JP2007031697A - Composition for forming coating film for alkali treatment, coating film for alkali treatment, method for producing the same, layered product, antireflection film and electronic part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for forming a coating film for alkali treatment capable of forming a coating film for alkali treatment having excellent alkali treatment resistance and excellent adhesiveness to the adjacent layer, a coating film for alkali treatment produced by using the composition for forming a coating film for alkali treatment, a method for forming the film, a layered product, an antireflection film and an electronic part. <P>SOLUTION: The composition for forming a coating film to be subjected to alkali treatment contains (a) a siloxane resin, (b) a solvent dissolving the component (a), and (c) a cure acceleration catalyst. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an alkali-treated film-forming composition, an alkali-treated film and a method for producing the same, a laminate, an antireflection film, and an electronic component.

  A film formed by a sol-gel reaction and using silica or the like as a raw material generally has low alkali treatment resistance as described in Patent Document 1 below. For this reason, it has been difficult to perform the alkali treatment on a substrate or the like where the film is exposed or the film is exposed by the alkali treatment even though it is not exposed before the alkali treatment. .

  For example, the coating film is used as an antireflection film. In this case, however, there is a problem that the coating film deteriorates in an alkali treatment performed when the antireflection film is attached to the deflecting plate. In addition, when a metal layer is formed on a substrate made of such a film and the metal layer is patterned with an alkali using a resist, there is a problem that the substrate is deteriorated.

On the other hand, Patent Document 1 below describes that alkali treatment resistance can be improved by combining a silica matrix with a fluorine-containing organic polymer, but these must be combined in consideration of mutual interaction. Has been. And in patent document 1, the coating (antireflection film) which is excellent in alkali processing tolerance by using the silica monomer which has the alkoxy group by which the substituent containing a polymerizable ethylenically unsaturated group was introduce | transduced as a raw material of a silica matrix. ) Is obtained. Patent Document 2 below discloses an antireflection film having a composition in which a polysiloxane resin having a substituent containing fluorine and colloidal silica are combined.
Japanese Patent Laid-Open No. 2002-243907 JP 2000-121803 A

  However, when a fluorine-containing organic polymer is combined or a fluorine-containing silica monomer is used as in the above prior art, the adhesion of the resulting coating to adjacent layers tends to be insufficient.

  Therefore, the present invention has been made in view of such circumstances, and has an alkali-treated film formation capable of forming an alkali-treated film having excellent alkali treatment resistance and excellent adhesion to an adjacent layer. It is an object to provide a composition for use. Another object of the present invention is to provide an alkali-treated film using the composition for forming an alkali-treated film, a method for producing the same, a laminate, an antireflection film, and an electronic component.

  It is estimated that the improvement effect of alkali treatment resistance by the combination of the fluorine-containing organic polymer as in the above prior art and the use of the fluorine-containing silica monomer is caused by the water repellency effect by fluorine atoms, fluorine-containing substituents or resins. Is done.

  On the other hand, the present inventors have examined a method for improving the alkali treatment resistance of a film using silica or the like as a raw material other than the conventional method using fluorine, and as a result, a raw material for forming the film As a result, the inventors have found a new finding that by using a composition for forming an alkali-treated film containing a specific siloxane resin, the mechanical strength and density of the film can be increased to improve resistance to alkali treatment. That is, it has been conceived that the alkali treatment resistance can be improved by increasing the density of the film made of silica or the like as a raw material and suppressing the penetration of the chemical solution.

  That is, the present invention is (1) a composition for forming an alkali-treated film to be subjected to an alkali-treated film, which comprises (a) component: a siloxane resin and (b) component: (a And (c) a solvent capable of dissolving the component, and (c) a component: a curing accelerating catalyst.

  Since the composition for forming an alkali-treated film of the present invention contains the component (a), an alkali-treated film mainly composed of a siloxane resin is formed. Moreover, since the said composition for alkali-treated film formation contains (b) component, when the said (b) component melt | dissolves (a) component, the composition for alkali-treated film formation can be apply | coated uniformly. In addition, since the composition for forming an alkali-treated film contains the component (c), curing is promoted in a state where the composition for forming an alkali-treated film is uniformly applied. As a result, the alkali-treated film obtained from the above-mentioned composition for forming an alkali-treated film has a dense structure, and it is very difficult for the chemical solution to enter. For this reason, the alkali-treated film obtained from the composition for forming an alkali-treated film of the present invention has excellent alkali treatment resistance.

  In addition, such an alkali-treated film can exhibit excellent alkali treatment resistance by taking such a dense structure, and it is not necessary to introduce excess fluorine as in the above-described prior art. It has sufficient adhesiveness to.

  Here, the alkali includes, for example, an alkali metal hydroxide aqueous solution. The alkali-treated film obtained from the alkali-treated film-forming composition of the present invention can exhibit excellent alkali treatment resistance when the alkali-treated film is exposed to an alkali metal hydroxide aqueous solution.

［式（１）中、Ｒ^１はＨ原子若しくはＦ原子、又は、Ｂ原子、Ｎ原子、Ａｌ原子、Ｐ原子、Ｓｉ原子、Ｇｅ原子若しくはＴｉ原子を含む基、又は炭素数１〜２０の有機基を示し、Ｘは加水分解性基を示し、ｎは０〜２の整数を示す。ただし、Ｒ^１又はＸが複数存在する場合、これらはそれぞれ同一でも異なっていてもよい。］ In the composition for forming an alkali-treated film, the siloxane resin is preferably obtained by hydrolytic condensation of a raw material component containing a silicon compound represented by the following general formula (1).

[In the formula (1), R ¹ represents an H atom or an F atom, or a group containing a B atom, an N atom, an Al atom, a P atom, a Si atom, a Ge atom or a Ti atom, or an organic compound having 1 to 20 carbon atoms. Represents a group, X represents a hydrolyzable group, and n represents an integer of 0 to 2. However, when two or more R < ¹ > or X exists, these may be same or different, respectively. ]

  When the siloxane resin is a compound represented by the above general formula (1), the composition for forming an alkali-treated film is more excellent in alkali treatment resistance and adhesion.

  In the siloxane resin, H atom, F atom, B atom, N atom, Al atom, P atom, Si atom, Ge atom bonded to Si atom per mole of Si atoms constituting the siloxane bond. The total content ratio M of atoms selected from the group consisting of atoms, Ti atoms and C atoms is preferably less than 1.0 mol, more preferably 0.55 to 0.90 mol, and 0.60 It is more preferable that it is -0.80 mol, and it is still more preferable that it is 0.62-0.75 mol. By satisfying these conditions, it becomes easy to achieve both excellent alkali treatment resistance and adhesion.

In the silicon compound represented by the general formula (1), the group represented by R ^{1 includes} an H atom, or a B atom, an N atom, an Al atom, a P atom, a Si atom, a Ge atom, or a Ti atom. It is preferable that it is a group or a C1-C20 organic group, and does not contain F atom. Among these, it is more preferable that the group represented by R ¹ is a methyl group. Thereby, the adhesiveness with respect to the adjacent layer of the to-be-alkali-treated film obtained can be obtained still better.

  In the composition for forming an alkali-treated film, the component (b) is preferably an organic solvent containing at least one aprotic solvent. If it carries out like this, the composition for alkali-treated film formation in which the siloxane resin which is (a) component was fully melt | dissolved or disperse | distributed in a solvent comes to be obtained. According to such a composition for forming an alkali-treated film, an alkali-treated film having a uniform and high density and further excellent alkali treatment resistance can be obtained.

  More specifically, the aprotic solvent is preferably at least one solvent selected from the group consisting of ether solvents, ether acetate solvents, ester solvents, and ketone solvents. The aprotic solvent preferably has a boiling point of 80 to 180 ° C. By using these solvents, it becomes easier to obtain an alkali-treated film having a uniform thickness.

  In the composition for forming an alkali-treated film, the curing accelerating catalyst as component (c) is preferably an onium salt, and more preferably an ammonium salt. By including such a curing accelerating catalyst, the composition for forming an alkali-treated film is rapidly and uniformly cured, and a denser film can be obtained. In addition, the composition for forming an alkali-treated film having such a configuration can improve the stability of the composition itself, and can further improve the electrical characteristics and mechanical characteristics of the alkali-treated film.

  In the composition for forming an alkali-treated film of the present invention, the siloxane resin is more preferably one that can be cured by heat or radiation. In this case, the adhesiveness to the substrate is further improved by forming a chemical bond with the substrate or the like in curing during the formation of the alkali-treated film.

  The method for producing an alkali-treated film of the present invention is a method for producing an alkali-treated film that is exposed to an alkali treatment, and the above-mentioned composition for forming an alkali-treated film is applied on a substrate and applied. After the film is formed and the solvent contained in the coating film is removed, the coating film is baked at a heating temperature of 200 to 500 ° C.

  According to the above-mentioned method for producing an alkali-treated film, since the above-described composition for forming an alkali-treated film is used, an alkali-treated film that is dense and excellent in alkali treatment resistance can be obtained. Moreover, according to this manufacturing method, an alkali-treated film can be easily obtained by baking the composition for forming an alkali-treated film of the present invention formed into a film.

  Furthermore, this invention provides the to-be-alkali-treated film obtained by the manufacturing method of the said invention. Such an alkali-treated film is formed from the above-described composition for forming an alkali-treated film of the present invention, and therefore has excellent alkali treatment resistance and adhesion to an adjacent layer.

  The alkali-treated film of the present invention preferably has a refractive index of 1.42 or less determined at ellipsometric wavelength of 633 nm. The relative dielectric constant is more preferably 4.0 or less. Furthermore, the Young's modulus measured by the nanoindentation method is more preferably 5 GPa or more. Furthermore, the transmittance of light of 300 to 800 nm is more preferably 90% or more. The alkali-treated film having these characteristics has extremely excellent alkali treatment resistance while maintaining sufficient adhesion to adjacent layers.

  The present invention also provides a laminate comprising a substrate and the alkali-treated film of the present invention provided on the substrate. Such a laminate can be used for various applications by changing the configuration of the substrate. For example, it can be applied as a transparent substrate by using a substrate made of a transparent material. The present invention also provides an antireflection film comprising a substrate and the alkali-treated film of the present invention provided on the substrate. Such an antireflection film can also be applied as an antireflection film for a display or the like. Furthermore, the present invention provides an electronic component comprising a substrate and the alkali-treated film of the present invention provided on the substrate. Such an electronic component can be applied as an electronic component constituting an electronic device such as a semiconductor device.

  ADVANTAGE OF THE INVENTION According to this invention, while having the outstanding alkali treatment tolerance, the composition for alkali treatment film formation which can form the alkali treatment film which has the outstanding adhesiveness with respect to an adjacent layer can be provided. Further, according to the present invention, it is possible to provide an alkali-treated film using the composition for forming an alkali-treated film, a method for producing the same, a laminate, an antireflection film, and an electronic component.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. In the drawings, positional relationships such as up, down, left and right are based on the positional relationships shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

[Alkaline treated coating]
First, the alkali-treated film obtained from the composition for forming an alkali-treated film according to the embodiment of the present invention will be described.

  The alkali-treated film (silica-based film) according to this embodiment has excellent alkali treatment resistance. Here, the alkali treatment resistance refers to resistance to treatment with an alkaline treatment liquid, and indicates a characteristic that hardly causes deterioration when the treatment liquid comes into contact. Examples of the alkaline treatment liquid include an aqueous solution of an alkali metal hydroxide. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, Examples include francium hydroxide. The alkali-treated film according to the present embodiment can exhibit more excellent alkali treatment resistance when the alkali-treated film is exposed to an alkali treatment liquid when the alkali treatment liquid is an alkali metal hydroxide aqueous solution.

  Moreover, the density | concentration of the alkali metal hydroxide aqueous solution in evaluation of alkali processing tolerance is generally 0.1-20 weight%, Preferably it is 1-20 weight%, More preferably, it is 5-10 weight%. Further, the aqueous solution can be heated and used as necessary.

  The alkali treatment resistance of the alkali treatment coating can be confirmed, for example, as follows.

(1) First, an alkali-treated film is formed, and its film thickness and refractive index are measured. Specifically, the composition for forming an alkali-treated film is placed in a 2 mL plastic syringe, and a 0.20 μm pore size filter made of PTFE (polytetrafluoroethylene) is attached to the tip. 5 mL is dropped on a 5-inch silicon wafer, and a coating film is formed by spin coating. In the formation of the coating film, the rotation speed is adjusted so that the film thickness of the coating film after curing is 225 ± 25 nm.

  Next, using a hot plate, the organic solvent in the coating film was removed at 250 ° C. over 3 minutes, and then the organic solvent was used in a quartz tube furnace in which the oxygen concentration was controlled at around 100 ppm at 350 ° C. over 30 minutes. The coating film after removal is cured to obtain an alkali-treated film. Then, the obtained alkali-treated film is irradiated with a He—Ne laser having a wavelength of 633 nm with an ellipsometer L116B manufactured by Gardner, and the film thickness and refractive index of the alkali-treated film are obtained from the phase difference caused by the irradiation. .

(2) Next, the silicon wafer on which the alkali-treated film is formed is immersed in a 10 wt% potassium hydroxide (KOH) aqueous solution heated to 50 ° C. for 10 minutes, and then the silicon wafer is washed with pure water. Then spin dry.

(3) Thereafter, the film thickness and refractive index of the alkali-treated film after immersion in the KOH aqueous solution are determined in the same manner as in the above method (1). And the to-be-alkali-treated film whose film thickness difference before and after immersion in the KOH aqueous solution is 50 nm or less and whose change in refractive index is 0.06 or less is determined to have good alkali treatment resistance.

  As the alkali-treated film, a film having a film thickness difference of preferably 30 nm or less, more preferably 20 nm or less, and even more preferably 10 μm or less is preferable because the alkali treatment resistance is further improved. Such an alkali-treated film having a film thickness difference exceeding 50 nm is not preferable from the viewpoint that it is difficult to control the film thickness. Further, the difference in refractive index of the alkali-treated film is preferably 0.03 or less, more preferably 0.01 or less, and further preferably 0.006 or less. It is considered that the alkali-treated film having this refractive index difference exceeding 0.06 is extremely deteriorated by the alkali treatment.

  When the alkali-treated film is used as an antireflection film, the refractive index is preferably 1.42 or less, more preferably 1.41 or less, and even more preferably 1.40 or less. When the refractive index exceeds 1.42, the function as an antireflection film tends to be insufficient. The refractive index can be measured by the same method as described above. Note that the alkali-treated film may not have such a refractive index when used for purposes other than the antireflection film.

Further, when used as an insulating film, the alkali-treated film has a relative dielectric constant of preferably 4.0 or less, more preferably 3.6 or less, and further preferably 3.5 or less. It is even more preferably 4 or less, particularly preferably 3.3 or less, and extremely preferably 3.0 or less. If the relative permittivity of the coating film to be treated with alkali exceeds 4.0, it will have a dielectric constant equivalent to that of a normal SiO ₂ film, and the inter-wiring capacity cannot be reduced sufficiently, making it difficult to use as an insulating film. It tends to be. In addition, when using a to-be-alkali-treated film for uses other than an insulating film, it does not necessarily have such a refractive index.

  The relative dielectric constant of the alkali-treated film can be measured, for example, as follows.

  First, an interlayer insulating film made of an alkali-treated film is formed. That is, first, the alkali-treated film-forming composition is placed in a 2 mL plastic syringe, a PTFE pore size 0.20 μm filter is attached to the tip, and the alkali-treated film-forming composition 1.5 mL is added with a resistance of 0. Dropped onto a 5-inch silicon wafer of 0.02 Ω · cm or less, and a coating film is formed by spin coating. In the formation of the coating film, the rotation speed is adjusted so that the film thickness of the coating film after curing is 225 ± 25 nm.

  Next, using a hot plate, the organic solvent in the coating film was removed at 250 ° C. over 3 minutes, and then the organic solvent was used in a quartz tube furnace in which the oxygen concentration was controlled at around 100 ppm at 350 ° C. over 30 minutes. The coating film after removal is cured to produce an alkali-treated film as an interlayer insulating film.

  Thereafter, using a vacuum deposition apparatus, Al metal is vacuum deposited on the alkali-treated film so as to have a circular shape with a diameter of 2 mm and a thickness of about 0.1 μm. As a result, an interlayer insulating film having a structure in which an alkali-treated film is disposed between the Al metal and the silicon wafer (low resistivity substrate) is formed.

The dielectric capacity (Yokogawa Electric Corp .: HP16451B) is applied to the LF impedance analyzer (Yokogawa Electric Corp .: HP4192A) for the charge capacity of the interlayer insulating film made of the alkali-treated film thus obtained. Using a connected device, measurement is performed under the conditions of a temperature of 23 ° C. ± 2 ° C., a humidity of 40% ± 10%, and a use frequency of 1 MHz. And the measured value of the obtained charge capacity is expressed by the following formula:
Dielectric constant of interlayer insulating film = 3.597 × 10 ⁻² × charge capacity (pF) × film thickness of interlayer insulating film (μm)
By substituting into, the relative dielectric constant of the interlayer insulating film can be calculated. In addition, as a value of the film thickness of the interlayer insulating film, a value obtained by measuring the film thickness of the alkali-treated film can be employed.

  The transmittance of light having a wavelength of 300 to 800 nm of the alkali-treated film is preferably 90% or more, more preferably 93% or more, still more preferably 95% or more, and 97% or more. Even more preferred. When the alkali-treated film has a light transmittance of less than 90% in the above wavelength range, the visibility is poor when the alkali-treated film is used as an antireflection film or an interlayer insulating film of an FPD (flat panel display). Tend to be.

  The light transmittance of such an alkali-treated film can be measured, for example, as follows.

  First, an alkali-treated film is formed in the same manner as described above, except that a substrate that is transparent in the wavelength region of 300 to 800 nm is used instead of a silicon wafer.

  Next, the substrate on which the alkali-treated film was formed was used with a UV-visible spectrophotometer (U-3310) manufactured by Hitachi, Ltd., and the substrate on which the alkali-treated film was not formed was used as a reference. The area up to is measured in the transmittance mode. Thereby, the transmittance | permeability of the light of the said wavelength range of a to-be-alkali-treated film can be measured.

  Furthermore, the Young's modulus measured by the nanoindentation method of the alkali-treated film is preferably 5 GPa or more, more preferably 7 GPa or more, further preferably 10 GPa or more, and further preferably 15 GPa or more. When the Young's modulus of the alkali-treated film is less than 5 GPa, for example, the alkali-treated film may be easily peeled off in a process where stress such as packaging is applied.

  The Young's modulus of the alkali-treated film is, for example, after forming an interlayer insulating film in the same manner as described above, then using nanoindenter SA2 (DCM, manufactured by MTS) at a temperature of 23 ° C. ± 2 ° C. and a frequency of 75 Hz. The rate can be obtained by measuring under the condition that the measurement range is 1/10 or less of the film thickness and does not vary with the indentation depth.

[Composition for forming alkali-treated film]
Next, a preferred embodiment of a composition for forming an alkali-treated film for forming an alkali-treated film will be described. The composition for forming an alkali-treated film (a composition for forming a silica-based film) contains (a) a siloxane resin, (b) a solvent, and (c) a curing accelerating catalyst. Hereinafter, each component contained in the composition for forming an alkali-treated film will be described.

［式（１）中、Ｒ^１はＨ原子若しくはＦ原子、又はＢ原子、Ｎ原子、Ａｌ原子、Ｐ原子、Ｓｉ原子、Ｇｅ原子若しくはＴｉ原子を含む基、又は炭素数１〜２０の有機基を示し、Ｘは加水分解性基を示し、ｎは０〜２の整数を示す。ただし、Ｒ^１又はＸが複数存在する場合、これらはそれぞれ同一でも異なっていてもよい。］ [(A) component]
The siloxane resin as component (a) is preferably obtained by hydrolytic condensation of a raw material component containing a silicon compound represented by the following general formula (1).

[In the formula (1), R ¹ represents an H atom or an F atom, or a group containing a B atom, an N atom, an Al atom, a P atom, a Si atom, a Ge atom or a Ti atom, or an organic group having 1 to 20 carbon atoms. , X represents a hydrolyzable group, and n represents an integer of 0 to 2. However, when two or more R < ¹ > or X exists, these may be same or different, respectively. ]

Here, the hydrolysis condensation refers to a reaction in which, after the hydrolyzable group in the silicon compound represented by the above formula (1) is converted into a hydroxy group by hydrolysis, the hydroxy groups cause dehydration condensation. . In the siloxane resin formed by such hydrolysis condensation, a silicon atom is bonded in a linear or three-dimensional network via an oxygen atom, and at least a part of the silicon atom is represented by the above R ^1. It has a structure in which groups are bonded. In addition, as a raw material component, as long as the silicon compound represented by the general formula (1) is included as an essential component, other components may be further included, but a viewpoint of obtaining an alkali-treated film having excellent characteristics. Therefore, most of the raw material components (90% or more) are preferably silicon compounds of the general formula (1), and more preferably, the raw material components are composed only of the silicon compounds of the general formula (1).

  In the silicon compound represented by the above formula (1) which is a raw material component of the siloxane resin, examples of the hydrolyzable group represented by X include an alkoxy group, a halogen atom, an acetoxy group, an isocyanate group, and a hydroxyl group. . Among these, an alkoxy group is preferable from the viewpoint of improving the stability and coating properties of the composition for forming an alkali-treated film.

  Examples of the silicon compound (alkoxysilane) in which the hydrolyzable group represented by X is an alkoxy group include tetraalkoxysilane, trialkoxysilane, and dialkoxysilane.

  Tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, tetra Examples include phenoxysilane.

  Trialkoxysilanes include trimethoxysilane, triethoxysilane, tri-n-propoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane, fluorotri-n-propoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxysilane. -N-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-iso-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriethoxysilane N-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-iso-butoxysilane, ethyltri-tert-butoxy Silane, ethyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane N-propyltri-iso-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, iso-propyltri-n-propoxy Silane, iso-propyltri-iso-propoxysilane, iso-propyltri-n-butoxysilane, iso-propyltri-iso-butoxysilane, iso-propyltri-tert-butoxysilane, iso-propyltrif Noxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltri-iso-propoxysilane, n-butyltri-n-butoxysilane, n-butyltri-iso-butoxy Silane, n-butyltri-tert-butoxysilane, n-butyltriphenoxysilane, sec-butyltrimethoxysilane, sec-butyltriethoxysilane, sec-butyltri-n-propoxysilane, sec-butyltri-iso-propoxysilane, sec-butyltri-n-butoxysilane, sec-butyltri-iso-butoxysilane, sec-butyltri-tert-butoxysilane, sec-butyltriphenoxysilane, t-butyltrimethoxysilane, t-butyl Triethoxysilane, t-butyltri-n-propoxysilane, t-butyltri-iso-propoxysilane, t-butyltri-n-butoxysilane, t-butyltri-iso-butoxysilane, t-butyltri-tert-butoxysilane, t -Butyltriphenoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-iso-propoxysilane, phenyltri-n-butoxysilane, phenyltri-iso-butoxysilane, phenyltri -Tert-butoxysilane, phenyltriphenoxysilane, trifluoromethyltrimethoxysilane, pentafluoroethyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3- Li-fluoropropyl triethoxysilane and the like.

  Dialkoxysilanes include methyldimethoxysilane, methyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-iso-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxy. Silane, dimethyldi-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldi-iso-propoxysilane, diethyldi-n-butoxysilane, diethyldi-sec-butoxysilane Diethyldi-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n Propyl di-n-propoxysilane, di-n-propyldi-iso-propoxysilane, di-n-propyldi-n-butoxysilane, di-n-propyldi-sec-butoxysilane, di-n-propyldi-tert-butoxysilane Di-n-propyldiphenoxysilane, di-iso-propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyldi-n-propoxysilane, di-iso-propyldi-iso-propoxysilane, di -Iso-propyldi-n-butoxysilane, di-iso-propyldi-sec-butoxysilane, di-iso-propyldi-tert-butoxysilane, di-iso-propyldiphenoxysilane, di-n-butyldimethoxysilane, di -N-butyldiethoxysilane, -N-butyldi-n-propoxysilane, di-n-butyldi-iso-propoxysilane, di-n-butyldi-n-butoxysilane, di-n-butyldi-sec-butoxysilane, di-n-butyldi-tert -Butoxysilane, di-n-butyldiphenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec-butyldi-n-propoxysilane, di-sec-butyldi-iso-propoxy Silane, di-sec-butyldi-n-butoxysilane, di-sec-butyldi-sec-butoxysilane, di-sec-butyldi-tert-butoxysilane, di-sec-butyldiphenoxysilane, di-tert-butyldimethoxy Silane, di-tert-butyldiethoxysilane, di-tert -Butyldi-n-propoxysilane, di-tert-butyldi-iso-propoxysilane, di-tert-butyldi-n-butoxysilane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxy Silane, di-tert-butyldiphenoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-iso-propoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxy Silane, diphenyldi-tert-butoxysilane, diphenyldiphenoxysilane, bis (3,3,3-trifluoropropyl) dimethoxysilane, methyl (3,3,3-trifluoropropyl) dimethoxysilane, etc. That.

  The silicon compound (halogenated silane) of the above general formula (1) in which the hydrolyzable group represented by X is a halogen atom (halogen group) is a compound in which the alkoxy group in the alkoxysilane described above is substituted with a halogen atom. Is mentioned. Examples of the silicon compound (acetoxysilane) of the above general formula (1) in which X is an acetoxy group include compounds in which the alkoxy group in the alkoxysilane described above is substituted with an acetoxy group. Examples of the compound of general formula (1) (isocyanate silane) in which X is an isocyanate group include compounds in which the alkoxy group in the alkoxysilane described above is substituted with an isocyanate group. Examples of the compound of the general formula (1) (hydroxysilane) in which X is a hydroxy group include compounds in which the alkoxy group in the alkoxysilane described above is substituted with a hydroxy group. In addition, the compound represented by the said General formula (1) can be used individually or in combination of 2 or more types.

N in the said General formula (1) shows the integer of 0-2. However, when n is 2, each R ¹ may be the same or different. Moreover, when n is 0-2, said X may be same or different, respectively. Note that n is preferably 0 to 1, and a compound represented by the general formula (1) in which n is 0 and a compound represented by the general formula (1) in which n is 1 It is more preferable to use in combination. When a compound in which n is 0 and a compound in which n is 1 are combined, the siloxane resin includes a unit represented by SiO ₂ and a unit represented by R ¹ SiO _3/2 . Such R ¹ is as defined above.

This siloxane resin is obtained by cohydrolyzing and condensing the above-mentioned tetraalkoxysilane and trialkoxysilane having polyfunctionality. The unit represented by SiO ₂ is a unit derived from tetraalkoxysilane, and the unit represented by R ¹ SiO _3/2 is a unit derived from trialkoxysilane. Since the siloxane resin contains these structural units, the crosslink density is improved, so that the film characteristics can be improved.

  As described above, the siloxane resin is obtained by hydrolytic condensation of a raw material component containing the silicon compound represented by the general formula (1) as an essential component, and is mainly composed of a polymer of this silicon compound. The This hydrolysis-condensation reaction can be caused, for example, by adding water to a silicon compound or other raw material components and stirring in a solvent. In this hydrolysis condensation reaction, a catalyst for promoting the reaction may be further added. Examples of such a catalyst include an acid catalyst, an alkali catalyst, and a metal chelate compound.

  Examples of the acid catalyst include formic acid, maleic acid, fumaric acid, phthalic acid, malonic acid, succinic acid, tartaric acid, malic acid, lactic acid, citric acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid and heptanoic acid. , Octanoic acid, nonanoic acid, decanoic acid, oxalic acid, adipic acid, sebacic acid, butyric acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzenesulfonic acid, benzoic acid, p-aminobenzoic acid, p- Examples thereof include organic acids such as toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and trifluoroethanesulfonic acid, and inorganic acids such as hydrochloric acid, phosphoric acid, nitric acid, boric acid, sulfuric acid and hydrofluoric acid. These may be used alone or in combination of two or more.

  Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, pyridine, monoethanolamine, diethanolamine, triethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, ammonia, tetramethylammonium hydroxide. , Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecacylamine, dodecylamine, cyclopentylamine, cyclohexyl Amine, N, N-dimethylamine, N, N-diethylamine, N, N- Propylamine, N, N-dibutylamine, N, N-dipentylamine, N, N-dihexylamine, N, N-dicyclopentylamine, N, N-dicyclohexylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, Examples include tripentylamine, trihexylamine, tricyclopentylamine, and tricyclohexylamine. These may be used alone or in combination of two or more.

  Examples of the metal chelate compound include trimethoxy mono (acetyl acetonate) titanium, triethoxy mono (acetyl acetonate) titanium, tri-n-propoxy mono (acetyl acetonate) titanium, tri-iso-propoxy mono ( Acetyl acetonate) titanium, tri-n-butoxy mono (acetyl acetonate) titanium, tri-sec-butoxy mono (acetyl acetonate) titanium, tri-tert-butoxy mono (acetyl acetonate) titanium, dimethoxy Mono (acetylacetonate) titanium, diethoxy-di (acetylacetonate) titanium, di-n-propoxy-di (acetylacetonate) titanium, diiso-propoxy-di (acetylacetonate) titanium, di-n-butoxy-di (Acetylacetonate) titanium, di-s c-butoxy-di (acetylacetonate) titanium, ditert-butoxy-di (acetylacetonate) titanium, monomethoxy-tris (acetylacetonate) titanium, monoethoxy-tris (acetylacetonate) titanium, mono-n- Propoxy tris (acetyl acetonate) titanium, mono iso-propoxy tris (acetyl acetonate) titanium, mono n-butoxy tris (acetyl acetonate) titanium, mono sec-butoxy tris (acetyl acetonate) titanium, mono tert-butoxy-tris (acetylacetonate) titanium, tetrakis (acetylacetonate) titanium, trimethoxy-mono (ethylacetoacetate) titanium, triethoxy-mono (ethylacetoacetate) titanium, tri-n-propoxy-mono (ethyl) Acetoacetate) titanium, tri-iso-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri-sec-butoxy mono (ethyl acetoacetate) titanium, tri-tert -Butoxy mono (ethyl acetoacetate) titanium, dimethoxy mono (ethyl acetoacetate) titanium, diethoxy di (ethyl acetoacetate) titanium, di-n-propoxy di (ethyl acetoacetate) titanium, diiso-propoxy di (Ethyl acetoacetate) titanium, di-n-butoxy di (ethyl acetoacetate) titanium, disec-butoxy di (ethyl acetoacetate) titanium, di tert-butoxy di (ethyl acetoacetate) titanium, monomethoxy Lith (ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono n-propoxy tris (ethyl acetoacetate) titanium, monoiso-propoxy tris (ethyl acetoacetate) titanium, mono n-butoxy Metal chelate compounds having titanium such as tris (ethyl acetoacetate) titanium, mono sec-butoxy tris (ethyl acetoacetate) titanium, mono tert-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, And compounds in which titanium of the metal chelate compound having titanium is substituted with zirconium, aluminum or the like. These may be used alone or in combination of two or more.

  The hydrolytic condensation of the silicon compound is preferably performed using the above catalyst. However, when the stability of the composition deteriorates, or when there is a concern about the influence of corrosion on other materials by including the catalyst, for example, The catalyst may be removed from the composition after hydrolysis, or may be reacted to deactivate the function as a catalyst. Although there is no restriction | limiting in particular as these methods, For example, distillation, an ion chromatography column, etc. are mentioned as a method of removing a catalyst first. Moreover, you may take out the hydrolyzate of the said silicon compound of General formula (1) from the reaction material after a hydrolysis by reprecipitation etc. On the other hand, as a method of deactivating the function as a catalyst by the reaction, for example, when the catalyst is an alkali catalyst, there are a method of neutralizing by adding an acid catalyst or making the pH acidic.

  The amount of the catalyst used in the hydrolysis condensation is preferably in the range of 0.0001 to 1 mol with respect to 1 mol of the compound represented by the general formula (1). If the amount used is less than 0.0001 mol, the effect of promoting hydrolysis condensation tends to be hardly obtained. On the other hand, when it exceeds 1 mol, undesired gelation tends to be promoted during hydrolysis condensation. In the hydrolysis-condensation reaction, alcohols and the like are produced as hydrolysis by-products, but these are protic solvents and are not preferred if included in the composition for forming an alkali-treated film. It is desirable to remove it.

  As described above, the siloxane resin in the present embodiment mainly has a structure in which the silicon compound represented by the general formula (1) is bonded in a linear or three-dimensional network via an oxygen atom. .

At least a part of the silicon atoms in the structure is a group derived from R ¹ in the silicon compound represented by the general formula (1), that is, any one atom of H atom and F atom, or It is preferable to have a group containing a B atom, N atom, Al atom, P atom, Si atom, Ge atom or Ti atom, or an organic group having 1 to 20 carbon atoms. However, when the amount of F atoms bonded to silicon atoms increases, the adhesion of the alkali-treated film tends to decrease. Therefore, when strong adhesion is to be obtained, the structure does not have F atoms. It is desirable to do. Among the above, the silicon atom in the siloxane resin preferably has a group containing an H atom, an N atom, or an Si atom, or an organic group. As a result, the dielectric properties and mechanical properties of the resulting alkali treated coating are improved. In particular, the silicon atom in the siloxane resin preferably has an organic group, and particularly preferably has a methyl group. The type of group bonded to the silicon atom in the siloxane resin can be arbitrarily changed by appropriately selecting the raw silicon compound, and a plurality of types can be combined.

In the siloxane resin, atoms directly bonded to silicon atoms in the group represented by R ¹ per mole of silicon (Si) atoms constituting the siloxane bond in the resin, that is, H atoms, F atoms , B atom, N atom, Al atom, P atom, Si atom, Ge atom, Ti atom and total content ratio M of atoms selected from the group consisting of C atom (this is a specific bonding atom (general formula (1) The total number of R ¹ ) is preferably less than 1.00 mol. That is, in the siloxane resin, a value obtained by dividing the total number of moles of the specific bond atom bonded to the silicon atom constituting the siloxane bond by the total number of moles of silicon atom constituting the siloxane bond, Preferably it is less than 1.00. In other words, in the siloxane resin, it can be said that an average of less than 1.00 of the above atoms is bonded per one silicon atom in the resin.

  When the value of M in the siloxane resin is within the above range, the resulting silica-based thin film has a dense structure and has excellent alkali treatment resistance, as well as sufficient adhesion to adjacent layers. Moreover, excellent mechanical strength can be obtained.

  The value of M is more preferably 0.21 to 1.00 mol, further preferably 0.30 to 1.00 mol, and further preferably 0.40 to 1.00 mol. 0.50 to 1.00 mol is even more preferable, 0.55 to 0.90 mol is particularly preferable, 0.60 to 0.80 mol is extremely preferable, and 0.62 Most preferred is ˜0.75 mol.

  When the value of M is less than 0.21, the antari processing resistance of the alkali-treated film tends to be inferior. Further, when the alkali-treated film is used as an antireflection film, the refractive index tends to increase. Also, the dielectric properties tend to be inferior when an alkali-treated film is used as an insulating film. On the other hand, when the value of M exceeds 1.00, there is a tendency that adhesion between the alkali-treated film and the adjacent layer, mechanical strength, and the like are lowered.

Specifically, the value of M described above can be calculated from the charged amount of the compound of the general formula (1), which is a raw material for the siloxane resin. For example:
M = [M1 + (M2 / 2) + (M3 / 3)] / MSi
Can be calculated. In the formula, M1 represents the total number of atoms bonded to a single (only one) Si atom among the specific bonded atoms, and M2 is an atom shared by two silicon atoms among the specific bonded atoms M3 represents the total number of atoms shared by three silicon atoms among the specific bonding atoms, and MSi represents the total number of Si atoms.

  It is preferable that the siloxane resin has an OH group at the terminal or side chain. Thereby, in the curing reaction at the time of forming the alkali-treated film, hydrolysis condensation for curing proceeds better.

  Such a siloxane resin preferably has a weight average molecular weight (Mw) of 500 to 1,000,000 from the viewpoint of solubility in a solvent, mechanical properties, moldability, etc., and is 500 to 500,000. More preferably, it is more preferably 500 to 100,000, still more preferably 500 to 10,000, and particularly preferably 500 to 5,000. When the Mw of the siloxane resin is less than 500, the film formability when forming the alkali-treated film tends to be inferior. On the other hand, when Mw exceeds 1,000,000, the compatibility with the solvent of the siloxane resin is lowered, and it tends to be difficult to obtain a dense film. In the present specification, Mw means a value measured by gel permeation chromatography (hereinafter referred to as “GPC”) and converted using a standard polystyrene calibration curve.

Such Mw can be measured, for example, by performing GPC under the following conditions.
Sample: Composition for forming an alkali-treated film Standard polystyrene: Tosoh Corporation standard polystyrene (Molecular weight 190,000, 17,900, 9,100, 2,980, 578, 474, 370, 266)
Detector: RI-monitor manufactured by Hitachi, Ltd., trade name “L-3000”
Integrator: GPC integrator manufactured by Hitachi, Ltd., trade name “D-2200”
Pump: Hitachi, Ltd., trade name “L-6000”
Degassing device: Showa Denko Co., Ltd., trade name "Shodex DEGAS"
Column: Hitachi Chemical Co., Ltd., trade names “GL-R440”, “GL-R430”, “GL-R420” connected in this order and used eluent: tetrahydrofuran (THF)
Measurement temperature: 23 ° C
Flow rate: 1.75 mL / min Measurement time: 45 minutes

  The siloxane resin is more preferably one that can be cured by heat or radiation. In this case, the adhesiveness to the substrate is further improved by forming a chemical bond with the substrate or the like in curing during the formation of the alkali-treated film.

  In addition, the said siloxane resin can also be used individually by 1 type, and can be used in combination of 2 or more type. As such two or more types of combinations, for example, a combination of two or more types of siloxane resins having different weight average molecular weights, or two types obtained by hydrolytic condensation of raw material components having different silicon compounds as essential components The combination of the above siloxane resin is mentioned.

[Component (b)]
The component (b) is a solvent that can dissolve the component (a). Examples of the solvent capable of dissolving the component (a) include aprotic solvents and protic solvents. You may contain these individually or in combination of 2 or more types.

  Examples of the aprotic solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-iso-propyl ketone, methyl-n-butyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, methyl-n- Hexyl ketone, diethyl ketone, dipropyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, γ-butyrolactone, γ-valerolactone, etc. Ketone solvents, diethyl ether, methyl ethyl ether, methyl-n-di-n-propyl ether, di-iso-propyl ether, tetrahydrofuran, methyltetrahydrofuran, dioxane, dimethyldioxane, ethyl Glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl mono-n-propyl ether, diethylene glycol methyl mono-n- Butyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, diethylene glycol methyl mono-n-hexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol methyl Non-n-butyl ether, triethylene glycol di-n-butyl ether, triethylene glycol methyl mono-n-hexyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetradiethylene glycol methyl ethyl ether, tetraethylene glycol methyl mono-n -Butyl ether, diethylene glycol di-n-butyl ether, tetraethylene glycol methyl mono-n-hexyl ether, tetraethylene glycol di-n-butyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol Dibutyl ether, dipropylene glycol dimethyl ether, Propylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl mono-n-butyl ether, dipropylene glycol di-n-propyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol methyl mono-n-hexyl Ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol methyl ethyl ether, tripropylene glycol methyl mono-n-butyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol methyl mono-n-hexyl ether, Tetrapropylene glycol dimethyl ether, tetrapropylene glycol diethyl ether, Ether type such as tetradipropylene glycol methyl ethyl ether, tetrapropylene glycol methyl mono-n-butyl ether, dipropylene glycol di-n-butyl ether, tetrapropylene glycol methyl mono-n-hexyl ether, tetrapropylene glycol di-n-butyl ether A solvent is mentioned.

  Further, methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, acetic acid Methylpentyl, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, nonyl acetate, methyl acetoacetate, ethyl acetoacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n acetate -Butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, glycol diacetate, methoxytriglycol acetate, ethyl propionate, propionic acid - butyl, propionic acid i- amyl, diethyl oxalate, and ester solvents such as oxalic di -n- butyl.

  Furthermore, ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol-n-butyl ether acetate, propylene glycol Examples include ether acetate solvents such as methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, dipropylene glycol methyl ether acetate, and dipropylene glycol ethyl ether acetate.

  Furthermore, acetonitrile, N-methylpyrrolidinone, N-ethylpyrrolidinone, N-propylpyrrolidinone, N-butylpyrrolidinone, N-hexylpyrrolidinone, N-cyclohexylpyrrolidinone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethyl sulfoxide and the like can also be mentioned.

  Among these, an ether solvent, an ether acetate solvent, or a ketone solvent is preferable from the viewpoint of thickening the alkali-treated film. In particular, from the viewpoint of suppressing coating unevenness and repelling during the formation of an alkali-treated film, an ether acetate solvent is preferable, then an ether solvent is preferable, and then a ketone solvent is preferable. Among ether solvents, dialkyl of dihydric alcohol, diester of dihydric alcohol, and alkyl ester of dihydric alcohol are preferable. Among ester solvents, alkyl acetates are preferred in addition to diesters of dihydric alcohols listed in ether solvents and alkyl esters of dihydric alcohols. More specifically, the solvent is preferably diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate or cyclohexanone. These are particularly excellent in compatibility with the siloxane resin and tend to particularly improve the mechanical strength and the like of the resulting alkali-treated film. These may be used alone or in combination of two or more.

  On the other hand, examples of the protic solvent include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2- Methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexane SANOL, benzyl alcohol, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, alcohol solvents Luo tripropylene glycol.

  Also, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol mono Examples include ether solvents such as -n-butyl ether, propylene glycol monomethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and tripropylene glycol monomethyl ether.

  Furthermore, ester solvents such as methyl lactate, ethyl lactate, n-butyl lactate, and n-amyl lactate are listed. Among these, alcohol-based solvents are preferable from the viewpoint of storage stability of the composition for forming an alkali-treated film. In particular, ethanol, isopropyl alcohol, propylene glycol propyl ether, and the like are preferable from the viewpoint of suppressing coating unevenness and repellency. These can be used alone or in combination of two or more.

  Note that a protic solvent typified by alcohol has hydrogen bonded to oxygen having a high electronegativity. For this reason, protic solvent molecules tend to solvate by forming hydrogen bonds with nucleophiles and the like. That is, since the protic solvent easily solvates with the siloxane resin obtained by hydrolyzing the silicon compound of the general formula (1), the solvent molecule becomes an obstacle in the condensation of the siloxane resin and inhibits curing at a low temperature. There is a case. Therefore, when a protic solvent is used, a large amount of solvent may remain in the film immediately after coating, which may increase the film shrinkage rate during curing. On the other hand, an aprotic solvent does not have a hydrogen atom on an element having a high electronegativity, and is considered to have a smaller factor of reaction inhibition than a protic solvent. Therefore, as a solvent, compared to a protic solvent, using an aprotic solvent tends to provide an alkali-treated film having a higher density and higher mechanical strength and excellent alkali treatment resistance. is there.

  For the reasons described above, the composition for forming an alkali-treated film according to this embodiment is 30% by weight or more, preferably 50% by weight or more, more preferably, based on the weight of the solvent as the component (b), the aprotic solvent. Is preferably 70% by weight or more, more preferably 80% by weight or more, and particularly preferably 90% by weight or more. When the content ratio of the aprotic solvent in the component (b) is small, the shrinkage rate during curing of the composition for forming an alkali-treated film is increased, and the temperature and time are shortened during curing. Tend to be difficult. Moreover, there exists a possibility that the raise of the dielectric constant of the silica film obtained and the fall of mechanical strength may arise.

  Moreover, it is preferable that the boiling point of the solvent which is (b) component is 80-180 degreeC, It is more preferable that it is 100 degreeC-180 degreeC, It is further more preferable that it is 100-160 degreeC, 120 degreeC-160 It is even more preferable that the temperature is C. Although the detailed mechanism is not clear, if the boiling point of the solvent is less than 80 ° C. or exceeds 180 ° C., film unevenness such as striation is likely to occur during the formation of the alkali-treated film, and the in-plane immediately after curing. The film thickness tends to be inferior.

  The method for adding the solvent as the component (b) to the composition for forming an alkali-treated film is not particularly limited. For example, a method for adding the solvent as a component when preparing the siloxane resin as the component (a), (A) The method of adding or preparing a solvent exchange after preparation of a component, The method of taking out only (a) component after preparation of (a) component, and mixing this and (b) component etc. are mentioned. The solvent may contain water in addition to the organic solvent as in the above-described example, but the content of such water does not deteriorate the properties of the composition for forming an alkali-treated film and the alkali-treated film. It is preferable to set the degree.

  The content of the solvent in the composition for forming an alkali-treated film is preferably an amount such that the concentration of the siloxane resin as the component (a) in the composition for forming an alkali-treated film is 3 to 35% by weight, More preferably, the amount is 5 to 30% by weight, still more preferably 5 to 25% by weight, still more preferably 5 to 20% by weight, and 5 to 15% by weight. The amount is particularly preferable. When the amount of the solvent is too large and the concentration of the component (a) is less than 3% by weight, it tends to be difficult to form an alkali-treated film having a desired film thickness. On the other hand, when the amount of the solvent is too small and the concentration of the component (a) exceeds 35% by weight, the film formability of the alkali-treated film is deteriorated, and the stability of the composition for forming an alkali-treated film itself is improved. There is a tendency to decrease.

  In consideration of the stability of the composition for forming an alkali-treated film, the component (b) preferably has water solubility or water solubility properties (water solubility). It is preferable that it has both solubility and water solubility. Moreover, it is preferable that (b) component has polarity. When the component (b) does not have polarity, the compatibility with the component (a) tends to be inferior, and the stability of the composition for forming an alkali-treated film may be insufficient. From these viewpoints, when the aprotic solvent does not have solubility in water or water, it is preferable to add a protic solvent in addition to the aprotic solvent.

[Component (c)]
The component (c) is a curing accelerating catalyst and has a function of satisfactorily causing a curing reaction when forming the alkali-treated film from the composition for forming an alkali-treated film.

  The curing accelerating catalyst is different from ordinary photoacid generators and photobase generators, and is preferably different from ordinary onium salts used in these applications. However, those having a curing acceleration catalyst ability in addition to the photoacid generation ability and photobase generation ability can be applied as the curing acceleration catalyst.

  Such a curing accelerating catalyst has a unique characteristic that it exhibits a curing accelerating catalytic ability mainly in the coating film after coating, not in the solution of the composition for forming an alkali-treated film. This curing acceleration catalytic ability can be confirmed, for example, by the methods shown in 1-4 below.

(1) First, a composition comprising the component (a) and the component (b) is prepared.
(2) Next, the composition of (1) was applied on a silicon wafer so that the film thickness after baking was 1.0 ± 0.1 μm, and this was baked at a predetermined temperature for 30 seconds, and then obtained. The film thickness of the resulting coating is measured.
(3) Thereafter, the silicon wafer on which the film was formed was immersed in a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution at 23 ± 2 ° C. for 30 seconds, washed with water, and dried to reduce the film thickness ( Observe the degree of thickness reduction). Then, the same temperature is observed for a plurality of samples made of the same composition while changing the baking temperature, and the minimum baking temperature at which the change in film thickness before and after immersion in TMAH can be within 20% is defined as the insoluble temperature. To do.
(4) After adding the compound whose curing promoting catalytic ability is to be confirmed to the same composition as 1 in an amount of 0.01% by weight of the component (a), the obtained composition is used for 2 and 3. The operation is performed to determine the insoluble temperature when the composition is used. And when the insoluble temperature falls by adding the compound which wants to confirm hardening acceleration | stimulation catalytic ability compared with the case where a compound is not added, it determines with the compound having hardening acceleration | stimulation catalytic ability.

  Examples of the curing accelerating catalyst having such curing accelerating catalytic ability include alkali metals such as sodium hydroxide, sodium chloride, potassium hydroxide and potassium chloride, onium salts and the like. These can be added singly or in combination of two or more. Among these, from the viewpoint that the alkali-treated film obtained can be reduced in refractive index and mechanical strength can be improved, and further, the stability of the composition for forming an alkali-treated film can be increased. Are preferred, and quaternary ammonium salts are more preferred.

  Examples of the onium salt having a curing accelerating catalytic ability include a salt formed from (c-1) a nitrogen-containing compound and (c-2) at least one of an anionic group-containing compound and a halogen atom. Can be mentioned. In the above (c-1) nitrogen-containing compound, the atoms bonded to nitrogen include H atoms, F atoms, B atoms, N atoms, Al atoms, P atoms, Si atoms, Ge atoms, Ti atoms, and C atoms. At least one atom selected from the group is preferred. Examples of the anionic group of the anionic group-containing compound include a hydroxyl group, a nitrate group, a sulfate group, a carbonyl group, a carboxyl group, a carbonate group, and a phenoxy group.

  Examples of such onium salt compounds include ammonium hydroxide, ammonium fluoride, ammonium chloride, ammonium bromide, ammonium iodide, ammonium phosphate, ammonium nitrate, ammonium borate, ammonium sulfate, ammonium formate, and maleic acid. Ammonium salt, ammonium fumarate, ammonium phthalate, ammonium malonate, ammonium succinate, ammonium tartrate, ammonium malate, ammonium lactate, ammonium citrate, ammonium acetate, ammonium propionate, Ammonium butanoate, ammonium pentanoate, ammonium hexanoate, ammonium heptanoate, ammonium octanoate, nonanoic acid Ammonium salt, ammonium decanoate, ammonium oxalate, ammonium adipate, ammonium sebacate, ammonium butyrate, ammonium oleate, ammonium stearate, ammonium linoleate, ammonium linoleate, ammonium salicylate Benzene sulfonic acid ammonium salt, benzoic acid ammonium salt, p-aminobenzoic acid ammonium salt, p-toluenesulfonic acid ammonium salt, methanesulfonic acid ammonium salt, trifluoromethanesulfonic acid ammonium salt, trifluoroethanesulfonic acid ammonium salt, etc. And ammonium salt compounds.

  As the onium salt, the ammonium moiety of the ammonium salt compound is methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium, ethylammonium, diethylammonium, triethylammonium, tetraethylammonium, propylammonium, dipropylammonium, tripropyl Examples thereof include ammonium salt compounds substituted with ammonium, tetrapropylammonium, butylammonium, dibutylammonium, tributylammonium, tetrabutylammonium, ethanolammonium, diethanolammonium, triethanolammonium, and the like.

  Among these onium salt compounds, tetramethylammonium nitrate, tetramethylammonium acetate, tetramethylammonium propionate, tetramethylammonium maleic acid are particularly effective in promoting curing when forming an alkali-treated film. Salts and ammonium salts such as tetramethylammonium sulfate are preferred. These can be used singly or in combination of two or more.

  The blending ratio of the curing accelerating catalyst as component (c) is preferably 0.001 to 1.0% by weight and more preferably 0.006 to 1.0% by weight with respect to the total amount of component (a). Preferably, it is 0.06 to 0.5% by weight. When the blending ratio of the curing accelerating catalyst is less than 0.001% by weight, it is difficult to sufficiently obtain the effect of accelerating curing at the time of forming the silica film. The storage stability of the forming composition tends to decrease.

  A curing accelerating catalyst such as an onium salt can be added to a desired concentration after being dissolved in water or diluted with water as necessary. Moreover, a hardening acceleration | stimulation catalyst can be added at arbitrary time points, for example, at the time of the start of hydrolysis condensation of the component (a), during hydrolysis condensation, at the end of hydrolysis condensation, or before and after solvent removal after the reaction.

  Although the cause of the effect of adding a curing acceleration catalyst such as an onium salt is not always clear, the curing acceleration catalyst promotes dehydration condensation of the siloxane resin immediately after being applied to a predetermined substrate. It is thought to be caused. This is thought to increase the density of siloxane bonds in the siloxane resin and reduce the residual silanol groups, thereby reducing the film shrinkage and improving the mechanical strength and dielectric properties of the film. However, the action is not limited to this.

[Other ingredients]
In addition to the above components (a), (b) and (c), the composition for forming an alkali-treated film according to this embodiment further contains other components as long as the object and effect of the present invention are not impaired. It may be.

  Examples of other components include dyes, surfactants, silane coupling agents, thickeners, inorganic fillers, thermally decomposable compounds such as polypropylene glycol, and volatile compounds. The thermally decomposable compound and volatile compound are preferably void-forming compounds that can be decomposed or volatilized by heat (preferably 200 to 500 ° C.) to form voids (hereinafter referred to as “component (d)”). From the viewpoint of satisfactorily forming voids in the alkali-treated film, it is preferable to include this component (d) in the composition for forming an alkali-treated film. In addition, you may provide void formation ability to the siloxane resin which is (a) component. Moreover, the composition for forming an alkali-treated film may be a radiation curable composition by containing a photoacid generator or a photobase generator (hereinafter referred to as “component (e)”). It is desirable to add these other components so that the effect of suppressing the film shrinkage rate is not impaired during the formation of the alkali-treated film.

  First, the thermally decomposable compound as component (d) will be described.

  The thermally decomposable compound or volatile compound as the component (d) is a compound that thermally decomposes or volatilizes at a heating temperature of 200 to 500 ° C. The component (d) can gradually form micropores (voids and vacancies) in the alkali-treated film. By the addition of the component (d), the pores can be further refined and the shape can be made uniform during the final curing. In order to satisfactorily exhibit such a function, the component (d) preferably has a reduction rate in a nitrogen gas atmosphere at a temperature of 200 to 500 ° C. of 95% by weight or more, more preferably 97% by weight or more. Preferably, it is 99 weight% or more. When the reduction rate is less than 95% by weight, decomposition or volatilization of the compound (d) component tends to be insufficient when the composition for forming an alkali-treated film of this embodiment is heated. That is, the component (d) itself, a part of the component (d) or the reaction product derived from the component (d) may remain in the finally obtained alkali-treated film. In this case, the electrical characteristics of the alkali-treated film may be easily deteriorated, such as an increase in relative dielectric constant.

Note that the “decrease rate” of the component (d) described above can be obtained, for example, by the following apparatus and conditions. That is, the “decrease rate” is a condition in which 10 mg of the void forming compound as component (d) is set to a temperature rising start temperature of 50 ° C., a temperature rising rate of 10 ° C./min, and a nitrogen (N ₂ ) gas flow rate of 200 ml / min. Below, it can measure using a differential scanning calorimeter (Seiko Instruments Inc. make, TG / DTA6300). In this measurement, α-alumina (manufactured by Seiko Instruments Inc.) is used as a reference, and an aluminum open sample pan (manufactured by Seiko Instruments Inc.) having a diameter of 5 mm is used as a sample container.

  In this measurement, the reference mass before starting decomposition of the component (d) is the mass at 150 ° C. during the temperature elevation. This is because the decrease in mass at 150 ° C. or less is due to the removal of adsorbed moisture and the like, and it is estimated that the decomposition of the component (d) itself has not substantially occurred. In addition, in the measurement of the “decrease rate”, when the component (d) is dissolved in a solvent and only the component (d) cannot be directly measured, the solution containing the component (d) is reduced to, for example, a metal petri dish. A residue obtained by taking about 2 g and drying in air at normal pressure at 150 ° C. for 3 hours may be used as a sample.

  The void-forming compound as the component (d) is not particularly limited as long as it has thermal decomposability or volatility. For example, a polymer having a polyalkylene oxide structure, a (meth) acrylate polymer, Examples thereof include polyester polymers, polycarbonate polymers, polyanhydride polymers, and tetrakissilanes. From the viewpoint of suppressing the film shrinkage when forming the alkali-treated film, it is preferable that the amount of hydroxyl groups (—OH) having a strong interaction with the siloxane resin is small. The thermally decomposable compound and volatile compound containing a hydroxy group (—OH) are solvated with the siloxane resin obtained by hydrolyzing the general formula (1). There is a tendency to inhibit the hardening of. For this reason, the film shrinkage rate during curing tends to increase. However, when there is no polar substituent such as a hydroxy group (—OH), the compatibility with the siloxane resin is lowered, resulting in poor film formation and excessive void size. There is. Therefore, as the void forming compound, those having a certain amount of hydroxy groups are preferable.

  In addition, if the thermally decomposable compound or volatile compound has thermal decomposability or volatility at a temperature lower than 200 ° C., thermal decomposition or volatilization occurs before the siloxane skeleton is formed. The dielectric properties may not be obtained. On the other hand, when the coating with alkali treatment is formed on a substrate having a wiring metal or the like if it is thermally decomposable or volatile at a temperature exceeding 500 ° C., the wiring metal may be deteriorated by the high temperature. There is. Therefore, if it is thermally decomposed or volatilized in these temperature ranges (200 to 500 ° C.), it is possible to obtain an effect that the dielectric characteristics of the insulating film can be easily adjusted while suppressing the deterioration of the wiring metal.

  Examples of the polyalkylene oxide structure include a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, a polybutylene oxide structure, and the like. Specific examples of the polymer having such a structure include polyoxyethylene alkyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene polyoxypropylene block Copolymer, ether type compound such as polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitol fatty acid ester, ether ester type compound such as polyoxyethylene fatty acid alkanolamide sulfate, polyethylene glycol fatty acid ester, Ethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, B propylene glycol fatty acid ester ether ester type compounds such like.

  The (meth) acrylate polymer has acrylic acid, methacrylic acid or an ester thereof as a monomer unit. Examples of the acrylic acid ester or methacrylic acid ester include acrylic acid alkyl ester, methacrylic acid alkyl ester, acrylic acid alkoxyalkyl ester, methacrylic acid alkyl ester, and methacrylic acid alkoxyalkyl ester.

  More specifically, examples of the alkyl acrylate ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, pentyl acrylate, and acrylic acid. C1-C6 alkylesters, such as hexyl, are mentioned. Moreover, as alkyl methacrylate, it is C1-C1 such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, hexyl methacrylate. 6 alkyl esters. Further, examples of the alkoxyalkyl acrylate include methoxymethyl acrylate and ethoxyethyl acrylate. Furthermore, examples of the alkoxyalkyl methacrylate include methoxymethyl methacrylate and ethoxyethyl methacrylate.

  Acrylic acid ester or methacrylic acid ester having a hydroxyl group is also suitable, for example, 2-hydroxylethyl acrylate, 2-hydroxylpropyl acrylate, 2-hydroxylethyl methacrylate, 2-hydroxylpropyl methacrylate, and the like. It is done.

  Furthermore, examples of the polyester polymer that is a void forming compound include polycondensates of hydroxycarboxylic acids, ring-opening polymers of lactones, polycondensates of aliphatic polyols and aliphatic polycarboxylic acids, and the like.

  Furthermore, examples of the polycarbonate polymer include polycondensates of carbonic acid and alkylene glycol such as polyethylene carbonate, polypropylene carbonate, polytrimethylene carbonate, polytetramethylene carbonate, polypentamethylene carbonate, and polyhexamethylene carbonate. .

  Examples of the polyanhydride include polycondensates of dicarboxylic acids such as polymalonyl oxide, polyadipoyl oxide, polypimeyl oxide, polysuberoyl oxide, polyazelayl oxide, and polysebacoyl oxide. .

  Further, examples of the tetrakissilanes include tetrakis (trimethylsiloxy) silane, tetrakis (trimethylsilyl) silane, tetrakis (methoxyethoxy) silane, tetrakis (methoxyethoxyethoxy) silane, tetrakis (methoxypropoxy) silane, and the like. As the void-forming compound as the component (d), these can be contained alone or in combination.

  In addition, it is preferable that Mw of (d) component is 200-10,000 from viewpoints, such as solubility to a solvent, compatibility with a siloxane resin, the mechanical property of a film | membrane, and the moldability of a film | membrane, 300- More preferably, it is 5,000, and it is still more preferable that it is 400-2,000. When this Mw exceeds 10,000, the compatibility with the siloxane resin tends to decrease. On the other hand, if it is less than 200, void formation tends to be insufficient.

  Next, the photoacid generator or photobase generator as component (e) will be described.

  In addition, the photoacid generator or photobase generator as the component (e) is not particularly limited, and examples thereof include the following. Specifically, as the photoacid generator, specifically, a diarylsulfonium salt, a triarylsulfonium salt, a dialkylphenacylsulfonium salt, a diaryliodonium salt, an aryldiazonium salt, an aromatic tetracarboxylic acid ester, an aromatic sulfonic acid ester, Nitrobenzyl ester, oxime sulfonic acid ester, aromatic N-oxyimide sulfonate, aromatic sulfamide, haloalkyl group-containing hydrocarbon compound, haloalkyl group-containing heterocyclic compound, naphthoquinone diazide-4-sulfonic acid ester, etc. . These compounds can be used in combination of two or more as required, or in combination with other sensitizers.

  Further, the photobase generator is specifically a nonionic compound group represented by the following general formulas (2) to (5), or nifedipines, etc. Quaternary ammonium salts represented by the formulas (6) and (7) are exemplified.

［式（２）中、Ｒ^２は炭素数１〜３０の１価の有機基であり、メトキシ基又はニトロ基が置換した芳香族環を含んでいてもよい、Ｒ^３は炭素数１〜２０の１〜４価の有機基、ｍは１〜４の整数である］

［式（３）中、Ｒ^３は一般式（２）と同じであり、Ｒ^４、Ｒ^５は各々独立に炭素数１〜３０の１価の有機基である。Ｒ^４及びＲ^５は互いが結合することにより環状構造を形成していても良い。また、ｍは１〜４の整数である］

［式（４）中、Ｒ^２は一般式（２）と同じであり、Ｒ^６、Ｒ^７は各々独立に炭素数１〜３０の１価の有機基である。Ｒ^６及びＲ^７は、互いが結合することで環状構造を形成していても良い。またどちらか一方は水素原子であってもよい］

［式（５）中、Ｒ^６及びＲ^７は一般式（４）と同じであり、Ｒ^８は炭素数１〜３０の１価の有機基であり、アルコキシ基、ニトロ基、アミノ基、アルキル置換アミノ基、アルキルチオ基が置換した芳香族環を含んでいてもよい。Ｒ^９は、炭素数１〜３０の２価の有機基を示す。］

[In formula (2), R ² is a monovalent organic group having 1 to 30 carbon atoms, a methoxy group or a nitro group may contain an aromatic ring substituted, R ³ is 1 to 20 carbon atoms 1 to 4 valent organic groups, m is an integer of 1 to 4]

[In the formula (3), R ³ is the same as in the general formula (2), and R ⁴ and R ⁵ are each independently a monovalent organic group having 1 to 30 carbon atoms. R ⁴ and R ⁵ may be bonded to each other to form a cyclic structure. M is an integer of 1 to 4]

[In Formula (4), R ² is the same as in General Formula (2), and R ⁶ and R ⁷ are each independently a monovalent organic group having 1 to 30 carbon atoms. R ⁶ and R ⁷ may form a cyclic structure by bonding to each other. Either one may be a hydrogen atom]

[In the formula (5), R ⁶ and R ⁷ are the same as those in the general formula (4), R ⁸ is a monovalent organic group having 1 to 30 carbon atoms, alkoxy group, nitro group, amino group, alkyl group An aromatic ring substituted with a substituted amino group or an alkylthio group may be contained. R ⁹ represents a divalent organic group having 1 to 30 carbon atoms. ]

［式（６）中、Ｒ^１０は炭素数１〜３０の１価の有機基、Ｒ^１１及びＲ^１２は各々独立に水素原子又は炭素数１〜３０の１価の有機基。Ｒ^１３、Ｒ^１４、Ｒ^１５及びＲ^１６は各々独立に炭素数１〜３０の１価の有機基、Ｒ^１７、Ｒ^１８及びＲ^１９は各々独立に単結合又は炭素数１〜３０の２価の有機基、Ｒ^２０及びＲ^２１は各々独立に炭素数１〜３０の３価の有機基、Ｙはアンモニウム塩の対イオンをあらわす。ｍは１〜３であり、ｑ及びｐは各々独立に０、１又は２であり、且つｍ＋ｑ＋ｐ＝３である。］

［式（７）中、Ｒ^１０〜Ｒ^２１、Ｙ、ｍ、ｑ及びｐは一般式（６）と同じである。］

Wherein ^{(6), R 10} is a monovalent organic ^group, a monovalent organic group of ^{R 11} and ^{R 12} each independently represent a hydrogen atom or a C1-30 C1-30. R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a monovalent organic group having 1 to 30 carbon atoms, and R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently a single bond or a divalent group having 1 to 30 carbon atoms. R ²⁰ and R ²¹ each independently represents a trivalent organic group having 1 to 30 carbon atoms, and Y represents a counter ion of an ammonium salt. m is 1 to 3, q and p are each independently 0, 1 or 2, and m + q + p = 3. ]

[In the formula (7), R ^{10 to} R ²¹ , Y, m, q and p are the same as those in the general formula (6). ]

  The amount of the photoacid generator or photobase generator as the component (e) depends on the sensitivity and efficiency, the light source used, the thickness of the desired cured product, and the like. It is preferable to determine appropriately. Specifically, it is preferably 0.0001 to 50% by weight, more preferably 0.001 to 20% by weight, more preferably 0.01 to 20% by weight with respect to the resin component weight of the composition for forming an alkali-treated film. More preferably, it is 10% by weight. When this addition amount is less than 0.0001% by weight, the photocurability is lowered and the exposure amount required for curing tends to be large. On the other hand, when the amount used exceeds 50% by weight, the stability and film formability of the composition for forming an alkali-treated film tend to be lowered, and the electrical properties and process suitability of the cured product may be lowered. is there.

  Moreover, you may add a photosensitizer other than the said (d) component and (e) component with respect to the composition for alkali-treated film formation which is a radiation curable composition. By using a photosensitizer, the energy of radiation can be efficiently absorbed, and for example, the sensitivity of the photobase generator can be improved. Examples of the photosensitizer include anthracene derivatives, perylene derivatives, anthraquinone derivatives, thioxanthone derivatives, and coumarins.

  Furthermore, you may add a pigment | dye to the composition for radiation-treatment film formation (radiation curable composition). By adding a dye, sensitivity can be adjusted and an effect of suppressing the standing wave effect can be obtained. Furthermore, a surfactant, a silane coupling agent, a thickener, an inorganic filler, and the like may be added to the composition for forming an alkali-treated film as long as the object and effect of the present invention are not impaired.

  Next, the preferable content of each component in the composition for forming an alkali-treated film will be described. The content of the siloxane resin as the component (a) in the composition for forming an alkali-treated film is preferably 3 to 25% by weight. When the concentration of the component (a) exceeds 25% by weight, the amount of the organic solvent becomes relatively small, the film formability at the time of forming the alkali-treated film is deteriorated, and the stability of the composition itself is also obtained. It tends to decrease. On the other hand, when the concentration of the component (a) is less than 3% by weight, the amount of the solvent is excessive, and it tends to be difficult to form an alkali-treated film having a desired film thickness. Moreover, suitable content of (b) component is (a) component, (c) component, and other components ((d) component, (e) component, etc.) in the total amount of the composition for alkali-treated film formation. It becomes the remainder except the total content of.

  The composition for forming an alkali-treated film according to a preferred embodiment includes the component (a) and the component (b) described above as essential components, and the component (c), the component (d), and the component (e) as necessary. It contains other components such as components. When an alkali-treated film comprising such an alkali-treated film-forming composition is applied as an interlayer insulating film, it is preferable that the alkali-treated film-forming composition does not contain an alkali metal or an alkaline earth metal. Even in the case where these are contained, the metal ion concentration in the composition is preferably 100 ppb or less, more preferably 20 ppb or less. When this metal ion concentration exceeds 100 ppb, metal ions are likely to flow into a semiconductor element having an alkali-treated film obtained from the composition for forming an alkali-treated film, which may adversely affect device performance. Accordingly, when an alkali metal or alkaline earth metal is contained in the composition for forming an alkali-treated film, if necessary, from the composition for forming an alkali-treated film by using an ion exchange filter or the like. It is effective to remove the metal.

[Method for producing alkali-treated film]
Next, a method for producing an alkali-treated film using the composition for forming an alkali-treated film according to the embodiment described above will be described.

  First, a composition for forming an alkali-treated film is uniformly applied on a predetermined substrate to form a coating film. As the substrate, both a substrate having a flat surface such as a silicon wafer and a substrate having electrodes (wiring metal) or the like and having irregularities (for example, a wiring substrate) can be applied. Examples of the substrate include those made of organic polymers such as polyethylene terephthalate, polyethylene naphthalate, polyamide, polycarbonate, polyacryl, nylon, polyethersulfone, polyvinyl chloride, polypropylene, and triacetyl cellulose. It is done. Also, plastic films such as these organic polymers can be used.

  As a method for applying the composition for forming an alkali-treated film on the substrate, a spin coating method is preferable. The coating method is not necessarily limited to the spin coating method, but the spin coating method is preferable because excellent film formability and film uniformity can be obtained.

  In the spin coating method, a coating film is formed by spin-coating the composition for forming an alkali-treated film on a substrate such as a silicon wafer, preferably at 500 to 5000 revolutions / minute, more preferably 700 to 3000 revolutions / minute. . At this time, if the rotational speed is less than 500 revolutions / minute, the uniformity of the film tends to deteriorate. On the other hand, when it exceeds 5000 rpm, the film formability may be deteriorated.

  Under the present circumstances, adjustment of a film thickness can be performed by adjusting the mixture ratio of the (a) component in the composition for alkali-treated film formation, for example. The film thickness can also be adjusted by adjusting the number of rotations and the number of coatings in the spin coating method. When the film thickness is controlled by adjusting the blending ratio of the component (a) as in the former, for example, when the film thickness is increased, the concentration of the component (a) is increased and the film thickness is decreased. Reduces the concentration of component (a). Also, when adjusting the number of rotations and the number of coatings, for example, when increasing the film thickness, the number of rotations is decreased or the number of coatings is increased, while when the film thickness is decreased, the number of rotations is increased. Or reduce the number of applications.

  Next, the organic solvent in the coating film is dried using a hot plate or the like at 50 to 350 ° C., more preferably 100 to 300 ° C., with respect to the obtained coating film. If the drying temperature is less than 50 ° C., the organic solvent tends to be insufficiently dried. On the other hand, when the drying temperature exceeds 350 ° C., for example, when the component (d) is included, the porous component (d) component is thermally decomposed and its volatilization amount before the siloxane skeleton of the siloxane resin is sufficiently formed. Increases undesirably, and it may be difficult to obtain an alkali-treated film having desired mechanical strength and low dielectric properties.

  Thereafter, the coating film from which the organic solvent has been removed is baked at a heating temperature of 200 to 500 ° C. to perform final curing. This heating temperature is preferably 250 to 500 ° C. Thus, an alkali-treated film that is resistant to alkali treatment is formed. The final curing is preferably performed in an inert atmosphere such as nitrogen, argon, or helium. In this case, the oxygen concentration is preferably 1000 ppm or less. When the heating temperature is less than 200 ° C., sufficient curing tends not to be achieved, and decomposition and volatilization of the component (d) tend not to be promoted sufficiently. On the other hand, when the heating temperature exceeds 500 ° C., when there is a metal wiring layer on the substrate, the amount of heat input may increase and the wiring metal may be deteriorated.

  The heating time for this curing is preferably 2 to 60 minutes, more preferably 2 to 30 minutes. If this heating time exceeds 60 minutes, the amount of heat input may increase excessively and the wiring metal may deteriorate. Moreover, as a heating apparatus, a heat treatment apparatus such as a quartz tube furnace, other furnaces, a hot plate, or rapid thermal annealing (RTA) can be used.

  The film thickness of the alkali-treated film thus formed is preferably 0.01 to 10 μm, for example, for use in an antireflection film, and the film thickness when used for an interlayer insulating film such as an LSI is 0.01 to 2 μm. Preferably, the film thickness when used for the passivation layer is 2 to 40 μm. The film thickness when used for liquid crystal is preferably 0.1 to 20 μm, the film thickness when used for a photoresist is preferably 0.1 to 2 μm, and the film thickness when used for an optical waveguide is 1 ˜50 μm is preferred. Further, in particular, when an antireflection film is used, a laminated structure may be obtained by combining with a highly refractive material.

  From the viewpoint described above, the film thickness of the alkali-treated film is preferably 0.010 to 10 μm, more preferably 0.01 to 5.0 μm, and preferably 0.010 to 3.0 μm. More preferably, it is still more preferably 0.010 to 2.0 μm, and particularly preferably 0.10 to 2.0 μm. The film thickness can be adjusted by controlling the film thickness at the application stage of the above-mentioned composition for forming an alkali-treated film on the substrate.

  In the case of a composition for forming an alkali-treated film that contains a photoacid generator or photobase generator as the component (e) and functions as a radiation curable composition, it is desirable as follows. It is also possible to form an alkali-treated film patterned on the surface. That is, first, after applying a composition for forming an alkali-treated film (radiation curable composition) on a predetermined substrate in the same manner as in the method for producing an alkali-treated film, a coating film is formed, and preferably 50 The organic solvent and water in the coating film are volatilized on a hot plate or the like at ~ 200 ° C, more preferably 70-150 ° C, and the coating film is dried. When the drying temperature is less than 50 ° C., the organic solvent tends to be not sufficiently volatilized. On the other hand, when the drying temperature exceeds 200 ° C., the coating film is difficult to dissolve in the developer during the subsequent development processing, and the pattern accuracy tends to be lowered. The radiation curable composition can be operated in an environment that does not include the photosensitive wavelength of the photoacid generator or sensitizer so that the contained photoacid generator is not excited until the development step is completed. preferable.

Next, exposure is performed by irradiating the coating film with radiation through a mask having a desired pattern. Thereby, the exposed part of the coating film irradiated with radiation is cured to form a cured film. Exposure at this time is preferably 5.0~5,000mJ / cm ^2, more preferably 5.0~1,000mJ / cm ^2, is 5.0~500mJ / cm ² It is still more preferable, and it is still more preferable that it is 5.0-100 mJ / cm < ² >. If the exposure amount is less than 5.0 mJ / cm ^2, it may be difficult to control depending on the light source. On the other hand, when it exceeds 5,000 mJ / cm ² , the exposure time becomes long, and the productivity tends to deteriorate. In addition, the exposure amount of the conventional general siloxane radiation-curable composition is about 500 to 5,000 mJ / cm ² .

  The radiation used for exposure refers to electromagnetic waves or particle beams, and examples thereof include visible light, ultraviolet light, infrared light, X-rays, α-rays, β-rays, and γ-rays. Among these, ultraviolet rays are particularly preferable. Examples of the ultraviolet ray generation source include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, and an excimer lamp.

  In addition, you may implement a heating (post exposure bake: PEB) process as needed after the said exposure. In the heat treatment in this step, at least an exposed portion (cured film) cured by exposure is heated by a heating means such as a hot plate. In that case, it is preferable to heat in the temperature range in which the solubility with respect to the developing solution of the coating film of an unexposed part does not fall. The heating temperature is preferably 50 to 200 ° C, more preferably 70 to 150 ° C, still more preferably 70 to 110 ° C, and still more preferably 70 to 100 ° C. In general, the higher the temperature, the more easily the generated acid diffuses, so the lower the heating temperature is better. In addition, the heating temperature in the PEB process of the conventional general siloxane type radiation curable composition is about 115-120 degreeC. However, when it is necessary to reliably avoid acid diffusion and to reduce production costs, it is preferable not to provide a heating step as described above after exposure and before development.

  After the exposure described above, removal of unexposed portions in the coating film of the composition for forming an alkali-treated film (radiation curable composition), that is, development is performed. The unexposed area where the irradiation of radiation is inhibited by the mask in the exposure process has sufficient solubility in the developer used in this development. On the other hand, in the exposed portion irradiated with radiation, an acidic active substance or a basic active substance is generated by exposure, and thereby a hydrolytic condensation reaction occurs in this part, and as a result, the solubility in the developer is lowered. By this action, only the unexposed part is removed in the development process, and only the exposed part (cured film) remains selectively on the substrate to form a pattern.

  For development, for example, a developer such as an alkaline aqueous solution can be used. Examples of the alkaline aqueous solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; diethylamine and di-n. Secondary amines such as propylamine; tertiary amines such as triethylamine and methyldiethylamine; alcohol amines such as dimethylethanolamine and triethanolamine; fourth amines such as tetramethylammonium hydroxide (TMAH) and tetraethylammonium hydroxide An aqueous solution of quaternary ammonium and the like can be mentioned. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or a surfactant to these alkaline aqueous solutions can also be used. When the composition for forming an alkali-treated film is used in the production of an electronic component, the electronic component tends to dislike contamination with an alkali metal, and therefore a tetramethylammonium hydroxide aqueous solution is preferable as the developer.

  The suitable development time depends on the thickness of the coating film and the cured film and the solvent, but is preferably 5 seconds to 5 minutes, more preferably 30 seconds to 3 minutes, and 30 seconds to 1 minute. More preferably it is. If the development time is less than 5 seconds, accurate time control for the entire surface of the wafer or substrate may be difficult, and if it exceeds 5 minutes, productivity tends to deteriorate. Although the processing temperature at the time of image development is not specifically limited, Generally it is 20-30 degreeC. As the developing method, for example, methods such as spraying, paddle, dipping, and ultrasonic can be applied.

  The pattern thus formed may be rinsed with distilled water or the like as necessary. The pattern in this state (cured film of the composition for forming an alkali-treated film) can be used as it is as a resist mask.

When the cured film patterned by exposure / development described above is left on the substrate or in the electronic component as an interlayer insulating film or a cladding layer, for example, the cured film is baked at a heating temperature of 100 to 500 ° C. It is preferable to perform final curing. This final curing is preferably performed under an inert atmosphere such as N ₂ , Ar, or He, in the air, under reduced pressure conditions, or the like. However, as long as the characteristics required for the application are satisfied, the ambient atmosphere and pressure are increased. There are no particular restrictions on the conditions. By setting the heating temperature in this final curing to 100 ° C. to 500 ° C., the curability of the exposed portion can be further improved and the electrical insulation can be improved. In addition, the lower heating temperature is preferable because deterioration of materials used for the lower layer of the coating film such as a substrate or a wafer tends to be suppressed.

  The heating time in this final curing is preferably 2 to 240 minutes, and more preferably 2 to 120 minutes. If the heating time exceeds 240 minutes, it tends to be undesirable from the viewpoint of mass productivity. Examples of the heating device include a furnace such as a quartz tube furnace, a hot plate, and rapid thermal annealing (RTA).

  The alkali-treated film as described above is applied to various uses as a single layer or in the form of a laminate provided on a predetermined substrate. For example, it can be applied as an antireflection film by combining with a substrate made of a highly refractive material as described above. In addition, the laminate can be applied as various electronic components and components thereof as described below by changing the type of the substrate.

[Electronic parts]
Next, an electronic component including the alkali-treated film according to the above-described embodiment will be described.

  Examples of the electronic component provided with the alkali-treated film include electronic devices such as semiconductor elements and multilayer wiring boards, and flat panel displays (FPD) having an alkali-treated film. In the semiconductor element, the alkali-treated film can be used as a surface protective film (passivation film), a buffer coat film, an interlayer insulating film, or the like. Moreover, in a multilayer wiring board, it can be suitably used as an interlayer insulating film. Further, in a flat panel display (FPD), it can be used as an insulating film, an interlayer insulating film, a low refractive index film, and a protective film of a transistor. Furthermore, the alkali-treated film can be used as an antireflection film such as FPD or glass.

  Specifically, as semiconductor elements, individual semiconductor elements such as diodes, transistors, compound semiconductors, thermistors, varistors, thyristors, DRAM (dynamic random access memory), SRAM (static random access memory), EPROM (Erasable Programmable Read Only Memory), Mask ROM (Mask Read Only Memory), EEPROM (Electrically Erasable Programmable Read Only Memory), Flash Memory and other Memory Elements, Microprocessor, Theoretical circuit elements such as DSP and ASIC, integrated circuit elements such as compound semiconductors represented by MMIC (monolithic microwave integrated circuit), hybrid integrated circuits (hybrid IC), Diodes, etc. The photoelectric conversion element such as a charge coupled device and the like. Examples of the multilayer wiring board include a high-density wiring board such as MCM. Further, examples of the flat panel display (FPD) include transistors such as liquid crystal, organic EL, and plasma display. Furthermore, other electronic components include optical waveguides, resists, solar cell panels, and the like, and the alkali-treated coating can be used for these coatings.

  Here, a TFT (thin film transistor) will be described with reference to FIG. 1 as an example of an electronic component having an alkali-treated film.

  FIG. 1 is a diagram schematically showing a cross-sectional configuration of a main part of a TFT according to a preferred embodiment. The TFT 100 is an electronic component used for a TFT liquid crystal display. In the TFT 100, an undercoat film 2 is formed on a glass substrate 1, and a transistor portion 20 including a source 4, a drain 5, a conductive layer 3, a gate oxide film 6, and a gate electrode 7 is provided on the undercoat film 2. It has the structure which was made. A metal wiring 9 is provided on the transistor portion 20 with the first interlayer insulating film 8 interposed therebetween. A second interlayer insulating film is formed on the metal wiring 9 so as to cover the transistor portion 20 and the metal wiring 9. 10 and the transparent electrode 11 are provided in this order.

The source 4 and the drain 5 in the transistor unit 20 are provided on the undercoat film 2 at a predetermined interval. Further, a conductive layer 3 made of polysilicon is disposed between these source 4 and drain 5 so as to be in contact with both. That is, the source 4 and the drain 5 are disposed so as to sandwich the conductive layer 3 in the in-plane direction. On the conductive layer 3, a gate oxide film 6 made of SiO ₂ is formed so as to cover it, and a gate electrode 7 is further formed on the gate oxide film 6. The gate oxide film 6 prevents the conductive layer 3 and the gate electrode 7 from being in direct contact with each other, and insulation between them is achieved.

  The first interlayer insulating film 8 is formed on the undercoat film 2 so as to cover the transistor portion 20 and has a function of preventing a short circuit. The first interlayer insulating film 8 has an opening so that part of the source 4 and the drain 5 is exposed. The metal wiring 9 is provided on the opening of the first interlayer insulating film 8. The metal wiring 9 has a lead-out portion 9a drawn into the opening, and is connected to the source 4 or the drain 5 by this.

  Further, the second interlayer insulating film 10 is provided so as to cover the lower structure including the metal wiring 9 and has a function of preventing a short circuit. The second interlayer insulating film 10 has an opening in the upper region of the metal wiring 9 connected to the drain 5. A transparent electrode 11 is formed on the second interlayer insulating film 10. The transparent electrode 11 has a lead portion 11 a formed inside the opening of the second interlayer insulating film 10, and is thereby connected to the metal wiring 9 connected to the drain 5.

  In the TFT 100 having the above structure, both the first interlayer insulating film 8 and the second interlayer insulating film 10 are formed by the alkali-treated film according to the preferred embodiment described above. These first and second interlayer insulating films 8 and 10 can be formed in the same manner as the above-described method for forming an alkali-treated film. That is, first, a composition for forming an alkali-treated film (radiation curable composition) according to a preferred embodiment of the present invention is applied onto a substrate as a base by spin coating or the like, and then dried to form a coating film. Get. In the case of the first interlayer insulating film 8, the base substrate in this case corresponds to a structure including the substrate 1, the undercoat film 2, and the transistor unit 20, and in the case of the second interlayer insulating film 10, the structure described above. Further, a structure including the first interlayer insulating film 8 and the metal wiring 9 is applicable.

  Next, the coating film is exposed through a mask having a predetermined pattern (a shape covering an area where an opening is to be formed), the portions other than the unexposed portions are cured, and heat treatment is performed as necessary. Then, the unexposed portion is removed by development to form first or second interlayer insulating films 8 and 10 made of an alkali-treated film. Thereafter, the alkali-treated film may be completely cured by further performing heat treatment as necessary. The first and second interlayer insulating films 8 and 10 may be formed from an alkali-treated film forming composition having the same composition, or an alkali-treated film forming composition having a different composition. It may be formed from an object.

  In the TFT 100 having the above-described configuration, the first and second interlayer insulating films 8 and 10 are made of an alkali-treated film of the present invention having excellent alkali treatment resistance. For this reason, for example, in the manufacture of the TFT 100, even when the patterning of the metal wiring 9 and the transparent electrode 11 is performed by alkali treatment via a resist, the first and second interlayer insulating films 8 and 10 are extremely deteriorated. It is hard to occur. As a result, it is possible to greatly reduce the occurrence of defects such as short circuits in the manufacture of the TFT 100. In addition, since the alkali-treated films that are the first and second interlayer insulating films 8 and 10 are sufficiently excellent in adhesion to adjacent layers, the TFT 100 is excellent in that peeling between layers is hardly caused. It has durability and reliability. In the TFT 100, both the first and second interlayer insulating films 8 and 10 are not necessarily formed by the alkali-treated film of the present invention, and any one of them may be formed, and at least the second It is preferable that the interlayer insulating film 10 is formed.

  As described above, according to the electronic parts and the like as exemplified above, the alkali-treated film has resistance to alkali treatment, so that the treatment process with alkali can be performed satisfactorily. Furthermore, due to the excellent properties of the alkali-treated film made of the composition for forming an alkali-treated film of the present invention, it is possible to provide an electronic component or the like having high density, high quality and excellent reliability.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.

[Example 1]
(Preparation of composition for forming alkali-treated film)
In a solution obtained by dissolving 5.34 g of tetraethoxysilane (silicon compound) and 9.19 g of methyltriethoxysilane (silicon compound) in 31.1 g of ethanol (solvent), 4.19 g of a 0.644 wt% nitric acid aqueous solution was added. The solution was added dropwise over 1 minute under stirring. After completion of the dropwise addition, the mixture is allowed to react for 1.5 hours, followed by addition of 0.21 g of a 2.38% tetramethylammonium nitrate aqueous solution (curing accelerator, pH 3.6), and stirring and dissolving at room temperature (25 ° C.) for 30 minutes. Thus, a composition for forming an alkali-treated film was prepared.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed as follows. That is, first, the composition for forming an alkali-treated film is placed in a 2 mL plastic syringe, a PTFE pore size 0.20 μm filter is attached to the tip, and 1.5 mL of the composition for forming an alkali-treated film is added. After dropping on a 5-inch silicon wafer, a coating film was formed by spin coating. At this time, in the formation of the coating film, the rotation speed was adjusted so that the film thickness after curing was 225 ± 25 nm. Next, after removing the organic solvent in the coating film at 250 ° C. over 3 minutes, the organic solvent was removed at 350 ° C. for 30 minutes using a quartz tube furnace in which the oxygen concentration was controlled at around 100 ppm. The coating film was finally cured to produce an interlayer insulating film made of an alkali-treated film.

[Example 2]
(Preparation of composition for forming alkali-treated film)
In a solution obtained by dissolving 5.34 g of tetraethoxysilane and 9.19 g of methyltriethoxysilane in 31.1 g of isopropanol (solvent, IPA), 4.19 g of a 0.644% by weight aqueous nitric acid solution was stirred for 1 minute. And dripped. After completion of the dropwise addition, the mixture is allowed to react for 1.5 hours. Then, 0.21 g of a 2.38% tetramethylammonium nitrate aqueous solution (pH 3.6) is added, and the mixture is stirred and dissolved at room temperature for 30 minutes. A composition was prepared.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed in the same manner as in Example 1.

[Example 3]
(Preparation of composition for forming alkali-treated film)
In a solution obtained by dissolving 10.7 g of tetraethoxysilane and 18.4 g of methyltriethoxysilane in 58.4 g of cyclohexanone (solvent, Cy = O), 8.39 g of a 0.644% by weight nitric acid aqueous solution was added with stirring. It was added dropwise over a period of minutes. After completion of the dropwise addition, the reaction was allowed to proceed for 1.5 hours, followed by the addition of 4.20 g of a 2.38% tetramethylammonium nitrate aqueous solution (pH 3.6), and the mixture was further stirred for 30 minutes. A part of cyclohexanone was distilled off to obtain 61.7 g of a polysiloxane solution. Next, 38.2 g of cyclohexanone was added, and the mixture was stirred and dissolved at room temperature for 30 minutes to prepare an alkali-treated film-forming composition.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed in the same manner as in Example 1.

[Example 4]
(Preparation of composition for forming alkali-treated film)
In a solution obtained by dissolving 10.7 g of tetraethoxysilane and 18.4 g of methyltriethoxysilane in 58.4 g of diethylene glycol dimethyl ether (solvent, DGDME), 8.39 g of a 0.644 wt% nitric acid aqueous solution was stirred for 1 minute. It was dripped over. After completion of the dropwise addition, the mixture was allowed to react for 1.5 hours. Subsequently, 4.20 g of a 2.38% tetramethylammonium nitrate aqueous solution (pH 3.6) was added, and the mixture was further stirred for 30 minutes. A part of diethylene glycol dimethyl ether was distilled off to obtain 64.3 g of a polysiloxane solution. Next, 35.7 g of diethylene glycol dimethyl ether was added, and the mixture was stirred and dissolved at room temperature for 30 minutes to prepare an alkali-treated film-forming composition.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed in the same manner as in Example 1.

[Example 5]
(Preparation of composition for forming alkali-treated film)
In a solution prepared by dissolving 10.7 g of tetraethoxysilane and 18.4 g of methyltriethoxysilane in 62.1 g of propylene glycol monomethyl ether acetate (solvent, PGMEA), 8.39 g of a 0.644 wt% nitric acid aqueous solution was stirred. The solution was added dropwise over 1 minute. After completion of the dropwise addition, the mixture was allowed to react for 1.5 hours, followed by addition of 0.423 g of a 2.38% tetramethylammonium nitrate aqueous solution (pH 3.6), and the mixture was further stirred for 30 minutes. A part of propylene glycol monomethyl ether acetate was distilled off to obtain 67.8 g of a polysiloxane solution. Next, 32.2 g of propylene glycol monomethyl ether acetate was added, and the mixture was stirred and dissolved at room temperature for 30 minutes to prepare an alkali-treated film-forming composition.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed in the same manner as in Example 1.

[Comparative Example 1]
(Preparation of composition for forming alkali-treated film)
To a solution obtained by dissolving 5.34 g of tetraethoxysilane and 9.19 g of methyltriethoxysilane in 31.1 g of ethanol, 4.19 g of a 0.644% by weight aqueous nitric acid solution was added dropwise over 1 minute with stirring. After completion of dropping, the mixture was reacted for 2 hours to prepare a composition for forming an alkali-treated film.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed in the same manner as in Example 1.

[Comparative Example 2]
(Preparation of composition for forming alkali-treated film)
To a solution obtained by dissolving 5.34 g of tetraethoxysilane and 9.19 g of methyltriethoxysilane in 31.1 g of isopropanol, 4.19 g of a 0.644% by weight aqueous nitric acid solution was added dropwise over 1 minute with stirring. After completion of dropping, the mixture was reacted for 2 hours to prepare a composition for forming an alkali-treated film.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed in the same manner as in Example 1.

[Comparative Example 3]
(Preparation of composition for forming alkali-treated film)
In a solution prepared by dissolving 10.7 g of tetraethoxysilane and 18.4 g of methyltriethoxysilane in 62.6 g of propylene glycol monomethyl ether acetate (PGMEA), 8.39 g of a 0.644% by weight nitric acid aqueous solution was added while stirring. It was added dropwise over a period of minutes. After completion of the dropwise addition, the mixture was reacted for 2 hours, and a part of the produced ethanol and propylene glycol monomethyl ether acetate was distilled off in a warm bath under reduced pressure to obtain 58.6 g of a polysiloxane solution. Next, 41.4 g of propylene glycol monomethyl ether acetate was added, and the mixture was stirred and dissolved at room temperature for 30 minutes to prepare an alkali-treated film-forming composition.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed in the same manner as in Example 1.

[Characteristic evaluation]
The refractive index, relative dielectric constant, film thickness, and light transmittance (300 to 800 nm) of the alkali-treated films obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were measured. The film thickness and the refractive index were determined by irradiating the obtained alkali-treated film with a He—Ne laser beam and determining the film thickness obtained from the phase difference caused by the light irradiation at a wavelength of 633 nm. L116B).

  Further, the silicon wafer having the alkali-treated film after the above measurement is immersed in a 10 wt% potassium hydroxide (KOH) aqueous solution heated to 50 ° C. for 10 minutes, and then the silicon wafer is washed with pure water. And spin-dried. Then, the film thickness and refractive index of the alkali-treated film after such treatment were determined in the same manner as described above. Then, the film thickness change and refractive index change before and after the KOH treatment were calculated from the film thickness and refractive index values before and after immersion in the KOH aqueous solution.

  Refractive index, relative dielectric constant, film thickness, light transmittance (300 to 800 nm), and film thickness change and refractive index before and after KOH treatment obtained by the above-described measurement using the alkali-treated film of each example or comparative example. The value of change is shown in Table 1. In Table 1, the value of M (total number of specific bonding atoms) of the siloxane resin contained in the composition for forming an alkali-treated film, the type of solvent (protic or aprotic), the name of the solvent, and the main The boiling point of the solvent and the content of the curing accelerating catalyst in the composition for forming an alkali-treated film are also shown.

  From Table 1, as for the alkali-treated film of Examples 1-5 containing a hardening acceleration | stimulation catalyst, the film thickness change before and behind KOH process was 50 nm or less, and the refractive index change was 0.06 or less. On the other hand, the alkali-treated films of Comparative Examples 1 and 2 that did not contain a curing accelerating catalyst were all removed by the KOH treatment, and no alkali-treated film was present after the KOH treatment. Further, the alkali-treated film of Comparative Example 3 containing no curing accelerating catalyst had a change in film thickness of 50 nm or less, but a change in refractive index of 0.06 or more. Thus, it was found that a curing accelerating catalyst is useful for improving resistance to alkali treatment.

[Example 6]
(Preparation of composition for forming alkali-treated film)
In a solution prepared by dissolving 26.6 g of methyltriethoxysilane in 65.7 g of propylene glycol monomethyl ether acetate (PGMEA), 7.29 g of a 0.644% by weight aqueous nitric acid solution was added dropwise over 1 minute with stirring. After completion of the dropwise addition, the mixture was allowed to react for 1.5 hours, followed by addition of 0.423 g of a 2.38% tetramethylammonium nitrate aqueous solution (pH 3.6), and the mixture was further stirred for 30 minutes. A part of propylene glycol monomethyl ether acetate was distilled off to obtain 50.8 g of a polysiloxane solution. Next, 49.2 g of propylene glycol monomethyl ether acetate was added, and the mixture was stirred and dissolved at room temperature for 30 minutes to prepare an alkali-treated film-forming composition.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed in the same manner as in Example 1.

[Example 7]
(Preparation of composition for forming alkali-treated film)
In a solution prepared by dissolving 5.26 g of tetraethoxysilane and 22.5 g of methyltriethoxysilane in 64.0 g of propylene glycol monomethyl ether acetate (PGMEA), 7.83 g of a 0.644% by weight nitric acid aqueous solution was added while stirring. It was added dropwise over a period of minutes. After completion of the dropwise addition, the reaction was allowed to proceed for 2 hours, followed by the addition of 0.420 g of a 2.38% tetramethylammonium nitrate aqueous solution (pH 3.6), and stirring for another 2 hours. A part of the monomethyl ether acetate was distilled off to obtain 64.1 g of a polysiloxane solution. Next, 35.9 g of propylene glycol monomethyl ether acetate was added, and the mixture was stirred and dissolved at room temperature for 30 minutes to prepare a composition for forming an alkali-treated film.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed in the same manner as in Example 1.

[Example 8]
(Preparation of composition for forming alkali-treated film)
In a solution prepared by dissolving 7.59 g of tetraethoxysilane and 20.8 g of methyltriethoxysilane in 63.2 g of propylene glycol monomethyl ether acetate (PGMEA), 8.07 g of a 0.644% by weight nitric acid aqueous solution was added while stirring. It was added dropwise over a period of minutes. After completion of the dropwise addition, the mixture was allowed to react for 1.5 hours, followed by addition of 0.424 g of a 2.38% tetramethylammonium nitrate aqueous solution (pH 3.6), and after stirring for another 30 minutes, A part of propylene glycol monomethyl ether acetate was distilled off to obtain 60.5 g of a polysiloxane solution. Next, 39.5 g of propylene glycol monomethyl ether acetate was added, and the mixture was stirred and dissolved at room temperature for 30 minutes to prepare an alkali-treated film-forming composition.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed in the same manner as in Example 1.

[Example 9]
(Preparation of a composition for forming an alkali-treated film)
In a solution prepared by dissolving 12.2 g of tetraethoxysilane and 17.2 g of methyltriethoxysilane in 61.6 g of propylene glycol monomethyl ether acetate (PGMEA), 8.54 g of a 0.644% by weight aqueous nitric acid solution was added with stirring. It was added dropwise over a period of minutes. After completion of the dropwise addition, the mixture was allowed to react for 1.5 hours, followed by addition of 0.423 g of a 2.38% tetramethylammonium nitrate aqueous solution (pH 3.6), and the mixture was further stirred for 30 minutes. A part of propylene glycol monomethyl ether acetate was distilled off to obtain 58.8 g of a polysiloxane solution. Next, 41.2 g of propylene glycol monomethyl ether acetate was added, and the mixture was stirred and dissolved at room temperature for 30 minutes to prepare an alkali-treated film-forming composition.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed in the same manner as in Example 1.

[Example 10]
(Preparation of a composition for forming an alkali-treated film)
In a solution prepared by dissolving 13.8 g of tetraethoxysilane and 16.0 g of methyltriethoxysilane in 61.1 g of propylene glycol monomethyl ether acetate (PGMEA), 8.71 g of a 0.644% by weight nitric acid aqueous solution was added while stirring. It was added dropwise over a period of minutes. After completion of the dropwise addition, the reaction was allowed to proceed for 2 hours, followed by addition of 0.420 g of a 2.38 wt% tetramethylammonium nitrate aqueous solution (pH 3.6). A part of glycol monomethyl ether acetate was distilled off to obtain 61.7 g of a polysiloxane solution. Next, 38.3 g of propylene glycol monomethyl ether acetate was added, and the mixture was stirred and dissolved at room temperature for 30 minutes to prepare a composition for forming an alkali-treated film.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed in the same manner as in Example 1.

[Example 11]
(Preparation of a composition for forming an alkali-treated film)
In a solution prepared by dissolving 16.9 g of tetraethoxysilane and 13.6 g of methyltriethoxysilane in 60.0 g of propylene glycol monomethyl ether acetate (PGMEA), 9.02 g of a 0.644% by weight nitric acid aqueous solution was added with stirring. It was added dropwise over a period of minutes. After completion of the dropwise addition, the reaction was allowed to proceed for 2 hours. Subsequently, 0.421 g of a 2.38 wt% tetramethylammonium nitrate aqueous solution (pH 3.6) was added, and the mixture was further stirred for 30 minutes. A part of glycol monomethyl ether acetate was distilled off to obtain 66.3 g of a polysiloxane solution. Next, 33.7 g of propylene glycol monomethyl ether acetate was added, and the mixture was stirred and dissolved at room temperature for 30 minutes to prepare a composition for forming an alkali-treated film.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed in the same manner as in Example 1.

[Example 12]
(Preparation of composition for forming alkali-treated film)
In a solution obtained by dissolving 20.0 g of tetraethoxysilane and 11.3 g of methyltriethoxysilane in 59.0 g of propylene glycol monomethyl ether acetate (PGMEA), 9.34 g of a 0.644% by weight aqueous nitric acid solution was added while stirring. It was added dropwise over a period of minutes. After completion of the dropwise addition, the reaction was allowed to proceed for 2 hours. Subsequently, 0.424 g of a 2.38 wt% tetramethylammonium nitrate aqueous solution (pH 3.6) was added, and the mixture was further stirred for 30 minutes. A part of the glycol monomethyl ether acetate was distilled off to obtain 58.6 g of a polysiloxane solution. Next, 41.4 g of propylene glycol monomethyl ether acetate was added, and the mixture was stirred and dissolved at room temperature for 30 minutes to prepare an alkali-treated film-forming composition.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed in the same manner as in Example 1.

[Example 13]
(Preparation of composition for forming alkali-treated film)
In a solution prepared by dissolving 26.9 g of tetraethoxysilane and 5.93 g of methyltriethoxysilane in 56.7 g of propylene glycol monomethyl ether acetate (PGMEA), 10.1 g of a 0.644% by weight aqueous nitric acid solution was added with stirring. It was added dropwise over a period of minutes. After completion of the dropwise addition, the reaction was allowed to proceed for 2 hours. Subsequently, 0.425 g of a 2.38% by weight tetramethylammonium nitrate aqueous solution (pH 3.6) was added, and the mixture was further stirred for 30 minutes. A part of the glycol monomethyl ether acetate was distilled off to obtain 55.3 g of a polysiloxane solution. Next, 44.7 g of propylene glycol monomethyl ether acetate was added, and the mixture was stirred and dissolved at room temperature for 30 minutes to prepare an alkali-treated film-forming composition.

(Formation of alkali-treated film (interlayer insulating film))
Using the obtained composition for forming an alkali-treated film, an alkali-treated film (interlayer insulating film) was formed in the same manner as in Example 1.

[Example 14]
(Preparation of composition for forming alkali-treated film)
Tetraethoxysilane 74.8g, methyltriethoxysilane 128.7g, photoacid generator (PAI-101, manufactured by Midori Chemical Co., Ltd.) 1.40g and 2.38 wt% tetramethylammonium nitrate aqueous solution (pH 3.6) An aqueous solution prepared by dissolving 0.378 g of 60 wt% nitric acid in 48.6 g of deionized water in a solution obtained by dissolving 0.296 g in 447.3 g of propylene glycol monomethyl ether acetate (PGMEA) was stirred for 3 minutes. And dripped. After the completion of the dropwise addition, the reaction was allowed to proceed for 4 hours, and then part of the produced ethanol and propylene glycol monomethyl ether acetate was distilled off in a 55 ° C. warm bath under reduced pressure to obtain 264.5 g of a polysiloxane solution. To this polysiloxane solution, 85.5 g of propylene glycol monomethyl ether acetate was added and dissolved by stirring at room temperature (25 ° C.) for 30 minutes to prepare a composition for forming an alkali-treated film (radiation curable composition).

(Evaluation of patterning)
Next, patterning (pattern formation) was performed using this composition for forming an alkali-treated film, thereby forming an alkali-treated film having a predetermined pattern. First, 2 mL of the above composition was dropped on the center of a 6-inch silicon wafer, and a coating film was formed on the wafer by spin coating (rotating at 700 rpm for 30 seconds). Dry for 30 seconds above. Then, the i line | wire is 100 mJ / cm with an exposure machine (FPA-3000 iW, Canon Inc.) through the negative mask which has a linear pattern with the minimum line | wire width of 2 micrometers with respect to the dried coating film. ² irradiated. The wafer provided with the coating film after exposure was heated on a hot plate at 100 ° C. for 30 seconds, and then cooled on a cooling plate (23 ° C.) for 30 seconds.

  Then, the wafer was subjected to paddle development for 30 seconds using a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution as a developer using a coater / developer (Mark 7, manufactured by Tokyo Electron Limited). Was dissolved. Thereafter, the wafer was washed with water and spin-dried. Then, using the furnace body, the spin-dried wafer was heated at 350 ° C. for 30 minutes in a nitrogen atmosphere, and a cured product of the composition for forming an alkali-treated film having a desired pattern on the wafer (alkali-treated). Treatment film) was formed.

  About the pattern shape of the obtained hardened | cured material, when the observation from the upper part by an optical microscope and the cross-sectional shape observation by SEM were performed, the line was formed with sufficient precision. From this, it was confirmed that when using the composition for forming an alkali-treated film of Example 14, a pattern accuracy of 2 μm or less can be obtained.

(Formation of alkali-treated film (interlayer insulating film))
An alkali-treated film was prepared in the same manner as described above except that exposure was performed without using a negative mask and development was not performed (that is, patterning was not performed).

[Characteristic evaluation]
The refractive index, relative dielectric constant, film thickness, and light transmittance (300 to 800 nm) of the alkali-treated films obtained in Examples 6 to 14 were measured in the same manner as described above, and the film thickness before and after the KOH treatment. Changes and refractive index changes were calculated in the same manner as described above. The obtained results are shown in Table 2. Similarly to Table 1, Table 2 also shows the value of M (total number of specific bonding atoms) of the siloxane resin contained in the composition for forming an alkali-treated film, the type of solvent (protic or aprotic), The name of the solvent, the boiling point of the main solvent, and the content of the curing accelerating catalyst in the composition for forming an alkali-treated film are also shown.

  From Table 2, in the alkali-treated films of Examples 6 to 14, the film thickness change was 50 nm or less before and after the alkali (KOH) treatment, and the refractive index change was 0.06 or less. Further, when Example 6 and Example 13 were compared, it was found that the larger the total number of specific bonding atoms (M), the smaller the difference in film thickness change and refractive index change, and the better the alkali treatment resistance. This is considered to be due to the improvement of the mechanical strength / density of the coating by using the curing accelerating catalyst and the improvement of water repellency by the large number of specific bonded atoms.

  Therefore, according to the present invention, an alkali-treated film having excellent alkali treatment resistance, a low refractive index, heat resistance, and good adhesion, a method for producing the same, and an alkali-coated film capable of forming the alkali-treated film It was confirmed that a composition for forming a treated film can be provided.

It is a figure which shows typically the cross-sectional structure of TFT which concerns on embodiment.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Board | substrate, 2 ... Undercoat film, 3 ... Conductive layer, 4 ... Source, 5 ... Drain, 6 ... Gate oxide film, 7 ... Gate electrode, 8 ... 1st interlayer insulation film, 9 ... Metal wiring, 9a ... Lead-out Part, 10 ... second interlayer insulating film, 11 ... transparent electrode, 11a ... lead-out part, 20 ... transistor part, 100 ... TFT.

Claims (24)

An alkali-treated film-forming composition for forming an alkali-treated film exposed to an alkali treatment,
(A) component: siloxane resin;
(B) component: (a) a solvent capable of dissolving the component;
(C) component: a curing accelerating catalyst;
A composition for forming an alkali-treated film, comprising:   The composition for forming an alkali-treated film according to claim 1, wherein the alkali treatment is treatment with an aqueous alkali metal hydroxide solution. The composition for forming an alkali-treated film according to claim 1 or 2, wherein the siloxane resin is obtained by hydrolytic condensation of a raw material component containing a silicon compound represented by the following general formula (1).

[In the formula (1), R ¹ represents an H atom or an F atom, or a group containing a B atom, an N atom, an Al atom, a P atom, a Si atom, a Ge atom, or a Ti atom, or a group having 1 to 20 carbon atoms. An organic group is shown, X shows a hydrolysable group, n shows the integer of 0-2. However, when two or more R < ¹ > or X exists, these may be same or different, respectively. ]   In the siloxane resin, H atom, F atom, B atom, N atom, Al atom, P atom, Si atom, Ge atom bonded to the Si atom with respect to 1 mol of Si atom constituting the siloxane bond. The composition for forming an alkali-treated film according to any one of claims 1 to 3, wherein the total content ratio M of atoms selected from the group consisting of Ti atoms and C atoms is less than 1.0 mol.   The composition for alkali-treated film formation according to claim 4, wherein the M is 0.55 to 0.90 mol.   The composition for alkali-treated film formation according to claim 4, wherein the M is 0.60 to 0.80 mol.   The composition for alkali-treated film formation according to claim 4, wherein the M is 0.62 to 0.75 mol. The group represented by R ¹ is an H atom, a group containing a B atom, an N atom, an Al atom, a P atom, a Si atom, a Ge atom, or a Ti atom, or an organic group having 1 to 20 carbon atoms. The composition for forming an alkali-treated film according to any one of claims 3 to 7, which does not contain F atoms. The group represented by R ¹ is a methyl group, the alkali-treated composition for forming a coating film according to any one of claims 3-7.   The composition for forming an alkali-treated film according to any one of claims 1 to 9, wherein the component (b) is an organic solvent containing at least one aprotic solvent.   The composition for forming an alkali-treated film according to claim 10, wherein the aprotic solvent contains at least one solvent selected from the group consisting of an ether solvent, an ether acetate solvent, an ester solvent, and a ketone solvent. .   The composition for forming an alkali-treated film according to any one of claims 1 to 11, wherein the solvent as the component (b) has a boiling point of 80 to 180 ° C.   The composition for forming an alkali-treated film according to any one of claims 1 to 12, wherein the curing accelerating catalyst is an onium salt.   The composition for forming an alkali-treated film according to any one of claims 1 to 12, wherein the curing accelerating catalyst is an ammonium salt.   The composition for forming an alkali-treated film according to any one of claims 1 to 14, wherein the siloxane resin is a resin curable by heat or radiation. A production method for producing an alkali-treated film exposed to an alkali treatment,
The composition for forming an alkali-treated film according to any one of claims 1 to 15 is applied on a substrate to form a coating film, and after removing the solvent contained in the coating film, the coating film is formed. A method for producing an alkali-treated film, which is baked at a heating temperature of 200 to 500 ° C.   An alkali-treated film obtained by the method for producing an alkali-treated film according to claim 16.   18. The alkali-treated film according to claim 17, wherein the refractive index obtained by ellipsometry at a wavelength of 633 nm is 1.42 or less.   The alkali-treated film according to claim 17 or 18, wherein the relative dielectric constant is 4.0 or less.   20. The alkali-treated film according to claim 17, wherein the Young's modulus measured by the nanoindentation method is 5 GPa or more.   The alkali-treated film according to any one of claims 17 to 20, wherein the transmittance of light at 300 to 800 nm is 90% or more.   A laminate comprising: a substrate; and the alkali-treated film according to any one of claims 17 to 21 provided on the substrate.   An antireflection film comprising: a substrate; and the alkali-treated film according to any one of claims 17 to 21 provided on the substrate.   An electronic component comprising: a substrate; and the alkali-treated film according to any one of claims 17 to 21 provided on the substrate.

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