KR20110115084A - Positive radiation-sensitive composition, interlayer insulating film and method for forming the same - Google Patents

Abstract

(Problem) Positive radiation sensitive composition which has the outstanding radiation sensitivity, and has the outstanding developability and pattern formation property which can respond also to the change of cured film formation conditions, while having the interlayer insulation film obtained having high light transmittance and voltage preservation rate, It is an object to provide an interlayer insulating film formed of the composition and a method of forming the interlayer insulating film.
(Solution means) The present invention provides a polymer having a structural unit and an epoxy group-containing structural unit containing a group represented by the following formula (1) in [A] the same or different polymer molecules, [B] photoacid generator, and [C] long chain It is a positive radiation sensitive composition containing an alkyl group containing compound.

Description

Positive radiation-sensitive composition, interlayer insulating film and method for forming the same {POSITIVE RADIATION-SENSITIVE COMPOSITION, INTERLAYER INSULATING FILM AND METHOD FOR FORMING THE SAME}

The present invention provides a positive radiation sensitive composition suitable as a material for forming an interlayer insulating film of a display device such as a liquid crystal display device (LCD), an organic EL display device (OLED), an interlayer insulating film formed from the composition, and the interlayer insulating film. It relates to a method of forming.

In the display element, an interlayer insulating film is formed in order to insulate between wirings arranged in a layer shape in general. As the material for forming the interlayer insulating film, a positive radiation-sensitive composition has been widely used because there are few processes for obtaining the required pattern shape, and it is preferable to have sufficient flatness. Good radiation sensitivity and the like are required for the positive radiation-sensitive composition used for forming such an interlayer insulating film, and excellent heat resistance and the like are required for the interlayer insulating film obtained therefrom.

In recent years, display devices such as liquid crystal display devices and organic EL display devices tend to have large screens, high luminance, high definition, high-speed response, and thinning. Therefore, the radiation sensitive composition for interlayer insulation film formation used for the display element of a display device has a high sensitivity with respect to radiation, and the interlayer insulation film formed has a high voltage preservation rate and a high light transmittance rather than conventionally. Better performance is required.

As a component of a positive radiation sensitive composition corresponding to such various needs, acrylic resins are widely adopted. For example, Japanese Patent Laid-Open No. 2004-4669 discloses a crosslinking agent, an acid generator, and itself in an aqueous alkali solution. It is insoluble or poorly soluble, but has a protecting group which can be dissociated by the action of an acid, and after the protecting group has dissociated, it contains a resin which is soluble in an aqueous alkali solution. Positive chemically amplified resist compositions have been proposed. In addition, Japanese Patent Laid-Open No. 2004-264623 proposes a radiation-sensitive resin composition characterized by containing an acetal structure and / or a ketal structure, a resin containing an epoxy group, and an acid generator.

However, when forming an interlayer insulation film using the above conventional radiation sensitive resin composition, for example, when prebaking is performed at comparatively low temperature after application | coating, or developing time is extended by apparatus trouble in a developing process, In such a case, developability, and furthermore, pattern formability may decrease. That is, the conventional radiation sensitive resin composition cannot fully respond to the various changes of the cured film formation conditions in an actual manufacture site, and there exists room for improvement in this point.

Japanese Laid-Open Patent Publication No. 2004-4669 Japanese Laid-Open Patent Publication No. 2004-264623

This invention is made | formed based on the above circumstances, The objective is the outstanding phenomenon which has the outstanding radiation sensitivity and the interlayer insulation film obtained can cope with the change of the cured film formation conditions, while having a high light transmittance and a voltage holding ratio. It is to provide a positive radiation-sensitive composition having properties and pattern formation properties, an interlayer insulating film formed from the composition, and a method of forming the interlayer insulating film.

The invention made to solve the above problems,

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

[B] mine generators,

[C] a compound represented by the following formula (2)

It is a positive radiation sensitive composition containing these.

(In formula (1), R <^1> and R <^2> is respectively independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and even if one part or all of the hydrogen atoms of these alkyl groups, a cycloalkyl group, or an aryl group are substituted by the substituent, Good, provided that 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 (M is Si, Ge or Sn and R ^3m is an alkyl group, and some or all of these hydrogen atoms may be substituted with a substituent, and R ¹ and R ³ may be linked to form a cyclic ether structure;

(In formula (2), X is a C6-C20 divalent linear aliphatic hydrocarbon group; Y ¹ and Y ² are each independently a single bond, an ester bond, an amide bond or a urethane bond; R ⁴ and R ⁵ are, each independently, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, sulfo, sulfonyl group, or the formula (i) ~ a group represented by any of (vi); However, Y ¹ or Y ² is unity coalescence When R ⁴ or R ⁵ connected with Y ¹ or Y ² is not an alkyl group having 1 to 6 carbon atoms;

(In formula (i)-(vi), R <^6> is a hydrogen atom or a C1-C6 alkyl group; R <^7> is a hydrogen atom or a methyl group; m is an integer of 0-6; However, said Formula (2) M in R <^4> or R <^5> connected with this Y <^1> or Y <^2> is 0 when Y <^1> or Y <^2> is a single bond.

Since the said positive radiation sensitive composition contains a [A] polymer and a [B] photo-acid generator, it has the outstanding radiation sensitivity. In addition, the said composition contains [C] the compound (henceforth "the [C] long-chain alkyl group containing compound") represented by said formula (2). According to this [C] long-chain alkyl group containing compound, hydrophobicity with respect to the alkaline developing solution of a hardened part with a long chain alkyl group, and the hydrophilicity of an unhardened part can be improved together with a functional group part. Therefore, according to the said composition, even when the cured film formation conditions change, the [C] long-chain alkyl group containing compound exhibits a buffer effect, and can exhibit the outstanding developability and pattern formation stability stably. Moreover, the said composition can exhibit the light transmittance and voltage retention of the cured film obtained by including such [A]-[C] component at the same high level as the conventional positive radiation sensitive composition.

[B] The photoacid generator may be a compound having an oxime sulfonate group represented by the following formula (3).

(In Formula (3), ^RB1 is a linear or branched alkyl group, a cycloalkyl group, or an aryl group, and some or all of the hydrogen atoms of these groups may be substituted by the substituent.).

When the said composition uses the compound which has the said structure as a [B] photo-acid generator, radiation sensitivity can improve more and it can exhibit the outstanding developability and pattern formation property.

The said positive radiation sensitive composition is used suitably in order to form the interlayer insulation film of a display element. By using this positive radiation sensitive composition for formation of the interlayer insulation film of a display element, the interlayer insulation film which can respond to the recent demand for various performances, such as a high light transmittance and a high voltage hold ratio, can be obtained.

Moreover, the formation method of the interlayer insulation film of the display element of this invention,

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

(2) irradiating at least a portion of the coating film formed in step (1) with radiation;

(3) developing the coating film irradiated with radiation in step (2), and

(4) Step of heating the coating film developed in step (3)

Have

In the said method, the display element which has a fine and fine pattern, even when a cured film formation condition is changed by forming a pattern by exposure, image development, and heating using radiation sensitivity using the said positive radiation sensitive composition. Interlayer insulating film can be formed.

In this specification, the "polymer" which is a [A] component has a structural unit containing the group represented by following formula (1) in one polymer molecule, and an epoxy group containing structure in a polymer molecule different from this one polymer molecule. The concept also includes the case of having a unit.

As explained above, since the positive radiation sensitive composition of this invention contains the said [A], [B], and [C] component, it has the outstanding radiation sensitivity, and the cured film obtained has a high light transmittance and a voltage retention rate. It is equipped with, and the responsiveness to the change of the cured film formation conditions is high, and it can exhibit the outstanding developability and pattern formation property. Therefore, the cured film obtained from the positive radiation sensitive composition of this invention has a fine and sophisticated pattern, even when the formation conditions in a manufacturing process change to some extent, and have a high light transmittance and a voltage holding ratio. Therefore, it can use suitably for an interlayer insulation film etc.

1: is typical sectional drawing which shows the cured film provided with a contact hole.

(Form to carry out invention)

The positive radiation-sensitive composition of the present invention is a structural unit (hereinafter, simply referred to as "structural unit (1)") and an epoxy group-containing structure containing a group represented by the following formula (1) in the same or different polymer molecules: [A] A polymer having a unit, a [B] photoacid generator, and a [C] long chain alkyl group-containing compound may be contained, and may further contain other optional components.

<[A] polymer>

The polymer (A) has a structural unit (1) and an epoxy group-containing structural unit in the same or different polymer molecules, and may have other structural units as necessary. It does not specifically limit as embodiment of the [A] polymer which has a structural unit (1) and an epoxy group containing structural unit, (i) It has both a structural unit (1) and an epoxy group containing structural unit in the same polymer molecule, and [A When one polymer molecule exists in a polymer, (ii) it has a structural unit (1) in one polymer molecule, and has an epoxy group containing structural unit in a different polymer molecule, and [2] When a polymer molecule of a species exists, (iii) it has both a structural unit (1) and an epoxy-group containing structural unit in one polymer molecule, and has a structural unit (1) in a different polymer molecule from these, When another polymer molecule has an epoxy-group containing structural unit and three polymer molecules exist in a polymer [A], in addition to the polymer molecule as described in (i ') (i)-(iii), a polymer [A] During The case containing another 1 type, or 2 or more types of polymer molecule, etc. are mentioned. In any case, the effects of the present invention can be obtained. Hereinafter, the structural unit (1), the epoxy group-containing structural unit, and other structural units will be described in order.

<Structural unit (1)>

In the structural unit (1), since the group represented by the formula (1) exists as a group (hereinafter, simply referred to as an "acid dissociable group") that dissociates in the presence of an acid to generate a polar group, the photon is irradiated by radiation. The acid dissociable group is dissociated by the acid generated from the generator, and as a result, the polymer [A] which is alkali insoluble 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.

As said alkyl group represented by R <^1> and R <^2> in said Formula (1), Preferably it is a C1-C30 linear and branched alkyl group, You may have an oxygen atom, a sulfur atom, and a nitrogen atom in this alkyl chain. As a specific example of the said 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, n- tetradecyl group, and branched alkyl groups such as linear alkyl groups such as n-octadecyl group, i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group and 3-hexyl group.

As said cycloalkyl group represented by R <^1> and R <^2> in said Formula (1), Preferably it is a C3-C20 cycloalkyl group, may be polycyclic, and may have an oxygen atom in a ring. As a specific example of the said 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 said aryl group represented by R <^1> and R <^2> in said formula (1), Preferably it is a C6-C14 aryl group, may be monocyclic, the structure which monocyclic ring connected, and condensed ring may be sufficient. As a specific example of the said aryl group, a phenyl group, a naphthyl group, etc. are mentioned, for example.

Some or all of the hydrogen atoms of R ¹ and R ² may be substituted with a substituent. As such a substituent, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (as this cycloalkyl group, description of the said cycloalkyl group can apply suitably), an aryl group (this As an aryl group, the description of the said aryl group is applicable suitably, and an alkoxy group (preferably a C1-C20 alkoxy group, For example, a methoxy group, an ethoxy group, a propoxy group, n-butoxy group) , Pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, etc.), acyl group (preferably acyl group having 2 to 20 carbon atoms, for example, acetyl group, propionyl group, butyryl group) , i-butyryl group and the like), acyloxy group (preferably acyloxy group having 2 to 10 carbon atoms, for example, acetoxy group, ethylyloxy group, butyryloxy group, t-butyryloxy group) , t-amyloxy group and the like), alkoxycarbo Group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc.), haloalkyl group (hydrogen of the alkyl group or cycloalkyl group) A part or all of the atoms is a group substituted with a halogen atom, for example, a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a fluorocyclopropyl group, a fluorocyclobutyl group, etc.) Etc. can be mentioned. About the cyclic structure in an aryl group, a cycloalkyl group, etc., the said alkyl group is mentioned as a new substituent.

Description of R <^1> and R <^2> can apply the alkyl group, cycloalkyl group, and aryl group which are represented by R <^3> in said Formula (1). As an aralkyl group represented by R <^3> in said Formula (1), Preferably, a C7-C20 aralkyl group is mentioned, For example, a benzyl group, a phenethyl group, a naphthyl methyl group, a naphthyl ethyl group, etc. are mentioned. Can be. As said group represented by -M ( ^R3m ) ₃ of R <^3> in said Formula (1), 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.

R ¹ and R ³ may be linked to each other to form a cyclic ether. As such a cyclic ether, 2-oxetanyl group, 2-tetrahydrofuranyl group, 2-tetrahydropyranyl group, 2-dioxanyl group, etc. are mentioned, for example. Some or all of the hydrogen atoms of this cyclic ether may be substituted by the said substituent.

The structural unit 1 may have acetal structure or a ketal structure by possessing a functional group which has an acetal structure or a ketal structure by bonding to other carbon atoms.

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 Period, (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-tetrahydropyranyloxy group And 1-trimethylsilanyloxyethoxy group, 1-trimethylgeryloxyethoxy group and the like.

Among these, 1-ethoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydropyranyloxy group, 1-n-propoxyoxy group, and 2-tetrahydropyranyloxy group are mentioned as a preferable thing. have.

As a functional group which has a ketal structure by couple | bonding with the said other carbon atom, for example, 1-methyl-1- methoxyethoxy group, 1-methyl-1- ethoxyethoxy group, 1-methyl-1- n-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-cyclohexyloxy Ethoxy 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 , 1-cyclohexyl-1-phenoxy ethoxy group, 1-cyclohexyl-1-benzyloxyethoxy group, 1-phenyl-1-methoxyethoxy group, 1-phenyl-1-ethoxyethoxy group, 1-phenyl-1-n-propoxyethoxy group, 1-phenyl-1-i-propoxyethoxy group, 1-phenyl-1-cyclohexyloxyethoxy group, 1-phenyl-1-phenyloxye Oxy group, 1-phenyl-1-benzyloxyethoxy group, 1-benzyl-1-methoxyethoxy group, 1-benzyl-1-ethoxyethoxy group, 1-benzyl-1-n-propoxy Oxy group, 1-benzyl-1-i-propoxyoxy group, 1-benzyl-1-cyclohexyloxyethoxy group, 1-benzyl-1-phenyloxyethoxy group, 1-benzyl-1-benzyloxy Ethoxy group, 2- (2-methyl-tetrahydrofuranyl) oxy group, 2- (2-methyl-tetrahydropyranyl) oxy group, 1-methoxy-cyclopentyloxy group, 1-methoxy-cyclo Hexyloxy group etc. are mentioned.

Among these, 1-methyl-1-methoxyethoxy group and 1-methyl-1-cyclohexyloxyethoxy group are mentioned as a preferable thing.

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

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

As a monomer which has the radical polymerizability which gives the structural unit (1) represented by said Formula (1-1)-(1-3) (henceforth simply a "acetal structure containing monomer"), for example, 1-alkoxy Alkyl (meth) acrylate, 1- (cycloalkyloxy) alkyl (meth) acrylate, 1- (haloalkoxy) alkyl (meth) acrylate, 1- (aralkyloxy) alkyl (meth) acrylate, tetrahydro (Meth) acrylate type acetal structure containing monomers, such as pyranyl (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, tetrahydropyranyloxystyrene are preferable, and 1-alkoxyalkyl (meth) acrylate is more preferable. desirable.

As a specific example of the acetal structure containing monomer which gives the said structural unit (1), 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 -(2-cyclohexylethoxy) ethyl methacrylate, 1-benzyloxyethyl methacrylate, 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) Ethyl acrylate, 1-benzyloxyethyl acrylate, 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 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 m-1-benzyloxyethoxy styrene. The said structural unit 1 can be used 1 type or in combination or 2 or more types.

Among the acetal structure-containing monomers which impart the structural unit (1), 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate and 1-benzyloxyethyl Methacrylate is preferred.

As an acetal structure containing monomer which gives a structural unit (1), a commercial thing may be used and what was synthesize | combined by a well-known method can also be used. For example, the acetal structure-containing monomer which gives the structural unit (1) 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 below. .

(Wherein R ′, R ¹ and R ³ respectively correspond to R ′, R ¹ and R ³ in Formula (1-1), and R ²¹ and R ²² are each —CH (R ²¹ ) (R ²² ), corresponding to R ² in the formula (1-1)).

The content of the structural unit (1) in the polymer (A) is not particularly limited as long as the polymer (A) exhibits alkali solubility by acid and the desired heat resistance of the cured film is exhibited. When both (1) and an epoxy group containing structural unit 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 the [A] polymer, and 10 mass% or more and 60 mass% The following is more preferable and 20 mass% or more and 50 mass% or less are especially preferable.

On the other hand, in the case of having a structural unit (1) in a single polymer molecule and an epoxy group-containing structural unit in another single polymer molecule, the structural unit (1) in a single polymer molecule having a structural unit (1) As content, 40 mass% or more and 99 mass% or less are preferable at a monomer input ratio with respect to the whole structural unit 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 % Or less is especially preferable.

<Epoxy group-containing structural unit>

The polymer (A) has an epoxy group-containing structural unit together with the structural unit (1). An epoxy group containing structural unit is a structural unit derived from the epoxy group containing monomer which has radical polymerizability. As this epoxy group, an oxiranyl group (1, 2- epoxy structure) and an oxetanyl group (1, 3- epoxy structure) are mentioned. When the polymer (A) has a structural unit containing an oxiranyl group, an oxetanyl group, or the like in the molecule, the hardness of the cured film obtained from the positive radiation-sensitive composition can be improved to further improve heat resistance.

As a specific example of the epoxy group containing monomer which provides the said epoxy group containing structural unit, For example, glycidyl acrylate, glycidyl methacrylate, 3, 4- epoxy butyl acrylate, 3, 4- epoxy butyl methacrylate, 3-methyl-3,4-epoxybutyl acrylate, 3-ethyl-3,4-epoxybutyl methacrylate, -5,6-epoxyhexyl acrylate, -5,6-epoxyhexyl methacrylate, methacrylic acid Acid-5-methyl-5,6-epoxyhexyl, methacrylic acid-5-ethyl-5,6-epoxyhexyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl,

3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylethyl methacrylate, 3,4-epoxycyclohexylpropyl methacrylate, 3,4 -Epoxycyclohexylbutyl methacrylate, 3,4-epoxycyclohexylhexyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylethyl Oxiranyl-group containing (meth) acrylic-type compounds, such as an acrylate, 3, 4- epoxy cyclohexyl propyl acrylate, 3, 4- epoxy cyclohexyl butyl acrylate, and 3, 4- epoxy cyclohexyl hexyl 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- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyl Oxymethyl) -3-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -3-methyloxetane, 3- (2-acryloyl Oxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -3-phenyloxetane,

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- ( Methacryloyloxymethyl) -3-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -3-methyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyl oxetane, 3- (2-methacryloyloxyethyl) -3-phenyloxetane,

2- (acryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) -2-methyloxetane, 2- (acryloyloxymethyl) -2-ethyloxetane, 2- (acryloyl Oxymethyl) -2-phenyloxetane, 2- (2-acryloyloxyethyl) oxetane, 2- (2-acryloyloxyethyl) -2-methyloxetane, 2- (2-acryloyl Oxyethyl) -2-ethyloxetane, 2- (2-acryloyloxyethyl) -2-phenyloxetane,

2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -2-methyloxetane, 2- (methacryloyloxymethyl) -2-ethyloxetane, 2- ( Methacryloyloxymethyl) -2-phenyloxetane, 2- (2-methacryloyloxyethyl) oxetane, 2- (2-methacryloyloxyethyl) -2-methyloxetane, 2- Oxetanyl group-containing (meth) acrylic compounds such as (2-methacryloyloxyethyl) -2-ethyl oxetane and 2- (2-methacryloyloxyethyl) -2-phenyl oxetane; have. The said epoxy group containing structural unit can be used individually or in combination of 2 or more types.

Among the said epoxy group containing monomers, methacrylic acid glycidyl, methacrylic acid 2-methylglycidyl, methacrylic acid-3,4-epoxycyclohexyl, methacrylic acid-3,4-epoxycyclohexylmethyl, 3 -(Methacryloyloxymethyl) -3-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane copolymerize with other radically polymerizable monomers, and positive radiation-sensitive composition It is preferable in terms of developability.

The content of the epoxy group-containing structural unit in the polymer (A) is not particularly limited as long as the desired heat resistance of the interlayer insulating film is exhibited, and when one polymer molecule includes the structural unit (1) and the epoxy group-containing structural unit, 10 mass% or more and 60 mass% or less are preferable with a monomer input ratio with respect to the all the structural units contained in the polymer (A), 15 mass% or more and 55 mass% or less are more preferable, 20 mass% or more and 50 mass% or less Is particularly preferred.

On the other hand, when one polymer molecule has a structural unit (1) and the other polymer molecule has an epoxy group-containing structural unit, the epoxy group-containing structural unit with respect to the entire structural unit contained in the other polymer molecule having an epoxy group-containing structural unit As content, 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, and 35 mass% or more and 65 mass% or less are especially preferable.

<Other structural units>

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

As a radical polymer monomer which has the said carboxyl group or its derivative (s), acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydro Monocarboxylic acids such as phthalic 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.

As an example of the radically polymerizable monomer which has the said hydroxyl group,

Acrylic acid hydroxyalkyl esters such as acrylic acid-2-hydroxyethyl ester, acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, and acrylic acid-4-hydroxymethylcyclohexylmethyl ester;

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 these radically polymerizable monomers having a hydroxyl group, acrylic acid-2-hydroxyethyl ester, acrylic acid-3-hydroxypropyl ester and acrylic acid- from the viewpoint of copolymerization reactivity with other radical polymerizable monomers and the heat resistance of the resulting interlayer insulating film. 4-hydroxybutyl ester, methacrylic acid-2-hydroxyethyl ester, methacrylic acid-4-hydroxybutyl ester, acrylic acid-4-hydroxymethyl-cyclohexylmethyl ester, methacrylic acid-4-hydroxy Methyl-cyclohexyl methyl ester is preferred.

As an example of another radically polymerizable monomer,

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 radically polymerizable 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, benzyl methacrylate, and the like It is preferable at the point of copolymerization reactivity with the radically polymerizable monomer which has, and developability of the said positive radiation sensitive composition.

The polystyrene reduced mass average molecular weight (hereinafter referred to as "Mw") by GPC (gel permeation chromatography) of the polymer is preferably 2.0x10 ^{3 to} 1.0x10 ⁵ , and more preferably 5.0x10. ^{3 to} 5.0 × 10 ⁴ . By making Mw of a polymer (A) into the said range, the radiation sensitivity and alkali developability of the said positive radiation sensitive composition can be improved.

The polystyrene reduced number average molecular weight (hereinafter referred to as "Mn") by GPC (gel permeation chromatography) of the polymer [A] is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ , more preferably 5.0 × 10 ^{3 to} 5.0 × 10 ⁴ . By making Mn of a copolymer into the said range, hardening reactivity at the time of hardening of the coating film of the said positive radiation sensitive composition can be improved.

In addition, the molecular weight distribution "Mw / Mn" of the polymer [A] is preferably 3.0 or less, and more preferably 2.6 or less. The developability of the interlayer insulation film 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.

<Method for Producing [A] Polymer>

The polymer (A) can be produced by radical copolymerization of an acetal structure-containing monomer, an epoxy group-containing monomer, or a monomer giving other structural units. When manufacturing [A] polymer containing both a structural unit (1) and an epoxy group containing structural unit in the same polymer molecule, it is good to copolymerize using the mixture containing at least an acetal structure containing monomer and an epoxy group containing monomer. On the other hand, when manufacturing [A] polymer which has a structural unit (1) in one polymer molecule, and has an epoxy group containing structural unit in a polymer molecule different from it, the polymerizable solution containing at least an acetal structure containing monomer Radical polymerization to obtain a polymer molecule having the structural unit (1), and separately polymerizing a polymerizable solution containing at least an epoxy group-containing monomer to obtain a polymer molecule having an epoxy group-containing structural unit, and finally mixing both [ A] What is necessary is just to set it as a polymer.

Examples of the solvent used in the polymerization reaction for producing the polymer [A] include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, and propylene glycol mono Alkyl ether acetate, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, other esters, etc. are mentioned.

As these solvents,

As alcohols, For example, methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, etc .;

As ethers, For example, tetrahydrofuran etc .;

As glycol ether, For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc .;

As ethylene glycol alkyl ether acetate, For example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc .;

As diethylene glycol alkyl ether, For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As propylene glycol monoalkyl ether, For example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc .;

As propylene glycol monoalkyl ether acetate, For example, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, a propylene glycol monopropyl ether acetate, a propylene glycol monobutyl ether acetate, etc .;

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;

As aromatic hydrocarbons, For example, toluene, xylene, etc .;

As ketones, For example, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl- 2-pentanone, etc .;

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, Methyl hydroxyacetic acid, ethyl hydroxyacetic acid, hydroxyacetic acid butyl, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate methyl, 3-hydroxypropionate ethyl, 3-hydroxypropionic acid propyl, 3- Butyl hydroxypropionate, 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 Propyl acid, butyl propoxyacetic acid, methyl butoxyacetic acid, ethyl butoxyacetic acid, butoxyacetic acid propyl, 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 A field, 3-propoxy propionate, butyl propionate, methyl 3-butoxy, 3-butoxy-ethyl, 3-butoxy propyl propionate, butyl propionate, 3-butoxy, etc. of esters there may be mentioned, respectively.

Among these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and butyl acetate are preferable, and in particular, diethylene glycol dimethyl ether and diethylene glycol ethylmethyl Ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and butyl acetate butyl acetate are preferable.

As a polymerization initiator used for the polymerization reaction for manufacturing [A] polymer, what is generally known as a radical polymerization initiator can be used. As a radical polymerization initiator, for example,

2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4-dimethyl Azo compounds such as valeronitrile) and 2,2'-azobis (methyl 2-methylpropionate);

Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1,1'-bis- (t-butylperoxy) cyclohexane; And hydrogen peroxide.

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 for producing the polymer (A), a molecular weight modifier can be used to adjust the molecular weight. As a specific example of a molecular weight modifier,

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;

Xanthogens, such as dimethyl xanthogen sulfide and diisopropyl xanthogen gen sulfide;

Terpinolene, (alpha) -methylstyrene dimer, etc. are mentioned.

<[B] mine generator>

The photoacid generator [B] is a compound that generates an acid by irradiation of radiation. Here, as the radiation, for example, visible light, ultraviolet light, far ultraviolet light or the like can be used. A positive radiation sensitive characteristic can be exhibited because the said composition contains the [B] photoacid generator and the [A] polymer which has an acid dissociable group. [B] The photoacid generator is not particularly limited as long as it is a compound that generates an acid (for example, carboxylic acid, sulfonic acid, etc.) by irradiation of radiation. [B] As the containing form in the said composition of photo-acid generator, even if it is a form of the photo-acid generator (Hereinafter, it may be called "[B] photo-acid generator.") Which is a compound mentioned later. It may be in the form of a photoacid generator incorporated as part of the polymer or in both of these forms.

Examples of the photoacid generator [B] include an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid esterified compound, a carboxylic acid ester compound, and the like.

(Oxime sulfonate compound)

As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by said formula (3) is preferable.

As a linear or branched alkyl group of R ^B1 , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. In addition, some or all of the hydrogen atoms of the linear or branched alkyl group or the cycloalkyl group of R ^B1 may be a C 1-10 alkoxy group or an alicyclic group (7,7-dimethyl-2-oxonorbornyl group). It may be substituted with the alicyclic group, Preferably it is a bicycloalkyl group etc.). As an aryl group of R <^B1> , a C6-C11 aryl group is preferable and a phenyl group or a naphthyl group is more preferable. The aryl group of R ^B1 may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group or a halogen atom.

It is more preferable that the said compound containing the oxime sulfonate group represented by said formula (3) is an oxime sulfonate compound represented by following formula (3-1).

In the formula (3-1), R ^B1 is a description of the same meaning of R ^B1 in the formula (3). Z is an alkyl group, an alkoxy group, or a halogen atom. M is an integer of 0-3. When m is 2 or 3, some Z may be same or different. The alkyl group as Z is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

As an alkoxy group as Z, a C1-C4 linear or branched alkoxy group is preferable. The halogen atom as Z is preferably a chlorine atom or a fluorine atom. M is preferably 0 or 1. In particular, in said Formula (3-1), the compound whose m is 1, Z is a methyl group, and the substitution position of Z is ortho is preferable.

As a specific example of an oxime sulfonate compound, For example, the compound (3-i), the compound (3-ii), the compound (3-iii) which are respectively represented by following formula (3-i)-(3-VII), The compound (3-i '), a compound (3-'), etc. are mentioned.

These acid generators can be used individually or in combination of 2 or more types, and can also be used in combination with the other photo-acid generator as a component [B]. The compound (3-i) [(5-propylsulfonyloxyimino-5H-thiophene-2-iridene)-(2-methylphenyl) acetonitrile], compound (3-ii) [(5-octylsulfonyl Oxyimino-5H-thiophene-2-iridene)-(2-methylphenyl) acetonitrile], compound (3-iii) [(camphorsulfonyloxyimino-5H-thiophene-2-iridene)-(2 -Methylphenyl) acetonitrile], compound (3-i ') [(5-p-toluenesulfonyloxyimino-5H-thiophene-2-iridene)-(2-methylphenyl) acetonitrile] and compound (3-ｖ) ) [(5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile] can be obtained as a commercial item.

(Onium salt)

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

As the diphenyl iodonium salt, for example, diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphonate, diphenyl iodonium hexafluoroarsenate, diphenyl iodonium Trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium butyltris (2,6-difluorophenyl) borate, 4- 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-toluene Sulfonate, bis (4-t-butylphenyl) iodonium camphor sulfonic acid, and the like.

Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, and triphenylsulfonium. -p-toluenesulfonate, a triphenylsulfonium butyl tris (2, 6- difluorophenyl) borate, etc. are mentioned.

As a sulfonium salt, an alkyl sulfonium salt, 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- Methoxybenzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, etc. Can be mentioned.

As the tetrahydrothiophenium salt, for example, 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalene-1 -Yl) tetrahydrothiopheniumtrifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiopheniumnonafluoro-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-tetrafluoro Roethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl ) -1,1,2,2-tetrafluoroethanesulfonate, 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 -(Camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoro Methylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenyl Maleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2. 1] hepto-5-ene-2 , 3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (trifluoromethanesulfonyloxy) bi Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (nonafluorobutanesulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyl Mead, N- (camphorsulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide, 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.

(Halogen-containing compound)

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

(Diazomethane compound)

As a diazomethane compound, bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexyl sulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolyl sulfide, for example) Ponyyl) diazomethane, bis (2, 4- xylylsulfonyl) diazomethane, bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyl diazomethane, 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, the 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.

(Carboxylic acid ester compound)

As a carboxylic acid ester compound, carboxylic acid o-nitrobenzyl ester is mentioned, for example.

Among these [B] photoacid generators, an oxime sulfonate compound is preferable from a viewpoint of solubility to a radiation sensitivity, a solvent, etc., and the compound containing the oxime sulfonate group represented by said Formula (3) is more preferable, The oxime sulfonate compound represented by said formula (3-1) is more preferable, and it is especially available as a commercial item, [(5-propylsulfonyloxyimino-5H-thiophene 2-iridene)-(2- Methylphenyl) acetonitrile], [(5-octylsulfonyloxyimino-5H-thiophene-2-iridene)-(2-methylphenyl) acetonitrile], [(5-p-toluenesulfonyloxyimino-5H- Thiophene-2-iridene)-(2-methylphenyl) acetonitrile], [(camphorsulfonyloxyimino-5H-thiophene-2-iridene)-(2-methylphenyl) acetonitrile], [(5- Octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile] is particularly preferred.

Moreover, onium salt is also preferable, tetrahydrothiophenium salt and benzylsulfonium salt are more preferable, 4,7-di-n-butoxy-1- naphthyl tetrahydrothiophenium trifluoromethanesulfonate and benzyl- 4-hydroxyphenylmethylsulfonium hexafluorophosphate is particularly preferred.

[B] The photoacid generator may be used individually by 1 type, and may mix and use 2 or more types. As content as a [B] photo-acid generator in the said composition, Preferably it is 0.1 mass part-10 mass parts, More preferably, it is 1 mass part-5 mass parts with respect to 100 mass parts of [A] polymers. When the content of the photoacid generator (B) is in the above range, the interlayer insulating film having a high voltage holding ratio can be formed while optimizing the radiation sensitivity of the composition, while maintaining transparency.

<[C] long-chain alkyl group containing compound>

[C] The long-chain alkyl group-containing compound is a compound represented by the above formula (2), and specifically, X (a C6-C20 divalent linear aliphatic hydrocarbon group) having hydrophobicity in one molecule, and both terminals or one terminal Has a functional group.

Since the [C] long-chain alkyl group-containing compound reacts with a part of [A] component by heating or using an alkali component in a developing solution as a catalyst, the hardness and density of a cured film can be improved. By improving the hardness and density of this cured film, various resistances, for example, resistance to an acid, an aqueous alkali solution, an organic solvent, an etching gas, etc., can be improved, and a remarkable effect can be exerted on the suppression of pattern defects.

Moreover, since the [C] component which reacted with a part of [A] component has a long-chain alkyl group which shows hydrophobicity, hydrophobicity with respect to the alkaline developing solution of a hardened part improves. On the other hand, the unreacted [C] component can exhibit the hydrophilicity of an unhardened part because a functional group is hydrophilic. Therefore, according to the said composition, even when the cured film formation conditions, such as prebaking at low temperature and an increase of image development time, change, the [C] long-chain alkyl-group containing compound exhibits the buffer effect, and it is excellent developability and pattern formation property. Can be exerted stably.

Moreover, also by containing this [C] component, the influence on the light transmittance and voltage retention of the cured film obtained is small, and the cured film obtained from the said composition can exhibit high light transmittance and voltage retention.

In addition, when the carbon number of X is 5 or less, since the hydrophilicity of both ends or one end is strongly expressed, there exists a tendency to promote the developing ability excessively, On the contrary, when X carbon number is 21 or more, developability falls This tends to cause the development residue to occur.

Although X is a C6-C20 divalent linear aliphatic hydrocarbon group, C6-C20 divalent alkylene group which does not contain an unsaturated bond is preferable. In addition, some or all of the hydrogen atoms may be substituted with this linear aliphatic hydrocarbon group.

As a specific example of such a [C] component, compounds, such as a fatty acid, alcohol, ester, sulfonic acid, an epoxy compound shown below, are mentioned, for example.

Examples of fatty acids having a divalent linear aliphatic hydrocarbon group having 6 to 20 carbon atoms include caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, and pentade. Silicic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid , Tuberculostearic acid, arachidic acid, arachidonic acid, arachidonic acid, decane diacid, hexadecane diacid, heptadecane diacid, nonadecan diacid, octadecane diacid , Pentadecane diacid, tridecane diacid, tetradecane diacid, stearic acid glycidyl, palmitic acid glycidyl, cis-9-hexadecenoic acid, elaidic acid, and the like.

Examples of the divalent linear aliphatic hydrocarbon group having 6 to 20 carbon atoms include n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonyl alcohol, n-decyl alcohol, n-undecyl alcohol, n-dodecyl alcohol , n-heptadecanol, n-octadecanol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, trans-9-octadecenol, oleyl alcohol, trans-2-dodecenol and the like.

Examples of the esters having a C6-20 divalent linear aliphatic hydrocarbon group include methyl caprylate, ethyl caprylate, methyl pelargonate, ethyl pellagonate, methyl caprate, ethyl caprate and lauric acid. Methyl, ethyl laurate, methyl myristic acid, methyl pentadecyl acid, methyl palmitate, methyl palmitoleic acid, methyl margarate, methyl stearate, methyl oleate, methyl vaxate, methyl linoleate, methyl linoleate, ele Methyl austearate, methyl tuberculostearate, methyl arachidate, methyl arachidonic acid, etc. are mentioned.

As sulfonic acid which has a C6-C20 divalent linear aliphatic hydrocarbon group, 1-dodecanesulfonic acid, 1-undecanesulfonic acid, dodecylbenzenesulfonic acid, 1-nonanesulfonic acid, etc. are mentioned.

As an epoxy compound (a compound in which R <^4> and / or R <^5> is represented by any of said Formula (i)-(iii)) which has a C6-C20 divalent linear aliphatic hydrocarbon group,

1,2-epoxytetedecane, 1,2-epoxyhexadecane, 1,2-epoxydecane, 1,2-epoxyheptadecane, 1,2-epoxynonadecane, 1,2-epoxyoctadecane, 1,2 Compounds in which R ⁴ and / or R ⁵ , such as epoxypentadecane, glycidyl stearate and glycidyl palmitate, are represented by the above formula (i),

1- (3,4-epoxycyclohexyl) -decane, 1- (3,4-epoxycyclohexyl) -dodecane, 1- (3,4-epoxycyclohexyl) -tetradecane, 1- (3,4 Compounds in which R ⁴ and / or R ⁵ , such as -epoxycyclohexyl) -hexadecane, are represented by the formula (ii),

Compounds in which R ⁴ and / or R ⁵ , such as 3-octyl oxetane, 3-ethyl-3-octyl oxetane, 3-nonyl oxetane, and 3-ethyl-3-nonyl oxetane, are represented by the above formula (iii)

Can be mentioned.

Also, [C] component, the epoxy compound is a case, and [A] a polymer by heating or the like, (R ⁴ and / or R ⁵ is, the formula (i) ~ one as a compound that appears in (iii)) The [ Since the component C] can be particularly firmly bonded, the synergistic effect of density and hydrophobicity of the cured film is remarkable. Therefore, when an epoxy compound is used as [C] component, the change responsiveness of the cured film formation conditions of the said composition becomes further high, and can develop more excellent developability and pattern formation property.

Moreover, as a [C] long-chain alkyl group containing compound, the compound which has a urethane group obtained by reaction of the compound which has an isocyanate group, and the compound which has a hydroxyl group, the compound which has an amide group obtained by reaction of the compound which has an amino group, and the compound which has a carboxyl group, carboxyl The compound which has an ester group obtained by reaction of the compound which has a group, and the compound which has a hydroxyl group, etc. are mentioned, As such a compound, the compound etc. which are represented by following formula (2-1)-(2-4) are mentioned specifically ,. have.

Among the above-mentioned [C] long-chain alkyl group-containing compounds, especially from the viewpoint of developability and pattern formation, fatty acids such as palmitic acid, stearic acid and tetradecane diacid, alcohols such as 1-dodecanol and 1,12-dodecanediol, Epoxy compounds such as 1,2-epoxytedecane, 1,2-epoxyhexadecane, stearic acid glycidyl, 1,3-epoxy-2-ethyl-2-dodecane, sulfonic acids of 1-dodecanesulfonic acid, and the like desirable.

[C] The long-chain alkyl group-containing compound can be used alone or in combination of two or more thereof. As the usage-amount of the [C] long-chain alkyl group containing compound in the said radiation sensitive composition, it is 0.01-20 mass parts with respect to 100 mass parts of [A] polymers, More preferably, it is 0.05-15 mass parts. By making the usage-amount of a long-chain alkyl-group containing compound (C) into the said range, even if cured film formation conditions change, developability and pattern formation property can be exhibited effectively.

<Other optional components>

In addition to the above-mentioned [A]-[C] components, the positive radiation sensitive composition of this invention is a [D] surfactant, an [E] adhesion | attachment adjuvant, [A] as needed in the range which does not impair the desired effect. F] It may contain other arbitrary components, such as a basic compound and a quinonediazide compound.

<[D] surfactant>

Surfactant can be used in order to improve the film formability of the said composition further. As such surfactant, a fluorochemical surfactant, silicone type surfactant, and other surfactant are mentioned, for example. When the said composition contains surfactant [D], the surface smoothness of a coating film can be improved and as a result, the film thickness uniformity of the interlayer insulation film formed can be improved further.

As a fluorine type surfactant, the compound which has a fluoroalkyl group and / or a fluoroalkylene group in at least any part of a terminal, a main chain, and a side chain is preferable. As the fluorine-based surfactant, 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 glycol di (1,1 , 2,2-tetrafluoro-n-butyl) ether, perfluoro-n-dodecanesulfonate, 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 ( Fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, purple To kill roal polyoxyethylene ethanol, alkyl alkoxylate, a carbonic acid-fluoro-perfluoroalkyl, and the like esters.

As a commercial item of a fluorine-type surfactant, BM-1000, BM-1100 (above, BM CHEMIE company), Megaface F142D, Megapack F172, Megapack F173, Megapack F183, Megapack F178, Mega Pack F191, Mega Pack F471, Mega Pack F476 (above, manufactured by Dainippon Inky Kagaku Kogyo Co., Ltd.), Fluorad FC-170C, Fluorad FC-171, Fluorad FC-430, Fluorad FC- 431 (above, Sumitomo 3M, Suplon S-112, Suplon S-113, Suplon S-131, Suplon S-141, Suplon S-145, Suplon S-382, Suplon SC-101, Suplon SC-102, Suplon SC-103, Suplon SC-104, Suplon SC-105, Suplon SC-106 (above, Asahi Glass Co., Ltd.), Ftop ) EF301, F-Top EF303, F-Top EF352 (above, Shin Akita Kasei Co., Ltd.), FTgent, FT-100, Pgentgent FT-110, Pgentgent FT-140A, Pgentgent FT-150, Pngent FT-250, Pleasant FT-251, Print Gentry may include FT-300, such as printers Gentry FT-310, FT-400S Gentry printers, printers Gentry FTX-218, printers Gentry FT-251 (above, whether or manufactured by Neos).

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

These [D] surfactant may be used individually by 1 type, and may mix and use 2 or more types. As content of the [D] surfactant in the said composition, Preferably it is 0.01 mass part or more and 2 mass parts or less with respect to 100 mass parts of [A] polymers, More preferably, they are 0.05 mass part or more and 1 mass part or less. . By making content of a [D] surfactant into the said range, the surface smoothness of a coating film can be improved more.

<[E] adhesion aid>

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] ] Adhesive adjuvant which is a component 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.

Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-glycol. Cidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimeth Oxysilane, etc. are mentioned. Among these, (gamma)-glycidoxy propyl alkyl dialkoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethyltrimethoxysilane, and (gamma)-methacryloxypropyl trimethoxysilane are preferable.

In a positive radiation sensitive composition, such an [E] adhesion adjuvant becomes like this. Preferably it is 0.5 mass part or more and 20 mass parts or less with respect to 100 mass parts of [A] polymers, More preferably, it is 1 mass part or more and 10 mass parts It is used in the following amounts. By setting the amount of the adhesion assistant (E) in the above range, the adhesion between the interlayer insulating film to be formed and the substrate is improved.

<[F] basic compound>

As a basic compound, it can select arbitrarily and can use from what is used by a chemical amplification register. As a basic compound, aliphatic amine, aromatic amine, heterocyclic amine, quaternary ammonium hydroxide, carboxylic acid quaternary ammonium salt, etc. are mentioned, for example. By containing the basic compound which is a [F] component in the said positive radiation sensitive composition, the diffusion length of the acid generate | occur | produced from the photo-acid generator by exposure can be controlled suitably, and pattern developability can be made favorable.

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

As aromatic amine, aniline, benzylamine, N, N- dimethylaniline, diphenylamine, etc. are mentioned, for example.

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- Oxyquinoline, pyrazine, pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4,3,0] -5- Nonene, 1,8-diazabicyclo [5,3,0] -7-undecene, and the like.

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

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

It is preferable to set it as 0.001-1 mass part with respect to 100 mass parts of [A] polymers, and, as for content of the [F] basic compound in the said positive radiation sensitive composition, it is more preferable to set it as 0.005-0.2 mass part. The pattern developability becomes favorable by making content of a [F] basic compound into the said range.

<Quinonediazide compound>

A quinonediazide compound is a compound which produces | generates a carboxylic acid by irradiation of a radiation. As a quinone diazide compound, the condensate of a phenolic compound or an alcoholic compound (henceforth "mother nucleus"), and 1,2-naphthoquinone diazide sulfonic-acid halide can be used.

Examples of the mother core include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother cores.

As trihydroxy benzophenone, 2,3,4- trihydroxy benzophenone, 2,4,6- trihydroxy benzophenone etc. are mentioned, for example.

As tetrahydroxybenzophenone, for example, 2,2'4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetra Hydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, and the like. .

As pentahydroxy benzophenone, 2,3,4,2'6'- pentahydroxy benzophenone etc. are mentioned, for example.

As hexahydroxy benzophenone, 2,4,6,3'4'5'-hexahydroxy benzophenone, 3,4,5,3'4'5'-hexahydroxy benzophenone etc. are mentioned, for example. Can be.

As the (polyhydroxyphenyl) alkanes, for example, 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'-trihydroxyflavane, etc. are mentioned.

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, etc. are 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. Examples of 1,2-naphthoquinone diazide sulfonic acid chloride include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphthoquinone diazide-5-sulfonic acid chloride. 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 between the phenolic compound or the alcoholic compound (parent nucleus) and 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 in which the ester bond of the above-described parent nucleus is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1, 2-naphthoquinone diazide-4-sulfonic acid amide etc. are also used suitably.

<Positive radiation sensitive composition>

The positive radiation sensitive composition of this invention is prepared by mixing the said [A] polymer, the [B] photo-acid generator, the [C] long-chain alkyl group containing compound, and arbitrary components as needed. The positive radiation-sensitive composition may be prepared and preferably used in a dissolved or dispersed state in a suitable solvent. For example, a positive radiation sensitive composition can be prepared by mixing [A], [B], [C] component, and arbitrary components in a predetermined ratio in a solvent.

<Solvent>

As a solvent which can be used for preparation of the said positive radiation sensitive composition, what melt | dissolves or disperse | distributes each component uniformly and does not react with each component is used suitably. Examples of such a solvent include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl ether propios. Nates, aromatic hydrocarbons, ketones, esters, etc. are mentioned.

As these solvents,

As alcohol, For example, benzyl alcohol, diacetone alcohol etc .;

Examples of the ethers include tetrahydrofuran, dialkyl ethers such as diisopropyl ether, di-n-butyl ether, di-n-pentyl ether, diisopentyl ether and di-n-hexyl ether;

As diethylene glycol alkyl ether, For example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;

As ethylene glycol alkyl ether acetates, For example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc .;

As propylene glycol monoalkyl ethers, For example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc .;

As propylene glycol monoalkyl ether acetates, For example, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, a propylene glycol monopropyl ether acetate, a propylene glycol monobutyl ether acetate, etc .;

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

As aromatic hydrocarbons, For example, toluene, xylene, etc .;

As ketones, For example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl- 2-pentanone, etc .;

As esters, for example, methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2- Ethyl methyl propionate, methyl hydroxyacetic acid, ethyl hydroxyacetic acid, hydroxyacetic acid butyl, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionic acid methyl, 3-hydroxypropionic acid, 3-hydroxypropionic acid Propyl, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoic acid, methyl methoxyacetic acid, ethyl methoxyacetic acid, methoxyacetic acid propyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl Propyl ethoxyacetic acid, butyl ethoxyacetic acid, methyl propoxyacetate, ethyl propoxyacetate, Lopoxyacetic acid propyl, butyl propoxyacetic acid, methyl butoxyacetic acid, ethyl butoxyacetate, butoxyacetic acid propyl, butyl butoxyacetic acid, 2-methoxypropionate methyl, 2-methoxypropionic acid propyl, 2-methoxypropionic acid propyl And butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, and the like.

Among these solvents, those having excellent solubility or dispersibility, being non-reactive with each component, and easy to form a coating film, ethers such as dialkyl ethers, diethylene glycol alkyl ethers, and ethylene glycol alkyl ether acetates Propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters are preferable, and in particular, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, and ethyl cello Solvent acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, propyl acetate, i-propyl acetate, butyl acetate, 2-hydroxypropionate ethyl , 2-hydroxy-2-methylpropionic acid , The 2-hydroxy-2-methylpropionic acid ethyl, methyl lactate, ethyl lactate, propyl lactate, butyl, 2-methoxy-propionic acid methyl, 2-methoxy-propionic acid ethyl are preferred. These solvents can be used alone or in combination.

Among these solvents, ethers such as dialkyl ethers such as diisopropyl ether, di-n-butyl ether, di-n-pentyl ether, diisopentyl ether, and di-n-hexyl ether are preferable. Isopentyl ether is most preferred. By using such a solvent, when apply | coating a radiation sensitive composition to a large size glass substrate by a slit coating method, it becomes possible to shorten a drying process time and to improve applicability | paintability further (suppressing application | coating nonuniformity).

In addition to the above-mentioned preferred solvents, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, capro, if necessary Acids, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylcellosolve High boiling point solvents, such as acetate and carbitol acetate, can also be used together.

When preparing a positive radiation sensitive composition as a solution or dispersion state, the ratio of components other than the solvent which occupies in a liquid (that is, the total amount of [A], [B] and [C] components, and other arbitrary components), Although it can set arbitrarily according to a purpose of use, a desired film thickness, etc., Preferably it is 5-50 mass%, More preferably, it is 10-40 mass%, More preferably, it is 15-35 mass%.

<Formation of Cured Films, such as an Interlayer Insulating Film>

Next, the method of forming cured films, such as an interlayer insulation film, on a board | substrate using the said positive radiation sensitive composition is demonstrated.

The method,

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

(2) irradiating at least a portion of the coating film formed in step (1) with radiation;

(3) developing the coating film irradiated with radiation in step (2), and

(4) Step of heating the coating film developed in step (3)

Respectively.

<(1) Process of Forming Coating Film of Positive Type Radiation-Sensitive Composition on Substrate>

In the process of said (1), after apply | coating this positive radiation sensitive composition or this solution or dispersion liquid on a board | substrate, Preferably, a solvent is removed by heating (prebaking) a coating surface, and a coating film is formed. Glass, quartz, silicon, resin, etc. are mentioned as an example of the board | substrate which can be used. Specific examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, ring-opening polymers of cyclic olefins, and hydrogenated substances thereof.

It does not specifically limit as a coating method of a composition solution or a dispersion liquid, For example, the appropriate method, such as a spray method, a roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, can be employ | adopted. . Among these coating methods, the spin coating method or the slit die coating method is preferable. Although the conditions of prebaking differ also according to the kind, compounding ratio, etc. of each component, Preferably, it can be made into about 1 to 10 minutes at 60-120 degreeC. According to the positive radiation sensitive composition of this invention, even when it is set as the comparatively low prebaking conditions at 60-80 degreeC, the outstanding pattern formation property can be exhibited.

<(2) Process of irradiating at least a part of coating film with radiation>

At the process of said (2), it exposes to at least one part of the formed coating film. In this case, when exposing to a part of coating film, it exposes normally through the photomask which has a predetermined pattern. As radiation used for exposure, the radiation used with respect to a photo-acid generator is suitable. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet rays of 365 nm is particularly preferable.

The exposure amount in the said process is the value which measured the intensity | strength in the wavelength of 365 nm of radiation with the illuminometer (OAI model356, OAI Optical Associates Inc. make), Preferably it is 500-6,000 J / m <2>, More preferably, Is 1,500-1,800 J / m 2.

<(3) image development process>

In the process of said (3), by developing the coating film after exposure, an unnecessary part (irradiation part of a radiation) is removed and a predetermined pattern is formed. As a developing solution used for a developing process, alkaline aqueous solution is preferable. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia; And quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to such an aqueous alkali solution. The concentration of alkali in the aqueous alkali solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of obtaining appropriate developability. As the developing method, for example, a suitable method such as a puddle method, a dipping method, a rocking dipping method or a shower method can be used. Although image development time changes with the composition of a positive radiation sensitive composition, Preferably it is about 10 to 180 second. Moreover, according to the said composition, even if there exist some pros and cons in this developing time, a stable pattern can be formed without being affected by this. Subsequent to such development treatment, for example, flowing water washing is performed for 30 to 90 seconds, followed by air drying with, for example, compressed air or compressed nitrogen, whereby a desired pattern can be formed.

<(4) heating process>

In the process of said (4), hardening reaction of the said [A] component is accelerated | stimulated and a hardened | cured material can be obtained by heating a patterned thin film using heating apparatuses, such as a hotplate and oven. Heating temperature in this process is 120-250 degreeC, for example. Although heating time changes with kinds of a heating apparatus, it can be set as 5 to 30 minutes, for example, when performing a heating process on a hotplate, and 30 to 90 minutes when performing a heating process in an oven. 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 or the like can be formed on the surface of the substrate.

<Cured films, such as an interlayer insulation film>

The film thickness of cured films, such as the interlayer insulation film formed in this way, becomes like this. Preferably it is 0.1-8 micrometers, More preferably, it is 0.1-6 micrometers, More preferably, it is 0.1-4 micrometers.

The interlayer insulating film formed from the positive radiation-sensitive composition of the present invention has excellent pattern formability, having high light transmittance and voltage holding ratio, as will be apparent from the following examples. Therefore, the cured film can be used for an interlayer insulating film, a spacer, a protective film, etc. of a display element, and is especially suitably used as an interlayer insulating film of a display element.

(Example)

Although an Example is shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

Below, the mass average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured by the gel permeation chromatography (GPC) by the following conditions.

Device: GPC-101 (Showa Denko KK)

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

Mobile phase: tetrahydrofuran

Column temperature: 40 ℃

Flow rate: 1.0mL / min

Sample concentration: 1.0 mass%

Sample injection volume: 100 μL

Detector: parallax refractometer

Standard material: monodisperse polystyrene

<Synthesis example of polymer [A]>

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. Subsequently, 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 nitrogen-substituting, stirring was started slowly. 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-1). The polystyrene reduced mass average molecular weight (Mw) of the polymer (A-1) was 9,000. In addition, the solid content concentration (the ratio which the mass of the polymer contained in a polymer solution occupies in the total mass of a polymer solution, hereafter same) of the polymer solution obtained here 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 tetrahydro-2H-pyran-2-yl methacrylate, 5 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate, 2-hydroxyethyl methacrylate 10 After mass part and 3 mass parts of (alpha) -methylstyrene dimers were added and nitrogen-substituted, stirring was started slowly. 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). The polystyrene reduced mass average molecular weight (Mw) of the polymer (A-2) was 9,000. In addition, solid content concentration of the polymer solution obtained here 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 methacrylic acid, 23 mass parts of benzyl methacrylate, and 10 mass parts of methacrylic acid were put, and nitrogen-substituted, stirring was started slowly. 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). The polystyrene reduced mass average molecular weight (Mw) of the polymer (a-1) was 9,000. In addition, solid content concentration of the polymer solution obtained here 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, after adding 90 mass parts of 1-benzyloxyethyl methacrylic acid, 6 mass parts of 2-hydroxyethyl methacrylic acid, and 4 mass parts of methacrylic acid, and nitrogen-substituted, stirring was started slowly. 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). The polystyrene reduced mass average molecular weight (Mw) of the polymer (a-2) was 9,000. In addition, solid content concentration of the polymer solution obtained here 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 adding 85 mass parts of tetrahydro-2H-pyran-2-yl methacrylates, 7 mass parts of 2-hydroxyethyl methacrylic acid, and 8 mass parts of methacrylic acid, and nitrogen-substituted, stirring was started slowly. 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). The polystyrene reduced mass average molecular weight (Mw) of the polymer (a-3) was 10,000. In addition, solid content concentration of the polymer solution obtained here 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 slowly. 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). The polystyrene reduced mass average molecular weight (Mw) of the polymer (aa-1) was 10,000. In addition, solid content concentration of the polymer solution obtained here 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, after adding 45 mass parts of 3, 4- epoxycyclohexyl methyl methacrylates, 45 mass parts of benzyl methacrylate, and 10 mass parts of methacrylic acid, and nitrogen-substituted, stirring was started slowly. 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). The polystyrene reduced mass average molecular weight (Mw) of the polymer (aa-2) was 10,000. In addition, solid content concentration of the polymer solution obtained here 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. Then, 35 mass parts of 1-n-butoxyethyl methacrylates, 35 mass parts of benzyl methacrylates, and 30 mass parts of glycidyl methacrylates were put, and nitrogen-substituted, and stirring was started slowly. 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). The polystyrene reduced mass average molecular weight (Mw) of the polymer (aa-3) was 10,000. In addition, solid content concentration of the polymer solution obtained here was 32.3 mass%.

[Preparation of Positive Type Radiation-Sensitive Composition]

Each component in Table 1 used by the Example and the comparative example is as follows.

(B) Component photoacid generator

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

B-2: benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate

B-3: [(5-propylsulfonyloxyimino-5H-thiophene-2-iridene)-(2-methylphenyl) acetonitrile] represented by the compound (3-i) (Chiba Specialty Chemicals Co., Ltd.) `` IRGACURE PAG 103 '' manufactured by Shikigaisha Corporation)

B-4: [(5-octylsulfonyloxyimino-5H-thiophene-2-iridene)-(2-methylphenyl) acetonitrile] represented by the compound (3-ii) (Chiba Specialty Chemicals Co., Ltd.) `` IRGACURE PAG 108 '' manufactured by Shikigaisha Corporation)

B-5: [(5-p-toluenesulfonyloxyimino-5H-thiophene-2-iridene)-(2-methylphenyl) acetonitrile] represented by the compound (3-i ') (chiba specialty chemical) `` IRGACURE PAG 121 '' of the company Corporation

B-6: [(Campersulfonyloxyimino-5H-thiophene-2-iridene)-(2-methylphenyl) acetonitrile] represented by the compound (3-iii) (Ciba Specialty Chemicals Co., Ltd.) `` CGI1380 '' of the production)

B-7: [(5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile] represented by the above compound (3-VII) ("CGI725" manufactured by Chiba Specialty Chemicals Co., Ltd.)

(C) component long-chain alkyl-group containing compound

C-1: palmitic acid

C-2: stearic acid

C-3: tetradecane diacid

C-4: 1-dodecanol

C-5: 1,12-dodecanediol

C-6: 1,2-epoxytetedecane

C-7: 1,2-epoxyhexadecane

C-8: Glycidyl Stearate

C-9: 3-ethyl-3-nonyloxetane

C-10: 1-dodecanesulfonic acid

C'-1: valeric acid (CH ₃ (CH ₂ ) ₃ COOH)

C'-2: lignoserine acid (CH ₃ (CH ₂ ) ₂₂ COOH)

C'-3: lignoceryl alcohol (CH ₃ (CH ₂ ) ₂₃ OH)

(D) component surfactant

D-1: Silicone type surfactant ("SH 8400 FLUID" made by Torre Dow Corning Co., Ltd.)

D-2: Fluorine-type surfactant ("aftergent FTX-218" by Neos Co., Ltd.)

(E) component adhesion aid

E-1: γ-glycidoxypropyltrimethoxysilane

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

E-3: gamma-methacryloxypropyl trimethoxysilane

(F) component basic compound

F-1: 4-dimethylaminopyridine

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

Example 1

(B-4) As a component (B-4) to the solution (quantity equivalent to 100 mass parts (solid content) of polymer (A-1)) containing polymer (A-1) obtained by the synthesis example 1 as [A] component [(5-octylsulfonyloxyimino-5H-thiophene-2-iridene)-(2-methylphenyl) acetonitrile] represented by the compound (3-ii) (manufactured by Chiba Specialty Chemicals Co., Ltd.) `` IRGACURE PAG 108 '') 3 parts by mass, (C-1) palmitic acid 4 parts by mass as the [C] component, (D-1) as the component (D-1) silicone surfactant (Tore Dow Corning Co., Ltd. product) Positive radiation-sensitive property by mixing 0.20 parts by mass of "SH 8400 FLUID" and 3.0 parts by mass of (E-1) -glycidoxypropyltrimethoxysilane as the [E] component and filtering with a membrane filter having a pore diameter of 0.2 μm. The composition was prepared.

[Examples 2 to 10 and Comparative Examples 1 to 7]

Except having performed the kind and quantity of each component as Table 1, it carried out similarly to Example 1, and prepared the positive radiation sensitive composition of Examples 2-10 and Comparative Examples 1-7.

<Property evaluation>

Using each positive radiation sensitive composition prepared as mentioned above, the said composition and various characteristics as its coating film or interlayer insulation film were evaluated as follows.

(1) radiation sensitivity

Hexamethyldisilazane (HMDS) was apply | coated on 550x650 mm chromium film-forming glass, and it heated at 60 degreeC for 1 minute (HMDS process). On the chromium film-forming glass after this HMDS process, the radiation sensitive composition prepared as mentioned above was apply | coated using the slit die coater "TR632105-CL", and the reached pressure was set to 100 Pa, and after removing a solvent under vacuum, it was further 90 By prebaking at 2 degreeC for 2 minutes, the coating film of 3.0 micrometers in film thicknesses was formed. Subsequently, using Canon MPA-600FA exposure machine, irradiating radiation to a coating film at a variable amount of exposure via a mask having a pattern of 60 µm line-and-space (10 to 1) And developed in a tetramethylammonium hydroxide aqueous solution of the concentration shown in Table 1 by the puddle method at 25 degreeC. Here, developing time was made into 80 second when the tetramethylammonium hydroxide concentration used the developing solution of 0.40 mass%, and 50 seconds when using the 2.38 mass% developing 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 in order for 6 micrometer space pattern to melt | dissolve completely was investigated. This value was shown in Table 1 as a radiation sensitivity. It can be said that sensitivity is favorable when this value is 500 J / m <2> or less.

(2) Shape stability of contact hole

After coating on a silicon substrate by using a spinner, the prebaking temperature is prebaked on a hot plate by two conditions of three minutes at 70 ° C. and three minutes at 90 ° C. to obtain a film thickness of 3.0 μm. Formed. Exposure of a coating film through the mask of a contact hole pattern of 10 micrometers x 10 micrometers by the required exposure amount evaluated in (1) evaluation of radiation sensitivity using the Canon PLA-501F exposure machine (super high pressure mercury lamp) by Canon Corporation. Done. Next, the image development process was performed at 25 degreeC by the puddle method using the tetramethylammonium hydroxide aqueous solution (developer) of 0.4 mass% of concentration. The development time was set to 100 seconds. After the development treatment, the coating film was washed with ultrapure water for 1 minute, dried, and a contact hole pattern was formed on the wafer. The formed pattern was observed with a SEM (scanning electron microscope).

When there is no difference in the contact hole pattern created under two conditions of prebaking temperature at 70 ° C. for 3 minutes and prebaking temperature at 90 ° C. for 3 minutes, the shape stability of the contact hole with respect to the temperature change of the prebaking is high and developability And pattern formability can be said to be good. On the other hand, when the size of the contact hole changes significantly or the peeling from the substrate occurs with respect to the change in the prebaking temperature, the shape stability of the contact hole with respect to the temperature change of the prebaking is low, and developability and pattern formation property are poor. Can be said.

(Evaluation standard)

The following evaluation criteria were judged with reference to typical sectional drawing of the cured film 2 provided with the contact hole 3 formed on the board | substrate 1 shown in FIG.

In the case of the contact hole shape of FIG. 1 (a), it was judged to be good (shown as A).

When the contact hole shape was greatly enlarged as in the case of Fig. 1 (b), it was judged to be defective (shown as B).

As in the case of Fig. 1 (c), it was determined that the shape in which the contact hole was cut off was defective (indicated by C). The results are shown in Table 1.

(3) light transmittance

On the silicon substrate, the coating film was formed similarly to the said evaluation of the radiation sensitivity. This silicon substrate was heated at 220 degreeC in clean oven for 1 hour, and the cured film was obtained. The light transmittance in wavelength 400nm was measured and evaluated using the spectrophotometer (150-20 type double beam (made by Hitachi Seisakusho Co., Ltd.)). At this time, when less than 90%, transparency can be said to be poor, and when 90% or more, transparency is favorable. The evaluation results are shown in Table 1.

(4) voltage holding ratio

The prepared liquid composition was spin-coated on a soda glass substrate on which a SiO ₂ film was formed on the surface to prevent elution of sodium ions, and further deposited an ITO (indium-tin oxide alloy) electrode in a predetermined shape. Prebaking was carried out in a clean oven for 10 minutes to form a coating film having a film thickness of 2.0 µm.

Subsequently, it exposed on the coating film with the exposure amount of 500 J / m <2> without interposing a photomask. Then, this board | substrate is immersed in the developing solution which consists of a 0.04 mass% potassium hydroxide aqueous solution at 23 degreeC for 1 minute, and after developing, it is wash | cleaned with ultrapure water, air-dried, and post-baking is carried out at 230 degreeC for 30 minutes, hardening a coating film And cured film were formed.

Subsequently, after bonding the board | substrate which formed this pixel and the board | substrate which only deposited the ITO electrode to a predetermined shape with the sealing compound which mixed 0.8 mm glass beads, the liquid crystal cell made by Merck MLC6608 (brand name) is injected, and a liquid crystal cell Made.

Subsequently, the liquid crystal cell was put into the thermostat of 60 degreeC, and the voltage holding ratio of the liquid crystal cell was measured by Toyo Technica make liquid crystal voltage holding ratio measuring system "VHR-1A type" (brand name). At this time, the applied voltage was 5.5V square wave and the measurement frequency was 60Hz. The voltage holding ratio is a value of (voltage applied at the liquid crystal cell potential difference / 0 millisecond after 16.7 milliseconds). If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot maintain the applied voltage at a predetermined level for a time of 16.7 milliseconds, and cannot align the liquid crystal sufficiently, and there is a fear of causing "burn-in" such as an afterimage. high.

As is apparent from the results in Table 1, the positive radiation-sensitive compositions of Examples 1 to 10 containing [A], [B] and [C] components do not contain [C] component. Compared with the positive radiation sensitive composition of 7, it was found that the contact hole had excellent shape stability and had high developability and pattern formability. Moreover, it turned out that each positive radiation sensitive composition of an Example can form the interlayer insulation film which fully satisfies the general required characteristics, such as a radiation sensitivity, a light transmittance, and a voltage hold ratio.

As described above, the positive radiation-sensitive composition of the present invention has excellent radiation sensitivity and excellent developability which can cope with changes in the formation conditions of the cured film while the resulting interlayer insulating film has a high light transmittance and a voltage holding ratio. It has a pattern formability. Therefore, the said positive radiation sensitive composition is used suitably in order to form the interlayer insulation film etc. of a display element.

1: substrate
2: cured film
3: contact hole

Claims (6)

[A] a polymer having a structural unit and an epoxy group-containing structural unit containing a group represented by the following formula (1) in the same or different polymer molecule,
[B] mine generators,
[C] a compound represented by the following formula (2)
Positive radiation sensitive compositions 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, and some or all of the hydrogen atoms of these alkyl groups, a cycloalkyl group, or an aryl group are substituted by a substituent, May be present, provided that 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 (M is Si, Ge Or Sn and R ^3m is an alkyl group, and some or all of these hydrogen atoms may be substituted with a substituent, and R ¹ and R ³ may be linked to form a cyclic ether structure;

(In formula (2), X is a C6-C20 divalent linear aliphatic hydrocarbon group; Y ¹ and Y ² are each independently a single bond, an ester bond, an amide bond or a urethane bond; R ⁴ and R ⁵ are, each independently, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, sulfo, sulfonyl group, or the formula (i) ~ a group represented by any of (vi); However, Y ¹ or Y ² is unity coalescence When R ⁴ or R ⁵ connected with Y ¹ or Y ² is not an alkyl group having 1 to 6 carbon atoms;

(In formula (i)-(vi), R <^6> is a hydrogen atom or a C1-C6 alkyl group; R <^7> is a hydrogen atom or a methyl group; m is an integer of 0-6; However, said Formula (2) M in R <^4> or R <^5> connected with this Y <^1> or Y <^2> is 0 when Y <^1> or Y <^2> is a single bond. The method of claim 1,
Positive radiation-sensitive property in which at least one of R <^4> and R <^5> of the compound represented by said Formula (2) contains the compound represented by either of said Formula (i), (ii), (iii), and (vi) Composition. The method of claim 1,
(B) The positive radiation sensitive composition in which a photo-acid generator has an oxime sulfonate group represented by following formula (3).

(In Formula (3), ^RB1 is a linear or branched alkyl group, a cycloalkyl group, or an aryl group, and some or all of the hydrogen atoms of these groups may be substituted by the substituent.). The method according to any one of claims 1, 2 or 3,
Positive type radiation sensitive composition used for forming the interlayer insulation film of a display element. (1) forming the coating film of the positive radiation sensitive composition of Claim 4 on a board | substrate,
(2) irradiating at least a portion of the coating film formed in step (1) with radiation;
(3) developing the coating film irradiated with radiation in step (2), and
(4) Step of heating the coating film developed in step (3)
A method of forming an interlayer insulating film of a display element having a structure. The interlayer insulation film of the display element formed from the positive radiation sensitive composition of Claim 4.

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