, and a resin film can be used. In these substrates, various semiconductor elements and the like may be formed if necessary. When the substrate is a film, gravure coating is also available. The drying step may be separately provided after application as desired. Further, the coating process may be repeated once or twice or more, if necessary, so that the film thickness of the formed coating film can be made desired.

(2) Prebaking process

It is preferable that the coating film is formed by applying the negative-type photosensitive siloxane composition, and then the coating film is prebaked (preheating treatment) to dry the coating film and reduce the residual amount of the solvent in the coating film. The prebake step is generally carried out at a temperature of 50 to 150 DEG C, preferably 90 to 120 DEG C, for 10 to 300 seconds, preferably 30 to 120 seconds for a hot plate, and 1 to 30 DEG for a clean oven Minute.

(3) Exposure process

After the coating film is formed, the surface of the coating film is irradiated with light. As the light source used for the light irradiation, any one conventionally used for the pattern formation method can be used. Examples of such light sources include lamps such as high-pressure mercury lamps, low-pressure mercury lamps, metal halides, and xenon, laser diodes, and LEDs. As the irradiation light, ultraviolet rays such as g line, h line and i line are usually used. Except ultrafine processing such as semiconductors, it is common to use light of 360 to 430 nm (high-pressure mercury lamp) in the patterning of several 탆 to several tens of 탆. Among them, in the case of a liquid crystal display device, light of 430 nm is often used. In such a case, it is advantageous to combine the sensitizing dye with the negative-working photosensitive siloxane composition of the present invention as described above. The energy of the irradiation light is generally 10 to 2000 mJ / cm 2, preferably 20 to 1000 mJ / cm 2, though it differs depending on the thickness of the light source or the coating film. If the irradiated light energy is lower than 10 mJ / cm 2, sufficient resolution may not be obtained. Conversely, if the irradiation light energy is higher than 2000 mJ / cm 2, the exposure may be excessive and the halation may occur.

Conventional photomasks can be used to irradiate light in a patterned manner. Such a photomask can be arbitrarily selected from well-known ones. The environment at the time of irradiation is not particularly limited, but the ambient atmosphere (in the atmosphere) or a nitrogen atmosphere may be used. When a film is formed on the entire surface of the substrate, the entire surface of the substrate may be irradiated with light. In the present invention, the pattern film also includes a case where a film is formed on the entire surface of the substrate.

(4) Post-exposure heating process

After exposure, Post Exposure Baking may be carried out if necessary in order to accelerate the inter-polymer reaction in the film by the reaction initiator occurring in the exposed portion. This heating treatment is not performed for completely curing the coating film, but is performed so that only a desired pattern is left on the substrate after development, and other parts can be removed by development.

When post-exposure heating is performed, a hot plate, open, or furnace may be used. The heating temperature should not be excessively high since it is not desirable that the acid in the exposed area generated by light irradiation diffuses to the unexposed area. From this viewpoint, the range of the heating temperature after exposure is preferably 40 to 150 DEG C, more preferably 60 to 120 DEG C. In order to control the curing rate of the composition, stepwise heating may be applied if necessary. The atmosphere at the time of heating is not particularly limited, but may be selected from among inert gases such as nitrogen, under vacuum, under reduced pressure, and in oxygen gas, for the purpose of controlling the curing rate of the composition. In addition, the heating time is preferably a predetermined value or more in order to maintain the uniformity of the temperature history in the wafer surface higher, and it is preferable that the heating time is not excessively long in order to suppress diffusion of generated acid. From this viewpoint, the heating time is preferably 20 to 500 seconds, more preferably 40 to 300 seconds.

(5) Development process

After the exposure, if necessary, after the post-exposure heating, the coating film is developed. As the developing solution to be used in development, any developing solution used for development of a conventionally known photosensitive siloxane composition may be used. In the present invention, a TMAH aqueous solution is used to specify the dissolution rate of the polysiloxane, but the developer used to form the cured film is not limited thereto. Preferable examples of the developing solution include alkaline solutions of alkaline compounds such as tetraalkylammonium hydroxide, choline, alkali metal hydroxides, alkali metal metasilicates (hydrates), alkali metal phosphates (hydrates), ammonia, alkylamines, alkanolamines, heterocyclic amines And a particularly preferable alkali developing solution is a tetramethylammonium hydroxide aqueous solution. These alkali developing solutions may further contain a water-soluble organic solvent such as methanol or ethanol or a surfactant, if necessary. The developing method can also be arbitrarily selected by a conventionally known method. Specifically, examples include a method of immersion (dip) into a developing solution, paddle, shower, slit, cap coating, and spraying. A pattern can be obtained by this phenomenon, and it is preferable that washing is carried out after development with the developer.

(6) Heating process

After development, the obtained pattern film is cured by heating. As the heating apparatus used in the heating step, the same ones as those used for post-exposure heating can be used. The heating temperature in this heating step is not particularly limited as long as it is a temperature at which the coating film can be cured, and is usually 150 to 400 占 폚, preferably 200 to 350 占 폚. If the temperature is lower than 150 ° C, unreacted silanol groups may remain. If the silanol group remains, the cured film may not exhibit sufficient chemical resistance or the dielectric constant of the cured film may be increased. From this point of view, the heating temperature is preferably 150 DEG C or higher. The heating time is not particularly limited and is generally 10 minutes to 24 hours, preferably 30 minutes to 3 hours. On the other hand, this heating time is the time after the temperature of the pattern film reaches the desired heating temperature. Usually, it takes several minutes to several hours until the pattern film reaches the desired temperature from the temperature before the heating.

The cured film thus obtained can achieve excellent heat resistance, transparency, relative dielectric constant, and the like. For example, the heat resistance is 400 占 폚 or higher, the light transmittance of the effect film is 95% or higher, and the relative dielectric constant is 4 or lower, preferably 3.3 or lower. As a result, it has a light transmittance and a relative dielectric constant characteristic not found in conventional acrylic materials and can be used as a flattening film for various devices such as a flat panel display (FPD), an interlayer insulating film for low temperature polysilicon or a buffer coating film for IC chips, A transparent protective film or the like.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited by these examples and comparative examples.

<Synthesis Example>

First, synthesis examples of the polysiloxane used in the present invention are shown below. In addition, the following apparatus and conditions were used for measurement.

Gel permeation chromatography was carried out using two HLC-8220 GPC high speed GPC systems (trade name, manufactured by Tosoh Corporation) and a Super Multipore HZ-N type GPC column (trade name, manufactured by Tosoh Corporation). The measurement was carried out under the conditions of a flow rate of 0.6 ml / min and a column temperature of 40 캜 using monodispersed polystyrene as a standard sample and tetrahydrofuran as a developing solvent.

For coating the composition, a spin coater Model MS-A100 (trade name, manufactured by Mikasa Chemical Co., Ltd.) was used, and the thickness of the formed coating film was measured using a film thickness VM-1200 model (trade name, manufactured by Dainippon Screen Chemicals Corporation) Respectively.

&Lt; Synthesis Example 1 (Synthesis of Ia-1) >

36.5 g of a 25 wt% tetramethylammonium hydroxide aqueous solution, 300 ml of isopropyl alcohol (hereinafter referred to as IPA) and 1.5 g of water were mixed in a 2 L flask equipped with a stirrer, a thermometer and a cooling tube to prepare a reaction solvent And kept at 10 ° C. Further, a mixed solution of 44.6 g of phenyltrimethoxysilane, 34.1 g of methyltrimethoxysilane and 3.8 g of tetramethoxysilane was prepared. The mixed solution was added dropwise to the reaction solvent using a dropping funnel at 10 캜, stirred for 2 hours while maintaining the temperature at 10 캜, and then neutralized with 10% aqueous HCl solution. 200 ml of toluene and 300 ml of water were added to the reaction solution, and the mixture was shaken and separated into two layers. The obtained organic layer was concentrated under reduced pressure to remove the solvent, and a solution containing polysiloxane Ia-1 was prepared by adding PGMEA to the concentrate so as to have a solid content concentration of 40% by weight. The average molecular weight (in terms of polystyrene) of the obtained polysiloxane Ia-1 was 2,180. The obtained polysiloxane solution was applied to a silicon wafer and the dissolution rate in 5% TMAH aqueous solution was measured under the above conditions. As a result, it was 2800 Å / sec.

For Synthesis Example 1, various polysiloxane solutions were prepared by changing the compounding ratio of monomers, the mixing ratio of mixed solvents, the reaction time, and the kind of catalyst. On the other hand, a hydrochloric acid aqueous solution was used as an acid catalyst. With respect to the obtained polysiloxane, the average molecular weight and the dissolution rate were measured by the same method. The results obtained are as shown in Table 1.

&Lt; Example 1 (Negative-type photosensitive siloxane composition) >

The polysiloxane mixture was adjusted to a 35 wt% PGMEA solution after mixing in the proportions of polysiloxane (Ia-1) :( Ib-7) = (10 wt%) :( 90 wt%). The dissolution rate of the polysiloxane mixture in a 2.38% TMAH aqueous solution after pre-baking was measured and found to be 105 Å / second. To the siloxane mixture, 1.5% by weight of a photoacid generator A1 (acid-releasing type) capable of functioning by irradiation of g-line or i-line, consisting of triphenylsulfonium cation and sulfonic acid anion, was added to the polysiloxane. 0.3% by weight of KF-53 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a surfactant was added to the polysiloxane to obtain a negative-type photosensitive siloxane composition.

This photosensitive siloxane composition was applied onto a silicon wafer by spin coating, and after the application, it was pre-baked on a hot plate at 100 DEG C for 90 seconds to adjust the film thickness to 2 mu m. After pre-baking, exposure was performed at 220 mJ / cm 2 using a Nikon FX-604 (NA = 0.1) g, h line exposing machine, and baking was performed on the hot plate at 100 캜 for 90 seconds on the hot plate to obtain a 2.38% aqueous TMAH solution For 60 seconds and rinsed with pure water for 30 seconds. As a result, it was confirmed that a 10-μm line-and-space (L / S) pattern and a contact hole (C / H) pattern were drawn without residue or the like. After formation of the pattern, firing was carried out at 250 DEG C, and the pattern was observed with an optical microscope. As a result, a pattern of 10 mu m was maintained. The dielectric constant was measured by a mercury probe method using Solid State Measurements 495. The relative dielectric constant was calculated from the saturation capacitance obtained by carrying out C-V measurement at a measurement frequency of 100 KHz using a mercury probe type capacitance measuring device Model 495 (manufactured by Solid State Instrument). At this time, the preparation of the measurement sample was carried out by coating the photosensitive siloxane composition on a silicon wafer by spin coating, prebaking on a hot plate at 100 캜 for 90 seconds, and adjusting the film thickness to 0.5 탆. Next, the entire exposure was carried out using an exposure amount (220 mJ / cm 2 in the case of Embodiment 1) to be irradiated at the time of pattern formation using a Nikon FX-604 (NA = 0.1) g / h line exposure machine, The plate was baked at 100 ° C for 90 seconds on the plate, immersed in a 2.38% TMAH aqueous solution for 30 seconds, rinsed with pure water, and baked at 250 ° C. The relative dielectric constant of the obtained cured product was 3.0.

Example 2 (Negative-type photosensitive siloxane composition)

The mixing ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-1) :( Ib-8) = (10 wt%) :( 90 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 1. This composition was applied to a substrate as in Example 1 and exposed at 220 mJ / cm 2 to form a pattern. As a result, it was confirmed that a line-and-space pattern and a contact hole pattern of 8 μm were drawn without residue. After formation of the pattern, firing was performed at 250 캜 and confirmed by an optical microscope. As a result, a cylindrical pattern of 8 탆 was maintained.

&Lt; Example 3 (Negative-type photosensitive siloxane composition) >

The compounding ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-2): (Ib-4) = (35 wt%) :( 65 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 1. This composition was applied to a substrate as in Example 1 and exposed to light at 65 mJ / cm 2 to form a pattern. As a result, a line-and-space pattern of 3 탆 and 10 탆 and a contact hole pattern of 3 탆, 5 탆, It was confirmed that it was drawn without any residue in any thing. After forming the pattern, firing was carried out at 250 DEG C and the appearance of each pattern was observed with an optical microscope. Fig. 1 shows an optical microscope photograph of the contact hole. As apparent from Fig. 1, the contact hole pattern of any size was maintained in a good shape.

Example 4 (Negative-type photosensitive siloxane composition)

The compounding ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-3): (Ib-5) = (15 wt%) :( 85 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 1. This composition was applied to a substrate as in Example 1 and exposed to light at 160 mJ / cm 2 to form a pattern. As a result, it was confirmed that a line-and-space pattern and a contact hole pattern of 6 μm were drawn without residue. After formation of the pattern, firing was carried out at 250 캜 and confirmed by an optical microscope. As a result, a pattern of 6 탆 was maintained well.

&Lt; Example 5 (Negative-type photosensitive siloxane composition) >

The mixing ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-3) :( Ib-6) = (15 wt%) :( 85 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 1. This composition was applied to a substrate as in Example 1 and exposed to light at 160 mJ / cm 2 to form a pattern. As a result, it was confirmed that a line-and-space pattern and a contact hole pattern of 6 μm were drawn without residue. After formation of the pattern, firing was carried out at 250 캜 and confirmed by an optical microscope. As a result, a pattern of 6 탆 was maintained well.

&Lt; Example 6 (Negative-type photosensitive siloxane composition) >

The mixing ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-2): (Ib-1) = (60 wt%) :( 40 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 1. This composition was applied to a substrate as in Example 1 and exposed to light at 105 mJ / cm 2 to form a pattern. As a result, it was confirmed that a 6-μm line-and-space pattern and a contact hole pattern were drawn without residue. After formation of the pattern, firing was performed at 250 캜, and the result was confirmed by an optical microscope. As a result, a good shape was maintained to the degree of rounding, and a pattern of 6 탆 was maintained.

Example 7 (Negative-type photosensitive siloxane composition)

The compounding ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-2) :( Ib-2) = (60 wt%) :( 40 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 1. This composition was applied to a substrate as in Example 1 and exposed to light at 105 mJ / cm 2 to form a pattern. As a result, it was confirmed that a 6-μm line-and-space pattern and a contact hole pattern were drawn without residue. After formation of the pattern, firing was performed at 250 캜, and the result was confirmed by an optical microscope. As a result, a good shape was maintained to the degree of rounding, and a pattern of 6 탆 was maintained.

&Lt; Example 8 (Negative-type photosensitive siloxane composition) >

The mixing ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-2) :( Ib-3) = (60 wt%) :( 40 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 1. This composition was applied to a substrate as in Example 1 and exposed to light at 110 mJ / cm 2 to form a pattern. As a result, it was confirmed that a line-and-space pattern and a contact hole pattern of 6 mu m were drawn without residue. After formation of the pattern, firing was performed at 250 캜, and the result was confirmed by an optical microscope. As a result, a good shape was maintained to the degree of rounding, and a pattern of 6 탆 was maintained.

&Lt; Example 9 (Negative-type photosensitive siloxane composition) >

The compounding ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-2): (Ib-4) = (35 wt%) :( 65 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

1.5% by weight of NCB-101 (B1, base releasing type) manufactured by Midori Kagaku Co., Ltd. as a photobase generator was added to this polysiloxane mixture in an amount of 1.5% by weight based on the total weight of the polysiloxane, and Anthracure UVS-1331 (trade name, (Manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.3 wt% of KF-53 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a surfactant were added to prepare a negative-type photosensitive siloxane composition. This composition was applied to a substrate as in Example 1 and exposed to light at 108 mJ / cm 2 to form a pattern. As a result, it was confirmed that a line-and-space pattern and a contact hole pattern of 4 μm were drawn without residue. After formation of the pattern, firing was carried out at 250 캜 and confirmed by an optical microscope. As a result, a pattern of 4 탆 was maintained well.

&Lt; Example 10 (Negative-type photosensitive siloxane composition) >

The compounding ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-2) :( Ib-4) = (60 wt%) :( 40 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 1. This composition was formed into a coating of 0.5 mu m in the same manner as in Example 1 and exposed at 109 mJ / cm &lt; 2 &gt; to form a pattern. As a result, a line and space pattern and a contact hole pattern of 4 mu m . After formation of the pattern, firing was carried out at 250 캜 and confirmed by an optical microscope. As a result, a pattern of 4 탆 was maintained well.

Example 11 (Negative-type photosensitive siloxane composition)

The mixing ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-2): (Ib-6) = (25 wt%) :( 75 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 1. This composition was formed into a 0.2 mu m film by the same method as in Example 1 and exposed at 60 mJ / cm &lt; 2 &gt; to form a pattern. As a result, a 3 mu m line and space pattern and a contact hole pattern were drawn without residue . After formation of the pattern, firing and curing were performed at 250 DEG C, and the result was confirmed by an optical microscope. As a result, a pattern of 3 mu m was maintained satisfactorily.

&Lt; Example 12 (Negative-type photosensitive siloxane composition) >

The compounding ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-2): (Ib-4) = (35 wt%) :( 65 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 1. A coating film having a thickness of 5 mu m was formed by the same method except that the composition was changed to a curing temperature of 110 DEG C for Example 1, and a pattern was formed by exposure at 165 mJ / cm2. As a result, a line- It was confirmed that the contact hole pattern was drawn without residue or the like. After formation of the pattern, firing was carried out at 250 캜, and the result was confirmed by an optical microscope. As a result, a pattern of 5 탆 was maintained well.

&Lt; Example 13 (Negative-type photosensitive siloxane composition) >

The polysiloxane mixture was adjusted to a 20% PGMEA solution after mixing in the proportions of polysiloxane (Ia-2) :( Ib-4) = (30 wt%) :( 70 wt%). The dissolution rate of this polysiloxane mixture in a 2.38% TMAH aqueous solution after pre-baking was measured and found to be 1,800 Å / second. To the siloxane mixture, 2.0% by weight based on the polysiloxane was added a photoacid generator (A2, acid-releasing type) capable of functioning by g-line or i-line irradiation, which was composed of a cationic sulfonium salt and an anionic addition salt. 0.3% by weight of KF-53 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a surfactant was added to the polysiloxane to obtain a negative-type photosensitive siloxane composition.

This photosensitive siloxane composition was applied on a silicon wafer by spin coating, and after the application, it was prebaked on a hot plate at 100 DEG C for 90 seconds to adjust the film thickness to 1.5 mu m. After pre-baking, the film was exposed at 40 mJ / cm 2 using a Nikon FX-604 (NA = 0.1) g / h exposure apparatus and baked at 100 ° C on a hot plate for 90 seconds to obtain a 2.38% aqueous solution of TMAH For 60 seconds and rinsed with pure water for 30 seconds. As a result, it was confirmed that a line-and-space (L / S) pattern and a contact hole (C / H) pattern of 3 mu m were drawn without residue or the like. After formation of the pattern, firing and curing were carried out at 350 DEG C, and the pattern was observed with an optical microscope. As a result, a pattern of 3 mu m was maintained.

&Lt; Example 14 (Negative-type photosensitive siloxane composition) >

The polysiloxane mixture was adjusted to a 20% PGMEA solution after mixing in the proportions of polysiloxane (Ia-2) :( Ib-4) = (35 wt%) :( 65 wt%). The dissolution rate of the polysiloxane mixture in a 2.38% TMAH aqueous solution after pre-baking was measured and found to be 1525 Å / second. The same additives as in Example 13 were added to the siloxane mixture to obtain a negative-type photosensitive siloxane composition.

This photosensitive siloxane composition was applied on a silicon wafer by spin coating, and after the application, it was prebaked on a hot plate at 100 DEG C for 90 seconds to adjust the film thickness to 1.0 mu m. After pre-baking, exposure was performed at 30 mJ / cm 2 using a Nikon FX-604 (NA = 0.1) g, h line exposing machine and baking was performed on the hot plate at 100 캜 for 90 seconds. For 60 seconds and rinsed with pure water for 30 seconds. As a result, it was confirmed that a line-and-space (L / S) pattern and a contact hole (C / H) pattern of 3 mu m were drawn without residue or the like. After formation of the pattern, firing and curing were carried out at 350 DEG C, and the pattern was observed with an optical microscope. As a result, a pattern of 3 mu m was maintained.

Example 15 (Negative-type photosensitive siloxane composition)

The polysiloxane mixture was adjusted to a 20% PGMEA solution after mixing in the proportions of polysiloxane (Ia-1) :( Ib-1) = (70 wt%) :( 30 wt%). The dissolution rate of the polysiloxane mixture in a 2.38% TMAH aqueous solution after pre-baking was measured and found to be 1,500 Å / second. The same additives as in Example 13 were added to the siloxane mixture to obtain a negative-type photosensitive siloxane composition.

The composition was coated on a substrate and cured at 100 占 폚 to form a coating of 1.0 占 퐉 and exposed at 50 mJ / cm2 to form a pattern. As a result, a 3 占 퐉 line and space pattern and a contact hole pattern were drawn without residue . After formation of the pattern, firing and curing were performed at 350 占 폚, and the result was confirmed by an optical microscope. As a result, a pattern of 3 占 퐉 was maintained well.

&Lt; Example 16 (Negative-type photosensitive siloxane composition) >

The polysiloxane mixture was adjusted to a 40% PGMEA solution after mixing in the proportions of polysiloxane (Ia-1) :( Ib-1) = (60 wt%) :( 40 wt%). The dissolution rate of the polysiloxane mixture in a 2.38% TMAH aqueous solution after pre-baking was measured and found to be 3,000 Å / second. The same additives as in Example 13 were added to the siloxane mixture to obtain a negative-type photosensitive siloxane composition.

This composition was coated on a substrate and cured at 100 占 폚 to form a 3.0 占 퐉 coating film and exposed at 120 mJ / cm2 to form a pattern. As a result, a 3 占 퐉 line and space pattern and a contact hole pattern were drawn without residue . After formation of the pattern, firing and curing were performed at 350 占 폚, and the result was confirmed by an optical microscope. As a result, a pattern of 3 占 퐉 was maintained well.

&Lt; Example 17 (Negative-type photosensitive siloxane composition) >

The polysiloxane mixture was adjusted to a 20% PGMEA solution after mixing in the proportions of polysiloxane (Ia-1) :( Ib-2) = (60 wt%) :( 40 wt%). The dissolution rate of this polysiloxane mixture in a 2.38% TMAH aqueous solution after pre-baking was measured and found to be 1,700 Å / sec. The same additives as in Example 13 were added to the siloxane mixture to obtain a negative-type photosensitive siloxane composition.

The composition was coated on a substrate and cured at 100 占 폚 to form a coating of 1.0 占 퐉 and exposed at 50 mJ / cm2 to form a pattern. As a result, a 3 占 퐉 line and space pattern and a contact hole pattern were drawn without residue . After formation of the pattern, firing and curing were performed at 350 占 폚, and the result was confirmed by an optical microscope. As a result, a pattern of 3 占 퐉 was maintained well.

&Lt; Example 18 (Negative-type photosensitive siloxane composition) >

The polysiloxane mixture was adjusted to a 20% PGMEA solution after mixing in the proportions of polysiloxane (Ia-4) :( Ib-9) = (10 wt%) :( 90 wt%). The dissolution rate of the polysiloxane mixture in a 2.38% TMAH aqueous solution after pre-baking was measured and found to be 1,220 Å / second. The same additives as in Example 13 were added to the siloxane mixture to obtain a negative-type photosensitive siloxane composition.

The composition was coated on a substrate and cured at 100 占 폚 to form a coating of 1.0 占 퐉 and exposed at 35 mJ / cm2 to form a pattern. As a result, a 10 占 퐉 line-and-space pattern and a contact hole pattern were drawn without residue . After the pattern formation, plastic curing was performed at 350 占 폚 and examination by an optical microscope revealed that a slight thermal deflection was observed, but a pattern of 10 占 퐉 was maintained.

Such a composition having a relatively large thermal deflection is effective when used as an insulating film for covering an element or the like described in the base.

Example 19 (Negative-type photosensitive siloxane composition)

The polysiloxane mixture was mixed with a mixture of polysiloxane (Ia-2) :( Ib-4) = (30 weight%) :( 70 weight%), and the polysiloxane mixture was adjusted to 35% ethyl lactate (hereinafter referred to as EL) . The dissolution rate of this polysiloxane mixture in a 2.38% TMAH aqueous solution after pre-baking was measured and found to be 1,800 Å / second. The same additives as in Example 13 were added to the siloxane mixture to obtain a negative-type photosensitive siloxane composition.

This composition was coated on a substrate and cured at 100 占 폚 to form a coating of 2.0 占 퐉 and exposed at 55 mJ / cm2 to form a pattern. As a result, a 4 占 퐉 line and space pattern and a contact hole pattern were drawn without residue . After formation of the pattern, firing and curing were carried out at 200 占 폚 and examination by an optical microscope revealed that a pattern of 4 占 퐉 was maintained well.

&Lt; Example 20 (Negative-type photosensitive siloxane composition) >

Except that 1.0% by weight of X-12-967C (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to the composition of Example 13 relative to the total weight of the polysiloxane mixture as the silane coupling agent, the negative-type photosensitive siloxane A composition was obtained.

This composition was coated on a substrate and cured at 100 占 폚 to form a film of 2.0 占 퐉 and exposed at 30 mJ / cm2 to form a pattern. As a result, a line-and-space pattern and a contact hole pattern of 5 占 퐉 were drawn without residue . After the pattern formation, plastic curing was carried out at 350 占 폚, and the result was confirmed by an optical microscope. As a result, a pattern of 5 占 퐉 was maintained well. As a result of evaluating the sensitivity of the formed film, it was found that the film was further improved in Example 13.

Example 21 (Negative-type photosensitive siloxane composition)

To the composition of Example 13, 0.3% by weight of 2,6-di-tert-butyl-4-methylpyridine (manufactured by TOKYO KASEI KOGYO KABUSHIKI KAISHA) was added as an amine-based additive to the total weight of the polysiloxane mixture, A negative photosensitive siloxane composition was obtained.

The composition was coated on a substrate and cured at 100 占 폚 to form a film of 2.0 占 퐉 and exposed at 35 mJ / cm2 to form a pattern. As a result, a line-and-space pattern and a contact hole pattern of 5 占 퐉 were drawn without residue . After the pattern formation, plastic curing was carried out at 350 占 폚, and the result was confirmed by an optical microscope. As a result, a pattern of 5 占 퐉 was maintained well. Further, as a result of evaluation of the storage stability at 40 캜, it was found that although it was slight, it was further improved in Example 13.

&Lt; Example 22 >

An antioxidant composition was prepared in the same manner as in Example 13 except that ANTHRACURE UVS-1331 (trade name, manufactured by Kawasaki Kasei Kogyo K.K.) as a sensitizer and a photoacid generator in which an anion moiety was an iodonium salt as a photoacid generator and an anion moiety was a borate, By weight based on the total weight of the polysiloxane mixture, and 4.0% by weight and 0.5% by weight, respectively, to obtain a negative-working photosensitive siloxane composition.

This composition was coated on a substrate and cured at 100 占 폚 to form a coating of 1.5 占 퐉 and exposed at 35 mJ / cm2 to form a pattern. As a result, a line-and-space pattern and a contact hole pattern of 5 占 퐉 were drawn without residue . After the pattern formation, plastic curing was carried out at 350 占 폚, and the result was confirmed by an optical microscope. As a result, a pattern of 5 占 퐉 was maintained well. The formed film was evaluated for its pattern shape using an optical microscope. As a result, it was found that a pattern was obtained moderately rounded.

&Lt; Comparative Example 1 &

The compounding ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-x) :( Ib-1) = (35 wt%) :( 65 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 1. This composition was applied to a substrate as in Example 1 and exposed to light at 20 mJ / cm 2 to form a pattern. As a result, a line-and-space pattern of 3 μm and 10 μm and a contact hole pattern of 3 μm, 5 μm, . After forming the pattern, firing was performed at 250 캜 and confirmed by an optical microscope. Fig. 2 shows an optical microscope photograph of the contact hole pattern. As apparent from Fig. 2, in Comparative Example 1, thermal deflection occurred, and no shape of the contact hole pattern, the line and space pattern was maintained.

&Lt; Comparative Example 2 &

The compounding ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-y): (Ib-x) = (10 wt%) :( 90 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 1. This composition was applied to a substrate as in Example 1, exposed at an exposure amount of 500 mJ / cm 2 or more, baked for 90 seconds on a hot plate at a temperature of 100 캜 on a hot plate, and developed with a 2.38% TMAH aqueous solution for 60 seconds. And rinsed with pure water for 30 seconds. As a result, due to lack of sensitivity, the pattern could not be described.

&Lt; Comparative Example 3 &

The compounding ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-y) :( Ib-y) = (10 wt%) :( 90 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 1. This composition was applied to a substrate as in Example 1, exposed at an exposure amount of 500 mJ / cm 2 or more, baked for 90 seconds on a hot plate at a temperature of 100 캜 on a hot plate, and developed with a 2.38% TMAH aqueous solution for 60 seconds. And rinsed with pure water for 30 seconds. As a result, due to lack of sensitivity, the pattern could not be described.

&Lt; Comparative Example 4 &

The compounding ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-z) :( Ib-2) = (60 wt%) :( 40 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 1. This composition was applied to a substrate as in Example 1 and exposed to light at 155 mJ / cm 2 to form a pattern. As a result, it was confirmed that a line-and-space pattern and a contact hole pattern of 6 μm were formed, but a lot of scum and residue remained .

&Lt; Comparative Example 5 &

The compounding ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-z) :( Ib-4) = (30 wt%) :( 70 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 1. This composition was applied to a substrate as in Example 1 and exposed to light at 150 mJ / cm 2 to form a pattern. As a result, it was confirmed that a line-and-space pattern and a contact hole pattern of 6 μm were formed, but a lot of scum and residue remained .

&Lt; Comparative Example 6 >

The compounding ratio of the polysiloxane mixture to the polysiloxane mixture used in Example 1 was changed to polysiloxane (Ia-z) :( Ib-4) = (30 wt%) :( 70 wt%) and the dissolution rate of the polysiloxane mixture was evaluated .

A negative-type photosensitive siloxane composition was prepared as in Example 9. This composition was applied to a substrate as in Example 1 and exposed to light at 195 mJ / cm 2 to form a pattern. As a result, it was confirmed that a 6-μm line-and-space pattern and a contact hole pattern were formed. .

The results of the respective Examples and Comparative Examples were as shown in Table 2.

Claims (15)

(I) (Ia) a polysiloxane obtained by hydrolyzing and condensing a silane compound (ia) selected from the group consisting of trialkoxysilane and tetraalkoxysilane in the presence of a basic catalyst, wherein the film after prebaking contains 5 wt% A polysiloxane soluble in an aqueous tetramethylammonium hydroxide solution and having a dissolution rate of 3,000 A / sec or less, and
(Ib) a polysiloxane obtained by hydrolysis / condensation of a silane compound (ib) selected from the group consisting of trialkoxysilane and tetraalkoxysilane in the presence of an acidic or basic catalyst, wherein 2.38% by weight of tetramethyl Lt; RTI ID = 0.0 &gt; / sec &lt; / RTI &gt; to an aqueous solution of ammonium hydroxide,
, &Lt; / RTI &gt;
(II) a curing aid capable of generating an acid or base with heat or radiation, and
(III) Solvent
Wherein the negative-type photosensitive polysiloxane composition is a negative-type photosensitive polysiloxane composition. The negative-working photosensitive polysiloxane composition according to claim 1, wherein at least one of the silane compound (ia) and the silane compound (ib) is represented by the following formula (i).
(I)
R ¹ _n Si (OR ² ) _4-n
In the above formula (i)
R ¹ is a linear, branched or cyclic alkyl group of 1 to 20 carbon atoms in which arbitrary methylene may be substituted with oxygen or an aryl group of 6 to 20 carbon atoms in which arbitrary hydrogen may be substituted by fluorine,
n is 0 or 1,
R ² is an alkyl group having 1 to 5 carbon atoms. 3. The negative-working photosensitive siloxane composition according to claim 1 or 2, wherein the weight ratio of polysiloxane (Ia) / polysiloxane (Ib) contained in the polysiloxane mixture (I) is 1/99 to 80/20. 3. The negative-working photosensitive siloxane composition of claim 1 or 2, wherein the dissolution rate of the film after pre-baking of the polysiloxane mixture (I) in an aqueous 2.38 wt% tetramethylammonium hydroxide solution is 50 to 3,000 A / sec. The positive photosensitive resin composition according to any one of claims 1 to 3, which comprises 0.1 to 40 mol% of a monomer unit derived from tetraalkoxysilane based on the total amount of the monomer units contained in the polysiloxane mixture (I) Siloxane composition. 3. The negative-working photosensitive siloxane composition according to claim 1 or 2, which contains 0.001 to 10 parts by weight of a curing aid for 100 parts by weight of the polysiloxane mixture (I). delete The negative photosensitive composition according to claim 1 or 2, further comprising an additive selected from the group consisting of a adhesion enhancer, a polymerization inhibitor, a defoamer, a surfactant, a photosensitizer, and a stabilizer. A negative-working photosensitive siloxane composition according to any one of claims 1 to 3, which is applied to a substrate to form a coating film, exposing the coating film to light, and heating the negative-type photosensitive siloxane composition. A cured film formed from the negative-type photosensitive siloxane composition according to claim 1 or 2. An element (element) comprising the cured film according to claim 10. The negative photoresist composition according to claim 1 or 2, wherein the curing assistant is a negative acid generator selected from a diazomethane compound, a diphenyliodonium salt, a triphenylsulfonium salt, a sulfonium salt, an ammonium salt, a phosphonium salt and a sulfonimide compound, Type photosensitive siloxane composition. 4. The negative-working photosensitive siloxane composition of claim 3, wherein the dissolution rate of the film after prebaking of the polysiloxane mixture (I) in an aqueous 2.38 wt% tetramethylammonium hydroxide solution is 50 to 3,000 A / sec. 4. The negative-working photosensitive siloxane composition according to claim 3, which contains 0.1 to 40 mol% of a monomer unit derived from tetraalkoxysilane based on the total amount of the monomer units contained in the polysiloxane mixture (I). 5. The negative-working photosensitive siloxane composition according to claim 4, which contains 0.1 to 40 mol% of a monomer unit derived from tetraalkoxysilane based on the total amount of the monomer units contained in the polysiloxane mixture (I).

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