KR20140104355A - Negative-type photosensitive siloxane composition - Google Patents

Abstract

Provided is a photosensitive siloxane composition which has high resolution, high thermal resistance, and high transparency; easily controls heat sagging occurring during heat curing while not increasing the molecular weight of a crosslinking agent and a siloxane compound; and has properties of high sensitivity and a high remaining rate. Provided is a negative type photosensitive polysiloxane characterized by comprising: (I) polysiloxane, (II) an aromatic imide compound releasing an acid by laser irradiation, and (III) a solvent.

Description

NEGATIVE-TYPE PHOTOSENSITIVE SILOXANE COMPOSITION [0002]

The present invention relates to a negative-type 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 a device having the cured film.

2. Description of the Related Art In recent years, various proposals have been made for optical devices such as a display, a light emitting diode, and a solar cell to improve 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 (Refer to Patent Document 1). The structure of the organic electroluminescence element (hereinafter also referred to as organic EL element) may be changed from a method in which a light emitting layer is deposited on a transparent pixel electrode formed on a substrate and light emission is taken out from the substrate side (bottom emission) There has been proposed a method of increasing the aperture ratio similarly to the liquid crystal display by forming the transparent pixel electrode on the flattening film formed on the element and the light emission from the light emitting layer thereon to the side opposite to the TFT element (top emission) 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, even if the response speed is improved by reducing the wiring resistance by extending the wiring board, there is a limit to the extension of the wiring width due to demands such as high resolution. For this reason, it has been proposed to solve the problem of signal delay by increasing the wiring thickness (see Non-Patent Document 1).

As one of the materials of the flattening film for a TFT substrate, a negative photosensitive material mainly comprising a polysiloxane compound and a curing assistant is known. 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 derived from an organic solvent which is produced by the high temperature, and is often an adverse effect on the luminous efficiency and lifetime of the organic EL device, so that it is not an optimal material for use. In addition, the resulting decomposition product may increase the dielectric constant, and the parasitic capacitance due to the insulating film increases. As a result, the power consumption increases, resulting in the delay of the liquid crystal element driving signal, and the quality of the image quality may be deteriorated. Even in an insulating material having a large dielectric constant, for example, the capacitance can be made small by increasing the film thickness. However, it is generally difficult to form a film having a uniform thickness, and the amount of material used is also increased.

A negative photosensitive composition comprising an amorphous polysiloxane compound obtained by polymerizing a silane compound containing a tetrafunctional functional group, for example, a silane compound containing 2 to 4 alkoxy groups from a bifunctional functional group, Since the diffusion is large, the residual film ratio after film formation is very small and the curing rate of the film progresses slowly, so that a large amount of exposure may be required. Further, in order to maintain the pattern shape after firing, more acid generator is required, so that the transmittance tends to decrease significantly (see Patent Document 4).

In addition, conventionally used acid generators, such as ionic acid generators having a sulfonium cation structure, are generally stable at high temperatures and have a thermal decomposition temperature of 350 ° C or higher. Therefore, if the composition containing such an acid generator is cured at a relatively low temperature, even if the curing temperature of the polysiloxane compound is low, there is a possibility that the undissolved product remains at a temperature lower than the decomposition temperature of the acid generator. Such residues have a risk of adversely affecting the light resistance, and therefore, acid generators usable at lower temperatures are desired.

Patent Document 1: Japanese Patent No. 2933879 Patent Document 2: JP-A 2006-236839 Patent Document 3: JP-A-2009-276777 Patent Document 4: JP-A 2006-18249 Patent Document 5: Japanese Patent Publication No. 2006-073021 Patent Document 6: JP-A No. 2011-190333

Non-Patent Document 1: IMID / IDMC / ASIA DISPLAY 2008 Digest (9 pages to 12 pages)

Disclosure of the Invention The present invention has been made based on the above-described circumstances, and an object of the present invention is to provide a high-resolution, high heat resistance, high transparency, A negative photosensitive siloxane composition having a high sensitivity and an acceptance film ratio property in which heat shedding which is liable to occur during thermal curing is suppressed by using a compound is provided. It is another object of the present invention 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 formed from the negative photosensitive siloxane composition and a solid state image pickup device comprising the cured film, , 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) polysiloxane,

(II) an aromatic imide compound which releases an acid by irradiation with radiation, and

(III) Solvent

And a control unit.

The method for producing a cured film according to the present invention comprises coating a substrate with the 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 from 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 a high sensitivity and a 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 deformation. In addition, it has excellent flatness and electrical insulation characteristics, and can be used as a flattening film for a thin film transistor (TFT) substrate or an interlayer insulating film of semiconductor devices used for a back plane 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 film, an optical filter, a high-luminance light emitting diode, a touch panel, a solar cell, or an optical element such as an optical waveguide.

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a diagram showing an ultraviolet visible absorption spectrum of an aromatic imide compound used in Example 1 and Comparative Example 1; FIG.

Negative  Photosensitive Polysiloxane  Composition

The negative-working photosensitive siloxane composition of the present invention is a composition containing a polysiloxane having a specific dissolution rate for a tetramethylammonium hydroxide aqueous solution (hereinafter referred to as a TMAH aqueous solution), a radiation absorbing agent capable of absorbing radiation, particularly light having a wavelength of 405 nm or 436 nm An aromatic imide compound generating an acid, and a solvent. Hereinafter, specific polysiloxanes, aromatic imide compounds, and solvents used in the negative-working photosensitive siloxane composition of the present invention will be described in detail in order.

(I) Polysiloxane

The composition according to the present invention contains polysiloxane as a main component. Polysiloxane refers to a polymer containing a Si-O-Si bond. In the present invention, polysiloxane is also referred to as an unsubstituted inorganic polysiloxane, including an organic polysiloxane substituted by an organic substituent. These polysiloxanes generally have a silanol group or an alkoxysilyl group. These silanol groups and alkoxysilyl groups mean hydroxyl groups and alkoxy groups directly bonded to the silicon forming the siloxane skeleton. Here, it is considered that the silanol group and the alkoxysilyl group have an action of accelerating the curing reaction when the composition is used to form a cured film, and also contribute to the reaction with a silicon-containing compound described later. Therefore, polysiloxane preferably has these groups.

The structure of the polysiloxane used in the present invention is not particularly limited, and any structure may be selected depending on the purpose. The skeleton structure of the polysiloxane has a silicon skeleton (the number of oxygen atoms bonded to silicon atoms is 2), a silsesquioxane skeleton (the number of oxygen atoms bonded to silicon atoms is 3), and a number of oxygen atoms bonded to silica And the skeleton (the number of oxygen atoms bonded to the silicon atom is 4). In the present invention, any of them may be used. Polysiloxane molecules may comprise a plurality of combinations of these backbone structures.

Further, when an organopolysiloxane is used, the substituent contained in the organopolysiloxane can be selected from any one as long as the effect of the present invention is not impaired. Examples of such a substituent include a substituent containing no Si-O bond constituting the siloxane structure, specifically, an alkyl group, an alkenyl group, a hydroxyalkyl group, and an aryl group.

The reactive group other than the silanol group or the alkoxysilyl group such as a carboxyl group, a sulfonyl group, an amino group and the like may be contained in the siloxane resin as long as the effect of the present invention is not impaired. However, It tends to deteriorate the storage stability of the film. Specifically, it is preferably 10 mol% or less with respect to the total number of hydrogen atoms or substituents bonded to the silicon atom, and it is particularly preferable that it is not contained at all.

Further, the composition according to the present invention is for forming a cured film by coating, pattern exposure, and development on a substrate. Therefore, it is necessary that the difference in solubility between the exposed portion and the unexposed portion occurs. In the present invention, a curing reaction takes place in the exposed part, and becomes insoluble in the developer, whereby an image is formed. Therefore, the polysiloxane in the unexposed portion should have a certain solubility to the developer. For example, when the dissolution rate into the aqueous solution of the 2.38% tetramethylammonium hydroxide (hereinafter sometimes referred to as TMAH) aqueous solution is 50 Å / second or more, formation of a negative pattern by exposure-development is possible . However, since the solubility required varies depending on the development conditions, it is necessary to appropriately select the polysiloxane according to the development conditions.

However, when a polysiloxane having a high dissolving speed is simply selected, problems such as a deformation of a pattern shape, a decrease in a residual film ratio, and a decrease in a transmittance may occur. To improve this problem, polysiloxane mixtures combining polysiloxanes having a low dissolution rate can be used.

Such polysiloxane mixtures may, for example,

(Ia) The membrane after prebaking is soluble in an aqueous 5 wt% tetramethylammonium hydroxide solution and has a dissolution rate of 3,000 Å / sec or less and a first polysiloxane

(Ib) of the membrane after pre-baking, the dissolution rate to the 2.38 wt% tetramethylammonium hydroxide aqueous solution is greater than or equal to 150 Å /

. These polysiloxanes will be described.

(a) a first polysiloxane

The first polysiloxane (Ia) is a polysiloxane wherein the membrane after pre-baking is soluble in a 5 wt% aqueous solution of tetramethylammonium hydroxide and has a dissolution rate of generally 3,000 A / sec or less, preferably 2,000 A / sec or less, It alone is poorly soluble in aqueous 2.38% TMAH solution.

The first polysiloxane can be 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 to be used as a raw material may be any arbitrary one. For example, the silane compound 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 represents a linear, branched or cyclic alkyl group of 1 to 20 carbon atoms in which arbitrary methylene may be substituted by 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 represents an alkyl group having 1 to 5 carbon atoms.

In the 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- , A 2-trifluoroethyl group, a 3,3,3-trifluoropropyl group, a cyclohexyl group, a phenyl group, and a tolyl group. Particularly, a compound in which R ¹ is a methyl group is preferable since it is easy to obtain a raw material, has a high film hardness after curing, and has high drug resistance. Further, the phenyl group is preferable because it increases the solubility of the polysiloxane in the solvent and makes cracking of the cured film difficult.

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 included, 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, N-propyltrimethoxysilane, n-butyltrimethoxysilane, n-butyltrimethoxysilane, n-butyltrimethoxysilane, n-butyltrimethoxysilane, n- Butyl triethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trifluoromethyltrimethoxysilane, tri Fluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, and the like. Of these, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are preferred because they are easily available.

Specific examples of the tetraalkoxysilane compound represented by the above formula (i) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and the like. Among them, Tetramethoxysilane, tetraethoxysilane and the like are preferable because of high reactivity.

The silane compound (ia) used in the production of the first polysiloxane (Ia) may be used singly or in combination of two or more. Here, when tetraalkoxysilane is used as the silane compound (ia), pattern sagging tends to be reduced. This is believed to be due to an increase in crosslinking density of the polysiloxane. However, if the blend ratio of tetraalkoxysilane is too large, 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 number of moles of trialkoxysilane and tetraalkoxysilane desirable.

The polysiloxane (Ia) used in the present invention is preferably 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 optionally subjected to purification by neutralization or washing, And then, if necessary, replacing the reaction solvent with the desired organic solvent.

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, propylene glycol 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 singly or in combination. 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 0 to 200 캜, preferably 10 to 60 캜. 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 30 minutes or more. Various conditions in the hydrolysis and condensation reaction can be obtained 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 do.

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 polysiloxane synthesized by using such a base catalyst is characterized by being able to start curing rapidly when a temperature of 150 ° C or higher is applied, and to maintain a clean shape without causing pattern sagging even after firing.

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 less than the above range, the degree of hydrolysis becomes low and formation of a film of the composition becomes difficult, which is undesirable. On the other hand, too much water is not preferable because gelation tends to occur and storage stability is deteriorated. 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 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 neutralized reaction solution may be washed and purified, if 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 stirred, and an organic solvent is contacted with the polysiloxane to dissolve at least the polysiloxane (Ia) in a hydrophobic organic solvent . As the hydrophobic organic solvent, a compound which dissolves the polysiloxane (Ia) and does not miscible with water is used. When the water and the hydrophobic organic solvent are thoroughly mixed and then left standing, it means that they are separated into an aqueous phase and an organic phase.

Preferable examples of the hydrophobic organic solvent include ether solvents such as diethyl ether and the like, ester solvents such as ethyl acetate, alcohol solvents having low solubility in water such as butanol, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, And aromatic solvents such as toluene and xylene. 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 included in the aqueous layer and substantially excluded from the organic layer. The number of rinses can be changed according to necessity.

The temperature at the time of washing is not particularly limited, but is preferably 0 ° C to 70 ° C, and more preferably 10 ° C to 60 ° C. The temperature at which the water phase and the organic phase are separated is not particularly limited, but is preferably 0 ° C to 70 ° C, and more preferably 10 ° C to 60 ° C from the standpoint of shortening the separation time.

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

The reaction solution after washing can be directly added to the composition according to the present invention. However, the concentration can be changed by removing the solvent or the by-product of the remaining reaction, that is, alcohol or water, . Concentration can be carried out under atmospheric 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. In addition, solvent may be substituted by adding a desired solvent in a timely manner so that the desired solvent composition is obtained and further concentrated.

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 is a polysiloxane in which the film after the prebaking is soluble in an aqueous solution of 2.38 wt% tetramethylammonium hydroxide and has a dissolution rate of 150 Å / second or more, preferably 500 Å / second or more.

The polysiloxane (Ib) can be produced 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, the same method as the production method of the polysiloxane (Ia) can be used as the conditions of this production method. However, in addition to the basic catalyst, an acid catalyst can be used as the reaction catalyst. Further, in order to achieve the desired dissolution rate, the conditions such as the amount of the reaction solvent, in particular, the amount of water, the reaction time, and the reaction temperature are appropriately 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), the pattern sagging 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 (1b) 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 the tetraalkoxysilane to the total moles of the silane compounds (ia) and (ib) as the raw materials of the polysiloxanes (Ia) and (Ib) is preferably 1 to 40 mol%, more preferably 1 to 20 mol % 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 suitably selected according to the pH of the reaction solution after the reaction, preferably 0.5 to 1.5 moles, more preferably 1 to 1.1 moles, based on 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 the 2.38% TMAH aqueous solution is required to be 150 angstroms / second or more as described later, and is preferably 500 angstroms / second or more. If the dissolution rate of the polysiloxane (Ib) in the 2.38% TMAH aqueous solution is less than 150 Å / second, the dissolution rate of the mixture of polysiloxane (Ia) and (Ib) in the aqueous 2.38% TMAH solution should be 50 to 5,000 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)

In the present invention, a polysiloxane mixture (I) containing the above polysiloxane (Ia) and polysiloxane (Ib) can be used. The weight ratio of the polysiloxane (Ia) / polysiloxane (Ib) contained in the polysiloxane mixture (I) is preferably 1/99 to 80/20, more preferably 20 / 80 to 50/50.

The dissolution rate of the polysiloxane (Ia) in a 5% aqueous solution of TMAH is 3,000 Å / sec or less and the dissolution rate of polysiloxane (Ib) in a 2.38% aqueous solution of TMAH is 150 Å / 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 from 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 kind and amount of the photosensitizer contained in the negative-type photosensitive siloxane composition. If the film thickness is 0.1 to 10 탆 (1,000 to 100,000 Å), the dissolution rate to the aqueous solution of 2.38% TMAH is preferably 50 to 5000 Å / second.

(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 shale having a diameter of 6 inches in which 100 ml of a predetermined concentration of a TMAH aqueous solution adjusted to 23.0 占 .1 占 폚 had been immersed, and then allowed to stand to stand until the film was lost The time was measured. The dissolution rate is obtained by dividing by the time until the film in the inner portion 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) aromatic Imide  compound

The negative-type photosensitive polysiloxane composition according to the present invention is characterized by using as the photo-acid generator an aromatic imide compound which absorbs radiation to generate an acid. The heat-shedding temperature of an ionic acid generator, for example, a sulfonium compound, which has been conventionally used, is generally 350 ° C or higher, whereas the aromatic imide compound is characterized in that pyrolysis is initiated at a low temperature of about 200 ° C. Therefore, film formation at a temperature lower than that of a composition using a conventional acid generator can be achieved. Such an aromatic imide compound can improve the sensitivity of the curable composition in such a wavelength range since it can generate an acid by absorbing light having a longer wavelength, for example, g line or h line, as compared with a conventional acid generator . In addition, since the aromatic imide compound has a relatively high solubility, the composition is easily prepared, and the compound attached to the cured film can be easily removed by washing. The synthesis of the compound is also simple and preferable from the viewpoint of cost.

In the present invention, among the aromatic imide compounds used as the photoacid generator, those having a structure represented by the following formula (A) are preferred.

(A)

In the above formula (A)

R ¹¹ is an aliphatic group having 1 to 7 carbon atoms, an aromatic group having 6 to 18 carbon atoms, or a group in which a part or all of the hydrogen atoms thereof are substituted with a halogen atom,

And R ¹² are each independently a halogen atom, an aliphatic group having 1 to 10 carbon atoms and an aromatic group having 6 to 18 carbon atoms. The aliphatic group and the aromatic group may be substituted or unsubstituted, may contain a hetero atom,

p each independently represents a number of 0 to 3, the total number of p is 1 or more,

When p is 2 or more, two or more R < ¹² > may be connected to each other to form a cyclic structure.

In formula (A), R ¹¹ represents an aliphatic group having 1 to 7 carbon atoms, an aromatic group having 6 to 18 carbon atoms, or a group in which a part or all of the hydrogen atoms thereof are substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkyl group may be any of straight chain, branched chain and cyclic alkyl groups. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Specific examples of the aryl group include a phenyl group and a tolyl group.

In the formula (A), R ¹² is hydrogen, a halogen atom, an aliphatic group having 1 to 10 carbon atoms and an aromatic group having 6 to 18 carbon atoms, and the aliphatic group and the aromatic group may be substituted or unsubstituted, For example, an oxygen atom, a nitrogen atom, or a sulfur atom. The compound represented by the formula (A) contains at least one substituent R ¹² , and the total amount of p is 1 or more. Two or more R < ¹² > may be connected to each other to form a cyclic structure. When p is 2 or more, it is preferable that each of the two p's is 1 or more.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the aliphatic group include an alkyl group and an alkenyl group, and an alkoxy group substituted with a hetero atom.

As the aliphatic group, an alkyl group having 1 to 10 carbon atoms is preferably used. The alkyl group may be substituted with a halogen atom. Specific examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, trifluoromethyl group and pentafluoroethyl group. An alkoxy group having 1 to 10 carbon atoms or an alkoxy group substituted with a halogen atom may also be used. Specific examples include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, n-amyloxy, Pentafluoroethoxy group and the like.

As the aromatic group, a substituted or unsubstituted phenyl group can be used. Specific examples thereof include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, an o-ethylphenyl group, Propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, a p-methoxyphenyl group, a p-methoxyphenyl group, an o-ethoxyphenyl group, a m-ethoxyphenyl group, a p- (t- (N-propoxy) phenyl group, p- (i-butoxy) phenyl group, p- (P-amyloxy) phenyl group, p- (t-amyloxy) phenyl group, p-chlorophenyl group, p- Bromophenyl group, p-fluorophenyl group, 2,4-dichlorophenyl group, 2,4-dibromophenyl group, 2,4-difluorophenyl group, 2,4,6- A 6-tribromophenyl group, a 2,4,6-trifluorophenyl group, a pentachlorophenyl group, a pent Bromo-phenyl group, a phenyl group, such as p- biphenyl group-pentafluorophenyl. Of these, the phenyl group is most preferable.

As the aromatic group, a substituted or unsubstituted naphthyl group can be used. Specific examples thereof include a naphthyl group, a 2-methyl-1-naphthyl group, a 3-methyl-1-naphthyl group, Methyl-2-naphthyl group, 4-methyl-2-naphthyl group, 4-methyl-2-naphthyl group, Naphthyl group, 6-methyl-2-naphthyl group, 7-methyl-2-naphthyl group and 8-methyl-2-naphthyl group.

In addition, as the aromatic group, a biphenyl group, a trityl group, a styryl group, a diphenylvinyl group, a phenylethynyl group, a naphthyl group, a fluorenyl group, an anthracenyl group, a phenanthryl group and the like may be used. The aryl group containing a hetero atom is not particularly limited, and specific examples include those obtained by converting the following compounds into functional groups.

The substituent R ¹² may include a divalent linking group L and may be bonded to the aromatic imide skeleton of the formula (A) via a linking group L. Herein, L may be selected arbitrarily and may be, for example, an alkylene group, an alkenylene group, an alkynylene group, an ethylene bond, an acetylene bond, an ether bond, an ester bond, a sulfonic acid ester bond, an imide bond, , Or a sulfide bond or the like is used.

The alkylene group is not particularly limited, and specific examples thereof include a methylene group, a methyleneoxymethylene group, a fluoromethylene group, an ethylene group, a propylene group, and a tetramethylene group.

The alkenylene group is not particularly limited, but specific examples thereof include a vinylene group, a 1-methylvinylene group, a propenylene group, a 1-butenylene group, a 2-butenylene group, a 1-pentenylene group, .

The alkynylene group is not particularly limited, but specific examples thereof include an ethynylene group, a propynylene group and a butanylene group.

The linking group L may contain a hetero atom such as an oxygen atom or a sulfur atom, or may be substituted by a halogen atom.

Among the aromatic imide compounds represented by the above formula (A), compounds represented by the following formula (A0) wherein L is an acetylene bond are particularly preferable.

(A0)

In the above formula (A0)

R ^l1 and R ¹² are as defined above.

Among the photoacid generators used in the present invention, the aromatic imide compound represented by the formula (A0) has high sensitivity to the g line (435 nm) and the h line (405 nm) and functions as an acid generator with high efficiency, Can also be used as a good compound.

Among the compounds represented by the above formula (A0), it is preferable that R ¹² is a phenyl group, naphthyl group, anthracenyl group, fluorophenyl group, methylphenyl group, methoxyphenyl group, phenoxyphenyl group, pyridyl group, thienyl group, . Among them, particularly preferred structures include those wherein R ¹² in the above formula (A 0) is substituted with a phenyl group.

Among these compounds, preferred are the following.

These aromatic imide compounds may be used singly or in combination.

The aromatic imide compound can improve the resolution by enhancing the shape of the pattern or raising the contrast of development. The aromatic imide compound used in the present invention is a photo acid generator that releases an acid, which is an active substance that decomposes upon irradiation with radiation to photo-cure the composition. Examples of the radiation used when forming the cured film using the composition of the present invention include visible light, ultraviolet ray, infrared ray, X-ray, electron ray,? -Ray,? -Ray and the like, and are not particularly limited. However, ultraviolet light, particularly g-line (wavelength 436 nm) or h-line (wavelength 405 nm) is preferably used. On the other hand, the aromatic imide compound used in the present invention preferably has a high extinction coefficient in a wavelength range of 400 to 440 nm. Specifically, when the ultraviolet visible absorption spectrum is measured, it is more preferable that the extinction coefficient at a wavelength of 400 to 440 nm is higher than the extinction coefficient at 365 nm. Here, the ultraviolet visible absorption spectrum is measured using dichloromethane as a solvent. The measurement apparatus is not particularly limited, but can be measured using, for example, a Varian Cary 4000 type ultraviolet and visible spectrophotometer (manufactured by Ajinoto Technology Co., Ltd.).

If necessary, photoacid generators other than aromatic imide compounds may be used in combination.

The amount of the aromatic imide compound to be added varies depending on the kind of the active material generated by the decomposition of the compound, the amount of the generated compound, the required sensitivity, and the dissolution contrast of the exposed and unexposed portions, Is 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 too low, and the addition effect may not be obtained. On the other hand, when the addition amount of the aromatic imide compound is more than 10 parts by weight, cracks may be generated in the formed film or the coloration due to decomposition of the aromatic imide compound may become remarkable. Therefore, when the colorless transparency of the film is 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 to a photoresist stripping solution containing a monoethanolamine or the like as a main agent may be lowered.

(III) Solvent

The negative-working photosensitive siloxane composition according to the present invention comprises a solvent. The solvent is not particularly limited as long as it uniformly dissolves or decomposes the polysiloxane, the aromatic imide compound, and the additive agent added as needed. 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 methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, ethyl lactate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate 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 a spray coat, the ratio of the solvent in the negative-working 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 largely vary depending on the amount of the solvent.

(IV) Additive

The negative-type photosensitive siloxane composition according to the present invention may contain other additives as required. 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, crown ethers can be used. As the crown ether, those having the simplest structure are represented by the formula (-CH ₂ -CH ₂ -O-) _n . In the present invention, n is preferably 4 to 7, among them. The crown ether is sometimes referred to as x-crown-y-ether, where x is the total number of atoms constituting the ring and y is the number of oxygen atoms contained therein. 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 preferable crown ethers are 21-crown-7 ether, 18-crown-6-ether, 15-crown-5-ether, 12-crown-4-ether, dibenzo-21- 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 amount thereof is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the polysiloxane.

The adhesion enhancer has an effect of preventing the pattern from being peeled off by the stress applied after firing when the cured film is formed using the negative photosensitive siloxane composition of the present invention. As the adhesion enhancer, imidazoles and silane coupling agents are preferable. Imidazoles include 2-hydroxybenzoimidazole, 2-hydroxyethylbenzoimidazole, benzoimidazole, 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, mercaptosilane coupling agents and the like, which are well known in the art. Specific examples thereof include 3-glycidoxypropyltrimethoxysilane, 3- Propyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane , 3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane and the like are preferable Do. These may be used alone or in combination of two or more, and the addition amount thereof is preferably 0.05 to 15 parts by weight based on 100 parts by weight of the polysiloxane.

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 the single silicon-containing compound has a plurality of acid groups.

Specific examples of such a silane coupling agent include a silane coupling agent represented by the following formula (B):

(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 group, ethyl group, n-propyl group, isopropyl group and n-butyl group. In the formula (A), a plurality of R ³ is included, 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 an acid group such as acetyl, aryl, amyl, benzyl, methoxymethyl , Those protected with mesyl, tolyl, trimethoxysilyl, triethoxysilyl, triisopropylsilyl, or trityl groups, and acid anhydride groups.

Of these, those having a methyl group as R ³ and a carboxylic acid anhydride group as X, for example, silicon containing an acid anhydride group are 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 terminal of the silicon- Polymers containing in the side chain are preferred. Also preferred are compounds obtained by adding acid groups such as thiol, phosphonium, borate, carboxyl, phenol, peroxide, nitro, cyano and sulfo groups to the terminals of dimethylsilicone. Examples of such compounds 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., .

When the silane coupling agent includes a silicon structure, if the molecular weight is too large, the compatibility with the polysiloxane contained in the composition becomes insufficient and the solubility in the developer does not improve, or a reactive group remains in the film, There is a possibility that adverse effects such as the inability to maintain tolerance may occur. 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 polymer having a weight average molecular weight of 1,000 or less, but in the case of a polymer having a silicon structure in other repeating units, the polymer having a weight average molecular weight of 1,000 or more desirable. When an silane compound having an acid group, a siloxane compound or the like is used as the silane coupling agent, the amount of the silane coupling agent is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the polysiloxane.

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

Examples of anti-foaming agent, an alcohol (C _{1 ~ 18),} higher fatty acid ester, polyethylene glycol higher fatty acids such as glycerin mono dilaurate such as oleic acid or stearic acid (PEG) (Mn 200 to 10,000), polypropylene glycol (PPG) ( Mn 200 to 10,000), silicone compounds such as dimethyl silicone oil, alkyl-modified silicone oil and fluorosilicone oil, and organosiloxane-based surfactants to be described in detail below. These may be used singly or in combination of two or more, and the addition amount thereof is preferably 0.1 to 3 parts by weight based on 100 parts by weight of the total of the polysiloxanes.

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, An oxyethylene fatty acid diester, a polyoxy fatty acid monoester, a polyoxyethylene polyoxypyrrole filament block polymer, an acetylene alcohol, an acetylene glycol, an acetylene glycol derivative such as polyethoxylate of acetylene alcohol, a polyethoxylate of acetylene glycol, (Trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Sulfuron (trade name, manufactured by Asahi Glass Co., Ltd.), or organosiloxane (trade name, manufactured by Sumitomo 3M Limited) A surfactant 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 coumarin, ketocoumarin and derivatives thereof, thiopyrylium salt and acetophenone, specifically, p-bis (o-methylstyryl ) Benzene, 7-dimethylamino-4-methylquinolone-2,7-amino-4-methylcoumarin, 4,6-dimethyl- Dihydroxy-4-methylcoumarin, 2,3,5,6-1H, 4H-tetrahydro-8-methylquinolinone- <9,9a, 1 4-trifluoromethylcoumarin, 7-amino-4-trifluoromethylcoumarin, 2,3,5,6-tetramethyluronium coumarin, 6-H, 4H-tetrahydroquinolinone- &lt; 9,9a, 1-gh> coumarin, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, Methylcoumarin, 2,3,5,6-1H, 4H-tetrahydro-9-carbo (2'-N-methylbenzimidazolyl) -7-N, N-diethylaminocoumarin, N-methyl-4-tri 3- (2'-benzimidazolyl) -7-N, N'-tetramethyluronium iodide, fluoromethylpiperidino- <3,2-g> coumarin, 2- (p- dimethylaminostyryl) N-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 dyes enables patterning using a low-cost light source such as a high-pressure mercury lamp (360 to 430 nm). The 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.

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

(C)

In the above formula (C)

R ³¹ each independently represents 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.

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 stabilizing effect is high. Of these aromatic amines, pyridine derivatives are preferred, and particularly those having relatively bulky substituents at the second and sixth positions are preferred. Specific examples thereof include the following.

Cured film  How to form

The method for forming a cured film according to the present invention comprises applying the above negative-type polysiloxane photosensitive composition onto a substrate surface and thermally curing the same. The method of forming the cured film will be 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 may be arbitrarily selected from immersion coating, roll coating, bar coating, brushing, 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 as necessary. When the substrate is a film, gravure coating is also available. The drying process may be separately provided after coating the coating layer 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 prebaked (preheating treatment) in order to dry the coating film after forming the coating film by applying the negative-type photosensitive siloxane composition and to reduce the amount of residual 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, or 1 minute for a clean oven To 30 minutes.

(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 of those 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 mu m to several tens of mu m. In particular, 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 2,000 mJ / cm 2, preferably 20 to 1,000 mJ / cm 2, though it depends on the light source and the film thickness. If the irradiated light energy is lower than 10 mJ / cm 2, sufficient resolution may not be obtained. Conversely, if it is higher than 2,000 mJ / cm 2, excessive exposure may occur and halation may occur.

In order to irradiate light in a pattern shape, a general photomask can be used. Such a photomask can be arbitrarily selected from well-known ones. The environment at the time of irradiation is not particularly limited, but it is generally preferable to use an ambient atmosphere (atmosphere) or a nitrogen atmosphere. When a film is formed on the entire surface of the substrate, it is preferable to perform light irradiation on the entire surface of the substrate. In the present invention, the pattern film 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 to promote the inter-polymer reaction in the film caused by the reaction initiator that has occurred in the exposed portion. This heat treatment is not performed for completely curing the coating film but is carried out so that only a desired pattern remains on the substrate after development and the other portions can be removed by development.

When post-exposure heating is performed, a hot plate, oven, furnace, or the like can 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 point of view, the range of the heating temperature after exposure is preferably 40 占 폚 to 150 占 폚, more preferably 60 占 폚 to 120 占 폚. Staged heating may be applied as needed to control the rate of cure of the composition. 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. The heating time is preferably set to a predetermined value or more in order to maintain the uniformity of the temperature history in the wafer surface, 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 seconds to 500 seconds, more preferably 40 seconds to 300 seconds.

(5) Development process

After the exposure, if necessary, after the post-exposure heating, the coating film is developed. As the developer to be used at the time of development, any developer used in the development of the conventional 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 alkaline developers 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 from a conventionally known method. Specifically, examples of the method include immersion (dip) into a developing solution, paddle, shower, slit, cap coat, spray and the like. It is preferable that washing with water is carried out after development with a developing solution which can obtain a pattern by this phenomenon.

(6) Heating process

After development, the obtained pattern film is cured by heating. As the heating apparatus used in the heating process, the same one as used for post-exposure baking may 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 is 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 chemical resistance of the cured film becomes insufficient, and 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 from 10 minutes to 24 hours, preferably from 30 minutes to 3 hours. The 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 can be 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. Therefore, it has a light transmittance and a relative dielectric constant characteristic which are 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, A film, a transparent protective film, and 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 to these examples and comparative examples.

<Synthesis Example>

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

Gel permeation chromatography was carried out using two HLC-8220 GPC type 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 analytical conditions of monodisperse polystyrene as a standard sample and tetrahydrofuran as a developing solvent at a flow rate of 0.6 ml / min and a column temperature of 40 캜.

For the application of 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.

<Synthesis Example Ia-1>

A reaction solvent was prepared by mixing 36.5 g of a 25 wt% TMAH aqueous solution, 800 ml of isopropyl alcohol (hereinafter referred to as IPA) and 2.0 g of water into a flask equipped with a stirrer, a thermometer and a cooling tube, Respectively. Further, a mixed solution of 39.7 g of phenyltrimethoxysilane, 34.1 g of methyltrimethoxysilane and 7.6 g of tetramethoxysilane was prepared. The mixed solution was added dropwise to the reaction solvent at 10 캜 using a dropping funnel, stirred for 2 hours while maintaining the temperature at 10 캜, and then neutralized with 10% aqueous HCl solution. To the reaction solution, 400 ml of toluene and 100 ml of water were added, shaken, and then separated into two layers. The obtained organic layer was concentrated under reduced pressure to remove the solvent. PGMEA was added to the concentrate so as to have a solid concentration of 40% by weight to prepare a solution containing the polysiloxane (Ia-1). The average molecular weight (in terms of polystyrene) of the obtained polysiloxane (Ia-1) was 2,700. The obtained polysiloxane solution was applied to a silicon wafer, and the dissolution rate in an aqueous solution of 5% TMAH was measured under the above-mentioned conditions, which was 490 Å / second.

&Lt; Synthesis Example Ia-2 >

The siloxane polymer (Ia-2) was obtained in the same manner as above except that the reaction time was changed to 4 hours. The average molecular weight (in terms of polystyrene) of the obtained polysiloxane (Ia-2) was 3,600. The obtained polysiloxane solution was applied to a silicon wafer and the dissolution rate in an aqueous solution of 5% TMAH was measured under the above-mentioned conditions, which was 180 Å / second.

<Synthesis Example Ia-3>

The siloxane polymer (Ia-3) was obtained in the same manner as above except that the reaction time was changed to 6 hours. The average molecular weight (in terms of polystyrene) of the obtained polysiloxane (Ia-3) was 4,900. The obtained polysiloxane solution was applied to a silicon wafer, and the dissolution rate in an aqueous 5% TMAH solution was measured under the above-described conditions, and found to be 70 Å / second.

<Synthesis Example Ib-1>

A reaction solvent was prepared by mixing 54.7 g of a 25 wt% TMAH aqueous solution, 800 ml of IPA and 2.0 g of water into a flask equipped with a stirrer, a thermometer and a cooling tube, and maintained at 10 캜. Further, a mixed solution of 39.7 g of phenyltrimethoxysilane, 34.1 g of methyltrimethoxysilane and 7.6 g of tetramethoxysilane was prepared. The mixed solution was added dropwise to the reaction solvent at 0? 3 占 폚 using a dropping funnel, stirred for 2 hours while keeping the temperature below 5 占 폚, and then neutralized with 10% aqueous HCl solution. To the reaction solution, 400 ml of toluene and 100 ml of water were added, shaken, and then separated into two layers. The obtained organic layer was concentrated under reduced pressure to remove the solvent, and PGMEA was added to the concentrate so as to have a solid concentration of 40% by weight to prepare a solution containing the polysiloxane (Ib-1). The average molecular weight (in terms of polystyrene) of the obtained polysiloxane (Ib-1) was 1,720. The obtained polysiloxane solution was applied to a silicon wafer, and the dissolution rate in a 2.38% TMAH aqueous solution was measured under the above-mentioned conditions, which was 4,830 Å / sec.

<Synthesis Example Ib-2>

The siloxane polymer (Ib-2) was obtained in the same manner as above except that the reaction time was changed to 6 hours. The average molecular weight (in terms of polystyrene) of the obtained polysiloxane (Ib-2) was 2,150. The obtained polysiloxane solution was applied to a silicon wafer, and the dissolution rate in a 2.38% TMAH aqueous solution was measured under the above-described conditions, which was 720 Å / second.

&Lt; Example 1 >

The polysiloxane (Ia-1) and polysiloxane (Ib-1) were mixed at a mixing ratio (30% by weight) :( 70% by weight). The polysiloxane mixture had a dissolution rate of 2.000 A / sec in a 2.38% TMAH aqueous solution after prebaking. This polysiloxane mixture was adjusted to be a 35% PGMEA solution, and 1.0% by weight of the photoacid generator represented by the above formula (A-1) was added to the polysiloxane. Further, KF-53 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a surfactant was added in an amount of 0.3% by weight based on 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 prebaked on a hot plate at 100 DEG C for 90 seconds to adjust the film thickness to 2 mu m. After pre-baking, the film was exposed at 20 mJ / cm 2 using a g-h line exposure machine of an FX-604-type stepper (trade name, manufactured by Nikon Corporation, NA = 0.1), and post-exposure reheating was performed at 100 캜 for 90 seconds Baking was carried out, and the mixture was allowed to stand for 40 seconds in a 2.38% TMAH aqueous solution and rinsed with pure water for 30 seconds. As a result, a line-and-space (L / S) pattern and a contact hole (C / H) pattern of 5 mu m were obtained. It was confirmed that the pattern had no defects such as residues.

After the pattern formation, plastic curing was carried out at 250 DEG C, and a pattern after curing was observed with an optical microscope. As a result, a pattern of 5 mu m was retained.

In addition, the dielectric constant was measured for the pattern obtained from this composition. For the measurement, a 495-type mercury probe Cv measuring device (manufactured by Solid State Co., Ltd.) was used. More specifically, the C-V measurement was carried out by the mercury probe method at a measurement frequency of 100 KHz, and the relative dielectric constant was calculated from the obtained saturation capacitance. A measurement sample for the measurement of the dielectric constant was prepared as follows. The photosensitive siloxane composition was coated on a silicon wafer with a spin coat, pre-baked on a hot plate at 100 DEG C for 90 seconds, and adjusted to a film thickness of 0.5 mu m. Next, using a g-h line exposure machine of an FX-604-type stepper (trade name, manufactured by Nikon Corporation, NA = 0.1), exposure was performed at an exposure amount (20 mJ / After exposure, the post-exposure reheating was baked on a hot plate at 100 占 폚 for 90 seconds, immersed in a 2.38% aqueous TMAH solution for 30 seconds, rinsed with pure water, and baked at 250 占 폚 for 1 hour. The relative dielectric constant of the obtained cured product was 2.9.

&Lt; Example 2 >

A negative-type photosensitive siloxane composition was obtained in the same manner as in Example 1 except that the mixing ratio of the polysiloxane (Ia-1) and the polysiloxane (Ib-1) was changed to (10 wt%) :( 90 wt%). The polysiloxane mixture had a dissolution rate of 4330 Å / sec in a 2.38% TMAH aqueous solution after prebaking.

Using this composition, pattern formation and firing curing were carried out in the same manner as in Example 1 except that the exposure amount was changed to 50 mJ / cm 2. When the obtained pattern was observed, a pattern of 5 mu m was retained. However, as compared with Example 1, the pattern ridge portion had a rounded shape at a level at which no practical problem occurred.

&Lt; Example 3 >

A negative-type photosensitive siloxane composition was obtained in the same manner as in Example 1 except that the mixing ratio of the polysiloxane (Ia-1) and the polysiloxane (Ib-1) was changed to (60 wt%) :( 40 wt%). The polysiloxane mixture had a dissolution rate of 750 angstroms / second in a 2.38% TMAH aqueous solution after prebaking.

Using this composition, a pattern was obtained by changing the development time to 150 seconds and the plastic hardening to 350 占 폚. As a result, a pattern of 5 mu m free of residues was retained.

<Example 4>

Except that the polysiloxane (Ib-2) was used in place of the polysiloxane (Ib-1), and the mixing ratio was changed to (Ia-1) :( Ib-2) = (10 wt%) :( 90 wt%) A negative type photosensitive siloxane composition was obtained in the same manner as in Example 1. The polysiloxane mixture had a dissolution rate of 6.20 A / sec in a 2.38% TMAH aqueous solution after prebaking.

Using this composition, pattern formation and firing and curing were carried out in the same manner as in Example 1, except that the development time was changed to 150 seconds. When the obtained pattern was observed, a pattern of 5 mu m was retained. However, as compared with Example 1, the pattern ridge portion had a rounded shape at a level at which no practical problem occurred.

&Lt; Example 5 >

Except that the polysiloxane (Ia-2) was used in place of the polysiloxane (Ia-1), and the mixing ratio was changed to (Ia-2): (Ib-1) = (25 wt%) :( 75 wt% A negative type photosensitive siloxane composition was obtained in the same manner as in Example 1. The polysiloxane mixture had a dissolution rate of 2105A / sec in a 2.38% aqueous solution of TMAH after prebaking.

Using this composition, pattern formation and firing and curing were carried out in the same manner as in Example 1. Observing the obtained pattern, a pattern of 5 mu m free of residues was retained.

&Lt; Example 6 >

Except that the polysiloxane (Ia-3) was used in place of the polysiloxane (Ia-1) and the mixing ratio was changed to (Ia-3) :( Ib-1) = (15 wt%) :( 85 wt% A negative type photosensitive siloxane composition was obtained in the same manner as in Example 1. The polysiloxane mixture had a dissolution rate of 2175 Å / sec in a 2.38% TMAH aqueous solution after prebaking.

Using this composition, pattern formation and firing and curing were carried out in the same manner as in Example 1. Observing the obtained pattern, a pattern of 5 mu m free of residues was retained.

&Lt; Example 7 >

A negative-type photosensitive siloxane composition was obtained in the same manner as in Example 1 except that the acid generator A-1 was changed to the acid generator A-4.

Using this composition, pattern formation and firing and curing were carried out in the same manner as in Example 1. Observing the obtained pattern, the composition had the same sensitivity as the composition of Example 1, and the pattern of 5 mu m was retained. In addition, it was confirmed that the film loss occurred during the calcination hardening was reduced to a small extent.

&Lt; Example 8 >

 A negative-type photosensitive siloxane composition was obtained in the same manner as in Example 1 except that the acid generator A-1 was changed to the acid generator A-6.

Using this composition, pattern formation and firing and curing were carried out in the same manner as in Example 1 except that the exposure amount was changed to 40 J / cm 2. When the obtained pattern was observed, a pattern of 5 mu m was retained.

&Lt; Example 9 >

Butyl-4-methylpyridine (manufactured by TOKYO KASEI KOGYO Co., Ltd.) as a stabilizer was added to the negative-type photosensitive siloxane compound described in Example 1 in an amount of 0.1 wt% based on the total weight of the polysiloxane mixture, To thereby obtain a negative type photosensitive siloxane composition.

Using this composition, pattern formation and firing and curing were carried out in the same manner as in Example 1. Observing the obtained pattern, the composition had the same sensitivity as the composition of Example 1, and a pattern of 5 mu m was retained. The storage stability of the composition at 40 캜 was evaluated, and it was found that the storage stability of the composition of Example 1 was improved.

&Lt; Example 10 >

A negative-type photosensitive siloxane composition was obtained in the same manner as in Example 1 except that the polysiloxane was changed to only (Ib-2). Using this composition, pattern formation and firing and curing were carried out in the same manner as in Example 1. Observing the obtained pattern, this composition had sensitivity equivalent to that of the composition of Example 1, and also a line-and-space (L / S) pattern and a contact hole (C / H) pattern of 5 mu m were obtained.

&Lt; Comparative Example 1 &

A negative-type photosensitive siloxane composition was obtained in the same manner as in Example 1 except that the acid generator A-1 was changed to the acid generator A-X. The ultraviolet-visible absorption spectrum of the aromatic imide compound used as an acid generator in Example 1 and Comparative Example 1 in dichloromethane was as shown in Fig. The acid generator A-X had a characteristic that it had an absorption peak at a wavelength of 340 nm and hardly absorbed light having a wavelength of 400 nm or more.

Using this composition, the test was carried out in the same manner as in Example 1. The post-exposure reheating was carried out on a hot plate at 100 DEG C for 90 seconds, but the film completely dissolved in the developer and no pattern could be obtained. This is because the photoacid generator does not absorb the light of g and h lines, and no acid is generated by exposure.

Claims (10)

Polysiloxane,
An aromatic imide compound which releases an acid by irradiation with radiation, and
solvent
Wherein the negative-working photosensitive siloxane composition is a negative-working photosensitive siloxane composition. The composition of claim 1, wherein the polysiloxane
(Ia) The membrane after prebaking is soluble in an aqueous 5 wt% tetramethylammonium hydroxide solution and has a dissolution rate of 3,000 Å / sec or less and a first polysiloxane
(Ib) of the membrane after pre-baking, the dissolution rate to the 2.38 wt% tetramethylammonium hydroxide aqueous solution is greater than or equal to 150 Å /
Wherein the negative-type photosensitive siloxane composition is a negative-working photosensitive siloxane composition. 3. The negative-working photosensitive siloxane composition according to claim 1 or 2, wherein the aromatic imide compound is represented by the following formula (A).
(A)

In the above formula (A)
R ¹¹ is an aliphatic group having 1 to 7 carbon atoms, an aromatic group having 6 to 18 carbon atoms, or a group in which a part or all of the hydrogen atoms thereof are substituted with a halogen atom,
And R ¹² are each independently a halogen atom, an aliphatic group having 1 to 10 carbon atoms and an aromatic group having 6 to 18 carbon atoms. The aliphatic group and the aromatic group may be substituted or unsubstituted, may contain a hetero atom,
p each independently represents a number of 0 to 3, the total number of p is 1 or more,
When p is 2 or more, two or more R &lt; ¹² &gt; may be connected to each other to form a cyclic structure. 4. The negative-working photosensitive siloxane composition according to any one of claims 1 to 3, wherein the aromatic imide compound has an extinction coefficient at a wavelength of 400 to 440 nm which is higher than an extinction coefficient at 365 nm. 5. The negative-working photosensitive siloxane composition according to any one of claims 1 to 4, comprising 0.001 to 10 parts by weight of the aromatic imide compound per 100 parts by weight of the polysiloxane. The positive photosensitive resin composition according to any one of claims 1 to 5, further comprising an additive selected from the group consisting of a adhesion enhancer, a polymerization inhibitor, a defoamer, a surfactant, a silane coupling agent, a stabilizer, and a photosensitizer, Type photosensitive siloxane composition. A method for producing a cured film, which comprises coating a substrate with a negative-working photosensitive siloxane composition according to any one of claims 1 to 6 to form a coated film, exposing the coated film to light, and developing. The method for producing a cured film according to claim 7, wherein after the development, the step of curing the coating film is not included. A cured film formed from the negative-working photosensitive siloxane composition according to any one of claims 1 to 8. A device comprising the cured film according to claim 9.

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