KR20120124496A - Positive radiation-sensitive composition, interlayer insulating film for display element, and formation method for same - Google Patents

Abstract

This invention is a polymer containing the structural unit (I) which has group represented by following formula (1), and epoxy group containing structural unit (II) in the same or different polymer molecule [A], [B] siloxane polymer, and [C It is a positive radiation sensitive composition containing a photo-acid generator. The siloxane polymer (B) is preferably a hydrolysis condensate of a hydrolyzable silane compound represented by the following formula (2). It is preferable that the mass ratio of the [A] polymer with respect to the sum total of the [A] polymer and the [B] siloxane polymer is 5 mass% or more and 95 mass% or less.

Description

Positive radiation-sensitive composition, interlayer insulating film for display element and method of forming the same {POSITIVE RADIATION-SENSITIVE COMPOSITION, INTERLAYER INSULATING FILM FOR DISPLAY ELEMENT, AND FORMATION METHOD FOR SAME}

The present invention relates to a positive radiation-sensitive composition, an interlayer insulating film for display elements, and a method of forming the same.

In the display element, an interlayer insulating film is formed in order to insulate between wirings arranged in a layer shape in general. As a material for forming the interlayer insulating film, a positive radiation-sensitive composition is widely used because it is preferable that the number of steps for obtaining a necessary pattern shape is small and furthermore, it is desired to have sufficient flatness.

As such a display element, display elements, such as a TFT type liquid crystal display element using an interlayer insulation film, are manufactured through the process of forming a transparent electrode film on an interlayer insulation film, and forming a liquid crystal aligning film on it further. In this case, since an interlayer insulation film is exposed to high temperature conditions in the formation process of a transparent electrode film, sufficient heat resistance is needed.

In recent years, the TFT type liquid crystal display device has a large screen, a high luminance, a high definition, a high speed response, a thinning, and the like, and the fineness of the wiring pattern is also remarkable. In connection with this, in addition to the improvement of transparency and refractive index, the improvement of the technique of refinement | miniaturization of a resist pattern is desired. In the case where the resist pattern is miniaturized, in the dry etching treatment step using the etching gas, if the treatment time is excessively even a little more than the optimum time, the shaving or peeling of the resist is likely to occur. In addition, by increasing the size of the display device including the display element, in order to uniformly treat the entire surface to be treated, it is necessary to increase the dry etching processing time or increase the concentration of the etching gas. The improvement of dry etching resistance and surface hardness of an interlayer insulation film with respect to dry etching conditions is calculated | required.

In order to realize such a high performance, for example, a polysiloxane material is added to an acrylic polymer generating a carboxyl group, a polymer having a functional group reacting with a carboxyl group (see JP-A-2009-98673), or an acrylic resin. The technique (refer Japanese Unexamined-Japanese-Patent No. 2009-98661 and Unexamined-Japanese-Patent No. 2009-116223) used as a component of a radioactive resin composition is proposed.

However, also in these techniques, in addition to high dry etching resistance, the interlayer insulation film for display elements which has favorable heat resistance, transparency, surface hardness, and a refractive index can be formed, and the radiation sensitive resin composition which has sufficient radiation sensitivity is still not obtained. I can't.

Japanese Laid-Open Patent Publication No. 2009-98673 Japanese Laid-Open Patent Publication No. 2009-98661 Japanese Laid-Open Patent Publication No. 2009-116223

The present invention has been made on the basis of the above circumstances, and an object thereof is to provide an interlayer insulating film for display elements having high dry etching resistance in addition to sufficient surface hardness, refractive index, heat resistance and transparency, and sufficient radiation. A positive radiation sensitive composition having a sensitivity, an interlayer insulating film for display elements formed from the composition, and a method of forming the same are provided.

The invention made to solve the above problems,

[A] A polymer comprising a structural unit (I) having a group represented by the following formula (1) and an epoxy group-containing structural unit (II) in the same or different polymer molecules (hereinafter also referred to as "[A] polymer"),

[B] siloxane polymers, and

[C] A positive radiation sensitive composition containing a photoacid generator:

(In formula (1), R <^1> and R <^2> is respectively independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. However, one part or all part of the hydrogen atom which the said alkyl group, a cycloalkyl group, and an aryl group has is substituted, and is substituted. And R ¹ and R ² are not all hydrogen atoms; R ³ is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or a group represented by -M (R ^3m ) ₃ ; Si, Ge, or Sn; each R ^3m is independently an alkyl group, and R ¹ and R ³ may be linked to each other to form a cyclic ether structure, provided that some or all of the hydrogen atoms of these groups represented by R ³ are present; May be substituted).

The positive radiation-sensitive composition can ensure sufficient radiation sensitivity by blending the [B] siloxane polymer in addition to the [A] polymer and [C] photoacid generator of the specific structure, and further, the surface hardness and the refractive index. It is possible to form a cured film such as an interlayer insulating film which satisfactorily satisfies heat resistance and transparency, and has high dry etching resistance.

The siloxane polymer (B) is preferably a hydrolysis condensate of a hydrolyzable silane compound represented by the following formula (2):

(In formula (2), R <^4> is a C1-C20 non-hydrolyzable organic group; R <^5> is a C1-C4 alkyl group; n is an integer of 0-3; However, R <^{4> is} And when there are a plurality of R ⁵ , a plurality of R ⁴ and R ⁵ may be the same or different, respectively).

In the positive radiation-sensitive composition, surface hardness and dry etching resistance are ensured while securing sufficient radiation sensitivity by using a hydrolysis-condensation product of the hydrolyzable silane compound represented by the formula (2) as the [B] siloxane polymer. It is possible to form an interlayer insulating film for a display element which is further improved.

In the positive radiation-sensitive composition, the mass ratio of the polymer [A] to the total of the polymer [A] and the [B] siloxane polymer is preferably 5 mass% or more and 95 mass% or less. By setting the mass ratio of the polymer [A] to the total of the polymer [A] and the polymer [B] siloxane in the above specific range, a positive radiation-sensitive composition having higher radiation sensitivity can be obtained, resulting in a higher refractive index, An interlayer insulating film for display elements having transparency and dry etching resistance can be formed.

The said positive radiation sensitive composition is suitable as a formation material of the interlayer insulation film for display elements. Moreover, the interlayer insulation film for display elements formed from the said positive radiation sensitive composition is also suitably contained in this invention.

The method for forming an interlayer insulating film for a display element of the present invention,

 (1) forming a coating film of the positive radiation-sensitive composition on a substrate;

 (2) a step of irradiating at least a part of the coating film with radiation,

 (3) developing the coating film irradiated with the radiation;

 (4) heating the developed coating film.

In this method, since the positive radiation sensitive composition has good radiation sensitivity and the interlayer insulating film for display elements to be formed has high dry etching resistance, a large dry etching margin can be ensured. The interlayer insulating film for display elements having a fine and elaborate pattern can be easily formed even in the interlayer insulating film for display elements for a large display device, in which it is difficult to process the whole uniformly and in a short time. Moreover, the interlayer insulation film for display elements which satisfy | filled the surface hardness, refractive index, heat resistance, and transparency well-balanced can be obtained.

As described above, the positive radiation-sensitive composition of the present invention has sufficient radiation sensitivity by containing the [A] polymer, the [B] siloxane polymer and the [C] photoacid generator. In addition, the interlayer insulating film for display elements having high dry etching resistance can be formed while satisfying well-balanced heat resistance, transparency, surface hardness and refractive index.

(Mode for carrying out the invention)

<Positive radiation sensitive composition>

The positive radiation sensitive composition of this invention contains a [A] polymer, a [B] siloxane polymer, and a [C] photoacid generator. Moreover, the said positive radiation sensitive composition may contain a [D] surfactant, an [E] adhesion adjuvant, a [F] basic compound, and a [G] quinonediazide compound as a suitable component. Moreover, you may contain other arbitrary components, unless the effect of this invention is impaired. Hereinafter, each component is explained in full detail.

<[A] polymer>

The polymer (A) contains the structural unit (I) and the epoxy group-containing structural unit (II) in the same or different polymer molecules. In addition, other structural units may be included as necessary. It does not specifically limit as an aspect of the [A] polymer containing a structural unit (I) and an epoxy-group containing structural unit (II), For example

(i) both of the structural unit (I) and the epoxy group-containing structural unit (II) are contained in the same polymer molecule so that one polymer molecule is present in the polymer [A];

(Ii) a structural unit (I) is contained in one polymer molecule, and an epoxy group-containing structural unit (II) is contained in a polymer molecule different from that, and two polymer molecules are present in the [A] polymer. ;

(Iii) a polymer comprising not only both structural unit (I) and epoxy group-containing structural unit (II) in one polymer molecule, but also including structural unit (I) in a different polymer molecule therefrom; When epoxy group containing structural unit (II) is contained in a molecule | numerator, and three polymer molecules exist in a polymer [A];

(Iii) In addition to the polymer molecule as described in (i)-(iv), the case where another 1 type, or 2 or more types of polymer molecule is contained in a polymer [A], etc. are mentioned. In any case, the effects of the present invention can be exhibited. In addition, the [A] polymer may contain 2 or more types of each structural unit. Hereinafter, each structural unit is explained in full detail.

[Structural unit (I)]

In the structural unit (I), since the group represented by the formula (1) exists as a group (acid dissociable group) which dissociates in the presence of an acid and generates a polar group, [C] photoacid generation by irradiation with radiation An acid dissociable group dissociates by the acid which generate | occur | produced from a sieve, As a result, an alkali-insoluble polymer [A] becomes alkali-soluble. The acid dissociable group has a relatively stable acetal structure or ketal structure with respect to alkali, and these are dissociated by the action of an acid.

In said formula (1), R <^1> and R <^2> is respectively independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group; However, one part or all part of the hydrogen atom which the said alkyl group, cycloalkyl group, and aryl group have may be substituted. In addition, neither R ¹ nor R ² is a hydrogen atom. R ³ is a group represented by an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or -M (R ^3m ) ₃ . This M is Si, Ge or Sn. R ^3m each independently represents an alkyl group. In addition, R ¹ and R ³ may be linked to each other to form a cyclic ether structure. Provided that some or all of the hydrogen atoms of these groups represented by R &lt; ³ &gt; may be substituted.

As an alkyl group represented by said R <^1> and R <^2> , a C1-C30 linear and branched alkyl group etc. are mentioned, for example. You may have an oxygen atom, a sulfur atom, and a nitrogen atom in this alkyl chain. As said C1-C30 linear and branched alkyl group, for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group Branched alkyl groups, such as linear alkyl groups, such as n- tetradecyl group and n-octadecyl group, i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group, and 3-hexyl group Alkyl group etc. are mentioned.

As a cycloalkyl group represented by said R <^1> and R <^2> , a C3-C20 cycloalkyl group etc. are mentioned, for example. In addition, this C3-C20 cycloalkyl group may be polycyclic, and may have an oxygen atom in a ring. As said C3-C20 cycloalkyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a bornyl group, a norbornyl group, an adamantyl group, etc. are mentioned, for example.

As an aryl group represented by said R <^1> and R <^2> , a C6-C14 aryl group etc. are mentioned, for example. The aryl group having 6 to 14 carbon atoms may be monocyclic, a structure in which a monocyclic ring is connected, or a condensed ring may be used. As said C6-C14 aryl group, a phenyl group, a naphthyl group, etc. are mentioned, for example.

As a substituent of the alkyl group, cycloalkyl group, and aryl group which may be substituted by the said R <^1> and R <^2> , For example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (for example, cyclo Propyl group, cyclopentyl group, cyclohexyl group, cycloheptyl, cyclooctyl, bornyl group, norbornyl group, adamantyl group, etc.), aryl group (for example, phenyl group, naphthyl group, etc.), alkoxy group (for example, C1-C20 alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group and the like, acyl group (for example, acetyl C2-C20 acyl groups, such as group, a propionyl group, butyryl group, i-butyryl group, etc., an acyloxy group (for example, an acetoxy group, an ethyloxy group, butyryloxy group, t-butyryloxy group) and acyloxy groups having 2 to 10 carbon atoms such as t-amiryloxy group), Alkoxycarbonyl group (for example, a C2-20 alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group), haloalkyl group (for example, methyl group, ethyl group, n-propyl group, n Linear alkyl groups such as -butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, i-propyl group, i-butyl group Alkyl groups, such as branched alkyl groups, such as a t-butyl group, a neopentyl group, a 2-hexyl group, and a 3-hexyl group; Cyclo, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a norbornyl group, an adamantyl group, etc. And some or all of the hydrogen atoms of the alkyl group are substituted with halogen atoms.

As an alkyl group, a cycloalkyl group, and an aryl group represented by said R <^3> , the group illustrated by said R <^1> and R <^2> is applicable, for example. As a substituent of these groups, the group illustrated as a substituent of the alkyl group, cycloalkyl group, and aryl group which may be substituted by the said R <^1> and R <^2> is applicable, for example. As an aralkyl group represented by said R <^3> , a C7-20 aralkyl group etc. are mentioned, for example. As said C7-C20 aralkyl group, a benzyl group, a phenethyl group, a naphthyl methyl group, a naphthyl ethyl group, etc. are mentioned, for example.

As group represented by said -M ( ^R3m ) ₃ , a trimethylsilanyl group, a trimethylgeryl group, etc. are mentioned, for example. As a substituent which may replace part or all of the hydrogen atoms of the aralkyl group represented by this R <^3> or the group represented by -M (R < ^3m ) ₃ , the said substituent can be employ | adopted suitably. As a substituent of this group, the group illustrated as a substituent of the alkyl group, cycloalkyl group, and aryl group which may be substituted by the said R <^1> and R <^2> is applicable, for example.

Examples of the group having a cyclic ether structure in which the R ¹ and R ³ may be linked to each other include a 2,2-oxetanediyl group, a 2,2-tetrahydrofurandiyl group, a 2-tetrahydropyrandiyl group, 2-dioxane diyl group etc. are mentioned.

The structural unit (I) may have the acetal structure or the ketal structure by having a functional group which has an acetal structure or a ketal structure by bonding to another carbon atom.

As a functional group which has an acetal structure by couple | bonding with the said other carbon atom, for example, 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-i-propoxy Ethoxy group, 1-n-butoxyethoxy group, 1-i-butoxyethoxy group, 1-sec-butoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclopentyloxye Oxy group, 1-cyclohexyloxyethoxy group, 1-norbornyloxyethoxy group, 1-bornyloxyethoxy group, 1-phenyloxyethoxy group, 1- (1-naphthyloxy) ethoxy group , 1-benzyloxyethoxy group, 1-phenethyloxyethoxy group, (cyclohexyl) (methoxy) methoxy group, (cyclohexyl) (ethoxy) methoxy group, (cyclohexyl) (n-propoxy) Methoxy group, (cyclohexyl) (i-propoxy) methoxy group, (cyclohexyl) (cyclohexyloxy) methoxy group, (cyclohexyl) (phenoxy) methoxy group, (cyclohexyl) (benzyloxy) methoxy group , (Phenyl) (methoxy) methoxy group, (phenyl) (ethoxy ) Methoxy group, (phenyl) (n-propoxy) methoxy group, (phenyl) (i-propoxy) methoxy group, (phenyl) (cyclohexyloxy) methoxy group, (phenyl) (phenoxy) methoxy group, (Phenyl) (benzyloxy) methoxy group, (benzyl) (methoxy) methoxy group, (benzyl) (ethoxy) methoxy group, (benzyl) (n-propoxy) methoxy group, (benzyl) (i-propoxy ) Methoxy group, (benzyl) (cyclohexyloxy) methoxy group, (benzyl) (phenoxy) methoxy group, (benzyl) (benzyloxy) methoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyl jade A time period, a 1-trimethylsilanyloxyethoxy group, a 1-trimethylgeryloxyethoxy group, etc. are mentioned.

Among these, 1-ethoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydropyranyloxy group, 1-n-propoxyoxy group, and 2-tetrahydropyranyloxy group are preferable.

As a functional group which has a ketal structure by couple | bonding with the said other carbon atom, it is a 1-methyl-1- methoxyethoxy group, 1-methyl-1- ethoxyethoxy group, 1-methyl-1-n, for example. -Propoxyethoxy group, 1-methyl-1-i-propoxyethoxy group, 1-methyl-1-n-butoxyethoxy group, 1-methyl-1-i-butoxyethoxy group, 1 -Methyl-1-sec-butoxyethoxy group, 1-methyl-1-t-butoxyethoxy group, 1-methyl-1-cyclopentyloxyethoxy group, 1-methyl-1-cyclohexyloxye Oxy group, 1-methyl-1-norbornyloxyethoxy group, 1-methyl-1-bornyloxyethoxy group, 1-methyl-1-phenyloxyethoxy group, 1-methyl-1- (1 -Naphthyloxy) ethoxy group, 1-methyl-1-benzyloxyethoxy group, 1-methyl-1-phenethyloxyethoxy group, 1-cyclohexyl-1-methoxyethoxy group, 1-cyclohexyl -1-ethoxyethoxy group, 1-cyclohexyl-1-n-propoxyethoxy group, 1-cyclohexyl-1-i-propoxyethoxy group, 1-cyclohexyl-1-cyclohexyloxye Toxi Group, 1-cyclohexyl-1-phenoxyethoxy group, 1-cyclohexyl-1-benzyloxyethoxy group, 1-phenyl-1-methoxyethoxy group, 1-phenyl-1-ethoxy ethoxy Period, 1-phenyl-1-n-propoxyethoxy group, 1-phenyl-1-i-propoxyethoxy group, 1-phenyl-1-cyclohexyloxyethoxy group, 1-phenyl-1-phenyl Oxyethoxy group, 1-phenyl-1-benzyloxyethoxy group, 1-benzyl-1-methoxyethoxy group, 1-benzyl-1-ethoxyethoxy group, 1-benzyl-1-n-pro Foxoxyethoxy group, 1-benzyl-1-i-propoxyethoxy group, 1-benzyl-1-cyclohexyloxyethoxy group, 1-benzyl-1-phenyloxyethoxy group, 1-benzyl-1- Benzyloxyethoxy group, 2- (2-methyltetrahydrofuranyl) oxy group, 2- (2-methyltetrahydropyranyl) oxy group, 1-methoxy-cyclopentyloxy group, 1-methoxy-cyclo Hexyloxy group etc. are mentioned.

Of these, 1-methyl-1-methoxyethoxy group and 1-methyl-1-cyclohexyloxyethoxy group are preferable.

As a structural unit (I) which has the said acetal structure or a ketal structure, the structural unit represented by following formula (1-1)-(1-3) etc. are mentioned, for example.

R 'is a hydrogen atom or a methyl group in said Formula (1-1) (1-3). R <^1> , R <^2> and R <^3> is synonymous with said formula (1).

As a monomer which gives the structural unit (I) represented by said Formula (1-1)-(1-3), for example,

1-alkoxyalkyl (meth) acrylate, 1- (cycloalkyloxy) alkyl (meth) acrylate, 1- (haloalkoxy) alkyl (meth) acrylate, 1- (aralkyloxy) alkyl (meth) acrylate (Meth) acrylate type acetal structure containing monomers, such as tetrahydropyranyl (meth) acrylate;

2,3-di (1- (trialkylsilanyloxy) alkoxy) carbonyl) -5-norbornene, 2,3-di (1- (trialkylgeryloxy) alkoxy) carbonyl) -5- Norbornene, 2,3-di (1-alkoxyalkoxycarbonyl) -5-norbornene, 2,3-di (1- (cycloalkyloxy) alkoxycarbonyl) -5-norbornene, 2, Norbornene-based acetal structure-containing monomers such as 3-di (1- (aralkyloxy) alkoxycarbonyl) -5-norbornene;

Styrene-based acetal structure containing monomers, such as 1-alkoxy alkoxy styrene, 1- (haloalkoxy) alkoxy styrene, 1- (aralkyloxy) alkoxy styrene, tetrahydropyranyloxy styrene, are mentioned.

Among these, 1-alkoxyalkyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 1-alkoxyalkoxy styrene, tetrahydropyranyloxy styrene are preferable, and 1-alkoxyalkyl (meth) acrylate is more preferable. desirable.

As a specific monomer which gives the structural unit (I) represented by said Formula (1-1)-(1-3), it is, for example

1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1-t-butoxyethyl methacrylate, 1 -(2-chloroethoxy) ethyl methacrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1 Methacrylate acetal structure-containing monomers such as-(2-cyclohexylethoxy) ethyl methacrylate, 1-benzyloxyethyl methacrylate and 2-tetrahydropyranyl methacrylate;

1-ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-t-butoxyethyl acrylate, 1- (2-chloro Ethoxy) ethyl acrylate, 1- (2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl acrylate, 1- (2-cyclohexyl ethoxy) Acrylate-based acetal structure-containing monomers such as ethyl acrylate, 1-benzyloxyethyl acrylate and 2-tetrahydropyranyl acrylate;

2,3-di (1- (trimethylsilanyloxy) ethoxy) carbonyl) -5-norbornene, 2,3-di (1- (trimethylgeryloxy) ethoxy) carbonyl) -5- Norbornene, 2,3-di (1-methoxyethoxycarbonyl) -5-norbornene, 2,3-di (1- (cyclohexyloxy) ethoxycarbonyl) -5-norborne Norbornene-based acetal structure-containing monomers such as nene and 2,3-di (1- (benzyloxy) ethoxycarbonyl) -5-norbornene;

p or m-1-ethoxyethoxystyrene, p or m-1-methoxyethoxystyrene, p or m-1-n-butoxyethoxystyrene, p or m-1-isobutoxyethoxystyrene, p or m-1- (1,1-dimethylethoxy) ethoxystyrene, p or m-1- (2-chloroethoxy) ethoxystyrene, p or m-1- (2-ethylhexyloxy) Ethoxystyrene, p or m-1-n-propoxyethoxystyrene, p or m-1-cyclohexyloxyethoxystyrene, p or m-1- (2-cyclohexylethoxy) ethoxystyrene, p Or styrene-based acetal structure-containing monomers such as m-1-benzyloxyethoxystyrene. In addition, these monomers can use individual or 2 types or more.

Examples of the monomer giving the structural unit (I) include 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, 1-benzyloxyethyl methacrylate The rate is preferred.

As a monomer which gives a structural unit (I), a commercial thing may be used and what was synthesize | combined by a well-known method can also be used. For example, the monomer which gives structural unit (I) represented by said Formula (1-1) can be synthesize | combined by making (meth) acrylic acid react with vinyl ether in presence of an acid catalyst, as shown by following formula.

In said formula, R ', R <^1> and R <^3> are synonymous with said Formula (1-1). R ²¹ and R ²² are, -CH (R ²¹⁾ a (R ^22), the same meaning as R ² in the formula (1-1).

The content of the structural unit (I) in the [A] polymer is not particularly limited as long as the polymer [A] exhibits alkali solubility with an acid and the desired heat resistance of the cured film is exhibited. When both (I) and an epoxy group containing structural unit (II) are included, 5 mass% or more and 70 mass% or less are preferable at a monomer input ratio with respect to the total structural unit contained in a [A] polymer, and 10 mass% or more 60 mass% or less is more preferable, 20 mass% or more and 50 mass% or less are especially preferable.

On the other hand, when one polymer molecule contains structural unit (I), and the polymer molecule containing epoxy group containing structural unit (II) differs from this, in the one polymer molecule which has structural unit (I), As content of the structural unit (I) of 40 mass% or more and 99 mass% or less are preferable at a monomer input ratio with respect to all the structural units contained in the polymer molecule, 50 mass% or more and 98 mass% or less are more preferable. 55 mass% or more and 95 mass% or less are especially preferable.

[Epoxy group-containing structural unit (II)]

It will not specifically limit, if it is a structural unit derived from an epoxy group containing monomer as an epoxy group containing structural unit (II). When the polymer (A) contains an epoxy group-containing structural unit (II) in a molecule, the surface hardness and heat resistance of the cured film obtained from the positive radiation-sensitive composition can be further increased. In addition, the epoxy group of this specification is a concept containing an oxiranyl group (1, 2- epoxy structure) and an oxetanyl group (1, 3- epoxy structure).

As a monomer which gives an epoxy group containing structural unit (II), for example

Glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 3-methyl-3,4-epoxybutyl acrylate, 3-ethyl-3,4-epoxybutyl methacrylate, (meth) acrylic acid 5 , 6-epoxyhexyl, 5-methyl-5,6-epoxyhexyl methacrylate, 5-ethyl-5,6-epoxyhexyl methacrylate, 6,7-epoxyheptyl (meth) acrylic acid, methacrylic acid 3, 4-epoxycyclohexyl, methacrylic acid 3,4-epoxycyclohexylmethyl, (meth) acrylic acid 3,4-epoxycyclohexylethyl, methacrylic acid 3,4-epoxycyclohexylpropyl, methacrylic acid 3,4- Epoxycyclohexylbutyl, (meth) acrylic acid 3,4-epoxycyclohexylhexyl, acrylic acid 3,4-epoxycyclohexylmethyl, acrylic acid 3,4-epoxycyclohexylethyl, acrylic acid 3,4-epoxycyclohexylpropyl, acrylic acid 3 Oxiranyl group-containing (meth) acrylic compound, such as 4,4-epoxycyclohexyl butyl and 3,4-epoxycyclohexylhexyl acrylate .;

o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycy Vinyl benzyl glycidyl ethers such as dil ether and α-methyl-p-vinyl benzyl glycidyl ether;

vinyl phenyl glycidyl ethers such as o-vinyl phenyl glycidyl ether, m-vinyl phenyl glycidyl ether and p-vinyl phenyl glycidyl ether;

3-acryloyloxymethyloxetane, 3-acryloyloxymethyl-3-methyloxetane, 3-acryloyloxymethyl-3-ethyloxetane, 3-acryloyloxymethyl-3-phenylox Cetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -3-ethyl oxetane, 3- (2-acryloyloxyethyl) -3-ethyl ox Cetane, 3- (2-acryloyloxyethyl) -3-phenyloxetane, 3-methacryloyloxymethyloxetane, 3-methacryloyloxymethyl-3-methyloxetane, 3-methacryl Royloxymethyl-3-ethyloxetane, 3-methacryloyloxymethyl-3-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyl Oxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-phenyloxetane, 2- Acryloyloxymethyloxetane, 2-acryloyloxymethyl-2-methyloxetane, 2-acryloyloxymethyl-2-ethyloxetane, 2-acryloyloxymethyl-2-phenyloxetane, 2- (2-ah Liloyloxyethyl) oxetane, 2- (2-acryloyloxyethyl) -2-ethyloxetane, 2- (2-acryloyloxyethyl) -2-ethyloxetane, 2- (2-acrylic Royloxyethyl) -2-phenyloxetane, 2-methacryloyloxymethyloxetane, 2-methacryloyloxymethyl-2-methyloxetane, 2-methacryloyloxymethyl-2-ethyl Oxetane, 2-methacryloyloxymethyl-2-phenyloxetane, 2- (2-methacryloyloxyethyl) oxetane, 2- (2-methacryloyloxyethyl) -2-ethyl jade Oxetanyl group-containing (meth) acrylic compounds such as cetane, 2- (2-methacryloyloxyethyl) -2-ethyl oxetane and 2- (2-methacryloyloxyethyl) -2-phenyl oxetane Etc. can be mentioned. These monomers can be used individually or in combination of 2 or more types.

Among these monomers, methacrylic acid glycidyl, methacrylic acid-2-methylglycidyl, methacrylic acid-3,4-epoxycyclohexyl, methacrylic acid-3,4-epoxycyclohexylmethyl, 3- ( From the viewpoint of methacryloyloxymethyl) -3-methyloxetane and 3- (methacryloyloxymethyl) -3-ethyloxetane in terms of copolymerization reactivity with other monomers and developability of a positive radiation-sensitive composition desirable.

The content of the epoxy group-containing structural unit (II) in the polymer (A) is not particularly limited as long as the desired heat resistance of the interlayer insulating film for display element is exhibited, and the structural unit (I) and the epoxy group-containing structure are contained in one polymer molecule. When it contains a unit (II), 10 mass% or more and 60 mass% or less are preferable with a monomer input ratio with respect to the whole structural unit contained in a [A] polymer, 15 mass% or more and 55 mass% or less are more preferable. 20 mass% or more and 50 mass% or less are especially preferable.

On the other hand, when the structural unit (I) is contained in one polymer molecule and the epoxy group-containing structural unit (II) is included in another polymer molecule, the entire structure contained in another polymer molecule containing the epoxy group-containing structural unit (II) As content of the epoxy group containing structural unit (II) with respect to a unit, 20 mass% or more and 80 mass% or less are preferable at a monomer input ratio, 30 mass% or more and 70 mass% or less are more preferable, 35 mass% or more and 65 mass% The following is especially preferable.

[Other structural units]

The polymer (A) may contain other structural units other than the structural unit (I) and the structural unit (II) within a range that does not impair the effects of the present invention.

As a monomer which provides another structural unit, the carboxyl group or its derivative (s), the monomer which has a hydroxyl group, etc. are mentioned.

As a monomer which has the said carboxyl group or its derivative (s), For example, acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexa Monocarboxylic acids such as hydrophthalic acid and 2-methacryloyloxyethyl hexahydrophthalic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And acid anhydrides of the dicarboxylic acids.

Examples of the monomer having a hydroxyl group include acrylic acid-2-hydroxyethyl ester, acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, acrylic acid-4-hydroxymethylcyclohexylmethyl ester, and the like. Acrylic acid hydroxyalkyl esters; Methacrylic acid-2-hydroxyethyl ester, methacrylic acid-3-hydroxypropyl ester, methacrylic acid-4-hydroxybutyl ester, methacrylic acid-5-hydroxypentyl ester, methacrylic acid-6- Methacrylic acid hydroxyalkyl esters, such as hydroxyhexyl ester and methacrylic acid 4-hydroxymethyl cyclohexyl methyl ester, etc. are mentioned.

Among the monomers having these hydroxyl groups, from the viewpoint of copolymerization reactivity with other monomers and the heat resistance of the interlayer insulating film for display elements obtained, acrylic acid-2-hydroxyethyl ester, acrylic acid-3-hydroxypropyl ester and acrylic acid-4-hydroxy Hydroxybutyl ester, methacrylic acid-2-hydroxyethyl ester, methacrylic acid-4-hydroxybutyl ester, acrylic acid-4-hydroxymethyl-cyclohexylmethyl ester, methacrylic acid-4-hydroxymethyl-cyclo Hexyl methyl ester is preferred.

As another monomer, for example

Acrylic acid alkyl esters such as methyl acrylate and i-propyl acrylate;

Methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate;

Cyclohexyl acrylate, -2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, acrylic acid-2- (tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy ) Acrylic alicyclic alkyl esters such as ethyl and isobornyl acrylate;

Methacrylic acid cyclohexyl, methacrylic acid-2-methylcyclohexyl, methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, methacrylic acid-2- (tricyclo [5.2.1.0 ^{2, 6]} decan-8-yloxy) ethyl methacrylate, isobornyl methacrylate, such as aliphatic alkyl esters;

Aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate and aralkyl esters of acrylic acid;

Aryl esters of methacrylic acid and aralkyl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate;

Dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;

Unsaturated hetero five-membered ring methacrylic acid esters and unsaturated hetero six-membered ring methacrylic acid esters containing one atom of oxygen such as methacrylic acid tetrahydrofurfuryl, methacrylic acid tetrahydrofuryl, and methacrylic acid tetrahydropyran-2-methyl ;

4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane , 4-methacryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- Unsaturated hetero 5-membered ring methacrylic acid esters containing oxygen 2 atoms such as methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane;

4-acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acrylo Iloxymethyl-2,2-diethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-acryloyloxy Methyl-2-cyclopentyl-1,3-dioxolane, 4-acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, 4-acryloyloxyethyl-2-methyl-2- Ethyl-1,3-dioxolane, 4-acryloyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxybutyl-2-methyl-2-ethyl- Unsaturated hetero five-membered ring acrylic acid esters containing oxygen two atoms such as 1,3-dioxolane;

Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene and 4-isopropenylphenol;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl N-position substituted maleimides such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

Conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;

And other unsaturated compounds such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, and vinyl acetate.

Among these other monomers, styrene, 4-isopropenylphenol, methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, methacrylic acid tetrahydrofurfuryl, 1,3-butadiene, 4- Acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenylmaleimide, methacrylic acid benzyl with the monomer which has said reaction functional group It is preferable at the point of copolymerization reactivity and the developability of the said positive radiation sensitive composition.

The polystyrene reduced weight average molecular weight (Mw) by gel permeation chromatography (GPC) of the polymer [A] is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ , and more preferably 5.0 × 10 ^{3 to} 5.0 × 10 ⁴ to be. By making Mw of a polymer into the said specific range, the radiation sensitivity of the said positive radiation sensitive composition and the surface hardness of the interlayer insulation film for display elements formed by this composition can be raised.

As polystyrene conversion number average molecular weight (Mn) by GPC of [A] polymer, Preferably it is 2.0 * 10 <^3> -1.0 * 10 <^5> , More preferably, it is 5.0 * 10 <^3> 5.0 * 10 <^4> . By making Mn of a polymer into the said specific range, hardening reactivity at the time of hardening of the coating film of the said positive radiation sensitive composition can be improved.

As molecular weight distribution (Mw / Mn) of the polymer (A), Preferably it is 3.0 or less, More preferably, it is 2.6 or less. The developability of the interlayer insulation film for display elements obtained can be improved by making Mw / Mn of a polymer [A] into 3.0 or less. The positive radiation sensitive composition containing the polymer (A) can easily form a desired pattern shape without developing developing residue when developing.

In addition, Mw and Mn of this specification were measured by GPC on condition of the following.

Device: GPC-101 (Showa Denko)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

Mobile phase: tetrahydrofuran

Column temperature: 40 DEG C

Flow rate: 1.0mL / min

Sample concentration: 1.0 mass%

Sample injection volume: 100 μL

Detector: parallax refractometer

Standard material: monodisperse polystyrene

<The synthesis method of the polymer [A]>

A polymer can be synthesize | combined by radical copolymerization of the monomer which gives each said structural unit. For example, when synthesize | combining the polymer [A] containing both a structural unit (I) and an epoxy group containing structural unit (II) in the same polymer molecule, the monomer which gives a structural unit (I), and an epoxy group containing structural unit ( What is necessary is just to copolymerize using the mixture containing the monomer which gives II). On the other hand, when synthesize | combining [A] polymer which has a structural unit (I) in one polymer molecule, and an epoxy group containing structural unit (II) in a polymer molecule different from it, it gives a structural unit (I) Radical polymerization of the polymerizable solution containing the monomer to obtain a polymer molecule having the structural unit (I), radical polymerization of the polymerizable solution containing the monomer to give a separate epoxy group-containing structural unit (II) to the epoxy group-containing structural unit What is necessary is just to obtain the polymer molecule which has (II), and, finally, mix both to make a polymer [A].

As a solvent used for the polymerization reaction of the polymer (A), the solvent illustrated in the term of preparation of the said composition mentioned later is mentioned, for example.

As a polymerization initiator used for a polymerization reaction, what is generally known as a radical polymerization initiator can be used, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- Azo compounds such as dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azobis (methyl 2-methylpropionate); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; Hydrogen peroxide etc. are mentioned. Among these, an azo compound is preferable and 2,2'- azobis- (2, 4- dimethylvaleronitrile) and 2,2'- azobis- (methyl 2-methylpropionate) are more preferable. When using a peroxide as a radical polymerization initiator, you may use a peroxide together with a reducing agent as a redox type initiator.

In the polymerization reaction of the polymer (A), in order to adjust the molecular weight, a molecular weight modifier may be used. As a molecular weight modifier, For example, Halogenated hydrocarbons, such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid; Azetidine derivatives such as dimethylzantogen sulfide and diisopropylzantogen disulfide; Terpinolene, alpha -methylstyrene dimer, and the like.

<[B] siloxane polymer>

[B] The siloxane polymer is not particularly limited as long as it is a polymer having a siloxane bond. This [B] siloxane polymer forms hardened | cured material by self-condensation by heating.

The siloxane polymer is preferably a hydrolysis condensate of the hydrolyzable silane compound represented by Formula (2). In the positive radiation-sensitive composition, surface hardness and dry etching resistance are ensured while securing sufficient radiation sensitivity by using a hydrolysis-condensation product of the hydrolyzable silane compound represented by the formula (2) as the [B] siloxane polymer. It is possible to form an interlayer insulating film for a display element which is further improved. In addition, the hydrolyzable silane compound in this specification is hydrolyzed by heating in the temperature range of room temperature (about 25 degreeC)-about 100 degreeC in the presence of a noncatalyst and excess water normally, and produces a silanol group. A silane compound having a hydrolyzable group which can be used, or a silane compound having a hydrolyzable group which can form a siloxane condensate. On the other hand, a non-hydrolyzable group means group which exists stably, without causing hydrolysis or condensation under such hydrolysis conditions.

In the hydrolysis reaction of the hydrolyzable silane compound represented by the formula (2), some hydrolyzable groups may remain in an unhydrolyzed state. In addition, the hydrolysis-condensation product of a hydrolyzable silane compound means the hydrolysis-condensation product which some silanol groups of the hydrolyzed silane compound reacted and condensed.

In said formula (2), R <^4> is a C1-C20 non-hydrolyzable organic group. R <^5> is a C1-C4 alkyl group. n is an integer of 0-3. However, when R <^4> and R <^5> is multiple, some R <^4> and R <^5> may be same or different, respectively.

As a C1-C20 non-hydrolyzable organic group represented by said R <^4> , a C1-C12 unsubstituted alkyl group (may be substituted by 1 or more of a vinyl group, a (meth) acryloyl group, or an epoxy group), and carbon number A 6-12 aryl group and a C7-12 aralkyl group are preferable. In addition, R ⁴ may include a structural unit having a hetero atom. Examples of such a structural unit include an ether, an ester, and a sulfide.

As a C1-C4 alkyl group represented by said R <^5> , a methyl group, an ethyl group, n-propyl group, i-propyl group, a butyl group etc. are mentioned, for example. Of these, methyl and ethyl groups are preferred from the viewpoint of ease of hydrolysis. As n, Preferably it is an integer of 0-2, More preferably, it is 0 or 1, Especially preferably, it is 1. In the case where n is an integer of 0 to 2, the progress of the hydrolysis-condensation reaction becomes easier, and as a result, the rate of the curing reaction by the self-condensation of the [B] siloxane polymer is further increased, and further, the interlayer for display element obtained. The surface hardness and heat resistance of the insulating film can be further improved.

Examples of the hydrolyzable silane compound represented by Formula (2) include a silane compound substituted with four hydrolyzable groups, a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, two non-hydrolyzable groups and two hydrolyzable groups. A substituted silane compound, a silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group, or a mixture thereof.

As the hydrolyzable silane compound represented by such Formula (2), for example

As a silane compound substituted with four hydrolyzable groups, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, tetra-n-propoxysilane, tetra-i-propoxy Silanes and the like;

As a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, chlorotrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane , Vinyltriethoxysilane, vinyltri-n-propoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3- Acryloxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like;

As the silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups, dichlorodimethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane and the like;

Examples of the silane compound substituted with three non-hydrolyzable groups and one hydrolyzable group include trichloromethoxysilane, tributylmethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, tributylethoxysilane, and the like.

Of these, a silane compound substituted with four hydrolyzable groups and a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups are preferable, and a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups is more preferable. Tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxy Silane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltri Ethoxysilane is particularly preferable, and methyltrimethoxysilane, phenyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane are most preferred. You may use such a hydrolysable silane compound individually or in combination of 2 or more types.

As conditions for hydrolyzing and condensing the hydrolyzable silane compound represented by the formula (2), at least a part of the hydrolyzable silane compound represented by the formula (2) is hydrolyzed, and the hydrolyzable group is converted into a silanol group to condense the reaction. The water used for the hydrolysis-condensation of the hydrolyzable silane compound represented by the formula (2) is, for example, as long as it causes the reaction to occur, such as reverse osmosis membrane treatment, ion exchange treatment, distillation, and the like. Preference is given to using water purified by the process. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. As the water amount, per 1 mol of the total amount of the hydrolyzable group (-OR ⁵⁾ of the hydrolyzable silane compound represented by the formula (2), preferably 0.1 mole? 3 mol, more preferably 0.3 mole? 2 mol, Especially preferably, they are 0.5 mol-1.5 mol. By using such an amount of water, the reaction rate of hydrolysis-condensation can be optimized.

As a solvent which can be used for hydrolysis and condensation of the hydrolyzable silane compound represented by said Formula (2), the same thing as the solvent used for preparation of the positive radiation sensitive composition mentioned later can be used normally. As such a solvent, ethylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates and propionic acid esters are preferable, and diethylene glycol dimethyl ether and diethylene are preferred. Glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate and methyl 3-methoxypropionate are more preferable.

The hydrolysis-condensation reaction of the hydrolyzable silane compound represented by the formula (2) is preferably an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, Nitrogen-containing compounds such as phosphoric acid, acidic ion exchange resins, various Lewis acids, base catalysts (for example, ammonia, primary amines, secondary amines, tertiary amines, pyridine), basic ion exchange resins, hydroxides such as sodium hydroxide; Carbonate, such as potassium carbonate, Carbonate, such as sodium acetate; Various Lewis bases), or an alkoxide (for example, zirconium alkoxide, titanium alkoxide, aluminum alkoxide), etc., are performed in presence of a catalyst. For example, tri-i-propoxy aluminum, tetra-i-propoxy aluminum, etc. can be used as aluminum alkoxide. The amount of the catalyst used is preferably 0.5 parts by mass or less, more preferably 0.00001 parts by mass to 0.3 parts by mass with respect to 100 parts by mass of the hydrolyzable silane compound from the viewpoint of promoting the hydrolysis-condensation reaction.

As reaction temperature in hydrolysis and condensation of the hydrolyzable silane compound represented by said Formula (2), Preferably it is 40 degreeC-200 degreeC, More preferably, it is 50 degreeC-150 degreeC. As reaction time, Preferably it is 30 minutes-24 hours, More preferably, it is 1 hour-12 hours. By setting it as such reaction temperature and reaction time, a hydrolysis-condensation reaction can be performed most efficiently. In this hydrolysis-condensation, the hydrolyzable silane compound, water, and catalyst may be added to the reaction system at once, and the reaction may be performed in one step, or the hydrolyzable silane compound, water, and catalyst may be added several times in the reaction system. And condensation reaction may be performed in multiple stages. In addition, after a hydrolysis-condensation reaction, a dehydrating agent can be added, and then water and the produced | generated alcohol can be removed from a reaction system by evaporation. As the dehydrating agent used in this step, since the dehydration capacity is generally consumed by adsorbing or entrapping excess water or completely removed by evaporation, [I] described later added to the positive radiation-sensitive composition ] We do not belong to category of dehydrating agent.

As Mw of the hydrolysis-condensation product of the hydrolyzable silane compound represented by said Formula (2), 5.0 * 10 <^2> -1.0 * 10 <^4> is preferable normally, and 1.0 * 10 <^3> -5.0 * 10 <^3> is more preferable. By making Mw into 5.0 * 10 <^2> or more, the film-forming property of the coating film of a positive radiation sensitive composition can be improved. On the other hand, the fall of the radiation sensitivity of a positive radiation sensitive composition can be prevented by making Mw into 1.0 * 10 <^4> or less.

In the positive radiation-sensitive composition, the mass ratio of the polymer [A] to the total of the polymer [A] and the [B] siloxane polymer is preferably 5% by mass or more and 95% by mass or less. By setting the mass ratio of the polymer [A] to the total of the polymer [A] and the polymer [B] siloxane in the above specific range, a positive radiation-sensitive composition having higher radiation sensitivity can be obtained, resulting in a higher refractive index, An interlayer insulating film for display elements having transparency and dry etching resistance can be formed. Moreover, 5 mass% or more and 85 mass% or more are more preferable from a viewpoint of surface hardness in addition to dry etching resistance.

<[C] photoacid generator>

[C] The photoacid generator is a compound which generates an acid by irradiation of radiation. As the radiation, for example, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, or the like can be used. When the positive radiation sensitive composition contains the [A] polymer having an acid dissociable group and the [C] photoacid generator, the positive radiation sensitive composition can exhibit positive radiation sensitive properties. [C] As the containing form in the positive radiation-sensitive composition of the photoacid generator, even if it is a form of a compound (hereinafter, also appropriately referred to as "[C] photoacid generator") as described later, It may be in the form of an acid generator incorporated as part of another polymer or in both of these forms.

[C] As a photoacid generator, an onium salt, a trihalomethyltriazine compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a phosphorus acid ester compound, a sulfonimide compound, a sulfone benzotriazole compound, an oxime sulfo Nate compound etc. are mentioned. In addition, these [C] photo-acid generators can be used individually or in combination of 2 or more types, respectively. In addition, the quinonediazide compound is not contained in the [C] photo-acid generator.

[Onium salt]

Examples of the onium salt include diphenyl iodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, ammonium salt compound, phosphonium salt compound, tetrahydrothiophenium salt and the like.

As the diphenyl iodonium salt, for example, diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphonate, diphenyl iodonium hexafluoroarsenate, and diphenyl iodonium tri Fluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium butyltris (2,6-difluorophenyl) borate, 4-meth Methoxyphenylphenyl iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarsenate, bis (4 -t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfo Nate, bis (4-t- butylphenyl) iodonium camphor sulfonic acid, etc. are mentioned.

As the triphenylsulfonium salt, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium- p-toluenesulfonate, triphenylsulfonium butyl tris (2,6-difluorophenyl) borate, and the like.

As a sulfonium salt, an alkyl sulfonium salt, a benzyl sulfonium salt, a dibenzyl sulfonium salt, a substituted benzyl sulfonium salt, etc. are mentioned, for example.

As an alkyl sulfonium salt, 4-acetoxy phenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxy phenyl dimethyl sulfonium hexafluoro arsenate, dimethyl-4- (benzyloxy carbonyloxy) phenyl, for example Sulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro 4-acetoxy phenylsulfonium hexafluoro antimonate etc. are mentioned.

Examples of the benzylsulfonium salts include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate and 4-acetoxyphenylbenzylmethylsulfonium hexa. Fluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro- 4-hydroxyphenylmethylsulfonium hexafluoro arsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluoro phosphate, etc. are mentioned.

Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, and 4-acetoxyphenyldibenzylsulfonium. Hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3- Methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, and the like.

Examples of the substituted benzylsulfonium salt include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p -Chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4- Hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and the like.

Examples of the benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3- (p-meth Oxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, etc. are mentioned. Can be.

Examples of the ammonium salt compound include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrosulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, N, N-dimethyl-N-benzylanilinium hexafluoroantimonate, N, N-dimethyl-N-benzylanilinium tetrafluoroborate, N, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl-N-benzyltrifluoromethanesulfonate, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate, N, N-diethyl-N- (4-methoxybenzyl) toludinium hexafluoro antimonate, etc. are mentioned.

As a phosphonium salt compound, ethyl triphenyl phosphonium hexafluoro antimonate, tetrabutyl phosphonium hexafluoro antimonate, etc. are mentioned, for example.

As the tetrahydrothiophenium salt, for example, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiopheniumtrifluoromethanesulfonate and 1- (4-n-butoxynaphthalene-1- Yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1,2,2-tetrafluoro- 2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 4,7-di-n-butoxy- 1-naphthyl tetrahydrothiophenium trifluoromethanesulfonate etc. are mentioned.

[Trihalomethyltriazine Compound]

As a trihalomethyl triazine compound, a haloalkyl group containing hydrocarbon compound, a haloalkyl group containing heterocyclic compound, etc. are mentioned, for example.

[Diazomethane compound]

Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane and bis (p-tolylsulfonyl). Diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl ( 1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane, etc. are mentioned.

[Sulfone Compound]

As a sulfone compound, the (beta) -keto sulfone compound, the (beta) -sulfonyl sulfone compound, a diaryl disulfone compound, etc. are mentioned, for example.

[Sulfonic acid ester compound]

As a sulfonic acid ester compound, an alkyl sulfonic acid ester, a haloalkyl sulfonic acid ester, an aryl sulfonic acid ester, an imino sulfonate, etc. are mentioned, for example.

[Inoxo-acid ester compound]

As the phosphorus acid ester compound, for example, trialkyl phosphate ester, triaryl phosphate ester, dialkyl phosphate ester, monoalkyl phosphate ester, trialkyl phosphite ester, triaryl phosphite ester, dialkyl phosphite ester, monoalkyl phosphite ester, tea Phosphorous acid ester etc. are mentioned.

[Sulfonimide compound]

As the sulfonimide compound, for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (Campersulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethyl Sulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide Mid, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1 ] Hepto-5-ene-2, 3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxylimide, N- (nonafluorobutanesulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide , N- (camphorsulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hepto -5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N -(4-methylphenylsulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1 ] Hepto-5-ene-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N -(2-trifluoromethylfe Sulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hepto- 5-ene-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N -(Trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane- 5,6-oxy-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- ( 2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2. 1] heptane-5,6-oxy-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) naphthyldicarboxyimide, N- (camphorsulfonyloxy) naphthyldicarboxyimide, N -(4-methylphenyl Ponyloxy) naphthyldicarboxylimide, N- (phenylsulfonyloxy) naphthyldicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) naphthyldicarboxyimide, N- (4-fluorophenyl Sulfonyloxy) naphthyldicarboxyimide, N- (pentafluoroethylsulfonyloxy) naphthyldicarboxyimide, N- (heptafluoropropylsulfonyloxy) naphthyldicarboxyimide, N- (nonnafluoro Butylsulfonyloxy) naphthyldicarboxylimide, N- (ethylsulfonyloxy) naphthyldicarboxyimide, N- (propylsulfonyloxy) naphthyldicarboxyimide, N- (butylsulfonyloxy) naphthyldica Foxyimide, N- (pentylsulfonyloxy) naphthyldicarboxyimide, N- (hexylsulfonyloxy) naphthyldicarboxyimide, N- (heptylsulfonyloxy) naphthyldicarboxyimide, N- (octylsul Phenyloxy) naphthyl dicarboxyl imide, N- (nonylsulfonyloxy) naphthyl dicarboxyl imide, etc. are mentioned.

[Sulfone Benzotriazole Compound]

Examples of the sulfone benzotriazole compound include 1-trifluoromethanesulfonyloxybenzotriazole, 1-nonafluorobutylsulfonyloxybenzotriazole and 1- (4-methylphenylsulfonyloxy) -benzotriazole. Etc. can be mentioned.

Oxime sulfonate compound

As an oxime sulfonate compound, the compound containing the oxime sulfonate group represented, for example by following formula (3) is preferable.

In said formula (3), R <^C1> is a linear or branched alkyl group, a cycloalkyl group, or an aryl group. However, some or all of the hydrogen atoms may be substituted for these groups.

As a linear or branched alkyl group represented by said R <^C1> , a ^C1 -C10 linear or branched alkyl group is preferable. The linear or branched alkyl group having 1 to 10 carbon atoms may be substituted, and examples of the substituent include Conjugating formulas such as an alkoxy group having 1 to 10 carbon atoms and a 7,7-dimethyl-2-oxonorbornyl group. An alicyclic group containing an alicyclic group etc. are mentioned. Moreover, as a preferable alicyclic group, it is a bicycloalkyl group. As an aryl group represented by said R <^C1> , a C6-C11 aryl group is preferable and a phenyl group and a naphthyl group are more preferable. The aryl group may be substituted, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group and a halogen atom.

As a compound containing the oxime sulfonate group represented by said formula (3), the oxime sulfonate compound represented, for example by following formula (4) is preferable.

In said formula (4), R <^C1> is synonymous with said formula (3). X is an alkyl group, an alkoxy group, or a halogen atom. m is an integer of 0-3. However, when X is multiple, some X may be same or different.

As an alkyl group which can be represented by said X, a C1-C4 linear or branched alkyl group is preferable. As an alkoxy group represented by said X, a C1-C4 linear or branched alkoxy group is preferable. As a halogen atom represented by said X, a chlorine atom and a fluorine atom are preferable. As m, 0 or 1 is preferable. In said Formula (4), the compound whose m is 1, X is a methyl group, and the substitution position of X is ortho is preferable.

As an oxime sulfonate compound represented by said Formula (4), the compound etc. which are respectively represented by following formula (4-1)-(4-5) are mentioned, for example.

Compound (4-1) (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, compound (4-2) (5-octylsulfonyloxyimino- 5H-thiophene-2-ylidene)-(2-methylphenyl) acetonitrile, compound (4-3) (camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl) acetonitrile , Compound (4-4) (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile and compound (4-5) (5-octylsulfonyloxy Mino)-(4-methoxyphenyl) acetonitrile can be obtained as a commercial item.

[C] As the photoacid generator, from the viewpoint of sensitivity and solubility, an oxime sulfonate compound and an onium salt are preferable. As an oxime sulfonate compound, the compound represented by said Formula (3) is more preferable, The compound represented by said Formula (4) is especially preferable, The said Formula (4-1)? (4-5) which can be obtained as a commercial item Most preferred are compounds represented by As the onium salt, tetrahydrothiophenium salt and benzylsulfonium salt are more preferable, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and benzyl-4- hydrate Particular preference is given to oxyphenylmethylsulfonium hexafluorophosphate.

As content of the [C] photo-acid generator in the said composition, when [C] photo-acid generator is a [C] photo-acid generator, Preferably it is 100 mass parts with respect to a total of 100 mass parts of a [A] polymer and a [B] siloxane polymer. Is 0.1 mass part-10 mass parts, More preferably, they are 1 mass part-5 mass parts. By setting the content of the photoacid generator (C) in the above specific range, a positive radiation-sensitive composition having good radiation sensitivity can be obtained, thereby forming an interlayer insulating film for display elements having sufficient surface hardness while maintaining transparency. Can be.

<[D] surfactant>

Surfactant (D) can be added in order to improve the applicability | paintability of the said positive radiation sensitive composition, to reduce application | coating stain, and to improve film thickness uniformity. [D] As the surfactant, for example, a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, and the like can be given. These [D] surfactant can be used individually or in combination of 2 or more types.

As a fluorine type surfactant, the compound which has a fluoroalkyl group and / or a fluoroalkylene group in at least any part of terminal, main chain, and side chain is preferable, For example, 1,1,2,2- tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1,1, 2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1, 2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycoldi (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro-n-dodecanesulfonic acid Sodium, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,3,3,9,9,10,10-decafluoro-n-dodecane Sodium fluoroalkylbenzenesulfonate, sodium fluoroalkyl phosphate, sodium fluoroalkyl carbonate, diglycerin tetrakis (fluoroalkylpolyoxy Styrene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, carboxylic acid fluoroalkyl ester, etc. Can be.

As a commercial item of a fluorine-type surfactant, BM-1000, BM-1100 (above, BM CHEMIE make), Megaface F142D, copper F172, copper F173, copper F183, copper F178, copper F191, copper F471, Copper F476 (above, Dai Nippon Inkaki Chemical Co., Ltd.), Fluorad FC-170C, Copper FC-171, Copper FC-430, Copper FC-431 (above, manufactured by Sumitomo 3M), Suflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, S SC-105, copper SC-106 (above, manufactured by Asahi Glass), Ftop EF301, copper EF303, copper EF352 (more, manufactured by Shin-Akita Kase), aftergent (FT-100), copper FT- 110, East FT-140A, East FT-150, East FT-250, East FT-251, East FT-300, East FT-310, East FT-400S, East FTX-218, East FT-251 Production).

As a commercial item of a silicone type surfactant, Toray silicone DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032 , SF-8428, DC-57, DC-190, SH 8400 FLUID (above, manufactured by Torre Dow Corning), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF -4452 (above, GE TOSHIBA silicone make), organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), etc. are mentioned.

As a nonionic surfactant, For example, polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (Meth) acrylic acid type copolymers etc. are mentioned. Examples of commercially available products of nonionic surfactants include Polyflow Nos. 57 and 95 (manufactured by Kyoesha Chemical Co., Ltd.).

As content of [D] surfactant in the said positive radiation sensitive composition, Preferably it is 0.01 mass part or more and 10 mass parts or less with respect to a total of 100 mass parts of a [A] polymer and a [B] siloxane polymer, More preferably, they are 0.05 mass part or more and 5 mass parts or less. The coating property of a positive radiation sensitive composition can be optimized by making content of [D] surfactant into the said specific range.

<[E] adhesion preparation>

In the positive radiation-sensitive composition, in order to improve the adhesion between the inorganic material serving as the substrate, for example, silicon compounds such as silicon, silicon oxide, silicon nitride, metals such as gold, copper, aluminum, and the insulating film, [E] ] Close preparation can be used. As this adhesion | attachment adjuvant, a functional silane coupling agent is used preferably. As an example of a functional silane coupling agent, the silane coupling agent etc. which have reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group (preferably oxiranyl group), a thiol group, etc. are mentioned. These [E] adhesion adjuvant can be used individually or in combination of 2 or more types.

Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane and γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, etc. are mentioned. Of these, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyl dialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-methacryloxypropyltrimeth Preferred are oxysilanes.

As content of the [E] adhesion | attachment adjuvant in the said positive radiation sensitive composition, Preferably it is 0.5 mass part or more and 20 mass parts or less with respect to a total of 100 mass parts of a [A] polymer and a [B] siloxane polymer. Preferably it is used in the quantity of 1 mass part or more and 10 mass parts or less. [E] The adhesion between the interlayer insulating film for display element to be formed and the substrate is improved by setting the amount of the adhesion assistant to the specific range described above.

<[F] basic compound>

When the positive radiation-sensitive composition contains the [F] basic compound, the diffusion length of the acid generated from the [C] photoacid generator by exposure can be appropriately controlled and the pattern developability can be improved. As a basic compound, it can select arbitrarily and can use from what is used by chemically amplified resist, For example, an aliphatic amine, an aromatic amine, a heterocyclic amine, a quaternary ammonium hydroxide, a carboxylic acid quaternary ammonium salt, etc. are mentioned. These [F] basic compounds can be used individually or in combination of 2 or more types.

Examples of the aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, Triethanolamine, dicyclohexylamine, dicyclohexyl methylamine, etc. are mentioned.

Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.

As the heterocyclic amine, for example, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4 -Dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxy Quinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4,3,0] -5-nonene And 1,8-diazabicyclo [5,3,0] -7-undecene.

As quaternary ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexyl ammonium hydroxide, etc. are mentioned, for example.

As a carboxylic acid quaternary ammonium salt, tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate, etc. are mentioned, for example.

As the [F] basic compound, a heterocyclic amine is preferable, and 4-dimethylaminopyridine and 1,5-diazabicyclo [4,3,0] -5-nonene are more preferable.

As content of the [F] basic compound in the said positive radiation sensitive composition, 0.001 mass part-1 mass part are preferable with respect to a total of 100 mass parts of a [A] polymer and a [B] siloxane polymer, and 0.005 mass part? 0.2 mass part is more preferable. By making content of a [F] basic compound into the said specific range, pattern developability improves more.

<[G] quinonediazide compound>

[G] The quinonediazide compound is a compound which generates carboxylic acid by irradiation of radiation. As a quinone diazide compound, the condensate of a phenolic compound or an alcoholic compound (henceforth a "mother nucleus"), and 1,2-naphthoquinone diazide sulfonic-acid halide can be used. These [G] quinonediazide compounds can be used individually or in combination of 2 or more types.

As said mother nucleus, trihydroxy benzophenone, tetrahydroxy benzophenone, pentahydroxy benzophenone, hexahydroxy benzophenone, (polyhydroxyphenyl) alkane, other mother nucleus, etc. are mentioned, for example.

As trihydroxy benzophenone, 2, 3, 4- trihydroxy benzophenone, 2, 4, 6- trihydroxy benzophenone etc. are mentioned, for example. As tetrahydroxy benzophenone, it is 2,2 ', 4,4'- tetrahydroxy benzophenone, 2,3,4,3'- tetrahydroxy benzophenone, 2,3,4,4'-, for example. Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, and the like. have. As pentahydroxy benzophenone, 2,3,4,2 ', 6'- pentahydroxy benzophenone etc. are mentioned, for example. As hexahydroxy benzophenone, it is 2,4,6,3 ', 4', 5'-hexahydroxy benzophenone, 3,4,5,3 ', 4', 5'-hexahydroxy benzo, for example. Phenone etc. are mentioned. Examples of the (polyhydroxyphenyl) alkane include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1 -Tris (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3 -Tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] Ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiindene-5 , 6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan and the like. As another mother nucleus, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl ) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3 -Dihydroxy benzene is mentioned.

Among these mother nuclei, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tri (p-hydroxyphenyl) ethane, 4,4 '-[1- [4- [1- [ 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. As 1, 2- naphthoquinone diazide sulfonic-acid chloride, a 1, 2- naphthoquinone diazide- 4-sulfonic acid chloride, a 1, 2- naphthoquinone diazide-5-sulfonic acid chloride, etc. are mentioned, for example. . Among these, 1,2-naphthoquinone diazide-5-sulfonic acid chloride is preferable.

As a condensate of a phenolic compound or an alcoholic compound with 1,2-naphthoquinone diazide sulfonic acid halide, 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinone diazide- Condensates with 5-sulfonic acid chloride, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinone Preference is given to condensates with diazide-5-sulfonic acid chlorides.

In the condensation reaction of the phenolic compound or the alcoholic compound (parent nucleus) with the 1,2-naphthoquinone diazide sulfonic acid halide, the molar ratio of the OH group in the phenolic compound or the alcoholic compound is preferably 30 mol% to 85 mol%. More preferably, 1,2-naphthoquinone diazide sulfonic-acid halide corresponding to 50 mol%-70 mol% can be used. Condensation reaction can be performed by a well-known method.

As the quinone diazide compound, 1,2-naphthoquinone diazide sulfonic acid amides, for example, 2,3,4-triaminobenzophenone-1, in which the ester bond of the above-described parent nucleus is changed to an amide bond, 2-naphthoquinone diazide-4-sulfonic acid amide etc. are also used suitably.

As the usage-amount of [G] quinonediazide compound, the sum total of a [C] photo-acid generator and a [G] quinone diazide compound becomes like this. Preferably it is 0.1 with respect to a total of 100 mass parts of [A] polymer and [B] siloxane polymer. A mass part-30 mass parts, More preferably, they are 1 mass part-20 mass parts.

<Other optional components>

In addition to the said [A]-[G] component, the said positive radiation sensitive composition is [H] a thermosensitive acid generator or a thermosensitive base generator as needed in the range which does not impair the effect of this invention, [ I] You may contain other arbitrary components, such as a dehydrating agent.

<[H] thermosensitive acid generator or thermosensitive base generator>

[H] The thermosensitive acid generator or the thermosensitive base generator self-condenses the [B] siloxane polymer (preferably a hydrolytic condensate of the hydrolyzable silane compound represented by the formula (2)) by heating. It is defined as a compound capable of releasing an acidic active substance or basic active substance which acts as a catalyst for curing. By using such a [H] thermosensitive acid generator or a thermosensitive base generator, the surface hardness and heat resistance of the interlayer insulation film for display elements obtained can be improved more. In addition, as a [H] thermosensitive acid generator or a thermosensitive base generator, it is acidic activity at the time of the prebaking of comparatively low temperature (for example, 70 degreeC-120 degreeC) in the coating film formation process of a positive radiation sensitive composition. It is preferable to have the property of releasing an acidic active substance or basic active substance at the time of postbaking of comparatively high temperature (for example, 120 degreeC-250 degreeC) in the heating process after image development, without releasing a substance or basic active substance. . These [H] thermosensitive acid generators or thermosensitive base generators can be used individually or in combination of 2 or more types.

As the [H] thermosensitive acid generator, the compounds listed in the description of the [C] photoacid generator can be suitably applied. In addition, the use can be distinguished by adjusting the exposure amount and the temperature to which the light or the heat is to be sensitive.

Examples of the [H] thermosensitive base generator include 2-nitrobenzylcyclohexylcarbamate, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, N- (2-nitrobenzyloxy Carbonyl) pyrrolidine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyloxime, 4- ( Methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1- (4-morph Polynophenyl) -butanone, hexaamine cobalt (III) tris (triphenylmethyl borate), etc. are mentioned. Among these [H] thermosensitive base generators, 2-nitrobenzylcyclohexyl carbamate and O-carbamoyl hydroxyamide are preferable from the viewpoint of improving the surface hardness and the heat resistance of the interlayer insulating film for display elements obtained.

As the usage-amount of the [H] thermosensitive acid generator or a thermosensitive base generator, 0.1 mass part-20 mass parts, More preferably, with respect to a total of 100 mass parts of a [A] polymer and a [B] siloxane polymer. Is 1 mass part-10 mass parts. [H] A positive radiation sensitive composition having excellent surface hardness and heat resistance of the interlayer insulating film for display elements formed can be obtained by setting the amount of the thermosensitive acid generator or the thermosensitive base generator to be within the above specific range, and further, the coating film. It is possible to prevent the occurrence of precipitates in the formation process of and to facilitate coating film formation.

<[I] dehydrating agent>

[I] The dehydrating agent is defined as a substance capable of converting water into a substance other than water by chemical reaction, or trapping water by physical adsorption or inclusion. The positive radiation-sensitive composition contains the [I] dehydrating agent, whereby water penetrating from the environment or water generated as a result of condensation of the [B] siloxane polymer in the heating step after development of the positive radiation-sensitive composition is produced. Can be reduced. As a result, the storage stability of a composition can be improved. Moreover, it is thought that the reactivity of the condensation of [B] siloxane polymer can be improved, and the heat resistance of a positive radiation sensitive composition can be improved. As these [I] dehydrating agents, carbonic acid ester, acetals (including ketals), carbonic anhydride, etc. are mentioned, for example.

As carboxylic acid ester, orthocarboxylic acid ester and carboxylic acid silyl ester are preferable. Examples of the orthocarboxylic acid ester include methyl ortho formate, ethyl ortho formate, propyl ortho formate, butyl ortho formate, methyl ortho acetate, ortho acetate, ortho acetate, butyl ortho acetate, methyl orthopropionate, ethyl orthopropionate, and the like. Can be mentioned. Of these orthocarboxylic acid esters, ortho formic acid esters such as methyl ortho formate are preferable. Examples of the carboxylic acid silyl esters include trimethylsilyl acetate, tributylsilyl acetate, trimethylsilyl formate, trimethylsilyl oxalate, and the like.

As acetals, the reactants of ketones and alcohols, the reactants of ketones and dialcohols, and ketensilyl acetals are preferable. As a reactant of ketones and alcohol, dimethyl acetal, diethyl acetal, dipropyl acetal, etc. are mentioned, for example.

Examples of the carbonic anhydride include formic acid anhydride, acetic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and benzoic anhydride acetate. Among these carbonic anhydrides, acetic anhydride and succinic anhydride are preferred in view of dehydration effect.

As the usage-amount of the [I] dehydrating agent, Preferably it is 0.001 mass part-10 mass parts, More preferably, it is 0.01 mass part-5 mass parts with respect to a total of 100 mass parts of a [A] polymer and a [B] siloxane polymer. Especially preferably, it is 0.03 mass part-1 mass part. The storage stability of a positive radiation sensitive composition can be improved by making the usage-amount of [I] dehydrating agent into the said specific range.

<Preparation method of positive radiation sensitive composition>

The positive radiation-sensitive composition is prepared in a dissolved or dispersed state by mixing a [A] polymer, a [B] siloxane polymer, a [C] photoacid generator, a suitable component, and other optional components, as necessary, in a solvent. do. For example, the said positive radiation sensitive composition can be prepared by mixing each component in a predetermined ratio in a solvent.

As a solvent, what dissolves or disperse | distributes each component uniformly and does not react with each component is used suitably. Examples of the solvent include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl ether propionates. , Aromatic hydrocarbons, ketones, other esters, and the like. In addition, these solvent can use individual or 2 types or more.

Examples of the alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like.

As ethers, tetrahydrofuran etc. are mentioned, for example.

As glycol ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc. are mentioned, for example.

As ethylene glycol alkyl ether acetates, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc. are mentioned, for example.

As diethylene glycol alkyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc. are mentioned, for example.

As propylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc. are mentioned, for example.

Examples of propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate.

Examples of the propylene glycol monoalkyl ether propionate include propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate, and the like. Can be mentioned.

As aromatic hydrocarbons, toluene, xylene, etc. are mentioned, for example.

As ketones, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl- 2-pentanone, etc. are mentioned, for example.

As other esters, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, and hydroxy Methyl hydroxyacetate, ethyl hydroxyacetate, hydroxyacetic acid butyl, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionic acid propyl, 3-hydroxy Butyl oxypropionate, methyl 2-hydroxy-3-methylbutanoic acid, methyl methoxyacetic acid, ethyl methoxyacetic acid, methoxyacetic acid propyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, ethoxyacetic acid propyl Butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propoxyacetate Acid propyl, butyl propoxyacetic acid, methyl butoxyacetic acid, ethyl butoxyacetic acid, butyl butoxyacetic acid, butyl butoxyacetic acid, 2-methoxypropionate, ethyl 2-methoxypropionic acid, 2-methoxypropionic acid propyl, 2 Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2- Propyl butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionic acid, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-E Ethyl oxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionate Butyl, 3-propoxy propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, and the like.

Among these solvents, those having excellent solubility or dispersibility, being non-reactive with each component, and ethers such as dialkyl ether, diethylene glycol alkyl ether, and ethylene glycol alkyl ether acetate from the viewpoint of ease of coating film formation Propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters are preferable, and in particular, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and methyl cello Sorbate acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, acetic acid profile, acetic acid i-propyl, butyl acetate, 2-hydroxyethyl propionate, 2-hydroxy Preferred are methyl-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, butyl butyl acetate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate. Do.

Moreover, in addition to the said solvent, if necessary, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, caproic acid, Caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylcellosolve acetate, carbi High boiling point solvents, such as tall acetate, can also be used together.

As solid content concentration of a positive radiation sensitive composition, although it can set arbitrarily according to a use purpose, a desired film thickness, etc., Preferably it is 10 mass% or more and 70 mass% or less, More preferably, it is 30 mass% or more and 60 mass% or less. .

<Method of Forming Interlayer Insulating Film for Display Element>

The said positive radiation sensitive composition is suitable as a formation material of the interlayer insulation film for display elements. Moreover, the interlayer insulation film for display elements formed from the said positive radiation sensitive composition is also suitably contained in this invention.

The method for forming an interlayer insulating film for a display element of the present invention,

(1) forming a coating film of the positive radiation-sensitive composition on a substrate;

(2) a step of irradiating at least a part of the coating film with radiation,

(3) developing the coating film irradiated with the radiation;

(4) heating the developed coating film.

In this method, since the positive radiation sensitive composition has good radiation sensitivity and the interlayer insulating film for display elements to be formed has high dry etching resistance, a large dry etching margin can be ensured. Even if it is difficult to process the whole uniformly and for a short time, the interlayer insulation film for display elements having a fine and elaborate pattern can be easily formed. Moreover, the interlayer insulation film for display elements which satisfy | filled the surface hardness, refractive index, heat resistance, and transparency well-balanced can be obtained. Hereinafter, each process is explained in full detail.

[Step (1)]

In this process, after apply | coating the solution or dispersion liquid of the said positive radiation sensitive composition on a board | substrate, Preferably, a solvent is removed by prebaking an application surface, and a coating film is formed. As a coating method, the spray method, the roll coating method, the rotary coating method (spin coating method), the slit die coating method, the bar coating method, etc. are mentioned, for example. Among these, the spin coating method and the slit die coating method are preferable, and the slit die coating method is more preferable.

As a board | substrate, glass, quartz, silicone, resin, etc. are mentioned, for example. As resin, a polyethylene terephthalate, a polybutylene terephthalate, a polyether sulfone, a polycarbonate, a polyimide, the ring-opening polymer of cyclic olefin, its hydrogenated substance, etc. are mentioned, for example. As conditions of prebaking, although it changes also with the kind, compounding ratio, etc. of each component, it can be made into about 70 degreeC-120 degreeC, 1 minute-about 10 minutes.

[Step (2)]

In this step, at least part of the formed coating film is exposed to radiation. When exposing, it exposes normally through the photomask which has a predetermined pattern. As radiation used for exposure, the radiation used with respect to the [C] photoacid generator is suitable. Among these radiations, radiation having a wavelength of 190 nm to 450 nm is preferable, and radiation containing 365 nm ultraviolet rays is more preferable. As an exposure amount, 300J / m <2> -3,000J / m <2> is preferable and 300J / m <2> -2,000J / is the value which measured the intensity | strength in the wavelength of 365 nm of radiation with the illuminometer (OAI model356, OAI Optical Associates make). 2 m <2> is more preferable and 400 J / m <2> -1,000 J / m <2> is especially preferable.

[Step (3)]

In this step, the coating film irradiated with the radiation is developed. By developing the coating film after exposure, an unnecessary part (irradiation part of radiation) is removed and a predetermined pattern is formed. As a developing solution used for a developing process, alkaline aqueous solution is preferable. As an alkali, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia; And quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

A suitable amount of water-soluble organic solvents and surfactants, such as methanol and ethanol, can also be added to aqueous alkali solution. As a density | concentration of alkali in aqueous alkali solution, 0.1 mass% or more and 5 mass% or less are preferable from a viewpoint of obtaining suitable developability. As the image development method, a puddle method, a dipping method, a rocking dipping method, a shower method, etc. are mentioned, for example. As image development time, although it changes with the composition of the said positive radiation sensitive composition, it is about 10 second-180 second. Subsequent to such developing treatment, for example, flowing water washing is performed for 30 seconds to 90 seconds, and then air dried with, for example, compressed air or compressed nitrogen, to form a desired pattern.

[Step (4)]

In this step, the developed coating film is heated. For heating, by heating a patterned thin film using a heating device such as a hot plate or an oven, the curing reaction of the [A] polymer and the [B] siloxane polymer can be promoted to obtain a cured product. As heating temperature, it is about 120 degreeC-about 250 degreeC, for example. As heating time, although it changes with kinds of heating apparatus, it is about 5 minutes-about 30 minutes in a hotplate, and about 30 minutes-about 90 minutes in an oven. Moreover, the step baking method etc. which perform two or more heating processes can also be used. In this manner, a patterned thin film corresponding to the target interlayer insulating film can be formed on the surface of the substrate. In addition, it is not limited to the interlayer insulation film for display elements as a use of the said cured film, It can use also as a spacer and a protective film.

As a film thickness of the formed interlayer insulation film for display elements, Preferably it is 0.1 micrometer-8 micrometers, More preferably, it is 0.1 micrometer-6 micrometers, Especially preferably, it is 0.1 micrometer-4 micrometers.

Example

Hereinafter, although this invention is explained based on an Example, this invention is not interpreted limitedly based on description of this Example.

<Synthesis of [A] Component>

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethylmethyl ether were placed. 5 parts by mass of methacrylic acid, 40 parts by mass of 1-ethoxyethyl methacrylate, 5 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, and α- After adding 3 parts by mass of methyl styrene dimer and replacing with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-1). Mw of the polymer (A-1) was 9,000. Solid content concentration of the polymer solution was 32.1 mass%.

[Synthesis Example 2]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethylmethyl ether were placed. Subsequently, 5 parts by mass of methacrylic acid, 40 parts by mass of 2-tetrahydropyranyl methacrylate, 5 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate and α- After adding 3 parts by mass of methyl styrene dimer and replacing with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-2). Mw of the polymer (A-2) was 9,000. Solid content concentration of the polymer solution was 31.3 mass%.

[Synthesis Example 3]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed. Subsequently, 67 mass parts of 1-n-butoxyethyl methacrylates, 23 mass parts of benzyl methacrylic acid, and 10 mass parts of methacrylic acid were put and substituted by nitrogen, and stirring was started gently. The temperature of the solution was raised to 80 ° C., and the temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-1). Mw of the polymer (a-1) was 9,000. Solid content concentration of the polymer solution was 30.3 mass%.

[Synthesis Example 4]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed. Subsequently, 90 mass parts of 1-benzyloxyethyl methacrylates, 6 mass parts of 2-hydroxyethyl methacrylic acid, and 4 mass parts of methacrylic acid were put, and nitrogen-substituted, and stirring was started gently. The temperature of the solution was raised to 80 ° C., and the temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-2). Mw of the polymer (a-2) was 9,000. Solid content concentration of the polymer solution was 31.2 mass%.

Synthesis Example 5

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed. Subsequently, after putting 85 mass parts of 2-tetrahydropyranyl methacrylates, 7 mass parts of 2-hydroxyethyl methacrylic acid, and 8 mass parts of methacrylic acid, and nitrogen-substituted, stirring was started gently. The temperature of the solution was raised to 80 ° C., and the temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-3). Mw of the polymer (a-3) was 10,000. Solid content concentration of the polymer solution was 29.2 mass%.

[Synthesis Example 6]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethylmethyl ether were placed. Subsequently, after putting 52 mass parts of glycidyl methacrylates and 48 mass parts of benzyl methacrylates, and nitrogen-substituted, stirring was started gently. The temperature of the solution was raised to 80 ° C., and the temperature was maintained for 6 hours to obtain a polymer solution containing polymer (aa-1). Mw of the polymer (aa-1) was 10,000. Solid content concentration of the polymer solution was 32.3 mass%.

[Synthesis Example 7]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethylmethyl ether were placed. Subsequently, 45 mass parts of methacrylic acid 3, 4- epoxycyclohexylmethyl, 45 mass parts of benzyl methacrylate, and 10 mass parts of methacrylic acid were put, and nitrogen-substituted, and stirring was started gently. The temperature of the solution was raised to 80 ° C., and the temperature was maintained for 6 hours to obtain a polymer solution containing polymer (aa-2). Mw of the polymer (aa-2) was 10,000. Solid content concentration of the polymer solution was 33.2 mass%.

[Synthesis Example 8]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethylmethyl ether were placed. Subsequently, 35 mass parts of 1-n-butoxyethyl methacrylates, 35 mass parts of benzyl methacrylate, and 30 mass parts of glycidyl methacrylate were put, and nitrogen-substituted, and stirring was started gently. The temperature of the solution was raised to 80 ° C., and the temperature was maintained for 6 hours to obtain a polymer solution containing polymer (aa-3). Mw of the polymer (aa-3) was 10,000. Solid content concentration of the polymer solution was 32.3 mass%.

Synthesis Example 9

In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobis (isobutyronitrile), 5 parts by mass of t-dodecanethiol, and 150 parts by mass of propylene glycol monomethyl ether acetate were placed. Thereafter, 30 parts by mass of methacrylic acid, 35 parts by mass of benzyl methacrylate, and 35 parts by mass of methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl were added thereto, and the mixture was stirred at room temperature for a while. After nitrogen substitution, the mixture was heated and stirred at 70 ° C. for 5 hours. Next, 15 mass parts of glycidyl methacrylate, 1 mass part of dimethylbenzylamine, and 0.2 mass part of p-methoxyphenols are added to the obtained solution, and it heat-stirred at 100 degreeC for 4 hours, and polymer (CA-1) solution Got. Mw of the polymer (CA-1) was 5,000, and Mw / Mn was 2. Solid content concentration of the polymer solution was 38.0 mass%.

<Synthesis of [B] siloxane polymer>

Synthesis Example 10

25 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, and then 30 mass parts of methyl trimethoxysilanes, 23 mass parts of phenyl trimethoxysilanes, and 0.5 mass parts of oxalic acid were heated, and it heated until solution temperature became 60 degreeC. did. After solution temperature reached 60 degreeC, 18 mass parts of ion-exchange water was added, it heated until it became 75 degreeC, and it preserve | saved for 3 hours. Subsequently, 28 mass parts of methyl ortho formate was added as a dehydrating agent, and it stirred for 1 hour. Furthermore, the solution temperature was 40 degreeC and the methanol which generate | occur | produced by ion-exchange water and hydrolysis condensation was removed by evaporating, maintaining temperature. The hydrolysis-condensation product (B-1) was obtained by the above. Mw of the obtained hydrolysis-condensation product (B-1) was 3,000, and Mw / Mn was 2. Solid content concentration of a hydrolysis-condensation product (B-1) was 40.5 mass%.

Synthesis Example 11

25 mass parts of propylene glycol monomethyl ethers were put into the container with a stirrer, and 22 mass parts of methyl trimethoxysilanes, 12 mass parts of (gamma)-glycidoxy propyl trimethoxysilanes, 20 mass parts of phenyl trimethoxysilanes, and tetra- 0.1 mass part of i-propoxy aluminum was put, and it carried out similarly to the synthesis example 10, and obtained the hydrolysis-condensation product (B-2). Mw of the obtained hydrolysis-condensation product (B-2) was 3,200, and Mw / Mn was 2. Solid content concentration of a hydrolysis-condensation product (B-2) was 39.8 mass%.

[Synthesis Example 12]

In a container with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was placed, followed by 22 parts by mass of methyltrimethoxysilane, 12 parts by mass of 3-methacryloxypropyltrimethoxysilane, 20 parts by mass of phenyltrimethoxysilane and 0.5 oxalic acid. A mass part was charged and operated in the same manner as in Synthesis example 10 to obtain a hydrolysis condensate (B-3). Mw of the obtained hydrolysis condensate (B-3) was 2,400, and Mw / Mn was 2. Solid content concentration of a hydrolysis-condensation product (B-3) was 41.0 mass%.

<Preparation of a positive radiation sensitive composition>

Hereinafter, the component used for preparation of the positive radiation sensitive composition of an Example and a comparative example is explained in full detail.

[C] mine generator

C-1: 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate

C-2: benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate

C-3: (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl) acetonitrile (made by Chiba Specialty Chemicals, IRGACURE PAG 103)

C-4: (5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (made by Chiba Specialty Chemicals, IRGACURE PAG 108)

C-5: (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (Ciba Specialty Chemicals make, IRGACURE PAG 121)

C-6: (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (Ciba Specialty Chemicals make, CGI1380)

C-7: (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile (Ciba Specialty Chemicals make, CGI725)

[D] surfactant

D-1: Silicone Surfactant (Tore Dow Corning Silicone, SH 8400 FLUID)

D-2: Fluorine-type surfactant (Neos make, Pgentgent FTX-218)

[E] close preparation

E-1: γ-glycidoxypropyltrimethoxysilane

E-2: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane

E-3: γ-methacryloxypropyltrimethoxysilane

[F] basic compounds

F-1: 4-dimethylaminopyridine

F-2: 1,5-diazabicyclo [4,3,0] -5-nonene

[G] quinonediazide compounds

G-1: Condensate of 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) with 1,2-naphthoquinone diazide-5-sulfonic acid chloride (2.0 mol)

Example 1

[A] 70 parts by mass of a solution containing (A-1) as a polymer (amount corresponding to solid content), 30 parts by mass of (B-1) as a [B] siloxane polymer, and (C- as a photoacid generator 1) Positive type by mixing 4 mass parts, (D-1) 0.20 mass part as [D] surfactant, and 3.0 mass parts of (E-1) as an [E] adhesion | attachment adjuvant, and filtering by a membrane filter with a pore size of 0.2 micrometer. A radiation sensitive composition was prepared.

[Examples 2 to 14 and Comparative Examples 1 to 6]

Except having made the kind and compounding quantity of each component as having shown in Table 1, it operated similarly to Example 1, and prepared each positive radiation sensitive composition. In addition, "?" In Table 1 shows that the corresponding component was not used.

<Evaluation>

The following evaluation was performed using each prepared positive radiation sensitive composition. The results are shown in Table 1 below.

[Radiation sensitivity (J / m2)]

Hexamethyldisilazane (HMDS) was apply | coated on 550x650 mm chromium film-forming glass, and it heated at 60 degreeC for 1 minute. On the chromium film-forming glass after this HMDS process, each positive radiation sensitive composition was apply | coated using a slit die coater (TR632105-CL, Tokyo-Kyokyo Co., Ltd.), after setting a reaching pressure to 100 Pa and removing a solvent under vacuum. Furthermore, the prebaking was carried out at 90 degreeC for 2 minutes, and the coating film of 3.0 micrometers in thickness was formed. Subsequently, radiation was irradiated with a variable amount of exposure to the coating film via a mask having a pattern of 60 µm line-and-space (10: 1) using an exposure machine (manufactured by Canon, MPA-600FA). Then, it developed for 80 second at 25 degreeC by the 0.4 mass% tetramethylammonium hydroxide aqueous solution. Subsequently, flowing water wash | cleaned with ultrapure water for 1 minute, and after that, the pattern was formed on the chromium film-forming glass substrate after HMDS process. At this time, the exposure amount required for the 6-micrometer space pattern to melt | dissolve completely was made into the radiation sensitivity (J / m <2>). When this value was 500 (J / m <2>) or less, it judged that the sensitivity was favorable.

[Surface hardness]

Except not having exposed through a mask, it carried out similarly to the said evaluation of the radiation sensitivity, and formed the cured film on the silicon substrate. The pencil hardness (surface hardness) of the cured film was measured by the 8.4.1 pencil scraping test of JIS K-5400-1990. When this value is 3H or more, it is judged that the surface hardness as an interlayer insulation film for display elements is favorable, and it can be said that it has sufficient hardenability.

Refractive Index (%)

It operated similarly to the evaluation of the said surface hardness, the cured film formed on the silicon substrate, and the refractive index (%) of the obtained cured film was measured at 633 nm using the Auto EL IV NIR III (made by Rudolf Research) liposometer. When this value was 1.50 or more, it was judged that the refractive index as an interlayer insulation film for display elements is a level which is satisfactory practically.

[Heat resistance (%)]

In the same manner as in the evaluation of the surface hardness, a cured film was formed on a silicon substrate, and the film thickness (T2) of the obtained cured film was measured. Subsequently, after baking this silicon substrate in which the cured film was formed at 240 degreeC for 1 hour in a clean oven, the film thickness (t2) of the said cured film was measured, and the film thickness change rate (%) by further baking is calculated from the following formula. It computed and made this heat resistance (%).

Heat resistance (%) = (| t2? T2 | / T2) × 100

When this value was 3% or less, it judged that heat resistance was favorable.

Transmittance (%)

Except having used the glass substrate (Corning 7059, Corning Corporation) instead of the silicon substrate, it operated similarly to the evaluation of the said surface hardness, and formed the cured film on the glass substrate. The light transmittance (%) of the glass substrate which has this cured film was measured with the wavelength of the range of 400 nm-800 nm using the spectrophotometer (150-20 type double beam, the Hitachi Sakusho company). When the minimum light transmittance was 95% or more, it was judged that the transmittance was good.

[Dry etching resistance (µm)]

In the same manner as in the evaluation of the surface hardness, a cured film was formed on a silicon substrate, and the etching gas CF ₄ 50 mL / min, O ₂ 10 mL / min using a dry etching apparatus (CDE-80N, manufactured by Shibaura Mechatronics) Dry etching was performed under conditions of an output of 400 mW and an etching time of 90 seconds, and the film thickness (µm) before and after the treatment was measured. It was judged that dry etching resistance was favorable when the film thickness reduction amount was 1.0 micrometer or less.

As is clear from the results of Table 1, the cured film formed of the positive radiation-sensitive composition containing all of the [A] polymer, the [B] siloxane polymer and the [C] photoacid generator was compared with the cured film obtained from the composition of the comparative example. It was found that dry etching resistance was improved. Moreover, it turned out that the cured film which fully satisfies heat resistance, transparency, surface hardness, and a refractive index can be formed. In addition, the cured film formed from the said positive radiation sensitive composition is excellent in dry etching property even if compared with the hardened | cured material formed from the composition of the comparative example containing a [G] quinonediazide compound instead of the [C] photo-acid generator. okay. Moreover, the cured film formed from the positive radiation sensitive composition of Example 10 in Example 1 whose mass ratio of the polymer [A] with respect to the sum total of the [A] polymer and the [B] siloxane polymer is 5 mass% or more and 95 mass% or less, Compared with the cured film obtained from the composition of Examples 11-14 other than the said specific range, it turned out that dry etching resistance and refractive index are high. Thereby, it turned out that it is preferable that the mass ratio of the polymer [A] with respect to the sum total of the [A] polymer and the [B] siloxane polymer is 5 mass% or more and 95 mass% or less.

The positive radiation sensitive composition of this invention can form the interlayer insulation film for display elements which has high dry etching resistance. Moreover, the positive radiation sensitive composition of this invention can form the interlayer insulation film for display elements which has sufficient radiation sensitivity and fully satisfies heat resistance, transparency, surface hardness, and a refractive index. Therefore, the said positive radiation sensitive composition is used suitably in order to form the interlayer insulation film for display elements for display elements.

Claims (6)

[A] A polymer comprising a structural unit (I) having an group represented by the following formula (1) and an epoxy group-containing structural unit (II) in the same or different polymer molecule,
[B] a siloxane polymer, and
[C] mine generator
Positive radiation sensitive composition containing:

(In formula (1), R <^1> and R <^2> is respectively independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. However, one part or all part of the hydrogen atom which the said alkyl group, a cycloalkyl group, and an aryl group has is substituted, and is substituted. And R ¹ and R ² are not all hydrogen atoms; R ³ is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or a group represented by -M (R ^3m ) ₃ ; Si, Ge, or Sn; each R ^3m is independently an alkyl group, and R ¹ and R ³ may be linked to each other to form a cyclic ether structure, provided that some or all of the hydrogen atoms of these groups represented by R ³ are present; May be substituted). The method of claim 1,
The positive radiation sensitive composition whose [B] siloxane polymer is a hydrolysis-condensation product of the hydrolyzable silane compound represented by following formula (2):

(In formula (2), R <^4> is a C1-C20 non-hydrolyzable organic group; R <^5> is a C1-C4 alkyl group; n is an integer of 0-3; However, R <^{4> is} And when there are a plurality of R ⁵ , a plurality of R ⁴ and R ⁵ may be the same or different, respectively). The method of claim 1,
The positive radiation sensitive composition whose mass ratio of the polymer [A] with respect to the sum total of the [A] polymer and the [B] siloxane polymer is 5 mass% or more and 95 mass% or less. The method of claim 1,
Positive type radiation sensitive composition used for formation of the interlayer insulation film for display elements. (1) forming the coating film of the positive radiation sensitive composition of Claim 4 on a board | substrate,
(2) irradiating at least a part of the coating film with radiation;
(3) developing the coating film irradiated with the radiation;
(4) heating the developed coating film
The formation method of the interlayer insulation film for display elements which has this. The interlayer insulation film for display elements formed from the positive radiation sensitive composition of Claim 4.