KR102590065B1 - Positive photosensitive polysiloxane composition - Google Patents

Abstract

[Problem] To provide a positive photosensitive polysiloxane composition that can produce a cured film with high surface smoothness and suppressed wrinkles without adding a curing aid or performing full exposure.
[Solution] A positive photosensitive polysiloxane composition, comprising (I) polysiloxane, (II) a carboxylic acid compound that is 200 to 50,000 ppm of a monocarboxylic acid or dicarboxylic acid based on the total weight of the composition, and (III) a diazonaphthoquinone derivative. , and (IV) a positive photosensitive polysiloxane composition containing a solvent, and a method for producing a cured film using the composition.

Description

Positive photosensitive polysiloxane composition

The present invention relates to a positive photosensitive polysiloxane composition. Additionally, the present invention relates to a method for producing a cured film using the same and an electronic device containing the cured film.

Recently, various proposals have been made to improve light use efficiency and save energy in optical devices such as displays, light-emitting diodes, and solar cells. For example, in a liquid crystal display, there is a known method of increasing the aperture ratio of the display element by forming a transparent planarization film on the TFT element and forming a pixel electrode on the planarization film.

As a planarization film material for such a TFT substrate, a material combining an acrylic resin and a quinone diazide compound is known. Because these materials have planarizing properties and photosensitivity, they can form contact holes and other patterns. However, as resolution and frame frequency increase, wiring becomes more complex, and planarization becomes more stringent, making it difficult to cope with these materials.

Polysiloxane, especially silsesquioxane, is known as a material with high heat resistance and high transparency. Silsesquioxane is a polymer composed of the trifunctional siloxane structural unit RSi (O _1.5 ), and is chemically and structurally intermediate between inorganic silica (SiO ₂ ) and organic silicon (R ₂ SiO). It is soluble in organic solvents, and its cured product is a specific compound that exhibits high heat resistance characteristic of inorganic silica.

Using a positive photosensitive composition containing 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 is not flat and wrinkles may occur. Next, to suppress the occurrence of wrinkles, a curing aid is added, or a full-scale flood exposure is performed after exposure and development.

(Patent Document 1) JP 2011-2517A

The present invention has been made in response to the above-described situation, and the object of the present invention is to produce a cured film with high surface smoothness and suppressed wrinkles without adding a curing auxiliary agent or performing full exposure. A composition is provided. Additionally, an object of the present invention is to provide a method for producing a cured film using the same.

The positive photosensitive polysiloxane composition according to the present invention is

(I) polysiloxane,

(II) 200 to 50,000 ppm of a carboxylic acid compound, which is a monocarboxylic acid or dicarboxylic acid, based on the total weight of the composition,

(III) diazonaphthoquinone derivatives, and

(IV) Solvent

Includes.

In addition, the method for producing a cured film according to the present invention is

(1) applying the composition according to the present invention on 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

Includes.

Additionally, the electronic device according to the present invention includes a cured film manufactured by the method described above.

By using the positive photosensitive polysiloxane composition according to the present invention, a cured film with high surface smoothness and suppressed occurrence of wrinkles can be produced without adding a curing aid or performing full exposure. The obtained films are highly sensitive and can contribute to the high throughput of the manufacturing process. Additionally, the pattern shape of the cured film may be such that the openings have a gentle shape, which is a desirable shape for subsequent processes. Subsequently, since the obtained cured film is flat and has excellent electrical insulation, it can be used as a planarization film for thin film transistor (TFT) substrates used in display backplanes such as liquid crystal display devices and organic EL display devices, interlayer insulating films of semiconductor devices, and solid-state imaging devices. , anti-reflection films, anti-reflection plates, optical filters, high-intensity light emitting diodes, touch panels, various film forming materials such as insulating films or transparent protective films for solar cells, etc., and even optical elements such as optical waveguides.

[Figure 1] Electron micrograph to illustrate “wrinkles” formed on the pattern surface.
[Figure 2] Electron micrograph to explain the pattern shape in the example.

Hereinafter, aspects of the present invention will be described in detail. In this specification, unless otherwise specified, symbols, units, abbreviations, and terms have the following meanings.

In this specification, unless specifically stated otherwise, the singular includes the plural and “a” or “that” means “at least one.” In this specification, unless specifically stated, a concept element may be expressed by a plurality of species, and when an amount (e.g. mass % or mol %) is described, it means the sum of the plurality of species. “And/or” includes any combination of elements, and also includes the use of any element alone.

In this specification, when “to” or “-” is used to indicate a numerical range, it includes that these two endpoints and units are common. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

As used herein, hydrocarbon is meant to contain carbon and hydrogen, and optionally oxygen or nitrogen. Hydrocarbon group refers to monovalent, divalent or higher hydrocarbons. In this specification, an aliphatic hydrocarbon refers to a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon, and an aliphatic hydrocarbon group refers to a monovalent, divalent, or higher aliphatic hydrocarbon. Aromatic hydrocarbon refers to a hydrocarbon containing an aromatic ring that can optionally contain an aliphatic hydrocarbon group as a substituent and can be condensed with an alicyclic ring. Aromatic hydrocarbon group refers to monovalent, divalent or higher aromatic hydrocarbons. In addition, an aromatic ring refers to a hydrocarbon having a conjugated unsaturated cyclic structure, and an alicyclic refers to a hydrocarbon having a cyclic structure but not containing a conjugated unsaturated cyclic structure.

As used herein, alkyl refers to a group formed by removing any one hydrogen from a straight-chain or branched-chain saturated hydrocarbon, and includes straight-chain alkyl and branched-chain alkyl, and cycloalkyl includes a cyclic structure, and the cyclic structure includes a straight-chain or branched chain. refers to a group formed by removing one hydrogen from a saturated hydrocarbon, optionally containing branched chain alkyl as a side chain.

As used herein, aryl refers to a group formed by removing any one hydrogen from an aromatic hydrocarbon. Alkylene refers to a group formed by removing any two hydrogens from a straight-chain or branched-chain saturated hydrocarbon. Arylene refers to a hydrocarbon group formed by removing two arbitrary hydrogens from an aromatic hydrocarbon.

As used herein, “C _xy ”, “C _x -C _y ” and “C _x ” refer to the number of carbons in a molecule or substituent. For example, C _1-6 alkyl refers to alkyl having 1 to 6 carbons (eg, methyl, ethyl, propyl, butyl, pentyl, and hexyl). Additionally, as used herein, fluoroalkyl refers to one or more hydrogens of alkyl replaced with fluorine, and fluoroaryl refers to one or more hydrogens of aryl replaced with fluorine.

In this specification, when the polymer has several types of repeating units, these repeating units are copolymerized. This copolymerization is one of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of any of these.

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 (hereinafter also referred to as composition) according to the present invention includes (I) polysiloxane, (II) carboxylic acid compound, (III) diazonaphthoquinone derivative, and (IV) solvent.

Hereinafter, each component included in the composition according to the present invention will be described in detail.

(I) polysiloxane

The structure of the polysiloxane used in the present invention is not particularly limited, and any one can be selected depending on the purpose. Depending on the number of oxygen atoms bonded to the silicon atom, the polysiloxane skeleton structure is a silicon skeleton (the number of oxygen atoms bonded to a silicon atom is 2), a silsesquioxane framework (the number of oxygen atoms bonded to a silicon atom is 3), and silica skeleton (the number of oxygen atoms bonded to silicon atoms is 4). In the present invention, any of these may be used. Polysiloxane molecules can contain several combinations of these framework structures.

Preferably, the polysiloxane used in the present invention contains repeating units represented by formula (Ia).

here,

R ^Ia is hydrogen or a C _1-30 linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group,

The aliphatic hydrocarbon group and the aromatic hydrocarbon group are each unsubstituted or substituted with fluorine, hydroxy or alkoxy, and in the aliphatic hydrocarbon group and the aromatic hydrocarbon group, methylene is not replaced or one or more methylenes are oxy, amino, imino or carbo. and nyl, provided that R ^Ia is not hydroxy or alkoxy.

Additionally, the methylene described above includes a terminal methyl.

In addition, the above-mentioned "substituted by fluorine, hydroxy or alkoxy" means that the hydrogen atom directly bonded to the carbon atom of the aliphatic hydrocarbon group and aromatic hydrocarbon group is replaced by fluorine, hydroxy or alkoxy. In this specification, the same applies to other similar descriptions.

In the repeating unit represented by formula (Ia),

R ^Ia is, for example, (i) alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and decyl, (ii) aryl such as phenyl, tolyl and benzyl, (iii) trifluoro. fluoroalkyl such as methyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, (iv) fluoroaryl, (v) cycloalkyl such as cyclohexyl, (vi) isocyanate and nitrogen-containing groups with amino or imide structures, such as amino, (vii) epoxy structures, such as glycidyl, or oxygen-containing groups with acryloyl or methacryloyl structures. These are preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, tolyl, glycidyl and isocyanate. As fluoroalkyl, perfluoroalkyl is preferred, and trifluoromethyl and pentafluoroethyl are particularly preferred. Compounds where R ^Ia is methyl are preferable because these unprocessed raw materials can be easily obtained, have high film hardness after curing, and have high chemical resistance. Additionally, a compound where R ^Ia is phenyl is preferable because the polysiloxane has high solubility in a solvent and the cured film is unlikely to crack. Additionally, it is preferable that R ^Ia has hydroxy, glycidyl, isocyanate, or amino because adhesion to the substrate improves.

The polysiloxane used in the present invention may further include a repeating unit represented by formula (Ib).

Here, R ^Ib is a group obtained by removing a plurality of hydrogens from a nitrogen and/or oxygen-containing alicyclic hydrocarbon compound having an amino group, an imino group, and/or a carbonyl group.

In formula (Ib), R ^Ib is preferably a nitrogen-containing aliphatic hydrocarbon ring having an imino group and/or a carbonyl group, more preferably a plurality of rings from a 5- or 6-membered ring containing nitrogen in the members. It is a group obtained by removing hydrogen, preferably two or three hydrogens. For example, there are groups obtained by removing two or three hydrogens from piperidine, pyrrolidine and isocyanurate. R ^Ib connects Si included in each of the plurality of repeating units.

The polysiloxane used in the present invention may further include a repeating unit represented by formula (Ic).

When the mixing ratio of the repeating units represented by formula (Ib) and formula (Ic) is high, cracks are likely to occur due to decreased sensitivity of the composition, decreased compatibility with solvents and additives, and increased membrane stress. Therefore, it is preferably 40 mol% or less, more preferably 20 mol% or less, relative to the total number of repeating units of the polysiloxane.

The polysiloxane used in the present invention may further include a repeating unit represented by formula (Id).

here,

R ^Id is each independently hydrogen or a C _1-30 linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group,

In the aliphatic hydrocarbon group and the aromatic hydrocarbon group, methylene is not replaced or is replaced with oxy, imide or carbonyl, and the carbon atom is not substituted or is replaced with fluorine, hydroxy or alkoxy.

In the repeating unit denoted by formula (Id),

R ^Id is, for example, (i) alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and decyl, (ii) aryl such as phenyl, tolyl and benzyl, (iii) trifluoro. fluoroalkyl such as methyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, (iv) fluoroaryl, (v) cycloalkyl such as cyclohexyl, (vi) isocyanate and nitrogen-containing groups with amino or imide structures, such as amino, (vii) epoxy structures, such as glycidyl, or oxygen-containing groups with acryloyl or methacryloyl structures. These are preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, tolyl, glycidyl and isocyanate. As fluoroalkyl, perfluoroalkyl is preferred, and trifluoromethyl and pentafluoroethyl are particularly preferred. Compounds where R ^Id is methyl are preferable because these unprocessed raw materials can be easily obtained, have high film hardness after curing, and have high chemical resistance. Additionally, a compound in which R ^Id is phenyl is preferable because the polysiloxane has high solubility in a solvent and the cured film is unlikely to crack. Additionally, it is preferable that R ^Id has hydroxy, glycidyl, isocyanate, or amino because adhesion to the substrate improves.

By having repeating units of formula (Id), the polysiloxane according to the invention can have a partially straight chain structure. However, since heat resistance decreases, it is preferable to have fewer linear structure parts. Specifically, it is preferable that the repeating unit of the formula (Id) is 30 mol% or less relative to the total number of repeating units of the polysiloxane.

Additionally, the polysiloxane may contain repeating units represented by formula (Ie).

Here, L ^Ie is -(CR ^Ie ₂ ) _n - or , where n is an integer from 1 to 3, and R ^Ie each independently represents hydrogen, methyl, or ethyl.

L ^Ie in formula (Ie) is preferably -(CR ^Ie ₂ ) _n -, and R ^Ie are the same or different in one repeating unit or in a polysiloxane molecule. R ^Ie in one molecule are preferably all the same, and are preferably all 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, having a repeating unit represented by formula (Ia) and a repeating unit represented by formula (Ic) wherein R ^Ia is methyl or phenyl.

The composition according to the present invention may contain two or more types of polysiloxane. For example, a polysiloxane containing any one of the repeating units of the above-described formulas (Ia) to (Id) is used as the first layer, and a repeating unit of the formula (Ie) and a repeating unit other than the formula (Ie) (preferably A polysiloxane containing repeating units of formula (Ia), (Ib) and/or (Id) may be used as the second layer.

Preferably, the one or more polysiloxanes have repeating units that are bulky groups in at least one of R ^Ia of formula (Ia), R ^Ib of formula (Ib), and/or R ^Id of formula (Id). Contains; A repeating unit of formula (Ia) wherein R ^Ia is a bulky C _3-20 saturated or unsaturated cyclic aliphatic hydrocarbon group or an aromatic hydrocarbon group (e.g. phenyl, naphthyl, anthracene) and a repeating unit of formula (Ie) It is also preferred to use polysiloxanes comprising: Since the presence of bulky groups tends to cause wrinkles, the suppression of wrinkles by the present invention is effective, and the inclusion of the repeating unit of formula (Ie) further enables control of the taper angle of the pattern, which is particularly It is advantageous.

The ratio of the number of repeating units (Ie) to the 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. Additionally, (Ia) is preferably 20 to 95 mol% and (Ie) is preferably 5 to 40 mol%.

In addition, the total ratio of the repeating units (Ia), (Ib) and (Id) containing the bulky group is preferably 10 mol% or more with respect to the total number of repeating units contained in the polysiloxane.

The polysiloxane used in the present invention has a structure in which the above-described repeating units are bonded, but preferably has a structure with silanol at the terminal. This silanol group is one in which -O _0.5 H is bonded to the bonding hand of the repeating unit or block described above.

The mass average molecular weight of the polysiloxane used in the present invention is not particularly limited. However, the higher the molecular weight, the higher the applicability tends to be. On the other hand, the lower the molecular weight, the fewer restrictions on synthesis conditions, the easier the synthesis, and the more difficult it is to synthesize polysiloxanes with very high molecular weights. For this reason, the mass average molecular weight of polysiloxane is generally 500 to 25,000, and is preferably 1,000 to 20,000 in terms of solubility in organic solvents and solubility in alkaline developers. Here, the mass average molecular weight is the mass average molecular weight in terms of polystyrene, which can be measured by gel permeation chromatography using polystyrene as a standard.

In addition, the polysiloxane used in the present invention is contained in a composition having positive photosensitivity, and the composition is applied on a substrate, and a cured film is formed by image-type exposure and development. At this time, it is necessary to create a difference in solubility between the exposed area and the non-exposed area, and the coating film on the exposed area has a solubility above a certain level in the developer. For example, the dissolution rate (hereinafter also referred to as alkali dissolution rate or ADR, described in detail below) of the pre-baked coating film in a 2.38% by mass tetramethylammonium hydroxide (hereinafter also referred to as TMAH) aqueous solution is 50 Å. If it is more than /sec, pattern formation by exposure-development is considered possible. However, since the required solubility varies depending on the thickness of the cured film formed and the development conditions, polysiloxane must be appropriately selected according to the development conditions. This varies depending on the type and addition amount of the diazonaphthoquinone derivative contained in the composition, but for example, if the film thickness is 0.1 to 100 μm (1,000 to 1,000,000 Å), the dissolution rate for the 2.38 mass% TMAH aqueous solution is preferably is 50 to 5,000 Å/sec, more preferably 200 to 3,000 Å/sec.

As the polysiloxane used in the present invention, a polysiloxane having any ADR within the above range can be selected depending on the application and required properties. It is also possible to combine some polysiloxanes with different ADRs to produce a mixture with the 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 using a combination of polysiloxanes with different alkali dissolution rates, it is possible to reduce insoluble matter remaining after development, reduce pattern reflow, and improve pattern stability.

These polysiloxanes are, for example,

(M) After pre-baking, the membrane contains a polysiloxane that is soluble in a 2.38% by mass TMAH aqueous solution and has a dissolution rate of 200 to 3,000 Å/sec.

Additionally, as needed,

(L) a polysiloxane that is soluble in a 5 mass% TMAH aqueous solution after pre-baking and has a dissolution rate of 1,000 Å/sec or less; or

(H) Polysiloxane in which the film after pre-baking has a dissolution rate of 4,000 Å/sec or more in a 2.38 mass% TMAH aqueous solution.

By mixing with, a composition having a desired dissolution rate can be obtained.

[Measurement of alkaline dissolution rate (ADR) and its calculation method]

Using an aqueous TMAH solution as an alkaline solution, the alkaline dissolution rate of polysiloxane or a mixture thereof is measured and calculated as follows.

Polysiloxane is diluted with PGMEA to 35% by weight and dissolved while stirring in a stirrer at room temperature for 1 hour. In a clean room with a temperature of 23.0 ± 0.5°C and a humidity of 50 ± 5.0%, using a pipette, 1 cc of the prepared polysiloxane solution was dropped onto the center of a 4-inch silicon wafer with a thickness of 525 μm and spun to a thickness of 2 ± 0.1 μm. After coating, heat on a 100°C hot plate for 90 seconds to remove the solvent. Measure the thickness of the coating film with a spectroscopic ellipsometer (manufactured by J.A. Woollam).

Next, the silicon wafer with this film was gently immersed in a 6-inch-diameter glass Petri dish containing 100 ml of TMAH aqueous solution of a predetermined concentration adjusted to 23.0 ± 0.1°C and left to stand, and the time until the coating film disappeared was measured. The dissolution rate is obtained by dividing the time until the film disappears 10 mm inside from the end of the wafer. If the dissolution rate is significantly slow, immerse the wafer in the TMAH aqueous solution for a certain period of time and then heat it on a hot plate at 200°C for 5 minutes. When measuring the dissolution rate, the moisture contained in the membrane is removed. Thereafter, the film thickness is measured, and the dissolution rate is calculated by dividing the amount of change before and after immersion by the immersion time. The average of the values obtained by performing the above measurement method 5 times 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 can be obtained, for example, by hydrolyzing and polymerizing the silane monomer represented by the formula (ia) in the presence of an acidic catalyst or a basic catalyst as needed.

R ^ia -Si-(OR ^ia' ) ₃ (ia)

here,

R ^ia is hydrogen or a C _1-30 linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group,

In the aliphatic hydrocarbon group and the aromatic hydrocarbon group, methylene is not replaced or is replaced with oxy, imide or carbonyl, and the carbon atom is not substituted or is replaced with fluorine, hydroxy or alkoxy,

R ^ia' is straight or branched C _1-6 alkyl.

Preferred R ^ia' in formula (ia) includes methyl, ethyl, n-propyl, isopropyl and n-butyl. Although the formula (ia) contains a plurality of R ^ia' , each R ^ia' may be the same or different.

Preferred R ^ia is the same as the preferred R ^Ia described above.

Specific embodiments of the silane monomer represented by formula (ia) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, and ethyltrimethoxy. Silane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n- Butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltrimethoxysilane Includes fluoromethyltriethoxysilane and 3,3,3-trifluoropropyltrimethoxysilane. Among them, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and phenyltrimethoxysilane are preferable. Two or more types of silane monomers represented by formula (ia) can be combined.

Additionally, silane monomers represented by the formula (ic) can be combined. Using a silane monomer represented by the formula (ic), a polysiloxane containing a repeating unit (Ic) can be obtained.

Si(OR ^ic' ) ₄ (ic)

Here, R ^ic' is straight or branched C _1-6 alkyl. Preferred R ^ic' in formula (ic) includes methyl, ethyl, n-propyl, isopropyl and n-butyl, etc. Although the formula (ic) contains a plurality of R ^ic' , each R ^ic' may be the same or different.

Specific embodiments of the silane monomer represented by formula (ic) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, and the like.

Silane monomers represented by formula (ib) may be additionally combined.

R ^ib -Si-(OR ^ib' ) ₃ (ib)

here,

R ^ib' is straight or branched C _1-6 alkyl and includes, for example, methyl, ethyl, n-propyl, isopropyl, and n-butyl. Although a plurality of R ^ib' are contained in one monomer, each R ^ib' may be the same or different.

R ^ib is a group obtained by removing a plurality of hydrogens, preferably two or three, from a nitrogen- and/or oxygen-containing alicyclic hydrocarbon compound having an amino group, an imino group, and/or a carbonyl group. Preferred R ^ib is the same as the preferred R ^ib described above.

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

Additionally, silane monomers represented by the formula (id) can be combined. Using a silane monomer represented by the formula (id), a polysiloxane containing a repeating unit (Id) can be obtained.

(R ^id ) ₂ -Si-(OR ^id' ) ₂ (id)

here,

R ^id' is each independently linear or branched C _1-6 alkyl, and includes, for example, methyl, ethyl, n-propyl, isopropyl, and n-butyl. Although a plurality of R ^id' are contained in one monomer, each R ^id' may be the same or different.

R ^id is each independently hydrogen or a C _1-30 linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group,

In the aliphatic hydrocarbon group and the aromatic hydrocarbon group, methylene is not replaced or is replaced with oxy, imide or carbonyl, and the carbon atom is not substituted or is replaced with fluorine, hydroxy or alkoxy. Preferred R ^id is the same as the preferred R ^Id described above.

Additionally, silane monomers represented by the formula (ie) can be combined.

(OR ^ie' ) ₃ -Si-L ^ie -Si-(OR ^ie' ) ₃ (ie)

here,

R ^ie' is each independently linear or branched C _1-6 alkyl, and includes, for example, methyl, ethyl, n-propyl, isopropyl, and n-butyl.

L ^ie is -(CR ^ie ₂ ) _n - or , preferably -(CR ^ie ₂ ) _n -, where n is each independently an integer of 1 to 3, and R ^ie is each independently hydrogen, methyl or ethyl.

(II) Carboxylic acid compounds

The carboxylic acid compound used in the present invention is 200 to 50,000 ppm of monocarboxylic acid or dicarboxylic acid based on the total weight 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, more preferably 3.5 or less.

Preferably, the monocarboxylic acid is represented by formula (i).

R ⁱ -COOH (i)

Here, R ⁱ is hydrogen or a C _1-4 saturated or unsaturated hydrocarbon group, more preferably a C _1-3 hydrocarbon group.

Examples of monocarboxylic acids used in the present invention include acetic acid, formic acid, acrylic acid, preferably acetic acid.

Preferably, the dicarboxylic acid is represented by formula (ii).

HOOC-L-COOH (ii)

where L is a single bond; C _1-6 unsubstituted alkylene, hydroxy-substituted alkylene or amino-substituted alkylene; C _2-4 substituted or unsubstituted alkenylene; C _2-4 substituted or unsubstituted alkynylene; or C _6-10 substituted or unsubstituted arylene.

Here, in the present invention, alkenylene refers to a divalent group having one or more double bonds. Likewise, alkynylene refers to a divalent group having one or more triple bonds.

Preferably, L is a single bond; C _2-4 hydroxy-substituted or unsubstituted alkylene; C _2-4 alkenylene with one C=C bond; or C _6-10 unsubstituted arylene,

More preferably, L is a single bond, C _1-2 unsubstituted alkenylene, vinylene, hydroxyethylene or phenylene.

Specific embodiments of dicarboxylic acids used in the present invention include oxalic acid, maleic acid, fumaric acid, o-phthalic acid, succinic acid, glutaconic acid, aspartic acid, glutamic acid, malic acid, itaconic acid, 3-aminohexanedioic acid, and malonic acid. and preferably oxalic acid, maleic acid, fumaric acid, o-phthalic acid, malic acid, or malonic acid.

The carboxylic acid compound used in the present invention is more preferably a dicarboxylic acid, and among these, those that can assume a cyclic structure by intramolecular dehydration condensation are particularly preferable. Examples of such dicarboxylic acids include oxalic acid, maleic acid, succinic acid, o-phthalic acid, glutaconic acid, and itaconic acid. Above all, dicarboxylic acids at which the temperature at which the intramolecular dehydration condensation reaction occurs is 100°C to 250°C are preferred, and maleic acid, succinic acid, and oxalic acid are also preferred.

Carboxylic acid compounds can be used in combination of two or more types.

In the composition according to the present invention, the content of the carboxylic acid compound used in the present invention is 200 to 50,000 ppm, more preferably 300 to 30,000 ppm, even more preferably 500 to 30,000 ppm, based on the total mass of the composition. Exceeding 50,000 ppm is not desirable because sensitivity decreases.

When an organic developer (eg, TMAH aqueous solution) is used in the development process, the content of compound (II) is preferably 300 to 10,000 ppm, more preferably 500 to 5,000 ppm.

When an inorganic developer (eg, KOH aqueous solution) is used in the development process, the content of compound (II) is preferably 1,000 to 30,000 ppm, more preferably 3,000 to 10,000 ppm.

The composition according to the present invention contains a specific carboxylic acid compound in a specific amount, which will have the effect of suppressing wrinkles in the cured film and improving the smoothness of the pattern surface. Although not intended to be bound by theory, it is assumed that:

The positive polysiloxane composition is applied, exposed, developed with an alkaline developer, washed, and cured by heating. Although the developer must always be washed by washing, the alkaline component remaining in the film, especially on the film surface, excessively accelerates the curing reaction of the film surface.

If a front exposure process is added after cleaning, the curing reaction will not be excessively promoted due to the front exposure. Therefore, the occurrence of wrinkles is suppressed.

Since the composition according to the present invention contains a specific carboxylic acid compound in a specific amount, the curing reaction is not excessively promoted and the formation of wrinkles can be suppressed by neutralizing the alkaline component with an alkaline developer in the absence of a full exposure process.

In particular, if the carboxylic acid compound is a compound that can form a cyclic structure through an intramolecular dehydration reaction at a specific temperature, the silanol group of the polysiloxane is protected by the carboxylic acid group until heating for curing. However, upon heating for curing, it is considered that curing takes place in stages such that curing is carried out from the unprotected silanol groups, the carboxylic acid compound is converted to anhydride and removed from the membrane and the unprotected silanol groups are then cured. Therefore, the wrinkle-suppressing effect is considered to be greater.

Alkaline developers are classified into organic and inorganic. Inorganic developers have a smaller molecular size than organic developers and easily penetrate the film during development, increasing the amount of acid required for neutralization. Therefore, when an inorganic developer is used, the content of carboxylic acid compounds is greater.

(III) Diazonaphthoquinone derivatives

The composition according to the invention comprises a diazonaphthoquinone derivative. A composition containing a diazonaphthoquinone derivative forms a positive image that is removed by development when the exposed portion is soluble in an alkaline developer. That is, the composition according to the present invention generally functions as a positive-type photoresist composition. The diazonaphthoquinone derivative of the present invention is a compound in which naphthoquinone diazide sulfonic acid is ester-bonded to a compound having a phenolic hydroxy group. The structure is not particularly limited, but is preferably a compound having at least one phenolic hydroxy group. It is an ester compound having. As naphthoquinone diazide sulfonic acid, 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid can be used. The 4-naphthoquinone diazide sulfonic acid ester compound has absorption in the i-line (wavelength 365 nm) region and is therefore suitable for i-line exposure. Additionally, the 5-naphthoquinone diazide sulfonic acid ester compound has absorption in a wide range of wavelengths and is therefore suitable for exposure in various wavelength ranges. It is preferable to select 4-naphthoquinone diazide sulfonic acid ester compound or 5-naphthoquinone diazide sulfonic acid ester compound according to the exposure wavelength. A mixture of 4-naphthoquinone diazide sulfonic acid ester compound and 5-naphthoquinone diazide sulfonic acid ester compound may be used.

Compounds having a phenolic hydroxy group are not particularly limited, but examples 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, TrisP-TC (trade name, Honshu Chemical Industry Co., Ltd., Ltd. manufacturing).

The amount of diazonaphthoquinone derivative added varies depending on the esterification ratio of naphthoquinone diazide sulfonic acid, the physical properties of the polysiloxane used, the required photosensitivity, and the dissolution contrast between exposed and unexposed areas, but the total amount of polysiloxane is 100 mass. It is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass. If the amount of the diazonaphthoquinone derivative added is 1 part by mass or less, the dissolution contrast between the exposed and unexposed areas is so low that it does not have realistic photosensitivity. Additionally, in order to obtain better dissolution contrast, 2 parts by mass or more is preferable. On the other hand, if the amount of the diazonaphthoquinone derivative added exceeds 20 parts by mass, the compatibility between the polysiloxane and the quinonediazide compound deteriorates, causing whitening of the coating film, or decomposition of the quinonediazide compound occurring during heat curing. Coloration may become significant, which may reduce the colorless transparency of the cured film. In addition, since the heat resistance of diazonaphthoquinone derivatives is lower than that of polysiloxane, if the addition amount increases, the electrical insulation of the cured film decreases due to thermal decomposition and gas is released, which may cause problems in subsequent processes. In addition, the resistance of the cured film to photoresist stripper mainly composed of monoethanolamine or the like may be reduced.

(IV) Solvent

The solvent is not particularly limited as long as it uniformly dissolves or disperses the polysiloxane, carboxylic acid compound, and optionally added additives. 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 cellosolve acetate and ethyl cellosolve acetate; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether; propylene glycol alkyl ether acetates, such as propylene glycol 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, glycerin; Esters such as ethyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate; Cyclic esters such as γ-butyrolactone. Each of these solvents is used alone or in combination of two or more of them, and the amount used varies depending on the application method and the film thickness required after application.

Taking into account the coating method adopted, the solvent content of the composition according to the invention can be appropriately selected depending on the mass average molecular weight of the polysiloxane used, its distribution and its structure. The composition according to the invention generally comprises from 40 to 90% by mass, preferably from 60 to 80% by mass, of solvent, based on the total mass of the composition.

The composition according to the invention essentially contains the above-mentioned (I) to (IV), but additional compounds may be optionally combined. These materials that can be combined are described below. In addition, the content of components other than (I) to (IV) contained in the entire composition is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass.

[Silanol condensation catalyst]

The composition according to the present invention may include a silanol condensation catalyst selected from the group consisting of a photoacid generator, a photobase generator, a photothermal acid generator, and a photothermal base generator. This is preferably selected depending on the polymerization reaction and crosslinking reaction used in the cured film manufacturing process.

Additionally, in the present invention, the photoacid generator does not include the diazonaphthoquinone derivative (III) described above.

As far as these contents are taken into consideration, the optimal amount varies depending on the type of active substance generated by decomposition, the amount generated, the required photosensitivity, and the dissolution contrast between exposed and unexposed areas, but preferably for 100 parts by mass of the total mass of polysiloxane. is 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass. If the addition amount is less than 0.1 parts by mass, the amount of acid or base generated is too small, making pattern reflow likely to occur. On the other hand, if the addition amount exceeds 10 parts by mass, the formed cured film may crack or coloring due to such decomposition may become noticeable, and the colorless transparency of the cured film may decrease. In addition, if the addition amount increases, the electrical insulation of the cured film decreases due to thermal decomposition and gas is released, which may cause problems in subsequent processes. In addition, the resistance of the cured film to photoresist stripper mainly composed of monoethanolamine or the like may be reduced.

In the present invention, a photoacid generator or photobase generator refers to a compound that generates an acid or base by causing bond cleavage upon exposure to light. The resulting acid or base is considered to contribute to the polymerization of the polysiloxane. Here, examples of light include visible light, ultraviolet rays, infrared rays, X-rays, electron beams, α-rays, γ-rays, etc.

The photoacid generator or photobase generator preferably generates an acid or base through an image-type exposure (hereinafter referred to as first exposure) for projecting a pattern and a subsequent full-scale exposure, preferably the first exposure. It has less absorption at the wavelength of time. For example, performing the first exposure to the g-line (peak wavelength 436 nm) and/or h-line (peak wavelength 405 nm) and changing the wavelength during the second exposure to the g + h + i line (peak wavelength 365 nm) In this case, the photoacid generator or photobase generator preferably has a greater absorbance at a wavelength of 365 nm than at a wavelength of 436 nm and/or 405 nm.

Specifically, the absorbance at a wavelength of 365 nm/absorbance at a wavelength of 436 nm or the absorbance at a wavelength of 365 nm/absorbance at a wavelength of 405 nm is preferably 2 or more, more preferably 5 or more, more preferably 10 or more, and most preferably It is more than 100.

Here, the UV-visible absorption spectrum is measured using dichloromethane as a solvent. The measuring device is not particularly limited, but includes, for example, a Cary 4000 UV-Vis spectrophotometer (manufactured by Agilent Technologies Japan, Ltd.).

The photo acid generator may be arbitrarily selected from those commonly used, for example, diazomethane compounds, triazine compounds, sulfonic acid esters, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, Includes ammonium salts, phosphonium salts, sulfonimide compounds, etc.

Specific embodiments of photoacid generators that can be used, including those described above, include 4-methoxyphenyl diphenyl sulfonium hexafluorophosphonate, 4-methoxyphenyl diphenyl sulfonium hexafluoroarsenate, 4-methoxyphenyl diphenyl sulfonium methane sulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, Triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, 4-methoxyphenyl diphenyl sulfonium-p-toluene sulfonate, 4-phenyl thiophenyl diphenyl tetrafluoroborate, 4-phenyl thiophenyl diphenyl hexafluorophosphonate, triphenyl sulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyl diphenylsulfonate Phonium tetrafluoroborate, 4-phenylthiophenyl diphenyl hexafluoroarsenate, 4-phenylthiophenyl diphenyl-p-toluenesulfonate, N-(trifluoromethylsulfonyloxy)succinimide, N -(Trifluoromethylsulfonyloxy)phthalimide, 5-norbornene-2,3-dicarboximidyl triflate, 5-norbornene-2,3-dicarboximidyl-p-toluenesulfonate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulphenyl) Ponyloxy)bicyclo[2.2.1]hept-5-en-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)naphthylimide, N-(nonafluorobutylsulfonyloxy) ) naphthylimide, etc.

In addition, 5-propylsulfonyloxyimino-5H-thiophen-2-ylidene-(2-methylphenyl)acetonitrile, 5-octylsulfonyl-oxyimino-5H-thiophen-2-ylidene-(2- Methylphenyl)-acetonitrile, 5-camphorsulfonyloxyimino-5H-thiophen-2-ylidene-(2-methylphenyl)acetonitrile, 5-methylphenyl-sulfonyloxyimino-5H-thiophen-2-yly Since den-(2-methyl-phenyl)acetonitrile and the like have light absorption in the h-ray wavelength region, their use should be avoided in cases where h-line light absorption is not desired.

Examples of photoacid generators include polysubstituted amide compounds having an amide group, lactams, imide compounds, or those containing structures thereof.

Additionally, an ionic photobase generator containing an amide anion, a methide anion, a borate anion, a phosphate anion, a sulfonate anion, or a carboxylate anion may be used.

In the present invention, a photothermal acid generator or photothermal base generator refers to a compound whose chemical structure changes upon exposure but does not generate an acid or base and then causes bond cleavage by heat to generate an acid or base. Among these, photothermal base generators are preferred. As photothermal base generators, those represented by the formula (II) are mentioned, more preferably hydrates or solvates. The compound represented by formula (II) is reversed to the cis form by exposure and becomes unstable, thereby lowering the decomposition temperature and generating a base in the subsequent process even when the bake temperature is about 100°C.

The photothermal base generator does not need to adjust the absorption wavelength of the diazonaphthoquinone derivative.

here,

x is an integer between 1 and 6,

R ^a' to R ^f' are each independently hydrogen, halogen, hydroxy, mercapto, sulfide, silyl, silanol, nitro, nitroso, sulfino, sulfo, sulfonato, phosphino, phosphinyl, phosphono. , phosphonato, amino, ammonium, a C _1-20 aliphatic hydrocarbon group optionally having a substituent, a C _6-22 aromatic hydrocarbon group optionally having a substituent, a C _1-20 alkoxy optionally having a substituent, or a substituent. It is an aryloxy group optionally having C _6-20 .

Among these, R ^a' to R ^d' are preferably hydrogen, hydroxy, a C _1-6 aliphatic hydrocarbon group or C _1-6 alkoxy, and R ^e' and R ^f' are particularly preferably hydrogen. am. Two or more of R ^a' to R ^d' combine to form a cyclic structure. In this case, the cyclic structure may contain heteroatoms.

N is a constituent atom of a nitrogen-containing heterocyclic ring, the nitrogen-containing heterocyclic ring is a 3 to 10 membered ring, and the nitrogen-containing heterocyclic ring is one or more rings different from C _x H ₂ It may additionally have a C _1-20 aliphatic hydrocarbon group, especially a C _1-6 group, which may contain a substituent.

R ^a' to R ^d' are preferably appropriately selected depending on the exposure wavelength to be used. In applications for displays, unsaturated hydrocarbon bonding functional groups such as vinyl and alkynyl, alkoxy, nitro, etc., which shift the absorption wavelength for the g-ray, h-ray and i-ray, are used, for example, methoxy and Ethoxy is particularly preferred.

Specifically, the following can be mentioned:

In the present invention, a thermal acid generator or thermal base generator refers to a compound that causes bond cleavage by heat to generate an acid or base. It is preferable that these do not generate acid or base or generate only a small amount due to heat during pre-baking after application of the composition.

Examples of thermal acid generators include salts and esters that generate organic acids, such as various aliphatic sulfonic acids and salts thereof; Various aliphatic carboxylic acids and salts thereof such as citric acid, acetic acid and maleic acid; various aromatic carboxylic acids and salts thereof such as benzoic acid and phthalic acid; aromatic sulfonic acids and their ammonium salts; various amine salts; aromatic diazonium salt; and phosphonic acid and its salts, etc., provided that the thermal acid generator used in the present invention does not include the above-mentioned (II) carboxylic acid compound. Among thermal acid generators, salts composed of an organic acid and an organic base are particularly preferable, and salts composed of a sulfonic acid and an organic base are more preferable. Preferred sulfonic acids include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalene-disulfonic acid, methanesulfonic acid, and the like. These acid generators can be used alone or in combination.

Examples of thermal base generators include base-generating compounds such as imidazole, tertiary amines, quaternary ammonium, and mixtures thereof. Examples of released bases include N-(2-nitrobenzyloxycarbonyl)imidazole, N-(3-nitrobenzyloxycarbonyl)imidazole, N-(4-nitrobenzyloxycarbonyl)imidazole, N- Imidazole derivatives such as (5-methyl-2-nitrobenzyloxycarbonyl)imidazole and N-(4-chloro-2-nitrobenzyloxycarbonyl)imidazole; Includes 1,8-diazabicyclo[5.4.0]undecen-7. These base generators, like acid generators, can be used alone or in combination.

Other additives include surfactants, developer dissolution accelerators, scum removers, adhesion enhancers, polymerization inhibitors, anti-foaming agents, and sensitizers.

Because surfactants can improve applicability, it is preferable to use them. Examples of surfactants that can be used in the polysiloxane composition of the present invention include nonionic surfactants, anionic surfactants, amphoteric surfactants, and the like.

Examples of the above-mentioned nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene cetyl ether; polyoxyethylene fatty acid diester; polyoxyethylene fatty acid monoester; polyoxyethylene polyoxypropylene block polymer; acetylene alcohol; acetylene glycol; Acetylene alcohol derivatives such as polyethoxylates of acetylene alcohol; Acetylene glycol derivatives such as polyethoxylates of acetylene glycol; Fluorine-containing surfactants such as Fluorad (trade name, manufactured by 3M Japan Limited), Megafac (trade name, manufactured by DIC Corporation), Surufuron (trade name, manufactured by AGC); or an organosiloxane surfactant, such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the acetylene glycols include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyn-3,6-diol, 2,4, 7,9-Tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyn-2,5-diol, 2,5 -Includes dimethyl-2,5-hexanediol, etc.

Additionally, examples of anionic surfactants 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, poly oxyethylene alkyl ether ammonium salt or organic amine salt of sulfuric acid, ammonium salt or organic amine salt of alkyl sulfuric acid, etc.

Additionally, examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauric acid amide propyl hydroxy sulfone betaine, and the like.

These surfactants can be used alone or in a mixture of two or more types, and their mixing ratio is usually 50 to 10,000 ppm, preferably 100 to 5,000 ppm, based on the total mass of the composition.

The developer dissolution accelerator or residue remover adjusts the solubility of the formed coating film in the developer and also has the effect of preventing residue from remaining on the substrate after development. Crown ether can be used as this additive.

The amount added is preferably 0.05 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total mass of polysiloxane.

Additionally, a sensitizer may be added as needed. Coumarin, ketocoumarin and its derivatives, acetophenone; and sensitizing dyes such as pyrylium salts and tripyllium salts; Anthracene skeleton-containing compounds may be included.

When using a sensitizer, the amount added is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the total mass of polysiloxane.

As polymerization inhibitors, nitrones, nitroxide radicals, hydroquinone, catechol, phenothiazine, phenoxazine, hindered amines and their derivatives and ultraviolet absorbers can be added. The amount added is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total mass of polysiloxane.

Examples of antifoaming agents include alcohol (C _1-18 ); higher fatty acids such as oleic acid and stearic acid; Higher fatty acid esters such as glycerin monolaurate; polyethers such as polyethylene glycol (PEG) (Mn 200 to 10,000), polypropylene glycol (PPG) (Mn 200 to 10,000); Silicone compounds such as dimethyl silicone oil, alkyl-modified silicone oil and fluorosilicone oil; and organosiloxane-based surfactants. These can be used alone or in combination, and the amount added is preferably 0.1 to 3 parts by weight based on 100 parts by weight of the total mass of polysiloxane.

The adhesion enhancer has the effect of preventing the pattern from peeling off due to stress applied after curing when a cured film is formed using the composition according to the present invention. Imidazole and silane coupling agents are preferred as adhesion enhancers.

These other additives can be used alone or in combination, and the amount added is 20 parts by weight or less, preferably 0.05 to 15 parts by weight, based on 100 parts by mass of the total mass of polysiloxane.

<Method for producing cured film>

The method for producing a cured film according to the present invention includes the following processes:

(1) A process of forming a composition layer by applying the composition according to the present invention on a substrate,

(2) a process of exposing the composition layer,

(3) a process of developing with an alkaline developer to form a pattern, and

(4) A process of heating the obtained pattern.

The process is explained in order as follows.

(1) Application process

First, the composition described above is applied onto the substrate. The formation of a coating film of the composition of the present invention can be performed by any conventionally known method for applying photosensitive compositions. Specifically, it can be arbitrarily selected from dip coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, and slit coating.

Additionally, an appropriate substrate such as a silicone substrate, glass substrate, resin film, etc. can be used as the substrate on which the composition is applied. Various semiconductor devices, etc. can be formed on this substrate as needed. If the substrate is a film, gravure application can also be used. If necessary, a drying process may be provided separately after film application. Additionally, the coating process can be repeated once or twice or more as needed to achieve a desired thickness of the formed coating film.

After applying the composition to form a coating film, it is preferable to pre-bake (heat treat) the coating film in order to dry the coating film and reduce the amount of solvent remaining in the coating film. The pre-bake process is generally carried out at a temperature of 70 to 150°C, preferably 90 to 120°C, for 10 to 300 seconds, preferably 30 to 120 seconds in a hot plate, and 1 to 30 minutes in a clean oven. can do.

(2) Exposure process

After forming the coating film, light irradiation is performed on the surface of the coating film. Additionally, in order to distinguish it from the full surface exposure described later, this process may be referred to as first exposure. As a light source used for light irradiation, any light source used in the pattern formation method can be used. Such light sources may include high-pressure mercury lamps, low-pressure mercury lamps, metal lamps such as halogen and xenon, laser diodes, LEDs, etc. Ultraviolet rays such as g-rays, h-rays, and i-rays are usually used as irradiation light. Except for ultra-fine processing such as semiconductors, it is common to use 360 to 430 nm light (high-pressure mercury lamp) for patterning from a few ㎛ to tens of ㎛. Above all, for liquid crystal display devices, light of 430 nm is often used. In such cases, as described above, it is advantageous to combine sensitizing dyes in the compositions according to the invention.

The irradiated light energy depends on the light source and the thickness of the coating film, but is generally 5 to 2,000 mJ/cm2, preferably 10 to 1,000 mJ/cm2. If the irradiated light energy is lower than 5mJ/cm2, sufficient resolution may not be obtained. On the other hand, if the irradiated light energy is higher than 2,000 mJ/cm2, overexposure may occur and halation may occur.

A general photomask can be used to irradiate light in a pattern shape. These photomasks can be chosen arbitrarily from among known ones. The environment during irradiation is not particularly limited, but may generally be an ambient atmosphere (atmosphere) or a nitrogen atmosphere. Additionally, when forming a film over the entire substrate surface, light can be irradiated to the entire substrate surface. In the present invention, the pattern film also includes cases where the film is formed on the entire surface of the substrate.

(3) Development process

After exposure, the film is developed. As the developer used during development, any developer conventionally used for developing photosensitive compositions can be used. The developer includes an organic developer and an inorganic developer, examples of the organic developer are TMAH aqueous solution, tetrabutylammonium hydroxide aqueous solution, methyl isobutyl ketone and isopropyl alcohol, preferably TMAH aqueous solution, more preferably 2.38% by mass. Contains an aqueous solution of TMAH. The inorganic developer includes an alkali metal salt, preferably an aqueous potassium hydroxide solution, 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, aqueous ammonia, and particularly preferably an aqueous potassium hydroxide solution. The concentration when using an aqueous potassium hydroxide solution is preferably 0.1 to 3.0 mass%, more preferably 0.5 to 2.0 mass%. This developer may additionally contain a water-soluble organic solvent such as methanol and ethanol or a surfactant if necessary.

The development method may be arbitrarily selected from conventionally known methods. Specifically, methods such as immersion (dip), paddle, shower, slit, cap coat, and spray in the developer may be included. The developing temperature is preferably room temperature (20 to 25°C), but may be heated to 30 to 50°C. The development time is preferably 15 to 180 seconds, more preferably 30 to 60 seconds. Through this phenomenon, a pattern can be obtained, and it is preferable to wash (wash with water) after development with a developing solution.

Washing is preferably carried out using water, and can be carried out in the same way as developing, preferably by showering for at least 60 seconds.

It is common to perform a front exposure process after development (and optional cleaning). This is because, as described above, the formation of wrinkles in the cured film can be suppressed by performing full-scale exposure. In addition to this, by full exposure, unreacted diazonaphthoquinone derivatives remaining in the film are photodecomposed and the light transparency of the film is further improved, so it is preferable to perform a full exposure process when transparency is required. The front exposure method involves exposing the entire surface to about 100 to 2000 mJ/cm2 (equivalent to exposure at a wavelength of 365 nm) using an ultraviolet-visible exposure machine made of PLA (e.g., PLA-501F, manufactured by Canon Inc.). there is.

When the composition according to the present invention is used, wrinkles can be suppressed even without full-side exposure, so unless excessive transparency is required, front-side exposure is not always performed.

(4) Curing process

After development, the obtained pattern film is heated and hardened. The heating temperature in this process is not particularly limited and can be determined arbitrarily as long as it is a temperature at which curing of the coating film can be performed. However, if the silanol group remains, the chemical resistance of the cured film may become insufficient or the dielectric constant of the cured film may increase. From this point of view, the heating temperature is generally selected to be relatively high. Specifically, it is preferable to cure by heating to 360°C or lower. In order to maintain a high percentage of film remaining after curing, the curing temperature is more preferably 300°C or lower, particularly preferably 250°C or lower. On the other hand, in order to promote the curing reaction and obtain a sufficiently cured film, the curing temperature is preferably 70°C or higher, more preferably 90°C or higher, and particularly preferably 100°C or higher. Additionally, the heating time is not particularly limited and is generally 10 minutes to 24 hours, preferably 30 minutes to 3 hours. Additionally, this heating time is the time after the temperature of the pattern film reaches the desired heating temperature. Generally, it takes approximately several minutes to several hours for the pattern film to reach the desired temperature from the temperature before heating.

By using the composition according to the present invention, the occurrence of wrinkles on the surface of the cured film during this curing process can be suppressed. Here, wrinkles refer to irregularities that occur near or away from the pattern portion of the cured film. Figure 1 shows an electron micrograph of a typical wrinkle forming on a patterned surface.

For a rough guide to the difference between no wrinkles (Figure 1(P)), minor wrinkles (Figure 1(Q)), and major wrinkles (Figure 1(R)), use a stylus surface measurement device (Dektak). Using, for a distance of 1.5 cm, the membrane surface is measured at a distance from the pattern after curing with a force of 3 mg for 50 seconds, which means that the surface irregularities are:

No wrinkles: Difference less than about 30nm;

Small wrinkles: steps of about 30 nm to 100 nm;

Large wrinkles: Steps exceeding 100 nm.

The obtained cured film can achieve excellent flatness, electrical insulation, etc. For example, a relative dielectric constant of 4 or less can be achieved. For this reason, it can be suitably used in a variety of fields, such as a planarization film for the various devices described above such as a flat panel display (FPD), an interlayer insulating film for low-temperature polysilicon, or a buffer coat film or transparent protective film for IC chips.

The present invention will be described in more detail using the following Examples and Comparative Examples, but the present invention is not limited by these Examples and Comparative Examples.

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

<Synthesis Example 1 (Synthesis of polysiloxane Pa-1)>

A 2L flask equipped with a stirrer, thermometer, and condenser tube was charged with 49.0 g of a 25% by mass TMAH aqueous solution, 600 mL of isopropyl alcohol (IPA), and 4.0 g of water, and then, in a dropping funnel, methyltrimethoxy A mixed solution of 68.0 g of silane, 79.2 g of phenyltrimethoxysilane, and 15.2 g of tetramethoxysilane was prepared. The mixed solution was added dropwise at 40°C, the product was stirred at the same temperature for 2 hours, and then neutralized by adding a 10% by mass HCl aqueous solution. 400 ml of toluene and 600 ml of water were added to the neutralization liquid to separate the product into two phases, and the aqueous phase was removed. Additionally, the product was washed three times with 300 ml of water, the obtained organic phase was concentrated under reduced pressure to remove the solvent, and PGMEA was added to the concentrate to adjust the solid content concentration to 35% by mass.

The molecular weight (in terms of polystyrene) of the obtained polysiloxane was measured by gel permeation chromatography, and the mass average molecular weight (hereinafter abbreviated as "Mw") was 1,700. Additionally, the obtained resin solution was applied on a silicon wafer using a spin coater (MS-A100, manufactured by Mikasa Co., Ltd.) so that the film thickness after pre-baking was 2 ㎛, and after pre-baking, 2.38 mass% TMAH was applied. As a result of measuring the dissolution rate (hereinafter abbreviated as "ADR") in aqueous solution, it was 1,200 Å/sec.

<Synthesis Example 2 (Synthesis of polysiloxane Pa-2)>

It was synthesized in the same manner as Synthesis Example 1, except that the amount of TMAH aqueous solution was changed to 32.5 g.

The obtained polysiloxane Pa-2 had Mw = 2500 and ADR = 300 Å/sec for a 5% by mass TMAH aqueous solution after pre-baking.

<Synthesis Example 3 (Synthesis of polysiloxane Pb-1)>

A 2L flask equipped with a stirrer, thermometer, and cooling pipe was charged with 102 g of a 25% by mass TMAH aqueous solution, 600 mL of IPA, and 4.0 g of water, and then, in a dropping funnel, 68.0 g of methyltrimethoxysilane and 79.2 g of phenyltrimethoxysilane were added. g and 68.1 g of bis(triethoxysilyl)methane were prepared. The mixed solution was added dropwise at 40°C, the mixture was stirred at the same temperature for 2 hours, and then neutralized by adding a 10% by mass HCl aqueous solution. 400 ml of toluene and 600 ml of water were added to the neutralization liquid to separate the product into two phases, and the aqueous phase was removed. Additionally, the product was washed three times with 400 ml of water, the obtained organic phase was concentrated under reduced pressure to remove the solvent, and PGMEA was added to the concentrate to adjust the solid content concentration to 35% by mass.

The obtained polysiloxane Pb-1 had Mw = 6,500, and ADR for a 2.38 mass% TMAH aqueous solution after pre-baking = 3,300 Å/sec.

<Synthesis Example 4 (Synthesis of polysiloxane Pb-2)>

A 2L flask equipped with a stirrer, thermometer, and cooling pipe was charged with 102 g of a 25% by mass TMAH aqueous solution, 600 mL of isopropyl alcohol (IPA), and 4.0 g of water, and then, in a dropping funnel, 68.0 g of methyltrimethoxysilane and phenyl A mixed solution of 79.2 g of trimethoxysilane and 54.0 g of bis(trimethoxysilyl)ethane was prepared. The mixed solution was added dropwise at 40°C, the mixture was stirred at the same temperature for 2 hours, and then neutralized by adding a 10% by mass HCl aqueous solution. 400 ml of toluene and 600 ml of water were added to the neutralization liquid to separate the product into two phases, and the aqueous phase was removed. Additionally, the product was washed three times with 400 ml of water, the obtained organic phase was concentrated under reduced pressure to remove the solvent, and PGMEA was added to the concentrate to adjust the solid content concentration to 35% by mass.

The Mw of the obtained polysiloxane was 9,000, and the ADR for a 2.38 mass% TMAH aqueous solution after pre-baking was 2,600 Å/sec.

In addition, the ADR for the 2.38% by mass TMAH aqueous solution after pre-baking of the entire polysiloxane was as follows.

ADR of polysiloxane (Pa-1:Pa-2:Pb-1 = 40:10:50) = 1,800Å/sec

ADR of polysiloxane (Pa-1:Pa-2:Pb-2 = 40:10:50) = 1,600Å/sec

ADR of polysiloxane (Pa-1:Pa-2 = 90:10) = 900Å/sec

<Examples 101 to 114 and Comparative Examples 101 to 108 (Preparation of positive photosensitive polysiloxane composition)>

Positive photosensitive polysiloxane compositions of Examples 101 to 114 and Comparative Examples 101 to 108 containing the compounds shown in Table 1 and the balance being PGMEA were prepared.

In the table,

Diazonaphthoquinone derivative: Modification of 4,4'-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol with 2.0 mol of diazonaphthoquinone sifter

Surfactant: KF-53, Shin-Etsu Chemical Co., Ltd. manufacturing

Also, “-” means that the addition amount was 0.

<Evaluation of wrinkles>

The state of wrinkles on the surface after curing, exposed to the optimal exposure amount obtained in the photosensitivity evaluation, was evaluated by visual observation. The evaluation criteria are as follows, and the evaluation results are as listed in Table 1.

A: No wrinkles were observed on the surface.

B: Small wrinkles were observed on the surface, but more than 80% of the area was not wrinkled.

C: Small wrinkles were observed on the surface, and the portion where wrinkles were not observed was less than 80%.

D: Large wrinkles were confirmed on the surface.

In addition, typical electron micrographs of a pattern with no wrinkles (P), a pattern with small wrinkles (Q), and a pattern with large wrinkles (R) are shown in FIG. 1.

<Evaluation of pattern shape>

The shape of the pattern after curing, exposed to the optimal exposure amount obtained in the photosensitivity evaluation, was observed and evaluated using a scanning electron microscope (SEM). The evaluation criteria are as follows, and the evaluation results are as listed in Table 1.

X: The edges of the formed pattern were gently rounded

Y: The corners of the formed pattern were rounded

Z: The corners of the formed pattern were not rounded

V: The missing pattern was smaller than the mask size

W: Pattern was not formed

Additionally, respective conventional electron micrographs corresponding to the above-described shapes are shown in Figure 2.

<Light sensitivity evaluation>

The compositions of Examples 101 to 105 were applied by spin coating so that the film thickness after pre-baking was 1.6 μm. The obtained coating film was pre-baked at 110°C for 90 seconds to volatilize the solvent. Next, a contact hole with a size of 5 μm was pattern exposed using a g+h-line mask aligner (FX-604F type, manufactured by Nikon Corporation) at the optimal exposure amount. After exposure, paddle development was performed for 70 seconds using a 2.38% by mass TMAH aqueous solution, washed with pure water for 60 seconds, and dried. Next, it was heated at 180°C in air for 20 minutes and then further heated at 230°C for 20 minutes to cure. Here, when patterning with a 5 micron mask, the exposure amount when the bottom width of the contact hole after curing is 5 microns was evaluated as the optimal exposure amount.

In the compositions of Examples 101 to 105, an exposure amount of less than 500 mJ was the optimal exposure amount and was a photosensitivity sufficient for practical use.

On the other hand, when the optimal exposure amount was evaluated in the same manner as described above using the same composition as Example 101 except that the maleic acid was 80,000 ppm, a pattern could not be formed even if the exposure amount was increased.

<Examples 201 and 202 and Comparative Examples 201 to 204 (Preparation of positive photosensitive polysiloxane composition)>

Positive-type photosensitive polysiloxane compositions of Examples 201 and 202 and Comparative Examples 201 to 204 containing the compounds shown in Table 2 and the balance being PGMEA were prepared.

In the table,

Diazonaphthoquinone derivative: Modification of 4,4'-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl)ethylidene)bisphenol with 2.0 mol of diazonaphthoquinone sifter

Surfactant: KF-53, Shin-Etsu Chemical Co., Ltd. manufacturing

Also, “-” means that the addition amount was 0.

Each composition was applied by spin coating so that the film thickness after pre-baking was 1.6 μm. The obtained coating film was pre-baked at 110°C for 90 seconds to volatilize the solvent. Next, a contact hole with a size of 5 μm was pattern exposed using a g+h-line mask aligner (FX-604F type, manufactured by Nikon Corporation) at the optimal exposure amount. After exposure, paddle development was performed for 70 seconds using a 1.0% by mass KOH aqueous solution, washed with pure water for 60 seconds, and dried. Subsequently, it was heated at 180°C in air for 20 minutes and then further heated at 230°C for 20 minutes to cure.

Wrinkle evaluation and pattern shape evaluation were performed according to the evaluation criteria described above. The evaluation results are as shown in Table 2.

Claims (15)

A positive photosensitive polysiloxane composition,
(I) polysiloxane,
(II) 200 to 50,000 ppm of a carboxylic acid compound, which is a monocarboxylic acid or dicarboxylic acid, based on the total weight of the composition,
(III) diazonaphthoquinone derivatives, and
(IV) Solvent
Including,
The polysiloxane of item (I) further comprises a repeating unit represented by the formula (Ie),

Here, L ^Ie is -(CR ^Ie ₂ ) _n - or , where n is an integer from 1 to 3, and R ^Ie each independently represents hydrogen, methyl, or ethyl,
A positive photosensitive polysiloxane composition, wherein the monocarboxylic acid of item (II) is represented by formula (i), and the dicarboxylic acid is represented by formula (ii).
R ⁱ -COOH (i)
Here, R ⁱ is hydrogen or a saturated or unsaturated hydrocarbon group of C _1-4 ,
HOOC-L-COOH (ii)
Here, L is C _1-6 unsubstituted alkylene, hydroxy-substituted alkylene or amino-substituted alkylene; C _2-4 substituted or unsubstituted alkenylene; C _2-4 substituted or unsubstituted alkynylene; or C _6-10 substituted or unsubstituted arylene. The composition of claim 1, wherein the first acid dissociation constant pKa ₁ of the monocarboxylic acid is 5.0 or less, and the first acid dissociation constant pKa ₁ of the dicarboxylic acid is 4.0 or less. delete The composition of claim 1, wherein the carboxylic acid compound is a dicarboxylic acid. The composition of claim 1, wherein the dicarboxylic acid can assume a cyclic structure by intramolecular dehydration condensation. The composition of claim 1, wherein the content of the carboxylic acid compound is 300 to 30,000 ppm based on the total weight of the composition. As a method for producing a cured film,
(1) forming a composition layer by applying the composition according to any one of claims 1, 2, and 4 to 6 on a substrate,
(2) exposing the composition layer,
(3) developing with an alkaline developer to form a pattern, and
(4) heating the obtained pattern
A method for producing a cured film, including. 8. The method of claim 7, not including a flood exposure process prior to step (4). The method according to claim 7, wherein the alkaline developer is an organic developer. The method according to claim 7, wherein the alkaline developer is an inorganic developer. An electronic device comprising a cured film manufactured by the method according to claim 7. delete delete delete delete