TWI611268B - Negative photosensitive decane composition, method for producing cured film, and cured film - Google Patents

Abstract

The subject of the present invention is to provide a photosensitive siloxane composition with high sensitivity and high residual film rate characteristics. The composition has high resolution, high heat resistance, and high transparency, and does not increase the crosslinking agent or the siloxane compound. Molecular weight, and it is possible to suppress thermal sagging which is likely to occur during thermal curing.

The solution of the present invention is a negative-type photosensitive polysiloxane composition, which is characterized by comprising (I) a polysiloxane, (II) an aromatic amidine compound which releases an acid by irradiating radiation, and (III) a solvent.

Description

Negative-type photosensitive silicone composition, method for producing cured film, and cured film

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 negative photosensitive silicone composition, a cured film formed from the negative photosensitive silicone composition, and an element having the cured film.

In recent years, various proposals have been made on optical elements such as displays, light-emitting diodes, and solar cells, with the aim of improving light utilization efficiency or saving energy. For example, it is known that in a liquid crystal display, a transparent planarizing film is formed by covering a thin film transistor (hereinafter referred to as a TFT) element, and a pixel electrode is formed on the planarizing film to improve the display device. A method of numerical aperture (see Patent Document 1). Regarding the structure of an organic electric field light-emitting element (hereinafter referred to as an “organic EL element”), it is also proposed to form a light-emitting layer by vapor deposition on a transparent pixel electrode formed on a substrate. (Emission), in which the light emitted from the transparent pixel electrode covering the planarizing film formed on the TFT element and the light-emitting layer thereon is output on the opposite side of the TFT element (top emission), so that it is the same as the liquid crystal display Method for increasing aperture ratio (refer to Patent Document 2).

In addition, the demand for high-resolution, large-scale, and high-quality displays has increased, and new technology guides such as 3D display have been added. The signal delay on the wiring becomes a problem. By increasing the rewriting speed (frame frequency) of the image information, the input time of the signal to the TFT is shortened. However, even if the response speed is improved by reducing the wiring resistance by expanding the wiring width, there is a limit to the expansion of the wiring width due to requirements such as high resolution. Therefore, there is a proposal to solve the problem of signal delay by increasing the wiring thickness (see Non-Patent Document 1).

One of such planarizing film materials for a TFT substrate is a negative-type photosensitive material mainly composed of a polysiloxane compound and a curing aid. Such a polysiloxane compound is obtained by polymerizing a silane compound having a difunctional functional group, for example, a dialkyldialkoxysilane in the presence of a catalyst. However, in the case of using such a polysiloxane compound, degassing may occur during the film formation process. The gas system generated here is derived from the decomposition of organic groups generated at high temperatures. Since it has many adverse effects on the luminous efficiency or life of the organic EL element, it cannot be said to be the most suitable material for use. In addition, the generated decomposition product may have a high dielectric constant. The parasitic capacitance caused by the insulating film is increased, so the power consumption is increased. As a result, the signal delay of the driving signal of the liquid crystal element is generated. , And cause problems with picture quality. Even for insulating materials with a large dielectric constant, for example, the capacity can be reduced by increasing the film thickness. However, it is often difficult to form a uniform thick film, and the amount of material used is not good (see Patent Document 3). ).

Negative photosensitive composition of a polysiloxane compound containing an amorphous structure obtained by polymerizing a difunctional to tetrafunctional silane compound, for example, a silane compound containing 2 to 4 alkoxy groups Due to the expansion of the molecular weight distribution of polysiloxane compounds, the residual film rate after film formation is lacking, and the hardening rate of the film is also proceeded slowly, so it must be a large amount of exposure. Further, in order to maintain the pattern shape after firing, more acid generators are required, and therefore the transmittance tends to be significantly attenuated (see Patent Document 4).

In addition, previously used acid generators, such as ionic acid generators having a sulfonium cation structure, are generally stable at high temperatures, and most often have a thermal decomposition temperature of 350 ° C or higher. Therefore, if a composition containing such an acid generator is to be cured at a relatively low temperature, even if the curing temperature of the polysiloxane compound is low, as long as the decomposition temperature of the acid generator is below the undecomposed matter, possibility. Since such a residue may cause effects such as deterioration in light resistance, I would like an acid generator that can be used at a lower temperature.

Advance technical literature Patent literature

Patent Document 1 Japanese Patent No. 2933879

Patent Document 2 Japanese Patent Laid-Open No. 2006-236839

Patent Document 3 Japanese Patent Laid-Open No. 2009-276777

Patent Document 4 JP 2006-18249

Patent Document 5 Japanese Re-examined Publication No. 2006-073021

Patent Document 6 Japanese Patent Application Laid-Open No. 2011-190333

Non-patent literature

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

The present invention has been completed based on the above circumstances, and it provides a negative-type photosensitive siloxane composition having high sensitivity and high residual film rate characteristics. The composition has high resolution, high heat resistance, and high transparency. An organic group capable of forming a polymerization site like an acrylfluorene group, and the use of a siloxane compound synthesized by controlling the molecular weight region in a reaction system can suppress heat sagging that easily occurs during thermal curing. Another object of the present invention is to provide a hardened film such as a planarizing film for a TFT substrate, an interlayer insulating film, and the like formed from the negative photosensitive siloxane composition, a solid-state imaging element including the hardened film, and antireflection. Optical elements or semiconductor elements such as thin films, anti-reflection plates, optical filters, high-brightness light-emitting diodes, touch panels, solar cells, and optical waveguides.

The negative-type photosensitive silicone composition of the present invention is characterized by comprising (I) a polysiloxane, (II) an aromatic amidine compound which releases an acid upon irradiation with radiation, and (III) a solvent By.

The method for producing a cured film of the present invention includes applying the negative photosensitive siloxane composition on a substrate to form a coating film, and exposing and heating the coating film.

The cured film of the present invention is characterized by being formed from the negative photosensitive siloxane composition.

In addition, the element of the present invention is characterized by including the cured film.

The negative photosensitive silicone composition of the present invention has high sensitivity and high resolution, and the resulting cured film has excellent heat resistance, chemical resistance, environmental tolerance, transparency, residual film rate, and no heat. Decrease in resolution due to sagging. In addition, since it has excellent flatness and electrical insulation properties, it is used as an interlayer insulation between a planarizing 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, or a semiconductor element. Films, including insulating films or transparent protective films in solid imaging display elements, anti-reflection films, anti-reflection plates, optical filters, high-brightness light-emitting diodes, touch panels, solar cells, etc. Various film-forming materials can be suitably used as optical elements such as optical waveguides.

FIG. 1 shows an ultraviolet-visible absorption spectrum chart of the aromatic fluorene imine compound used in Example 1 and Comparative Example 1. FIG.

[Form of Implementing Invention] Negative-type photosensitive polysiloxane composition

The negative-type photosensitive silicone composition of the present invention is characterized in that it comprises at least: polysiloxane, which has a specific dissolution rate for an aqueous tetramethylammonium hydroxide solution (hereinafter referred to as a TMAH aqueous solution); an aromatic amidine compound As a photoacid generator, it absorbs radiation, especially the wavelength Those that generate acid for 405nm or 436nm light; and solvents. The specific polysiloxane, aromatic sulfonimine compound, and solvent used in the negative-type photosensitive silicone composition of the present invention will be described in detail below in order.

(I) Polysiloxane

The composition of the present invention contains polysiloxane as a main component. Polysiloxane refers to polymers containing Si-O-Si bonds, but in the present invention, in addition to unsubstituted inorganic polysiloxanes, organic polysiloxanes substituted with organic substituents are also called For polysiloxane. Such polysiloxanes generally have a silanol group or an alkoxysilyl group. Such a silanol group and an alkoxysilyl group mean that a hydroxyl group and an alkoxy group are directly bonded to the silicon forming a siloxane skeleton. Here, I think that the silanol group and the alkoxysilyl group not only promote the hardening reaction when the composition is used to form a hardened film, but also contribute to the reaction with the silicon-containing compound described below. Therefore, it is preferable that the polysiloxane has these groups.

The structure of the polysiloxane used in the present invention is not particularly limited, and may be selected from any substance according to the purpose. The skeleton structure of polysiloxanes can be classified into polysiloxane skeletons (the number of oxygen atoms bonded to silicon atoms is 2), and silsesquioxane skeletons (bonded to silicon) according to the number of oxygen atoms bonded to silicon atoms. The number of oxygen atoms of the atom is 3) and the silicon dioxide skeleton (the number of oxygen atoms bonded to the silicon atom is 4). In the present invention, these may be any of them. The polysiloxane molecule may also be a plurality of combinations including these framework structures.

Further, in the case of using an organopolysiloxane, the substituents contained therein may be selected from any substances as long as the effects of the present invention are not impaired. Examples of such a substituent include substituents that do not include a Si—O bond constituting a siloxane structure, and specific examples include an alkyl group, an alkenyl group, a hydroxyalkyl group, and an aryl group.

In addition, as long as the effect of the present invention is not impaired, reactive groups other than the silanol group or the alkoxysilyl group, such as a carboxyl group, a sulfonyl group, and an amine group, may be included in the siloxane resin. Since these reactive groups generally tend to deteriorate the storage stability of the coating composition, those having less reactive groups are preferred. Specifically, it is preferably 10 mol% or less with respect to the total number of hydrogen or substituents bonded to the silicon atom, and it is particularly preferable that all of them are not contained.

In addition, the composition of the present invention is a substance for forming a cured film by coating on a substrate, image-like exposure, and development. Therefore, there must be a difference in solubility between the exposed portion and the unexposed portion. In the present invention, an image is formed by causing a hardening reaction in an exposed portion to become insoluble in a developing solution. Therefore, the polysiloxane in the unexposed portion must have a certain solubility in the developing solution. In my opinion, for example, as long as the formed film has a dissolution rate of a 2.38% tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution of 50 Å / sec or more, formation of a negative pattern of exposure-development can be performed. However, since the solubility required by the development conditions is different, the polysiloxane according to the development conditions should be appropriately selected.

However, if only a polysiloxane having a high dissolution rate is selected, problems such as deformation of a pattern shape, reduction of a residual film rate, and deterioration of transmittance may occur. In order to improve such a problem, a polysiloxane mixture in which a slow-dissolving polysiloxane is combined can be used.

Such a polysiloxane compound, for example, comprises: the first polysiloxane (Ia), wherein the pre-baked film is soluble to a 5% by weight tetramethylammonium hydroxide aqueous solution, and its dissolution rate is 3,000Å / Less than seconds; and Polysiloxane (Ib), in which the pre-baking film has a dissolution rate of a solution of 2.38% by weight of tetramethylammonium hydroxide in water of 150 Å / sec or more.

These polysiloxanes are described below.

(a) First polysiloxane

The first polysiloxane (Ia) is a pre-baked film that is soluble in a 5% by weight tetramethylammonium hydroxide aqueous solution, and its dissolution rate is generally below 3,000 Å / s, preferably below 2,000 Å / s. Polysiloxane alone is insoluble to 2.38% TMAH aqueous solution.

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.

Any silane compound (ia) selected from the group consisting of trialkoxysilane and tetraalkoxysilane used as raw materials can be used, and for example, a compound represented by the following general formula (i) can be used.

R ¹ _n Si (OR ² ) _4-n (i)

(In the formula, R ¹ represents a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms in which any methylene group may be substituted with oxygen, or an arbitrary hydrogen group in which 6 to 20 carbon atoms are substituted with fluorine. Aryl; n is 0 or 1; R ² represents an alkyl group having 1 to 5 carbons).

Examples of R ¹ in the general formula (i) include methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-hexyl, n-decyl, trifluoromethyl, and 2,2 , 2-trifluoroethyl, 3,3,3-trifluoropropyl, cyclohexyl, phenyl, and tolyl. Especially, a compound in which R ¹ is a methyl group is preferable because the raw material is easy to obtain, the hardness of the cured film is high, and the compound has high drug resistance. In addition, phenyl group is preferred because it increases the solubility in the polysiloxane solvent and makes cracking of the cured film difficult.

On the other hand, in the general formula (i), as R ² , for example, methyl, ethyl, n-propyl, isopropyl, n-butyl and the like can be mentioned. In the general formula (i), R ² includes a plurality, but each of R ² may be the same or different.

Specific examples of the trialkoxysilane compound represented by the general formula (i) include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and methylformate. Tritri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n- Propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, phenyltrimethylsilane Oxysilane, phenyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, etc. Among these, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are preferable compounds which are easily available.

In addition, specific examples of the tetraalkoxysilane compound represented by the general formula (i) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxy. Silane and the like, among which tetramethoxysilane and tetraethoxysilane are highly reactive.

The silane compound (ia) used in the production of the first polysiloxane (Ia) may be one kind, or two or more kinds may be used in combination. Here, when tetraalkoxysilane is used as the silane compound (ia), pattern sag tends to be reduced. I think this is due to the increase in the crosslinking density of polysiloxane. However, if the blending ratio of tetraalkoxysilane is too large, the sensitivity may decrease. Therefore, tetraalkoxysilane is used as the raw material of polysiloxane (Ia) In the case, relative to the total mole number of trialkoxysilane and tetraalkoxysilane, the blending ratio is preferably 0.1 to 40 mole%, and more preferably 1 to 20 mole%.

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

For example, a silane compound or a mixture of silane compounds can be dropped into a reaction solvent containing an organic solvent, a basic catalyst, and water, followed by hydrolysis and condensation reaction, and can be purified by using neutralization, washing, or concentration as required. It can be produced by replacing the reaction solvent with a desired organic solvent as required.

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 and propylene glycol monomethyl ethyl acetate Ester-based solvents; alcohol-based solvents such as methanol, ethanol, isopropanol, butanol, and 1,3-dipropanol; ketone-based solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; these organic solvents can be used alone , Or a combination of multiple uses. The amount of the organic solvent used is generally 0.1 to 10 times the weight of the mixed solution of the silane compound, and preferably 0.5 to 2 times the weight.

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 dropped silane compound and the temperature of the reaction solvent may be the same or different. The reaction time varies depending on the type of the silane compound and the like, but it is usually tens of minutes to tens of hours, preferably 30 minutes or more. Various conditions in the hydrolysis and condensation reactions take into consideration the scale of the reaction, the size and shape of the reaction vessel, for example, By setting the amount of the alkaline catalyst, the reaction temperature, the reaction time, and the like, physical properties suitable for the intended use can be obtained.

Examples of basic catalysts include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, and amine groups. Organic bases such as alkoxysilane; inorganic bases such as sodium hydroxide and potassium hydroxide; anion exchange resins or quaternary ammonium salts such as tetrabutylammonium hydroxide, tetraethylammonium hydroxide, and tetramethylammonium hydroxide. The amount of catalyst is preferably 0.0001 to 10 mol times relative to the mixture of silane compounds. The polysiloxane synthesized by using this alkali catalyst is characterized in that the hardening starts to accelerate at a temperature of 150 ° C or higher, and no pattern depression occurs after firing, and the beautiful shape can be maintained.

The degree of hydrolysis can be adjusted by the amount of water added to the reaction solvent. Generally, it is desirable to react water at a ratio of 0.01 to 10 mol times, preferably 0.1 to 5 mol times, relative to the hydrolyzable alkoxy group of the silane compound. When the amount of water added is too small compared with the above range, the degree of hydrolysis is reduced, and the formation of a film of the composition becomes difficult, which is not good. On the one hand, when the amount of water is too large, gelation is liable to occur, and storage stability is poor, which is not good. The water used is preferably ion-exchanged water or distilled water.

After the reaction is completed, the reaction solution may be made neutral or weakly acidic using an acidic compound as a neutralizing agent. Examples of the acidic compounds include inorganic acids such as phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, and hydrofluoric acid, or acetic acid, trifluoroacetic acid, formic acid, lactic acid, acrylic acid, oxalic acid, maleic acid, succinic acid, or citric acid. Polycarboxylic acids and their anhydrides, organic acids such as sulfonic acids such as p-toluenesulfonic acid and methanesulfonic acid. Moreover, you may neutralize using a cation exchange resin.

The amount of the neutralizing agent can be appropriately selected according to the pH of the reaction solution after the reaction, but it is preferably 0.5 to 1.5 mole times, and more preferably 1 to 1.1 mole times, relative to the alkaline catalyst. When a cation exchange resin is used, the number of ionic groups contained in the cation exchange resin is preferably set within this range.

The neutralized reaction solution may be washed or purified according to necessity. The washing method is not particularly limited. For example, a hydrophobic organic solvent is added to the reaction solution after neutralization, and water may be added as needed, and the mixture is stirred. The organic solvent is contacted in the polysiloxane, and at least the polysiloxane (Ia) is dissolved. In hydrophobic organic solvent phase. In this case, as the hydrophobic organic solvent, a compound that dissolves polysiloxane (Ia) and does not mix with water is used. Does not mix with water means that when water and a hydrophobic organic solvent are sufficiently mixed, when they are left to stand, they are separated into an aqueous phase and an organic phase.

Preferred hydrophobic organic solvents include ether solvents such as diethyl ether; ester solvents such as ethyl acetate; alcohol solvents such as butanol which are insoluble in water; methyl ethyl ketone, methyl isobutyl ketone, etc. Ketone solvents; 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, and may be used by mixing two or more kinds. By this washing, most of the alkaline catalyst, neutralizing agent, and salt produced by the neutralization in the reaction process are contained in the water layer as most of the alcohol or water which is a by-product of the reaction. It can be substantially removed from the organic layer. Washing times can be changed as necessary.

The temperature during washing is not particularly limited, but is preferably 0 ° C to 70 ° C, and more preferably 10 ° C to 60 ° C. Separating the water phase and the organic phase The temperature is not particularly limited, but is preferably 0 ° C to 70 ° C, and from the viewpoint of shortening the liquid separation time, more preferably 10 ° C to 60 ° C.

Such washing may improve the coating properties and storage stability of the composition.

The washed reaction solution can also be added to the composition of the present invention as required. The solvent or alcohol or water remaining as a by-product of the reaction can be removed by concentration as required. The concentration can be changed or the solvent can be replaced with another solvent. . When concentration is performed, it can be performed under normal pressure (atmospheric pressure) or reduced pressure, and the degree of concentration can be arbitrarily changed by controlling the amount of distillation. The temperature during concentration is generally 30 to 150 ° C, preferably 40 to 100 ° C. In addition, by adding a desired solvent at an appropriate time and further concentrating, solvent substitution can be performed to obtain a desired solvent composition.

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

(b) Second polysiloxane

The second polysiloxane-based pre-baked film is soluble to a 2.38 wt% tetramethylammonium hydroxide aqueous solution, and its dissolution rate is 150 Å / sec or more, preferably 500 Å / sec or more.

The polysiloxane (Ib) can hydrolyze and condense a silane compound (ib) selected from the group consisting of trialkoxysilane and tetraalkoxysilane in the presence of an acidic or basic catalyst. Manufacturing.

Here, the conditions of this manufacturing method can use the same method as the manufacturing method of a polysiloxane (Ia). However, in the case of a reaction catalyst, an acid catalyst may be used in addition to an alkaline catalyst. In order to achieve the desired dissolution rate, conditions such as the amount of the reaction solvent, particularly the amount of water added, the reaction time, and the reaction temperature can be appropriately adjusted.

The silane compound (ib) may be the same as or different from the silane compound (ia) used as a raw material of the polysiloxane (Ia). When a tetraalkoxysilane is used as the silane compound (ib), the pattern sag tends to be reduced.

In addition, as a raw material of the first polysiloxane (Ia), when a relatively large amount of tetraalkoxysilane is used, as a raw material of the second polysiloxane (Ib), a tetraalkoxysilane is preferred. Those with lower deployment ratios. This is because when the compounding ratio of the tetraalkoxysilane as a whole is high, silane compounds may be precipitated, or the sensitivity of the formed film may be reduced. Therefore, the blending ratio of the tetraalkoxysilane is preferably 1 to 40 moles relative to the total moles of the silane compounds (ia) and (ib) which are the raw materials of the polysiloxanes (Ia) and (Ib). Ear%, more preferably 1 to 20 mole%.

In the production of polysiloxane (Ib), an acidic catalyst can be used as the catalyst. Examples of usable acid catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acids, or anhydrides thereof. The amount of catalyst to be added depends on the strength of the acid, but it is preferably 0.0001 to 10 mol times for the mixture of silane compounds.

In the case of using an acidic catalyst in the production of polysiloxane (Ib), as in the case of using an alkaline catalyst, the reaction solution may be neutralized after completion of the reaction. In this case, a basic compound can be used as a neutralizing agent. Examples of the basic compound used for neutralization include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, or Organic bases such as diethanolamine; inorganic bases such as sodium hydroxide or potassium hydroxide; tetrabutylammonium hydroxide, tetraethylammonium hydroxide, hydroxide Quaternary ammonium salts such as tetramethylammonium. Anion exchange resins can be used. The amount of the neutralizing agent may be the same as that in the case of using an alkaline catalyst. Depending on the pH of the reaction solution after the reaction, it can be appropriately selected, but for acid catalysts, it is preferably 0.5 to 1.5 mole times, and more preferably 1 to 1.1 mole times.

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

The dissolution rate of the polysiloxane (Ib) to a 2.38% TMAH aqueous solution, as described later, must be 150 Å / sec or more, and preferably 500 Å / sec or more. When the dissolution rate of the polysiloxane (Ib) to the 2.38% TMAH aqueous solution is less than 150 Å / s, in order to set the dissolution rate of the mixture of the polysiloxane (Ia) and (Ib) to the 2.38% TMAH aqueous solution to 50 to 5,000 Å / sec. It is necessary to reduce the content of the poorly soluble polysiloxane (Ia) as much as possible. However, when the content of the polysiloxane (Ia) is small, it is difficult to prevent the heat of the pattern from sagging.

(c) Polysiloxane mixture (I)

In the present invention, a polysiloxane mixture (I) containing the above-mentioned polysiloxane (Ia) and polysiloxane (Ib) can be used. The blending ratio of the polysiloxane (Ia) and the polysiloxane (Ib) is not particularly limited, but the polysiloxane (Ia) / polysiloxane contained in the polysiloxane mixture (I) is preferred. The weight ratio of (Ib) is 1/99 to 80/20, and more preferably 20/80 to 50/50.

As long as the dissolution rate of polysiloxane (Ia) to 5% TMAH aqueous solution is below 3,000 Å / sec, and the dissolution rate of polysiloxane (Ib) to 2.38% TMAH aqueous solution is above 150 Å / sec, undissolved residue ( The problem of remaining) or reduced sensitivity is no longer significant, but the thickness of the cured film formed from the negative photosensitive silicone composition of the present invention Or the development time, etc., the dissolution rate of the polysiloxane mixture (I) to a 2.38% TMAH aqueous solution can also be appropriately set. The dissolution rate of the polysiloxane mixture (I) can be adjusted by changing the mixing ratio of the polysiloxanes (Ia) and (Ib), although the type of the photosensitizer contained in the negative-type photosensitive silicone composition is adjusted. Or the addition amount is different. For example, as long as the film thickness is 0.1 to 10 μm (1,000 to 100,000 Å), the dissolution rate is preferably 50 to 5,000 Å / sec with respect to a 2.38% TMAH aqueous solution.

(d) Alkali dissolution rate relative to TMAH aqueous solution

In the present invention, each of the polysiloxanes (Ia) and (Ib) has a specific dissolution rate with respect to the TMAH aqueous solution. The dissolution rate of polysiloxane in a TMAH aqueous solution can be measured as follows. Polysiloxane was diluted to 35% by weight in propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), and dissolved while stirring at room temperature for 1 hour with a stir bar. In a clean room under a temperature of 23.0 ± 0.5 ° C and a humidity of 50 ± 5.0%, use a pipette on a 4-inch silicon wafer with a thickness of 525 μm to drop the prepared polysiloxane solution to 1 cc silicon crystal. The center part of the circle was spin-coated to a thickness of 2 ± 0.1 μm, and the solvent was removed by heating on a hot plate at 100 ° C. for 90 seconds. The thickness of the coating film was measured using a spectroscopic ellipsometer (manufactured by J.A. Woollam).

Thereafter, the silicon wafer having the film was smoothly immersed in a 6-inch glass petri dish having a predetermined concentration of 100 ml of a TMAH aqueous solution adjusted to 23.0 ± 0.1 ° C, and the silicon wafer having the film was allowed to stand and measured until the film disappeared. Time. The dissolution rate is calculated from the time until the end of the wafer is divided by the disappearance of the film on the inner part of 10 mm. When the dissolution rate is significantly slow, the wafer is immersed in TMAH aqueous solution for a certain period of time. Then, by heating on a hot plate at 200 ° C. for 5 minutes to remove the moisture captured in the film during the measurement of the dissolution rate, the film thickness was measured to determine the change in the film thickness before and after the immersion in the immersion time. Remove and calculate the dissolution rate. The above-mentioned measurement method was performed 5 times, and the average of the obtained values was set as the dissolution rate of polysiloxane.

(II) Aromatic amidine compounds

One of the characteristics of the negative-type photosensitive polysiloxane composition of the present invention is the use of an aromatic amidine compound which generates an acid by absorbing radiation as a photoacid generator, which is generated by absorbing radiation as a photoacid generator. acid. Although the previously used ionic acid generators, such as phosphonium salt compounds, generally have a thermal decomposition temperature above 350 ° C, in contrast, aromatic sulfonium imine compounds have the characteristic of starting thermal decomposition at a low temperature of about 200 ° C. . Therefore, it is possible to form a film at a lower temperature than a composition using a conventional acid generator. Next, compared with the previous acid generator, this aromatic sulfonium imine compound can absorb light at a longer wavelength, for example, it can absorb the g-line or h-line to generate an acid, so the hardening composition can be improved in this wavelength region. The sensitivity of things. Furthermore, since the solubility of the aromatic sulfonium imine compound is relatively high, it is easy to prepare the composition, and the compound adhering to the cured film can be easily removed by washing. Next, the synthesis of the compound is simple, and it is preferable from the viewpoint of cost.

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

(In the formula, 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 part or all of these hydrogen atoms are substituted with a halogen atom; R ¹² is each independently a halogen Atoms, aliphatic groups having 1 to 10 carbon atoms, and aromatic groups having 6 to 18 carbon atoms, the aliphatic and aromatic groups may be substituted or unsubstituted, and may also contain heteroatoms; p is independent of each other The ground represents a number from 0 to 3, and the total 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 ring structure.)

In the 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 some or all of the hydrogen atoms 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 a linear, branched, or cyclic alkyl group. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl. Moreover, as an aryl group, specifically, a phenyl group or a tolyl group is mentioned.

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. The aliphatic group and the aromatic group may be substituted or unsubstituted. The hetero atom may contain, for example, an oxygen atom, a nitrogen atom, or a sulfur atom. In addition, p is a number of 1 or more and 0 to 3, and the compound represented by formula (A) contains one or more substituents R ¹² , and the total of p is 1 or more. In addition, two or more R ¹² may be connected to each other to form a ring structure. When p is 2 or more, each of the two ps is preferably 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, an alkenyl group, and the like, and an alkoxy group substituted with a hetero atom.

As the aliphatic group, an alkyl group having 1 to 10 carbon atoms can be preferably used. The alkyl group may be substituted with a halogen atom. Specific examples of such an alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, and isopropyl. Amyl, secondary pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, trifluoromethyl, pentafluoroethyl and the like. Alternatively, an alkoxy group substituted with an alkoxy group having 1 to 10 carbon atoms or a halogen atom may be used. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, n-pentoxy, n-octyloxy, n-decoxy, and trifluoromethoxy And pentafluoroethoxy.

As the aromatic group, a substituted or unsubstituted phenyl group can be used. Specifically, phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, p- (n-propyl) phenyl, p- ( Isopropyl) phenyl, p- (n-butyl) phenyl, p- (isobutyl) phenyl, p- (secondary butyl) phenyl, p- (tertiary butyl) phenyl, p- (n-pentyl) ) Phenyl, p- (isopentyl) phenyl, p- (tertiary pentyl) benzene Methyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-ethoxyphenyl, m-ethoxyphenyl, p-ethoxyphenyl, p- (n-propoxy ) Phenyl, p- (isopropoxy) phenyl, p- (n-butoxy) phenyl, p- (isobutoxy) phenyl, p- (secondary butoxy) phenyl, p- (tertiary butyl) (Oxy) phenyl, p- (n-pentyloxy) phenyl, p- (isopentyloxy) phenyl, p- (tertiary pentyloxy) phenyl, p-chlorophenyl, p-bromophenyl, p-fluorobenzene Group, 2,4-dichlorophenyl, 2,4-dibromophenyl, 2,4-difluorophenyl, 2,4,6-dichlorophenyl, 2,4,6-tribromophenyl , 2,4,6-trifluorophenyl, pentachlorophenyl, pentabromophenyl, pentafluorophenyl, parabiphenylyl, etc. Among these, phenyl is the best.

As the aromatic group, a substituted or unsubstituted naphthyl group can be used. Specifically, naphthyl, 2-methyl-1-naphthyl, 3-methyl-1-naphthyl, 4-methyl-1-naphthyl, 5-methyl-1-naphthyl, 6 -Methyl-1-naphthyl, 7-methyl-1-naphthyl, 8-methyl-1-naphthyl, 1-methyl-2-naphthyl, 3-methyl-2-naphthyl, 4 -Methyl-2-naphthyl, 5-methyl-2-naphthyl, 6-methyl-2-naphthyl, 7-methyl-2-naphthyl, 8-methyl-2-naphthyl, and the like.

In addition, as the aromatic group, biphenyl, trityl, styryl, distyryl, phenylethynyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, and the like can also be used. The aryl group containing a hetero atom is not particularly limited, but specifically, a functional group of the following compounds may be mentioned.

Further, the substituent R ¹² may contain a divalent linking group L, and may be bonded to the aromatic sulfonimide skeleton of the formula (A) via the linking group L. Here, L can be arbitrarily selected, and for example, an alkylene group, an alkenylene group, an alkynyl group, a vinyl bond, an acetylene bond, an ether bond, an ester bond, a sulfonate bond, a fluorenimine bond, and fluorenamine can be used. Bond, azo bond, or sulfido bond.

The alkylene group is not particularly limited, and specific examples include methylene, methoxymethylene, fluoromethylene, ethylene, propyl, and butylene.

There is no particular limitation on the alkenyl group, and specific examples include vinylidene, 1-methyl vinylidene, acrylyl, 1-butenyl, 2-butenyl, 1-butenyl Pentenyl, 2-pentenyl and the like.

The alkynyl group is not particularly limited, and specific examples include ethynyl, propynyl, and butynyl.

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

Among the aromatic sulfonium imine compounds represented by the formula (A), a compound represented by the following formula (A0) in which L is an acetylene bond is particularly preferred.

(Wherein R ¹¹ and R ¹² are as described above).

In the photoacid generator used in the present invention, the aromatic sulfonium imine compound represented by the formula (A0) can also be used as a highly sensitive and efficient acid with respect to the g-line (435 nm) and h-line (405 nm). As a generator, a compound having good solubility in general organic solvents can be used.

In the compound represented by the above formula (A0), R ¹² is phenyl, naphthyl, anthracenyl, fluorophenyl, methylphenyl, methoxyphenyl, phenoxyphenyl, pyridyl, thienyl, etc. The synthetic point of view is better. Among these, particularly preferable structures include those in which R ¹² in the formula (A0) is substituted with a phenyl group.

Among such compounds, the following are preferable.

These aromatic sulfonimine compounds can be used alone or in combination. Aromatic sulfonium imine compounds can improve the resolution by strengthening the pattern shape or enhancing the contrast of development. The aromatic sulfonium imine compound used in the present invention is a photoacid generator that decomposes when irradiated with radiation to release an acid, wherein the acid is an active material that photocures the composition quality. The radiation used in the case of forming a cured film using the composition of the present invention includes visible light, ultraviolet rays, infrared rays, X-rays, electron beams, alpha rays, and gamma rays, and is not particularly limited. However, ultraviolet light, particularly g-line (wavelength 436 nm) or h-line (wavelength 405 nm) can be used as appropriate. On the other hand, the aromatic fluorene imine compound used in the present invention is preferably one having a high absorption coefficient in a wavelength region of 400 to 440 nm. Specifically, in the case of measuring the ultraviolet-visible absorption spectrum, a substance having a higher absorption coefficient at any wavelength of 400 to 440 nm than that at 365 nm is more preferable. The ultraviolet-visible absorption spectrum is measured here using dichloromethane as a solvent. The measurement device is not particularly limited, but it can be measured using, for example, a Varian Cary 4000 UV-visible spectrophotometer (manufactured by Agilent Technologies).

In addition, a photoacid generator other than the aromatic sulfonium imine compound may be used in combination as necessary.

The addition amount of the aromatic sulfonium imine compound is due to the type, amount of active material, and the required sensitivity due to the decomposition of the compound. The dissolution contrast between the exposed and unexposed areas is different. The polysiloxane is preferably 0.001 to 10 parts by weight, and more preferably 0.01 to 5 parts by weight. When the added amount is less than 0.001 parts by weight, the dissolution contrast between the exposed portion and the unexposed portion is too low, and there may be cases where the addition effect is not obtained. On the one hand, when the amount of the aromatic sulfonium imine compound is more than 10 parts by weight, cracks may occur in the formed film, or the coloration due to the decomposition of the aromatic sulfonium imine compound becomes significant, so there will be a coating. The colorless transparency is reduced. In addition, when the amount of addition is increased, the thermal insulation of the hardened material may deteriorate due to thermal decomposition or gas release. Situation where steps become problems. Furthermore, the resistance of the film to a photoresist peeling liquid, such as a monoethanolamine as a main agent, may decrease.

(III) Solvent

The negative-type photosensitive silicone composition of the present invention contains a solvent. The solvent is not particularly limited as long as it is a substance that uniformly dissolves or disperses the aforementioned polysiloxane, aromatic sulfonimide compound, and additives that can be added as needed. Examples of solvents that can be used in the present invention include ethylene glycol such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Monoalkyl ethers; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and other diethylene glycol dialkyl ethers; methyl solvents Cellulose acetate, ethyl cellosolve acetate and other glycol alkyl ether acetates; propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl Propylene glycol alkyl ether acetates such as ether acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as methyl ethyl ketone, acetone, methylpentyl ketone, methyl isobutyl ketone, and cyclohexanone; ethanol , Alcohols such as propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol; esters such as ethyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate; Cyclic esters such as γ-butyrolactone and the like. Among these, propylene glycol alkyl ether acetates or esters are preferably used from the viewpoints of availability, ease of handling, and polymer solubility. These solvents are used singly or in combination of two or more kinds, and the amount used varies depending on the coating method or the thickness of the film after coating.

The solvent content of the negative photosensitive silicone composition can be arbitrarily adjusted in accordance with the method of coating the composition and the like. For example, by spraying When the composition is applied by spray coating, the proportion of the solvent in the negative-type photosensitive silicone composition may be 90% by weight or more. The gap coating used for coating a large substrate is usually 60% by weight or more, and preferably 70% by weight or more. The characteristics of the negative-type photosensitive siloxane composition of the present invention do not vary greatly depending on the amount of the solvent.

(IV) Additives

The negative-type photosensitive siloxane composition of the present invention may contain other additives as required. Examples of such additives include a developer dissolution accelerator, a dross removing agent, an adhesion enhancer, a polymerization inhibitor, a defoaming agent, a surfactant, and a sensitizer.

The developer dissolving accelerator or the dross removing agent adjusts the solubility of the developing solution of the formed film, and has a function of preventing dross from remaining on the substrate after development. As such an additive, crown ether can be used. As the crown ether, a substance having the simplest structure is represented by the general formula (-CH ₂ -CH ₂ -O-) _n . Among the preferable ones in the present invention are those in which n is 4 to 7. The total number of atoms constituting the ring of the crown ether is x, and the number of oxygen atoms contained therein is y, which is called x-crown-y-ether. In the present invention, crown ethers of x = 112, 15, 18 or 21, and y = x / 3 are preferred, and those selected from the group consisting of these benzocondensates and cyclohexyl condensates. Specific examples of more preferable crown ethers include 21-crown-7-ether, 18-crown-6-ether, 15-crown-5-ether, 12-crown-4-ether, and dibenzo-21-crown-7. -Ether, dibenzo-18-crown-6-ether, dibenzo-15-crown-5-ether, dibenzo-12-crown-4-ether, dicyclohexyl-21-crown-7-ether , Dicyclohexyl-18-crown-6-ether, dicyclohexyl-15-crown-5-ether and dicyclohexyl-12-crown-4-ether. In the present invention, these are most preferably selected from the group consisting of 18-crown-6-ether and 15-crown-5-ether. For 100 parts by weight of polysiloxane, the addition amount is preferably 0.05 to 15 parts by weight, and more preferably 0.1 to 10 parts by weight.

When the adhesion-enhancing agent is used to form a cured film using the negative photosensitive siloxane composition of the present invention, it has an effect of preventing pattern peeling due to the stress applied after firing. In terms of adhesion enhancers, imidazoles or silane coupling agents are preferred. Among imidazoles, 2-hydroxybenzimidazole, 2-hydroxyethylbenzimidazole, benzimidazole, and 2-hydroxyimidazole are preferred. , Imidazole, 2-hydrothioimidazole, 2-aminoimidazole, particularly preferably 2-hydroxybenzimidazole, benzimidazole, 2-hydroxyimidazole, imidazole.

A well-known thing can be used for a silane coupling agent suitably, For example, an epoxy silane coupling agent, an amino silane coupling agent, a hydrogen thio silane coupling agent, etc. are mentioned, Specifically, 3-glycidoxypropyl trimethoxy is preferable Silane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3 -Aminopropyltriethoxysilane, 3-Aminopropyltrimethoxysilane, 3-Aminopropyltriethoxysilane, 3-Ureapropyltriethoxysilane, 3-chloropropyltriethoxy Silyl, 3-hydrothiopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like. These can be used singly or in combination of plural kinds, and the added amount is preferably 0.05 to 15 parts by weight relative to 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 can also be used. Examples of the acid group include a carboxyl group, an acid anhydride group, and a phenolic hydroxyl group. When a monobasic acid group such as a carboxyl group or a phenolic hydroxyl group is contained, it is preferable that a single silicon-containing compound has a plurality of acid groups.

Specific examples of such a silane coupling agent include compounds represented by the following general formula (B): X _n Si (OR ³ ) _4-n (B)

Alternatively, the polymer may be used as a polymerization unit. In this case, a plurality of polymerization units having different X or R ³ may be used in combination.

In the formula, R ³ includes a hydrocarbon group, for example, an alkyl group such as methyl, ethyl, n-propyl, isopropyl, or n-butyl. In the general formula (A), R ³ includes plural kinds, but each of R ³ may be the same or different.

In terms of X, thiol, amidine, borate, carboxyl, phenol, peroxide, nitro, cyano, sulfonic acid, and alcoholic groups have acid groups, and these acid groups Acetyl, aryl, pentyl, benzyl, methoxymethyl, mesyl, tricresyl, trimethoxysilyl, triethoxysilyl, triisopropylsilyl Or protected by trityl, etc., acid anhydride group.

Among these, R ³ is a methyl group, and X is a substance having a carboxylic acid anhydride group, and for example, polysiloxane containing an acid anhydride group is preferred. More specifically, a compound represented by the following general formula (B-1) (X-12-967C (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.)) or a polymer containing silicon in polysiloxane or the like is preferred. The polymer terminal or side chain contains a polymer equivalent to these structures. Further, a compound in which an acid group such as a thiol, a fluorene, a borate, a carboxyl group, a phenol group, a peroxide, a nitro group, a cyano group, and a sulfonic acid group is provided at a terminal portion of the dimethylpolysiloxane. Examples of such compounds include compounds represented by the following general formulae (B-2) and (B-3) (X-22-2290AS and X-22-1821 (both trade names, Shin-Etsu Chemical Industry Co., Ltd. Co., Ltd.)).

When the silane coupling agent contains a polysiloxane structure, when the molecular weight is too large, there is a lack of mutual solubility with the polysiloxane contained in the composition, and the solubility to the developing solution cannot be improved, and reactive groups remain in the film , And can not tolerate the possibility of adverse effects such as drug resistance in subsequent steps. Therefore, the weight average molecular weight of the silicon-containing compound is preferably 5,000 or less, and more preferably 4,000 or less. In addition, the polymer corresponding to (B-1) is preferably a relatively small one having a weight average molecular weight of 1,000 or less. However, in the case where the polymer contains a polysiloxane structure in another repeating unit, the weight average molecular weight is preferable. 1,000 or more. When a silane compound, a siloxane compound, or the like having an acid group is used as the silane coupling agent, the addition amount is preferably 0.01 to 15 parts by weight based on 100 parts by weight of the polysiloxane.

For the polymerization inhibitor, a nitrin derivative and a nitrogen oxide (nitroxide) free radical derivative can be added, such as hydroquinone derivatives such as hydroquinone, methoquinone, and buthydroquinone. These can be used singly or in combination of plural kinds, and the addition amount thereof is preferably 0.1 to 10 parts by weight relative to 100 parts by weight of the polysiloxane.

As the defoaming agent, higher fatty acids such as alcohol (C ₁ to ₁₈ ), oleic acid or stearic acid, higher fatty acid esters such as glyceryl monolaurate, polyethylene glycol (PEG) (Mn200 to Polyethers such as 10,000), polypropylene glycol (PPG) (Mn200 to 10,000); polysiloxanes such as dimethylpolysiloxane, alkyl-modified polysiloxane, and fluoropolysiloxane; and details are shown below The content of organosiloxane-based surfactants. These can be used singly or in combination of plural kinds, and the addition amount thereof is preferably 0.1 to 3 parts by weight relative to 100 parts by weight of the total of the polysiloxane.

In addition, the negative-type photosensitive silicone composition of the present invention may contain a surfactant as needed. The surfactant is added for the purpose of improving coating properties, developability, and the like. Examples of the surfactant that can be used in the present invention include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

Examples of the non-ionic surfactants include polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene cetyl ether. Type; or polyoxyethylene fatty acid diester, polyoxy fatty acid monoester, polyoxyethylene polyoxypropylene block polymer, acetylene alcohol, acetylene glycol, polyethoxylate of acetylene alcohol, polyethoxylate of acetylene glycol And other acetylene glycol derivatives; surfactants containing fluorine, such as Fluorad (trade name, Sumitomo 3M Limited Company), Megafac (trade name, manufactured by DIC Corporation), Sulfron (trade name, manufactured by Asahi Glass Co., Ltd.), or an organosiloxane surfactant such as KP341 (trade name, Shin-Etsu Chemical Industry Co., Ltd.制) and so on. Examples of the acetylene glycol include 3-methyl-1-butyne-3-ol, 3-methyl-1-heptyne-3-ol, and 3,6-dimethyl-4-octyne -3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyne-3-ol, 2 , 5-dimethyl-3-hexyne-2,5-diol, 2,5-dimethyl-2,5-hexanediol, and the like.

Examples of the anionic surfactant include ammonium or organic amine salts of alkyl diphenyl ether disulfonic acid, ammonium or organic amine salts of alkyl diphenyl ether sulfonic acid, and alkylbenzene sulfonic acid. An ammonium salt or an organic amine salt of an acid, an ammonium salt or an organic amine salt of a polyoxyethylene alkyl ether sulfate, an ammonium salt or an organic amine salt of an alkyl sulfate, and the like.

Examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, amidopropyl hydroxyhydroxybetaine laurate, and the like.

These surfactants can be used singly or in combination of two or more kinds. The compounding amount of the surfactant is generally 50 to 2,000 ppm, preferably 100 to 1,000 ppm, relative to the negative-type photosensitive silicone composition of the present invention.

并-<9,9a,1-gh>香豆素、7-二乙胺基-4-三氟甲基香豆素、7-二甲胺基-4-三氟甲基香豆素、7-胺基-4-三氟甲基香豆素、2,3,5,6-1H,4H-四氫喹

并-<9,9a,1-gh>香豆素、7-乙胺基-6-甲基-4-三氟甲基香豆素、7-乙胺基-4-三氟甲基香豆素、2,3,5,6-1H,4H-四氫-9-碳乙氧基喹

并-<9,9a,1-gh>香豆素、3-(2’-N-甲基苯并咪唑基)-7-N,N-二乙胺基香豆素、N-甲基-4-三氟甲基-N-六氫吡啶基-<3,2-g>香豆素、2-(對二甲胺基苯乙烯基)-苯并噻唑基乙基碘化物、3-(2’-苯并咪唑基)-7-N,N-二乙胺基香豆素、3-(2’-苯并噻唑基)-7-N,N-二乙胺基香豆素、以及下述化學式所示之吡喃鎓鹽及硫基吡喃鎓鹽等增感色素。藉由添加增感色素，而使用了高壓汞燈(360至430nm)等廉價光源的圖案化為可行。相對於100重量份的聚矽氧烷，其添加量較佳為0.05至15重量份，更佳為0.1至10重量份。 A sensitizer may be added to the negative-type photosensitive silicone composition of the present invention as necessary. Examples of the sensitizer which can be preferably used in the negative photosensitive silicone composition of the present invention include coumarin, coumarin and its derivatives, and thiopyrylium salt. ), Acetophenones, etc., specifically, p-bis (o-methylstyryl) benzene, 7-dimethylamino-4-methylquinolinone-2,7-amino-4 -Methylcoumarin, 4,6-dimethyl-7-ethylaminocoumarin, 2- (p-dimethylaminostyryl) -pyridylmethyliodide, 7-diethylamine Coumarin, 7-diethylamino-4-methylcoumarin, 2,3,5,6-1H, 4H-tetrahydro-8-methylquine

And- <9,9a, 1-gh> coumarin, 7-diethylamino-4-trifluoromethylcoumarin, 7-dimethylamino-4-trifluoromethylcoumarin, 7 -Amine-4-trifluoromethylcoumarin, 2,3,5,6-1H, 4H-tetrahydroquine

And- <9,9a, 1-gh> coumarin, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, 7-ethylamino-4-trifluoromethylcoumarin Element, 2,3,5,6-1H, 4H-tetrahydro-9-carbonethoxyquin

Benzo- <9,9a, 1-gh> coumarin, 3- (2'-N-methylbenzimidazolyl) -7-N, N-diethylaminocoumarin, N-methyl- 4-trifluoromethyl-N-hexahydropyridyl- <3,2-g> coumarin, 2- (p-dimethylaminostyryl) -benzothiazolyl ethyl iodide, 3- ( 2'-benzimidazolyl) -7-N, N-diethylaminocoumarin, 3- (2'-benzothiazolyl) -7-N, N-diethylaminocoumarin, and Sensitizing pigments such as pyranium salts and thiopyranium salts represented by the following chemical formulas. By adding a sensitizing dye, patterning using inexpensive light sources such as high-pressure mercury lamps (360 to 430 nm) is possible. The added amount is preferably 0.05 to 15 parts by weight, and more preferably 0.1 to 10 parts by weight, with respect to 100 parts by weight of the polysiloxane.

Moreover, a compound containing an anthracene skeleton can also be used as a sensitizer. Specifically, a compound represented by the following general formula (C) is mentioned.

In the formula, 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, an epoxypropyl 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 amine group, and a carboalkoxy group; the k series Each is independently selected from an integer of 0, 1 to 4.

A sensitizer having such an anthracene skeleton is also disclosed in Patent Documents 5 or 6. When a sensitizer having such an anthracene skeleton is used, the addition amount thereof is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the polysiloxane.

Furthermore, a stabilizer may be added to the negative-type photosensitive silicone composition of the present invention as necessary. The stabilizer can be arbitrarily selected and used from generally used ones, but in the composition of the present invention, the effect of stabilizing the aromatic amine is high, so it is preferable. Among such aromatic amines, a pyridine derivative is preferable, and it is particularly preferable to have a relatively bulky substituent at the 2nd position and the 6th position. Specifically, the following are mentioned.

Method for forming hardened film

The method for forming a cured film of the present invention includes applying the negative-type polysiloxane composition to the surface of a substrate and curing it by heating. The method for forming the cured film is described below in the order of steps.

(1) Coating step

First, the substrate is coated with the negative photosensitive polysiloxane composition. The formation of the coating film of the photosensitive polysiloxane composition in the present invention can be performed by any known method as a coating method of the photosensitive composition. Specifically, it can be arbitrarily selected from dip coating, roll coating, bar coating, brush coating, spray coating, blade coating, flow coating, spin coating, and slit coating. In addition, as the substrate for coating the composition, a suitable substrate such as a silicon substrate, a glass substrate, or a resin film can be used. Various semiconductor elements and the like can be formed on these substrates as needed. When the substrate is a thin film, it may be coated by gravure printing. A drying step may also be provided after coating the film as desired. In addition, the coating step may be repeated once or twice as needed to make the formed coating film into a desired thickness.

(2) Pre-baking step

After forming a coating film by coating a negative photosensitive siloxane composition, the coating film is dried and the residual amount of the solvent in the coating film is reduced, so it is preferable to pre-bake the coating film (before Heat treatment). The pre-baking step is generally performed at a temperature of 50 to 150 ° C, preferably 90 to 120 ° C, in the case of a hot plate, for 10 to 300 seconds, preferably 30 to 120 seconds. Can be implemented for 1 to 30 minutes.

(3) Exposure steps

After the coating film is formed, the surface of the coating film is irradiated with light. The light source used for the light irradiation can be any material previously used in the pattern forming method. Examples of such light sources include high-pressure mercury lamps, low-pressure mercury lamps, lamps such as metal halide, xenon, laser diodes, and LEDs. In terms of irradiation light, ultraviolet rays such as g-line, h-line, and i-line are generally used. In addition to semiconductor-like ultra-fine processing, patterning in the range of several μm to several tens of μm is generally performed using light (high-pressure mercury lamp) of 360 to 430 nm. Among them, in the case of a liquid crystal display device, light at 430 nm is mostly used. In this case, when the sensitizing dye is combined with the negative-type photosensitive silicone composition of the present invention, the advantages are as described above. Although the energy of the irradiation light depends on the film thickness of the light source or the coating film, it is generally 10 to 2000 mJ / cm ² , preferably 20 to 1000 mJ / cm ² . When the irradiation light energy is less than 10 mJ / cm ² , sufficient resolution cannot be obtained. Conversely, when the irradiation light energy is higher than 2000 mJ / cm ² , the exposure is excessive and the halo effect may occur.

In order to irradiate light into a pattern, a general photomask can be used. Such a mask can be arbitrarily selected from well-known things. The environment at the time of exposure, There is no particular limitation, but it is generally preferable to set the surrounding environment (in the atmosphere) or a nitrogen environment. When a film is formed on the entire surface of the substrate, light irradiation may be performed on the entire surface of the substrate. In the present invention, the pattern film also includes a case where a film is entirely formed on the surface of such a substrate.

(4) Post-exposure heating step

After the exposure, the reaction between the polymers in the film is promoted due to the reaction initiator generated at the exposure, so post-exposure heating (Post Exposure Baking) can be performed as needed. This heat treatment is not performed to completely harden the coating film, but is performed until only a desired pattern remains on the substrate after development, and the other parts are removed by development.

In the case of heating after exposure, a hot plate, an oven, a furnace, or the like can be used. Since the acid in the exposed area due to light irradiation does not diffuse well into the unexposed area, the heating temperature should not be made excessively high. From this viewpoint, in the range of the heating temperature after exposure, it is preferably 40 ° C to 150 ° C, and more preferably 60 ° C to 120 ° C. In order to control the hardening speed of the composition, stepwise heating can be applied as required. The environment during heating is not particularly limited, but may be selected from an inert gas such as nitrogen, under vacuum, under reduced pressure, oxygen, or the like for the purpose of controlling the hardening speed of the composition. In addition, in order to maintain the uniformity of the temperature history in the wafer surface to a higher degree, the heating time is preferably a certain value or more, and in order to suppress the diffusion of the acid that has been generated, it is preferably an elderly person who is not excessive. From this viewpoint, it is known that the heating time is preferably from 20 seconds to 500 seconds, and more preferably from 40 seconds to 300 seconds.

(5) Development step

After exposure, post-exposure heating may be performed as necessary, and then the coating film is developed. As the developer used for development, a usable developer is an arbitrary developer used for the development of a conventionally known photosensitive siloxane composition. In the present invention, in order to specify the dissolution rate of polysiloxane, a TMAH aqueous solution is used, but the developer used when forming a cured film is not limited to this. As a preferred developing solution, tetraalkylammonium hydroxide, choline, alkali metal hydroxide, alkali metal metasilicate (hydrate), alkali metal phosphate (hydrate), ammonia water, alkyl Alkali developing solutions, such as amines, alkanolamines, and heterocyclic amines, which are aqueous solutions of basic compounds, are particularly preferred. The 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 development method can also be arbitrarily selected from previously known methods. Specifically, methods such as dipping, puddle, rinsing, slitting, gland coating, and spraying of the developer are listed. A pattern can be obtained by this development, and it is preferable to wash with water after developing with a developing solution.

(6) Heating step

After development, the obtained pattern film is hardened by heating. In the heating device used in the heating step, the same thing as the thing used for heating after the said exposure 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 is hardened, and is usually 150 to 400 ° C, preferably 200 to 350 ° C. At less than 150 ° C, unreacted silanol groups may remain. When the silanol group remains, the drug resistance of the cured film is insufficient, and the dielectric constant of the cured film is increased. high. From this viewpoint, the heating temperature is preferably 150 ° C or higher. The heating time is not particularly limited, but is generally set to 10 minutes to 24 hours, and preferably 30 minutes to 3 hours. In addition, the heating time is a time after the temperature of the pattern film reaches a desired heating temperature. Generally, it takes several minutes to several hours before the pattern film reaches a desired temperature from the temperature before heating.

The cured film thus obtained can achieve excellent heat resistance, transparency, relative permittivity, and the like. For example, the heat resistance is 400 ° C 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 the characteristics of light transmittance and relative dielectric constant that are not available in previously used acrylic materials. It is used as flat film for various elements such as flat panel displays (FPD) and low-temperature polysilicon interlayer insulation. Films, buffer coating films for IC wafers, transparent protective films, and the like can be suitably used in various aspects.

Examples and comparative examples are listed below to further describe the present invention, but the present invention is not limited by these examples and comparative examples.

<Synthesis example>

First, the synthesis example of the polysiloxane used in the present invention is as follows. In the measurement, the following devices and conditions were used.

Gel permeation chromatography was performed using HLC-8220GPC high-speed GPC system (trade name, manufactured by Tosoh Corporation) and two Super Multipore HZ-N GPC columns (trade name, manufactured by Tosoh Corporation). Determination. The measurement was performed using monodisperse polystyrene as a standard sample and tetrahydrofuran as a developing solvent under analysis conditions of a flow rate of 0.6 ml / min and a column temperature of 40 ° C.

The coating of the composition was performed using a spin coater MS-A100 (trade name, manufactured by Mikasa Co., Ltd.), and the thickness of the formed film was measured using a film thickness meter VM-1200 (trade name, Dainippon Screen Mfg. Co., Ltd.制) Measurement.

<Synthesis example Ia-1>

In a flask equipped with a stirrer, a thermometer, and a cooling tube, 36.5 g of a 25% by weight TMAH aqueous solution, 800 ml of isopropyl alcohol (hereinafter referred to as IPA), and 2.0 g of water were mixed to prepare a reaction solvent, and the temperature was maintained at 10 ° C. Further, a mixed solution of 39.7 g of phenyltrimethoxysilane, 34.1 g of methyltrimethoxysilane, and 7.6 g of tetramethoxysilane was prepared. This mixed solution was dropped into the reaction solvent using a dropping funnel at 10 ° C, and while maintaining the temperature at 10 ° C, while stirring for 2 hours, a 10% HCl aqueous solution was added for neutralization. 400 ml of toluene and 100 ml of water were added to the reaction solution, and after shaking, the mixture was separated into two layers. The solvent was removed by concentrating the obtained organic layer under reduced pressure, and after adding and adjusting PGMEA so that the solid content concentration in the concentrate became 40% by weight, a solution containing polysiloxane (Ia-1) was adjusted. The average weight molecular weight (polystyrene equivalent) of the obtained polysiloxane (Ia-1) was 2,700. The obtained polysiloxane solution was applied to a silicon wafer, and the dissolution rate in a 5% TMAH aqueous solution was measured under the aforementioned conditions, and it was 490 Å / sec.

<Synthesis Example Ia-2>

A siloxane polymer (1a-2) was obtained in the same manner as above except that the reaction time was changed to 4 hours. The average weight molecular weight (in terms of polystyrene) of the obtained polysiloxane (Ia-2) was 3,600. The obtained polysiloxane solution was coated on a silicon wafer, and then the aforementioned Conditionally, the dissolution rate to a 5% TMAH aqueous solution was 180 Å / sec.

<Synthesis example Ia-3>

A siloxane polymer (1a-3) was obtained in the same manner as above except that the reaction time was changed to 6 hours. The average weight molecular weight (polystyrene equivalent) of the obtained polysiloxane (Ia-3) was 4,900. The obtained polysiloxane solution was applied to a silicon wafer, and the dissolution rate in a 5% TMAH aqueous solution was measured under the aforementioned conditions, and it was 70 Å / sec.

<Synthesis example Ib-1>

In a flask equipped with a stirrer, a thermometer, and a cooling tube, 54.7 g of a 25% by weight TMAH aqueous solution, 800 ml of IPA, and 2.0 g of water were mixed to prepare a reaction solvent, and the temperature was maintained at 10 ° C. In addition, a mixed solution of 39.7 g of phenyltrimethoxysilane, 34.1 g of methyltrimethoxysilane, and 7.6 g of tetramethoxysilane was adjusted. The mixed solution was dropped into the reaction solvent using a dropping funnel at 0 to 3 ° C, maintained at 5 ° C or lower while stirring for 2 hours, and then neutralized by adding a 10% HCl aqueous solution. 400 ml of toluene and 100 ml of water were added to the reaction solution, and the mixture was separated into two layers after shaking. The obtained organic layer was concentrated under reduced pressure to remove the solvent, and then PGMEA was added to adjust the solid content concentration in the concentrate to 40% by weight, and then a solution containing polysiloxane (Ib-1) was adjusted. The average weight 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 aforementioned conditions, and it was 4,830 Å / sec.

<Synthesis Example Ib-2>

A siloxane polymer (1b-2) was obtained in the same manner as above except that the reaction time was changed to 6 hours. The average weight molecular weight (polystyrene equivalent) of the obtained polysiloxane (Ib-2) was 2,150. The obtained polysiloxane solution was coated on a silicon wafer, and the dissolution rate in a 2.38% TMAH aqueous solution was measured under the aforementioned conditions, and it was 720 Å / sec.

<Example 1>

Polysiloxane (Ia-1) and polysiloxane (Ib-1) were mixed at a mixing ratio (30% by weight): (70% by weight). After pre-baking of the polysiloxane mixture, the dissolution rate of the 2.38% TMAH aqueous solution was 2010 Å / s. The polysiloxane mixture was prepared to be a 35% PGMEA solution, and a photoacid generator represented by the formula (A-1) was added at 1.0% by weight based on the polysiloxane. KF-53 (trade name, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) as a surfactant was added in an amount of 0.3% by weight based on polysiloxane to obtain a negative-type photosensitive silicone composition.

This photosensitive siloxane composition was spin-coated on a silicon wafer, and after coating, it was pre-baked on a hot plate at 100 ° C for 90 seconds to adjust the film thickness to 2 μm. After pre-baking, use FX-604 type stepper (trade name, manufactured by Nikon Co., Ltd., NA = 0.1) g and h-ray exposure machine to expose at 20mJ / cm ² , and then heat it on a hot plate Baking was performed at 100 ° C. for 90 seconds, and development was performed with a 2.38% TMAH aqueous solution for 40 seconds, followed by washing with water for 30 seconds. As a result, a 5 μm line and gap (L / S) pattern and a contact hole (C / H) pattern can be obtained. It was confirmed that there were no defects such as residue on the pattern.

After the pattern was formed, it was fired and hardened at 250 ° C, and the pattern after the hardening was observed with an optical microscope, and the pattern was maintained at 5 μm.

The pattern obtained from the composition was measured for dielectric constant. As the measurement system, a Model 495 mercury probe Cv measurement device (manufactured by Solid State Measurement) was used. Specifically, the CV measurement was performed using a mercury probe method at a measurement frequency of 100 KHz, and the relative dielectric constant was calculated using the obtained saturation capacitance. The measurement sample in the dielectric constant measurement was prepared in the following manner. The photosensitive siloxane composition was coated on a silicon wafer by spin coating, and pre-baked at 100 ° C. for 90 seconds on a hot plate after the coating, and adjusted to a film thickness of 0.5 μm. Thereafter, a g and h-ray exposure machine of the FX-604 type stepper (trade name, manufactured by Nikon Co., Ltd., NA = 0.1) was used to expose the amount of exposure during pattern formation (in the case of Example 1, 20 mJ / cm ² ) after full exposure, heating and heating on a hot plate at 100 ° C for 90 seconds after exposure, immersion in a 2.38% TMAH aqueous solution for 30 seconds, and washing with pure water at 250 Firing and hardening were performed at 1 degreeC for 1 hour. The relative dielectric constant of the obtained hardened | cured material was 2.9.

<Example 2>

A negative type was obtained in the same manner as in Example 1 except that the mixing ratio of polysiloxane (Ia-1) and polysiloxane (Ib-1) was changed to (10% by weight): (90% by weight). Photosensitive silicone composition. After pre-baking, the polysiloxane mixture had a dissolution rate of 4330 Å / sec in a 2.38% TMAH aqueous solution.

Except that this composition was used and the exposure amount was changed to 50 mJ / cm ² , pattern formation and firing and hardening were performed in the same manner as in Example 1. After observing the obtained pattern, it maintained a pattern of 5 μm. However, compared to Example 1, the pattern ridge line portion was rounded at a practically non-problematic level.

<Example 3>

Except that the mixing ratio of polysiloxane (Ia-1) and polysiloxane (Ib-1) was changed to (60% by weight): (40% by weight), it was performed in the same manner as in Example 1 to obtain a negative Type photosensitive silicone composition. After pre-baking, the polysiloxane mixture had a dissolution rate of 750 Å / s in a 2.38% TMAH aqueous solution.

By using this composition, the development time was changed to 150 seconds, and the firing and hardening was changed to 350 ° C to obtain a pattern. As a result, a 5 μm pattern without residue was maintained.

<Example 4>

In addition to using polysiloxane (1b-2) instead of polysiloxane (Ib-1), and changing the mixing ratio to (Ia-1): (Ib-2) (10% by weight): (90% by weight) Except), it carried out similarly to Example 1, and obtained the negative photosensitive siloxane composition. After pre-baking, the polysiloxane mixture has a dissolution rate of 620 Å / second in a 2.38% TMAH aqueous solution.

Except that this composition was used to change the development time to 150 seconds, pattern formation and firing were performed in the same manner as in Example 1. After observing the obtained pattern, it maintained a pattern of 5 μm. However, compared to Example 1, the pattern ridge line portion was rounded at a practically non-problematic level.

<Example 5>

In addition to using polysiloxane (1a-2) instead of polysiloxane (Ia-1), and changing the mixing ratio to (Ia-2): (Ib-1) = (25% by weight): (75 Other than weight%), it carried out similarly to Example 1, and obtained the negative photosensitive siloxane composition. After pre-baking, the polysiloxane mixture had a dissolution rate of 2.105% TMAH in water at 2105 Å / sec.

Using this composition, patterning and firing were performed in the same manner as in Example 1. After observing the obtained pattern, it remained a 5 μm pattern without residue.

<Example 6>

In addition to using polysiloxane (1a-3) instead of polysiloxane (Ia-1) and changing the mixing ratio to (Ia-3): (Ib-1) = (15% by weight): (85% by weight) Other than%), it carried out similarly to Example 1, and obtained the negative photosensitive siloxane composition. After pre-baking of the polysiloxane mixture, the dissolution rate of the 2.38% TMAH aqueous solution was 2175 A / sec.

Using this composition, patterning and firing were performed in the same manner as in Example 1. After observing the obtained pattern, it remained a 5 μm pattern without residue.

<Example 7>

A negative-type photosensitive silicone 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, patterning and firing were performed in Example 1. After observing the obtained pattern, the composition had the same sensitivity as the composition of Example 1 and maintained a pattern of 5 μm. In addition, although slightly, it was confirmed that the film loss occurring during firing and hardening continued to decrease.

<Example 8>

A negative-type photosensitive silicone 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.

Except that this composition was used and the exposure amount was changed to 40 mJ / cm ² , pattern formation and firing were performed in the same manner as in Example 1. After observing the obtained pattern, it maintained a pattern of 5 μm.

<Example 9>

To the negative photosensitive siloxane compound described in Example 1, 2,6-di-tertiary-butyl-4-methyl is added as a stabilizer to the total weight of the polysiloxane mixture in an amount of 0.1% by weight. Pyridyl (manufactured by Tokyo Chemical Industry Co., Ltd.) to obtain a negative photosensitive siloxane composition.

Using this composition, patterning and firing were performed in Example 1. After observing the obtained pattern, the composition had the same sensitivity as the composition of Example 1 and maintained a pattern of 5 μm. Furthermore, I know that after evaluating the storage stability of the composition at 40 ° C., compared with the composition of Example 1, the storage stability can be improved.

<Example 10>

A negative-type retarding silicone composition was obtained in the same manner as in Example 1 except that only the polysiloxane was changed to (Ib-2). Using this composition, patterning and firing were performed in Example 1. After observing the obtained pattern, the composition has the same sensitivity as the composition of Example 1, and a 5 μm line and gap (L / S) pattern and a contact hole (C / H) pattern can be obtained.

<Comparative example 1>

A negative-type photosensitive silicone 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. Moreover, in Example 1 and Comparative Example 1, the ultraviolet-visible absorption spectrum system in dichloromethane using the aromatic sulfonium imine compound as an acid generator is shown in FIG. 1. The acid generator A-X has an absorption peak at a wavelength of 340 nm, but most of them do not absorb light at a wavelength of 400 nm or more.

After using this composition and performing a test in the same manner as in Example 1, the film was heated at 100 ° C. for 90 seconds and baked after exposure. However, the film was completely dissolved in the developing solution, and no pattern was obtained. This is because the photoacid generator does not absorb the light of g and h, so there is no generation of acid caused by exposure.

Claims (8)

A negative-type photosensitive siloxane composition comprising a polysiloxane, an aromatic sulfonimide compound represented by the following formula (A0) that releases an acid by irradiating radiation, and a solvent; and The aromatic amidine compound is 0.001 to 10 parts by weight relative to 100 parts by weight of polysiloxane;

(Wherein 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 part or all of these hydrogen atoms are substituted with a halogen atom; R ¹² is each independently Is a halogen atom, an aliphatic group having 1 to 10 carbon atoms, and an aromatic group having 6 to 18 carbon atoms, wherein the aliphatic group and the aromatic group may be substituted or unsubstituted, and may also contain hetero atoms). For example, the negative-type photosensitive silicone composition according to claim 1, wherein the polysiloxane system comprises: a first polysiloxane (Ia), wherein the pre-baked film is 5% by weight of tetramethylammonium hydroxide The aqueous solution is soluble and its dissolution rate is below 3,000Å / s; Polysiloxane (Ib), in which the pre-baking film has a dissolution rate of a solution of 2.38% by weight of tetramethylammonium hydroxide in water of 150 Å / sec or more. For example, the negative-type photosensitive silicone composition of claim 1 or 2, wherein the aromatic fluorene imine compound has a higher light absorption coefficient at any wavelength from 400 to 440 nm than that of 365 nm. The negative-type photosensitive silicone composition according to claim 1 or 2, further comprising a member selected from the group consisting of adhesion enhancers, polymerization inhibitors, defoamers, surfactants, silane coupling agents, stabilizers, and photosensitizers. From the group of additives. A method for manufacturing a cured film, which comprises applying a negative photosensitive siloxane composition according to any one of claims 1 to 4 on a substrate to form a coating film, and exposing and developing the coating film. The method for manufacturing a cured film as claimed in claim 5 does not include a heating step for hardening the coating film after development. A cured film formed from the negative-type photosensitive siloxane composition according to any one of claims 1 to 4. The cured film of claim 7 is a cured film for element formation.