JP2015018226A - Negative-type photosensitive composition curable at low temperature - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a negative-type photosensitive composition which can be cured at a low temperature and provide a cured film with high transparency and chemical resistance, and a pattern forming method using the same.SOLUTION: A negative-type photosensitive composition comprises a polysiloxane, a (meth)acryloyl polymer, a compound comprising two or more (meth) acryloyl groups, a polymerization initiator, and a solvent.

Description

  The present invention relates to a negative photosensitive 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).

  Such a flat film can be formed by condensing a compound having a silanol group such as polysiloxane. In general, heating at a high temperature of 150 ° C. or higher is necessary to allow the silanol group condensation reaction to proceed rapidly. In order to reduce the manufacturing cost, it is preferable that the heating temperature is low. Therefore, if the reactivity of the silanol group is increased in order to lower the heating temperature, the compound containing the silanol group or the composition containing the same is stored. Stability is often impaired. For this reason, a composition that can achieve both low-temperature curing and composition stability has not been found.

Japanese Patent No. 2933879 No. 2006-073021 JP 2011-190333 A

  The present invention has been made based on the above-described circumstances, and is a negative photosensitive composition capable of forming a cured film or pattern excellent in transparency, chemical resistance, and environmental resistance at a low temperature. Is intended to provide.

  The negative photosensitive composition according to the present invention comprises polysiloxane, a (meth) acrylic polymer, a compound containing two or more (meth) acryloyl groups, a polymerization initiator, and a solvent. .

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

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

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

  The negative photosensitive composition of the present invention is optically transparent, can form a pattern or a cured film having high chemical resistance and environmental resistance, and is stable over time. Also excellent. In addition, it can be cured in a low temperature region, and a cured film or pattern can be produced at a lower cost without requiring a heating process after exposure. And since the obtained cured film is excellent in flatness and electrical insulation characteristics, a flattening film for a thin film transistor (TFT) substrate used for a backplane of a display such as a liquid crystal display element or an organic EL display element, Various film-forming materials such as insulating films and transparent protective films in solid-state imaging devices, anti-reflection films, anti-reflection plates, optical filters, high-intensity light-emitting diodes, touch panels, solar cells, etc. It can be suitably used as an optical element such as an optical waveguide.

Negative photosensitive composition The negative photosensitive composition according to the present invention contains at least a polysiloxane, a (meth) acrylic polymer, a compound containing two or more (meth) acryloyl groups, a polymerization initiator, and a solvent. It is a feature. Hereinafter, each component used with the negative photosensitive composition of this invention is demonstrated in detail sequentially.

(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, a hydroxyalkyl group, and an aryl group, and a hydrogen atom of these groups is an unsaturated hydrocarbon. Examples include a group substituted by a 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, the required solubility differs depending on the thickness of the coating film to be formed and the development conditions, and therefore polysiloxanes 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) (wherein 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, Alternatively, an aryl group having 6 to 20 carbon atoms in which arbitrary hydrogen may be replaced with fluorine, 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 The second polysiloxane has a pre-baked film that is soluble in an aqueous 2.38 wt% tetramethylammonium hydroxide solution, and has a dissolution rate of 150 kg / sec or more, preferably 300 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 kg / second or more, and preferably 300 kg / second or more, as will be 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. The dissolution rate of the polysiloxane mixture (I) in the 2.38% TMAH aqueous solution depends on the thickness of the cured film formed from the negative photosensitive composition of the present invention, the development time, and the like. 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 differs depending on the type and amount of the photosensitive agent contained in the negative photosensitive composition. For example, when the film thickness is 0.1 to 10 μm (1,000 to 100,000 Å), the dissolution rate in the 2.38% TMAH aqueous solution is preferably 50 to 5,000 Å / sec.

  In addition, when using a polysiloxane mixture, it is preferable that the weight average molecular weight of the whole polysiloxane is 5,000 or less, and it is more preferable that it is 4000 or less. The same applies when a single polysiloxane is used instead of the polysiloxane mixture. Moreover, when using a polysiloxane mixture, it is preferable that the weight average molecular weight of each polysiloxane is 5,000 or less. In addition, in this invention, a weight average molecular weight is a styrene conversion weight average molecular weight by gel permeation chromatography.

(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) (Meth) acrylic polymer The negative photosensitive composition according to the present invention comprises a (meth) acrylic polymer. Here, the (meth) acrylic polymer is a general term for polymers obtained by polymerizing at least one monomer selected from the group consisting of acrylic acid, methacrylic acid, acrylate, and methacrylate. These polymers may be copolymers obtained by polymerizing different monomers, and may contain monomers other than those described above as long as the effects of the present invention are not impaired. As such a (meth) acrylic polymer, any conventionally known one can be used. In the present invention, from the viewpoint of reactivity, a (meth) acrylic polymer containing a repeating unit having an unsaturated bond is used. Or a (meth) acrylic polymer containing a repeating unit having an acid group is preferably used, and both of these are more preferably used.

  As the (meth) acrylic polymer containing a repeating unit having an unsaturated bond, a vinyl group, an acryloyl group, a methacryloyl group, an acetylenyl group, an acid anhydride typified by maleic acid or itaconic acid, an imido acid such as maleimide, etc. Examples thereof include acrylic polymers and methacrylic polymers having a group containing a carbon-carbon unsaturated bond such as an anhydride. Such a compound reacts with other reactive components contained in the composition by the unsaturated bond to form a crosslinked structure.

  Further, the (meth) acrylic polymer containing a repeating unit having an unsaturated bond is preferably one having a silicon-containing group in order to improve the compatibility of the polysiloxane. Specifically, (meth) acrylic polymers substituted with siloxy groups or silanol groups, silane coupling agents having carbon-carbon unsaturated bonds, silicone oligomers, or (meth) acrylic polymers reacted with silicone oil, etc. Is preferable, and a copolymer of a silicone coupling agent and a (meth) acrylic polymer is particularly preferable. Here, KBM-1003, KME-1003, KBM-1403, and KBM-5103 are used as silicone coupling agents, and X-40-9272B, KR-513, X-40-2672B, and X-40 are used as silicone oligomers. -9272B, silicone oils include X-22-174DX, X-22-2426, X-22-2475, and X-22-1602 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

  The weight average molecular weight of such a polymer is not particularly limited, but is preferably 2,000 to 100,000, and more preferably 3,000 to 30,000. The number of unsaturated bonds is not particularly limited, but the double bond equivalent is preferably 10 to 500 g / eq from the viewpoint of achieving both reactivity and storage stability.

  Examples of the (meth) acrylic polymer containing a repeating unit having an acid group include an acrylic polymer and a methacrylic polymer having a carboxyl group, a sulfo group, a phenolic hydroxy group and the like in the side chain. When these polymers have an acid group, the solubility of the uncured portion is promoted during development.

  The weight average molecular weight of such a polymer is not particularly limited, but is preferably 2,000 to 100,000, and more preferably 3,000 to 30,000. The number of acid groups is not particularly limited, but the acid value is preferably 50 to 500 mgKOH / g from the viewpoint of achieving both reactivity and storage stability.

  When a (meth) acrylic polymer containing a repeating unit having an unsaturated bond and a (meth) acrylic polymer containing a repeating unit having an acid group are used in combination, their blending ratio is not particularly limited, but during development It is preferably 8: 2 to 2: 8 from the viewpoint of ensuring both the solubility of the uncured portion and the reactivity at the time of curing.

  Furthermore, it is also preferable to use a (meth) acrylic polymer containing both a repeating unit having an unsaturated bond and a repeating unit having an acid group. In such a meth) acrylic polymer, the number of unsaturated bonds and the number of acid groups are not particularly limited, but the double bond equivalent is preferably 10 to 500 g / eqm, and the acid value is preferably 5 to 150 mgKOH / g. .

  Further, the blending ratio of the polysiloxane and the (meth) acrylic polymer is not particularly limited, but it is preferable that the blending ratio of the (meth) acrylic polymer is large from the viewpoint of heat resistance and transparency after curing. From the viewpoint of chemical resistance, it is preferable that the compounding ratio of polysiloxane is large. For these reasons, the blending ratio of polysiloxane and (meth) acrylic polymer is preferably 90:10 to 10:90, and more preferably 75:25 to 25:75.

(III) Compound containing two or more (meth) acryloyl groups The negative photosensitive composition according to the present invention is a compound containing two or more (meth) acryloyl groups (hereinafter referred to as a (meth) acryloyl group-containing compound for the sake of simplicity). In some cases).
Here, the (meth) acryloyl group is a general term for an acryloyl group and a methacryloyl group. This compound is a compound that can react with the polysiloxane and the (meth) acrylic polymer to form a crosslinked structure. Here, in order to form a crosslinked structure, a compound containing two or more acryloyl groups or methacryloyl groups which are reactive groups is necessary, and in order to form a higher order crosslinked structure, three or more acryloyl groups or methacryloyl groups are required. Preferably it contains a group. Examples of the compound containing two or more such (meth) acryloyl groups include esters in which (α) a polyol compound having two or more hydroxyl groups and (β) two or more (meth) acrylic acids have reacted. Is preferably used. As this polyol compound (α), a saturated or unsaturated aliphatic hydrocarbon, aromatic hydrocarbon, heterocyclic hydrocarbon, primary, secondary, or tertiary amine, ether or the like is used as a basic skeleton, and 2 as a substituent. Examples thereof include compounds having two or more hydroxyl groups. The polyol compound may contain other substituents such as a carboxyl group, a carbonyl group, an amino group, an ether bond, a thiol group, and a thioether bond as long as the effects of the present invention are not impaired. Preferred polyol compounds include alkyl polyols, aryl polyols, polyalkanolamines, cyanuric acid, or dipentaerythritol. Here, when a polyol compound ((alpha)) has a 3 or more hydroxyl group, it is not necessary for all the hydroxyl groups to react with meta (acrylic acid), and it may be esterified partially. That is, these esters may have an unreacted hydroxyl group. Such esters include tris (2-acryloxyethyl) isocyanurate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipropylene glycol diacrylate , Tripropylene glycol diacrylate, trimethylolpropane triacrylate, polytetramethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, tricyclodecane dimethanol diacrylate, 1,9-nonanediol diacrylate, 1 , 6-hexanediol diacrylate, 1,10-decanediol diacrylate, and the like. Of these, tris (2-acryloxyethyl) isocyanurate and dipentaerythritol hexaacrylate are preferred from the viewpoint of reactivity and the number of crosslinkable groups. Moreover, in order to adjust the shape of the pattern to be formed, two or more of these compounds can be combined. Specifically, a compound containing three (meth) acryloyl groups and a compound containing two (meth) acryloyl groups can be combined.

  Such a compound is preferably a molecule relatively smaller than the polymer from the viewpoint of reactivity. For this reason, it is preferable that molecular weight is 2000 or less, and it is preferable that it is 1500 or less.

  The blending amount of the acryloyl group-containing compound is adjusted according to the type of the polymer used and the acryloyl group-containing compound. From the viewpoint of compatibility with the resin, the total weight of polysiloxane and (meth) acrylic polymer is 100. It is preferable that it is 3-50 weight part with respect to a weight part. Moreover, these acryloyl group containing compounds may be used independently or may be used in combination of 2 or more types.

(IV) Polymerization initiator The negative photosensitive composition according to the present invention comprises a polymerization initiator. The polymerization initiator includes a polymerization initiator that generates an acid, a base, or a radical by radiation, and a polymerization initiator that generates an acid, a base, or a radical by heat.

  The polymerization initiator can improve the resolution by strengthening the pattern shape or increasing the contrast of development. As a polymerization initiator used in the present invention, a photoacid generator that releases an acid, which is an active substance that decomposes upon irradiation with radiation to photocure the composition, a photobase generator that releases a base, and a radical are released. Photo-radical generators, thermal acid generators that release acids that are active substances that decompose by heat to thermally cure the composition, thermal base generators that release bases, thermal radical generators that release radicals, etc. can give. Here, examples of the radiation include visible light, ultraviolet rays, infrared rays, X-rays, electron beams, α rays, and γ rays.

The amount of polymerization initiator added varies depending on the type of active substance generated by decomposition of the polymerization initiator, the amount generated, and the required sensitivity / dissolution contrast between exposed and unexposed areas. Preferably it is 0.001-10 weight part with respect to 100 weight part of total weights of a (meth) acrylic polymer, 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 polymerization initiator added is more than 10 parts by weight, cracks may occur in the formed film, or coloring due to decomposition of the polymerization initiator may become prominent. There are things to do. 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.

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

Here, R ⁺ represents an organic ion selected from the group consisting of an alkyl group, an aryl group, an alkenyl group, an acyl group, and an alkoxyl group modified with hydrogen, a carbon atom or other hetero atom, such as diphenyliodonium ion, triphenyl Represents a sulfonium ion.

Further, X ⁻ is preferably any counter ion represented by the following general formula.
SbY ₆ ⁻
AsY ₆ ⁻
R ^a _p PY _6-p ^-
R ^a _q BY _4-q ⁻
R ^a _q GaY _4-q ⁻
R ^a SO ₃ ⁻
(R ^a SO ₂ ) ₃ C ⁻
(R ^a SO ₂ ) ₂ N ⁻
R ^b COO ⁻
SCN ^-
(Where
Y is a halogen atom,
R ^a is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, which is substituted with a substituent selected from fluorine, a nitro group, and a cyano group;
R ^b is hydrogen or an alkyl group having 1 to 8 carbon atoms;
p is a number from 0 to 6,
q is a number from 0 to 4. )

Specific counter ions include BF ₄ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ B ⁻ , PF ₆ ⁻ , (CF ₃ CF ₂ ) ₃ PF ₃ ^−. , SbF ₆ ⁻ , (C ₆ F ₅ ) ₄ Ga ⁻ , ((CF ₃ ) ₂ C ₆ H ₃ ) ₄ Ga ⁻ , SCN ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ SO ₂ ) ₂ N ^-, formate ions, acetate ions, trifluoromethanesulfonate ions, consisting nonafluorobutanesulfonate ion, methanesulfonate ion, butane sulfonic acid ion, benzenesulfonic acid ion, p- toluenesulfonate ion, and a sulfonate ion Those selected from the group can be mentioned.

式中、
Ａはそれぞれ独立に、炭素数１〜２０のアルキル基、炭素数１〜２０のアルコキシ基、炭素数６〜２０のアリール基、炭素数１〜２０のアルキルカルボニル基、炭素数６〜２０のアリールカルボニル基、水酸基、およびアミノ基から選ばれる置換基であり、
ｐはそれぞれ独立に０〜５の整数であり、
Ｂ⁻は、フッ素化されたアルキルスルホネート基、フッ素化されたアリールスルホネート基、フッ素化されたアルキルボーレート基、アルキルスルホネート基、アリールスルホネート基などが挙げられる。これらの式に示されたカチオンおよびアニオンを相互に交換した化合物や、これらの式に示されたカチオンまたはアニオンと、前記した各種のカチオンまたはアニオンとを組み合わせた光酸発生剤を用いることもできる。例えば、式により表されたスルホニウムイオンのいずれかとテトラ（パーフルオロフェニル）ホウ酸イオンとを組み合わせたもの、式により表されたヨードニウムイオンのいずれかとテトラ（パーフルオロフェニル）ホウ酸イオンとを組み合わせたものも光酸発生剤として用いることができる。 Among the photoacid generators used in the present invention, those that generate sulfonic acids or boric acids are particularly preferable. For example, tricumyliodonium tetrakis (pentafluorophenyl) boric acid (PHOTINITITOR 2074 (trade name) manufactured by Rhodia), Examples thereof include diphenyliodonium tetra (perfluorophenyl) borate, a cation part composed of a sulfonium ion, and an anion part composed of a pentafluoroborate ion.
In addition, triphenylsulfonium trifluoromethanesulfonic acid, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetra (perfluorophenyl) boric acid, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenic acid, 1- (4-n-butoxynaphthalene- 1-yl) tetrahydrothiophenium trifluoromethanesulfonic acid, 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonic acid, diphenyliodonium trifluoromethanesulfonic acid, diphenyliodonium hexafluoroarsenic acid, etc. Can be mentioned. Furthermore, a photoacid generator represented by the following formula can also be used.

Where
A is independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylcarbonyl group having 1 to 20 carbon atoms, and an aryl having 6 to 20 carbon atoms. A substituent selected from a carbonyl group, a hydroxyl group, and an amino group;
p is each independently an integer of 0 to 5;
Examples of B ⁻ include a fluorinated alkyl sulfonate group, a fluorinated aryl sulfonate group, a fluorinated alkyl borate group, an alkyl sulfonate group, and an aryl sulfonate group. A compound obtained by exchanging the cation and anion shown in these formulas with each other, or a photoacid generator combining the cation or anion shown in these formulas with the above-mentioned various cations or anions can also be used. . For example, a combination of any of the sulfonium ions represented by the formula and a tetra (perfluorophenyl) borate ion, a combination of any of the iodonium ions represented by the formula and a tetra (perfluorophenyl) borate ion Those can also be used as photoacid generators.

  Examples of the thermal acid generator include various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids and salts thereof such as citric acid, acetic acid, and maleic acid, and various aromatic carboxylic acids such as benzoic acid and phthalic acid. Examples thereof include salts and esters that generate organic acids, such as salts thereof, aromatic sulfonic acids and ammonium salts thereof, various amine salts, aromatic diazonium salts, and phosphonic acids and salts thereof. Among the thermal acid generators used in the present invention, a salt composed of an organic acid and an organic base is preferable, and a salt composed of a sulfonic acid and an organic base is more preferable.

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

  Examples of the photobase generator include a polysubstituted amide compound having an amide group, a lactam, an imide compound, or a compound containing the structure.

  Examples of the thermal base generator include N- (2-nitrobenzyloxycarbonyl) imidazole, N- (3-nitrobenzyloxycarbonyl) imidazole, N- (4-nitrobenzyloxycarbonyl) imidazole, N- (5 -Methyl-2-nitrobenzyloxycarbonyl) imidazole, imidazole derivatives such as N- (4-chloro-2-nitrobenzyloxycarbonyl) imidazole, 1,8-diazabicyclo (5,4,0) undecene-7, third Secondary amines, quaternary ammonium salts, and mixtures thereof.

  Examples of the photoradical generator include azo, peroxide, acylphosphine oxide, alkylphenone, oxime ester, and titanocene initiators. Of these, alkylphenone-based, acylphosphine oxide-based and oxime ester-based initiators are preferable, and 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6- Trimethylbenzoyl) phenylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

  Examples of the thermal radical generator include 2,2'-azobis (2-methylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and the like.

  These base generators and radicals can be used alone or as a mixture, like the acid generator.

(V) Solvent The negative photosensitive 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 (meth) acrylic polymer, the (meth) acryloyl group-containing compound, and an 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 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 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 composition of the present invention do not vary greatly depending on the amount of the solvent.

(VI) Silicon compound containing thiol group The negative photosensitive composition according to the present invention comprises a silicon compound containing a thiol group, if necessary. Here, the silicon compound forming the main structure is not particularly limited, such as polysiloxane, silsesquioxane, polysilazane, polysiloxazan, silane, and silanol.
Moreover, it is not limited to an inorganic compound, The organic silicon compound which substituted the hydrogen of the inorganic silicon compound with the hydrocarbon group etc., The organic compound mainly having the hydrocarbon substituted by the siloxy group or the silanol group can also be used. And the thiol group can couple | bond with the silicon compound which forms these main structures directly or through arbitrary coupling groups.

Specifically, the compound which contains the following partial structures (a) and (b) in a repeating unit can be mentioned.
[SiR ¹ O _1.5 ] (a)
[Si (R ² SH) O _1.5 ] (b)
(In the formula, R ¹ is a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, and R ² is a single bond or a hydrocarbon chain having 1 to 10 carbon atoms.)

  Also, a silicone oligomer such as X-41-1818, X-41-1810, or X-41-1805 (both trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), or a silane coupling agent such as KBM-802, or KBM-803 (both trade names, manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used. Of these, those in which a thiol group is bonded to polysiloxane or silsesquioxane are preferable from the viewpoint of compatibility with polysiloxane which is the main component of the composition and crosslinkability by reaction.

  When the silicon compound containing a thiol group is a polymer compound, the weight average molecular weight is preferably 500 to 10,000, and more preferably 1,000 to 5,000. In addition, the number of thiol groups per molecule of the compound is not particularly limited, but is preferably large in order to form a crosslinked structure, and is preferably not more than a certain value in order to prevent unnecessary reactions from proceeding. . From such a viewpoint, when the silicon compound containing a thiol group is a polymer compound, the thiol group per equivalent is preferably 0.2 to 3.5, and 0.5 to 3.2. Preferably there is. The compounding amount of the silicon compound containing a thiol group is preferably large in order to keep good chemical resistance after curing, and is preferably a certain amount or less in order to keep the storage stability. From these viewpoints, the blending amount of polysiloxane and (meth) acrylic polymer with respect to 100 parts by weight of the total weight is preferably 0.5 to 50 parts by weight.

(VII) Additive The negative photosensitive 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, or 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, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total weight of the polysiloxane and the (meth) acrylic polymer.

  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 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 the total weight of polysiloxane and (meth) acrylic polymer.

  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 an acid group such as phosphonium, borate, carboxyl, phenol, peroxide, nitro, cyano, sulfo, and an alcohol group, and these acid groups are acetyl, aryl, amyl, benzyl, methoxymethyl, mesyl, Examples include those protected with 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 which has an acid group, a siloxane compound, etc. as a silane coupling agent, the addition amount is 0.01-15 weight part with respect to 100 weight part of total weight of polysiloxane and a (meth) acrylic polymer. It is preferable that

  As a polymerization inhibitor, in addition to nitrone, nitroxide radical, hydroquinone, catechol, phenothiazine, phenoxazine, hindered amine and derivatives thereof, an ultraviolet absorber can be added. Among these, TINUVIN 144, 292, 5100 (manufactured by BASF) as catechol, 4-t-butylcatechol, 3-methoxycatechol, phenothiazine, chlorpromazine, phenoxazine, hindered amine, TINUVIN 326, 328, 384 as ultraviolet absorbers 2,400,477 (made by BASF) are preferable. These can be used singly or in combination, and the addition amount is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the total weight of polysiloxane and (meth) acrylic polymer.

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 weight of polysiloxane and (meth) acrylic polymer.

  Further, the negative photosensitive 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, (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 10,000 ppm, preferably 100 to 1 with respect to the negative photosensitive composition of the present invention. 1,000 ppm.

Moreover, a sensitizer can be added to the negative photosensitive composition of this invention as needed.
Sensitizers preferably used in the negative photosensitive composition of the present invention include coumarins, ketocoumarins and derivatives thereof, 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-trifluoromethyl Coumarin, 7-dimethylamino-4-trifluoromethylcoumarin, 7-amino-4-trif Olomethylcoumarin, 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) -benzothiazoli Ruethyl iodide, 3- (2′-benzimidazolyl) -7-N, N-diethylaminocoumarin, 3- (2′-benzothiazolyl) -7-N, N-diethylaminoc Phosphorus, 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, and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total weight of the polysiloxane and the (meth) acrylic polymer.

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 2 or 3 and the like. When such a sensitizer having an anthracene skeleton is used, the addition amount is preferably 0.01 to 5 parts by weight with respect to 100 parts by weight of the total weight of the polysiloxane and the (meth) acrylic polymer.

Moreover, a stabilizer can be added to the negative photosensitive 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-mentioned negative 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) Coating process First, the above-described negative photosensitive composition is coated on a substrate. Formation of the coating film of the photosensitive 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-baking step After forming a coating film by applying a negative photosensitive composition, the coating film is dried, and the coating film is pre-baked in order to reduce the amount of solvent remaining in the coating film. (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 composition of the present invention.
The energy of the irradiation light, depending on the thickness of the light source and the coating film, generally 5~2000mJ / cm ^2, preferably a 10~1000mJ / 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. Unlike the heating step (6) described later, this heat treatment is not performed to completely cure the coating film, but only a desired pattern is left on the substrate after development, and other portions are removed by development. It is done so that it can be done. Therefore, it is not essential in the present invention.

  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 conventionally used for developing a photosensitive 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, and a particularly preferred alkaline developer is an aqueous tetramethylammonium hydroxide solution, an aqueous potassium hydroxide solution, or an aqueous sodium 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 it can cure the coating film, and can be arbitrarily determined. However, 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 generally selected as a relatively high temperature. However, the negative photosensitive composition according to the present invention can be cured at a relatively low temperature. Specifically, it is preferable to cure by heating at 360 ° C. or lower, and in order to keep the residual film ratio after curing high, the curing temperature is more preferably 300 ° C. or lower, and 150 ° C. or lower. Particularly preferred. On the other hand, in order to accelerate the curing reaction and obtain a sufficient cured film, the curing temperature is preferably 70 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 110 ° 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 transparency, chemical resistance, environmental resistance and the like. For example, the film loss at 280 ° C. of the film cured at 120 ° C. is 5% or less, sufficient heat resistance is achieved, and the light transmittance of the cured film is 95% or more and the relative dielectric constant is 4 or less. can do. 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.

<Example 1>
Polysiloxane S1 having a dissolution rate in a 2.38% TMAH aqueous solution after pre-baking of 1,200 kg / second and a weight average molecular weight of 1,750, a dissolution rate in a 5.00% TMAH aqueous solution of 500 kg / second, and a weight average molecular weight of 2,700 Polysiloxane S2, vinyl polymer-containing acrylic polymer A1-1 (weight average molecular weight 12,000, double bond equivalent 24 g / eq, acid value 19 mgKOH / g), carboxyl group-containing acrylic polymer A2-1 (weight average molecular weight) 7,500, acid value 120-130 mgKOH / g) was mixed at a ratio of 10: 20: 40: 30 to obtain a polymer mixture. To this polymer mixture, 25 parts by weight and 12 parts by weight of tris (2-acryloxyethyl) isocyanurate (M1) and dipentaerythritol hexaacrylate (M2) as a (meth) acryloyl group-containing compound, respectively, as a polymerization initiator 6.0 parts by weight of Irgacure OXE-02 (PI) and 8 parts by weight of silicon compound SQ containing a thiol group were added. Here, compound SQ is a silsesquioxane-like condensate having a thiol group, in which a thiol group is bonded to a silicon atom via a butylene group, and the thiol group equivalent is 535 g / eq. Further, 0.3 part by weight of KF-53 manufactured by Shin-Etsu Chemical Co., Ltd. was added as a surfactant and adjusted to a 35% PGMEA solution to obtain a negative photosensitive composition. Here, the blending ratio (polymerization part) of each component is based on 100 parts by weight of the total weight of polysiloxane and (meth) acrylic polymer.

This negative photosensitive composition was applied onto a silicon wafer by spin coating, and after application, pre-baked on a hot plate at 70 ° C. for 90 seconds to adjust the film thickness to 1.5 μm.
After confirming that the film obtained after pre-baking is not tacky or tacky, it was exposed at 20 mJ / cm ² using an i-line exposure machine, immersed in a 2.38% TMAH aqueous solution for 60 seconds, and purified water for 30 seconds. Rinse by. As a result, it was confirmed that the 10 μm line and space (L / S) pattern and the contact hole (C / H) pattern were missing. After pattern formation, baking and curing were performed at 120 ° C., and when confirmed with an optical microscope, a 10 μm pattern was retained. Moreover, after heating the obtained pattern to 60 degreeC, it was immersed in 3% KOH solution for 3 minutes, and when the presence or absence of the pattern was confirmed, holding | maintenance of the pattern was confirmed. Further, when the composition was stored at room temperature of 23 ° C. and humidity of 45%, changes in sensitivity and pattern shape after one week were not observed.

表中：
アクリルポリマーＡ１−２：ビニル基を有するアクリルポリマー（重量平均分子量１０，０００、二重結合当量１０５ｇ／ｅｑ、酸価２０ｍｇＫＯＨ／ｇ）
アクリルポリマーＡ２−２：カルボキシル基を有するアクリルポリマー（重量平均分子量１５，０００、酸価１２０〜１３０ｍｇＫＯＨ／ｇ） <Examples 2 to 13 and Comparative Examples 1 to 4>
With respect to Example 1, a negative photosensitive composition having a composition changed as shown in Table 1 was prepared and evaluated in the same manner as in Example 1. The obtained results were as shown in Table 1.

In the table:
Acrylic polymer A1-2: Acrylic polymer having a vinyl group (weight average molecular weight 10,000, double bond equivalent 105 g / eq, acid value 20 mgKOH / g)
Acrylic polymer A2-2: Acrylic polymer having a carboxyl group (weight average molecular weight 15,000, acid value 120 to 130 mgKOH / g)

The evaluation criteria for each characteristic were as follows.
The film surface after the residue developed after development was evaluated by observing with an optical microscope.
A: No residue B: Some residue at the bottom of the pattern C: Thin layered residue D: Thick layered residue
Residual film ratio after development or curing The film thickness before development and the film thickness after development or after curing were observed with an optical microscope, and the rate of change was evaluated.
A: 90% or more B: 70% or more C: 50% or more D: Less than 50% N / A: Cannot be measured (no remaining film)
The probe was brought into contact with the sticky film surface of the film surface and observed visually.
A: There is no stickiness, and no fogging is recognized even when touching the film surface. B: Practical level although slight fogging is recognized when touching the film surface C: Many stickiness, impractical
After heating the chemical resistance pattern to 60 ° C., it was immersed in a 3% KOH solution for 3 minutes, the presence or absence of the pattern was observed with an optical microscope, and the remaining rate of the film before and after immersion was evaluated.
A: 90% or more B: 70% or more C: 50% or more D: less than 50% N / A: impossible to measure (no residual film)

Claims (14)

  A negative photosensitive composition comprising polysiloxane, a (meth) acrylic polymer, a compound containing two or more (meth) acryloyl groups, a polymerization initiator, and a solvent. (Ia) A film after pre-baking is soluble in a 5% by weight tetramethylammonium hydroxide aqueous solution, and the dissolution rate thereof is 3,000 kg / sec or less, and (Ib) of the film after pre-baking. 2. The negative photosensitive composition according to claim 1, comprising a second polysiloxane having a dissolution rate with respect to an aqueous 2.38 wt% tetramethylammonium hydroxide solution of 150 kg / sec or more.   The negative photosensitive composition of Claim 1 or 2 whose weight average molecular weight of the polysiloxane contained in a composition is 5,000 or less.   The compound according to any one of claims 1 to 3, comprising 3 to 50 parts by weight of a compound containing two or more (meth) acryloyl groups based on 100 parts by weight of the total weight of polysiloxane and (meth) acrylic polymer. Negative photosensitive composition.   The negative type according to any one of claims 1 to 4, comprising a (meth) acrylic polymer containing a repeating unit having an unsaturated bond and a (meth) acrylic polymer containing a repeating unit having an acid group. Photosensitive composition.   The negative photosensitive composition of any one of Claims 1-5 which further contains the silicon compound containing a thiol group.   The negative photosensitive composition of Claim 6 whose silicon compound containing the said thiol group is a polymer which contains a thiol group containing siloxane as a repeating unit.   The negative photosensitive composition of Claim 6 or 7 which contains 0.5-50 weight part of silicon compounds containing the said thiol group with respect to 100 weight part of total weight of polysiloxane and a (meth) acrylic polymer.   The negative photosensitive resin according to any one of claims 1 to 8, comprising 0.001 to 10 parts by weight of a polymerization initiator with respect to 100 parts by weight of the total weight of the polysiloxane and the (meth) acrylic polymer. Composition.   The additive further comprising an additive selected from the group consisting of a developer dissolution accelerator, a scum remover, an adhesion enhancer, a polymerization inhibitor, an antifoaming agent, a surfactant, and a photosensitizer. The negative photosensitive composition of any one of 9.   A method for producing a cured film, comprising applying the negative photosensitive composition according to claim 1 to a substrate to form a coating film, exposing the coating film, and developing the coating film. .   The manufacturing method of the cured film of Claim 11 heated at the temperature of 70 degreeC or more and 360 degrees C or less in order to harden a coating film after image development.   A cured film formed from the negative photosensitive composition according to claim 1.   An element comprising the cured film according to claim 13.