TWI853901B - Positive photosensitive polysiloxane composition and method for producing cured film - Google Patents

Abstract

Provided are a positive photosensitive polysiloxane composition and a manufacturing method using the same. The positive photosensitive polysiloxane composition can produce a cured film with high surface smoothness and suppressed wrinkle generation even when the entire surface is exposed without adding a curing aid.

A positive photosensitive polysiloxane composition and a method for producing a cured film using the composition, wherein the positive photosensitive polysiloxane composition comprises the following: (I) polysiloxane; (II) a carboxylic acid compound, which is a monocarboxylic acid or a dicarboxylic acid in an amount of 200 to 50,000 ppm based on the total mass of the composition; (III) a diazonaphthoquinone derivative; and (IV) a solvent.

Description

Positive photosensitive polysiloxane composition and method for manufacturing hardened film

The present invention relates to a positive photosensitive polysiloxane composition. In addition, the present invention relates to a method for manufacturing a cured film using the composition and an electronic component including the cured film.

In recent years, various proposals have been made to further improve light utilization efficiency and save energy in optical elements such as displays, LEDs, and solar cells. For example, in liquid crystal displays, there is a known method of increasing the aperture ratio of a display device by coating a transparent planarization film on a TFT element and forming a pixel electrode on the planarization film.

As a material for the planarization film for this TFT substrate, a material combining acrylic resin and quinone diazide compound is known. Since these materials have planarization properties and photosensitivity, contact holes and other patterns can be formed. However, as the resolution and frame frequency increase, the wiring becomes more complex, so the planarization becomes more stringent and these materials become difficult to cope with.

As a material with high heat resistance and high transparency, polysiloxane, especially silsesquioxane, is known. Silsesquioxane is a polymer composed of trifunctional siloxane structural units RSi (O _1.5 ), and is a special compound that is intermediate between inorganic silica (SiO ₂ ) and organic polysilicon (R ₂ SiO) in chemical structure. It is soluble in organic solvents, and its cured product shows high heat resistance, which is characteristic of inorganic silica.

Using a positive photosensitive composition containing such polysiloxane and a photosensitive agent, a pattern can be formed by exposure and development, and a cured film can be formed by heating. In the cured film formed in this way, the film surface may not become flat and wrinkles may occur. In order to suppress the generation of wrinkles, a curing aid may be added, or the entire surface may be exposed after exposure and development. [Prior art literature] [Patent literature]

Patent Document 1 Japanese Patent Application Publication No. 2011-2517

[The problem that the invention wants to solve]

The present invention is completed based on the above situation, and its purpose is to provide: a positive photosensitive polysiloxane composition, which can produce a cured film with high surface smoothness and suppressed wrinkle generation even without adding a curing aid and performing full-surface exposure. Another purpose is to provide a method for producing a cured film using the same. [Means for solving the problem]

The positive photosensitive polysiloxane composition of the present invention comprises the following: (I) polysiloxane; (II) a carboxylic acid compound, which is a monocarboxylic acid or a dicarboxylic acid in an amount of 200 to 50,000 ppm based on the total mass of the composition; (III) a diazonaphthoquinone derivative; and (IV) a solvent.

Furthermore, the method for manufacturing the hardened film of the present invention comprises the following steps: (1) applying the positive photosensitive polysiloxane composition of the present invention to a substrate to form a composition layer, (2) exposing the aforementioned composition layer, (3) developing with an alkaline developer to form a pattern, and (4) heating the obtained pattern.

Furthermore, the electronic component of the present invention comprises a cured film produced by the above method. [Effect of the invention]

By using the positive photosensitive polysiloxane composition of the present invention, even without adding a curing aid and performing full-surface exposure, a cured film with high surface smoothness and suppressed wrinkles can be produced. The obtained film is highly sensitive and can contribute to high throughput of the manufacturing process. In addition, the pattern shape of the cured film can also be made into a shape with a smooth opening portion as desired in the subsequent steps. Furthermore, the obtained cured film has excellent flatness and electrical insulation properties, and therefore can be suitably used as a variety of film-forming materials such as planarizing films for thin-film transistor (TFT) substrates used in backplanes of displays such as liquid crystal display elements and organic EL display elements, interlayer insulation films of semiconductor elements, solid-state imaging elements, antireflection films, antireflection plates, optical filters, high-brightness light-emitting diodes, touch panels, insulating films in solar cells, transparent protective films, and optical elements such as optical waveguides.

[Form used to implement the invention]

The following is a detailed description of the implementation form of the present invention. In this specification, unless otherwise specified, symbols, units, abbreviations, and terms have the following meanings. In this specification, unless otherwise specified, the singular includes the plural, and "1" and "it" mean "at least 1". In this specification, unless otherwise specified, the elements of a certain concept can be expressed in plural forms, and when recording their quantity (for example, mass%, molar%), their quantity means the sum of their plural forms. "And/or" includes all combinations of elements and also includes the use of monomers.

In this specification, when ~ or - is used to indicate a numerical range, both ends are included and the unit is common. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

In the present specification, alkyl means a hydrocarbon containing carbon and hydrogen, and containing oxygen or nitrogen as required. A alkyl group means a hydrocarbon with a valency of one or more than two. In the present specification, an aliphatic hydrocarbon means a linear, branched or cyclic aliphatic hydrocarbon, and an aliphatic alkyl group means an aliphatic hydrocarbon with a valency of one or more than two. An aromatic hydrocarbon means a hydrocarbon containing an aromatic ring which may have an aliphatic hydrocarbon group as a substituent as required and may be condensed with an aliphatic ring. An aromatic alkyl group means an aromatic hydrocarbon with a valency of one or more than two. Furthermore, an aromatic ring means a hydrocarbon having a conjugated unsaturated ring structure, and an aliphatic ring means a hydrocarbon having a ring structure but not containing a conjugated unsaturated ring structure.

In this specification, the so-called alkyl group means a group in which an arbitrary hydrogen is removed from a linear or branched saturated hydrocarbon group, and includes linear alkyl groups and branched alkyl groups; the so-called cycloalkyl group means a group in which a hydrogen is removed from a saturated hydrocarbon group having a ring structure, and the ring structure may contain a linear or branched alkyl group as a side chain as needed.

The term "aryl" as used herein means a group formed by removing one arbitrary hydrogen atom from an aromatic hydrocarbon. The term "alkylene" means a group formed by removing two arbitrary hydrogen atom from a linear or branched saturated hydrocarbon. The term "arylene" means a hydrocarbon group formed by removing two arbitrary hydrogen atom from an aromatic hydrocarbon.

In this specification, "C _x-y ", "C _x ~C _y " and "C _x " refer to the number of carbon atoms in a molecule or a substituent. For example, C _1-6 alkyl refers to an alkyl group having 1 to 6 carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). In addition, the fluoroalkyl group in this specification refers to an alkyl group in which one or more hydrogen atoms are replaced by fluorine atoms; the fluoroaryl group refers to an aryl group in which one or more hydrogen atoms are replaced by fluorine atoms.

In this specification, when a polymer has multiple repeating units, these repeating units are copolymerized. These copolymerizations are alternating copolymerizations, random copolymerizations, block copolymerizations, graft copolymerizations, or any of these mixed existences. In this specification, % represents mass %, and ratio represents mass ratio.

In this specification, the unit of temperature is Celsius. For example, 20 degrees means 20 degrees Celsius.

<Positive photosensitive polysiloxane composition> The positive photosensitive polysiloxane composition of the present invention (hereinafter, sometimes simply referred to as the composition) comprises the following: (I) polysiloxane, (II) carboxylic acid compound, (III) diazonaphthoquinone derivative, and (IV) solvent. The following is a detailed description of each component included in the composition of the present invention.

(I) Polysiloxane The structure of the polysiloxane used in the present invention is not particularly limited and can be selected from any of them according to the purpose. The skeleton structure of polysiloxane can be classified into polysiloxane skeleton (the number of oxygen atoms bonded to silicon atoms is 2), silsesquioxane skeleton (the number of oxygen atoms bonded to silicon atoms is 3), and silica skeleton (the number of oxygen atoms bonded to silicon atoms is 4) according to the number of oxygen atoms bonded to silicon atoms. In the present invention, any of these can be used. The polysiloxane molecule can be a combination of multiple of these skeleton structures.

Preferably, the polysiloxane used in the present invention comprises repeating units represented by the following formula (Ia): (In the formula, R ^Ia represents hydrogen, a C _1-30 linear, branched or cyclic saturated or unsaturated aliphatic alkyl group, or an aromatic alkyl group, the aforementioned aliphatic alkyl group and the aforementioned aromatic alkyl group are each unsubstituted or substituted with fluorine, hydroxyl or alkoxy, and in the aforementioned aliphatic alkyl group and the aforementioned aromatic alkyl group, the methylene group is unsubstituted, or one or more methylene groups are substituted with oxy, amino, imino or carbonyl, but R ^Ia is not a hydroxyl or alkoxy group. In addition, here, the aforementioned methylene group also includes the terminal methyl group. In addition, the above-mentioned "substituted with fluorine, hydroxyl or alkoxy" means that the hydrogen atom directly bonded to the carbon atom in the aliphatic alkyl group and the aromatic alkyl group is substituted with fluorine, hydroxyl or alkoxy. The same applies to other similar descriptions in this manual.

In the repeating unit represented by formula (Ia), R ^Ia may be exemplified as: (i) alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl; (ii) aryl groups such as phenyl, tolyl, and benzyl; (iii) fluoroalkyl groups such as trifluoromethyl, 2,2,2-trifluoroethyl, and 3,3,3-trifluoropropyl; (iv) fluoroaryl groups; (v) cycloalkyl groups such as cyclohexyl; (vi) nitrogen-containing groups having an amino or imide structure such as isocyanate and amine; (vii) oxygen-containing groups having an epoxy structure, or an acryl structure or a methacryl structure such as glycidyl. Methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, tolyl, glycidyl, and isocyanate are preferred. As the fluoroalkyl group, a perfluoroalkyl group is preferred, and a trifluoromethyl group and a pentafluoroethyl group are particularly preferred. When R ^Ia is a methyl group, it is preferred because the raw materials are easily available, the hardness of the cured film is high, and it has high chemical resistance. In addition, when R ^Ia is a phenyl group, it is preferred because the solubility of the polysiloxane in the solvent is increased and the cured film is less likely to crack. In addition, when R ^Ia has a hydroxyl group, a glyoxypropyl group, an isocyanate group, or an amine group, it is preferred because the adhesion to the substrate is improved.

The polysiloxane used in the present invention may further comprise repeating units represented by the following formula (Ib): (wherein, R ^Ib is a group obtained by removing a plurality of hydrogen atoms from a cyclic aliphatic hydrocarbon compound containing an amine group, an imine group and/or a carbonyl group and containing nitrogen and/or oxygen).

In formula (Ib), R ^Ib is preferably a nitrogen-containing aliphatic alkyl ring containing an imino group and/or a carbonyl group, and more preferably a group obtained by removing a plurality of, preferably two or three, hydrogen atoms from a five-membered or six-membered ring containing nitrogen as a constituent. Examples thereof include groups obtained by removing two or three hydrogen atoms from piperidine, pyrrolidine, and isocyanurate. R ^Ib is a group that links Si atoms contained in a plurality of repeating units.

The polysiloxane used in the present invention may further comprise repeating units represented by the following formula (Ic): .

If the mixing ratio of the repeating units represented by formula (Ib) and formula (Ic) is high, the sensitivity of the composition decreases, the compatibility with the solvent or additive decreases, and the film stress increases, which makes turtle cracking more likely to occur. Therefore, the total number of repeating units relative to the polysiloxane is preferably less than 40 mol %, and more preferably less than 20 mol %.

The polysiloxane used in the present invention may further comprise repeating units represented by the following formula (Id): (wherein, R ^Id each independently represents hydrogen, a C _1-30 linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group, in the aforementioned aliphatic hydrocarbon group and the aforementioned aromatic hydrocarbon group, the methylene group is unsubstituted or substituted by an oxy group, an imide group or a carbonyl group, and the carbon atom is unsubstituted or substituted by a fluorine group, a hydroxyl group or an alkoxy group).

In the repeating unit represented by formula (Id), R ^Id may be, for example: (i) alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl; (ii) aryl groups such as phenyl, tolyl, and benzyl; (iii) fluoroalkyl groups such as trifluoromethyl, 2,2,2-trifluoroethyl, and 3,3,3-trifluoropropyl; (iv) fluoroaryl groups; (v) cycloalkyl groups such as cyclohexyl; (vi) nitrogen-containing groups having an amino or imide structure such as isocyanate and amine; (vii) oxygen-containing groups having an epoxy structure, or an acryl structure or a methacryl structure such as glycidyl. Methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, tolyl, glycidyl, and isocyanate are preferred. As the fluoroalkyl group, a perfluoroalkyl group is preferred, and trifluoromethyl and pentafluoroethyl are particularly preferred. When R ^Id is a methyl group, it is preferred because the raw materials are easily available, the hardness of the cured film is high, and it has high chemical resistance. In addition, when R ^Id is a phenyl group, it is preferred because the solubility of the polysiloxane in the solvent is increased and the cured film is less likely to crack. In addition, when R ^Id has a hydroxyl group, a glyoxypropyl group, an isocyanate group, or an amine group, it is preferred because the adhesion to the substrate is improved.

By having the repeating unit of the above formula (Id), the polysiloxane of the present invention can partially form a linear structure. However, since the heat resistance is reduced, it is preferred that the linear structure portion is small. Specifically, the repeating unit of formula (Id) is preferably less than 30 mol% relative to the total number of repeating units of the polysiloxane.

Furthermore, the polysiloxane may contain repeating units represented by the following formula (Ie): (where L ^Ie is -(CR ^Ie ₂ ) _n - or , wherein n is an integer from 1 to 3, and R ^Ie each independently represents hydrogen, methyl, or ethyl).

In formula (Ie), L ^Ie is preferably -(CR ^Ie ₂ ) _n -, and R ^Ie in one repeating unit or in one polysiloxane molecule may be the same or different, but preferably all R ^Ie in one molecule are the same, and preferably all are hydrogen.

The polysiloxane used in the present invention may contain two or more types of repeating units. For example, it may contain three types of repeating units, such as a repeating unit represented by formula (Ia) in which R ^Ia is a methyl group or a phenyl group, and a repeating unit represented by formula (Ic).

The composition of the present invention may include two or more polysiloxanes. The first type may include, for example, a polysiloxane including any of the above-mentioned formulae (Ia) to (Id), and the second type may include a polysiloxane including a repeating unit of formula (Ie) and a repeating unit other than formula (Ie) (preferably a repeating unit of formula (Ia), (Ib) and/or (Id)). Preferably, one or more polysiloxanes contain repeating units in which at least one of R ^Ia of formula (Ia), R ^Ib of formula (Ib) and/or R ^Id of formula (Id) is a bulky group, and more preferably, a polysiloxane containing repeating units in which R ^Ia of formula (Ia) is a bulky C _3-20 saturated or unsaturated cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group (e.g., phenyl, naphthyl, anthracene) and repeating units of formula (Ie) are used. If a bulky group is present, wrinkles tend to be generated, thereby effectively demonstrating the wrinkle suppression of the present invention, and by containing repeating units of formula (Ie), the taper angle of the pattern can be further controlled, which is particularly advantageous. The ratio of the total number of repeating units (Ie) and repeating units (Ia) relative to the total number of repeating units contained in the polysiloxane is preferably 60 mol% or more, more preferably 70 mol% or more. Furthermore, it is preferably 20 to 95 mol% for (Ia) and 5 to 40 mol% for (Ie). Furthermore, the total ratio of the repeating units (Ia), (Ib) and (Id) containing the aforementioned substantial base relative to the total number of repeating units contained in the polysiloxane is preferably 10 mol% or more.

The polysiloxane used in the present invention has a structure in which the repeating units are bonded as described above, but preferably has a silanol group at the end. The silanol group is a connecting bond of the repeating units or blocks, and is bonded with -O _0.5 H.

The mass average molecular weight of the polysiloxane used in the present invention is not particularly limited. However, a higher molecular weight tends to improve the coating properties. On the other hand, a lower molecular weight has fewer restrictions on the synthesis conditions and is easier to synthesize, while a polysiloxane with a very high molecular weight is difficult to synthesize. For this reason, the mass average molecular weight of the polysiloxane is usually between 500 and 25,000, and is preferably between 1,000 and 20,000 from the perspective of solubility in organic solvents and solubility in alkaline developers. The mass average molecular weight here is a polystyrene-converted mass average molecular weight, which can be measured by gel permeation chromatography based on polystyrene.

Furthermore, the polysiloxane used in the present invention is contained in a composition having positive photosensitivity, and this composition is applied to a substrate, image-exposed, and developed to form a cured film. At this time, it is necessary to have a difference in solubility between the exposed portion and the unexposed portion, and the coating in the exposed portion should have a solubility in the developer above a certain level. For example, if the dissolution rate of the coating after pre-baking in a 2.38 mass% tetramethylammonium hydroxide (hereinafter, sometimes referred to as TMAH) aqueous solution (hereinafter, sometimes referred to as the alkali dissolution rate or ADR. Details are described below) is 50Å/sec or more, it is considered that a pattern can be formed by exposure-development. However, since the solubility required varies depending on the film thickness of the cured film to be formed and the development conditions, the polysiloxane corresponding to the development conditions should be appropriately selected. Depending on the type and amount of the diazonaphthoquinone derivative contained in the composition, for example, if the film thickness is 0.1-100 μm (1,000-1,000,000 Å), the dissolution rate relative to a 2.38 mass % TMAH aqueous solution is preferably 50-5,000 Å/sec, and more preferably 200-3,000 Å/sec.

The polysiloxane used in the present invention can be selected from any polysiloxane having an ADR within the above range according to the application and required properties. In addition, polysiloxanes with different ADRs can be combined to form a mixture having a desired ADR.

Polysiloxanes with different alkali dissolution rates and mass average molecular weights can be prepared by changing the catalyst, reaction temperature, reaction time or polymer. By combining polysiloxanes with different alkali dissolution rates, it is possible to reduce residual insoluble matter after development, reduce pattern collapse, and improve pattern stability.

Such polysiloxanes include, for example, (M) polysiloxanes whose film after prebaking is soluble in a 2.38 mass % TMAH aqueous solution and whose dissolution rate is 200-3,000 Å/sec.

Furthermore, a composition having a desired dissolution rate can be obtained by mixing (L) a polysiloxane whose film after prebaking is soluble in a 5 mass % TMAH aqueous solution and whose dissolution rate is 1,000Å/sec or less, or (H) a polysiloxane whose film after prebaking dissolves at a rate of 4,000Å/sec or more relative to a 2.38 mass % TMAH aqueous solution.

[Measurement and calculation method of alkali dissolution rate (ADR)] The alkali dissolution rate of polysiloxane or its mixture is measured and calculated as follows using TMAH aqueous solution as the alkali solution.

Polysiloxane was diluted to 35% by mass in PGMEA and dissolved by stirring for 1 hour at room temperature. In a clean room at a temperature of 23.0±0.5°C and a humidity of 50±5.0%, 1cc of the prepared polysiloxane solution was dripped onto the center of a 4-inch, 525μm thick silicon wafer using a pipette, and then the solution was applied by rotating to a thickness of 2±0.1μm. The solution was then heated on a heating plate at 100°C for 90 seconds to remove the solvent. The film thickness of the coating was measured using a spectroscopic elliptical polarizer (manufactured by J.A.Woollam).

Next, the silicon wafer with this film is gently immersed in a 6-inch diameter glass culture dish filled with 100 ml of TMAH aqueous solution adjusted to a specified concentration of 23.0±0.1℃, and then left to stand, and the time until the coating disappears is measured. The dissolution rate is obtained by dividing it by the time until the film disappears in the part 10 mm inside the end of the wafer. In the case where the dissolution rate is significantly slow, after immersing the wafer in the TMAH aqueous solution for a certain period of time, it is heated on a heating plate at 200℃ for 5 minutes to remove the water that has entered the film during the dissolution rate measurement, and then the film thickness is measured. The dissolution rate is calculated by dividing the 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.

<Method for synthesizing polysiloxane> The method for synthesizing the polysiloxane used in the present invention is not particularly limited, but for example, it can be obtained by hydrolyzing and polymerizing a silane monomer represented by the following formula in the presence of an acidic catalyst or an alkaline catalyst as needed; R ^ia -Si-(OR ^{ia '} ) ₃ (ia) (wherein, R ^ia represents hydrogen, a C _1~30 linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group, or an aromatic hydrocarbon group, and in the aforementioned aliphatic hydrocarbon group and the aforementioned aromatic hydrocarbon group, the methylene group is unsubstituted or substituted by an oxy group, an amide group or a carbonyl group, and the carbon atom is unsubstituted or substituted by a fluorine group, a hydroxyl group or an alkoxy group, and R ^ia' is a linear or branched C _1~6 alkyl group).

In formula (ia), preferred R ^ia' includes methyl, ethyl, n-propyl, isopropyl, and n-butyl. In formula (ia), although R ^ia' includes plural numbers, each R ^ia' may be the same or different. Preferred R ^ia is the same as the preferred R ^Ia mentioned above.

Specific examples of the silane monomer represented by formula (ia) include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, and 3,3,3-trifluoropropyltrimethoxysilane. Among them, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane and phenyltrimethoxysilane are preferred. The silane monomer represented by formula (ia) is preferably a combination of two or more.

The silane monomers shown in the following formula (ic) can be further combined. If the silane monomers shown in formula (ic) are used, a polysiloxane containing repeating units (Ic) can be obtained. Si(OR ^{ic '} ) ₄ (ic) In the formula, R ^ic' is a linear or branched C _1~6 alkyl group. In formula (ic), preferred R ^ic' can be exemplified by methyl, ethyl, n-propyl, isopropyl, and n-butyl. In formula (ic), although R ^ic' includes a plurality of R ic', each R ^ic' can be the same or different. As specific examples of the silane monomers shown in formula (ic), tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, etc. can be exemplified.

The silane monomers shown in the following formula (ib) can also be further combined. R ^ib -Si-(OR ^{ib '} ) ₃ (ib) In the formula, R ^ib' is a linear or branched C _1~6 alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, and n-butyl. Although R ^ib' includes multiple R ib's in one monomer, each R ^ib' can be the same or different. R ^ib is a group obtained by removing multiple, preferably 2 or 3 hydrogen atoms from a cyclic aliphatic hydrocarbon compound containing an amino group, an imino group and/or a carbonyl group and containing nitrogen and/or oxygen. The preferred R ^ib is the same as the preferred R ^Ib mentioned above.

Specific examples of the silane monomer represented by formula (ib) include tris-(3-trimethoxysilylpropyl) isocyanurate, tris-(3-triethoxysilylpropyl) isocyanurate, tris-(3-trimethoxysilylethyl) isocyanurate, and the like.

Furthermore, the silane monomers represented by the following formula (id) can be combined. If the silane monomers represented by the formula (id) are used, a polysiloxane containing repeating units (Id) can be obtained. (R ^id ) ₂ -Si-(OR ^{id '} ) ₂ (id) In the formula, R ^id' is independently a linear or branched C _1~6 alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, and n-butyl. Although multiple R ^id's are included in one monomer, each R ^id' may be the same or different. R ^id's each independently represent hydrogen, a linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group or an aromatic hydrocarbon group _{having 1 to 30} carbon atoms. In the aforementioned aliphatic hydrocarbon group and the aforementioned aromatic hydrocarbon group, the methylene group is unsubstituted or substituted by an oxy group, an amide group or a carbonyl group, and the carbon atom is unsubstituted or substituted by a fluorine group, a hydroxyl group or an alkoxy group. Preferred R ^id is the preferred R ^Id described above.

Furthermore, the silane monomers represented by the following formula (ie) can also be combined. (OR ^{ie '} ) ₃ -Si-L ^ie -Si-(OR ^{ie '} ) ₃ (ie) In the formula (ie), R ^ie ' is independently a linear or branched C _1~6 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, and n-butyl. L ^ie is -(CR ^ie ₂ ) _n - or , preferably -(CR ^ie ₂ ) _n -, wherein n is independently an integer of 1 to 3, and R ^ie is independently hydrogen, methyl, or ethyl.

(II) Carboxylic acid compound The carboxylic acid compound used in the present invention is a monocarboxylic acid or a dicarboxylic acid in an amount of 200 to 50,000 ppm based on the total mass of the composition. Preferably, the first acid dissociation constant pKa ₁ of the monocarboxylic acid is 5.0 or less. Preferably, the first acid dissociation constant pKa ₁ of the dicarboxylic acid is 4.0 or less, and more preferably, 3.5 or less.

Preferably, the monocarboxylic acid is represented by formula (i): R ⁱ -COOH Formula (i) wherein R ⁱ is hydrogen or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms.

Examples of the monocarboxylic acid used in the present invention include acetic acid, formic acid and acrylic acid, with acetic acid being preferred.

Preferably, the dicarboxylic acid is represented by formula (ii). HOOC-L-COOH   Formula (ii) Wherein, L is a single bond, an unsubstituted alkylene group having 1 to 6 carbon atoms, a hydroxyl-substituted alkylene group or an amino-substituted alkylene group, a substituted or unsubstituted alkenylene group having 2 to 4 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 4 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms. Here, in the present invention, the so-called alkenylene group means a divalent group having one or more double bonds. Similarly, the so-called alkynylene group means a divalent group having one or more trivalent bonds.

Preferably, L is a single bond, a hydroxyl-substituted or unsubstituted alkylene group with 2 to 4 carbon atoms, an unsubstituted alkenyl group with 1 C=C bond with 2 to 4 carbon atoms, or an unsubstituted aryl group with 6 to 10 carbon atoms. More preferably, L is a single bond, an unsubstituted alkylene group with 1 to 2 carbon atoms, a vinyl group, a hydroxyethyl group, or a phenyl group.

Specific examples of the dicarboxylic acid used in the present invention include oxalic acid, maleic acid, fumaric acid, phthalic acid, succinic acid, glutaconic acid, aspartic acid, glutamine, apple acid, itaconic acid, 3-aminoadipic acid, and malonic acid, preferably oxalic acid, maleic acid, fumaric acid, phthalic acid, apple acid, or malonic acid.

As the carboxylic acid compound used in the present invention, dicarboxylic acids are more preferably used, and those that can form a ring structure by intramolecular dehydration condensation are particularly preferred. Examples of such dicarboxylic acids include oxalic acid, maleic acid, succinic acid, phthalic acid, glutaconic acid, and itaconic acid. Among them, dicarboxylic acids that cause intramolecular dehydration condensation reactions at a temperature of 100°C to 250°C are more preferred, and maleic acid, succinic acid, and oxalic acid are further preferred.

The carboxylic acid compounds may be used in combination of two or more.

In the composition of the present invention, the content of the carboxylic acid compound used in the present invention is 200-50,000 ppm, preferably 300-30,000 ppm, and more preferably 500-30,000 ppm based on the total mass of the composition. The content of more than 50,000 ppm is not preferable because it causes a decrease in sensitivity. In the case of using an organic developer (e.g., TMAH aqueous solution) in the developing step, the content of the compound (II) is preferably 300-10,000 ppm, and more preferably 500-5,000 ppm. In the case of using an inorganic developer (e.g., KOH aqueous solution) in the developing step, the content of the compound (II) is preferably 1,000-30,000 ppm, and more preferably 3,000-10,000 ppm.

The composition of the present invention suppresses wrinkles in the cured film by containing a specific amount of a specific carboxylic acid compound, thereby improving the smoothness of the pattern surface. Although we do not wish to be bound by theory, it is believed that this is due to the following reasons. The positive polysiloxane composition is coated, exposed, developed with an alkaline developer, rinsed, and then cured by heating. Although the developer is washed away by rinsing, the alkaline components remaining in the film, especially on the surface of the film, excessively accelerate the curing reaction on the surface of the film. If the entire surface is exposed after rinsing, the curing reaction will not be excessively accelerated due to the entire surface exposure. Therefore, the generation of wrinkles is suppressed. The composition of the present invention can neutralize the alkaline component from the alkaline developer even without a full-surface exposure process by containing a specific amount of a specific carboxylic acid compound, thereby preventing the curing reaction from being excessively accelerated and suppressing the formation of wrinkles. In particular, when the carboxylic acid compound is a compound that can form a ring structure by an intramolecular dehydration reaction at a specific temperature, it is believed that the silanol group of the polysiloxane is protected by the carboxylic acid group until heating for curing, but during heating for curing, curing starts from the unprotected silanol group, and the carboxylic acid compound is anhydrous and removed from the film, and the unprotected silanol group is then cured. This staged curing occurs, and it is believed that the wrinkle suppression effect becomes higher. Although alkaline developers are classified into organic and inorganic types, inorganic developers have smaller molecular sizes than organic developers and are easier to enter the film during development, so the amount of acid required for neutralization is also larger. Therefore, when using inorganic developers, the content of carboxylic acid compounds is higher.

(III) Diazo naphthoquinone derivatives The composition of the present invention comprises a diazonaphthoquinone derivative. In the composition comprising a diazonaphthoquinone derivative, the exposed portion becomes soluble in an alkaline developer and forms a positive image that is removed by development. That is, the composition of the present invention generally functions as a positive photoresist composition. The diazonaphthoquinone derivative of the present invention is a compound in which a compound having a phenolic hydroxyl group is ester-bonded with a naphthoquinone diazide sulfonic acid. The structure is not particularly limited, but it is preferably an ester compound with a compound having one or more phenolic hydroxyl groups. As the naphthoquinone diazide sulfonic acid, 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid can be used. Since 4-naphthoquinone diazide sulfonate compounds have absorption in the i-line (wavelength 365nm) region, they are suitable for i-line exposure. Moreover, since 5-naphthoquinone diazide sulfonate compounds have absorption in a wide range of wavelength regions, they are suitable for exposure in a wide range of wavelengths. It is preferred to select 4-naphthoquinone diazide sulfonate compounds and 5-naphthoquinone diazide sulfonate compounds according to the wavelength of exposure. 4-naphthoquinone diazide sulfonate compounds and 5-naphthoquinone diazide sulfonate compounds may also be used in combination.

The compound having a phenolic hydroxyl group is not particularly limited, but examples thereof include bisphenol A, BisP-AF, BisOTBP-A, Bis26B-A, BisP-PR, BisP-LV, BisP-OP, BisP-NO, BisP-DE, BisP-AP, BisOTBP-AP, TrisP-HAP, BisP-DP, TrisP-PA, BisOTBP-Z, BisP-FL, TekP-4HBP, TekP-4HBPA, and TrisP-TC (trade names, manufactured by Honshu Chemical Industries, Ltd.).

The optimal amount of the naphthoquinone diazide derivative to be added varies depending on the esterification rate of naphthoquinone diazide sulfonic acid, the physical properties of the polysiloxane used, the required sensitivity, and the dissolution contrast between the exposed part and the unexposed part. However, it is preferably 1 to 20 parts by mass, and more preferably 2 to 15 parts by mass, relative to 100 parts by mass of the total mass of the polysiloxane. When the amount of the naphthoquinone diazide derivative to be added is less than 1 part by mass, the dissolution contrast between the exposed part and the unexposed part is too low, and there is no practical photosensitivity. In order to obtain a better dissolution contrast, it is preferably 2 parts by mass or more. On the other hand, when the amount of the naphthoquinone diazo derivative added is more than 20 parts by mass, the coating film whitens due to the poor compatibility between polysiloxane and quinone diazide compound, or the coloring caused by the decomposition of the quinone diazide compound during thermal curing becomes prominent, so the colorless transparency of the cured film decreases. In addition, since the heat resistance of the naphthoquinone diazo derivative is inferior to that of polysiloxane, if the amount of addition increases, the electrical insulation of the cured film deteriorates due to thermal decomposition and gas is released, which becomes a problem in the subsequent steps. In addition, there are cases where the resistance of the cured film to photoresist stripping liquids such as monoethanolamine as the main agent decreases.

(IV) Solvents The solvent is not particularly limited as long as it can uniformly dissolve or disperse the aforementioned polysiloxane and carboxylic acid compound, and additives that can be added as needed. Examples of solvents that can be used in the present invention include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellulose acetate and ethyl cellulose acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; Propylene glycol alkyl ether acetates such as monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate; aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerol; esters such as ethyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate; cyclic esters such as γ-butyrolactone, etc. The solvents are used alone or in combination of two or more, and the amount used varies depending on the coating method and the film thickness required after coating.

The solvent content of the composition of the present invention can be appropriately selected according to the mass average molecular weight, distribution and structure of the polysiloxane used, taking into account the coating method adopted. The composition of the present invention generally contains 40-90 mass %, preferably 60-80 mass % of the solvent based on the total mass of the composition.

The composition of the present invention is based on the aforementioned (I) to (IV), but other compounds can be combined as needed. The description of these materials that can be combined is as follows. In addition, the components other than (I) to (IV) in the entire composition are preferably less than 10% by mass, and more preferably less than 5% by mass, relative to the total mass.

[Silanol condensation catalyst] The composition of the present invention may include a silanol condensation catalyst selected from the group consisting of a photoacid generator, a photoalkali generator, a photothermal acid generator, and a photothermal alkali generator. These are preferably selected in response to the polymerization reaction and crosslinking reaction used in the curing film manufacturing process. In addition, in the present invention, the photoacid generator does not include the (III) diazonaphthoquinone derivative described above.

The optimum amount of these varies depending on the type of active substances produced by decomposition, the amount produced, the required sensitivity, the dissolution contrast between the exposed and unexposed parts, and the shape of the pattern, but is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total mass of polysiloxane. If the added amount is less than 0.1 parts by mass, the amount of acid or base produced is too small, and it becomes easy to cause pattern collapse. On the other hand, if the added amount is more than 10 parts by mass, cracks will occur in the formed cured film, or the coloring caused by the decomposition will become prominent, so the colorless transparency of the cured film will be reduced. In addition, if the added amount increases, the electrical insulation of the cured product will deteriorate due to thermal decomposition, and gas will be released, which will become a problem in the subsequent steps. Furthermore, the resistance of the cured film to a photoresist stripping liquid containing monoethanolamine as a main agent may decrease.

In the present invention, the photoacid generator or photobase generator refers to a compound that generates an acid or base by causing bond cleavage through exposure. It is believed that the generated acid or base contributes to the polymerization of polysiloxane. Here, the light may include visible light, ultraviolet light, infrared light, X-rays, electron rays, α rays, or γ rays. The photoacid generator or photobase generator preferably generates acid or base during the subsequent full-surface exposure rather than the imaging exposure for projecting the pattern (hereinafter referred to as the initial exposure), and preferably has less absorption at the wavelength of the initial exposure. For example, when the initial exposure is performed with g-line (peak wavelength 436nm) and/or h-line (peak wavelength 405nm), and the wavelength during the second exposure is g+h+i-line (peak wavelength 365nm), the absorbance of the photoacid generator or photobase generator at wavelength 365nm is preferably greater than the absorbance at wavelength 436nm and/or 405nm. Specifically, the absorbance at wavelength 365nm/absorbance at wavelength 436nm, or the absorbance at wavelength 365nm/absorbance at wavelength 405nm is preferably 2 or more, more preferably 5 or more, further preferably 10 or more, and most preferably 100 or more. Here, the ultraviolet visible light absorption spectrum is measured using dichloromethane as a solvent. The measuring device is not particularly limited, but an example thereof may be Cary 4000 UV-Vis spectrophotometer (manufactured by Agilent Technologies, Inc.).

The photoacid generator can be selected from any of those commonly used, but examples thereof include diazomethane compounds, triazine compounds, sulfonates, diphenyliodonium salts, triphenylsiron salts, sebum salts, ammonium salts, phosphonium salts, sulfonimide compounds, etc.

Specific examples of the photoacid generators that can be used include 4-methoxyphenyldiphenylcoppersulfonate, 4-methoxyphenyldiphenylcoppersulfonate, 4-methoxyphenyldiphenylcoppersulfonate, 4-methoxyphenyldiphenylcoppersulfonate, 4-methoxyphenyldiphenylcoppersulfonate, 4-methoxyphenyldiphenylcoppersulfonate, 4-methoxyphenyldiphenylcoppersulfonate, 4-methoxyphenyldiphenylcoppersulfonate, 4-methoxyphenyldiphenylcoppersulfonate, 4-methoxyphenyldiphenylcoppersulfonate, 4-phenylthio ... triphenylmethanesulfonate, triphenylmethanesulfonate, triphenylmethanesulfonate, triphenylmethanesulfonate, triphenylmethanesulfonate, 4-methoxyphenylmethanesulfonate, 4-phenylthiophenylmethanesulfonate, 4-phenylthiophenylmethanesulfonate, N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, 5-norbornene-2,3-dicarboximidyl trifluoromethanesulfonate triflate), 5-norbornene-2,3-dimethylimide-toluenesulfonate, 4-phenylthiophenyl diphenyl trifluoromethanesulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate, N-(trifluoromethylsulfonyloxy) diphenyl maleimide, N-(trifluoromethylsulfonyloxy) bicyclo[2.2.1]hept-5-ene-2,3-dimethylimide, N-(trifluoromethylsulfonyloxy) naphthyl imide, N-(trifluoromethylsulfonyloxy) naphthyl imide, N-(nonafluorobutylsulfonyloxy) naphthyl imide, etc. In addition, 5-propylsulfonyloxyimino-5H-thiophen-2-ylidene-(2-methylphenyl)acetonitrile, 5-octylsulfonyloxyimino-5H-thiophen-2-ylidene-(2-methylphenyl)acetonitrile, 5-camphorsulfonyloxyimino-5H-thiophen-2-ylidene-(2-methylphenyl)acetonitrile, 5-methylphenylsulfonyloxyimino-5H-thiophen-2-ylidene-(2-methylphenyl)acetonitrile, etc. have absorption in the wavelength region of the h line, so their use should be avoided when the h line absorption is not desired.

Examples of photoalkali generators include polysubstituted amide compounds, lactams, imide compounds, or structures containing them having an amide group. In addition, ionic photoalkali generators containing amide anions, methide anions, borate anions, phosphate anions, sulfonate anions, or carboxylate anions as anions may also be used.

In the present invention, the so-called photothermal acid generator or photothermal alkali generator refers to a compound that changes its chemical structure by exposure but does not generate acid or base, and then generates acid or base by causing bond cleavage by heat. Among these, photothermal alkali generator is preferred. As the photothermal alkali generator, those represented by the following formula (II) can be listed, and their hydrates or solvent compounds can be more preferably listed. The compound represented by formula (II) will be reversed to the cis form by exposure and become unstable, so the decomposition temperature decreases, and alkali will be generated even if the baking temperature in the subsequent step is about 100°C. The photothermal alkali generator does not need to be adjusted to the absorption wavelength of the diazonaphthoquinone derivative. wherein x is an integer from 1 to 6, and each of R ^a' to R ^{f '} is independently hydrogen, halogen, hydroxyl, sulfide, silyl, silanol, nitro, nitroso, sulfinic acid, sulfonic acid, sulfonic acid, phosphinyl, phosphinyl, phosphonato, phosphonato, amino, ammonium, a C _1-20 aliphatic hydrocarbon group which may contain a substituent, a C _6-22 aromatic hydrocarbon group which may contain a substituent, an C _1-20 alkoxy group which may contain a substituent, or a C _6-20 aryloxy group which may contain a substituent.

Among them, Ra ^' to ^{Rd '} are particularly preferably hydrogen, hydroxyl, _C1-6 aliphatic alkyl, or _C1-6 alkoxy, and ^Re' and Rf ^' are particularly preferably hydrogen. Two or more of ^Ra' to ^{Rd '} may be bonded to form a ring structure. In this case, the ring structure may contain heteroatoms. N is a constituent atom of a nitrogen-containing heterocyclic ring, the nitrogen-containing heterocyclic ring is a 3-10-membered ring, and the nitrogen-containing heterocyclic ring may further have one or more _C1-20 , especially _{C1-6 aliphatic alkyl groups that may contain substituents, which are different from CxH2XOH shown in} formula (II).

Ra ^' to ^{Rd '} are preferably selected appropriately according to the exposure wavelength used. In the application for display, unsaturated hydrocarbon functional groups such as vinyl and alkynyl groups that shift the absorption wavelength to g, h, and i lines, or alkoxy and nitro groups are used, and methoxy and ethoxy groups are particularly preferred.

Specifically, the following can be cited.

In the present invention, the so-called thermal acid generator or thermal alkali generator refers to a compound that generates acid or base by causing bond cleavage by heat. It is preferred that after the composition is applied, no acid or base is generated due to the heat during pre-baking, or only a small amount is generated. As examples of thermal acid generators, various aliphatic sulfonic acids and their salts, various aliphatic carboxylic acids and their salts such as citric acid, acetic acid, and maleic acid, various aromatic carboxylic acids and their salts such as benzoic acid and phthalic acid, aromatic sulfonic acids and their ammonium salts, various amine salts, aromatic diazonium salts, and phosphonic acids and their salts, etc., which generate salts or esters of organic acids, etc. can be listed. However, the thermal acid generator used in the present invention does not include the above-mentioned (II) carboxylic acid compound. Among the thermal acid generators, salts composed of organic acids and organic bases are particularly preferred, and salts composed of sulfonic acids and organic bases are further preferred. Preferred sulfonic acids include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalene disulfonic acid, and methanesulfonic acid. These acid generators can be used alone or in combination.

Examples of the thermal alkali generator include compounds that generate alkalis such as imidazole, tertiary amine, and quaternary ammonium, and mixtures thereof. Examples of the released alkali include imidazole derivatives such as N-(2-nitrobenzyloxycarbonyl)imidazole, N-(3-nitrobenzyloxycarbonyl)imidazole, N-(4-nitrobenzyloxycarbonyl)imidazole, N-(5-methyl-2-nitrobenzyloxycarbonyl)imidazole, and N-(4-chloro-2-nitrobenzyloxycarbonyl)imidazole, and 1,8-diazabicyclo[5.4.0]undecene-7. These alkali generators are similar to the acid generators and can be used alone or in combination.

As other additives, there can be listed surfactants, developer dissolution accelerators, scum removers, adhesion enhancers, polymerization inhibitors, defoamers, or sensitizers.

It is preferred to use a surfactant because it can improve the coating properties. Examples of surfactants that can be used in the polysiloxane composition of the present invention include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

Examples of the non-ionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene cetyl ether, or polyoxyethylene fatty acid diesters, polyoxyethylene fatty acid monoesters, polyoxyethylene polyoxypropylene block polymers, acetylene alcohols, acetylene glycols, acetylene alcohol derivatives such as polyethoxylate of acetylene alcohols, acetylene glycol derivatives such as polyethoxylate of acetylene glycols, fluorine-containing surfactants such as Fluorad (trade name, manufactured by 3M Co., Ltd.), MEGAFAC (trade name, manufactured by DIC Co., Ltd.), SURFLON (trade name, manufactured by Asahi Glass Co., Ltd.), or organosilicone surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the acetylene diol 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-decyn-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyn-2,5-diol, and 2,5-dimethyl-2,5-hexanediol.

Furthermore, examples of the anionic surfactant include ammonium salts or organic amine salts of alkyl diphenyl ether disulfonic acid, ammonium salts or organic amine salts of alkyl diphenyl ether sulfonic acid, ammonium salts or organic amine salts of alkyl benzene sulfonic acid, ammonium salts or organic amine salts of polyoxyethylene alkyl ether sulfate, and ammonium salts or organic amine salts of alkyl sulfate.

Furthermore, as amphoteric surfactants, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, laurylamidopropyl hydroxyl sulfonate betaine, etc. can be cited.

These surfactants can be used alone or in combination of two or more, and their blending ratio relative to the total mass of the composition is usually 50-10,000 ppm, preferably 100-5,000 ppm.

The developer dissolution promoter or scum remover has the function of adjusting the solubility of the formed coating film in the developer or preventing scum from remaining on the substrate after development. Crown ether can be used as such an additive. The amount added is preferably 0.05 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the total mass of the polysiloxane.

Furthermore, a sensitizer may be added as needed, and examples thereof include coumarin, ketocoumarin and their derivatives, acetophenones, sensitizing dyes such as pyrylium salts and thiopyrylium salts, and compounds containing an anthracene skeleton.

When a sensitizer is used, its addition amount is preferably 0.01 to 5 parts by weight relative to 100 parts by weight of the total weight of the polysiloxane.

As polymerization inhibitors, in addition to nitrone, nitroxide radical, hydroquinone, catechol, phenanthridine (phenothiazine), coffee In addition to phenoxazine, hindered amine and their derivatives, ultraviolet absorbers can also be added. The amount added is preferably 0.01 to 20 parts by weight relative to 100 parts by weight of the total weight of the polysiloxane.

As defoaming agents, alcohol (C ₁ ~ ₁₈ ), higher fatty acids such as oleic acid or stearic acid, higher fatty acid esters such as glycerol monolaurate, polyethers such as polyethylene glycol (PEG) (Mn200~10,000) and polypropylene glycol (PPG) (Mn200~10,000), polysilicone compounds such as dimethyl silicone oil, alkyl modified silicone oil, fluorosilicone oil, and organic silicone surfactants can be listed. These can be used alone or in combination, and the addition amount is preferably set to 0.1~3 parts by weight relative to 100 parts by weight of the total weight of polysiloxane.

The adhesion enhancer has the effect of preventing the pattern from peeling off due to applied stress after curing when the cured film is formed using the composition of the present invention. Preferred adhesion enhancers include imidazoles, silane coupling agents, and the like.

These other additives may be used alone or in combination, and the amount thereof added is less than 20 parts by mass, preferably 0.05-15 parts by mass, relative to 100 parts by mass of the total mass of the polysiloxane.

<Method for producing a cured film> The method for producing a cured film of the present invention comprises the following steps: (1) applying the composition of the present invention to a substrate to form a composition layer, (2) exposing the composition layer, (3) developing with an alkaline developer to form a pattern, and (4) heating the obtained pattern. The steps are described in order as follows.

(1) Coating step First, the aforementioned composition is coated on a substrate. The coating film of the composition in the present invention can be formed by any method known in the art for coating photosensitive compositions. Specifically, it can be selected from immersion coating, roller coating, bar coating, brush coating, spray coating, blade coating, shower coating, spin coating, and slit coating. In addition, as a substrate for coating the composition, a suitable substrate such as a silicon substrate, a glass substrate, a resin film, etc. can be used. Such substrates can be formed with various semiconductor elements, etc. as needed. In the case where the substrate is a thin film, gravure coating can also be used. A drying step can also be provided after coating as needed. Furthermore, the coating step may be repeated once or twice or more as needed to achieve a desired coating thickness.

After the coating composition is used to form a coating film, in order to dry the coating film and reduce the amount of solvent residue in the coating film, it is preferred to pre-bake the coating film (pre-heat treatment). The pre-bake step can generally be performed at a temperature of 70-150°C, preferably at a temperature of 90-120°C, for 10-300 seconds, preferably 30-120 seconds, when using a heating plate, and for 1-30 minutes when using a clean oven.

(2) Exposure step After the coating is formed, the surface of the coating is irradiated with light. In order to distinguish this step from the full-surface exposure described later, it is called the initial exposure. The light source used for light irradiation can be any light source used in the pattern forming method in the past. Examples of such light sources include high-pressure mercury lamps, low-pressure mercury lamps, lamps of metal halides, xenon, etc., or laser diodes, LEDs, etc. As irradiation light, ultraviolet rays such as g-line, h-line, and i-line are usually used. Except for ultrafine processing such as semiconductors, 360~430nm light (high-pressure mercury lamp) is generally used for patterning of several μm to tens of μm. Among them, 430nm light is mostly used in the case of liquid crystal display devices. In this case, as described above, it is advantageous to combine the sensitizing dye in the composition of the present invention. The energy of the irradiation light depends on the light source and the film thickness of the coating, but is generally set to 5~2,000mJ/ ^cm2 , preferably 10~1,000mJ/ ^cm2 . If the irradiation light energy is lower than 5mJ/ ^cm2 , sufficient resolution cannot be obtained. On the contrary, if it is higher than 2,000mJ/ ^cm2 , it becomes overexposure and may cause blurring.

In order to irradiate light in a pattern, a general photomask can be used. Such a photomask can be arbitrarily selected from well-known ones. The environment during irradiation is not particularly limited, but can generally be set to an ambient gas environment (in the atmosphere) or a nitrogen environment. In addition, in the case of forming a film on the entire surface of the substrate, it is sufficient to irradiate the entire surface of the substrate with light. In the present invention, the so-called patterned film also includes the case of forming a film on the entire surface of such a substrate.

(3) Development step After exposure, the coating is developed. As the developer used in the development, any developer used for the development of the photosensitive composition in the past can be used. The developer includes an organic developer and an inorganic developer. Examples of the organic developer include a TMAH aqueous solution, a tetrabutylammonium hydroxide aqueous solution, methyl isobutyl ketone, and isopropyl alcohol. Preferably, the TMAH aqueous solution is used, and more preferably, a 2.38 mass% TMAH aqueous solution is used. As the inorganic developer, an alkaline metal salt is used, preferably, an aqueous potassium hydroxide solution, or an aqueous sodium hydroxide solution, an aqueous sodium carbonate solution, an aqueous sodium bicarbonate solution, an aqueous sodium silicate solution, an aqueous sodium metasilicate solution, and an aqueous ammonia solution. The potassium hydroxide aqueous solution is particularly preferred. When using an aqueous potassium hydroxide solution, its concentration is preferably 0.1-3.0% by mass, more preferably 0.5-2.0% by mass. Such developer may further contain a water-soluble organic solvent such as methanol or ethanol, or a surfactant as needed. The developing method may also be arbitrarily selected from the known methods. Specifically, methods such as dipping, puddle, spraying, slit, cap coating, and atomization of the developer may be listed. The developing temperature is preferably room temperature (20-25°C), but may be heated to 30-50°C. The developing time is preferably 15-180 seconds, more preferably 30-60 seconds. By developing in this way, a pattern can be obtained. It is preferred that the image is developed with a developer and then rinsed (washed with water).

Rinsing is preferably performed with water in the same manner as developing, preferably by spraying for more than 60 seconds.

After development (and washing as needed), a step of full-surface exposure is generally performed. This is because, as described above, wrinkle formation of the cured film can be suppressed by performing this full-surface exposure. In addition, by performing full-surface exposure, the unreacted naphthoquinone diazide derivative remaining in the film is photodecomposed, and the optical transparency of the film is further improved. Therefore, in cases where transparency is required, it is preferred to perform a full-surface exposure step. As a method for full-surface exposure, there is a method of using an ultraviolet visible light exposure machine such as PLA (for example, PLA-501F manufactured by Canon) to expose the entire surface at about 100 to 2000 mJ/ ^cm2 (converted to an exposure amount of 365 nm in wavelength). In the case of using the composition of the present invention, wrinkles can be suppressed even without performing full-surface exposure, so full-surface exposure may not be performed in cases where excessive transparency is not required.

(4) Curing step After development, the obtained pattern film is cured by heating. The heating temperature in this step is not particularly limited as long as it is a temperature at which the coating can be cured, and can be determined arbitrarily. However, if silanol groups remain, the chemical resistance of the cured film becomes insufficient, or the dielectric constant of the cured film becomes high. From this point of view, the heating temperature is generally selected to be relatively high. Specifically, it is preferred to cure by heating at 360°C or less, and in order to maintain a high residual film rate after curing, the curing temperature is more preferably 300°C or less, and particularly preferably 250°C or less. On the other hand, in order to promote the curing reaction and obtain a sufficient cured film, the curing temperature is preferably 70°C or more, more preferably 90°C or more, and particularly preferably 100°C or more. The heating time is not particularly limited, but is generally 10 minutes to 24 hours, preferably 30 minutes to 3 hours. In addition, the heating time is the time from when the temperature of the pattern film reaches the desired heating temperature. Usually, it takes several minutes to several hours from the temperature before heating to the desired temperature of the pattern film.

By using the composition of the present invention, the generation of wrinkles on the surface of the cured film during the curing step can be suppressed. Here, the so-called wrinkles refer to the bumps generated near or far from the pattern part of the cured film. Figure 1 shows an electron microscope photo of typical wrinkles formed on the pattern surface. The rough standard for the difference between no wrinkles (Fig. 1(P)), small wrinkles (Fig. 1(Q)), and large wrinkles (Fig. 1(R)) is to use a stylus surface measuring device (Dektak) to measure the surface of the film not covered by the pattern far away from the pattern after curing with a force of 3mg and a distance of 1.5cm for 50 seconds. The surface unevenness is less than about 30nm in the case of no wrinkles, about 30nm to 100nm in the case of small wrinkles, and more than 100nm in the case of large wrinkles.

The cured film thus obtained can achieve excellent flatness and electrical insulation properties. For example, the specific dielectric constant can be less than 4. Therefore, it can be suitably used in many aspects, such as a flattening film for various components such as flat panel displays (FPDs), an interlayer insulating film for low-temperature polysilicon, a buffer coating for IC chips, a transparent protective film, etc.

The present invention is further specifically described with the following embodiments and comparative examples, but the present invention is not limited to these embodiments and comparative examples.

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

<Synthesis Example 1 (Synthesis of polysiloxane Pa-1)> In a 2L flask equipped with a stirrer, a thermometer, and a cooling tube, 49.0 g of a 25 mass% TMAH aqueous solution, 600 ml of isopropyl alcohol (IPA), and 4.0 g of water were charged, and then a mixed solution of 68.0 g of methyltrimethoxysilane, 79.2 g of phenyltrimethoxysilane, and 15.2 g of tetramethoxysilane was prepared in a dropping funnel. The mixed solution was dropped at 40°C, stirred at the same temperature for 2 hours, and then neutralized by adding a 10 mass% HCl aqueous solution. 400 ml of toluene and 600 ml of water were added to the neutralized solution to separate it into two phases, and the aqueous phase was removed. The organic phase was further washed three times with 300 ml of water, and the solvent was removed by concentrating the obtained organic phase under reduced pressure, and PGMEA was added to the concentrate so that the solid content concentration was adjusted to 35% by mass. The molecular weight (polystyrene conversion) of the obtained polysiloxane was measured by gel permeation chromatography, and the mass average molecular weight (hereinafter sometimes referred to as "Mw") was 1,700. In addition, the obtained resin solution was applied to a silicon wafer by a rotary coater (MS-A100 (Mikasa)) so that the film thickness after pre-baking was 2μm, and the dissolution rate (hereinafter sometimes referred to as "ADR") to a 2.38% by mass TMAH aqueous solution was measured after pre-baking, and the result was 1,200Å/second.

<Synthesis Example 2 (Synthesis of polysiloxane Pa-2)> Synthesis was performed in the same manner as in Synthesis Example 1 except that the TMAH aqueous solution was changed to 32.5 g. The obtained polysiloxane Pa-2 had a Mw = 2500 and an ADR = 300 Å/sec relative to a 5 mass % TMAH aqueous solution after prebaking.

<Synthesis Example 3 (Synthesis of polysiloxane Pb-1)> In a 2L flask equipped with a stirrer, a thermometer, and a cooling tube, 102g of a 25% by mass TMAH aqueous solution, 600ml of IPA, and 4.0g of water were charged, and then a mixed solution of 68.0g of methyltrimethoxysilane, 79.2g of phenyltrimethoxysilane, and 68.1g of bis(triethoxysilyl)methane was prepared in a dropping funnel. The mixed solution was dropped at 40°C, stirred at the same temperature for 2 hours, and then neutralized by adding a 10% by mass HCl aqueous solution. 400ml of toluene and 600ml of water were added to the neutralized solution to separate it into two phases, and the aqueous phase was removed. The organic phase was further washed three times with 400 ml of water, and the solvent was removed by concentrating the obtained organic phase under reduced pressure. PGMEA was added to the concentrate to adjust the solid content to 35% by mass. The obtained polysiloxane Pb-1 had an Mw of 6,500 and an ADR of 3,300 Å/sec relative to a 2.38% by mass TMAH aqueous solution after prebaking.

<Synthesis Example 4 (Synthesis of polysiloxane Pb-2)> In a 2L flask equipped with a stirrer, a thermometer, and a cooling tube, 102g of a 25% by mass TMAH aqueous solution, 600ml of isopropyl alcohol (IPA), and 4.0g of water were charged, and then a mixed solution of 68.0g of methyltrimethoxysilane, 79.2g of phenyltrimethoxysilane, and 54.0g of bis(trimethoxysilyl)ethane was prepared in a dropping funnel. The mixed solution was dropped at 40°C, stirred at the same temperature for 2 hours, and then neutralized by adding a 10% by mass HCl aqueous solution. 400ml of toluene and 600ml of water were added to the neutralized solution to separate it into two phases, and the aqueous phase was removed. The organic phase was further washed three times with 400 ml of water, and the solvent was removed by concentrating the obtained organic phase under reduced pressure. PGMEA was added to the concentrate to adjust the solid content to 35% by mass. The Mw of the obtained polysiloxane was 9,000, and the ADR relative to a 2.38% by mass TMAH aqueous solution after prebaking was 2,600 Å/sec. In addition, the ADR of the entire polysiloxane relative to a 2.38% by mass TMAH aqueous solution after prebaking was as follows. Polysiloxane Pa-1:Pa-2:Pb-1=40:10:50 ADR=1,800Å/sec Polysiloxane Pa-1:Pa-2:Pb-2=40:10:50 ADR=1,600Å/sec Polysiloxane Pa-1:Pa-2=90:10 ADR=900Å/sec

<Examples 101 to 114 and Comparative Examples 101 to 108 (Preparation of positive photosensitive polysiloxane compositions)> Positive photosensitive polysiloxane compositions of Examples 101 to 114 and Comparative Examples 101 to 108 were prepared, containing the compounds shown in Table 1 below and the remainder being PGMEA. [Table 1] Table 1 Composition Reviews Polysiloxane (mass percentage) Diazonaphthoquinone derivatives (mass fraction) Carboxylic acid compounds (ppm) Surfactant (ppm) Wrinkle Evaluation Pattern shape evaluation Pa-1 Pa-2 Pb-1 Pb-2 Embodiment 101 40 10 - 50 6 Maleic Acid 300 1000 B Y 102 40 10 - 50 6 Maleic Acid 500 1000 A Y 103 40 10 - 50 6 Maleic acid 1000 1000 A Y 104 40 10 - 50 6 Maleic acid 12000 1000 A X 105 40 10 - 50 6 Maleic acid 50000 1000 A X 106 40 10 50 - 6 Maleic acid 1000 1000 A X 107 40 10 50 - 6 Maleic Acid 500 1000 A X 108 50 - - 50 6 Maleic Acid 500 1000 A X 109 90 10 - - 6 Maleic acid 1000 1000 A X 110 90 10 - - 6 Maleic acid 9000 1000 A X 111 40 10 - 50 6 Acetic acid 10000 1000 B X 112 40 10 - 50 6 Oxalic acid 3000 1000 A Z 113 40 10 - 50 6 Malonic acid 3000 1000 A Y 114 40 10 - 50 6 Apple acid 3000 1000 A Z Comparison Example 101 40 10 50 - 6 - 1000 D Z 102 40 10 50 - 6 Maleic Acid 100 1000 C Z 103 40 10 - 50 6 - 1000 D Z 104 40 10 - 50 6 Maleic Acid 100 1000 C Z 105 90 10 - - 6 - 1000 D X 106 90 10 - - 6 Maleic Acid 100 1000 C X 107 40 10 - 50 6 Citric Acid 300 1000 D Z 108 40 10 - 50 6 Citric acid 10000 1000 D Z In the table, naphthoquinone diazide derivative: 2.0 mol modified naphthoquinone diazide of 4,4'-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol; Surfactant: KF-53, manufactured by Shin-Etsu Chemical Co., Ltd. In addition, "-" means that the added amount is zero.

<Evaluation of wrinkles> The state of wrinkles on the surface after curing by exposure at the optimal exposure obtained in the sensitivity evaluation was evaluated by visual observation. The evaluation criteria were as follows, and the evaluation results were recorded in Table 1. A: No wrinkles were found on the surface B: Small wrinkles were found on the surface, but the portion without wrinkles was 80% or more C: Small wrinkles were found on the surface, and the portion without wrinkles was less than 80% D: Large wrinkles were found on the surface In addition, typical electron microscope photographs of a pattern with no wrinkles (P), a pattern with small wrinkles (Q), and a pattern with large wrinkles (R) are shown in Figure 1.

<Evaluation of pattern shape> The shape of the pattern after curing after exposure at the optimal exposure amount obtained by sensitivity evaluation was observed and evaluated using a scanning electron microscope (SEM). The evaluation criteria are as follows, and the evaluation results are shown in Table 1. X: The corners of the formed pattern have large roundness Y: The corners of the formed pattern have roundness Z: The corners of the formed pattern have no roundness V: The detached pattern is smaller than the mask size W: No pattern is formed In addition, typical electron microscope photographs corresponding to each of the above shapes are shown in Figure 2.

<Evaluation of sensitivity> The compositions of Examples 101 to 105 were applied by spin coating to a film thickness of 1.6 μm after pre-baking. The obtained coating was pre-baked at 110°C for 90 seconds to volatilize the solvent. After that, a contact hole of 5 μm in size was patterned with an optimal exposure using a g+h line mask alignment exposure machine (FX-604F, manufactured by Nikon Co., Ltd.). After exposure, a 2.38 mass% TMAH aqueous solution was used for coating development for 70 seconds, and then rinsed with pure water for 60 seconds and dried. Then, after heating at 180°C in the atmosphere for 20 minutes, it was further heated at 230°C for 20 minutes to harden. Here, when patterning is performed using a 5-micron mask, the exposure amount at which the bottom width of the contact hole after curing becomes 5 microns is regarded as the optimal exposure amount. The compositions of Examples 101 to 105 have an exposure amount of less than 500 mJ as the optimal exposure amount, which is a sensitivity that can be fully used in practical use. On the other hand, when the composition is the same as that of Example 101 except that the maleic acid is 80,000 ppm, and the optimal exposure amount is obtained in the same manner as above, a pattern cannot be formed even if the exposure amount is increased.

<Examples 201, 202 and Comparative Examples 201-204 (Preparation of positive photosensitive polysiloxane composition)> Positive photosensitive polysiloxane compositions of Examples 201, 202 and Comparative Examples 201-204 were prepared, containing the compounds shown in Table 2 below and the remainder being PGMEA. [Table 2] Table 2 Composition Reviews Polysiloxane (mass percentage) Diazonaphthoquinone derivatives (mass fraction) Carboxylic acid compounds (ppm) Surfactant (ppm) Wrinkle Evaluation Pattern shape evaluation Pa-1 Pa-2 Pb-2 Embodiment 201 40 10 50 6 Maleic Acid 3000 1000 A X 202 90 10 - 6 Maleic acid 10000 1000 A X Comparison Example 201 90 10 - 6 - 1000 D X 202 40 10 50 6 - 1000 D Z 203 90 10 - 6 Citric Acid 3000 1000 D X 204 90 10 - 6 Apple acid 3000 1000 D X In the table, naphthoquinone diazide derivative: 2.0 mol modified naphthoquinone diazide of 4,4'-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol; Surfactant: KF-53, manufactured by Shin-Etsu Chemical Co., Ltd. In addition, "-" means that the added amount is zero.

Each component was applied by spin coating so that the film thickness after pre-baking was 1.6 μm. The obtained coating was pre-baked at 110°C for 90 seconds to evaporate the solvent. After that, a contact hole with a size of 5 μm was patterned with an optimal exposure using a g+h line mask alignment exposure machine (FX-604F, manufactured by Nikon Co., Ltd.). After exposure, a 1.0 mass% KOH aqueous solution was used for liquid development for 70 seconds, and then rinsed with pure water for 60 seconds and dried. Then, after heating at 180°C in the atmosphere for 20 minutes, it was further heated at 230°C for 20 minutes to harden.

The wrinkle evaluation and pattern shape evaluation were evaluated using the same evaluation criteria as above. The evaluation results are shown in Table 2.

without.

[Figure 1] An electron microscope photograph used to illustrate the "wrinkles" formed on the surface of the pattern. [Figure 2] An electron microscope photograph used to illustrate the shape of the pattern in the embodiment.

Claims (13)

A positive photosensitive polysiloxane composition comprises the following: (I) polysiloxane; (II) a carboxylic acid compound, which is a monocarboxylic acid or a dicarboxylic acid in an amount of 200 to 50,000 ppm based on the total mass of the composition; (III) a diazonaphthoquinone derivative; and (IV) a solvent, wherein the polysiloxane comprises a repeating unit represented by the following formula (Ic):

The monocarboxylic acid is represented by formula (i): R ⁱ -COOH formula (i) (wherein R ⁱ is hydrogen or a saturated or unsaturated alkyl group having 1 to 4 carbon atoms); and the dicarboxylic acid is represented by formula (ii): HOOC-L-COOH formula (ii) (wherein L is a single bond, an unsubstituted alkylene group having 1 to 6 carbon atoms or an amino-substituted alkylene group, a substituted or unsubstituted alkenylene group having 2 to 4 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 4 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms). A positive photosensitive polysiloxane composition comprises the following: (I) polysiloxane; (II) a carboxylic acid compound, which is a monocarboxylic acid or a dicarboxylic acid in an amount of 200 to 50,000 ppm based on the total mass of the composition; (III) a diazonaphthoquinone derivative; and (IV) a solvent, wherein the polysiloxane comprises a repeating unit represented by the following formula (Ie):

(where L ^Ie is -(CR ^Ie ₂ ) _n - or

wherein n is an integer of 1 to 3, and R ⁱ each independently represents hydrogen, methyl, or ethyl) the monocarboxylic acid is represented by formula (i): R ⁱ -COOH formula (i) (wherein R ⁱ is hydrogen, or a saturated or unsaturated alkyl group having 1 to 4 carbon atoms); and the dicarboxylic acid is represented by formula (ii): HOOC-L-COOH formula (ii) (wherein L is a single bond, an unsubstituted alkylene group having 1 to 6 carbon atoms, or an amino-substituted alkylene group, a substituted or unsubstituted alkenylene group having 2 to 4 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 4 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms). The composition of claim 1 or 2, wherein the first acid dissociation constant pKa ₁ of the monocarboxylic acid is less than 5.0, and the first acid dissociation constant pKa ₁ of the dicarboxylic acid is less than 4.0. The composition of claim 1 or 2, wherein the carboxylic acid compound is a dicarboxylic acid. The composition of claim 1 or 2, wherein the dicarboxylic acid is capable of forming a ring structure by intramolecular dehydration condensation. For example, in the composition of claim 1 or 2, the content of the carboxylic acid compound is 300-30,000 ppm based on the total mass of the composition. The composition of claim 1 or 2, wherein the polysiloxane further comprises repeating units represented by the following formula (Ia):

(wherein, R ^Ia represents hydrogen, a C _1-30 linear, branched or cyclic saturated or unsaturated aliphatic alkyl group, or an aromatic alkyl group, the aliphatic alkyl group and the aromatic alkyl group are each unsubstituted or substituted with fluorine, hydroxyl or alkoxy, and in the aliphatic alkyl group and the aromatic alkyl group, the methylene group is unsubstituted, or one or more methylene groups are substituted with oxy, amine, imino or carbonyl, but R ^Ia is not a hydroxyl or alkoxy). The composition of claim 7, wherein R ^Ia is a C _3-20 saturated or unsaturated cyclic aliphatic hydrocarbon group or an aromatic hydrocarbon group. A method for manufacturing a hardened film comprises the following steps: (1) applying a composition as described in any one of claims 1 to 8 to a substrate to form a composition layer, (2) exposing the composition layer, (3) developing with an alkaline developer to form a pattern, and (4) heating the obtained pattern. The method of claim 9, wherein the step of performing full-surface exposure is not included before step (4). The method of claim 9 or 10, wherein the alkaline developer is an organic developer. The method of claim 9 or 10, wherein the alkaline developer is an inorganic developer. An electronic component having a cured film produced by the method of any one of claims 9 to 12.