CN113631672B

CN113631672B - Positive photosensitive polysiloxane composition

Info

Publication number: CN113631672B
Application number: CN202080021204.7A
Authority: CN
Inventors: 福家崇司; 吉田尚史; 能谷敦子
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2019-03-15
Filing date: 2020-03-12
Publication date: 2022-12-13
Anticipated expiration: 2040-03-12
Also published as: SG11202106225UA; JP2020154282A; KR102590065B1; CN113631672A; JP6639724B1; JP2020154276A; KR20210141574A; TW202039640A

Abstract

[ problem ] to provide a positive photosensitive polysiloxane composition which can produce a cured film having suppressed generation of wrinkles and high surface smoothness without adding a curing assistant or performing full exposure. [ solution ] A positive photosensitive polysiloxane composition comprising: (I) Polysiloxane, (II) 200 to 50000ppm of a carboxylic acid compound, i.e., a monocarboxylic acid or a dicarboxylic acid, (III) a diazonaphthoquinone derivative, and (IV) a solvent, based on the total mass of the composition, and a method for producing a cured film using the composition.

Description

Positive photosensitive polysiloxane composition

Technical Field

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

Background

In recent years, various proposals have been made for further improving light utilization efficiency and energy saving in optical devices such as displays, light emitting diodes, and solar cells. For example, in a liquid crystal display, a method is known in which a transparent planarization film is coated on a TFT device and a pixel electrode is formed on the planarization film to improve the aperture ratio of the display apparatus.

As a material for a planarization film of a TFT substrate, a material in which an acrylic resin and a quinone diazide compound are combined is known. These materials have planarization properties and photosensitivity, and thus contact holes and other patterns can be made. However, as the resolution and frame rate increase, the wiring becomes more complex, making planarization difficult and difficult to handle these materials.

Polysiloxanes, particularly silsesquioxanes, are known as materials having high heat resistance and high transparency. The silsesquioxane is composed of a trifunctional siloxane structural unit RSi (O) _1.5 ) Polymers of composition which, in chemical structure, are intermediate between inorganic Silicas (SiO) ₂ ) And organosiloxane (R) ₂ SiO) but is a specific compound which is soluble in organic solvents and whose cured product exhibits high heat resistance characteristic of inorganic silica.

A cured film can be formed by forming a pattern by exposure and development using a positive photosensitive composition comprising such a polysiloxane and a photosensitizer, and heating. In the cured film thus formed, the film surface is not flat, and wrinkles may be generated. Then, in order to suppress the generation of wrinkles, a curing assistant may be added, and after exposure and development, full exposure may be performed.

Documents of the prior art

Patent literature

Patent document 1: japanese patent laid-open publication No. 2011-2517

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide a positive photosensitive polysiloxane composition that can produce a cured film having high surface smoothness with suppressed wrinkle formation without adding a curing assistant or performing full exposure. Another object of the present invention is to provide a method for producing a cured film using the positive photosensitive polysiloxane composition.

Means for solving the problems

The positive photosensitive polysiloxane composition according to the present invention comprises:

(I) A polysiloxane,

(II) 200 to 50000ppm of a carboxylic acid compound, i.e. a monocarboxylic or dicarboxylic acid,

(III) diazonaphthoquinone derivatives, and

(IV) a solvent.

Further, the method for manufacturing a cured film according to the present invention includes the steps of:

(1) The positive photosensitive polysiloxane composition according to the present invention is applied to a substrate to form a composition layer,

(2) Exposing the layer of the composition to light,

(3) Developing with an alkaline developer to form a pattern, and

(4) The resulting pattern is heated.

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

ADVANTAGEOUS EFFECTS OF INVENTION

When the positive photosensitive polysiloxane composition according to the present invention is used, a cured film with suppressed generation of wrinkles and high surface smoothness can be produced even without performing addition of a curing assistant or full exposure. The obtained film has high sensitivity and can contribute to high throughput of the production process. In addition, the pattern shape of the cured film may be formed into a gentle shape of the opening portion required in the subsequent step. The cured film thus obtained is excellent in flatness and electrical insulation properties, and therefore is suitable for use as a planarization film for a Thin Film Transistor (TFT) substrate used in a back sheet of a display of a liquid crystal display element or an organic EL display element, an interlayer insulating film of a semiconductor device, various film-forming materials such as a solid-state imaging element, an antireflection film, an antireflection plate, an optical filter, a high-luminance light-emitting diode, an insulating film in a touch panel, a solar cell, and the like, a transparent protective film, and an optical device such as an optical waveguide.

Drawings

Fig. 1 is an electron micrograph for explaining "wrinkles" formed on the pattern surface.

Fig. 2 is an electron micrograph for explaining the shape of the pattern in the example.

Detailed Description

Hereinafter, embodiments of the present invention will be described in detail.

In the present specification, symbols, units, abbreviations and terms have the following meanings unless otherwise specified.

In this specification, the singular forms include the plural forms unless otherwise specified, and "a" and "the" mean "at least one". In the present specification, unless otherwise specified, elements of a concept may be represented by a plurality of kinds, and in the case where a content thereof (for example, mass% or mol%) is described, the content thereof represents a sum of the plurality of kinds. "and/or" includes all combinations of elements and also includes use alone.

In this specification, when numerical ranges are expressed by using "-" or "-" they include both endpoints, and the units are general. For example, 5 to 25mol% means 5mol% or more and 25mol% or less.

In the present specification, the hydrocarbon contains carbon and hydrogen, and oxygen or nitrogen as necessary. The hydrocarbon group means a monovalent or divalent or higher hydrocarbon. In the present specification, the aliphatic hydrocarbon means a straight-chain, branched-chain or cyclic aliphatic hydrocarbon, and the aliphatic hydrocarbon group means a monovalent or divalent or higher aliphatic hydrocarbon. The aromatic hydrocarbon means a hydrocarbon containing an aromatic ring, which may have an aliphatic hydrocarbon group as a substituent or may be fused with an alicyclic ring, as required. The aromatic hydrocarbon group means a monovalent or divalent or higher aromatic hydrocarbon. The aromatic ring refers to a hydrocarbon having a conjugated unsaturated ring structure, and the alicyclic ring refers to a hydrocarbon having a ring structure but not including a conjugated unsaturated ring structure.

In the present specification, an alkyl group means a group obtained by removing any one hydrogen from a linear or branched saturated hydrocarbon, and includes a linear alkyl group and a branched alkyl group, and a cycloalkyl group means a group obtained by removing one hydrogen from a saturated hydrocarbon containing a cyclic structure containing a linear or branched alkyl group as a side chain as necessary.

In the present specification, an aryl group means a group obtained by removing any one hydrogen from an aromatic hydrocarbon. Alkylene refers to a group obtained by removing any two hydrogens from a straight or branched chain saturated hydrocarbon. Arylene refers to a hydrocarbon group obtained by removing any two hydrogens from an aromatic hydrocarbon.

In the present specification, "C" or "C" is used _x-y ”、“C _x -C _y "and" C _x "etc. describe refers to the number of carbons in a molecule or substituent. E.g. C _1-6 Alkyl refers to alkyl groups having 1 to 6 carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). In addition, the fluoroalkyl group in the present specification means that one or more hydrogens in the alkyl group are substituted with fluorine, and the fluoroaryl group means that one or more hydrogens in the aryl group are substituted with fluorine.

In the present specification, when the polymer has a plurality of types of repeating units, these repeating units are copolymerized. These copolymers may be any of alternating copolymers, random copolymers, block copolymers, graft copolymers or mixtures thereof.

In the present specification, "%" represents% by mass, and "ratio" represents a mass ratio.

In this specification, the temperature in degrees Celsius (Celsius) is used as the temperature unit. For example, 20 degrees means 20 degrees celsius.

< Positive photosensitive polysiloxane composition >

The positive photosensitive polysiloxane composition according to the present invention (hereinafter simply referred to as composition) comprises (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) Polysiloxanes

The structure of the polysiloxane used in the present invention is not particularly limited and may be arbitrarily selected according to the purpose. The skeleton structure of polysiloxane is classified into a siloxane skeleton (the number of oxygen atoms bonded to silicon atoms is 2), a silsesquioxane skeleton (the number of oxygen atoms bonded to silicon atoms is 3), and a silica skeleton (the number of oxygen atoms bonded to silicon atoms is 4) according to the number of oxygen atoms bonded to silicon atoms. In the present invention, any one may be used. The polysiloxane molecule may comprise a combination of a plurality of these backbone structures.

Preferably, the polysiloxane used in the present invention comprises a repeating unit represented by the following formula (Ia):

(in the formula, wherein,

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

said aliphatic hydrocarbon group and said aromatic hydrocarbon group are each unsubstituted or substituted with fluorine, hydroxyl or alkoxy, and

in the aliphatic hydrocarbon group and the aromatic hydrocarbon group, methylene groups are not replaced, or one or more methylene groups are replaced by an oxy group, an amino group, an imino group or a carbonyl group, but R ^Ia Not hydroxy, alkoxy).

Here, the above methylene group also includes a terminal methyl group.

Further, the above "substituted with fluorine, hydroxyl group or alkoxy group" means that the hydrogen atom directly bonded to the carbon atom in the aliphatic hydrocarbon group and the aromatic hydrocarbon group is replaced with fluorine, hydroxyl group or alkoxy group. The same applies to other similar descriptions herein.

In the repeating unit represented by the formula (Ia),

R ^Ia examples of (b) include (i) an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a decyl group, (ii) an aryl group such as a phenyl group, a tolyl group, and a benzyl group, (iii) a fluoroalkyl group such as a trifluoromethyl group, a 2, 2-trifluoroethyl group, and a 3, 3-trifluoropropyl group, (iv) a fluoroaryl group, (v) a cycloalkyl group such as a cyclohexyl group, (vi) a nitrogen-containing group having an amino group or an imide structure such as an isocyanate group and an amino group, (vii) an epoxy structure such as a glycidyl group, or an oxygen-containing group having an acryloyl structure or a methacryloyl structure. Preferred are methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, tolyl, glycidyl, isocyanate groups. As the fluoroalkyl group, a perfluoroalkyl group is preferable, and particularly, a trifluoromethyl group and a pentafluoroethyl group are preferable. When R is ^Ia The methyl group is preferred because it is easy to obtain a raw material, and the cured film has high hardness and high chemical resistance. This is achieved byWhen R is outside ^Ia The phenyl group is preferable because the solubility of the polysiloxane in a solvent increases and the cured film is not easily broken. In addition, R ^Ia It is preferable to have a hydroxyl group, a glycidyl group, an isocyanate group or an amino group because adhesion to a substrate is improved.

The polysiloxane used in the present invention may further comprise a repeating unit represented by the following formula (Ib):

(in the formula (I), the compound (I),

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

In the formula (Ib), R ^Ib Preferred is a group obtained by removing a plurality of preferably two or three hydrogens from a nitrogen-containing aliphatic hydrocarbon ring containing an imino group and/or a carbonyl group, more preferably from a 5-membered ring and a 6-membered ring containing nitrogen as constituent members. For example, groups obtained by removing two or three hydrogens from piperidine, pyrrolidine, and isocyanurate can be cited. R is ^Ib Si contained in the plurality of repeating units is linked.

The polysiloxane according to the invention may also comprise recurring units of formula (Ic):

when the mixing ratio of the repeating units represented by the formulae (Ib) and (Ic) is high, the composition is reduced in photosensitivity, reduced in compatibility with solvents or additives, and easily cracked due to increase in film stress, and therefore the mixing ratio of the repeating units represented by the formulae (Ib) and (Ic) is preferably 40mol% or less, more preferably 20mol% or less, based on the total number of the repeating units of polysiloxane.

The polysiloxanes according to the present invention may also comprise recurring units of formula (Id):

(in the formula, wherein,

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

in the aliphatic hydrocarbon group and the aromatic hydrocarbon group, a methylene group is not substituted, or is substituted by an oxy group, an imide group, or a carbonyl group, and a carbon atom is not substituted, or is substituted by a fluorine, a hydroxyl group, or an alkoxy group).

In the repeating unit represented by the formula (Id),

R ^Id examples of (b) include (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-trifluoroethyl, 3-trifluoropropyl, (iv) fluoroaryl groups, (v) cycloalkyl groups such as cyclohexyl, (vi) nitrogen-containing groups having an amino group or an imide structure such as an isocyanate group and an amino group, (vii) epoxy structures such as a glycidyl group, or oxygen-containing groups having an acryloyl structure or a methacryloyl structure. Preferred are methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, tolyl, glycidyl, isocyanate groups. As the fluoroalkyl group, a perfluoroalkyl group is preferable, and particularly, a trifluoromethyl group and a pentafluoroethyl group are preferable. When R is ^Id The methyl group is preferred because it is easy to obtain a raw material, and the cured film has high hardness and high chemical resistance. In addition, when R is ^Id The phenyl group is preferable because the solubility of the polysiloxane in a solvent increases and the cured film is not easily broken. In addition, R ^Id It is preferable to have a hydroxyl group, a glycidyl group, an isocyanate group or an amino group because adhesion to a substrate is improved.

By having a repeating unit of the above formula (Id), the polysiloxane according to the invention may have a partially linear structure. However, since the heat resistance is lowered, the number of linear structural portions is preferably small. Specifically, the repeating unit of the formula (Id) is preferably 30mol% or less with respect to the total number of repeating units of the polysiloxane.

In addition, the polysiloxane comprises repeating units represented by the following formula (Ie):

(in the formula (I), the compound (I),

L ^Ie is- (CR) ^Ie ₂ ) _n -or

Where n is an integer of 1 to 3,

R ^Ie each independently represents hydrogen, methyl or ethyl).

In the formula (Ie), L ^Ie Preferably- (CR) ^Ie ₂ ) _n -, and R ^Ie The same or different in one repeating unit or polysiloxane molecule, although it is preferred that all R in one molecule be present ^Ie Are all the same, and preferably R ^Ie Are all hydrogen.

The polysiloxane used in the present invention may contain two or more kinds of repeating units. For example, it may comprise three repeat units having R ^Ie A repeating unit represented by the formula (Ia) which is a methyl group or a phenyl group, or a repeating unit represented by the formula (Ic).

The composition according to the invention may contain two or more polysiloxanes. For example, the first type uses a polysiloxane containing a repeating unit of any one of the above formulae (Ia) to (Id), and the second type uses a polysiloxane containing a repeating unit of the formula (Ie) and a repeating unit other than the formula (Ie) (preferably, a repeating unit of the formulae (Ia), (Ib), and/or (Id)).

Preferably, one or more polysiloxanes are present at R of formula (Ia) ^Ia R of the formula (Ib) ^Ib And/or R of formula (Id) ^Id Contains a repeating unit which is a bulky group, further preferably R containing the formula (Ia) ^Ia Is a large volume of C _3-20 A polysiloxane of repeating units of saturated or unsaturated cyclic aliphatic or aromatic hydrocarbon groups (e.g., phenyl, naphthyl, anthracene) and repeating units of formula (Ie). Since wrinkles tend to be easily generated when having bulky radicals, the wrinkle-suppressing effect according to the present invention is effectively exhibited, and by including the repeating unit of formula (Ie), the taper angle of the pattern can be further controlled, which is particularly advantageous.

The ratio of the total number of the repeating units (Ie) and (Ia) to the total number of the repeating units contained in the polysiloxane is preferably 60mol% or more, and more preferably 70mol% or more. Further, (Ia) is preferably 20 to 95mol%, and (Ie) is preferably 5 to 40mol%.

Further, the total proportion of the repeating units (Ia), (Ib), and (Id) containing the bulky group is preferably 10mol% 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 repeating units as described above are bonded to each other, but preferably has a silanol group at the end. The silanol group is-O _0.5 H is bonded to the bond of the repeating unit or block.

The mass average molecular weight of the polysiloxane used in the present invention is not particularly limited. However, the higher the molecular weight, the better the coatability tends to be. Conversely, the lower the molecular weight, the less the restrictions on the synthesis conditions, the easier the synthesis, and the more difficult the synthesis of polysiloxanes having very high molecular weights. Therefore, the polysiloxane has a mass average molecular weight of usually 500 to 25000, and is preferably 1000 to 20000 from the viewpoint of solubility in an organic solvent and solubility in an alkaline developer. The mass average molecular weight herein is a mass average molecular weight in terms of polystyrene, and can be measured by gel permeation chromatography based on polystyrene.

Further, the polysiloxane used in the present invention is contained in a composition having positive type photosensitivity, and a cured film is formed by coating the composition on a substrate, imagewise exposing, and developing. At this time, it is necessary to generate a difference in solubility between the exposed portion and the unexposed portionThe coating film in the exposed portion should have a solubility in the developer above a certain level. For example, the dissolution rate (hereinafter sometimes referred to as alkali dissolution rate or ADR; described in detail later) of the pre-baked coating film in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (hereinafter sometimes referred to as TMAH) is

In the above, it is considered that a pattern can be formed by exposure and development. However, since the required solubility differs depending on the film thickness of the cured film to be formed and the development conditions, the polysiloxane should be appropriately selected to be suitable for the development conditions. Although it differs depending on the type and amount of the diazonaphthoquinone derivative contained in the composition, for example, if the film thickness is 0.1 to 100 μm

The dissolution rate in a 2.38 mass% TMAH aqueous solution is preferably

More preferably

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 the desired characteristics. Polysiloxanes with different ADRs can also be combined to obtain a mixture with the desired ADR.

Polysiloxanes having different alkali dissolution rates and mass average molecular weights can be prepared by varying the catalyst, reaction temperature, reaction time or polymer. By using a combination of polysiloxanes having different alkali dissolution rates, residual insoluble substances after development can be reduced, pattern dripping can be reduced, and pattern stability can be improved.

Such a polysiloxane is, for example, (M) a film after prebaking is soluble in a 2.38 mass% aqueous TMAH solution and has a dissolution rate of 200 to 200

Is polymerized byA siloxane.

In addition, according to the need, will

(L) the film after prebaking was soluble in a 5 mass% aqueous TMAH solution at a dissolution rate of

The following polysiloxanes, or

(H) The pre-baked film was soluble in a 2.38 mass% aqueous TMAH solution at a rate of

The above polysiloxane

Mixing to obtain the composition with required dissolution rate.

[ method for measuring and calculating the Alkali Dissolution Rate (ADR) ]

The alkali dissolution rate of the polysiloxane or a mixture thereof was measured and calculated as follows using an aqueous TMAH solution as an alkali solution.

The polysiloxane was diluted to 35 mass% with PGMEA and dissolved with stirring at room temperature for 1 hour. In a clean room under an atmosphere of 23.0. + -. 0.5 ℃ and a humidity of 50. + -. 5.0%, 1cc of the prepared polysiloxane solution was dropped on the center of a 4-inch silicon wafer having a thickness of 525 μm using a pipette, and after reaching a thickness of 2. + -. 0.1 μm by spin coating, the solvent was removed by heating on a hot plate at 100 ℃ for 90 seconds. The film thickness of the coating film was measured by an ellipsometer (manufactured by j.a. woollam).

Next, the silicon wafer having the film was gently dipped into a 6-inch diameter glass petri dish containing 100ml of an aqueous TMAH solution having a predetermined concentration adjusted to 23.0 ± 0.1 ℃, and then left to stand, and the time until the coated film disappeared was measured. The dissolution rate was determined by dividing by the time until the film disappeared 10mm inside the edge of the wafer. If the dissolution rate is extremely slow, the wafer is immersed in an aqueous solution of TMAH for a certain period of time, then heated on a hot plate at 200 ℃ for 5 minutes to remove water incorporated into the film during the dissolution rate measurement, and then the thickness is measured, and the dissolution rate is calculated by dividing the change in film thickness before and after immersion by the immersion time. The measurement method described above was carried out 5 times, and the average value of the obtained values was 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, and for example, it can be obtained by hydrolyzing and polymerizing the silane monomer represented by the formula (ia) in the presence of an acidic catalyst and a basic catalyst as necessary.

R ^ia -Si-(OR ^ia' ) ₃ (ia)

(in the formula (I), the compound (I),

in the aliphatic hydrocarbon group and the aromatic hydrocarbon group, a methylene group is unsubstituted or substituted with an oxy group, an imide group or a carbonyl group, and a carbon atom is unsubstituted or substituted with a fluorine, a hydroxyl group or an alkoxy group, and

R ^ia' is straight chain or branched C _1-6 Alkyl groups).

In formula (ia), R is preferred ^ia' Including methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like. In formula (ia), comprising a plurality of R ^ia' But each R ^ia' May be the same or different.

Preferred R ^ia With the above preferred R ^Ia The same is true.

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, 3-trifluoropropyltrimethoxysilane. Among them, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and phenyltrimethoxysilane are preferable. Preferably, two or more silane monomers represented by formula (ia) may be combined.

Further, a silane monomer represented by the following formula (ic) may be combined. When the silane monomer represented by the formula (Ic) is used, a polysiloxane containing the repeating unit (Ic) can be obtained.

Si(OR ^ic' ) ₄ (ic)

In the formula, R ^ic' Is straight or branched C _1-6 An alkyl group. In the formula (ic), R is preferred ^ic' Methyl, ethyl, n-propyl, isopropyl, n-butyl and the like may be included. In the formula (ic), a plurality of R are contained ^ic' But each R ^ic' May be the same or different.

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

Silane monomers represented by the following formula (ib) may also be further combined.

R ^ib -Si-(OR ^ib' ) ₃ (ib)

In the formula, R ^ib' Is straight or branched C _1-6 Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, and n-butyl. One monomer containing a plurality of R ^ib' But each R ^ib' Which may be the same or different from each other,

R ^ib are groups which contain amino, imino and/or carbonyl groups and are obtained by removing a plurality of preferably two or three hydrogens from nitrogen-and/or oxygen-containing cyclic aliphatic hydrocarbon compounds. Preferred R ^ib With the above preferred R ^Ib The same is true.

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

Further, a silane monomer represented by the following formula (id) may be combined. By using the silane monomer represented by the formula (Id), a polysiloxane containing the repeating unit (Id) can be obtained.

(R ^id ) ₂ -Si-(OR ^id' ) ₂ (id)

In the formula (I), the compound is shown in the specification,

R ^id' each independently is a straight or branched chain C _1-6 Alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like. One monomer containing a plurality of R ^id' But each R ^id' May be the same or different.

R ^id Each independently represents hydrogen or C _1-30 A linear, branched or cyclic saturated or unsaturated aliphatic hydrocarbon group or aromatic hydrocarbon group,

in the aliphatic hydrocarbon group and the aromatic hydrocarbon group, a methylene group is unsubstituted or substituted with an oxy group, an imide group or a carbonyl group, and a carbon atom is unsubstituted or substituted with a fluorine, a hydroxyl group or an alkoxy group. Preferred R ^id With the above preferred R ^Id The same is true.

Further, a silane monomer represented by the following formula (ie) may be combined.

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

In the formula (ie) above, the compound,

R ^ie' each independently is a straight or branched chain C _1-6 Alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, and the like.

L ^ie Is- (CR) ^ie ₂ ) _n -or

Is preferably- (CR) ^ie ₂ ) _n -. Here, the first and second liquid crystal display panels are,

each n is independently an integer of 1 to 3.

R ^ie Each 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 50000ppm based on the total mass of the composition.

Preferably, the monocarboxylic acid has a first acid dissociation constant pKa ₁ Is 5.0 or less. Preferably, the dicarboxylic acid has a first acid dissociation constant pKa ₁ Is 4.0 or less, more preferably 3.5 or less.

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

R ⁱ -COOH formula (i)

In the formula, R ₁ 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 monocarboxylic acids useful 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, a double bond,

unsubstituted alkylene, hydroxy-substituted alkylene or amino-substituted alkylene having 1 to 6 carbon atoms,

substituted or unsubstituted alkenylene having 2 to 4 carbon atoms,

a substituted or unsubstituted alkynylene group having 2 to 4 carbon atoms, or

Substituted or unsubstituted arylene having 6 to 10 carbon atoms.

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

Preferably, L is

A single bond, a double bond,

a hydroxy-substituted or unsubstituted alkylene group having 2 to 4 carbon atoms,

an unsubstituted alkenylene group having 2 to 4 carbon atoms with one C = C bond, or an unsubstituted arylene group having 6 to 10 carbon atoms,

more preferably, L is a single bond, an unsubstituted alkylene group having 1 to 2 carbon atoms, a vinylene group, a hydroxyethyl group, a phenylene group.

Specific examples of the dicarboxylic acid used in the present invention include oxalic acid, maleic acid, fumaric acid, phthalic acid, succinic acid, glutaric acid, aspartic acid, glutamic acid, malic acid, itaconic acid, 3-aminoadipic acid, malonic acid, preferably oxalic acid, maleic acid, fumaric acid, phthalic acid, malic acid, or malonic acid.

The carboxylic acid compound used in the present invention is more preferably a dicarboxylic acid, and particularly preferably a dicarboxylic acid having a cyclic structure due to intramolecular dehydration condensation. Examples of such dicarboxylic acids include oxalic acid, maleic acid, succinic acid, phthalic acid, glutaric acid, and itaconic acid. Among them, dicarboxylic acids which undergo an intramolecular dehydration condensation reaction at a temperature of 100 to 250 ℃ are preferable, and maleic acid, succinic acid, and oxalic acid are more preferable.

Two or more types of carboxylic acid compounds may be used in combination.

In the composition according to the present invention, the content of the carboxylic acid compound used in the present invention is 200 to 50000ppm, more preferably 300 to 30000ppm, and still more preferably 500 to 30000ppm, based on the total mass of the composition. If it exceeds 50000ppm, the photosensitivity decreases, which is not preferable.

When an organic developer (e.g., aqueous TMAH solution) is used in the developing step, the content of the compound (II) is preferably 300 to 10000ppm, more preferably 500 to 5000ppm.

When an inorganic developer (for example, an aqueous KOH solution) is used in the developing step, the content of the compound (II) is preferably 1000 to 30000ppm, more preferably 3000 to 10000.

The composition according to the present invention has the effect of suppressing wrinkles in a cured film and improving the smoothness of a pattern surface by containing a specific amount of a specific carboxylic acid compound, but is not intended to be bound by theory, and it is thought to be due to the following reasons.

The positive-working polysiloxane composition is coated, exposed, developed with an alkaline developer, developed and cured by heating. The developer is washed away by washing, but the alkaline component remaining in the film, particularly the film surface, excessively accelerates the curing reaction of the film surface.

If a full exposure step is added after the rinse, the full exposure does not result in excessive acceleration of the curing reaction. Therefore, generation of wrinkles is suppressed.

The composition according to the present invention contains a specific amount of a specific carboxylic acid compound, and even when the full exposure step is not performed, the formation of wrinkles can be suppressed by neutralizing the alkaline component with an alkaline developer so that the curing reaction is not excessively accelerated.

In particular, when the carboxylic acid compound is a compound capable of forming a cyclic structure by an intramolecular dehydration reaction at a specific temperature, the silanol group of the polysiloxane is protected by the carboxylic acid group until curing by heating, and upon heating for curing, the carboxylic acid compound is cured from the unprotected silanol group, becomes an anhydride, is removed from the film, and the deprotected silanol group is cured, and it is considered that the wrinkle-suppressing effect is higher due to the occurrence of such stepwise curing.

The alkaline developer is classified into an organic developer and an inorganic developer, and the inorganic developer has a smaller molecular size than the organic developer and easily penetrates into a film during development, so that the amount of acid required for neutralization is also high. Therefore, when an inorganic developer is used, the content of the carboxylic acid compound is higher.

(III) diazonaphthoquinone derivatives

The composition according to the invention contains a diazonaphthoquinone derivative. The composition containing the diazonaphthoquinone derivative can form 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 is generally used as a positive type photoresist composition. The diazonaphthoquinone derivative of the present invention is a compound produced by ester-bonding naphthoquinone diazide sulfonic acid and a compound having a phenolic hydroxyl group, and the structure thereof is not particularly limited, but an ester compound with a compound having one or more phenolic hydroxyl groups is preferable. As the naphthoquinone diazide sulfonic acid, 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid can be used. The 4-naphthoquinone diazide sulfonate compound has absorption in the i-line (wavelength 365 nm) region and is therefore suitable for i-line exposure. In addition, since the 5-naphthoquinone diazide sulfonate compound has absorption in a wide wavelength range, it is suitable for exposure in a wide wavelength range. The 4-naphthoquinone diazide sulfonate compound and the 5-naphthoquinone diazide sulfonate compound are preferably selected according to the wavelength of exposure. A4-naphthoquinone diazide sulfonate compound and a 5-naphthoquinone diazide sulfonate compound may also be used in combination.

The compound having ase:Sub>A phenolic hydroxyl group is not particularly limited, and 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 name, manufactured by chemical industries, ltd., japan).

The amount of the diazonaphthoquinone derivative to be added varies depending on the esterification rate of naphthoquinone diazide sulfonic acid, the nature of the polysiloxane used, the required photosensitivity, and the solubility contrast between exposed and unexposed regions, and is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass, based on 100 parts by mass of the total mass of the polysiloxane. When the amount of the diazonaphthoquinone derivative added is less than 1 part by mass, the solubility contrast between the exposed portion and the unexposed portion is too low, and the photosensitivity is not realistic. In addition, in order to obtain a better dissolution contrast, 2 parts by mass or more is preferable. When the amount of the diazonaphthoquinone derivative added exceeds 20 parts by mass, whitening of the coating film may occur due to poor compatibility between the polysiloxane and the quinone diazide compound, or coloring due to decomposition of the quinone diazide compound occurring during heat curing may become significant, so that colorless transparency of the cured film may be reduced. Further, since the diazonaphthoquinone derivative is inferior in heat resistance to polysiloxane, if the amount added is large, the thermal decomposition causes deterioration of electrical insulation properties of the cured film and degassing, which becomes a problem in the subsequent step. Further, the cured film may have a reduced resistance to a photoresist stripping solution containing monoethanolamine or the like as a main component.

(IV) solvent

The solvent is not particularly limited as long as it uniformly dissolves or disperses the aforementioned polysiloxane, carboxylic acid compound, and additives added as needed. Examples of the solvent usable 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 pentanone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanone, ethylene glycol, and glycerol; esters such as ethyl lactate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate; cyclic esters such as gamma-butyrolactone. These solvents may be used alone or in combination of two or more, and the amount thereof varies depending on the coating method and the desired film thickness after coating.

The solvent content of the composition according to the present invention may be appropriately selected in consideration of the coating method to be employed, depending on the mass average molecular weight of the polysiloxane used, its distribution, and structure. The composition according to the invention generally comprises 40 to 90 mass%, preferably 60 to 80 mass%, of solvent based on the total mass of the composition.

The essential components of the composition according to the present invention are the above-mentioned (I) to (IV), but other compounds may be combined as needed. Substances that can be combined are as follows. The components other than (I) to (IV) contained in the entire composition are preferably 10% by mass or less, more preferably 5% by mass or less, of the total mass.

[ silanol condensing catalyst ]

The composition according to the invention contains a silanol condensation catalyst selected from the group consisting of photoacid generators, photobase generators, photothermal acid generators and photothermal base generators. These silanol condensing catalysts are preferably selected according to the polymerization reaction and the crosslinking reaction used in the production process of the cured film.

In the present invention, the photoacid generator does not contain the aforementioned (II) diazonaphthoquinone derivative.

The optimum amount of the silanol condensation catalyst to be contained varies depending on the type of the active material produced by decomposition, the amount produced, the required photosensitivity, and the solubility contrast between the exposed portion and the unexposed portion, and the pattern shape, and is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total mass of the polysiloxane. If the amount is less than 0.1 part by mass, the amount of acid or alkali produced is too small, and pattern dripping tends to occur. On the other hand, when the addition amount is more than 10 parts by mass, cracks may occur in the formed cured film, or coloring due to these decompositions may become significant, so that the colorless transparency of the cured film may be lowered. Further, if the addition amount is large, thermal decomposition may cause deterioration of electrical insulation of the cured film and outgassing, which may cause problems in subsequent steps. Further, the cured film may have a reduced resistance to a photoresist stripping solution containing monoethanolamine or the like as a main component.

In the present invention, a photoacid generator or a photobase generator refers to a compound that causes bond cleavage by exposure to generate an acid or a base. The acid or base generated is believed to assist in the polymerization of the polysiloxane. Here, examples of the light include visible light, ultraviolet light, infrared light, X-ray, electron beam, alpha ray, gamma ray, or the like.

The photo-acid generator or the photo-base generator is not used for image-like exposure of the projection pattern (hereinafter referred to as first exposure), but preferably generates an acid or a base during the subsequent full exposure, and preferably has little absorption at the wavelength at the time of the first exposure. For example, when the first exposure is performed using g-rays (peak wavelength 436 nm) and/or h-rays (peak wavelength 405 nm) and the wavelength of the second exposure is set to g + h + i-rays (peak wavelength 365 nm), the absorbance of the photoacid generator or the photobase generator at the 365nm wavelength is preferably higher than the absorbance at the 436nm and/or 405nm wavelength.

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

Here, the ultraviolet-visible absorption spectrum was measured using methylene chloride as a solvent. The measuring apparatus is not particularly limited, and examples thereof include a Cary 4000UV-Vis spectrophotometer (manufactured by agilent technologies, ltd.).

The photoacid generator may be freely selected from commonly used photoacid generators, such as diazomethane compounds, triazine compounds, sulfonic acid esters, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, ammonium salts, quaternary phosphonium salts, sulfonimide compounds, and the like.

Specific examples of the photoacid generator which can be used include those described above, including 4-methoxyphenyl diphenylsulfonium hexafluorophosphate, 4-methoxyphenyl diphenylsulfonium hexafluoroarsenate, 4-methoxyphenyl diphenylsulfonium methanesulfonate, 4-methoxyphenyl diphenylsulfonium trifluoroacetic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, 4-methoxyphenyl diphenylsulfonium p-toluenesulfonate, 4-phenylthiophenyldiphenyl tetrafluoroborate, 4-phenylthiophenyldiphenyl hexafluorophosphate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium p-toluenesulfonate, 4-methoxyphenyl diphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenyl hexafluoroarsenate, 4-phenylthiophenyldiphenyl p-toluenesulfonate, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, 5-norbornene-2, 3-dicarboxylimidotrifluoromethanesulfonate, 4-trifluoromethylsulfonyloxy p-toluenesulfonate, 4-phenylphenylphenylenedinaphthylimidotrifluoromethanesulfonate, 4-trifluoromethylsulfonyloxy [ 1.3 ] maleinimide, 4-dicarboxylimido ] trifluoromethanesulfonate, N- (3-trifluoromethylsulfonyloxy) heptanesulfonate, N- (3-dicarboxylimido-bis (4-trifluoromethylsulfonimide) N- (trifluoromethyl sulfonyl) naphthalimide, N- (nonafluorobutyl sulfonyl) naphthalimide and the like.

Further, 5-propylsulfonyloxyimino-5H-thiophen-2-ylidene- (2-methylphenyl) acetonitrile, 5-octylsulfonyloxyimino-5H-thiophen-2-ylidene- (2-methylphenyl) acetonitrile, 5-camphenosulfonyloxyimino-5H-thiophen-2-ylidene- (2-methylphenyl) acetonitrile, 5-methylphenylsulfonyloxyiimino-5H-thiophen-2-ylidene- (2-methylphenyl) acetonitrile and the like are used in a case where they do not absorb H-rays because they have absorption in the H-ray wavelength range.

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

In addition, an ionic photobase generator comprising an amide anion, a methyl anion, a borate anion, a phosphate anion, a sulfonate anion, a carboxylate anion, or the like may also be used as the anion.

In the present invention, the photothermal acid generator or photothermal base generator is a compound that changes its chemical structure by exposure to light but does not generate an acid or a base, and then generates an acid or a base by thermally induced bond cleavage. Among them, the photothermal alkali generating agent is preferable. Examples of the photothermal alkali producing agent include those represented by the following formula (II), and more preferably a hydrate or solvate thereof. Since the compound represented by the formula (II) becomes cis and becomes unstable by exposure, the decomposition temperature is lowered, and a base is generated even if the baking temperature is about 100 ℃ in the subsequent step.

The photothermal alkali generating agent does not need to be adjusted according to the absorption wavelength of the diazonaphthoquinone derivative.

Wherein x is an integer of 1 to 6 inclusive,

R ^a′ to R ^f′ Each independently hydrogen, halogen, hydroxyl group, mercapto group, thioether group, silyl group, silanol group, nitro group, nitroso group, sulfoxide group, sulfo group, sulfonate group, phosphino group, phosphinic group, phosphonyl group, phosphonate group, amino group, ammonium group, C which may have a substituent _1-20 Aliphatic hydrocarbon group, C which may have a substituent _6-22 Aromatic hydrocarbon group, and optionally substituted C _1-20 Alkoxy or C which may have a substituent _6-20 An aryloxy group.

Wherein R is ^a' To R ^d' Particularly preferably hydrogen, hydroxy, C _1-6 Aliphatic hydrocarbon radicals or C _1-6 Alkoxy radical, R ^e' And R ^f' Hydrogen is particularly preferred. R ^a' To R ^d' Two or more of which may be bonded to form a ring structure. Here, the cyclic structure may include a heteroatom.

N is a constituent atom of a nitrogen-containing heterocycle which is a 3-to 10-membered ring and which may contain C represented by the formula (II) _x H _2X One or more substituents different from OH may further comprise C _1-20 In particular C _1-6 An aliphatic hydrocarbon group.

R is preferably appropriately selected according to the exposure wavelength to be used ^a' To R ^d' . In the application of the display, for example, a functional group in which an unsaturated hydrocarbon such as a vinyl group and an alkynyl group, which change absorption wavelengths to g, h, and i rays, is bonded, or an alkoxy group, a nitro group, or the like is used, and a methoxy group and an ethoxy group are particularly preferable.

Specifically, the following substances can be listed.

In the present invention, the thermal acid generator or the thermal base generator refers to a compound that generates an acid or a base by thermally causing bond cleavage. Preferably, after the composition is applied, it does not generate acid or alkali, or only generates a small amount, from the heat during the pre-baking.

Examples of the thermal acid generator include various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids and salts thereof such as citric acid, acetic acid, maleic acid, and the like, various aromatic carboxylic acids and salts thereof such as benzoic acid and phthalic acid, aromatic sulfonic acids and ammonium salts thereof, various amine salts, aromatic diazonium salts, salts and esters of organic acids such as phosphonic acid and salts thereof, and the like. However, the above-mentioned (II) carboxylic acid compound is not contained in the thermal acid generator used in the present invention. Among the thermal acid generators, a salt composed of an organic acid and an organic base is particularly preferable, and a salt composed of a sulfonic acid and an organic base is more preferable. Preferred sulfonic acids include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1, 4-naphthalenedisulfonic acid, methanesulfonic acid, and the like. These acid generators may be used alone or in combination.

Examples of the thermal base generator include, for example, imidazole, tertiary amine, quaternary ammonium, and the like, and a mixture thereof. Examples of the released base are imidazole derivatives such as N- (2-nitrobenzyloxycarbonyl) imidazole, N- (3-nitrobenzyloxycarbonyl) imidazole, N- (4-nitrobenzyloxycarbonyl) imidazole, N- (5-methyl-2-nitrobenzyloxycarbonyl) imidazole, N- (4-chloro-2-nitrobenzyloxycarbonyl) imidazole, and 1, 8-diazabicyclo [5.4.0] undecene-7. These base generators may be used alone or in combination, as with the acid generator.

Examples of other additives include surfactants, developer dissolution promoters, scum removers, tackifiers, polymerization inhibitors, defoamers, and sensitizers.

The surfactant is preferably used because it can improve coatability. Examples of surfactants that can be used in the polysiloxane compositions of the present invention include nonionic surfactants, anionic surfactants, amphoteric surfactants, and the like.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether and polyoxyethylene cetyl ether, polyoxyethylene fatty acid diesters, polyoxyethylene fatty acid monoesters, polyoxyethylene polyoxypropylene block polymers, acetylene alcohol derivatives such as acetylene alcohols, acetylene glycols and polyethoxylates of acetylene alcohols, acetylene glycol derivatives such as polyethoxylates of acetylene glycols, fluorine-containing surfactants such as Fluorad (trade name, manufactured by Sumitomo 3M Co., ltd.), megafac (trade name, manufactured by DIC corporation), surflon (trade name, manufactured by Asahi Nippon Kabushiki Kaisha), and organosiloxane surfactants such as KP341 (trade name, manufactured by shin 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-octyn-3, 6-diol, 2,4,7, 9-tetramethyl-5-decene-4, 7-diol, 3, 5-dimethyl-1-hexyn-3-ol, 2, 5-dimethyl-3-hexyn-2, 5-diol, 2, 5-dimethyl-2, 5-hexanediol, and the like.

Further, examples of the anionic surfactant include ammonium salts or organic amine salts of alkyldiphenyl ether disulfonic acid, ammonium salts or organic amine salts of alkyldiphenyl ether sulfonic acid, ammonium salts or organic amine salts of alkylbenzenesulfonic acid, ammonium salts or organic amine salts of polyoxyethylene alkylether sulfuric acid, ammonium salts or organic amine salts of alkylsulfuric acid, and the like.

In addition, examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazoline betaine, lauric acid amidopropyl hydroxysulfone betaine, and the like.

These surfactants may be used singly or in combination, and the mixing ratio thereof is usually 50 to 10000ppm, preferably 100 to 5000ppm, based on the total mass of the composition.

The developer dissolution promoter or scum remover regulates the solubility of the formed coating film in the developer, and has the effect of preventing scum from remaining on the substrate after development. Crown ethers may be used as such additives.

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

Further, a sensitizer may be added as necessary. Examples thereof include sensitizing dyes such as coumarins, ketocoumarins and derivatives thereof, acetophenones, pyrylium salts and thiopyrylium salts, and compounds having an anthracene skeleton.

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

Besides nitrone, nitroxide free radical, hydroquinone, catechol, phenothiazine, phenoxazine, hindered amine and their derivatives, an ultraviolet absorber can be added as a polymerization inhibitor. The amount of addition is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the total mass of the polysiloxane.

Examples of the antifoaming agent include alcohol (C) _1-18 ) Higher fatty acids such as oleic acid and stearic acidHigher fatty acid esters such as monolaurin, polyethers such as polyethylene glycol (PEG) (Mn: 200 to 10000) and polypropylene glycol (PPG) (Mn: 200 to 10000), silicone compounds such as dimethyl silicone oil, alkyl-modified silicone oil and silicone tetrafluoride, and the aforementioned organosilicone-based surfactants. These may be used alone or in combination of two or more, and the amount thereof added is preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the total mass of the polysiloxane.

When a cured film is formed using the composition according to the present invention, the tackifier has an effect of preventing the pattern from being peeled off due to stress applied after curing. As the tackifier, imidazole, a silane coupling agent, and the like are preferable.

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

< method for producing cured film >

The method for producing a cured film according to the present invention comprises the steps of:

(1) The composition according to the present invention is applied to a substrate to form a composition layer,

(2) (ii) exposing the layer of the composition to light,

(3) Developing with an alkaline developer to form a pattern, and

(4) The resulting pattern is heated.

The following description is made in order of steps.

(1) Coating step

First, the composition is applied to a substrate. The coating film of the composition of the present invention can be formed by any method known as a coating method of a photosensitive composition. Specifically, it can be arbitrarily selected from dip coating, roll coating, bar coating, brush coating, spray coating, blade coating, flow coating, spin coating, slit coating, and the like.

As the substrate to which the composition is applied, an appropriate substrate such as a silicon substrate, a glass substrate, or a resin film can be used. Various semiconductor elements and the like can be formed on these substrates as needed. When the substrate is a thin film, gravure coating may also be used. A drying step may be separately provided after the film is coated, as needed. Further, the coating step may be repeated once or twice or more as needed to obtain a desired film thickness of the coating film to be formed.

After the coating film is formed by the coating composition, in order to dry the coating film and reduce the residual amount of solvent in the coating film, the coating film is preferably subjected to prebaking (pre-heating treatment). The pre-baking step 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, using a hot plate, and for 1 to 30 minutes, using a clean oven.

(2) Exposure step

After the coating film is formed, the surface of the coating film is irradiated with light. In order to distinguish this step from the full exposure described later, this step is referred to as a primary exposure. As the light source for light irradiation, any light source generally used for a pattern forming method can be used. Examples of such light sources include lamps such as high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, xenon lamps, laser diodes, LEDs, and the like. As the irradiation light, ultraviolet rays such as g-ray, h-ray, i-ray, etc. are generally used. In addition to ultra-fine processing of semiconductors and the like, patterning of several micrometers to several tens of micrometers is generally performed using light of 360 to 430nm (high-pressure mercury lamp). Most importantly, in the case of a liquid crystal display device, light of 430nm is generally used. In this case, it is advantageous to use a sensitizing dye in combination in the composition according to the invention, as described above.

The irradiation light energy depends on the light source and the film thickness of the coating film, and is usually 5 to 2000mJ/cm ² Preferably 10 to 1000mJ/cm ² . If the irradiation light energy is less than 5mJ/cm ² Sufficient resolution may not be obtained, whereas if the irradiation light energy is higher than 2000mJ/cm ² Overexposure may occur and result in the occurrence of halos.

A general photomask may be used to pattern-wise irradiate light. Such a photomask may be arbitrarily selected from known photomasks. The environment at the time of irradiation is not particularly limited, and may be an ambient atmosphere (atmospheric pressure) or a nitrogen atmosphere in general. Further, when the film is formed on the entire surface of the substrate, the entire surface of the substrate may be irradiated with light. In the present invention, the patterned film also includes a case where a film is formed on the entire surface of the substrate.

(3) Developing step

After the exposure, the coating film is subjected to a development treatment. As the developer used in the development, any developer generally used for developing photosensitive compositions can be used. The developer includes an organic developer and an inorganic developer, and examples of the organic developer include aqueous TMAH solution, aqueous tetrabutylammonium hydroxide solution, methyl isobutyl ketone, and isopropyl alcohol, preferably aqueous TMAH solution, more preferably 2.38 mass% aqueous TMAH solution. Examples of the inorganic developer include alkali metal salts, preferably aqueous potassium hydroxide solution or aqueous sodium hydroxide solution, aqueous sodium carbonate solution, aqueous sodium bicarbonate solution, aqueous sodium silicate solution, aqueous sodium metasilicate solution and aqueous ammonia, particularly preferably aqueous potassium hydroxide solution. When an aqueous solution of potassium hydroxide is used, the concentration thereof is preferably 0.1 to 3.0% by mass, more preferably 0.5 to 2.0% by mass. These developers may further contain a water-soluble organic solvent such as methanol, ethanol, etc., or a surfactant, as necessary.

The developing method may also be arbitrarily selected from conventionally known methods. Specific examples thereof include methods such as dipping in developer (dropping), spin immersion (paddle), spraying, slit, cap coating (cap coating), spraying, and the like. The developing temperature is preferably room temperature (20 to 25 ℃ C.), but may be 30 to 50 ℃ C. The developing time is preferably 15 to 180 seconds, and more preferably 30 to 60 seconds. The pattern can be obtained by this development, and it is preferable to perform rinsing (water washing) after the development with a developer.

The rinsing is preferably performed using water, which may be performed in the same manner as the developing, and the rinsing is preferably performed for a time of 60 seconds or more.

After development (development if necessary), a general full exposure step is performed. This is because, as described above, by performing the full exposure, the wrinkle formation of the cured film can be suppressed. In addition, the film is exposed to light with the diazonaphthoquinone derivative remaining unreactedDecomposition further improves the optical transparency of the film, and therefore, when transparency is required, it is preferable to perform a full exposure step. The full exposure method includes using an ultraviolet visible exposure machine such as PLA (e.g., PLA-501F, manufactured by Canon Inc.) at about 100-2000 mJ/cm ² (conversion of 365nm wavelength exposure) exposing the entire surface.

When the composition according to the present invention is used, wrinkles can be suppressed even without full exposure, and thus, if excessive transparency is not required, full exposure may not be performed.

(4) Curing step

After development, the resulting patterned 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 film can be cured, and may be arbitrarily set. However, if silanol groups remain, chemical resistance of the cured film may be insufficient or the dielectric constant of the cured film may increase. From this point of view, a relatively high heating temperature is generally selected. Specifically, the curing is preferably carried out by heating at 360 ℃ or lower, and the curing temperature is more preferably 300 ℃ or lower, particularly preferably 250 ℃ or lower, in order to maintain a high residual film ratio after curing. On the other hand, in order to accelerate the curing reaction and obtain a sufficient cured film, the curing temperature is preferably 70 ℃ or higher, more preferably 90 ℃ or higher, and particularly preferably 100 ℃ or higher. The heating time is not particularly limited, and is usually 10 minutes to 24 hours, preferably 30 minutes to 3 hours. The heating time is a time after the temperature of the pattern film reaches a desired heating temperature. Generally, it takes several minutes to several hours from the temperature before heating to the temperature at which the patterned film reaches the desired temperature.

By using the composition according to the present invention, generation of wrinkles on the surface of the cured film in this curing step can be suppressed. Here, the wrinkle refers to an unevenness generated near or far from a pattern portion of the cured film. Fig. 1 shows an electron micrograph of a typical wrinkle formed on the pattern surface.

Rough criteria for differences between no wrinkles ((P) of fig. 1), small wrinkles ((Q) of fig. 1) and large wrinkles ((R) of fig. 1) were as follows, and when the surface of the film not covered with the pattern at the position of pattern release after curing was measured with a stylus type surface measuring instrument (Dectak) at a force of 3mg and a distance of 1.5cm for 50 seconds, the irregularities on the surface were such that the height difference was less than 30nm in the case of no wrinkles, 30nm or more and 100nm or less in the case of small wrinkles, and greater than 100nm in the case of large wrinkles.

The cured film thus obtained can realize excellent flatness, electrical insulation properties, and the like. For example, a relative dielectric constant of 4 or less can be realized. Therefore, the film can be applied to various fields as a planarization film, an interlayer insulating film for low-temperature polysilicon, a buffer coating film for IC chips, a transparent protective film, and the like of the aforementioned various elements such as Flat Panel Displays (FPDs).

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples.

Gel Permeation Chromatography (GPC) was carried out using a HLC-8220GPC type high-speed GPC system (trade name, manufactured by Tosoh corporation) and two Super Multipore HZ-N type GPC columns (trade name, manufactured by Tosoh corporation). The measurement was carried out under the analysis conditions of a flow rate of 0.6ml/min and a column temperature of 40 ℃ using monodisperse polystyrene as a standard sample and tetrahydrofuran as a developing agent.

Synthesis example 1 (Synthesis of polysiloxane Pa-1) >

A2L flask equipped with a stirrer, a thermometer, and a cooling tube was charged with 49.0g of a 25 mass% TMAH aqueous solution, 600ml of isopropyl alcohol (IPA), and 4.0g of water, and then a mixed solution of 68.0g of methyltrimethoxysilane, 79.2g of phenyltrimethoxysilane, and 15.2g of tetramethoxysilane was prepared in a dropping funnel. The mixed solution was added dropwise at 40 ℃, and the mixture was stirred at the same temperature for 2 hours and then neutralized by adding 10 mass% aqueous HCl. 400ml of toluene and 600ml of water were added to the neutralized solution, which was separated into two layers, and the water layer was removed. The mixture was washed with 300ml of water 3 times, the resulting organic layer was concentrated under reduced pressure to remove the solvent, and PGMEA was added to the concentrate to adjust the solid content concentration to 35 mass%.

The molecular weight (in terms of polystyrene) and the mass average molecular weight of the obtained polysiloxane were measured by gel permeation chromatography (seeHereinafter sometimes simply referred to as "Mw") of 1700. The obtained resin solution was applied to a silicon wafer by a spin coater (MS-A100 (manufactured by Mikasa corporation)) so that the film thickness after the pre-baking became 2 μm, and the dissolution rate in a 2.38 mass% TMAH aqueous solution (hereinafter, sometimes abbreviated as "ADR") after the pre-baking was measured

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

Synthesis was carried out in the same manner as in Synthesis example 1, except that the amount of the aqueous TMAH solution was changed to 32.5 g.

The Mw of the resulting polysiloxane Pa-2 was 2500, and the ADR relative to a 5 mass% TMAH aqueous solution after prebaking was

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

A2L flask equipped with a stirrer, a thermometer and a cooling tube was charged with 102g of a 25 mass% TMAH aqueous solution, 600ml IPA and 4.0g water, and then a mixed solution of 68.0g methyltrimethoxysilane, 79.2g phenyltrimethoxysilane and 68.1g bis (triethoxysilyl) methane was prepared in a dropping funnel. The mixed solution was added dropwise at 40 ℃, and the mixture was stirred at the same temperature for 2 hours and then neutralized by adding 10 mass% aqueous HCl. 400ml of toluene and 600ml of water were added to the neutralized solution, which was allowed to separate into two layers, and the aqueous layer was removed. The mixture was washed with 400ml of water 3 times, the resulting organic layer was concentrated under reduced pressure to remove the solvent, and PGMEA was added to the concentrate to adjust the solid content concentration to 35 mass%.

The Mw of the resulting polysiloxane Pb-1 was 6500 and the ADR relative to a 2.38 mass% TMAH aqueous solution after prebaking was

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

A2L flask equipped with a stirrer, a thermometer and a cooling tube was charged with 102g of a 25 mass% TMAH aqueous solution, 600ml IPA and 4.0g water, and then a mixed solution of 68.0g methyltrimethoxysilane, 79.2g phenyltrimethoxysilane and 54.0g bis (trimethoxysilyl) ethane was prepared in a dropping funnel. The mixed solution was added dropwise at 40 ℃, and the mixture was stirred at the same temperature for 2 hours and then neutralized by adding 10 mass% aqueous HCl. 400ml of toluene and 600ml of water were added to the neutralized solution, which was allowed to separate into two layers, and the aqueous layer was removed. The mixture was washed with 400ml of water 3 times, the resulting organic layer was concentrated under reduced pressure to remove the solvent, and PGMEA was added to the concentrate to adjust the solid content concentration to 35 mass%.

The resulting polysiloxane had an Mw of 9000 and an ADR of 2.38 mass% TMAH aqueous solution after prebaking

ADR of all polysiloxanes with respect to a 2.38 mass% TMAH aqueous solution after prebaking was as follows.

Polysiloxane Pa-1

Polysiloxane Pa-1

Polysiloxane Pa-1 Pa-2=90

< 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, which contained the compounds shown in table 1 below with the balance being PGMEA, were prepared.

TABLE 1

In the table, it is shown that,

diazonaphthoquinone derivative: 2.0 mol modified product of diazonaphthoquinone of 4,4' - (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol

Surfactant (b): KF-53, manufactured by shin-Etsu chemical Co.

Further, "-" indicates that the addition amount is zero.

< evaluation of wrinkles >

The evaluation was performed by visually observing the state of wrinkles on the surface after curing, which was exposed to the optimum exposure amount obtained in the evaluation of photosensitivity. The evaluation criteria are as follows, and the evaluation results are shown in table 1.

A: no wrinkles were recognized on the surface

B: the surface was found to have small wrinkles, but wrinkles were not found in 80% or more of the surface

C: the surface was found to have small wrinkles, and no wrinkles were found in 80% or less of the surface

D: confirmation of surface Large wrinkles

Fig. 1 shows typical electron micrographs confirming a pattern (P) without wrinkles, a pattern (Q) with small wrinkles, and a pattern (R) with large wrinkles.

< evaluation of Pattern shape >

The shape of the pattern after curing exposed to the optimum exposure amount obtained in the photosensitivity evaluation was observed using a Scanning Electron Microscope (SEM) to perform the evaluation. The evaluation criteria are as follows, and the evaluation results are shown in table 1.

X: the corners of the formed pattern are very rounded

Y: the corners of the formed pattern are rounded

Z: the corners of the formed pattern are not rounded

V: the missing pattern is smaller than the mask size

W: without forming a pattern

Fig. 2 shows typical electron micrographs corresponding to the above-described shapes.

< evaluation of photosensitivity >

The compositions of examples 101 to 105 were spin-coated so that the film thickness after prebaking was 1.6. Mu.m. The resulting coating film was prebaked at 110 ℃ for 90 seconds to volatilize the solvent. Then, a contact hole having a size of 5 μm was pattern-exposed with an optimum exposure amount using a g + h line mask aligner (FX-604F type, manufactured by Nikon corporation). After the exposure, paddle development was performed for 70 seconds using a 2.38 mass% TMAH aqueous solution, and the substrate was further rinsed with pure water for 60 seconds and dried. Then, the mixture was heated at 180 ℃ for 20 minutes in the air, and then further heated at 230 ℃ for 20 minutes to cure the mixture.

Here, the optimum exposure amount is defined as an exposure amount at which the bottom width of the contact hole after curing becomes 5 micrometers when patterning is performed using a 5 micrometer mask.

In the compositions of examples 101 to 105, the exposure amount of less than 500mJ was the optimum exposure amount, and the photosensitivity was sufficient for practical use.

On the other hand, when the optimum exposure amount was obtained in the same manner as described above using the same composition as in example 101 except that the amount of maleic acid was 80000ppm, a pattern could not be formed even if the exposure amount was increased.

< examples 201, 202 and comparative examples 201 to 204 (preparation of Positive photosensitive polysiloxane compositions) >

Examples 201, 202 and comparative examples 201 to 204, which contained the compounds shown in table 2 below with the balance being PGMEA, were prepared.

TABLE 2

In the table, it is shown that,

Surfactant (B): KF-53, manufactured by shin-Etsu chemical Co., ltd.

Further, "-" indicates that the addition amount is zero.

Each composition was spin-coated to a film thickness of 1.6 μm after prebaking. The resulting coated film was pre-baked at 110 ℃ for 90 seconds to volatilize the solvent. Then, a contact hole having a size of 5 μm was pattern-exposed using a g + h line mask aligner (model FX-604F, manufactured by Nikon K.K.) at an optimum exposure amount. After the exposure, the substrate was subjected to spin-on immersion development using a 1.0 mass% KOH aqueous solution for 70 seconds, further rinsed with pure water for 60 seconds, and dried. Then, the mixture was heated at 180 ℃ for 20 minutes in the air, and then further heated at 230 ℃ for 20 minutes to cure the mixture.

The wrinkle evaluation and the pattern shape evaluation were performed using the same evaluation criteria as described above. The evaluation results are shown in table 2.

Claims

1. A positive photosensitive polysiloxane composition comprising:

(I) A polysiloxane,

(II) a carboxylic acid compound which is a monocarboxylic acid or a dicarboxylic acid in an amount of 200 to 50000ppm based on the total mass of the composition,

(III) diazonaphthoquinone derivatives, and

(IV) a solvent is added into the mixture,

wherein the amount of the diazonaphthoquinone derivative added is 1 to 20 parts by mass relative to 100 parts by mass of the total mass of the polysiloxane.

2. The composition of claim 1, wherein the monocarboxylic acid has a first acid dissociation constant pKa ₁ 5.0 or less, a first acid dissociation constant pKa of the dicarboxylic acid ₁ Is 4.0 or less.

3. The composition of claim 1 or 2, wherein the monocarboxylic acid is represented by formula (i):

R ⁱ -COOH formula (i)

In the formula, R ⁱ Is hydrogen, or a saturated or unsaturated hydrocarbon radical having from 1 to 4 carbon atoms,

the dicarboxylic acid is represented by formula (ii):

HOOC-L-COOH formula (ii)

Wherein L is a single bond,

substituted or unsubstituted alkenylene 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.

4. The composition of claim 1 or 2, wherein the carboxylic acid compound is a dicarboxylic acid.

5. The composition according to claim 1 or 2, wherein the dicarboxylic acid may have a cyclic structure by intramolecular dehydration condensation.

6. The composition according to claim 1 or 2, wherein the content of the carboxylic acid compound is 300 to 30000ppm of the total mass of the composition.

7. The composition of claim 1 or 2, wherein the polysiloxane comprises repeating units represented by the following formula (Ia):

in the formula (I), the compound is shown in the specification,

in the aliphatic hydrocarbon group and the aromatic hydrocarbon group, methylene groups are not replaced, or one or more methylene groups are replaced by an oxy group, an amino group, an imino group or a carbonyl group, but R ^Ia Is not a hydroxyl group,An alkoxy group.

8. The composition of claim 7, wherein the polysiloxane comprises repeating units represented by the following formula (Ic):

9. the composition of claim 7, wherein the polysiloxane comprises repeating units represented by the following formula (Ie):

in the formula (I), the compound is shown in the specification,

L ^Ie is- (CR) ^Ie ₂ ) _n -or

Where n is an integer of 1 to 3,

R ^Ie each independently represents hydrogen, methyl or ethyl.

10. The composition of claim 7, wherein R ^Ia Is C _3-20 Saturated or unsaturated cyclic aliphatic hydrocarbon groups or aromatic hydrocarbon groups.

11. A method for manufacturing a cured film, comprising the steps of:

(1) Applying the composition of any one of claims 1 to 10 to a substrate to form a composition layer,

(2) (ii) exposing the layer of the composition to light,

(3) Developing with an alkaline developer to form a pattern, and

(4) The resulting pattern is heated.

12. The method of claim 11, wherein step (4) is preceded by a step of performing a full exposure.

13. The method according to claim 11 or 12, wherein the alkaline developer is an organic developer.

14. The method according to claim 11 or 12, wherein the alkaline developer is an inorganic developer.

15. An electronic device comprising a cured film produced by the method of any one of claims 11 to 14.