KR20110110713A - Positive radiation-sensitive composition, interlayer insulating film and method for forming the same - Google Patents

Abstract

(Problem) In addition to excellent heat resistance and transparency, it is possible to form an interlayer insulating film having high flatness (film thickness uniformity) without coating unevenness, and to apply at high speed, and to provide positive radiation with high radiation sensitivity. It is aimed at providing a sex composition.
(Measures) 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] fluorine It is a positive radiation sensitive composition containing the copolymer which has a structural unit which has a structural unit which has and a silicon.

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. The positive radiation sensitive composition used when forming such an interlayer insulating film requires excellent radiation sensitivity and storage stability, and the interlayer insulating film obtained requires excellent heat resistance and transparency.

As a component of the said positive radiation sensitive composition, acrylic resin is widely employ | adopted, For example, Unexamined-Japanese-Patent No. 2004-4669 has a crosslinking agent, an acid generator, and itself insoluble in an aqueous alkali solution, or Positive chemical amplification resistor, although it is poorly soluble, 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. Compositions have been proposed. However, in the insulating film obtained from this composition, adhesiveness is not enough and it is not satisfactory in order to manufacture a high quality liquid crystal display element. In addition, Japanese Patent Laid-Open No. 2004-264623 proposes a radiation sensitive resin composition comprising an acetal structure and / or a ketal structure, a resin containing an epoxy group, and an acid generator, but having a low radiation sensitivity, It is not enough.

On the other hand, with the spread of the recent large-screen TV, the glass substrate size used for manufacture is also enlarged. Therefore, application of the radiation sensitive composition to a large sized board | substrate becomes difficult by the spin coating method conventionally employ | adopted in the interlayer insulation film formation process. Therefore, instead of such a spin coating method, the slit coating method which discharges a radiation sensitive composition from a slit-shaped nozzle and apply | coats on a glass substrate is employ | adopted.

In the slit coating method, specifically, the substrate is adhered to the application stage by vacuum adsorption, after which the application nozzle is sweeped in a predetermined direction to form a coating film on the substrate. By raising the support pin stored, the board | substrate is lifted from the application | coating stage and conveyed to the next process. This slit coating method can reduce the amount of the radiation-sensitive composition required for the application compared with the spin coating method, and can be applied in a predetermined direction while discharging the radiation-sensitive composition. The time can also be shortened, which also contributes to reducing the manufacturing cost of the display element.

However, in this series of processes, coating unevenness may occur at the time of coating, or unevenness may occur in the coating film due to unevenness caused by pores for vacuum adsorption, which is required as a characteristic of the interlayer insulating film. There is a problem in achieving flatness.

In such a situation, it is possible to form a cured film having excellent heat resistance and transparency, which is generally required as an interlayer insulating film, and having high flatness (film thickness uniformity) without coating unevenness, and high-speed coating, and high radiation. There is a strong demand for the development of positive radiation-sensitive compositions having sensitivity.

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 to form the interlayer insulation film which has the high flatness (film thickness uniformity) without application | coating nonuniformity in addition to the outstanding heat resistance and transparency, and high speed. The present invention provides a positive radiation-sensitive composition having a high radiation sensitivity, 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 molecule,

[B] mine generators,

[C] Copolymer having a structural unit having a fluorine and a structural unit having a silicon

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; R ¹ and R ³ may be linked to form a cyclic ether).

Furthermore, the [C] copolymer,

(c1) the polymeric compound represented by following formula (2),

(c2) a polymeric compound represented by the following formula (3), and

(c3) Polymerizable compound which has group represented by following formula (4).

Copolymer having at least a structural unit derived from

It is a positive radiation sensitive composition containing these.

(In formula (2), R ⁴ is a hydrogen atom or a methyl group; α is an integer of 0 to 6; β is an integer of 1 to 20);

(In formula (3), R ⁵ is a hydrogen atom or a methyl group; R ⁶ is an alkyl group having 1 to 12 carbon atoms; γ is 2 or 3; a is the number of structural units and the number average is 1 to 30.) ;

(In formula (4), R <^7> , R <^8> , R <^9> , R <^10> and R <^11> are respectively independently group represented by a C1-C20 alkyl group, a phenyl group, or following formula (5); b is 0- An integer of 3);

(In formula (5), R <^12> , R <^13> and R <^14> is respectively independently a C1-C20 alkyl group or a phenyl group; c is an integer of 0-3.).

In the positive radiation-sensitive composition, in addition to the [A] polymer and [B] photoacid generator having the specific structure, the [C] copolymer formed of a polymerizable compound having a specific structure has a high surface tension-lowering performance. By functioning as a surfactant, it is possible to form an interlayer insulating film having a high degree of flatness (film thickness uniformity) without satisfactorily satisfying the general required characteristics of heat resistance and transparency, and without coating unevenness. In addition, the positive radiation-sensitive composition can be applied at high speed and has excellent radiation sensitivity.

In the positive radiation sensitive composition, it is preferable that the [C] copolymer further has a structural unit derived from the polymerizable compound having an (c4) unsubstituted alkyl ester group having 1 to 8 carbon atoms. Thereby, the affinity of the [C] copolymer with respect to another component and a solvent can be improved, and the film thickness uniformity of the interlayer insulation film obtained can be improved more.

In the said positive radiation sensitive composition, it is preferable that [C] copolymer further has a structural unit derived from the polymeric compound which has a 2 or more unsaturated bond in 1 molecule (c5). Thereby, intensity | strength can be raised with the film thickness uniformity of the interlayer insulation film obtained, and general characteristics, such as heat resistance, can also be improved.

In the said positive radiation sensitive composition, a compound (c1) is a polymeric compound represented by following formula (6), and a compound (c2) is a polymeric compound represented by following formula (7),

The copolymer (C) is based on the total amount of the polymerizable compounds (c1) to (c5),

25-35 mass% of polymeric compounds (c1),

20-30 mass% of polymeric compounds (c2),

15-20 mass% of polymeric compounds (c3),

25-35 mass% of polymeric compounds (c4),

1-5 mass% of polymeric compounds (c5)

It is preferable that it consists of a composition containing a.

(In formula (6), R <^4> is synonymous with the thing in said Formula (2); (beta) is an integer of 1-8.);

(In formula (7), R <^5> and R <^6> is synonymous with the thing in said Formula (3), respectively; the number average value of a structural unit number (a) is 4-12.).

[C] copolymer of such a specific structure functions as a surfactant having high surface tension lowering performance, and even when used in a small ratio, the surface smoothness of the coating film can be improved, and as a result, the film of the interlayer insulating film formed. Thickness uniformity can be further improved.

It is preferable that the said positive radiation sensitive composition further contains [D] adhesion | attachment adjuvant. By using such an adhesion | attachment adjuvant, it becomes possible to improve the adhesiveness to the board | substrate of the cured film obtained further.

It is preferable that the said positive radiation sensitive composition contains a [E] basic compound further. Thereby, the diffusion of the acid generated from the photoacid generator can be appropriately controlled to increase the pattern developability of the positive radiation-sensitive composition.

Moreover, the formation method of the interlayer insulation film for display elements 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)

It includes.

In this method, it is possible to achieve high-speed application and to form a pattern by exposure, development and heating using radiation, using the positive radiation-sensitive composition having excellent radiation sensitivity. And an interlayer insulating film for display elements which has a fine pattern can be formed. In addition, the interlayer insulating film thus formed has excellent general balance of required properties, that is, heat resistance and transparency, and is free from coating unevenness and has high flatness.

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

As described above, the positive radiation-sensitive composition of the present invention includes the above-mentioned [A], [B], and [C] components, while satisfactorily satisfying the general required characteristics of heat resistance and transparency, An interlayer insulating film having a high flatness without coating unevenness can be formed. Moreover, the said positive radiation sensitive composition can be apply | coated at high speed and expresses the outstanding radiation sensitivity.

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

<Polymer [A]>

The polymer [A] has a structural unit (1) and an epoxy group containing structural unit in the same or different polymer molecule, and may have other structural units as needed. It does not specifically limit as embodiment of the polymer [A] 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 polymer [ When one kind of polymer molecule is present in A], (ii) it has a structural unit (1) in one polymer molecule, has an epoxy group containing structural unit in a different polymer molecule, and 2 in a polymer [A] 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, In the case where another polymer molecule has an epoxy group-containing structural unit and three polymer molecules are present in the polymer [A], in addition to the polymer molecules specified in (i ') (i) to (iii), the 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 dissociates 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, Branched alkyl groups, such as linear alkyl groups, such as n-octadecyl group, i-propyl group, i-butyl group, t-butyl group, neopentyl group, 1-hexyl group, 2-hexyl group, and 3-hexyl group Can be mentioned.

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, they are a C6-C14 aryl group, may be monocyclic, the structure which monocyclic linked, 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 etc.), alkoxycarbonyl (Preferably a C2-C20 alkoxycarbonyl group, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, etc. are mentioned), a halo alkyl group (the hydrogen atom of the said alkyl group or cycloalkyl group) A part or all of which 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. can be mentioned. 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 in a total structural unit contained in a polymer [A], 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>

Polymer [A] has an epoxy group containing structural unit with the said 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 polymer [A] has a structural unit containing an oxiranyl group, an oxetanyl group, etc. in a molecule | numerator, the hardness of the cured film obtained from the said positive radiation sensitive composition can be improved and heat resistance can be improved further.

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 contains 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 all the structural units contained in a 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 [A] is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ , and more preferably 5.0 × 10 ^{3 to} 5.0 × 10 ⁴ . By making Mw of polymer [A] into the said range, the radiation sensitivity and alkali developability of the said positive radiation sensitive composition can be improved.

Further, 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 , and 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.

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

<Method for producing Polymer [A]>

Polymer [A] can be manufactured by radical copolymerization of an acetal structure containing monomer, an epoxy group containing monomer, and the monomer which gives another structural unit. When manufacturing polymer [A] 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 polymer [A] 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 polymers It is good to make [A].

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-methylbutyrate, methyl methoxyacetic acid, ethyl methoxyacetic acid, methoxyacetic acid propyl, methoxyacetic acid butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, ethoxyacetic acid Propyl, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propoxyacetate Acid propyl, butyl propoxyacetic acid, methyl butoxyacetic acid, ethyl butoxyacetic acid, butyl butoxyacetic acid, butyl butoxyacetic acid, 2-methoxypropionate, ethyl 2-methoxypropionic acid, 2-methoxypropionic acid propyl, 2 Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2- Propyl butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionic acid, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-E Ethyl oxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionate Ester, such as a pill, 3-propoxy propionate butyl, 3-butoxy propionate methyl, 3-butoxy ethyl propionate, 3-butoxy propionic acid propyl, and 3-butoxy propionate butyl, is 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 [A], 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);

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], in order to adjust the molecular weight, a molecular weight modifier can be used. 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 rays, ultraviolet rays, far ultraviolet rays, electron beams, X rays and the like can be used. When the positive radiation-sensitive composition contains the photo acid generator [B], the positive radiation-sensitive characteristic can be exhibited. [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 a containing form in the said positive radiation sensitive composition of a photo-acid generator, even if it is the form of the photo-acid generator which is a compound mentioned later, or the form of the photo-acid generator incorporated as a part of polymer [A] or other polymers, Or both of these forms. Examples of the photoacid generator [B] include an oxime sulfonate compound, and include a diphenyl iodonium salt, a triphenylsulfonium salt, a sulfonium salt, a benzothiazonium salt, an ammonium salt, a phosphonium salt and a tetrahydrothiophenium salt. Onium salts, sulfonimide compounds, and quinonediazide compounds.

<Oxime sulfonate compound>

As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by following formula (8) is preferable.

In said Formula (8), R <^B1> is the linear, branched, cyclic alkyl group which may be substituted, or the aryl group which may be substituted. As an alkyl group of R <^B1> , a C1-C10 linear or branched alkyl group is preferable. The alkyl group of R ^B1 may be substituted with an alkoxy group having 1 to 10 carbon atoms or an alicyclic group (preferably a bicycloalkyl group or the like including a crosslinked alicyclic group such as 7 and 7-dimethyl-2-oxonorbornyl group). . 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 (8) is an oxime sulfonate compound represented by following formula (9).

In the formula (9), R ^B1 has the same meaning as that of R ^B1 described in the formula (8). X 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 X may be same or different. The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

As an alkoxy group as X, a C1-C4 linear or branched alkoxy group is preferable. The halogen atom as X is preferably a chlorine atom or a fluorine atom. M is preferably 0 or 1. In particular, in said Formula (9), the compound whose m is 1, X is a methyl group, and the substitution position of X is ortho is preferable.

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

These 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 compounds (i) to (iii) can be obtained as a commercial item.

<Onium salt>

Among the onium salts, examples of the diphenyl iodonium salt include diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphonate, diphenyl iodonium hexafluoroarsenate, and diphenyl iodo. Donium 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, etc. are mentioned.

Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, and triphenylsulfonium-p- Toluenesulfonate, triphenylsulfonium butyl tris (2,6-difluorophenyl) borate, and the like.

Examples of the sulfonium salt include alkyl sulfonium salts, benzyl sulfonium salts, dibenzyl sulfonium salts, substituted benzyl sulfonium salts, and the like.

As these sulfonium salts,

As the alkylsulfonium salt, for example, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenyl Sulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro 4-acetoxyphenylsulfonium hexafluoroantimonate, etc .;

As the benzylsulfonium salt, for example, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexa Fluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro- 4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, etc .;

As the dibenzylsulfonium salt, for example, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium 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;

As the substituted benzylsulfonium salt, for example, 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, 3- (p-methoxybenzyl) Benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, etc. are mentioned.

Examples of tetrahydrothiophenium salts include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiopheniumtrifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) Tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1,2,2-tetrafluoro-2- (Norbornan-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxybicyclo [2.2 .1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6 -t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4,7-dibutoxy-1-naph Thalenyl) tetrahydrothiophenium trifluoromethanesulfonate, etc. are mentioned.

Among these onium salts, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt, and sulfonimide compound are used in view of improving the radiation sensitivity of the positive radiation-sensitive composition and the adhesiveness of the cured product obtained. It is suitably used. Among them, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate and benzyl-4-hydroxyphenylmethylsulfonium hexafluoro Antimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroanti Monate, 3-benzylbenzothiazonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiope Niumtrifluoromethanesulfonate and 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiopheniumtrifluoromethanesulfonate are preferably used.

<Sulfonimide compound>

As an example of a sulfonimide compound, N- (trifluoromethylsulfonyloxy) succinimide (brand name "SI-105" (made by Midori Chemical Co., Ltd.)) and N- (camphor sulfonyloxy) succinimide (Brand name "SI-106" (manufactured by Midori Kagaku Co., Ltd.)), N- (4-methylphenylsulfonyloxy) succinimide (brand name "SI-101" (manufactured by Midori Kagaku Co., Ltd.)), N -(2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- ( Campersulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulphur Phenyloxy) diphenyl maleimide (brand name "PI-105" (made by Midori Chemical Co., Ltd.)), N- (camphor sulfonyloxy) diphenyl maleimide, 4-methylphenyl sulfonyloxy) diphenyl mal Imide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) Diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide (trade name "NDI-100" (manufactured by Midorikagaku Co., Ltd.)) , N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide (trade name "NDI-101" (manufactured by Midorikagaku KK)), N -(Trifluoromethanesulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide (trade name "NDI-105" (manufactured by Midorikagaku KK)), N- (Nonafluorobutanesulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide (trade name "NDI-109" (manufactured by Midorikagaku KK)), N- ( Camphorsulfonyloxy) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyl Mead (brand name "NDI-106" (made by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5-ene-2,3- dicarboxyl Mead, 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-trifluoromethylphenylsulfonyloxy ) -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- (tri Fluoromethylsulfonyl Bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2, 3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyl Oxy) bicyclo [2.2.1] heptan-5,6-oxy-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptan-5,6- Oxy-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) naphthyldicarboxyimide (brand name "NAI-105" (made by Midori Chemical Co., Ltd.)), N- (camphorsulfonyl Oxy) naphthyl dicarboxyl imide (brand name "NAI-106" (made by Midori Chemical Co., Ltd.)), N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylic imide (brand name "NAI-101" (midorikka) Gaku Corporation make), N- (phenylsulfonyloxy) naphthyl dicarboxyimide (brand name "NAI-100 (Manufactured by Midori Kagaku Co., Ltd.)), N- (2-trifluoromethylphenylsulfonyloxy) naphthyldicarboxyimide, N- (4-fluorophenylsulfonyloxy) naphthyldicarboxyimide, N- (Pentafluoroethylsulfonyloxy) naphthyldicarboxyimide, N- (heptafluoropropylsulfonyloxy) naphthyldicarboxyimide, N- (nonafluorobutylsulfonyloxy) naphthyldicarboxyimide (brand name `` NAI-109 '' (manufactured by Midori Kagaku Co., Ltd.), N- (ethylsulfonyloxy) naphthyldicarboxyimide, N- (propylsulfonyloxy) naphthyldicarboxyimide, N- (butylsulfonyl Oxy) naphthyl dicarboxyl imide (brand name "NAI-1004" (made by Midori Chemical Co., Ltd.)), N- (pentylsulfonyloxy) naphthyl dicarboxylic imide, N- (hexylsulfonyloxy) naphthyl dica Foxyimide, N- (heptylsulfonyloxy) naphthyldicarboxyimide, N- (octylsulfonyloxy) naphthyldicarboxyimide, N- (nonylsul Carbonyl oxy), and the naphthyl Fifi dicarboxylic imide, etc.

<Quinonediazide-compound>

The quinonediazide compound is a compound that generates carboxylic acid upon irradiation with radiation. As the quinonediazide-compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as "nucleus") and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

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

As these mother cores,

Examples of the trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, and the like;

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, it is 2,3,4,2'6'- pentahydroxy benzophenone etc., for example;

Examples of the hexahydroxybenzophenone include 2,4,6,3'4'5'-hexahydroxybenzophenone, 3,4,5,3'4'5'-hexahydroxybenzophenone, and the like;

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'-trihydroxyflavan and the like;

As another mother nucleus, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl ) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3 -Dihydroxy benzene is mentioned.

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

As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. Specific 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, it is especially preferable to use 1,2-naphthoquinone diazide-5-sulfonic acid chloride.

Suitable examples of condensates of phenolic or alcoholic compounds with 1,2-naphthoquinonediazidesulfonic acid halides include 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinonediazide Condensates with -5-sulfonic acid chloride, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphtho And condensates with quinonediazide-5-sulfonic acid chloride.

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

Moreover, as a quinone diazide compound, the 1, 2- naphthoquinone diazide sulfonic-acid amides which changed the ester bond of the above-mentioned mother core to the amide bond, for example, 2,3, 4- triamino benzophenone 1,2 -Naphthoquinone diazide-4-sulfonic acid amide etc. are also used suitably. These [B] components can be used individually or in combination of 2 or more types.

As content as a [B] photo-acid generator in the said positive radiation sensitive composition, Preferably it is 1-20 mass parts with respect to 100 mass parts of polymers [A], More preferably, it is 1-10 mass parts. . When the content of the component (B) is within the above range, the difference in solubility between the irradiated portion and the unirradiated portion of the alkaline aqueous solution serving as the developing solution is large, so that the patterning performance is good, and the solvent resistance of the resulting interlayer insulating film is also high. It becomes good.

<Copolymer [C]>

Copolymer [C] is a copolymer which has a structural unit which has a silicon as a structural unit which has a fluorine, and has a specific structure to the polymeric compound (c1), polymeric compound (c2), and polymeric compound (c3) It is a copolymer which has at least a structural unit derived. In the positive radiation-sensitive composition, the copolymer [C] functions as a surfactant having high surface tension lowering performance, and even when used in a small proportion, the flatness of the surface of the interlayer insulating film formed is remarkably improved. Can be.

In the positive radiation-sensitive composition, the copolymer [C] is also referred to as (c4) a polymerizable unsaturated compound having an unsubstituted alkyl ester group having 1 to 8 carbon atoms (hereinafter, simply referred to as "polymerizable compound (c4)"). It is preferable to have a structural unit derived from the same), and furthermore, the structural unit derived from the polymerizable unsaturated compound (henceforth simply called "polymerizable compound (c5)") which has two or more unsaturated bonds in (c5) 1 molecule. It is more preferable to have, and especially what consists of the composition containing the said polymeric compound (c1), a polymeric compound (c2), a polymeric compound (c3), a polymeric compound (c4), and a polymeric compound (c5) desirable.

The group -C _α H _{2 α} -in the formula (2) is a methylene group or an alkylmethylene group or a linear or branched alkylene group. When the group -C _α H _{2 α} − is asymmetric, the direction of the bond is not asked. The carbon number α of the group -C _α H _{2 α} − is preferably 2 to 4. Specific examples of the group -C _α H _{2 α} − include 1,2-ethylene groups, 1,2-propylene groups, 1,3-propylene groups, 1,4-butylene groups, and the like. 1,2-ethylene group or 1,3-propylene group is preferable and 1,2-ethylene group is especially preferable.

The group -C _β F _{2β + 1} in the formula (2) is a linear or branched fluoroalkyl group. _Carbon number (beta) of group -C ( _beta) F2 ( _{beta) +1} is 1-20, Preferably it is 1-12, More preferably, it is 1-8, Especially preferably, it is 2-8. Group -C _β F _{2β + 1} is preferably a fluoroalkyl group of a straight chain.

As a polymeric compound (c1) in this invention, it is preferable that it is a compound represented by said formula (6). As a specific example of a compound (c1), the compound etc. which are represented by each of following formula (c1-1)-(c1-8) are mentioned.

.

.

The group -C _γ H _{2 γ} -in the formula (3) is a linear or branched alkylene group. When the group -C _γ H _{2 γ} -is asymmetric, the direction of the bond is not asked. As a specific example of group -C ( _gamma) H2 _{( gamma)} -, a 1,2-ethylene group and a 1,2-propylene group are mentioned, for example, It is preferable that it is a 1,2-ethylene group.

Compound (c2) is used as a mixture of compounds in which the value of the repeating unit number a in the said Formula (3) differs. The number average value of a is 1-30, Preferably it is 2-20, It is especially preferable that it is 4-12. In the compound (c2), when γ is 2, ethylene oxide is reacted with (meth) acrylic acid, and when γ is 3, propylene oxide is reacted with (meth) acrylic acid, respectively. At this time, the value of a varies depending on the number of moles of ethylene oxide or propylene oxide introduced with respect to 1 mole of (meth) acrylic acid. The value of a is obtained from the number of moles of ethylene oxide or propylene oxide introduced into 1 mole of (meth) acrylic acid by obtaining the number average molecular weight of polystyrene conversion measured by gel permeation chromatography for compound (c2). It can obtain | require by calculating the value used as the calculated number average molecular weight.

As a compound (c2), a commercial item can be used suitably. As an example of such a commercial item, NK-ester M-40G, NK-ester M-90G, AM-90G by Shin-Nakamura Kagaku Kogyo Co., Ltd .; Blemmer PME-200, PME-400, PME-550 by Nichiyu Corp., etc. are mentioned.

The compounds (c3), in the above formula (4), when the R ⁸ and R ⁹ present in plurality, respectively, or different, each R ⁸ may be the same, each R ⁹ may be the same or different. In addition, in said Formula (5), when two or more R <^13> and R <^14> exist, each R <^13> may be same or different, and each R <^14> may be same or different. In addition, as a compound (c3), in said Formula (4), R <^7> , R <^8> and R <^9> are respectively a C1-C20 alkyl group or a phenyl group, and R <^10> and R <^11> are respectively said Formula (5) It is preferable that it is a polymerizable unsaturated compound which has group represented by).

As compound (c3), Preferably, the compound represented by a following formula (c3-1) can be used.

(In formula (c3-1), R ^Si is a group represented by the formula (4), R ¹⁵ is a hydrogen atom or a methyl group, and d is an integer of 1 to 3).

As a specific example of a compound (c3-1), the compound etc. which are represented by each of following formula (c3-1-1), (c3-1-2), and (c3-1-3) are mentioned.

(In formula (c3-1-1), Me is a methyl group and r, s, and t are each an integer of 0-3.);

(In formula (c3-1-2), Me and r, s and t are defined similarly to said formula (c3-1-1).);

(In formula (c3-1-3), Me and r, s, and t are defined similarly to said formula (c3-1-1), and Ph is a phenyl group).

As a compound (c4), the alkyl (meth) acrylate etc. which have a C1-C8 unsubstituted alkylester group are mentioned, for example. Specific examples of the compound (c4) include n-butyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate, and the like.

As a compound (c5), the compound which methacrylated both ends, such as tetramethylene glycol, the polyethyleneglycol of the polymerization degrees 1-20, and the polypropylene glycol of the polymerization degrees 1-20, is mentioned, for example. As a compound (c5), a commercial item can be used suitably. As an example of such a commercial item, NK ester 1G, copper 2G, copper 3G, copper 4G, copper 9G, copper 14G etc. by Shin-Nakamura Kagaku Kogyo Co., Ltd. are mentioned.

When the copolymer [C] has structural units derived from the polymerizable compound (c1), the polymerizable compound (c2), and the polymerizable compound (c3) as described above, each polymerization with respect to the total amount of these polymerizable compounds The use ratio of a polymeric compound is 10-55 mass% with respect to a polymeric compound (c1), it is 10-50 mass% with respect to a polymeric compound (c2), and 5-45 mass% with respect to a polymeric compound (c3). to be.

When the copolymer [C] further has a structural unit derived from the polymerizable compound (c4), the use ratio of each polymerizable compound to the total amount of the polymerizable compound is from 20 to 20 relative to the polymerizable compound (c1). It is 50 mass%, it is 15-40 mass% with respect to a polymeric compound (c2), it is 10-30 mass% with respect to a polymeric compound (c3), and is 20-35 mass% with respect to a polymeric compound (c4).

When the copolymer [C] further has a structural unit derived from the polymerizable compound (c5), the use ratio of each polymerizable compound to the total amount of the polymerizable unsaturated compound is 25 to the polymerizable compound (c1). It is -35 mass%, It is 20-30 mass% with respect to a polymeric compound (c2), It is 15-20 mass% with respect to a polymeric compound (c3), It is 25-35 mass% with respect to a polymeric compound (c4). And 1 to 5% by mass in the polymerizable compound (c5). Each of the compounds (c1) to (c5) for forming the copolymer [C] may be used alone or in combination of a plurality of kinds thereof.

Although the mass mean molecular weight (Mw) of copolymer [C] is 5,000-25,000, it is preferable that it is 10,000-25,000, and it is especially preferable that it is 15,000-25,000. The molecular weight distribution (Mw / Mn) (ratio of Mw to number average molecular weight Mn) of copolymer [C] becomes like this. Preferably it is 1-10, More preferably, it is 2-4.

The manufacturing method of copolymer [C] is not specifically limited, Based on well-known methods, for example, polymerization mechanisms, such as a radical polymerization method, a cation polymerization method, and an anion polymerization method, solution polymerization method and block polymerization. It can manufacture by a method, an emulsion polymerization method, etc. Among these manufacturing methods, since the radical polymerization method in a solution is simple, it is industrially preferable.

As a polymerization initiator used when manufacturing copolymer [C], For example, Peroxides, such as benzoyl peroxide and diacyl peroxide; Azo compounds, such as 2,2'- azobisisobutyronitrile and phenyl azo triphenylmethane, etc. are mentioned.

Although manufacture of copolymer [C] can be performed in the presence or absence of a solvent, it is preferable to carry out in presence of a solvent from a workability point. Examples of the solvent include alcohols, ketones, alkyl esters of monocarboxylic acids, ethers, propylene glycol and esters thereof, halogenated hydrocarbons, aromatic hydrocarbons, fluorinated inert liquids, other polar solvents, and the like.

Examples of these solvents

As said alcohol, For example, ethanol, isopropyl alcohol, n-butanol, iso-butanol, tert-butanol, etc .;

As said ketone, For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amino ketone, etc .;

As the alkyl ester of the monocarboxylic acid, for example, methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, 2-oxypropionate methyl, 2-oxypropionate ethyl, 2-oxypropionic acid propyl, 2- Butyl oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, butyl 2-methoxypropionate and the like;

As said ether, For example, methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, ethyl cellosolve acetate, tetrahydrofuran, dioxane, etc .;

As said propylene glycol and its ester, For example, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, a propylene glycol monobutyl ether acetate, etc .;

Examples of the halogenated hydrocarbons include 1,1,1-trichloroethane, chloroform and the like;

As said aromatic hydrocarbon, For example, benzene, toluene, xylene, etc .;

As said fluorinated inert liquid, For example, perfluorooctane, perfluoro tri-n-butylamine, etc .;

As said other polar solvent, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. are mentioned, for example.

These solvent may be used individually by 1 type, and may mix and use 2 or more types as appropriate.

In the manufacture of copolymer [C], you may further use chain transfer agents, such as lauryl mercaptan, 2-mercaptoethanol, ethyl thioglycolic acid, and octyl thioglycolic acid, as needed.

The use ratio of the copolymer [C] in the positive radiation-sensitive composition is preferably 0.01 to 3 parts by mass, and more preferably 0.05 to 2 parts by mass with respect to 100 parts by mass of the component [A]. . By using the component (C) in such a ratio, an interlayer insulating film having a high flatness without coating unevenness can be formed.

<Other optional components>

The positive radiation-sensitive composition of the present invention is, in addition to the above-mentioned [A] to [C] components, if necessary, such as a [D] adhesion aid, an [E] basic compound, and the like. It may contain other optional components.

<[D] 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 [D ] Adhesion aids as ingredients 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 a [D] adhesion | attachment adjuvant becomes like this. Preferably it is 0.5 mass part or more and 20 mass parts or less, More preferably, 1 mass part or more and 10 mass parts with respect to 100 mass parts of polymers [A]. It is used in the following amounts. By setting the amount of the adhesion assistant [D] to the above range, the adhesion between the interlayer insulating film to be formed and the substrate is improved.

<[E] 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 an [E] 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 polymer [A], and, as for content of the [E] basic compound in the said positive radiation sensitive composition, it is more preferable to set it as 0.005-0.2 mass part. Pattern developability becomes favorable by making content of a basic compound (E) into the said range.

<Positive radiation sensitive composition>

The positive radiation sensitive composition of this invention is prepared by mixing the said [A] polymer, the [B] photoacid generator, the copolymer formed from the monomer of the [C] specific structure, and arbitrary components as needed. Usually, a positive radiation sensitive composition is prepared and used in the state melt | dissolved or disperse | distributed in a suitable [F] solvent preferably. 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.

<[F] solvent>

As [F] 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 solvents, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetonyl acetone, isophorone, and caproic acid may be further added as necessary. , Caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenylcellosolve acetate And high boiling point solvents such as carbitol acetate.

When preparing a positive radiation sensitive composition as a solution or dispersion state, the ratio of components other than the [F] solvent in a liquid (that is, the total amount of [A], [B] and [C] components, and other arbitrary components) Although silver can be arbitrarily set 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 Interlayer Insulating Film>

Next, the method of forming the cured film of an interlayer insulation film on a board | substrate using the said positive radiation sensitive composition is demonstrated. The method includes the following steps in the order described below.

(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) A step of heating the coating film developed in the step (3).

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

In the process of said (1), after apply | coating the solution or dispersion liquid of the said positive radiation sensitive composition on a board | substrate, Preferably, a solvent is removed by 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, and the slit die coating method is particularly preferable. Although the conditions of prebaking differ according to the kind, compounding ratio, etc. of each component, Preferably it can be made into about 1 to 10 minutes at 70-120 degreeC.

<(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, the aqueous solution of alkali (basic compound) 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 water-soluble organic solvents and surfactants such as methanol and ethanol 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. In such a developing process, for example, the desired pattern can be formed by performing flowing water washing for 30 to 90 seconds and then air drying with, for example, compressed air or compressed nitrogen.

<(4) heating process>

In the process of said (4), hardening reaction of the said [A] component and [C] component can be 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 way, a patterned thin film corresponding to the target interlayer insulating film can be formed on the surface of the substrate.

<Interlayer Insulation Film>

The film thickness of the interlayer insulation film thus formed is preferably 0.1 to 8 µm, more preferably 0.1 to 6 µm, still more preferably 0.1 to 4 µm.

The interlayer insulating film formed from the positive radiation-sensitive composition of the present invention, as will be apparent from the examples below, satisfies the general required characteristics of heat resistance and transparency, and has a high flatness without application unevenness. . Therefore, the said interlayer insulation film is used suitably for a display element.

(Example)

Although a synthesis example and an Example are 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, 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, the same below) 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%.

<Synthesis of Copolymer [C]>

Synthesis Example 9

28.4 parts by mass of the compound represented by the formula (c1-1) as the compound (c1) in the glass flask provided with a stirring device, a condenser and a thermometer, and `` NK-ester '' manufactured by Shinnakamura Chemical Co., Ltd. as the compound (c2). 20.7 parts by mass of M-90G '', 18.1 parts by mass of the compound represented by the following formula (c3-1-1-1) as the compound (c3), 5.9 parts by mass of methyl methacrylate and 2-ethylhexyl acrylate as the compound (c4). 23.5 mass parts, 3.4 mass parts of compounds which methacrylated both ends of tetramethylene glycol as a compound (c5), and 414 mass parts of isopropyl alcohols as a solvent are put as 2, as a polymerization initiator in reflux in nitrogen gas stream. After adding 0.7 mass part of 2'- azobisisobutyronitrile (AIBN) and 4 mass parts of lauryl mercaptans as a chain transfer agent, copolymerization is carried out by refluxing at 75 degreeC for 8 hours, and a copolymer (C-1) A solution containing was obtained. Then, copolymer (C-1) was isolated by removing a solvent on 70 degreeC or less heating conditions using the evaporator. The number average molecular weight Mn of the obtained copolymer (C-1) was 2,800, the mass average molecular weight Mw was 5,300, and the molecular weight distribution (Mw / Mn) was 1.9.

Wherein Me is a methyl group.

Synthesis Example 10

A copolymer (C-2) was obtained in the same manner as in Synthesis Example 9 except that the amount of lauryl mercaptan added as a chain transfer agent was 1 part by mass. The number average molecular weight Mn of the obtained copolymer (C-2) was 4,700, the mass average molecular weight Mw was 11,000, and the molecular weight distribution (Mw / Mn) was 2.3.

Synthesis Example 11

A copolymer (C-3) was obtained in the same manner as in Synthesis Example 9 except that the temperature and time of the copolymerization were 73 ° C and 10 hours, respectively, without using lauryl mercaptan as the chain transfer agent. The number average molecular weight Mn of the obtained copolymer (C-3) was 5,600, the mass average molecular weight Mw was 21,000, and the molecular weight distribution (Mw / Mn) was 3.8.

Synthesis Example 12

In the glass flask provided with a stirring apparatus, a condenser, and a thermometer, 31.8 mass parts of compounds represented by said formula (c1-3) as a (c1) compound, and "NK-ester by Shin-Nakamura Kagaku Co., Ltd. as a (c2) compound. M-90G "31.6 mass parts, 29.0 mass parts of compounds represented by said formula (c3-1-1-1) as a compound (c3), and 414 mass parts of isopropyl alcohols are put, and it is a polymerization initiator in reflux in nitrogen gas stream. After adding 0.7 mass part of AIBN as 4 mass parts and 4 mass part of lauryl mercaptans as a chain transfer agent, it refluxed at 75 degreeC for 8 hours and copolymerized, and the solution containing copolymer (C-4) was obtained. Then, copolymer (C-4) was isolated by removing a solvent on 70 degreeC or less heating conditions using the evaporator. The number average molecular weight Mn of the obtained copolymer (C-4) was 3,500, and the mass average molecular weight Mw was 7,000. In addition, the molecular weight distribution (Mw / Mn) was 2.0.

[Synthesis Example 13]

24.2 parts by mass of the compound represented by the formula (c1-5) as the compound (c1), and (c2) the compound `` NK-ester '' manufactured by Shin-Nakamura Chemical Co., Ltd. M-90G ", 20.7 parts by mass, 21.5 parts by mass of the compound represented by formula (c3-1-1-1) as the compound (c3), 29.4 parts by mass of n-butyl methacrylate as the compound (c4), and isopropyl alcohol 414 parts by mass was added, and under nitrogen reflux, 0.7 parts by mass of AIBN as a polymerization initiator and 4 parts by mass of lauryl mercaptan as a chain transfer agent were added, and the mixture was refluxed at 75 ° C. for 8 hours to perform copolymerization. A solution containing C-6) was obtained. Then, copolymer (C-5) was isolated by removing a solvent on 70 degreeC or less heating conditions using the evaporator. The number average molecular weight Mn of the obtained copolymer (C-6) was 3,500, and the mass average molecular weight Mw was 6,000. In addition, the molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis Example 14]

In a glass flask equipped with a stirring device, a condenser and a thermometer, 16.6 parts by mass of the compound represented by the formula (c1-7) as the compound (c1), and `` NK-ester '' manufactured by Shin-Nakamura Kagaku Co., Ltd. as the (c2) compound. M-90G ", 20.7 parts by mass, 21.5 parts by mass of the compound represented by formula (c3-1-1-1) as the compound (c3), 29.4 parts by mass of n-butyl methacrylate as the compound (c4), and isopropyl alcohol 414 parts by mass was added, and under nitrogen reflux, 0.7 parts by mass of AIBN as a polymerization initiator and 4 parts by mass of lauryl mercaptan as a chain transfer agent were added, and the mixture was refluxed at 75 ° C. for 8 hours to perform copolymerization. A solution containing C-6) was obtained. Then, the copolymer (C-6) was isolated by removing a solvent on 70 degreeC or less heating conditions using the evaporator. The number average molecular weight Mn of the obtained copolymer (C-6) was 4,000, and the mass average molecular weight Mw was 7,000. Moreover, molecular weight distribution (Mw / Mn) was 1.8.

<Preparation of a positive radiation sensitive composition>

Example 1

IRGACURE PAG as a component [B] in the solution (Amount equivalent to 100 mass parts (solid content) of hydrolysis-condensation product (A-1)) containing the polymer (A-1) obtained by the synthesis example 1 as [A] component. 3 parts by mass of 103 (manufactured by Chiba Specialty Chemicals Co., Ltd.) and 0.50 parts by mass of the copolymer (C-1) obtained in Synthesis Example 9 as the [C] component were further mixed as a solvent such that the solid content concentration was 25% by mass. After adding diethylene glycol ethyl methyl ether, the positive radiation sensitive composition (S-1) was prepared by filtering by the membrane filter of 0.2 micrometer of diameters.

[Examples 2 to 12 and Comparative Examples 1 to 5]

A positive radiation sensitive composition was prepared in the same manner as in Example 1 except that the type and amount of each component were as described in Table 1. In addition, the components used by each Example and the comparative example are as follows.

(Mining generator: [B] component)

B-1: Said compound (i) ("IRGACURE PAG 103" by Chiba Specialty Chemicals)

B-2: Said compound (ii) ("IRGACURE PAG 108" by Chiba Specialty Chemicals)

B-3: the said compound (iii) ("CGI 1380" by Chiba Specialty Chemicals)

B-4: the said compound (i ') ("IRGACURE PAG 121" by Chiba Specialty Chemicals)

B-5: the said compound (VII) ("CGI 725" by Chiba Specialty Chemicals)

(Surfactants)

c-1 (comparative example 1): Silicone type surfactant ("SH-193" by Toray Dow Corning Silicone Co., Ltd.)

c-2 (Comparative Example 2): Fluorine-type surfactant ("Fluorad F-430" by 3M Corporation)

(Adhesive Auxiliary: [D] Component)

D-1: γ-glycidoxypropyltrimethoxysilane

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

D-3: γ-methacryloxypropyltrimethoxysilane

(Basic Compound: [E] Component)

E-1: 4-dimethylaminopyridine

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

<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) Appearance Evaluation of Coating Film

On the 550 * 650mm chromium film-forming glass, the radiation sensitive composition prepared as mentioned above was apply | coated using a slit die coater (The Tokyo Ogyo Co., Ltd. make, model "TR632105-CL"), and the arrival pressure was set to 100 Pa. The solvent was removed under vacuum, and then prebaked at 90 ° C. for 2 minutes to form a coating film having a film thickness of 3.0 μm. Under a sodium lamp, the appearance of this coating film was visually observed. At this time, the appearance of the fog was observed in the fog-like stain generated in the entire coating film, and the stain derived from the proxy pin of the prebaking furnace was referred to as "pin stain". In the case where all of these spots were hardly seen, "○ (good)" and the case where some of these spots were slightly seen were evaluated as "(defective)" and the case where it was clearly seen as "x (bad)". The evaluation results are shown in Table 1.

(2) Evaluation of film thickness uniformity (uniformity)

The film thickness of the coating film on the chromium film-forming glass produced as mentioned above was measured using the needle contact measuring device (AS200 by KLA Tencor company). It calculated from the film thickness in nine measuring points as unity. Nine measuring points mean that the short axis direction of the substrate is X and the long axis direction is Y, where (X [mm], Y [mm]) is (275, 20), (275, 30), (275, 60), ( 275, 100), (275, 325), (275, 550), (275, 590), (275, 620), (275, 630).

The formula of the uniformity is represented by the following formula. FT (X, Y) max in the following formula is the maximum value in the film thickness at nine measurement points, FT (X, Y) min is the minimum value in the film thickness at nine measurement points, and FT (X, Y) avg. It is an average value in the film thickness in nine measuring points. When uniformity is 2% or less, it can be judged that film thickness uniformity is favorable. The evaluation results are shown in Table 1.

(Uniformity formula)

Uniformity (%) = {FT (X, Y) max-FT (X, Y) min} × 100 / {2 × FT (X, Y) avg.}

(3) Evaluation of high speed applicability

The coating liquid is applied onto a 550mm × 650mm alkali-free glass substrate using a slit coater, and the coating liquid is applied from the nozzle so that the film thickness after exposure and the thickness of the base and the nozzle are 150 μm and the thickness is 2.5 μm. Was discharged, the moving speed of the nozzle was varied in the range of 120 mm / sec to 220 mm / sec, and the maximum speed at which streaky irregularities due to liquid breakup did not occur was determined. At this time, when the stripe-shaped irregularity does not generate | occur | produce even at the speed of 180 mm / sec or more, it can be judged that correspondence with high speed application is possible. The evaluation results are shown in Table 1.

(4) Evaluation of the radiation sensitivity of the radiation sensitive composition

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, after irradiating radiation to a coating film with a variable exposure amount through the mask which has a 60-micrometer line-and-space (10 to 1) pattern using Canon MPA-600FA exposure machine, It developed by the puddle method at 25 degreeC in the tetramethylammonium hydroxide aqueous solution of the density | concentration shown in Table 1. 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 a 6 micrometer space pattern to melt | dissolve completely was investigated. This value is shown in Table 1 as radiation sensitivity. It can be said that sensitivity is favorable when this value is 500 J / m <2> or less.

(5) Evaluation of heat resistance of interlayer insulating film

In the same manner as in the case of [evaluation of solvent resistance of the interlayer insulating film], a cured film was formed on the chromium film-forming glass. The film thickness (T2) of the cured film obtained here was measured. Subsequently, after further heating the chromium film-formed glass substrate on which the cured film was formed at 240 ° C. for 1 hour in a clean oven, the film thickness t2 of the cured film was measured again, and the film thickness change rate due to further heating was obtained by the following formula. Calculated by When this value is 5% or less, it can be said that heat resistance is favorable. The evaluation results are shown in Table 1.

(Calculation formula of film thickness change rate)

Film thickness change rate (%) = {| t2-T2 | / T2} × 100

(6) Evaluation of the transparency of the interlayer insulating film

A glass substrate of 550 × 650 mm (“NA35” manufactured by NH Techno Glass Co., Ltd.) was used in place of the chromium film-forming glass substrate. A cured film was formed. The light transmittance of the glass substrate which has a cured film formed using the spectrophotometer "150-20 type double beam (made by Hitachi Seisakusho)" is made into 400-800 nm of the glass substrate which does not have a cured film as a reference side. It measured by the wavelength of the range. Table 1 shows the values of the minimum light transmittance at that time. When this value is 90% or more, it can be said that transparency is favorable.

As is clear from the results in Table 1, the positive radiation-sensitive compositions of Examples 1 to 12 containing the components [A], [B] and [C] do not contain the components [C]. Compared with the positive radiation sensitive composition of 3, it turns out that it is remarkably excellent also in the application | coating nonuniformity in the external appearance of a coating film, and the point of the flatness of an interlayer insulation film in high speed application | coating. Moreover, it turns out that the positive radiation sensitive composition of these Examples can form the interlayer insulation film which has high radiation sensitivity and fully satisfies the general required characteristic of heat resistance and transparency.

As described above, the positive radiation-sensitive composition of the present invention can be formed at high speed, has a high radiation sensitivity, and can form a cured film having excellent flatness in addition to sufficient heat resistance and transparency. Therefore, the said positive radiation sensitive composition is used suitably in order to form the interlayer insulation film for display elements.

Claims (10)

[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] Copolymer having a structural unit having a fluorine and a structural unit having a silicon
Positive radiation sensitive composition containing:

(In formula (1), R <^1> and R <^2> is respectively independently a hydrogen atom, an alkyl group, a cycloalkyl, or an aryl group, and even if one part or all part of the hydrogen atom of these alkyl groups, a cycloalkyl group, or an aryl group is 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; R ¹ and R ³ may be linked to form a cyclic ether). The method of claim 1,
[C] the copolymer is,
(c1) the polymeric compound represented by following formula (2),
(c2) a polymeric compound represented by the following formula (3), and
(c3) Positive radiation sensitive composition which is a copolymer which has a structural unit derived from the polymeric compound which has group represented by following formula (4) at least:

(In formula (2), R ⁴ is a hydrogen atom or a methyl group; α is an integer of 0 to 6; β is an integer of 1 to 20);

(In formula (3), R ⁵ is a hydrogen atom or a methyl group; R ⁶ is an alkyl group having 1 to 12 carbon atoms; γ is 2 or 3; a is the number of structural units and the number average is 1 to 30.) ;

(In formula (4), R <^7> , R <^8> , R <^9> , R <^10> and R <^11> are respectively independently group represented by a C1-C20 alkyl group, a phenyl group, or following formula (5); b is 0- An integer of 3);

(In formula (5), R <^12> , R <^13> and R <^14> is respectively independently a C1-C20 alkyl group or a phenyl group; c is an integer of 0-3.). The method of claim 2,
[C] The positive radiation-sensitive composition in which the copolymer further has (c4) a structural unit derived from the polymeric compound which has a C1-C8 unsubstituted alkylester group. The method of claim 3,
[C] The positive radiation-sensitive composition in which the copolymer further has a structural unit derived from the polymerizable compound which has a 2 or more unsaturated bond in 1 molecule (c5). The method of claim 4, wherein
A compound (c1) is a polymeric compound represented by following formula (6), and a compound (c2) is a polymeric compound represented by following formula (7),
The copolymer (C) is based on the total amount of the polymerizable compounds (c1) to (c5),
25-35 mass% of polymeric compounds (c1),
20-30 mass% of polymeric compounds (c2),
15-20 mass% of polymeric compounds (c3),
25-35 mass% of polymeric compounds (c4),
1-5 mass% of polymeric compounds (c5)
A positive radiation sensitive composition comprising a composition comprising:

(In formula (6), R ⁴ has the same meaning as in formula (2); β is an integer of 1 to 8);

(In formula (7), R <^5> and R <^6> is synonymous with the thing in said Formula (3), respectively; the number average value of a structural unit number (a) is 4-12.). The method according to any one of claims 1 to 5,
(D) Positive radiation sensitive composition which further contains an adhesion | attachment adjuvant. The method according to any one of claims 1 to 5,
[E] A positive radiation sensitive composition further containing a basic compound. The method according to any one of claims 1 to 5,
Positive type radiation sensitive composition used for forming the interlayer insulation film for display elements. (1) forming the coating film of the positive radiation sensitive composition of Claim 8 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)
Method of forming an interlayer insulating film for a display element comprising a. The interlayer insulation film for display elements formed from the positive radiation sensitive composition of Claim 8.