JP2014160199A - Negative type photosensitive siloxane composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive siloxane composition having high resolution, high thermostability and high transparency, and having properties of high sensitivity and high residual film rate while inhibiting thermal sagging easily caused during thermal hardening without increasing a molecular weight of a crosslinking agent or a siloxane compound.SOLUTION: There is provided a negative photosensitive siloxane composition containing (I) polysiloxane, (II) an aromatic imide compound releasing acid by irradiating radiation, and (III) a solvent.

Description

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

  In recent years, various proposals have been made for the purpose of improving light utilization efficiency and energy saving in optical elements such as displays, light emitting diodes, and solar cells. For example, in a liquid crystal display, a transparent flattening film is formed on a thin film transistor (hereinafter also referred to as TFT) element, and a pixel electrode is formed on the flattening film, thereby increasing the aperture ratio of the display device. A method is known (see Patent Document 1). The structure of an organic electroluminescent element (hereinafter, also referred to as an organic EL element) is a TFT which is formed by depositing a light emitting layer on a transparent pixel electrode formed on a substrate and taking out light emission from the substrate side (bottom emission). The aperture ratio is the same as that of a liquid crystal display by adopting a method (top emission) in which light emitted from the transparent pixel electrode on the planarizing film coated on the element and the light emitting layer thereon is extracted to the opposite side of the TFT element. A method for improving this has been proposed (see Patent Document 2).

  In addition, the need for higher resolution, larger size, and higher image quality of displays has increased, and with the introduction of new technologies such as 3D display, signal delay on wiring has become a problem. Due to the increase in the rewrite speed (frame frequency) of image information, the signal input time to the TFT is shortened. However, even if an attempt is made to improve the response speed by expanding the wiring width to lower the wiring resistance, there is a limit to the expansion of the wiring width due to the demand for high resolution and the like. 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 for such a flattening film for a TFT substrate, a negative photosensitive material mainly comprising a polysiloxane compound and a curing aid is known. Such a polysiloxane compound is obtained by polymerizing a silane compound having a bifunctional functional group, for example, a dialkyl dialkoxysilane in the presence of a catalyst. However, when such a polysiloxane compound is used, degassing may occur during the film forming process. The gas generated here is a decomposition product derived from an organic group generated at a high temperature and often has an adverse effect on the light emission efficiency and life of the organic EL device, and thus is not an optimal material for use. In addition, the decomposed product may increase the dielectric constant, and the parasitic capacitance due to the insulating film increases, resulting in increased power consumption, resulting in a delay in the liquid crystal element drive signal, resulting in higher image quality. May give problems. Even with an insulating material having a high dielectric constant, the capacitance can be reduced by increasing the film thickness, for example, but it is generally difficult to form a uniform thick film and the amount of material used is also increased. It is not preferable (see Patent Document 3).

  A negative photosensitive composition containing an amorphous polysiloxane compound obtained by polymerizing a bifunctional to tetrafunctional silane compound, for example, a silane compound containing 2 to 4 alkoxy groups, is a polysiloxane compound. Since the spread of the molecular weight distribution is large, the remaining film rate after film formation is poor, and the film curing rate proceeds slowly, so that a large amount of exposure may be required. Moreover, in order to maintain the pattern shape after baking, since more acid generators are required, there exists a tendency for the transmittance | permeability to fall large (refer patent document 4).

  In addition, conventionally used acid generators, for example, ionic acid generators having a sulfonium cation structure, are generally stable at high temperatures and many have a thermal decomposition temperature of 350 ° C. or higher. Therefore, when a composition containing such an acid generator is to be cured at a relatively low temperature, an undecomposed product remains below the decomposition temperature of the acid generator even if the curing temperature of the polysiloxane compound is low. There was a possibility. Since such a residue has a risk of affecting light resistance and the like, an acid generator that can be used at a lower temperature has been desired.

Japanese Patent No. 2933879 JP 2006-236839 A JP 2009-276777 A JP 2006-18249 A No. 2006-073021 JP 2011-190333 A

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

  The present invention has been made on the basis of the circumstances as described above, has high resolution, high heat resistance, and high transparency, does not contain an organic group that can be a polymerization site such as an acrylic group, and depends on the reaction system. Use of a siloxane compound synthesized with a controlled molecular weight range to provide a negative photosensitive siloxane composition having characteristics of high sensitivity and high residual film rate, in which thermal sag that is likely to occur during thermosetting is suppressed It is. Another object of the present invention is to provide a planarized film for a TFT substrate, a cured film such as an interlayer insulating film formed from the above negative photosensitive siloxane composition, a solid-state imaging device including the cured film, and an antireflection coating. An object of the present invention is to provide optical elements and semiconductor elements such as films, antireflection plates, optical filters, high-intensity light emitting diodes, touch panels, solar cells, and optical waveguides.

The negative photosensitive siloxane composition according to the present invention comprises (I) polysiloxane,
(II) An aromatic imide compound that releases an acid when irradiated with radiation, and (III) a solvent.

  The manufacturing method of the cured film by this invention comprises apply | coating the said negative photosensitive siloxane composition to a board | substrate, forming a coating film, exposing a coating film, and heating.

  The cured film according to the present invention is formed from the above-mentioned negative photosensitive siloxane composition.

  Moreover, the element by this invention comprises the said cured film, It is characterized by the above-mentioned.

  The negative photosensitive siloxane composition of the present invention has high sensitivity and high resolution, and the obtained cured film is excellent in heat resistance, chemical resistance, environmental resistance, transparency, and remaining film ratio, and is due to thermal sag. There is no reduction in resolution. In addition, since it has excellent flatness and electrical insulation characteristics, it is a flattening film for thin film transistor (TFT) substrates used for display backplanes such as liquid crystal display elements and organic EL display elements, and an interlayer insulating film for semiconductor elements. , Various film forming materials such as insulating films and transparent protective films in solid-state imaging devices, antireflection films, antireflection plates, optical filters, high-intensity light-emitting diodes, touch panels, solar cells, and optical elements such as optical waveguides Can be suitably used.

The figure which shows the ultraviolet visible absorption spectrum of the aromatic imide compound used in Example 1 and Comparative Example 1. FIG.

Negative photosensitive polysiloxane composition The negative photosensitive siloxane composition of the present invention is a polysiloxane having a specific dissolution rate in a tetramethylammonium hydroxide aqueous solution (hereinafter referred to as TMAH aqueous solution), a photoacid generator. And at least an aromatic imide compound that generates an acid by absorbing light, particularly light having a wavelength of 405 nm or 436 nm, and a solvent. Hereinafter, the specific polysiloxane, the aromatic imide compound, and the solvent used in the negative photosensitive siloxane composition of the present invention will be sequentially described in detail.

(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, in addition to an unsubstituted inorganic polysiloxane, an organic polysiloxane substituted with an organic group substituent is referred to as a polysiloxane. Such polysiloxanes generally have silanol groups or alkoxysilyl groups. Such silanol group and alkoxysilyl group mean a hydroxyl group and an alkoxy group directly bonded to silicon forming a siloxane skeleton. Here, the silanol group and the alkoxysilyl group are considered to contribute to the reaction with the silicon-containing compound described later in addition to the action of accelerating the curing reaction when forming a cured film using the composition. Yes. For this reason, the polysiloxane preferably has these groups.

  The structure of the polysiloxane used in the present invention is not particularly limited, and can be selected from any one according to the purpose. Depending on the number of oxygen atoms bonded to silicon atoms, the polysiloxane skeleton structure has a silicone skeleton (two oxygen atoms bonded to silicon atoms) and a silsesquioxane skeleton (the number of oxygen atoms bonded to silicon atoms is 3) and a silica skeleton (the number of oxygen atoms bonded to silicon atoms is 4). Any of these may be used in the present invention. The polysiloxane molecule may contain a plurality of combinations of these skeleton structures.

  Moreover, when using organic polysiloxane, the substituent contained in it can be selected from arbitrary things, unless the effect of this invention is impaired. Examples of such a substituent include a substituent that does not contain a Si—O bond constituting a siloxane structure, specifically, an alkyl group, an alkenyl group, a hydroxyalkyl group, and an aryl group.

  In addition, reactive groups other than silanol group or alkoxysilyl group, for example, carboxyl group, sulfonyl group, amino group and the like may be contained in the siloxane resin as long as the effects of the present invention are not impaired. In general, there is a tendency to deteriorate the storage stability of the coating composition, so that it is preferable that the content of the coating composition be small. Specifically, it is preferably 10 mol% or less, particularly preferably not contained at all, with respect to the total number of hydrogen or substituents bonded to the silicon atom.

  The composition according to the present invention is for forming a cured film on a substrate by coating, imagewise exposure, and development. For this reason, it is necessary to generate a difference in solubility between the exposed part and the unexposed part. In the present invention, an image is formed by causing a curing reaction in the exposed portion and becoming insoluble in the developer. Therefore, the polysiloxane in the unexposed part should have a certain solubility or higher in the developer. For example, a negative pattern can be formed by exposure-development if the dissolution rate of a formed film in a 2.38% aqueous solution of tetramethylammonium hydroxide (hereinafter sometimes referred to as TMAH) is 50 kg / sec or more. It is believed that there is. However, since the required solubility differs depending on the development conditions, a polysiloxane corresponding to the development conditions should be appropriately selected.

  However, if a polysiloxane having a high dissolution rate is selected, problems such as deformation of the pattern shape, a decrease in the remaining film rate, and a decrease in transmittance may occur. In order to improve such a problem, a polysiloxane mixture in which a polysiloxane having a low dissolution rate is combined can be used.

Such a polysiloxane mixture includes, for example, (Ia) a first polysiloxane in which the pre-baked film is soluble in a 5 wt% tetramethylammonium hydroxide aqueous solution and the dissolution rate is 3,000 kg / sec or less. And (Ib) polysiloxane having a dissolution rate of the pre-baked film in a 2.38 wt% tetramethylammonium hydroxide aqueous solution of 150 kg / sec or more. These polysiloxanes will be described.

(A) First polysiloxane The first polysiloxane (Ia) has a pre-baked film that is soluble in a 5 wt% tetramethylammonium hydroxide aqueous solution, and the dissolution rate is generally 3,000 kg / sec or less. The polysiloxane is preferably 2,000 kg / sec or less, and it is hardly soluble in a 2.38% TMAH aqueous solution by itself.

  This 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.

As the silane compound (ia) selected from the group consisting of trialkoxysilane and tetraalkoxysilane used as a raw material, any compound can be used. For example, a compound represented by the following general formula (i) should be used. Can do.
R ¹ _n Si (OR ² ) _4-n (i)
(In the formula, R ¹ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms in which arbitrary methylene may be replaced by oxygen, or arbitrary hydrogen in 6 to 20 carbon atoms is replaced by fluorine. Represents an aryl group that may be substituted, n is 0 or 1, and R ² represents an alkyl group having 1 to 5 carbon atoms.)

In general formula (i), as R ¹ , for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 2, Examples include 2,2-trifluoroethyl group, 3,3,3-trifluoropropyl group, cyclohexyl group, phenyl group, and tolyl group. In particular, a compound in which R ¹ is a methyl group is preferable because raw materials are easily available, film hardness after curing is high, and chemical resistance is high. A phenyl group is preferred because it increases the solubility of the polysiloxane in a solvent and the cured film is less likely to crack.

On the other hand, in the general 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 general formula (i), a plurality of R ² are included, but each R ² may be the same or different.

  Specific examples of the trialkoxysilane compound represented by the general formula (i) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrin-butoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, and the like. Ethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-to Trifluoropropyl trimethoxy silane and the like. Among these, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane are preferable compounds because they are easily available.

  Specific examples of the tetraalkoxysilane compound represented by the general formula (i) include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like. Among these, tetramethoxysilane, Tetraethoxysilane and the like are preferable because of their high reactivity.

  The silane compound (ia) used for the production of the first polysiloxane (Ia) may be one type or a combination of two or more types. Here, when tetraalkoxysilane is used as the silane compound (ia), there is a tendency that pattern dripping is reduced. This is presumably because the crosslink density of the polysiloxane increases. However, when there are too many compounding ratios of a tetraalkoxylane, a sensitivity may fall. For this reason, when using tetraalkoxysilane as a raw material of polysiloxane (Ia), the compounding ratio is 0.1 to 40 mol% with respect to the total number of moles of trialkoxysilane and tetraalkoxysilane. Preferably, it is 1-20 mol%.

  The polysiloxane (Ia) used in the present invention is preferably produced 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 dropped into a reaction solvent consisting of an organic solvent, a basic catalyst, and water to cause hydrolysis and condensation reactions, and if necessary, purification or concentration by neutralization or washing is performed. After performing, it can manufacture by substituting the reaction solvent with the desired organic solvent as needed.

  Examples of the organic solvent used as the reaction solvent include hydrocarbon solvents such as hexane, toluene, xylene and benzene, ether solvents such as diethyl ether and tetrahydrofuran, ester solvents such as ethyl acetate and propylene glycol monomethyl ethyl acetate, Examples include alcohol solvents such as methanol, ethanol, isopropanol, butanol and 1,3-dipropanol, and ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. These organic solvents may be used alone or in combination. Can be used. Moreover, generally the usage-amount of an organic solvent is 0.1-10 weight times of the liquid mixture of a silane compound, and 0.5-2 weight times is preferable.

  Generally the reaction temperature which implements a hydrolysis and a condensation reaction is 0-200 degreeC, and 10-60 degreeC is preferable. At this time, the temperature of the dropping silane compound and the temperature of the reaction solvent may be the same or different. The reaction time varies depending on the type of silane compound, but is usually several tens of minutes to several tens of hours, preferably 30 minutes or longer. Various conditions in the hydrolysis and condensation reaction are set to the intended application by setting the amount of basic catalyst, reaction temperature, reaction time, etc., taking into account the reaction scale, reaction vessel size, shape, etc. Suitable physical properties can be obtained.

  Examples of the basic catalyst include triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, diethanolamine, an organic base such as alkoxysilane having an amino group, Examples thereof include inorganic bases such as sodium hydroxide and potassium hydroxide, anion exchange resins, and quaternary ammonium salts such as tetrabutylammonium hydroxide, tetraethylammonium hydroxide, and tetramethylammonium hydroxide. The amount of the catalyst is preferably 0.0001 to 10 mol times with respect to the mixture of silane compounds. The polysiloxane synthesized using such a base catalyst is characterized in that when it is applied at a temperature of 150 ° C. or higher, the curing starts quickly, and a beautiful shape can be maintained without causing pattern drift after firing. is there.

  The degree of hydrolysis can be adjusted by the amount of water added to the reaction solvent. In general, it is desirable to react water at a ratio of 0.01 to 10 mol times, preferably 0.1 to 5 mol times, with respect to the hydrolyzable alkoxy group of the silane compound. If the amount of water added is less than the above range, the degree of hydrolysis will be low and it will be difficult to form a film of the composition, which is not preferable. On the other hand, if too much, gelation will occur and storage stability will be poor. Absent. The water used is preferably ion exchange 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 acidic compounds include inorganic acids such as phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid, or hydrofluoric acid, acetic acid, trifluoroacetic acid, formic acid, lactic acid, acrylic acid, oxalic acid, maleic acid, succinic acid, or citric acid And organic acids such as sulfonic acid such as p-toluenesulfonic acid or methanesulfonic acid. Moreover, it can also neutralize 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 with respect to the basic catalyst. .1 mole times. Moreover, when using a cation exchange resin, it is preferable that the number of the ionic groups contained in a cation exchange resin be in the said range.

  The reaction solution after neutralization can be washed and purified as necessary. The washing method is not particularly limited. For example, at least polysiloxane (Ia) is obtained by adding a hydrophobic organic solvent and water as necessary to the reaction solution after neutralization, stirring, and bringing the polysiloxane into contact with the organic solvent. Is dissolved in the hydrophobic organic solvent phase. At this time, a compound that dissolves polysiloxane (Ia) and is immiscible with water is used as the hydrophobic organic solvent. “Immiscible with water” means that water and a hydrophobic organic solvent are sufficiently mixed and then allowed to stand to separate 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 poorly soluble in water such as butanol, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, toluene And aromatic solvents such as 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 a mixture of two or more types may be used. By such washing, most of the basic catalyst used in the reaction process, the neutralizing agent, the salt generated by the neutralization, and the alcohol and water that are by-products of the reaction are contained in the aqueous layer. Virtually eliminated. The number of washings can be changed according to need.

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

  By such washing, there are cases where the coating property and storage stability of the composition can be improved.

  The reaction solution after washing can be added as it is to the composition according to the present invention, but if necessary, the concentration can be changed by removing the solvent and remaining reaction by-products such as alcohol and water by concentration. Further, the solvent can be replaced with another solvent. When carrying out the concentration, it can be carried out 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 at the time of concentration is generally 30 to 150 ° C, preferably 40 to 100 ° C. In addition, the solvent can be replaced by adding a desired solvent at appropriate times and further concentrating so as to obtain a target solvent composition.

  The polysiloxane (Ia) used for the siloxane resin composition of this invention can be manufactured by the above method.

(B) Second polysiloxane As for the second polysiloxane, the pre-baked film is soluble in 2.38 wt% tetramethylammonium hydroxide aqueous solution, and the dissolution rate is 150 kg / second or more, preferably 500 kg. Polysiloxane which is at least / sec.

  This 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, as the conditions of this production method, the same method as the production method of polysiloxane (Ia) can be used. However, as the reaction catalyst, an acidic catalyst can be used in addition to the basic catalyst. In order to achieve the desired dissolution rate, conditions such as the amount of reaction solvent, particularly the amount of water added, the reaction time, and the reaction temperature are appropriately prepared.

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

  When a relatively large amount of tetraalkoxysilane is used as the raw material for the first polysiloxane (Ia), the compounding ratio of tetraalkoxysilane as the raw material for the second polysiloxane (Ib) is preferably low. . This is because precipitation of the silane compound occurs or sensitivity of the formed film is reduced when the compounding ratio of the tetraalkoxysilane is high as a whole. Therefore, the compounding ratio of tetraalkoxysilane is 1 to 40 mol% with respect to the total number of moles of silane compounds (ia) and (ib), which are raw materials of polysiloxanes (Ia) and (Ib). Preferably, it is 1-20 mol%.

  Moreover, an acidic catalyst can be used as a catalyst for manufacture of polysiloxane (Ib). 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, polyvalent carboxylic acid, and anhydrides thereof. The addition amount of the catalyst is preferably 0.0001 to 10 mol times with respect to the mixture of silane compounds, although it depends on the strength of the acid.

  When an acidic catalyst is used for production of 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 basic compounds used for neutralization include organic compounds such as triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, diethylamine, triethanolamine, or diethanolamine. Examples include bases, inorganic bases such as sodium hydroxide or potassium hydroxide, and quaternary ammonium salts such as tetrabutylammonium hydroxide, tetraethylammonium hydroxide, and tetramethylammonium hydroxide. An anion exchange resin can also be used. The amount of the neutralizing agent may be the same as that when a basic catalyst is used. Although it is appropriately selected according to the pH of the reaction solution after the reaction, it is preferably 0.5 to 1.5 mol times, more preferably 1 to 1.1 mol times with respect to the acidic catalyst.

  The polysiloxane (Ib) used for the siloxane resin composition of this invention can be manufactured by the above.

  The dissolution rate of the polysiloxane (Ib) in the 2.38% TMAH aqueous solution needs to be 150 Å / second or more, and preferably 500 Å / second or more, as described later. When the dissolution rate of the polysiloxane (Ib) in the 2.38% TMAH aqueous solution is less than 150 kg / sec, the dissolution rate of the mixture of the polysiloxane (Ia) and (Ib) in the 2.38% TMAH aqueous solution is 50 to 5, In order to achieve 000 kg / sec, it is necessary to reduce the content of the poorly soluble polysiloxane (Ia) as much as possible. However, if the content of the polysiloxane (Ia) is small, it is difficult to prevent thermal sag of the pattern. become.

(C) Polysiloxane mixture (I)
In the present invention, the polysiloxane mixture (I) containing the polysiloxane (Ia) and the polysiloxane (Ib) can be used. The compounding ratio of polysiloxane (Ia) and polysiloxane (Ib) is not particularly limited, but the weight ratio of polysiloxane (Ia) / polysiloxane (Ib) contained in polysiloxane mixture (I) is 1/99 to 80 / 20 is preferable, and 20/80 to 50/50 is more preferable.

  If the dissolution rate of polysiloxane (Ia) in 5% TMAH aqueous solution is 3,000 kg / sec or less and the dissolution rate of polysiloxane (Ib) in 2.38% TMAH aqueous solution is 150 kg / sec or more, it remains undissolved and sensitivity decreases. However, depending on the film thickness and development time of the cured film formed from the negative photosensitive siloxane composition of the present invention, the polysiloxane mixture (I) can be dissolved in 2.38% TMAH aqueous solution. The speed can also be set as appropriate. The dissolution rate of the polysiloxane mixture (I) can be adjusted by changing the mixing ratio of the polysiloxanes (Ia) and (Ib), and varies depending on the type and amount of the photosensitive agent contained in the negative photosensitive siloxane composition. For example, if the film thickness is 0.1 to 10 μm (1,000 to 100,000 mm), the dissolution rate in the 2.38% TMAH aqueous solution is preferably 50 to 5,000 mm / sec.

(D) Alkali dissolution rate in TMAH aqueous solution In the present invention, polysiloxanes (Ia) and (Ib) each have a specific dissolution rate in a TMAH aqueous solution. The dissolution rate of the polysiloxane in the TMAH aqueous solution is measured as follows. Polysiloxane is diluted with propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) to 35% by weight and dissolved with stirring with a stirrer at room temperature for 1 hour. In a clean room with a temperature of 23.0 ± 0.5 ° C. and humidity of 50 ± 5.0%, the prepared polysiloxane solution is pipetted onto a 4 inch, 525 μm thick silicon wafer and the center of a 1 cc silicon wafer. And then spin-coated to a thickness of 2 ± 0.1 μm, and then heated on a hot plate at 100 ° C. for 90 seconds to remove the solvent. The film thickness of the coating film is measured with a spectroscopic ellipsometer (manufactured by JA Woollam).

  Next, the silicon wafer having this film was gently immersed in a 6-inch diameter glass petri dish containing 100 ml of a TMAH aqueous solution having a predetermined concentration adjusted to 23.0 ± 0.1 ° C., and then left to stand. The time until the film disappeared was measured. The dissolution rate is determined by dividing by the time until the film in the portion 10 mm inside from the edge of the wafer disappears. If the dissolution rate is extremely slow, the wafer is immersed in a TMAH aqueous solution for a certain period of time and then heated on a hot plate at 200 ° C. for 5 minutes to remove moisture taken into the film during the dissolution rate measurement. Thickness is measured, and the dissolution rate is calculated by dividing the amount of change in film thickness before and after immersion by the immersion time. The above measurement method is performed 5 times, and the average of the obtained values is taken as the dissolution rate of polysiloxane.

(II) Aromatic imide compound The negative photosensitive polysiloxane composition according to the present invention is characterized in that an aromatic imide compound that absorbs radiation and generates an acid is used as a photoacid generator. Conventionally used ionic acid generators, for example, sulfonium compounds generally have a thermal decomposition temperature of 350 ° C. or higher, whereas aromatic imide compounds start thermal decomposition at a low temperature of about 200 ° C. There are features. For this reason, it becomes possible to form a film at a temperature lower than that of a composition using a conventional acid generator. And, such an aromatic imide compound can generate acid by absorbing longer wavelength light, such as g-line and h-line, as compared with conventional acid generators. The sensitivity of the curable composition can be improved in the region. Furthermore, since the aromatic imide compound has relatively high solubility, the preparation of the composition is easy, and the compound attached to the cured film can be easily removed by washing. And the synthesis | combination of a compound is also simple and preferable from a viewpoint of cost.

（式中、Ｒ^１１は、炭素数１〜７の脂肪族基、炭素数６〜１８の芳香族基、またはそれらの水素原子の一部又は全部をハロゲン原子で置換した基であり、
Ｒ^１２はそれぞれ独立に、ハロゲン原子、炭素数１〜１０の脂肪族基、炭素数６〜１８の芳香族基であって、前記脂肪族基および芳香族基は、置換されていても非置換であってもよく、またヘテロ原子を含有していてもよく、
ｐはそれぞれ独立に０〜３の数を表し、ｐの総計は１以上であり、
ｐが２以上である時には、二つ以上のＲ^１２が相互に連結して環状構造を形成してもよい。） In the present invention, among the aromatic imide compounds used as the photoacid generator, preferred 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 obtained by substituting a part or all of hydrogen atoms with a halogen atom,
R ¹² is independently a halogen atom, an aliphatic group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms, and the aliphatic group and the aromatic group are unsubstituted even if they are substituted. Or may contain heteroatoms,
p independently represents a number of 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 cyclic structure. )

In 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 obtained by substituting part or all of the hydrogen atoms with a halogen atom. Here, 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 a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Further, 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, or an aromatic group having 6 to 18 carbon atoms, and the aliphatic group and the aromatic group are substituted. It may be unsubstituted or substituted, and may contain a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom. In addition, each p is a number of 1 or more and 0 to 3, but the compound represented by the formula (A) includes one or more substituents R ¹² , and the total of p is 1 or more. Incidentally, two or more R ¹² may form a cyclic structure interconnected. Moreover, when p is 2 or more, it is preferable that two p is 1 or more respectively.

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 also include 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 methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-amyl. Group, i-amyl group, s-amyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, trifluoromethyl group, pentafluoroethyl group and the like. . Moreover, the alkoxy group substituted by the C1-C10 alkoxy group and the halogen atom can also be used. Specific examples include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, n-amyloxy group, n-octyloxy group, n-decyloxy group, trifluoromethoxy group, pentafluoroethoxy. Groups and the like.

  As the aromatic group, a substituted or unsubstituted phenyl group can be used. Specifically, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, o-ethylphenyl group, m-ethylphenyl group, p-ethylphenyl group, p- (n-propyl) phenyl group P- (i-propyl) phenyl group, p- (n-butyl) phenyl group, p- (i-butyl) phenyl group, p- (s-butyl) phenyl group, p- (t-butyl) phenyl group P- (n-amyl) phenyl group, p- (i-amyl) phenyl group, p- (t-amyl) phenyl group, o-methoxyphenyl group, m-methoxyphenyl group, p-methoxyphenyl group, o -Ethoxyphenyl group, m-ethoxyphenyl group, p-ethoxyphenyl group, p- (n-propoxy) phenyl group, p- (i-propoxy) phenyl group, p- (n-butoxy) phenyl group, p- ( i-Butoki ) Phenyl group, p- (s-butoxy) phenyl group, p- (t-butoxy) phenyl group, p- (n-amyloxy) phenyl group, p- (i-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-dichlorophenyl group, 2,4,6-tribromophenyl group, 2,4,6-trifluorophenyl group, pentachlorophenyl group, pentabromophenyl group, pentafluorophenyl group, p-biphenylyl group, etc. Can be mentioned. Of these, the phenyl group is most preferred.

  Moreover, a substituted or unsubstituted naphthyl group can be used as an aromatic group. Specifically, naphthyl group, 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5-methyl-1-naphthyl group, 6-methyl-1- Naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl-2-naphthyl group, 4-methyl-2-naphthyl group, 5- Examples thereof include a methyl-2-naphthyl group, a 6-methyl-2-naphthyl group, a 7-methyl-2-naphthyl group, and an 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 can be used. Moreover, the aryl group containing a hetero atom is not particularly limited, and specific examples thereof include those obtained by functionalizing the following compounds.

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 the linking group L. Here, L can be arbitrarily selected, for example, alkylene group, alkenylene group, alkynylene group, ethylene bond, acetylene bond, ether bond, ester bond, sulfonate ester bond, imide bond, amide bond, azo bond, Or a sulfide bond etc. are used.

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

  Although it does not restrict | limit especially as an alkenylene group, Specifically, a vinylene group, 1-methyl vinylene group, a propenylene group, 1-butenylene group, 2-butenylene group, 1-pentenylene group, 2-pentenylene group etc. are mentioned.

  Although it does not restrict | limit especially as an alkynylene group, Specifically, an ethynylene group, a propynylene group, a butanylene group etc. are mentioned.

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

（式中、Ｒ^１１およびＲ^１２は前記した通りである。） Of the aromatic imide 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.)

  Among the photoacid generators used in the present invention, the aromatic imide compound represented by the formula (A0) is a highly sensitive and highly efficient acid generator for g-line (435 nm) and h-line (405 nm). It can function and can be used as a compound having good solubility in general-purpose organic solvents.

A compound represented by the above formula (A0) is synthesized, and R ¹² is a phenyl group, naphthyl group, anthracenyl group, fluorophenyl group, methylphenyl group, methoxyphenyl group, phenoxyphenyl group, pyridyl group, thienyl group, etc. From the point of view, it is preferable. Among them, a particularly preferable structure is one in which R ^{12 in the} above formula (A0) is substituted with a phenyl group.

Among these compounds, the following can be mentioned as preferable ones.

These aromatic imide compounds can be used alone or in combination.
The aromatic imide compound can improve the resolution by strengthening the shape of the pattern or increasing the contrast of development. The aromatic imide compound used in the present invention is a photoacid generator that releases an acid, which is an active substance that decomposes upon irradiation with radiation and photocures the composition. Examples of the radiation used for forming a cured film using the composition according to the present invention include visible light, ultraviolet light, infrared light, X-rays, electron beams, α rays, and γ rays, and are not particularly limited. However, ultraviolet light, particularly g-line (wavelength 436 nm) and h-line (wavelength 405 nm) are preferably used. On the other hand, the aromatic imide compound used in the present invention preferably has a high extinction coefficient in the wavelength region of 400 to 440 nm. Specifically, when an ultraviolet-visible absorption spectrum is measured, it is more preferable that the extinction coefficient at any wavelength of 400 to 440 nm is higher than the extinction coefficient at 365 nm. Here, the UV-visible absorption spectrum is measured using dichloromethane as a solvent. The measuring device is not particularly limited, and for example, it can be measured using a Varian Cary 4000 type ultraviolet / visible spectrophotometer (manufactured by Agilent Technologies) .

  If necessary, a photoacid generator other than the aromatic imide compound can be used in combination.

  The amount of aromatic imide compound added varies depending on the type of active substance generated by decomposition of the compound, the amount generated, and the required sensitivity / dissolution contrast between the exposed and unexposed areas. Preferably it is 0.001-10 weight part with respect to a weight part, More preferably, it is 0.01-5 weight part. If the addition amount is less than 0.001 part by weight, the dissolution contrast between the exposed part and the unexposed part is too low, and the additive effect may not be obtained. On the other hand, when the amount of the aromatic imide compound added is more than 10 parts by weight, the formed film may be cracked, or coloring due to the decomposition of the aromatic imide compound may be remarkable. May decrease. Further, when the amount added is increased, thermal decomposition may cause deterioration of the electrical insulation of the cured product or outgassing, which may cause a problem in the subsequent process. Furthermore, the resistance of the coating to a photoresist stripping solution containing monoethanolamine or the like as a main ingredient may be reduced.

(III) Solvent The negative photosensitive siloxane composition according to the present invention comprises a solvent. The solvent is not particularly limited as long as it uniformly dissolves or disperses the polysiloxane, the aromatic imide compound, and the additive added as necessary. Examples of the solvent that can be used in the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol dialkyl ethers such as diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, Propylene glycol alkyl ether acetates such as propylene glycol monopropyl ether acetate, aromatic hydrocarbons such as benzene, toluene, xylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, propanol, Examples include alcohols such as butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, esters such as ethyl lactate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone. Among these, it is preferable to use propylene glycol alkyl ether acetates and esters from the viewpoints of easy availability, easy handling, and polymer solubility. These solvents are used singly or in combination of two or more, and the amount used varies depending on the coating method and the requirements of the film thickness after coating.

  The solvent content of the negative photosensitive siloxane composition can be arbitrarily adjusted according to the method of applying the composition. For example, when the composition is applied by spray coating, the proportion of the solvent in the negative photosensitive siloxane composition can be 90% by weight or more. In the slit coating used for coating a large substrate, it is usually 60% by weight or more, preferably 70% by weight or more. The characteristics of the negative photosensitive siloxane composition of the present invention do not vary greatly depending on the amount of the solvent.

(IV) Additive The negative 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 remover, an adhesion enhancer, a polymerization inhibitor, an antifoaming agent, a surfactant, and a sensitizer.

The developer dissolution accelerator or scum remover adjusts the solubility of the coating film to be formed in the developer, and has a function of preventing scum from remaining on the substrate after development. As such an additive, crown ether can be used. The crown ether having the simplest structure is represented by the general formula (—CH ₂ —CH ₂ —O—) _n . Among these, those in which n is 4 to 7 are preferable in the present invention. Crown ethers are sometimes called x-crown-y-ethers 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, those selected from the group consisting of crown ethers where x = 12, 15, 18, or 21, y = x / 3, and benzo condensates and cyclohexyl condensates thereof are preferred. Specific examples of more preferred crown ethers include 21-crown-7 ether, 18-crown-6-ether, 15-crown-5-ether, 12-crown-4-ether, 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, among these, those selected from 18-crown-6-ether and 15-crown-5-ether are most preferable. The addition amount is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of polysiloxane.

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

  Known silane coupling agents are preferably used, and examples include epoxy silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, and the like. Specifically, 3-glycidoxypropyltrimethoxysilane 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane Methoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-chloropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane and the like are preferable. These can be used singly or in combination, and the addition amount is preferably 0.05 to 15 parts by weight with respect to 100 parts by weight of polysiloxane.

  Moreover, as a silane coupling agent, a silane compound having an acid group, a siloxane compound, or the like can 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 silane coupling agents include the following general formula (B):
^{_{X n Si (OR 3) 4}} -n (B)
Or a polymer having the same as a polymerization unit. At this time, a plurality of polymer units having different X or R ³ can be used in combination.

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

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

Of these, those having a methyl group as R ^{3 and a} carboxylic acid anhydride group as X, such as an acid anhydride group-containing silicone, are preferred. More specifically, a compound represented by the following general formula (B-1) (X-12-967C (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)) or a silicon-containing polymer such as silicone having a structure corresponding thereto. The polymer contained in the terminal or side chain of is preferred. A compound in which an acid group such as thiol, phosphonium, borate, carboxyl, phenol, peroxide, nitro, cyano, or sulfo group is added to the terminal portion of dimethyl silicone is also preferable. As such compounds, compounds represented by the following general formulas (B-2) and (B-3) (X-22-2290AS and X-22-1821 (both trade names, manufactured by Shin-Etsu Chemical Co., Ltd.)) ).

  When the silane coupling agent contains a silicone structure, if the molecular weight is too large, the compatibility with the polysiloxane contained in the composition will be poor, the solubility in the developer will not be improved, and reactive groups will remain in the film. There is a possibility that there is an adverse effect such as inability to maintain chemical resistance that can withstand subsequent processes. For this reason, it is preferable that the weight average molecular weight of a silicon containing compound is 5000 or less, and it is more preferable that it is 4,000 or less. In addition, the polymer corresponding to (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 containing a silicone structure in other repeating units, The weight average molecular weight is preferably 1,000 or more. Moreover, when using the silane compound, siloxane compound, etc. which have an acid group as a silane coupling agent, it is preferable that the addition amount shall be 0.01-15 weight part with respect to 100 weight part of polysiloxane.

  As the polymerization inhibitor, nitrone derivatives and nitroxide radical derivatives such as hydroquinone derivatives such as hydroquinone, methylhydroquinone and butylhydroquinone can be added. These can be used singly or in combination, and the addition amount is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of polysiloxane.

As the antifoaming agent, an alcohol _{(C 1 ~ 18),} higher fatty acids such as oleic acid and stearic acid, higher fatty acid esters such as glycerol monolaurate, polyethylene glycol (PEG) (Mn200~10,000), polypropylene glycol ( PPG) (Mn 200 to 10,000) and the like, dimethyl silicone oil, alkyl-modified silicone oil, silicone compounds such as fluorosilicone oil, and organosiloxane surfactants described in detail below. These can be used singly or in combination, and the addition amount is preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the total polysiloxane.

  The negative photosensitive siloxane composition of the present invention may contain a surfactant as necessary. 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 nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether and polyoxyethylene cetyl ether, and polyoxyethylene fatty acids. Acetylene glycol derivatives such as diesters, polyoxy fatty acid monoesters, polyoxyethylene polyoxypropylene block polymers, acetylene alcohol, acetylene glycol, polyethoxylates of acetylene alcohol, polyethoxylates of acetylene glycol, fluorine-containing surfactants such as Fluorado (Product name, manufactured by Sumitomo 3M Co., Ltd.), Megafuck (Product name, manufactured by DIC Corporation), Sulfron (Product name, Asahi Glass Co., Ltd.) Ltd.), or organosiloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the acetylene glycol include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 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 etc. are mentioned.

  Anionic surfactants include alkyl diphenyl ether disulfonic acid ammonium salt or organic amine salt, alkyl diphenyl ether sulfonic acid ammonium salt or organic amine salt, alkylbenzene sulfonic acid ammonium salt or organic amine salt, polyoxyethylene alkyl ether sulfate. And ammonium salts and organic amine salts of alkyl sulfates.

  Further, examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauric acid amidopropyl hydroxysulfone betaine, and the like.

  These surfactants can be used alone or in admixture of two or more, and the blending amount thereof is usually 50 to 2,000 ppm, preferably 100 to 2,000, based on the negative photosensitive siloxane composition of the present invention. 1,000 ppm.

Moreover, a sensitizer can be added to the negative photosensitive siloxane composition of the present invention as necessary. Sensitizers preferably used in the negative photosensitive siloxane composition of the present invention include coumarins, ketocoumarins and their derivatives, thiopyrylium salts, acetophenones, etc., specifically, p-bis (o-methylstyryl) benzene. 7-dimethylamino-4-methylquinolone-2, 7-amino-4-methylcoumarin, 4,6-dimethyl-7-ethylaminocoumarin, 2- (p-dimethylaminostyryl) -pyridylmethyl iodide, 7 -Diethylaminocoumarin, 7-diethylamino-4-methylcoumarin, 2,3,5,6-1H, 4H-tetrahydro-8-methylquinolidino- <9,9a, 1-gh> coumarin, 7-diethylamino-4-trifluoro Methylcoumarin, 7-dimethylamino-4-trifluoromethylcoumarin, 7-amino- -Trifluoromethylcoumarin, 2,3,5,6-1H, 4H-tetrahydroquinolidino- <9,9a, 1-gh> coumarin, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, 7-ethylamino-4-trifluoromethylcoumarin, 2,3,5,6-1H, 4H-tetrahydro-9-carboethoxyquinolidino- <9,9a, 1-gh> coumarin, 3- (2 ′ -N-methylbenzimidazolyl) -7-N, N-diethylaminocoumarin, N-methyl-4-trifluoromethylpiperidino- <3,2-g> coumarin, 2- (p-dimethylaminostyryl) -benzo Thiazolylethyl iodide, 3- (2′-benzimidazolyl) -7-N, N-diethylaminocoumarin, 3- (2′-benzothiazolyl) -7-N, N-diethi Amino coumarin, as well as a sensitizing dye such as pyrylium salts and thiopyrylium salts represented by the following chemical formula. By adding a sensitizing dye, patterning using an inexpensive light source such as a high-pressure mercury lamp (360 to 430 nm) becomes possible. The addition amount is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, relative to 100 parts by weight of polysiloxane.

式中、Ｒ^３１はそれぞれ独立にアルキル基、アラルキル基、アリル基、ヒドロキシアルキル基、アルコキシアルキル基、グリシジル基、およびハロゲン化アルキル基からなる群から選択される置換基を示し、
Ｒ^３２はそれぞれ独立して、水素原子、アルキル基、アルコキシ基、ハロゲン原子、ニトロ基、スルホン酸基、水酸基、アミノ基、およびカルボアルコキシ基からなる群から選択される置換基を示し、
ｋはそれぞれ独立に０、１〜４から選ばれる整数である。 An anthracene skeleton-containing compound can also be used as a sensitizer. Specifically, the compound represented by the following general formula (C) is mentioned.

In the formula, each R ³¹ 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,
Each of R ³² 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 and 1-4.

  Such a sensitizer having an anthracene skeleton is also disclosed in Patent Document 5 or 6 or the like. When using the sensitizer which has such an anthracene skeleton, the addition amount is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the polysiloxane.

Moreover, a stabilizer can be added to the negative photosensitive siloxane composition according to the present invention as necessary. The stabilizer can be arbitrarily selected from those generally used, but in the composition according to the present invention, an aromatic amine is preferable because of its high stabilizing effect. Of such aromatic amines, pyridine derivatives are preferred, and those having relatively bulky substituents at the 2-position and the 6-position are particularly preferred. Specific examples include the following.

Method for Forming Cured Film A method for forming a cured film according to the present invention comprises applying the above-described negative polysiloxane photosensitive composition to the surface of a substrate and curing it by heating. The method for forming the cured film will be described in the order of steps as follows.

(1) Application process First, the negative photosensitive polysiloxane composition described above is applied to a substrate. Formation of the coating film of the photosensitive polysiloxane composition in this invention can be performed by the arbitrary methods conventionally known 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, doctor coating, flow coating, spin coating, slit coating, and the like. Moreover, as a base material which apply | coats a composition, suitable base materials, such as a silicon substrate, a glass substrate, and a resin film, can be used. Various semiconductor elements etc. may be formed in these base materials as needed. When the substrate is a film, gravure coating can also be used. If desired, a drying step can be separately provided after the coating. Further, if necessary, the coating process can be repeated once or twice or more to obtain a desired coating film thickness.

(2) Pre-bake process After forming a coating film by applying a negative photosensitive siloxane composition, the coating film is dried and the residual solvent in the coating film is reduced. Pre-baking (preheating treatment) is preferable. The pre-baking step is generally carried out at a temperature of 50 to 150 ° C., preferably 90 to 120 ° C., for 10 to 300 seconds when using a hot plate, preferably 30 to 120 seconds, and for 1 to 30 minutes when using a clean oven. be able to.

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

  A general photomask can be used to irradiate light in a pattern. Such a photomask can be arbitrarily selected from known ones. The environment at the time of irradiation is not particularly limited, but generally an ambient atmosphere (in the air) or a nitrogen atmosphere may be used. In addition, 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 includes the case where a film is formed on the entire surface of the substrate.

(4) Post-exposure heating step After exposure, post-exposure baking can be performed as necessary in order to promote the interpolymer reaction in the film by the reaction initiator generated at the exposure site. This heat treatment is not performed in order to completely cure the coating film, but is performed so that only a desired pattern remains on the substrate after development and other portions can be removed by development. is there.

  When heating after exposure, a hot plate, an oven, a furnace, or the like can be used. The heating temperature should not be excessively high because it is not desirable for the acid in the exposed areas generated by light irradiation to diffuse to the unexposed areas. From such a viewpoint, the range of the heating temperature after exposure is preferably 40 ° C to 150 ° C, more preferably 60 ° C to 120 ° C. Stepwise heating can be applied as needed to control the cure rate of the composition. The atmosphere during heating is not particularly limited, but can be selected from an inert gas such as nitrogen, a vacuum, a reduced pressure, and an oxygen gas for the purpose of controlling the curing rate of the composition. . Further, the heating time is preferably a certain value or more in order to maintain higher uniformity of temperature history in the wafer surface, and is preferably not excessively long in order to suppress the diffusion of the generated acid. From such a viewpoint, the heating time is preferably 20 seconds to 500 seconds, and more preferably 40 seconds to 300 seconds.

(5) Development step After the exposure, if necessary, after the post-exposure heating, the coating film is developed. As a developing solution used in the development, any developing solution that has been conventionally used for developing a known photosensitive siloxane composition can be used. In the present invention, a TMAH aqueous solution is used to specify the dissolution rate of polysiloxane, but the developer used for forming a cured film is not limited thereto. Preferred developers include tetraalkylammonium hydroxide, choline, alkali metal hydroxide, alkali metal metasilicate (hydrate), alkali metal phosphate (hydrate), ammonia, alkylamine, alkanolamine, complex Examples include an alkaline developer that is an aqueous solution of an alkaline compound such as a cyclic amine. A particularly preferred alkaline developer is an aqueous tetramethylammonium hydroxide solution. These alkaline developers may further contain a water-soluble organic solvent such as methanol and ethanol, or a surfactant, if necessary. The developing method can be arbitrarily selected from conventionally known methods. Specific examples include immersion (dip) in a developer, paddle, shower, slit, cap coat, and spray. A pattern can be obtained by this development. After development with a developer, washing is preferably performed.

(6) Heating step After the development, the obtained pattern film is cured by heating. As the heating apparatus used for the heating process, the same apparatus as used for the post-exposure heating described above can be used. The heating temperature in this heating step is not particularly limited as long as the coating film can be cured, and is usually 150 to 400 ° C, preferably 200 to 350 ° C. Below 150 ° C., unreacted silanol groups may remain. If the silanol group remains, the chemical resistance of the cured film may be insufficient, or the dielectric constant of the cured film may be increased. From such a viewpoint, the heating temperature is preferably 150 ° C. or higher. The heating time is not particularly limited, and is generally 10 minutes to 24 hours, preferably 30 minutes to 3 hours. The heating time is a time after the temperature of the pattern film reaches a desired heating temperature. Usually, it takes about several minutes to several hours for the pattern film to reach a desired temperature from the temperature before heating.

  The cured film thus obtained can achieve excellent heat resistance, transparency, dielectric constant, 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. For this reason, it has light transmittance and relative dielectric constant characteristics that are not found in acrylic materials that have been used in the past, such as flat panel display (FPD) and other flattening films of various elements as described above, low-temperature polysilicon It can be suitably used in various fields as an interlayer insulating film for use, a buffer coat film for IC chips, a transparent protective film, and the like.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, 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 shown below. In the measurement, the following apparatus and conditions were used.

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

  A spin coater MS-A100 type (trade name, manufactured by Mikasa Co., Ltd.) was used for coating the composition, and the thickness of the formed film was a film thickness meter VM-1200 type (trade name, manufactured by Dainippon Screen Mfg. Co., Ltd.). ).

<Synthesis Example Ia-1>
In a flask equipped with a stirrer, a thermometer, and a condenser, 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. Maintained at ° C. 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 using a dropping funnel at 10 ° C., stirred for 2 hours while maintaining at 10 ° C., and neutralized by adding 10% HCl aqueous solution. To the reaction solution, 400 ml of toluene and 100 ml of water were added and shaken, and then separated into two layers. The solvent was removed by concentrating the obtained organic layer under reduced pressure, and PGMEA was added to the concentrate to adjust the solid content concentration to 40% by weight to prepare a solution containing polysiloxane (Ia-1). The average weight molecular weight (polystyrene conversion) 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 conditions described above.

<Synthesis Example Ia-2>
A siloxane polymer (1a-2) was obtained using the same method as above except that the reaction time was changed to 4 hours. The average weight molecular weight (polystyrene conversion) of the obtained polysiloxane (Ia-2) was 3,600. The obtained polysiloxane solution was applied to a silicon wafer, and the dissolution rate in a 5% TMAH aqueous solution was measured under the above-described conditions.

<Synthesis Example Ia-3>
A siloxane polymer (1a-3) was obtained using the same method as above except that the reaction time was changed to 6 hours. The obtained polysiloxane (Ia-3) had an average weight molecular weight (polystyrene conversion) of 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 above-described conditions.

<Synthesis Example Ib-1>
In a flask equipped with a stirrer, a thermometer, and a condenser, a reaction solvent was prepared by mixing 54.7 g of 25 wt% TMAH aqueous solution, 800 ml of IPA, and 2.0 g of water, and maintained at 10 ° C. 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 using a dropping funnel at 0 to 3 ° C. and stirred for 2 hours while maintaining the temperature at 5 ° C. or lower, and neutralized by adding a 10% HCl aqueous solution. To the reaction solution, 400 ml of toluene and 100 ml of water were added and shaken, and then separated into two layers. The solvent was removed by concentrating the obtained organic layer under reduced pressure, and PGMEA was added to the concentrate to adjust the solid content concentration to 40% by weight to prepare a solution containing polysiloxane (Ib-1). The obtained polysiloxane (Ib-1) had an average weight molecular weight (in terms of polystyrene) of 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-described conditions.

<Synthesis Example Ib-2>
A siloxane polymer (1b-2) was obtained using the same method as above except that the reaction time was changed to 6 hours. The average weight molecular weight (polystyrene conversion) 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.

<Example 1>
Polysiloxane (Ia-1) and polysiloxane (Ib-1) were mixed at a mixing ratio (30% by weight) :( 70% by weight). The dissolution rate of this polysiloxane mixture in the 2.38% TMAH aqueous solution after pre-baking was 2010 kg / sec. This polysiloxane mixture was prepared to be a 35% PGMEA solution, and 1.0% by weight of the photoacid generator represented by the formula (A-1) was added to the polysiloxane. Moreover, 0.3% by weight of KF-53 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) as a surfactant was added to the polysiloxane to obtain a negative photosensitive siloxane composition.

This photosensitive siloxane composition was applied on a silicon wafer by spin coating, and after application, pre-baked on a hot plate at 100 ° C. for 90 seconds to adjust the film thickness to 2 μm. After prebaking, FX-604 type stepper (trade name, manufactured by Nikon Corporation, NA = 0.1) is exposed at 20 mJ / cm ² using a g and h-line exposure machine, and after exposure, reheating is performed on a hot plate at 100 ° C. Was baked for 90 seconds, allowed to stand with a 2.38% TMAH aqueous solution for 40 seconds, and rinsed with pure water for 30 seconds. As a result, a 5 μm line and space (L / S) pattern and a contact hole (C / H) pattern were obtained. It was confirmed that there was no defect such as residue in the pattern.

  After pattern formation, baking and curing were performed at 250 ° C., and the cured pattern was observed with an optical microscope, and a pattern of 5 μm was retained.

Moreover, the dielectric constant was measured about the pattern obtained from this composition. For the measurement, a 495 type mercury probe Cv measuring device (manufactured by Solid State Measurements) was used. Specifically, CV measurement was performed at a measurement frequency of 100 KHz by the mercury probe method, and the relative dielectric constant was calculated from the obtained saturation capacitance. In the dielectric constant measurement, a measurement sample was prepared as follows. The photosensitive siloxane composition was applied onto a silicon wafer by spin coating, and after application, pre-baked on a hot plate at 100 ° C. for 90 seconds to adjust the film thickness to 0.5 μm. Next, exposure dose (20 mJ / cm ^{2 in} the case of Example 1) irradiated during pattern formation using g and h-line exposure machine of FX-604 type stepper (trade name, manufactured by Nikon Corporation, NA = 0.1). ), And after re-exposure, the substrate was baked on a hot plate at 100 ° C. for 90 seconds, immersed in a 2.38% TMAH aqueous solution for 30 seconds, rinsed with pure water, and then at 250 ° C. for 1 hour. It was baked and cured. The relative permittivity of the obtained cured product was 2.9.

<Example 2>
Negative photosensitive siloxane in the same manner as in Example 1 except that the mixing ratio of polysiloxane (Ia-1) and polysilokinesan (Ib-1) was changed to (10 wt%) :( 90 wt%). A composition was obtained. The dissolution rate of this polysiloxane mixture in the 2.38% TMAH aqueous solution after pre-baking was 4330 kg / sec.

Pattern formation and baking hardening were performed in the same manner as in Example 1 except that the exposure amount was changed to 50 mJ / cm ² using this composition. When the obtained pattern was observed, a 5 μm pattern was retained. However, as compared with Example 1, the pattern ridge line portion was rounded at a level that is not problematic in practical use.

<Example 3>
Negative photosensitive siloxane composition as in Example 1, except that the mixing ratio of polysiloxane (Ia-1) and polysiloxane (Ib-1) was changed to (60 wt%) :( 40 wt%). I got a thing. The dissolution rate of this polysiloxane mixture in the 2.38% TMAH aqueous solution after pre-baking was 750 kg / sec.

  A pattern was obtained by changing the development time to 150 seconds and baking and curing to 350 ° C. using this composition. As a result, a 5 μm pattern having no residue was retained.

<Example 4>
Other than using polysiloxane (1b-2) instead of polysiloxane (Ib-1) and changing the mixing ratio to (Ia-1) :( Ib-2) (10 wt%) :( 90 wt%) In the same manner as in Example 1, a negative photosensitive siloxane composition was obtained. The dissolution rate of this polysiloxane mixture in the 2.38% TMAH aqueous solution after pre-baking was 620 kg / sec.

  Using this composition, pattern formation and baking hardening were performed 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 5 μm pattern was retained. However, as compared with Example 1, the pattern ridge line portion was rounded at a level that is not problematic in practical use.

<Example 5>
Other than using polysiloxane (1a-2) instead of polysiloxane (Ia-1) and changing the mixing ratio to (Ia-2) :( Ib-1) = (25 wt%) :( 75 wt%) In the same manner as in Example 1, a negative photosensitive siloxane composition was obtained. This polysiloxane mixture had a dissolution rate of 2.105% / second in a 2.38% TMAH aqueous solution after pre-baking.

  Using this composition, pattern formation and baking hardening were performed in the same manner as in Example 1. When the obtained pattern was observed, a 5 μm pattern having no residue was retained.

<Example 6>
Other than using polysiloxane (1a-3) instead of polysiloxane (Ia-1) and changing the mixing ratio to (Ia-3) :( Ib-1) = (15 wt%) :( 85 wt%) In the same manner as in Example 1, a negative photosensitive siloxane composition was obtained. The dissolution rate of this polysiloxane mixture in the 2.38% TMAH aqueous solution after pre-baking was 2175 kg / sec.

  Using this composition, pattern formation and baking hardening were performed in the same manner as in Example 1. When the obtained pattern was observed, a 5 μm pattern having no residue was retained.

<Example 7>
A negative 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 baking hardening were performed in Example 1. When the obtained pattern was observed, this composition had the same sensitivity as the composition of Example 1, and a pattern of 5 μm was retained. In addition, it was confirmed that the film loss occurring during the baking and curing was reduced although it was slight.

<Example 8>
A negative 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.

Pattern formation and baking hardening were performed in the same manner as in Example 1 except that this composition was used and the exposure amount was changed to 40 mJ / cm ² . When the obtained pattern was observed, a 5 μm pattern was retained.

<Example 9>
For the negative photosensitive siloxane compound described in Example 1, 2,6-di-tert-butyl-4-methylpyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a stabilizer was added to the total weight of the polysiloxane mixture. In addition, 0.1% by weight was added to obtain a negative photosensitive siloxane composition.

  Using this composition, pattern formation and baking hardening were performed in Example 1. When the obtained pattern was observed, this composition had the same sensitivity as the composition of Example 1, and a pattern of 5 μm was retained. Furthermore, when the storage stability at 40 ° C. of this composition was evaluated, it was found that the storage stability was improved with respect to the composition of Example 1.

<Example 10>
A negative-acting siloxane composition was obtained in the same manner as in Example 1 except that the polysiloxane was changed to (Ib-2) only. Using this composition, pattern formation and baking hardening were performed in Example 1. When the obtained pattern was observed, this composition had the same sensitivity as the composition of Example 1, and also had a 5 μm line and space (L / S) pattern and a contact hole (C / H) pattern. was gotten.

<Comparative Example 1>
A negative 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 AX. In addition, the ultraviolet-visible absorption spectrum in the dichloromethane of the aromatic imide compound used as an acid generator in Example 1 and Comparative Example 1 was as shown in FIG. The acid generator AX has an absorption peak at a wavelength of 340 nm, but has a feature of hardly absorbing light having a wavelength of 400 nm or more.

  When this composition was used and tested in the same manner as in Example 1, reheating after exposure was baked on a hot plate at 100 ° C. for 90 seconds, but all the film was dissolved in the developer and the pattern was Couldn't get. This is because the photoacid generator does not absorb the light of g and h rays, so that no acid was generated by exposure.

Claims (10)

Polysiloxane,
An aromatic imide compound that releases acid upon irradiation,
And a negative photosensitive siloxane composition comprising a solvent. The film after the polysiloxane (Ia) pre-baking is soluble in a 5 wt% tetramethylammonium hydroxide aqueous solution, and the dissolution rate thereof is 3,000 kg / sec or less and the (Ib) pre-baking 2. The negative photosensitive siloxane composition according to claim 1, comprising a polysiloxane having a dissolution rate in a 2.38 wt% tetramethylammonium hydroxide aqueous solution of the subsequent film of 150 kg / sec or more. The negative photosensitive siloxane compound according to claim 1 or 2, wherein the aromatic imide compound is 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 obtained by substituting a part or all of hydrogen atoms with a halogen atom,
R ¹² is independently a halogen atom, an aliphatic group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms, and the aliphatic group and the aromatic group are unsubstituted even if they are substituted. Or may contain heteroatoms,
p independently represents a number of 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 cyclic structure. )   The negative photosensitive siloxane according to any one of claims 1 to 3, wherein the aromatic imide compound has a higher extinction coefficient at any wavelength of 400 to 440 nm than an extinction coefficient at 365 nm. Compound.   The negative 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 with respect to 100 parts by weight of polysiloxane.   The adhesion enhancer, polymerization inhibitor, antifoaming agent, surfactant, silane coupling agent, stabilizer, and additive further selected from the group consisting of a photosensitizer. The negative photosensitive siloxane composition of any one of Claims 1.   A negative-type photosensitive siloxane composition according to any one of claims 1 to 6 is applied to a substrate to form a coating film, and the coating film is exposed and developed to produce a cured film. Method.   The manufacturing method of the cured film of Claim 7 which does not include the heating process for hardening a coating film after image development.   A cured film formed from the negative photosensitive siloxane composition according to claim 1.   An element comprising the cured film according to claim 9.

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