JP6639724B1 - Positive photosensitive polysiloxane composition - Google Patents

Abstract

A positive photosensitive polysiloxane composition capable of producing a cured film with suppressed surface wrinkles and high surface smoothness without adding a curing aid or performing overall exposure. And a production method using the same. The present invention relates to (I) a polysiloxane, (II) 200 to 50,000 ppm, based on the total mass of the composition, of a carboxylic acid compound which is a monocarboxylic acid or a dicarboxylic acid, (III) a diazonaphthoquinone derivative, and (IV) A) A positive photosensitive polysiloxane composition comprising a solvent, and a method for producing a cured film using the composition. [Selection diagram] Fig. 1

Description

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

2. Description of the Related Art In recent years, various proposals have been made for optical elements such as displays, light emitting diodes, and solar cells to further improve light use efficiency and save energy. For example, in a liquid crystal display, a method of increasing the aperture ratio of a display device by forming a transparent flattening film on a TFT element and forming a pixel electrode on the flattening film is known.
As a material for such a flattening film for a TFT substrate, a material combining an acrylic resin and a quinonediazide compound is known. Since these materials have planarization characteristics and photosensitivity, contact holes and other patterns can be formed. However, as the resolution and the frame frequency are improved, the wiring becomes more complicated, so that the flattening becomes severe and it is difficult to cope with these materials.

Polysiloxane, particularly silsesquioxane, is known as a material having high heat resistance and high transparency. Silsesquioxane is a polymer composed of a trifunctional siloxane structural unit RSi (O _1.5 ), and is chemically intermediate between inorganic silica (SiO ₂ ) and organic silicone (R ₂ SiO). However, while cured in an organic solvent, the cured product is a specific compound exhibiting high heat resistance characteristic of inorganic silica.

  A cured film can be formed by using a positive photosensitive composition containing such a polysiloxane and a photosensitive agent to form a pattern by exposure and development, and then heating the pattern. In the cured film thus formed, the film surface may not be flat and wrinkles may occur. In order to suppress the generation of wrinkles, a curing assistant may be added, or the entire surface may be exposed after exposure and development.

JP 2011-2517 A

  The present invention has been made based on the above-described circumstances, and without the addition of a curing aid and without performing overall exposure, the occurrence of wrinkles is suppressed, and a cured film having a high surface smoothness. It is an object of the present invention to provide a positive photosensitive polysiloxane composition which can be used for the production of It is another object of the present invention to provide a method for producing a cured film using the same.

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

The method for producing a cured film according to the present invention comprises the following steps:
(1) applying a positive photosensitive polysiloxane composition according to the present invention to a substrate to form a composition layer;
(2) exposing the composition layer,
(3) developing with an alkali developing solution to form a pattern; and (4) heating the obtained pattern.

  Further, an electronic device according to the present invention comprises a cured film produced by the above method.

  By using the positive photosensitive polysiloxane composition according to the present invention, it is possible to produce a cured film in which wrinkling is suppressed and surface smoothness is high, without adding a curing aid or performing overall exposure. be able to. The obtained film has high sensitivity and can contribute to high throughput of the manufacturing process. Further, the pattern shape of the cured film may be a shape having a gentle opening, which is a desirable shape for the subsequent steps. Since the obtained cured film has excellent flatness and electrical insulation properties, a flattening film for a thin film transistor (TFT) substrate used for a backplane of a display such as a liquid crystal display device or an organic EL display device, or the like. Various film-forming materials such as insulating films for solid-state imaging devices, anti-reflection films, anti-reflection plates, optical filters, high-brightness light-emitting diodes, touch panels, solar cells, etc. It can be suitably used as an optical element such as an optical waveguide.

An electron micrograph for explaining "wrinkles" formed on a pattern surface. An electron microscope photograph for explaining the shape of a pattern in an example.

Hereinafter, embodiments 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, the singular forms include the plural forms, and "a" or "the" means "at least one", unless otherwise specified. In the present specification, unless otherwise specified, an element of a concept can be expressed by a plurality of species, and when the amount (for example, mass% or mol%) is described, the amount is expressed by the plurality of species. Means sum. "And / or" includes all combinations of the elements, and also includes the use alone.

  In the present specification, when numerical ranges are indicated by using-or-, they include both end points and have a common unit. For example, 5 to 25 mol% means 5 to 25 mol%.

  As used herein, hydrocarbon means those containing carbon and hydrogen and, if necessary, oxygen or nitrogen. The hydrocarbon group means a monovalent or divalent or higher valent hydrocarbon. In the present specification, the aliphatic hydrocarbon means a linear, branched or cyclic aliphatic hydrocarbon, and the aliphatic hydrocarbon group means a monovalent or divalent or higher aliphatic hydrocarbon. I do. Aromatic hydrocarbon means a hydrocarbon containing an aromatic ring, which can have an aliphatic hydrocarbon group as a substituent or can be condensed with an alicyclic ring, if necessary. The aromatic hydrocarbon group means a monovalent or divalent or higher valent aromatic hydrocarbon. In addition, the aromatic ring means a hydrocarbon having a conjugated unsaturated ring structure, and the alicyclic means a hydrocarbon having a ring structure but not containing a conjugated unsaturated ring structure.

  In the present specification, alkyl means a group obtained by removing one arbitrary hydrogen from a linear or branched saturated hydrocarbon, includes linear alkyl and branched alkyl, and cycloalkyl has a cyclic structure. Means a group in which one hydrogen has been excluded from a saturated hydrocarbon containing, and optionally includes a linear or branched alkyl as a side chain in a cyclic structure.

  In the present specification, aryl means a group obtained by removing one arbitrary hydrogen from an aromatic hydrocarbon. Alkylene means a group in which two arbitrary hydrogens have been removed from a linear or branched saturated hydrocarbon. Arylene means a hydrocarbon group obtained by removing two arbitrary hydrogens from an aromatic hydrocarbon.

In the present specification, the term such as _{"C x to y", "C} x -C _y" and _{"C x"} means the number of carbons in the molecule or substituent. For example, C _1-6 alkyl means an alkyl having 1 or more and 6 or less carbons (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). The term “fluoroalkyl” used in the present specification refers to one in which one or more hydrogens in an alkyl are replaced with fluorine, and the term “fluoroaryl” refers to one in which one or more hydrogens in an aryl are replaced with fluorine. Say.

In the present specification, when the polymer has a plurality of types of repeating units, these repeating units copolymerize. These copolymerizations are any of alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof.
In the present specification,% indicates mass%, and ratio indicates mass ratio.

  In this specification, the unit of temperature uses Celsius (Celsius). For example, 20 degrees means 20 degrees Celsius.

<Positive photosensitive polysiloxane composition>
The positive photosensitive polysiloxane composition according to the present invention (hereinafter, sometimes simply referred to as the composition) comprises (I) a polysiloxane, (II) a carboxylic acid compound, (III) a diazonaphthoquinone derivative, and (IV) a solvent. .
Hereinafter, each component contained 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 can be selected from arbitrary ones according to the purpose. The skeleton structure of the polysiloxane has a silicone skeleton (the number of oxygen atoms bonded to the silicon atom is 2) and a silsesquioxane skeleton (the number of oxygen atoms bonded to the silicon atom is changed depending on the number of oxygen bonded to the silicon atom). 3) and a silica skeleton (the number of oxygen atoms bonded to a silicon atom is 4). In the present invention, any of these may be used. The polysiloxane molecule may include a plurality of combinations of these skeletal structures.

Preferably, the polysiloxane used in the present invention has the following formula (Ia):
(Where
R ^Ia represents hydrogen, C _1-30 , linear, branched or cyclic, saturated or unsaturated, aliphatic 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 methylene is replaced by oxy, amino, imino or carbonyl, provided that R ^Ia is not hydroxy, alkoxy).
Here, the above-mentioned methylene includes terminal methyl.
Further, the above `` substituted by fluorine, hydroxy or alkoxy '' means that a hydrogen atom directly bonded to a carbon atom in an aliphatic hydrocarbon group and an aromatic hydrocarbon group is replaced by fluorine, hydroxy or alkoxy. Means that In this specification, the same applies to other similar descriptions.

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

The polysiloxane used in the present invention has the following formula (Ib):
(Where
R ^Ib is a group obtained by removing a plurality of hydrogens from a nitrogen and / or oxygen-containing cycloaliphatic hydrocarbon compound containing an amino group, an imino group, and / or a carbonyl group.
May be further included.

In Formula (Ib), R ^Ib is preferably a nitrogen-containing aliphatic hydrocarbon ring containing an imino group and / or a carbonyl group, more preferably a 5- or 6-membered ring containing nitrogen as a member. It is a group from which a plurality, preferably two or three hydrogens have been removed. Examples include groups in which two or three hydrogens have been removed from piperidine, pyrrolidine, and isocyanurate. ^RIb connects Si contained in a plurality of repeating units.

The polysiloxane used in the present invention has the following formula (Ic):
May be further included.

  When the blending ratio of the repeating units represented by the formulas (Ib) and (Ic) is high, cracks occur because the sensitivity of the composition decreases, the compatibility with solvents and additives decreases, and the film stress increases. In some cases, the amount is preferably 40 mol% or less, more preferably 20 mol% or less, based on the total number of polysiloxane repeating units.

The polysiloxane used in the present invention has the following formula (Id):
(Where
R ^Id independently represents hydrogen, 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 unsubstituted, or fluorine, hydroxy, Or substituted with alkoxy)
May be further included.

In the repeating unit represented by the formula (Id),
Examples of R ^Id include (i) alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl; (ii) aryl such as phenyl, tolyl, and benzyl; and (iii) trifluoro. Methyl, 2,2,2-trifluoroethyl, fluoroalkyl such as 3,3,3-trifluoropropyl, (iv) fluoroaryl, (v) cycloalkyl such as cyclohexyl, (vi) isocyanate, and amino Examples include a nitrogen-containing group having an amino or imide structure, (vii) an epoxy structure such as glycidyl, or an oxygen-containing group having an acryloyl structure or a methacryloyl structure. Preferred are methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, tolyl, glycidyl and isocyanate. As the fluoroalkyl, a perfluoroalkyl, particularly trifluoromethyl or pentafluoroethyl, is preferred. The case where R ^Id is methyl is preferable because the raw material is easily available, the film hardness after curing is high, and the chemical resistance is high. When R ^Id is phenyl, it is preferable because the solubility of the polysiloxane in the solvent is increased and the cured film is less likely to crack. Further, it is preferable that ^Re has hydroxy, glycidyl, isocyanate, or amino, because the adhesion to the substrate is improved.

  By having the repeating unit of the above formula (Id), the polysiloxane according to the present invention can have a partially linear structure. However, since the heat resistance is reduced, it is preferable that the linear structure portion is small. Specifically, the content of the repeating unit of the formula (Id) is preferably 30 mol% or less based on the total number of the repeating units of the polysiloxane.

The polysiloxane has the following formula (Ie):
(Where
L ^{Ie is-} (CR ^Ie ₂ ) _n -or
And
Here, n is an integer of 1 to 3,
R ^Ie each independently represents hydrogen, methyl, or ethyl)
May be included.

In the formula (Ie), L ^Ie is preferably — (CR ^Ie ₂ ) _n —, and R ^Ie is the same or different in one repeating unit or in a polysiloxane molecule. However, it is preferable that all R ^{Ie in} one molecule are the same and that all are hydrogen.

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

The composition according to the invention can comprise more than one polysiloxane. The first type is, for example, a polysiloxane containing a repeating unit of any of the above formulas (Ia) to (Id), and the second type is a repeating unit of the formula (Ie) and a repeating unit other than the formula (Ie) (preferably Can be a polysiloxane containing the formula (Ia), (Ib) and / or (Id).
Preferably one or ^{R Ia} of two or more polysiloxane Formula (Ia), repeating at least one bulky group of ^{R Ib} and / or ^{R Id} of formula (Id) of the formula (Ib) comprises units, more bulky R ^Ia of formula (Ia), the C _{3 to 20,} saturated or unsaturated, cyclic aliphatic hydrocarbon group or an aromatic hydrocarbon group, (for example, phenyl, naphthyl, anthracene It is preferable to use a polysiloxane comprising a repeating unit of formula (I)) and a repeating unit of formula (Ie). The presence of a bulky group tends to cause wrinkles, so that the suppression of wrinkles according to the present invention is effectively exhibited, and by including the repeating unit of the formula (Ie), the taper angle of the pattern can be further controlled. This is particularly advantageous because it becomes possible.
The ratio of the total number of the repeating units (Ie) and the repeating units (Ia) to the total number of the repeating units contained in the polysiloxane is preferably 60 mol% or more, and more preferably 70 mol% or more. More preferred. Further, it is preferable that (Ia) is 20 to 95 mol% and (Ie) is 5 to 40 mol%.
In addition, the total proportion of the above-mentioned bulky group-containing repeating units (Ia), (Ib) and (Id) is preferably at least 10 mol% with respect to the total number of repeating units contained in the polysiloxane. preferable.

The polysiloxane used in the present invention has a structure in which repeating units are bonded as described above, and preferably has a silanol at a terminal. Such a silanol group is one in which —O _0.5 H is bonded to a bond of the above-described 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 more the coating properties tend to be improved. On the other hand, when the molecular weight is low, the synthesis conditions are less limited, and the synthesis is easy, and the synthesis of a polysiloxane having a very high molecular weight is difficult. For these reasons, the weight average molecular weight of the polysiloxane is usually 500 or more and 25,000 or less, and the solubility in an organic solvent and the solubility in an alkali developer are 1,000 or more and 20,000 or less. Preferably, there is. Here, the mass average molecular weight 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 a positive photosensitivity, and the composition forms a cured film on a substrate through application, imagewise exposure, and development. At this time, it is necessary that there is a difference in solubility between the exposed part and the unexposed part, and the coating film in the exposed part should have a certain or more solubility in the developing solution. For example, the dissolution rate of the coating film after pre-baking in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter, may be referred to as TMAH) (hereinafter, may be referred to as an alkali dissolution rate or ADR; details will be described later) is 50 °. It is considered that a pattern can be formed by exposure-development at a rate of / sec or more. However, the required solubility differs depending on the thickness of the cured film to be formed and the development conditions. Therefore, the polysiloxane should be appropriately selected according to the development conditions. For example, if the film thickness is 0.1 to 100 μm (1,000 to 1,000,000 Å), it depends on the type of the diazonaphthoquinone derivative and the amount of the diazonaphthoquinone derivative contained in the composition. The dissolution rate is preferably from 50 to 5,000 ° / sec, and more preferably from 200 to 3,000 ° / sec.

  As the polysiloxane used in the present invention, a polysiloxane having an ADR in any of the above ranges may be selected according to the application and required characteristics. Also, polysiloxanes having different ADRs can be combined into a mixture having a desired ADR.

  Polysiloxanes having 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 having different alkali dissolution rates, it is possible to reduce residual insoluble matter after development, reduce pattern drooling, and improve pattern stability.

Examples of such a polysiloxane include (M) a polysiloxane in which a film after prebaking is soluble in a 2.38% by mass aqueous solution of TMAH and has a dissolution rate of 200 to 3,000 ° / sec.

Also, if necessary, (L) the pre-baked film is soluble in a 5% by mass aqueous solution of TMAH, and the dissolution rate is 1,000 Å / sec or less, or (H) the pre-baked film, A composition having a desired dissolution rate can be obtained by mixing with a polysiloxane having a dissolution rate in a 2.38 mass% TMAH aqueous solution of 4,000 ° / sec or more.

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

  The polysiloxane is diluted to 35% by mass in PGMEA and dissolved while stirring with a stirrer at room temperature for 1 hour. In a clean room at a temperature of 23.0 ± 0.5 ° C. and a humidity of 50 ± 5.0%, the prepared polysiloxane solution was pipetted on a 4-inch, 525 μm-thick silicon wafer using a pipette at the center of a 1 cc silicon wafer. And spin-coated to a thickness of 2 ± 0.1 μm, and then heated on a hot plate at 100 ° C. for 90 seconds to remove the solvent. The thickness of the coating film is measured with a spectroscopic ellipsometer (manufactured by JA Woollam).

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

<Method of synthesizing polysiloxane>
The method for synthesizing the polysiloxane used in the present invention is not particularly limited.
^Ria- Si- ( ^{ORia '} ) ₃ (ia)
(Where
R ^ia represents hydrogen, 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 unsubstituted, or fluorine, hydroxy, Or R ^{ia ′} is straight or branched, C _1-6 alkyl)
May be hydrolyzed and polymerized in the presence of an acidic catalyst or a basic catalyst, if necessary.

In the formula (ia), preferred R ^{ia ′} includes methyl, ethyl, n-propyl, isopropyl, and n-butyl. In the formula (ia), a plurality of R ^{ia ′} are included, and each R ^{ia ′} may be the same or different.
Preferred R ^ia are the same as R ^Ia described above.

  Specific examples of the silane monomer represented by the formula (ia) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Ethyltriisopropoxysilane, ethyltri-n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyl Triethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyl Trimethoxy silane. Among them, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, and phenyltrimethoxysilane are preferable. It is preferable that two or more silane monomers represented by the formula (ib) are 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)
^Wherein R ^{ic ′} is straight-chain or branched, C _1-6 alkyl. In the formula (ic), preferable R ^{ic ′} includes methyl, ethyl, n-propyl, isopropyl, n-butyl and the like. In the formula (ic), a plurality of R ^{ic ′} are included, and each R ^{ic ′} may be the same or different.
Specific examples of the silane monomer represented by the formula (ic) include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetra-n-butoxysilane.

A silane monomer represented by the following formula (ib) can be further combined.
R ^ib —Si— (OR ^{ib ′} ) ₃ (ib)
R ^{ib ′} is a linear or branched C _1-6 alkyl, and includes, for example, methyl, ethyl, n-propyl, isopropyl, and n-butyl. R ^{ib 'is} included more in one monomer, each R ^ib' may be the same or different,
R ^ib is a group obtained by removing a plurality, preferably two or three hydrogens from a nitrogen- and / or oxygen-containing cyclic aliphatic hydrocarbon compound containing an amino group, an imino group, and / or a carbonyl group. Preferred ^{R ib} is the same as the preferred ^{R Ib.}

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

Further, a silane monomer represented by the following formula (id) may be combined. When the silane monomer represented by the formula (id) is used, a polysiloxane containing the repeating unit (Id) can be obtained.
_{^{(R id) 2 -Si- (OR}} id ') 2 (id)
Where:
R ^{id ′} is each independently a straight-chain or branched C _1-6 alkyl, and examples include methyl, ethyl, n-propyl, isopropyl, and n-butyl. R ^{id 'is} included more in one monomer, each R ^id' may be the same or different,
R ^id each independently represents hydrogen, C _1-30 , a linear, branched or cyclic, saturated or unsaturated, aliphatic 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 unsubstituted, or fluorine, hydroxy, Or it is substituted by alkoxy. Preferred ^{R id} is the preferred ^{R Id.}

Further, a silane monomer represented by the following formula (ie) may be combined.
( ^{ORie '} ) _3- Si- ^Lie- Si- ( ^ORie' ) ₃
In the formula (ie),
R ^ie ′ is each independently a straight-chain or branched C _1-6 alkyl, and examples include methyl, ethyl, n-propyl, isopropyl, and n-butyl.
L ^{ie _{is, - (CR ie 2) n}} - or
And preferably-(CR ^ie ₂ ) _n- . here,
n is each independently an integer of 1 to 3,
R ^ie is 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 50,000 ppm based on the total mass of the composition.
Preferably, the first acid dissociation constant pKa ₁ of the monocarboxylic acid is 5.0 or less. Preferably, the first acid dissociation constant pKa ₁ of the dicarboxylic acid is 4.0 or less, more preferably 3.5 or less.

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

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

Preferably, the dicarboxylic acid is represented by formula (ii).
HOOC-L-COOH Formula (ii)
Where L is
Single bond,
C1-C6 unsubstituted alkylene, hydroxy-substituted alkylene or amino-substituted alkylene,
A substituted or unsubstituted alkenylene having 2 to 4 carbon atoms,
It is a substituted or unsubstituted alkynylene having 2 to 4 carbon atoms, or a 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 shall mean a divalent group having one or more triple bonds.

Preferably, L is
Single bond,
A hydroxy-substituted or unsubstituted alkylene having 2 to 4 carbon atoms,
Unsubstituted alkenylene having one C = C bond and having 2 to 4 carbon atoms, or unsubstituted arylene having 6 to 10 carbon atoms;
More preferably, L is a single bond, an unsubstituted alkylene having 1 to 2 carbon atoms, vinylene, hydroxyethylene, or phenylene.

  Specific examples of the dicarboxylic acid 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, and 3-aminohexanediacid And malonic acid, 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 particularly preferably a compound capable of forming a cyclic structure due to intramolecular dehydration condensation. Such dicarboxylic acids include oxalic acid, maleic acid, succinic acid, o-phthalic acid, glutaconic acid, and itaconic acid. Among them, a dicarboxylic acid having a temperature at which an intramolecular dehydration condensation reaction occurs is 100 ° C. to 250 ° C., and more preferably maleic acid, succinic acid, and oxalic acid.

  Two or more carboxylic acid compounds can 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 50,000 ppm, more preferably 300 to 30,000 ppm, further preferably, based on the total mass of the composition. Is 500 to 30,000 ppm. If it is more than 50,000 ppm, the sensitivity is lowered, which is not preferable.
When an organic developer (for example, an aqueous solution of TMAH) is used in the development step, the content of the compound (II) is preferably from 300 to 10,000 ppm, more preferably from 500 to 5,000 ppm. is there.
In the case where an inorganic developer (for example, an aqueous KOH solution) is used in the development step, the content of the compound (II) is preferably from 1,000 to 30,000 ppm, more preferably from 3,000 to 30,000 ppm. It is 10,000 ppm.

The composition according to the present invention, which contains a specific amount of a specific carboxylic acid compound, suppresses wrinkles of the cured film and has an effect of improving the smoothness of the pattern surface, but is bound by theory. We do not want to do that, but we believe that:
The positive working polysiloxane composition is coated, exposed, developed with an alkaline developer, rinsed, and cured by heating. Although the developer is washed away by rinsing, an alkali component remaining in the film, particularly on the film surface, excessively accelerates the curing reaction on the film surface.
If a process of overall exposure is performed after rinsing, excessive exposure of the curing reaction due to the overall exposure does not occur. Therefore, generation of wrinkles is suppressed.
The composition according to the present invention contains a specific amount of a specific carboxylic acid compound, so that the curing reaction is excessively accelerated by neutralizing an alkali component by an alkali developer even without a process of overall exposure. And the formation of wrinkles can be suppressed.
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 with a carboxylic acid group before heating for curing. During heating for curing, the uncured silanol groups are cured, the carboxylic acid compound is converted to an anhydride, removed from the film, and the unprotected silanol groups are cured next. It is thought that the effect of suppressing wrinkles would be higher because it would occur.
Alkaline developers are classified into organic and inorganic.Inorganic developers are smaller in molecular size than organic developers, and easily enter the film during development. The amount of acid required will also increase. Therefore, when an inorganic developer is used, the content of the carboxylic acid compound is higher.

(III) Diazonaphthoquinone derivative The composition according to the present invention comprises a diazonaphthoquinone derivative. The composition comprising the diazonaphthoquinone derivative forms a positive image in which the exposed portions become soluble in an alkaline developer and are removed by development. That is, the composition according to the present invention generally functions as a positive photoresist composition. The diazonaphthoquinone derivative of the present invention is a compound in which naphthoquinonediazidosulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group, and is not particularly limited in structure, but is preferably an ester compound with a compound having one or more phenolic hydroxyl groups. Preferably, there is. As naphthoquinonediazidesulfonic acid, 4-naphthoquinonediazidosulfonic acid or 5-naphthoquinonediazidosulfonic acid can be used. The 4-naphthoquinonediazidosulfonic acid ester compound is suitable for i-line exposure because it has absorption in the i-line (wavelength 365 nm) region. Further, the 5-naphthoquinonediazidosulfonic acid ester compound has an absorption in a wide wavelength range, and is therefore suitable for exposure to a wide range of wavelengths. It is preferable to select a 4-naphthoquinonediazidosulfonic acid ester compound or a 5-naphthoquinonediazidosulfonic acid ester compound depending on the wavelength to be exposed. A mixture of a 4-naphthoquinonediazidesulfonic acid ester compound and a 5-naphthoquinonediazidosulfonic acid ester compound can also be used.

  The compound having a phenolic hydroxyl group is not particularly limited. For example, bisphenol A, BisP-AF, BisOTBP-A, Bis26BA, 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, manufactured by Honshu Chemical Industry Co., Ltd.) Is mentioned.

  The optimum amount of the diazonaphthoquinone derivative added depends on the esterification rate of naphthoquinonediazidosulfonic acid, or the physical properties of the polysiloxane used, and the required sensitivity / dissolution contrast between the exposed part and the unexposed part. The amount is 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 addition amount of the diazonaphthoquinone derivative is less than 1 part by mass, the dissolution contrast between the exposed and unexposed portions is too low, and does not have a practical photosensitivity. Further, in order to obtain a better dissolution contrast, the amount is preferably 2 parts by mass or more. On the other hand, when the addition amount of the diazonaphthoquinone derivative is more than 20 parts by mass, whitening of the coating film occurs due to poor compatibility between the polysiloxane and the quinonediazide compound, and coloring due to decomposition of the quinonediazide compound which occurs at the time of heat curing is remarkable. , The colorless transparency of the cured film may decrease. In addition, the heat resistance of the diazonaphthoquinone derivative is inferior to that of polysiloxane, so that when added in a large amount, thermal decomposition may cause deterioration of the electrical insulation of the cured film and release of gas, resulting in a problem in a post-process. There is. Further, the resistance of the cured film to a photoresist stripping solution containing monoethanolamine or the like as a main component may be reduced.

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

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

  The composition according to the present invention essentially comprises the above-mentioned (I) to (IV), but may further comprise other compounds as required. The materials that can be combined are described below. The components other than (I) to (IV) in the whole composition are 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 can 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. These are preferably selected according to a polymerization reaction or a cross-linking reaction used in a cured film production process.
In the present invention, the photoacid generator does not include the above-mentioned diazonaphthoquinone derivative (III).

  The optimum amount of these contents varies depending on the type and amount of the active substance generated by decomposition, the required sensitivity, the dissolution contrast between the exposed and unexposed parts, and the pattern shape. The amount is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 5 parts by mass with respect to parts by mass. When the addition amount is less than 0.1 parts by mass, the amount of the generated acid or base is too small, so that pattern dripping is likely to occur. On the other hand, when the addition amount is more than 10 parts by mass, cracks are generated in the formed cured film, and coloring due to decomposition thereof may be remarkable, so that the colorless transparency of the cured film may be reduced. . In addition, when the added amount is large, thermal decomposition may cause deterioration of the electrical insulation of the cured product and release of gas, which may cause a problem in a subsequent process. Further, the resistance of the cured film to a photoresist stripping solution containing monoethanolamine or the like as a main component may be reduced.

In the present invention, a photoacid generator or a photobase generator refers to a compound that generates an acid or a base by causing bond cleavage upon exposure. The generated acid or base is considered to contribute to the polymerization of the polysiloxane. Here, examples of the light include visible light, ultraviolet light, infrared light, X-ray, electron beam, α-ray, and γ-ray.
The photoacid generator or photobase generator is preferably not an imagewise exposure for projecting a pattern (hereinafter, referred to as the first exposure), but generates an acid or a base during the subsequent overall exposure. It is preferable that the absorption at the wavelength at the first exposure is small. For example, when the first exposure is performed with the g-line (peak wavelength 436 nm) and / or the h-line (peak wavelength 405 nm) and the wavelength at the time of the second exposure is set as the g + h + i line (peak wavelength 365 nm), a photoacid generator is used. Alternatively, the photobase generator preferably has a larger absorbance at a wavelength of 365 nm than an absorbance at a wavelength of 436 nm and / or 405 nm.
Specifically, the ratio of absorbance at a wavelength of 365 nm / absorbance at a wavelength of 436 nm or absorbance at a wavelength of 365 nm / absorbance at a wavelength of 405 nm is preferably 2 or more, more preferably 5 or more, still more preferably 10 or more, and most preferably Preferably it is 100 or more.
Here, the ultraviolet-visible absorption spectrum is measured using dichloromethane as a solvent. The measuring device is not particularly limited, and examples thereof include a Cary 4000 UV-Vis spectrophotometer (manufactured by Agilent Technologies).

  The photoacid generator can be arbitrarily selected from commonly used ones, for example, diazomethane compounds, triazine compounds, sulfonic esters, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, ammonium salts, phosphonium salts And sulfonimide compounds.

The photoacid generators that can be specifically used, including those described above, include 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium methanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium- p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoro Rate, 4-phenylthiophenyldiphenylhexafluorophosphonate, triphenylsulfonium methanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-phenylthio Phenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate, N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, 5-norbornene-2,3- Dicarboxyimidyl triflate, 5-norbornene-2,3-dicarboximidyl-p-toluenesulfonate, 4-phenyl Ophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (nonafluorobutylsulfonyloxy) naphthylimide and the like.
Also, 5-propylsulfonyloxyimino-5H-thiophen-2-ylidene- (2-methylphenyl) acetonitrile, 5-octylsulfonyloxyimino-5H-thiophen-2-ylidene- (2-methylphenyl) acetonitrile, 5- Campphorsulfonyloxyimino-5H-thiophen-2-ylidene- (2-methylphenyl) acetonitrile, 5-methylphenylsulfonyloxyimino-5H-thiophen-2-ylidene- (2-methylphenyl) acetonitrile, etc. Since it has absorption in the wavelength region, its use should be avoided if it is not desired to have h-line absorption.

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 containing an amide anion, a methide anion, a borate anion, a phosphate anion, a sulfonate anion, or a carboxylate anion as the anion can also be used.

In the present invention, a photothermal acid generator or a photothermal base generator is a compound that changes its chemical structure by exposure but does not generate an acid or a base, and then undergoes bond cleavage by heat to generate an acid or a base. Means Of these, photothermal base generators are preferred. Examples of the photothermal base generator include those represented by the following formula (II), and more preferably hydrates or solvates thereof. The compound represented by the formula (II) is inverted to the cis-type upon exposure and becomes unstable, so that the decomposition temperature is lowered, and a base is generated in a subsequent step even if the baking temperature is about 100 ° C.
The photothermal base generator does not need to be adjusted to the absorption wavelength of the diazonaphthoquinone derivative.
Here, x is an integer of 1 or more and 6 or less,
R ^{a ′ to} R ^{f ′} each independently represent hydrogen, halogen, hydroxy, mercapto, sulfide, silyl, silanol, nitro, nitroso, sulfino, sulfo, sulfonato, phosphino, phosphinyl, phosphono, phosphonate, amino, ammonium, substituted A C _1-20 aliphatic hydrocarbon group which may contain a group, a C _6-22 aromatic hydrocarbon group which may contain a substituent, a C _1-20 alkoxy group which may contain a substituent, or a substituent. _C6-20 aryloxy which may be contained.

Among them, R ^{a ′ to} R ^{d ′} are particularly 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. Is preferred. R 1 ^{'~R 4'} 2 or more of may be bonded to form a cyclic structure. At this time, the cyclic structure may include a hetero atom.
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 of C _x H _{2X represented} by the formula (II). It may further have a C _1-20 , especially C _1-6 aliphatic hydrocarbon group which may contain a substituent different from OH.

It is preferable that R ^{a ′ to} R ^{d ′} be appropriately selected depending on the exposure wavelength to be used. For display applications, for example, unsaturated hydrocarbon bonding functional groups such as vinyl and alkynyl that shift the absorption wavelength to g, h, and i lines, and alkoxy and nitro are used, and methoxy and ethoxy are particularly preferable.

Specifically, the following are mentioned.

In the present invention, a thermal acid generator or a thermal base generator refers to a compound that generates an acid or a base by causing bond cleavage by heat. It is preferred that these do not generate an acid or a base or generate only a small amount by heat during prebaking after application of the composition.
Examples of the thermal acid generator include various aliphatic sulfonic acids and salts thereof, citric acid, acetic acid, various aliphatic carboxylic acids and salts thereof such as maleic acid, benzoic acid, various aromatic carboxylic acids such as phthalic acid and the like. Salts and esters that generate organic acids, such as salts, aromatic sulfonic acids and ammonium salts thereof, various amine salts, aromatic diazonium salts, and phosphonic acids and salts thereof, can be given. Among the thermal acid generators, a salt composed of an organic acid and an organic base is particularly preferred, and a salt composed of a sulfonic acid and an organic base is more preferred. Preferred sulfonic acids include p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, and the like. These acid generators can be used alone or in combination.

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

  Other additives include a surfactant, a developer dissolution accelerator, a scum remover, an adhesion enhancer, a polymerization inhibitor, an antifoaming agent, and a sensitizer.

  Surfactants are preferred because they can improve coatability. Examples of the surfactant that can be used in the polysiloxane composition according to the present invention include a nonionic surfactant, an anionic surfactant, and an amphoteric surfactant.

  Examples of the nonionic surfactant include polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene cetyl ether, polyoxyethylene fatty acid diester, and polyoxyethylene fatty acid monoester. , Polyoxyethylene polyoxypropylene block polymers, acetylene alcohol, acetylene glycol, acetylene alcohol derivatives such as polyethoxylate of acetylene alcohol, acetylene glycol derivatives such as polyethoxylate of acetylene glycol, fluorine-containing surfactants such as Florard (products Name, manufactured by 3M Co., Ltd.), Mega Fac (product name, manufactured by DIC Corporation), Sulfuron (product name, manufactured by Asahi Glass Co., Ltd.), The organosiloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the acetylene glycol include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, and 2,4. 7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, 2,5 -Dimethyl-2,5-hexanediol and the like.

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

  Further, examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, amide amidopropylhydroxysulfone betaine and the like.

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

  Further, a sensitizer can be added as needed. Coumarins, ketocoumarins and their derivatives, acetophenones, and sensitizing dyes such as pyrylium salts and thiopyrylium salts, and compounds containing an anthracene skeleton.

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

  As a polymerization inhibitor, an ultraviolet absorber can be added in addition to nitrone, nitroxide radical, hydroquinone, catechol, phenothiazine, phenoxazine, hindered amine and derivatives thereof. The addition amount is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the total mass of the polysiloxane.

As the antifoaming agent, an alcohol _{(C 1 ~ 18),} higher fatty acids such as oleic acid and stearic acid, higher fatty acid esters such as glycerol monolaurate, polyethylene glycol (PEG) (Mn200~10,000), polypropylene glycol ( Examples thereof include polyethers such as PPG) (Mn 200 to 10,000), silicone compounds such as dimethyl silicone oil, alkyl-modified silicone oil and fluorosilicone oil, and organosiloxane surfactants. These can be used alone or in combination of two or more, and the addition amount is preferably 0.1 to 3 parts by mass based on 100 parts by mass of the total mass of the polysiloxane.

  The adhesion enhancer has an effect of preventing a pattern from peeling off due to stress applied after curing when a cured film is formed using the composition according to the present invention. As the adhesion enhancer, imidazoles, silane coupling agents and the like are preferable.

  These other additives can be used alone or in combination of two or more, and the addition amount 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 acrylic polymerized polysiloxane. Parts by weight.

<Production method of cured film>
The cured film according to the present invention comprises the following steps:
(1) applying the composition according to the present invention to a substrate to form a composition layer;
(2) exposing the composition layer,
(3) developing with an alkali developer to form a pattern, and (4) heating the obtained pattern.
It is as follows if it demonstrates in order of a process.

(1) Coating Step First, the above-described composition is applied to a substrate. The coating film of the composition in the present invention can be formed by any method conventionally known as a method for applying a photosensitive composition. Specifically, it can be arbitrarily selected from dip coating, roll coating, bar coating, brush coating, spray coating, doctor coating, flow coating, spin coating, slit coating, and the like.
As a substrate on which the composition is applied, a suitable substrate such as a silicon substrate, a glass substrate, a resin film, or the like can be used. Various semiconductor elements and the like may be formed on these substrates as needed. If the substrate is a film, gravure coating can also be used. If desired, a drying step can be separately provided after the coating. In addition, the coating step can be repeated one or more times as necessary to make the thickness of the formed coating film desired.

  After forming the coating film by applying the composition, it is preferable to dry the coating film and to pre-bake (preheat) the coating film in order to reduce the residual amount of the solvent in the coating film. . The pre-bake step is generally performed at a temperature of 70 to 150 ° C., preferably 90 to 120 ° C., for 10 to 300 seconds, preferably 30 to 120 seconds when using a hot plate, and for 1 to 30 minutes when using a clean oven. be able to.

(2) Exposure Step After forming the coating film, the coating film surface is irradiated with light. Note that this step is sometimes referred to as first exposure in order to distinguish this step from the overall exposure described below. As a light source used for light irradiation, any light source conventionally used in a pattern forming method can be used. Examples of such a light source include high-pressure mercury lamps, low-pressure mercury lamps, lamps such as metal halides and xenon, laser diodes, and LEDs. Ultraviolet rays such as g-rays, h-rays and i-rays are usually used as the irradiation light. Except for ultra-fine processing such as a semiconductor, it is common to use light (high-pressure mercury lamp) of 360 to 430 nm in patterning of several μm to several tens μm. Above all, in the case of a liquid crystal display device, light of 430 nm is often used. As described above, in such a case, it is advantageous to combine a sensitizing dye with the composition according to the present invention.
The energy of the irradiation light, depending on the thickness of the light source and the coating film, generally 5~2,000mJ / cm ^2, preferably a 10~1,000mJ / cm ^2. If the irradiation light energy is lower than 5 mJ / cm ² , a sufficient resolution may not be obtained. On the other hand, if the irradiation light energy is higher than 2,000 mJ / cm ² , overexposure may occur and halation may occur.

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

(3) Development Step After exposure, the coating film is developed. As a developer used in the development, any developer conventionally used for developing a photosensitive composition can be used. The developer includes an organic developer and an inorganic developer. Examples of the organic developer include a TMAH aqueous solution, a tetrabutylammonium hydroxide aqueous solution, methyl isobutyl ketone, and isopropyl alcohol, and preferably a TMAH aqueous solution. And more preferably a 2.38% by mass aqueous TMAH solution. Examples of the inorganic developer include alkali metal salts, preferably aqueous potassium hydroxide, or aqueous sodium hydroxide, aqueous sodium carbonate, aqueous sodium bicarbonate, aqueous sodium silicate, aqueous sodium metasilicate, and aqueous ammonia. Particularly preferred is an aqueous solution of potassium hydroxide. When an aqueous potassium hydroxide solution is used, the concentration is preferably 0.1 to 3.0% by mass, and more preferably 0.5 to 2.0% by mass. These developers may further contain a water-soluble organic solvent such as methanol or ethanol, or a surfactant, if necessary.
The developing method can also be arbitrarily selected from conventionally known methods. Specific examples include methods such as immersion (dip) in a developer, paddle, shower, slit, cap coat, and spray. The development temperature is preferably room temperature (20 to 25C), but may be heated to 30 to 50C. The development time is preferably 15 to 180 seconds, more preferably 30 to 60 seconds. A pattern can be obtained by this development, and it is preferable that rinsing (washing) is performed after the development with the developing solution.

  The rinsing is preferably performed using water, and can be performed in the same manner as the development, and it is preferable to perform showering for 60 seconds or more.

After the development (rinse if necessary), it is general to carry out a step of overall exposure. As described above, by performing the entire surface exposure, it is possible to suppress the formation of wrinkles in the cured film. In addition, by performing the entire surface exposure, the unreacted diazonaphthoquinone derivative remaining in the film is photolyzed, and the light transparency of the film is further improved. It is preferred to do so. As an entire surface exposure method, there is a method of exposing the entire surface to about 100 to 2000 mJ / cm ² (equivalent to a wavelength of 365 nm) using an ultraviolet-visible exposure apparatus such as PLA (for example, PLA-501F manufactured by Canon Inc.).
When the composition according to the present invention is used, the wrinkles can be suppressed without performing the entire surface exposure. Therefore, when the excessive transparency is not required, the entire surface exposure need not be performed.

(4) Curing Step After the development, the obtained pattern film is cured by heating. The heating temperature in this step is not particularly limited as long as the coating film can be cured, and can be arbitrarily determined. However, if the silanol group remains, the cured film may have insufficient chemical resistance or the cured film may have a high dielectric constant. From such a viewpoint, a relatively high temperature is generally selected as the heating temperature. Specifically, it is preferable to cure by heating at 360 ° C. or less, and in order to maintain a high residual film ratio after curing, the curing temperature is more preferably 300 ° C. or less, and preferably 250 ° C. or less. Particularly preferred. On the other hand, in order to accelerate the curing reaction and obtain a sufficient cured film, the curing temperature is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, and particularly preferably 100 ° C. or higher. The heating time is not particularly limited, and is generally 10 minutes to 24 hours, preferably 30 minutes to 3 hours. The heating time is a time after the temperature of the pattern film reaches a desired heating temperature. Usually, it takes several minutes to several hours for the pattern film to reach a desired temperature from the temperature before heating.

By using the composition according to the present invention, it is possible to suppress the occurrence of wrinkles generated on the surface of the cured film in this curing step. Here, the wrinkle refers to unevenness generated near or away from the pattern portion of the cured film. FIG. 1 shows an electron micrograph of a typical wrinkle formed on the pattern surface.
The rough guide of the difference between no wrinkles (FIG. 1 (P)), small wrinkles (FIG. 1 (Q)), and large wrinkles (FIG. 1 (R)) is obtained by curing with a stylus type surface measuring device (Daektak). When the film surface which does not cover the pattern at a distance from the pattern is measured at a force of 3 mg and a distance of 1.5 cm over a period of 50 seconds, the unevenness of the surface is less than about 30 nm without wrinkles. The step is about 30 nm or more and 100 nm or less, and a large wrinkle means a step larger than 100 nm.

  The cured film thus obtained can achieve excellent flatness, electrical insulation properties, and the like. For example, a relative dielectric constant of 4 or less can be achieved. Therefore, it can be suitably used in various fields as a flattening film for various elements such as a flat panel display (FPD), an interlayer insulating film for low-temperature polysilicon, a buffer coat film for an IC chip, and a transparent protective film. Can be.

  Hereinafter, the present invention will be described more specifically 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 measured using two HLC-8220GPC high-speed GPC systems (trade name, manufactured by Tosoh Corporation) and two Super Multipore HZ-N type GPC columns (trade name, manufactured by Tosoh Corporation). . The measurement was performed using monodisperse polystyrene as a standard sample, tetrahydrofuran as a developing solvent, and analysis conditions at a flow rate of 0.6 ml / min and a column temperature of 40 ° C.

<Synthesis Example 1 (Synthesis of Polysiloxane Pa-1)>
A 2 L flask equipped with a stirrer, a thermometer, and a condenser was charged with 49.0 g of a 25% by mass aqueous TMAH solution, 600 ml of isopropyl alcohol (IPA), and 4.0 g of water, and then methyltrimethoxysilane was added to a dropping funnel. A mixed solution of 0 g, 79.2 g of phenyltrimethoxysilane, and 15.2 g of tetramethoxysilane was prepared. The mixed solution was added dropwise at 40 ° C., stirred at the same temperature for 2 hours, and neutralized by adding a 10% by mass aqueous solution of HCl. 400 ml of toluene and 600 ml of water were added to the neutralized solution, separated into two phases, and the aqueous phase was removed. Further, the resultant 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 to a solid concentration of 35% by mass.
When the molecular weight (in terms of polystyrene) of the obtained polysiloxane was measured by gel permeation chromatography, the weight average molecular weight (hereinafter sometimes abbreviated as “Mw”) was 1,700. Further, the obtained resin solution was applied to a silicon wafer by a spin coater (MS-A100 (manufactured by Mikasa)) so that the film thickness after prebaking was 2 μm, and after the prebaking, the dissolution rate in a 2.38% by mass TMAH aqueous solution ( Hereinafter, it may be abbreviated as “ADR”.) Was 1,200 ° / sec.

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

<Synthesis Example 3 (Synthesis of Polysiloxane Pb-1)>
A 2 L flask equipped with a stirrer, a thermometer, and a condenser was charged with 102 g of a 25% by mass aqueous TMAH solution, 600 ml of IPA, and 4.0 g of water, and then 68.0 g of methyltrimethoxysilane and phenyltrimethoxysilane were added to a dropping funnel. A mixed solution of 2 g and 68.1 g of bis (triethoxysilyl) methane was prepared. The mixed solution was added dropwise at 40 ° C., stirred at the same temperature for 2 hours, and neutralized by adding a 10% by mass aqueous solution of HCl. 400 ml of toluene and 600 ml of water were added to the neutralized solution, separated into two phases, and the aqueous phase was removed. Further, the resultant 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 to 35% by mass.
The Mw of the obtained polysiloxane Pb-1 was 6,500, and the ADR with respect to the 2.38% by mass aqueous TMAH solution after prebaking was 3,300 ° / sec.

<Synthesis Example 4 (Synthesis of Polysiloxane Pb-2)>
A 2 L flask equipped with a stirrer, a thermometer, and a cooling tube 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 68.0 g of methyltrimethoxysilane and phenyl in a dropping funnel. 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., stirred at the same temperature for 2 hours, and neutralized by adding a 10% by mass aqueous solution of HCl. 400 ml of toluene and 600 ml of water were added to the neutralized solution, separated into two phases, and the aqueous phase was removed. Further, the resultant 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 to 35% by mass.
The Mw of the obtained polysiloxane was 9,000, and the ADR with respect to the 2.38% by mass aqueous TMAH solution after prebaking was 2,600 ° / sec.
The ADR of the entire polysiloxane with respect to the 2.38% by mass TMAH aqueous solution after prebaking was as follows.
ADR of polysiloxane Pa-1: Pa-2: Pb-1 = 40: 10: 50 = 1,800 ° / sec.ADR of polysiloxane Pa-1: Pa-2: Pb-2 = 40: 10: 50 = 1 , 600 ° / second ADR of polysiloxane Pa-1: Pa-2 = 90: 10 = 900 ° / second

<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 below and the balance being PGMEA were prepared.
In the table,
Diazonaphthoquinone derivative: 2.0 mol modified diazonaphthoquinone of 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol Surfactant: KF- 53, manufactured by Shin-Etsu Chemical Co., Ltd.
"-" Means that the addition amount was zero.

<Evaluation of wrinkles>
The state of wrinkles on the surface after curing, which was exposed at the optimum exposure amount obtained in the sensitivity evaluation, was visually observed and evaluated. The evaluation criteria are as follows, and the evaluation results are as described in Table 1.
A: No wrinkles were found on the surface B: Small wrinkles were found on the surface, but 80% or more of the portions were not wrinkled C: Small wrinkles were found on the surface, and 80 wrinkles were not found %: D: large wrinkles were observed on the surface. Typical patterns of a pattern (P) in which no wrinkles were observed, a pattern (Q) with small wrinkles, and a pattern (R) with large wrinkles. An electron micrograph is shown in FIG.

<Evaluation of pattern shape>
The shape of the cured pattern exposed at the optimal exposure amount obtained in the sensitivity evaluation was observed and evaluated using a scanning electron microscope (SEM). The evaluation criteria are as follows, and the evaluation results are as described in Table 1.
X: The corners of the formed pattern were largely 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 W smaller than the mask size: no pattern was formed. Note that FIG. 2 shows typical electron micrographs corresponding to each of the above shapes.

<Evaluation of sensitivity>
The compositions of Examples 101 to 105 were applied by spin coating so that the film thickness after prebaking was 1.6 μm. The obtained coating film was prebaked at 110 ° C. for 90 seconds to evaporate the solvent. Thereafter, a contact hole having a size of 5 μm was subjected to pattern exposure at an optimum exposure amount using a g + h-line mask aligner (FX-604F, manufactured by Nikon Corporation). After the exposure, paddle development was performed for 70 seconds using a 2.38% by mass aqueous solution of TMAH, followed by rinsing with pure water for 60 seconds and drying. Then, after heating in the air at 180 ° C. for 20 minutes, it was further heated at 230 ° C. for 20 minutes to be cured.
Here, the exposure amount at which the bottom width of the contact hole after curing when patterned with a 5-micron mask becomes 5 microns was defined as the optimal exposure amount.
In the compositions of Examples 101 to 105, the exposure amount less than 500 mJ was the optimum exposure amount, and the sensitivity was sufficient for practical use.
On the other hand, using the same composition as in Example 101 except that the maleic acid content was 80,000 ppm, the optimum exposure amount was determined in the same manner as described above. Even when the exposure amount was increased, no pattern could be formed.

<Examples 201 and 202 and Comparative Examples 201 to 204 (Preparation of positive photosensitive polysiloxane composition)>
Positive photosensitive polysiloxane compositions of Examples 201 and 202 and Comparative Examples 201 to 204 containing the compounds shown in Table 2 below and the balance being PGMEA were prepared.
In the table,
Diazonaphthoquinone derivative: 2.0 mol modified diazonaphthoquinone of 4,4 '-(1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol Surfactant: KF- 53, manufactured by Shin-Etsu Chemical Co., Ltd.
"-" Means that the addition amount was zero.

  Each composition was applied by spin coating so that the film thickness after prebaking was 1.6 μm. The obtained coating film was prebaked at 110 ° C. for 90 seconds to evaporate the solvent. Thereafter, a contact hole having a size of 5 μm was subjected to pattern exposure at 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 1.0% by mass aqueous KOH solution, followed by rinsing with pure water for 60 seconds and drying. Then, after heating in the air at 180 ° C. for 20 minutes, it was further heated at 230 ° C. for 20 minutes to cure.

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

Claims (13)

A positive photosensitive polysiloxane composition,
(I) polysiloxane,
(II) 200 to 50,000 ppm of a carboxylic acid compound which is a monocarboxylic acid or a dicarboxylic acid, based on the total mass of the composition,
(III) Ri name contains diazonaphthoquinone derivatives, and (IV) a solvent,
The polysiloxane has the following formula (Ia):
(Where
R ^Ia represents hydrogen, C _1-30 , linear, branched or cyclic, saturated or unsaturated, aliphatic 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 methylene is replaced with oxy, amino, imino, or carbonyl, provided that R ^la is hydroxy, A repeating unit represented by not alkoxy), and
The following formula (Ie):
(Where
L ^{Ie is-} (CR ^Ie ₂ ) _n -or
And
Here, n is an integer of 1 to 3,
R ^Ie each independently represents hydrogen, methyl, or ethyl)
A positive photosensitive polysiloxane composition comprising a repeating unit represented by the formula: The composition according to 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. The monocarboxylic acid has the formula (i):
R ⁱ -COOH Formula (i)
Wherein R ⁱ is hydrogen or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.
And the dicarboxylic acid is represented by the formula (ii):
HOOC-L-COOH Formula (ii)
(Where L is
Single bond,
C1-C6 unsubstituted alkylene, hydroxy-substituted alkylene or amino-substituted alkylene,
A substituted or unsubstituted alkenylene having 2 to 4 carbon atoms,
A substituted or unsubstituted alkynylene having 2 to 4 carbon atoms, or a substituted or unsubstituted arylene having 6 to 10 carbon atoms)
The composition according to claim 1, represented by the formula:   The composition according to any one of claims 1 to 3, wherein the carboxylic acid compound is a dicarboxylic acid.   The composition according to any one of claims 1 to 4, wherein the dicarboxylic acid can have a cyclic structure by intramolecular dehydration condensation.   The composition according to any one of claims 1 to 5, wherein the content of the carboxylic acid compound is 300 to 30,000 ppm based on the total mass of the composition. The polysiloxane has the following formula (Ic):
The composition according to any one of claims 1 to 6 , further comprising a repeating unit represented by the formula: R ^Ia is a C _{3 to 20,} saturated or unsaturated, cyclic aliphatic hydrocarbon group or an aromatic hydrocarbon group, A composition according to any one of claims 1 to 7. The following steps:
(1) applying the composition according to any one of claims 1 to 8 to a substrate to form a composition layer;
(2) exposing the composition layer,
(3) A method for producing a cured film, comprising: developing with an alkali developer to form a pattern; and (4) heating the obtained pattern. The method according to claim 9 , wherein the method does not include a step of performing an overall exposure before the step (4). The method according to claim 9 , wherein the alkaline developer is an organic developer. The method according to claim 9 , wherein the alkaline developer is an inorganic developer. A method for manufacturing an electronic device , comprising a cured film manufactured by the method according to claim 9 .