JP4591625B1 - Positive radiation-sensitive composition, interlayer insulating film and method for forming the same - Google Patents

Abstract

【選択図】なしIt is possible to form an interlayer insulating film having high flatness (film thickness uniformity) without application unevenness in addition to excellent heat resistance and transparency, and can be applied at high speed, and high radiation. An object is to provide a positive radiation-sensitive composition having sensitivity.
The present invention relates to [A] a polymer having a structural unit containing a group represented by the following formula (1) and an epoxy group-containing structural unit in the same or different polymer molecules, and [B] a photoacid. Generator, [C] (c1) a polymerizable compound represented by the following formula (2), (c2) a polymerizable compound represented by the following formula (3), and (c3) represented by the following formula (4) It is a positive radiation sensitive composition containing a copolymer having at least a structural unit derived from a polymerizable compound having a group.

[Selection figure] None

Description

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

  The display element is generally provided with an interlayer insulating film for the purpose of insulating between wirings arranged in layers. As the material for forming the interlayer insulating film, positive radiation-sensitive compositions are widely used because the number of steps for obtaining a necessary pattern shape is small and a material having sufficient flatness is preferable. The positive radiation sensitive composition used in forming such an interlayer insulating film is required to have good radiation sensitivity and storage stability, and the obtained interlayer insulating film is required to have excellent heat resistance and transparency. .

  As a component of the positive radiation sensitive composition, an acrylic resin is widely employed. For example, in JP-A-2004-4669, a crosslinking agent, an acid generator, and itself are insoluble in an alkaline aqueous solution or A positive chemically amplified resist composition comprising a resin which is hardly soluble but has a protecting group which can be cleaved by the action of an acid, and which is soluble in an alkaline aqueous solution after cleaving the protecting group Things have been proposed. However, the insulating film obtained from this composition does not have sufficient adhesion and is not satisfactory for producing a high-quality liquid crystal display element. JP 2004-264623 A proposes a radiation-sensitive resin composition comprising an acetal structure and / or a ketal structure and a resin containing an epoxy group and an acid generator. The radiation sensitivity is low and not satisfactory.

  On the other hand, with the recent widespread use of large-screen televisions, the size of the glass substrate used for the production is also increasing. For this reason, it has become difficult to apply a radiation-sensitive composition to a large substrate by the spin coating method conventionally employed in the interlayer insulating film forming step. Therefore, instead of such a spin coating method, a slit coating method in which a radiation-sensitive composition is ejected from a slit-like nozzle and applied onto a glass substrate has been adopted.

  In the slit coating method, specifically, after the substrate is brought into close contact with the coating stage by vacuum suction, the coating nozzle is swept in a certain direction to form a coating film on the substrate. As the support pins stored in the holes are raised, the substrate is lifted from the coating stage and transferred to the next step. Such a slit coating method can reduce the amount of the radiation-sensitive composition required for coating compared to the spin coating method, and can be applied by sweeping in a certain direction while discharging the radiation-sensitive composition. For this reason, the coating time can be shortened, and the manufacturing cost of the display element can be reduced.

  However, in this series of processes, uneven coating may occur during coating, or unevenness may occur in the coating film due to minute irregularities caused by holes for vacuum adsorption. This is an obstacle to achieving the required high level of flatness.

  Under such circumstances, it is possible to form a cured film having excellent heat resistance and transparency generally required as an interlayer insulating film, and having high flatness (film thickness uniformity) without coating unevenness. There is a strong demand for the development of positive-type radiation-sensitive compositions that can be applied at high speed and have high radiation sensitivity.

JP 2004-4669 A JP 2004-264623 A

  The present invention has been made based on the circumstances as described above, and its purpose is interlayer insulation having high flatness (film thickness uniformity) without coating unevenness in addition to excellent heat resistance and transparency. A positive-type radiation-sensitive composition capable of forming a film and capable of being applied at high speed and having high radiation sensitivity, an interlayer insulating film formed from the composition, and a method for forming the interlayer insulating film Is to provide.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立して、水素原子、アルキル基、シクロアルキル基又はアリール基であり、これらのアルキル基、シクロアルキル基又はアリール基の水素原子の一部又は全部が置換基で置換されていてもよい（但し、Ｒ^１及びＲ^２が共に水素原子である場合はない）。Ｒ^３は、アルキル基、シクロアルキル基、アラルキル基、アリール基又は−Ｍ（Ｒ^３ｍ）_３で表される基（ＭはＳｉ、Ｇｅ又はＳｎであり、Ｒ^３ｍはアルキル基である。）であり、これらの水素原子の一部又は全部が置換基で置換されていてもよい。Ｒ^１とＲ^３とが連結して環状エーテルを形成してもよい。）

（式（２）中、Ｒ^４は水素原子又はメチル基である。αは０〜６の整数である。βは１〜２０の整数である。）

（式（３）中、Ｒ^５は水素原子又はメチル基である。Ｒ^６は炭素数１〜１２のアルキル基である。γは２又は３である。ａは構造単位数であり、その数平均値が１〜３０である。）

（式（４）中、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０及びＲ^１１は、それぞれ独立して、炭素数１〜２０のアルキル基、フェニル基、又は下記式（５）で表される基である。ｂは０〜３の整数である。）

（式（５）中、Ｒ^１２、Ｒ^１３及びＲ^１４は、それぞれ独立して、炭素数１〜２０のアルキル基又はフェニル基である。ｃは０〜３の整数である。） The invention made to solve the above problems is
[A] a polymer having a structural unit containing a group represented by the following formula (1) and an epoxy group-containing structural unit in the same or different polymer molecules;
[B] a photoacid generator, and [C] (c1) a polymerizable compound represented by the following formula (2),
(C2) a positive compound containing a polymerizable compound represented by the following formula (3), and (c3) a copolymer having at least a structural unit derived from the polymerizable compound having a group represented by the following formula (4) Type radiation sensitive composition.

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and one of the hydrogen atoms of these alkyl group, cycloalkyl group, or aryl group) Part or all may be substituted with a substituent (provided that R ¹ and R ² are not both hydrogen atoms) R ³ represents 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, R ^3m is an alkyl group), and some or all of these hydrogen atoms are substituted with substituents; R ¹ and R ³ may be linked to form a cyclic ether.)

(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 thereof. The average value is 1-30.)

(In Formula (4), R < ⁷ >, R < ⁸ >, R <^9> , R < ¹⁰ > and R < ¹¹ > are each independently represented by a C1-C20 alkyl group, a phenyl group, or the following formula (5). And b is an integer of 0 to 3.)

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

  The positive radiation sensitive composition includes a [C] copolymer formed from a polymerizable compound having a specific structure in addition to the [A] polymer and [B] photoacid generator having the specific structure. By functioning as a surfactant with high surface tension reduction performance, it satisfies the general requirements of heat resistance and transparency in a well-balanced manner, and has a high level of flatness (film thickness uniformity) without coating unevenness. It is possible to form a film. The positive radiation sensitive composition can be applied at high speed and has excellent radiation sensitivity.

  In the positive radiation-sensitive composition, the [C] copolymer preferably further includes (c4) a structural unit derived from a polymerizable compound having an unsubstituted alkyl ester group having 1 to 8 carbon atoms. Thereby, the affinity of the [C] copolymer for other components and solvents can be improved, and the film thickness uniformity of the obtained interlayer insulating layer can be further increased.

  In the positive radiation sensitive composition, the [C] copolymer preferably further has (c5) a structural unit derived from a polymerizable compound having two or more unsaturated bonds in one molecule. Thereby, the strength can be increased together with the film thickness uniformity of the obtained interlayer insulating film, and general characteristics such as heat resistance can also be improved.

（式（６）中、Ｒ^４は上記式（２）におけるのと同義である。βは１〜８の整数である。）

（式（７）中、Ｒ^５及びＲ^６は、それぞれ上記式（３）におけるのと同義である。構造単位数ａの数平均値は４〜１２である。） In the positive radiation sensitive composition, the compound (c1) is a polymerizable compound represented by the following formula (6), and the compound (c2) is a polymerizable compound represented by the following formula (7).
[C] The copolymer is based on the total amount of the polymerizable compounds (c1) to (c5).
Polymerizable compound (c1) 25-35% by mass,
Polymerizable compound (c2) 20-30% by mass,
Polymerizable compound (c3) 15-20% by mass,
Polymerizable compound (c4) 25-35 mass%, and Polymerizable compound (c5) 1-5 mass%
It is preferable to consist of a composition containing.

(In Formula (6), R ⁴ has the same meaning as in Formula (2) above. Β is an integer of 1 to 8.)

(In the formula (7), ^{R 5} and ^{R 6} are each the same definition as in the formula (3). The number average value of the structural unit number a is 4-12.)

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

  The positive radiation sensitive composition preferably further contains [D] an adhesion assistant. By using such an adhesion assistant, it is possible to further improve the adhesion of the obtained cured film to the substrate.

  The positive radiation-sensitive composition preferably further contains an [E] basic compound. Thereby, the diffusion of the acid generated from the photoacid generator is appropriately controlled, and the pattern developability of the positive radiation sensitive composition can be enhanced.

Moreover, the method for forming an interlayer insulating film for a display element of the present invention includes:
(1) The process of forming the coating film of the said positive type radiation sensitive composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) a step of developing the coating film irradiated with radiation in step (2), and (4) a step of heating the coating film developed in step (3).

  In this method, the positive-type radiation-sensitive composition that can be applied at high speed and has excellent radiation sensitivity is used, and a pattern is formed by exposure, development, and heating using radiation sensitivity. Thus, an interlayer insulating film for a display element having a fine and elaborate pattern can be easily formed. Furthermore, the interlayer insulating film formed in this way is excellent in general required characteristics, that is, heat resistance and transparency in a well-balanced manner, and has high flatness without application unevenness.

  In the present specification, the “polymer” of the component [A] has the structural unit (1) in one polymer molecule and contains an epoxy group in a polymer molecule different from the one polymer molecule. It is a concept including the case of having a structural unit.

  As described above, the positive radiation-sensitive composition of the present invention includes the above-mentioned [A], [B], and [C] components, thereby providing general required characteristics such as heat resistance and transparency. It is possible to form an interlayer insulating film satisfying a good balance and having high flatness without coating unevenness. In addition, the positive radiation sensitive composition can be applied at high speed and exhibits excellent radiation sensitivity.

  The positive-type radiation-sensitive composition of the present invention includes a structural unit containing a group represented by the following formula (1) in the same or different polymer molecule (hereinafter also simply referred to as “structural unit (1)”). It is formed from a polymer having an epoxy group-containing structural unit (hereinafter also simply referred to as “polymer [A]”), [B] a photoacid generator, and [C] a polymerizable compound having a specific structure. It contains a copolymer (hereinafter also referred to simply as “copolymer [C]”), and may contain other optional components.

<Polymer [A]>
The polymer [A] has the structural unit (1) and the epoxy group-containing structural unit in the same or different polymer molecules, and may have other structural units as necessary. The embodiment of the polymer [A] having the structural unit (1) and the epoxy group-containing structural unit is not particularly limited, and (i) both the structural unit (1) and the epoxy group-containing structural unit in the same polymer molecule. In the case where one polymer molecule is present in the polymer [A], (ii) in one polymer molecule, the structural unit (1) is present in a different polymer molecule. When the polymer [A] has two polymer molecules in the polymer [A], (iii) the structural unit (1) and the epoxy group-containing structure in one polymer molecule. Having both of the units, the structural unit (1) in a different polymer molecule, and further having an epoxy group-containing structural unit in a different polymer molecule, the polymer [A] When three polymer molecules are present in (iv) (i) to (iii), The addition to the polymer molecule, etc. When the polymer [A] comprising one or more polymer molecules yet another during the like. In either case, the effects of the present invention can be enjoyed. 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), the group represented by the above formula (1) exists as a group that dissociates in the presence of an acid to generate a polar group (hereinafter, also simply referred to as “acid-dissociable group”). Therefore, the acid-dissociable group is dissociated by the acid generated from the photoacid generator upon irradiation with radiation, and as a result, the polymer [A] that has been alkali-insoluble becomes alkali-soluble. The acid dissociable group has an acetal structure or a ketal structure that is relatively stable with respect to an alkali, and these are dissociated by the action of an acid.

In the above formula (1), the alkyl group represented by R ¹ and R ² is preferably a linear or branched alkyl group having 1 to 30 carbon atoms, and an oxygen atom and a sulfur atom in the alkyl chain. And may have a nitrogen atom. Specific examples of the alkyl group include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, and n-tetradecyl group. A branched alkyl group such as a straight-chain alkyl group such as n-octadecyl group, i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group, 3-hexyl group Can do.

In the above formula (1), the cycloalkyl group represented by R ¹ and R ² is preferably a cycloalkyl group having 3 to 20 carbon atoms, may be polycyclic, and has an oxygen atom in the ring. Also good. Specific examples of the cycloalkyl group include cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl, cyclooctyl, bornyl group, norbornyl group, adamantyl group and the like.

In the above formula (1), the aryl group represented by R ¹ and R ² is preferably an aryl group having 6 to 14 carbon atoms, which may be a single ring or a structure in which single rings are connected, It may be a condensed ring. Specific examples of the aryl group include a phenyl group and a naphthyl group.

Some or all of the hydrogen atoms of R ¹ and R ² may be substituted with a substituent. As such a substituent, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (for this cycloalkyl group, the description of the cycloalkyl group can be preferably applied. ), An aryl group (as the aryl group, the description of the aryl group can be preferably applied), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, ethoxy Group, propoxy group, n-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, etc.), acyl group (preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl Group, propionyl group, butyryl group, i-butyryl group, etc.), acyloxy group (preferably An acyloxy group having 2 to 10 carbon atoms, for example, an acetoxy group, an ethylyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, etc.), an alkoxycarbonyl group (preferably having a carbon number of 2 to 20). An alkoxycarbonyl group, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, etc.), a haloalkyl group (a part or all of the hydrogen atoms of the alkyl group or cycloalkyl group are substituted with halogen atoms). And examples thereof include a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a fluorocyclopropyl group, and a fluorocyclobutyl group. As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the further substituent include the above alkyl groups.

In the above formula (1), the description of R ¹ and R ² can be applied to the alkyl group, cycloalkyl group and aryl group represented by R ³ . In the above formula (1), the aralkyl group represented by R ³ is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group. . The group represented by ^{-M (R} _{3m) 3} of ^{R 3} in the above formula (1), for example trimethylsilanyl group, trimethylgermyl group and the like. As the substituent which may substitute part or all of the hydrogen atoms of the aralkyl group represented by R ³ or the group represented by —M (R ^3m ) ₃ , the above substituents are preferably employed. be able to.

R ¹ and R ³ may be linked to form a cyclic ether. Examples of such cyclic ethers include 2-oxetanyl group, 2-tetrahydrofuranyl group, 2-tetrahydropyranyl group, 2-dioxanyl group and the like. Part or all of the hydrogen atoms of this cyclic ether may be substituted with the above substituents.

  The structural unit (1) can have an acetal structure or a ketal structure by having a functional group that should have an acetal structure or a ketal structure by bonding to another carbon atom.

  Examples of the functional group that should have an acetal structure by bonding to the other carbon atom include 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-i-propoxyethoxy. Group, 1-n-butoxyethoxy group, 1-i-butoxyethoxy group, 1-sec-butoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclopentyloxyethoxy group, 1-cyclohexyloxyethoxy group, 1- Norbornyloxyethoxy group, 1-bornyloxyethoxy group, 1-phenyloxyethoxy group, 1- (1-naphthyloxy) ethoxy group, 1-benzyloxyethoxy group, 1-phenethyloxyethoxy group, (cyclohexyl) (Methoxy) methoxy group, (cyclohexyl) (ethoxy) methoxy group (Cyclohexyl) (n-propoxy) methoxy group, (cyclohexyl) (i-propoxy) methoxy group, (cyclohexyl) (cyclohexyloxy) methoxy group, (cyclohexyl) (phenoxy) methoxy group, (cyclohexyl) (benzyloxy) methoxy group , (Phenyl) (methoxy) methoxy group, (phenyl) (ethoxy) methoxy group, (phenyl) (n-propoxy) methoxy group, (phenyl) (i-propoxy) methoxy group, (phenyl) (cyclohexyloxy) methoxy group , (Phenyl) (phenoxy) methoxy group, (phenyl) (benzyloxy) methoxy group, (benzyl) (methoxy) methoxy group, (benzyl) (ethoxy) methoxy group, (benzyl) (n-propoxy) methoxy group, Benzyl) (i-propo Ii) methoxy group, (benzyl) (cyclohexyloxy) methoxy group, (benzyl) (phenoxy) methoxy group, (benzyl) (benzyloxy) methoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group, 1 -A trimethylsilanyloxyethoxy group, a 1-trimethylgermyloxyethoxy group, etc. can be mentioned.

  Among these, 1-ethoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydropyranyloxy group, 1-n-propoxyethoxy group, and 2-tetrahydropyranyloxy group can be mentioned as preferable examples.

  Examples of the functional group that should have a ketal structure by bonding to the other carbon atom include 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-cyclohexyloxyethoxy group, 1-methyl-1-norbornyloxy Ethoxy group, 1-methyl-1-bornyloxyethoxy group, 1-methyl-1-phenyloxyethoxy group, 1-methyl-1- (1-na Tiloxy) ethoxy group, 1-methyl-1-benzyloxyoxyethoxy 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-cyclohexyloxyethoxy group, 1-cyclohexyl-1-phenoxyethoxy group, 1-cyclohexyl-1-benzyl Oxyethoxy group, 1-phenyl-1-methoxyethoxy group, 1-phenyl-1-ethoxyethoxy group, 1-phenyl-1-n-propoxyethoxy group, 1-phenyl-1-i-propoxyethoxy group, Phenyl-1-cyclohexyloxyethoxy group 1-phenyl-1-phenyloxyethoxy group, 1-phenyl-1-benzyloxyethoxy group, 1-benzyl-1-methoxyethoxy group, 1-benzyl-1-ethoxyethoxy group, 1-benzyl-1-n- Propoxyethoxy group, 1-benzyl-1-i-propoxyethoxy group, 1-benzyl-1-cyclohexyloxyethoxy group, 1-benzyl-1-phenyloxyethoxy group, 1-benzyl-1-benzyloxyethoxy group, 2 -(2-Methyl-tetrahydrofuranyl) oxy group, 2- (2-methyl-tetrahydropyranyl) oxy group, 1-methoxy-cyclopentyloxy group, 1-methoxy-cyclohexyloxy group and the like can be mentioned.

  Among these, 1-methyl-1-methoxyethoxy group and 1-methyl-1-cyclohexyloxyethoxy group can be mentioned as preferable ones.

  Specific examples of the structural unit (1) having the acetal structure or ketal structure include structural units represented by the following formulas (1-1) to (1-3).

（式（１−１）及び（１−３）中、Ｒ´は水素原子又はメチル基である。Ｒ^１、Ｒ^２及びＲ^３は上記式（１）の説明と同義である。）

(In formulas (1-1) and (1-3), R ′ is a hydrogen atom or a methyl group. R ¹ , R ^2, and R ³ have the same meanings as those in formula (1) above.)

As a monomer having radical polymerizability that gives the structural unit (1) represented by the above formulas (1-1) to (1-3) (hereinafter also simply referred to as “acetal structure-containing monomer”). For example, 1-alkoxyalkyl (meth) acrylate, 1- (cycloalkyloxy) alkyl (meth) acrylate, 1- (haloalkoxy) alkyl (meth) acrylate, 1- (aralkyloxy) alkyl (meth) acrylate, tetrahydropyrani (Meth) acrylate-based acetal structure-containing monomers such as ru (meth) acrylate;
2,3-di (1- (trialkylsilanyloxy) alkoxy) carbonyl) -5-norbornene, 2,3-di (1- (trialkylgermyloxy) alkoxy) carbonyl) -5-norbornene, 2, 3-di (1-alkoxyalkoxycarbonyl) -5-norbornene, 2,3-di (1- (cycloalkyloxy) alkoxycarbonyl) -5-norbornene, 2,3-di (1- (aralkyloxy) alkoxycarbonyl ) Norbornene-based acetal structure-containing monomers such as -5-norbornene;
Examples thereof include styrene acetal structure-containing monomers such as 1-alkoxyalkoxystyrene, 1- (haloalkoxy) alkoxystyrene, 1- (aralkyloxy) alkoxystyrene, and tetrahydropyranyloxystyrene.

  Among these, 1-alkoxyalkyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 1-alkoxyalkoxystyrene, and tetrahydropyranyloxystyrene are preferable, and 1-alkoxyalkyl (meth) acrylate is more preferable.

Specific examples of the acetal structure-containing monomer that gives the structural unit (1) include, 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-chloroethoxy) ethyl acrylate, 1- (2 -Ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl acrylate, 1- (2-cyclohexylethoxy) ethyl acrylate, 1-benzyloxyethyl acrylate, 2-tetrahydropyranyl acrylate,
2,3-di (1- (trimethylsilanyloxy) ethoxy) carbonyl) -5-norbornene, 2,3-di (1- (trimethylgermyloxy) ethoxy) carbonyl) -5-norbornene, 2,3- Di (1-methoxyethoxycarbonyl) -5-norbornene, 2,3-di (1- (cyclohexyloxy) ethoxycarbonyl) -5-norbornene, 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-propoxyethoxy Examples include styrene, p or m-1-cyclohexyloxyethoxystyrene, p or m-1- (2-cyclohexylethoxy) ethoxystyrene, p or m-1-benzyloxyethoxystyrene. The said structural unit (1) can be used 1 type or in combination of 2 or more types.

  Among the acetal structure-containing monomers that give the structural unit (1), 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, and 1-benzyloxyethyl methacrylate are preferable.

  A commercially available thing may be used for the acetal structure containing monomer which gives structural unit (1), and what was synthesize | combined by the well-known method can also be used. For example, the acetal structure-containing monomer that gives the structural unit (1) represented by the above formula (1-1) reacts (meth) acrylic acid with vinyl ether in the presence of an acid catalyst as shown below. Can be synthesized.

（式中、Ｒ´、Ｒ^１及びＲ^３は、それぞれ上記式（１−１）におけるＲ´、Ｒ^１及びＲ^３に対応し、Ｒ^２１及びＲ^２２は、−ＣＨ（Ｒ^２１）（Ｒ^２２）として、上記式（１−１）におけるＲ^２に対応する。）

(In the formula, R ′, R ¹ and R ³ respectively correspond to R ′, R ¹ and R ³ in the above formula (1-1), and R ²¹ and R ²² represent —CH (R ²¹ ) (R ²² ) corresponds to R ² in the above 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 with an acid and exhibits the desired heat resistance of the cured film. When the polymer molecule contains both the structural unit (1) and the epoxy group-containing structural unit, the monomer charge ratio is 5% by mass or more and 70% by mass or less with respect to all the structural units contained in the polymer [A]. Is preferably 10% by mass or more and 60% by mass or less, and particularly preferably 20% by mass or more and 50% by mass or less.

  On the other hand, when one polymer molecule has the structural unit (1) and the polymer molecule different from this has an epoxy group-containing structural unit, the structure in the one polymer molecule having the structural unit (1) The content of the unit (1) is preferably 40% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 98% by mass or less, based on the monomer charge ratio with respect to all the structural units contained in the polymer molecule. Is more preferable, and 55 mass% or more and 95 mass% or less are especially preferable.

<Epoxy group-containing structural unit>
The polymer [A] has an epoxy group-containing structural unit together with the structural unit (1). The epoxy group-containing structural unit is a structural unit derived from an epoxy group-containing monomer having radical polymerizability. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure). When the polymer [A] has a structural unit containing an oxiranyl group or an oxetanyl group in the molecule, the hardness of the cured film obtained from the positive radiation-sensitive composition can be improved to further increase the heat resistance. it can.

Specific examples of the epoxy group-containing monomer that gives the epoxy group-containing structural unit include, for example, glycidyl acrylate, glycidyl methacrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, and acrylic. Acid-3-methyl-3,4-epoxybutyl, methacrylate-3-ethyl-3,4-epoxybutyl, acrylic acid-5,6-epoxyhexyl, methacrylic acid-5,6-epoxyhexyl, methacrylic 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-epoxycyclohex Xylbutyl methacrylate, 3,4-epoxycyclohexylhexyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylethyl acrylate, 3,4 -Oxylanyl group-containing (meth) acrylic compounds such as epoxycyclohexylpropyl acrylate, 3,4-epoxycyclohexylbutyl acrylate, 3,4-epoxycyclohexylhexyl acrylate;

o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl Vinyl benzyl glycidyl ethers such as benzyl glycidyl ether;
vinyl phenyl glycidyl ethers such as o-vinyl phenyl glycidyl ether, m-vinyl phenyl glycidyl ether, p-vinyl phenyl glycidyl ether;

  3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -3-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -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-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -3 -Phenyloxetane,

  2- (acryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) -2-methyloxetane, 2- (acryloyloxymethyl) -2-ethyloxetane, 2- (acryloyloxymethyl) -2-phenyloxetane, 2- (2-acryloyloxyethyl) oxetane, 2- (2-acryloyloxyethyl) -2-ethyloxetane, 2- (2-acryloyloxyethyl) -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-ethyloxetane, 2- (2-methacryloyloxyethyl) -2-ethyloxetane, 2- (2-methacryloyloxyethyl) -2 An oxetanyl group-containing (meth) acrylic compound such as phenyl oxetane can be used. The said epoxy group containing structural unit can be used individually or in combination of 2 or more types.

  Among the above epoxy group-containing monomers, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3- (methacryloyloxymethyl) -3-Methyloxetane and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable from the viewpoint of copolymerization reactivity with other radical polymerizable monomers and developability of the positive radiation sensitive composition.

  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 the structural unit (1) and the epoxy group are contained in one polymer molecule. When the structural unit is included, the monomer charge ratio is preferably 10% by mass or more and 60% by mass or less, and more preferably 15% by mass or more and 55% by mass or less with respect to all the structural units contained in the polymer [A]. It is preferably 20% by mass or more and 50% by mass or less.

  On the other hand, when one polymer molecule has the structural unit (1) and the other polymer molecule has an epoxy group-containing structural unit, the entire structure contained in the other polymer molecule having the epoxy group-containing structural unit The content of the epoxy group-containing structural unit relative to the unit is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 70% by mass, and more preferably 35% by mass to 65% by mass in terms of monomer charge. The following are particularly preferred:

<Other structural units>
Examples of the radical polymerizable monomer that gives other structural units include a carboxyl group or a derivative thereof, a radical polymerizable monomer having a hydroxyl group, and the like.
Examples of the radical polymer monomer having a carboxyl group or a derivative thereof include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthal Acids, monocarboxylic acids such as 2-methacryloyloxyethyl hexahydrophthalic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
The acid anhydride of the said dicarboxylic acid etc. can be mentioned.

As an example of the radical polymerizable monomer having a hydroxyl group,
Acrylic acid hydroxyalkyl esters such as acrylic acid-2-hydroxyethyl ester, acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, 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-hydroxyhexyl ester, methacrylic acid-4- Mention may be made of methacrylic acid hydroxyalkyl esters such as hydroxymethyl-cyclohexylmethyl ester.

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

Examples of other radical polymerizable monomers include
Alkyl acrylates such as methyl acrylate and i-propyl acrylate;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;
Cyclohexyl acrylate, acrylate-2-methylcyclohexyl, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, acrylate-2- (tricyclo [5.2.1.0 ^{2, 6} ] Acrylic alicyclic alkyl ester such as decan-8-yloxy) ethyl, isobornyl acrylate;
Cyclohexyl methacrylate, 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} ] decane-8-yloxy) ethyl, methacrylic acid alicyclic alkyl ester such as isobornyl methacrylate;
Aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate and aralkyl esters of acrylic acid;
Aryl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate and aralkyl esters of methacrylic acid;
Dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Unsaturated 5-membered ring methacrylates and unsaturated 6-membered ring methacrylates containing one oxygen atom, such as tetrahydrofurfuryl methacrylate, tetrahydrofuryl methacrylate, tetrahydropyran-2-methyl methacrylate;
4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-cyclohexyl- 2 oxygen atoms such as 1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane Unsaturated heterocyclic 5-membered methacrylates containing:

4-acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2, 2-diethyl- 1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-acryloyloxymethyl-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-1,3-dioxola Unsaturated five-membered heterocyclic acrylic acid esters containing oxygen 2 atoms and the like;
Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, 4-isopropenylphenol;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -N-substituted maleimides such as maleimide propionate, N- (9-acridinyl) maleimide;
Conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;
Other unsaturated compounds such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride and vinyl acetate can be mentioned.

Among these other radical polymerizable monomers, styrene, 4-isopropenylphenol, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tetrahydrofurfuryl methacrylate, 1, 3-Butadiene, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenylmaleimide, benzyl methacrylate and the like have the above-mentioned reactive functional groups. It is preferable in terms of copolymerization reactivity with monomers and developability of the positive radiation sensitive composition.

The polystyrene equivalent mass average molecular weight (hereinafter referred to as “Mw”) of the polymer [A] by GPC (gel permeation chromatography) is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ , 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 type radiation sensitive composition can be improved.

Moreover, the number average molecular weight (hereinafter referred to as “Mn”) in terms of polystyrene by GPC (gel permeation chromatography) of the polymer [A] is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ , and more. Preferably it is 5.0 * 10 < ³ > -5.0 * 10 < ⁴ >. By setting Mn of the copolymer within the above range, the curing reactivity at the time of curing the coating film of the positive radiation sensitive composition can be improved.

  Furthermore, the molecular weight distribution “Mw / Mn” of the polymer [A] is preferably 3.0 or less, more preferably 2.6 or less. By making Mw / Mn of the polymer [A] 3.0 or less, the developability of the obtained interlayer insulating film can be improved. The positive-type radiation-sensitive composition containing the polymer [A] can easily form a desired pattern shape without causing a development residue during development.

<Method for Producing Polymer [A]>
The polymer [A] can be produced by radical copolymerization of an acetal structure-containing monomer, an epoxy group-containing monomer, and other monomers that give structural units. When producing the polymer [A] containing both the structural unit (1) and the epoxy group-containing structural unit in the same polymer molecule, a mixture containing at least an acetal structure-containing monomer and an epoxy group-containing monomer May be used for copolymerization. On the other hand, when the polymer [A] having the structural unit (1) in one polymer molecule and the epoxy group-containing structural unit in a different polymer molecule is produced, at least an acetal structure-containing monomer A polymer solution containing the structural unit (1) is obtained by radical polymerization of a polymerizable solution containing, and a polymer solution containing at least an epoxy group-containing monomer is radically polymerized to have an epoxy group-containing structural unit. What is necessary is just to obtain a polymer molecule | numerator and finally to mix both into a polymer [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 monoalkyls. Examples include ether acetate, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, and other esters.

These solvents include
Examples of alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of the ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, and the like;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like;

Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;
As propylene glycol monoalkyl ether propionate, for example, propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like;
Examples of aromatic hydrocarbons include toluene and xylene;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone and the like;

  Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, Methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionic acid Butyl, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate Methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate Propyl acid, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropionic acid Ethyl, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3- Butyl toxipropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxy Examples include esters such as propyl propionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  Of these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and butyl methoxyacetate are preferred, particularly diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate and butyl methoxyacetate are preferred.

As the polymerization initiator used in the polymerization reaction for producing the polymer [A], those generally known as radical polymerization initiators can be used. Examples of radical polymerization initiators include:
2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), Azo compounds such as 2,2′-azobis (methyl 2-methylpropionate);
And organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide.

  When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

In the polymerization reaction for producing the polymer [A], a molecular weight modifier can be used to adjust the molecular weight. Specific examples of molecular weight regulators include
Halogenated hydrocarbons such as chloroform and carbon tetrabromide;
mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thioglycolic acid;
Xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide;
Examples include terpinolene and α-methylstyrene dimer.

<[B] Photoacid generator>
[B] The photoacid generator is a compound that generates an acid upon irradiation with radiation. Here, as the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. By including the polymer [A] having an acid dissociable group and the [B] photoacid generator, the positive radiation sensitive composition can exhibit positive radiation sensitive characteristics. [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 with radiation. [B] The photoacid generator is contained in the positive radiation-sensitive composition in a form as described below, and is a photoacid generator (hereinafter, also simply referred to as “[B] photoacid generator”). Or in the form of a photoacid generating group incorporated as part of the polymer [A] or other polymer, or both forms. [B] The photoacid generator typically includes oxime sulfonate compounds, such as diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, ammonium salt, phosphonium salt, and 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 the above formula (8), R ^B1 is a linear, branched, or cyclic alkyl group that may be substituted, or an aryl group that may be substituted. The alkyl group for R ^B1 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ^B1 includes an alkoxy group having 1 to 10 carbon atoms or an alicyclic group (including a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group, preferably bicycloalkyl. Group) and the like. The aryl group for R ^B1 is preferably an aryl group having 6 to 11 carbon atoms, and more preferably a phenyl group or a naphthyl group. 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.

  The compound containing the oxime sulfonate group represented by the above formula (8) is more preferably an oxime sulfonate compound represented by the following formula (9).

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

  The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X is preferably a chlorine atom or a fluorine atom. m is preferably 0 or 1. In particular, in the above formula (9), a compound in which m is 1, X is a methyl group, and the substitution position of X is ortho is preferable.

  Specific examples of the oxime sulfonate compound include, for example, compound (i), compound (ii), compound (iii), compound (iv) and compound (v) represented by the following formulas (i) to (v), respectively. Is mentioned.

  These can be used individually or in combination of 2 or more types, and can also be used in combination with other photoacid generators as the [B] component. The said compounds (i)-(v) can be obtained as a commercial item.

<Onium salt>
Among the above onium salts, examples of diphenyliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p -Toluenesulfonate, diphenyliodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butyl) Phenyl) iodonium hexafluoroarsenate, bis (4-t-butylphenyl) iodo Um trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate, bis (4-tert-butylphenyl) iodonium camphorsulfonic acid Etc.

  Examples of triphenylsulfonium salts include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenyl Examples include sulfonium butyl tris (2,6-difluorophenyl) borate.

  Examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts and the like.

As these sulfonium salts,
Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- ( Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate, etc .;
Examples of benzylsulfonium salts include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, and benzyl-4-methoxyphenylmethyl. Sulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethyl Sulfonium hexafluorophosphate, etc .;
Examples of dibenzylsulfonium salts include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexa Fluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-4 -Hydroxyphenylsulfonium hexafluorophosphate and the like;
Examples of substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenylmethylsulfonium. Hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro Examples include -4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Examples of benzothiazonium salts include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxy Benzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

  Examples of tetrahydrothiophenium salts include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 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) tetrahydro Ofenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl) -1,1,2,2-tetrafluoroethanesulfonate, 1- (4,7-dibutoxy-1 -Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate and the like.

  Among these onium salts, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophenium from the viewpoint of improving the radiation sensitivity of the positive-type radiation-sensitive composition and the adhesion of the resulting cured product. Salts and sulfonimide compounds are preferably used. Among these, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium Hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexa Fluorophosphate, 1- (4-n-butoxynaphtha Down-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate are preferred.

<Sulfonimide compound>
Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide (trade name “SI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) succinimide (trade name “SI-”). 106 "(manufactured by Midori Chemical Co., Ltd.)), N- (4-methylphenylsulfonyloxy) succinimide (trade name" SI-101 "(manufactured by Midori Chemical Co., Ltd.)), N- (2-trifluoromethylphenyl) Sulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide N- (2-fluoropheny Sulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide (trade name “PI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy ) Diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyl) Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (trade name “NDI-100” (manufactured by Midori Chemical Co., Ltd.)), N- (4-methylphenylsulfonyloxy) ) Bishik [2.2.1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-101” (manufactured by Midori Chemical Co., Ltd.)), N- (trifluoromethanesulfonyloxy) bicyclo [2. 2.1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (nonafluorobutanesulfonyloxy) bicyclo [2.2. 1] Hept-5-ene-2,3-dicarboxylimide (trade name “NDI-109” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) bicyclo [2.2.1] hept- 5-ene-2,3-dicarboxylimide (trade name “NDI-106” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 5- Ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4- Methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept -5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- ( 2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4- (Luorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- ( Camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5 6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane- , 6-oxy-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- ( Trifluoromethylsulfonyloxy) naphthyl dicarboximide (trade name “NAI-105” (manufactured by Midori Chemical Co., Ltd.)), N- (camphorsulfonyloxy) naphthyl dicarboxyimide (trade name “NAI-106” (Midori Chemical) N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-101” (manufactured by Midori Chemical Co., Ltd.)), N- (phenylsulfonyloxy) naphthyl dicarboxylimide (Trade name “NAI-100” (manufactured by Midori Chemical Co., Ltd.)), N- (2-trifluoromethylphenol) Nylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxyl Imido, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-109” (manufactured by Midori Chemical Co., Ltd.)), N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-1004” (manufactured by Midori Chemical Co., Ltd.)), N- (pentylsulfonyloxy) na Tildicarboxylimide, N- (hexylsulfonyloxy) naphthyldicarboxylimide, N- (heptylsulfonyloxy) naphthyldicarboxylimide, N- (octylsulfonyloxy) naphthyldicarboxylimide, N- (nonylsulfonyloxy) naphthyldi Examples include carboxyl imide

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

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

As these mother cores,
Examples of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone;
Examples of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3, 4,2′-tetrahydroxy-4′-methylbenzophenone, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone, etc .;
Examples of pentahydroxybenzophenone include 2,3,4,2 ′, 6′-pentahydroxybenzophenone and the like;
Examples of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone and the like;

  Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p-hydroxyphenyl). ) Ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4) -Hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl- 4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiin Down -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', 4'-trihydroxy flavan like;

  As other 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 and 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.

  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.

  The 1,2-naphthoquinone diazide sulfonic acid halide is preferably 1,2-naphthoquinone diazide sulfonic acid chloride. 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 particularly preferable to use 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

  Preferable examples of the condensate of a phenolic compound or alcoholic compound and 1,2-naphthoquinonediazide sulfonic acid halide include 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinonediazide-5. -Condensate with sulfonic acid chloride, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5 A condensate with sulfonic acid chloride is mentioned.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazide sulfonic acid halide, preferably 30 to 85 mol% based on the number of OH groups in the phenolic compound or alcoholic compound. More preferably, 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide- 4-sulfonic acid amide and the like are also preferably used. These [B] components can be used individually or in combination of 2 or more types.

  The content of [B] photoacid generator in the positive radiation sensitive composition is preferably 1 to 20 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polymer [A]. 10 parts by mass. When the content of the component [B] is in the above range, the difference in solubility between the irradiated portion and the unirradiated portion in the alkaline aqueous solution serving as the developer is large, the patterning performance is improved, and the obtained interlayer insulating film The solvent resistance is also improved.

<Copolymer [C]>
The copolymer [C] is a copolymer having at least a structural unit derived from the polymerizable compound (c1), the polymerizable compound (c2), and the polymerizable compound (c3) having the specific structure. In the positive radiation sensitive composition, the copolymer [C] functions as a surfactant having a high surface tension reducing performance, and even when used in a small proportion, the copolymer [C] Flatness can be remarkably improved.

  In the positive radiation-sensitive composition, the copolymer [C] further comprises (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 above), and (c5) a polymerizable unsaturated compound having two or more unsaturated bonds in one molecule (hereinafter simply referred to as “polymerizable compound (c5)”. It is more preferable to have a structural unit derived from the above-mentioned polymerizable compound (c1), polymerizable compound (c2), polymerizable compound (c3), polymerizable compound (c4), and polymerizable. It is preferable to consist of a composition containing a compound (c5).

The group —C _α H _2α — in the above formula (2) is a methylene group or an alkylmethylene group, or a linear or branched alkylene group. When the group -C [ _alpha] H2 [ _{alpha] -is} asymmetrical, the direction of the bond is not limited. The carbon number α of the group —C _α H _2α — is preferably 2-4. Specific examples of the group —C _α H _2α — include, for example, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, and the like. Of these, a 1,2-ethylene group or a 1,3-propylene group is preferable, and a 1,2-ethylene group is particularly preferable.

The group —C _β F _{2β + 1} in the above 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, Most preferably, it is 2-8. The group —C _β F _{2β + 1} is preferably a linear fluoroalkyl group.

  The polymerizable compound (c1) in the present invention is preferably a compound represented by the above formula (6). Specific examples of the compound (c1) include compounds represented by the following formulas (c1-1) and (c1-8).

The formula (3) group -C in _gamma H _{2 [gamma} - is a linear or branched alkylene group. When the group -C [ _gamma] H2 [ _{gamma] -is} asymmetrical, the direction of the bond is not limited. Specific examples of the group —C _γ H _2γ — include a 1,2-ethylene group and a 1,2-propylene group, and a 1,2-ethylene group is preferable.

  The compound (c2) is used as a mixture of compounds having different values of the repeating unit number a in the above formula (3). The number average value of a is 1 to 30, preferably 2 to 20, and particularly preferably 4 to 12. In the compound (c2), when γ is 2, (meth) acrylic acid is reacted with ethylene oxide, and when γ is 3, (meth) acrylic acid is reacted with propylene oxide. At this time, the value of a varies depending on the number of moles of ethylene oxide or propylene oxide introduced per mole of (meth) acrylic acid. The value of a is the number average molecular weight in terms of polystyrene measured by gel permeation chromatography for compound (c2), and is the mole of ethylene oxide or propylene oxide charged per 1 mole of (meth) acrylic acid. It can be determined by calculating a value that is the number average molecular weight determined above from the number.

  As the compound (c2), a commercially available product can be suitably used. Examples of such commercially available products include NK-ester M-40G, NK-ester M-90G, AM-90G manufactured by Shin-Nakamura Chemical Co., Ltd .; Bremer PME-200, PME manufactured by NOF Corporation. -400, PME-550 and the like.

In the compound (c3), when a plurality of R ⁸ and R ⁹ are present in the formula (4), each R ⁸ may be the same or different, and each R ⁹ may be the same. May be different. In the above formula (5), when a plurality of R ¹³ and R ¹⁴ are present, each R ¹³ may be the same or different, and each R ¹⁴ may be the same or different. . As the compound (c3), in the above formula (4), R ⁷ , R ⁸ and R ⁹ are each an alkyl group having 1 to 20 carbon atoms or a phenyl group, and R ¹⁰ and R ¹¹ are Each is preferably a polymerizable unsaturated compound having a group represented by the above formula (5).

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

（式（ｃ３−１）中、Ｒ^Ｓｉは上記式（４）で表される基であり、Ｒ^１５は水素原子又はメチル基であり、ｄは１〜３の整数である。）

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

  Specific examples of the compound (c3-1) include compounds represented by the following formulas (c3-1-1), (c3-1-2) and (c3-1-3). Can do.

（式（ｃ３−１−１）中、Ｍｅはメチル基であり、ｒ、ｓ及びｔは、それぞれ０〜３の整数である。）

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

（式（ｃ３−１−２）中、Ｍｅ並びにｒ、ｓ及びｔは、上記式（ｃ３−１−１）と同様に定義される。）

(In formula (c3-1-2), Me and r, s, and t are defined in the same manner as in formula (c3-1-1) above.)

（式（ｃ３−１−３）中、Ｍｅ並びにｒ、ｓ及びｔは、上記式（ｃ３−１−１）と同様に定義され、Ｐｈはフェニル基である。）

(In the formula (c3-1-3), Me and r, s, and t are defined in the same manner as in the above formula (c3-1-1), and Ph is a phenyl group.)

  Examples of the compound (c4) include alkyl (meth) acrylates having an unsubstituted alkyl ester group having 1 to 8 carbon atoms. Specific examples of the compound (c4) include n-butyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate and the like.

  Examples of the compound (c5) include compounds obtained by methacrylate formation at both ends, such as tetramethylene glycol, polyethylene glycol having a polymerization degree of 1 to 20, and polypropylene glycol having a polymerization degree of 1 to 20. As the compound (c5), a commercially available product can be suitably used. Examples of such commercially available products include NK Ester 1G, 2G, 3G, 4G, 9G, and 14G manufactured by Shin-Nakamura Chemical Co., Ltd.

  When the copolymer [C] has a structural unit 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 the polymerizable compound is 10 to 55% by mass for the polymerizable compound (c1), 10 to 50% by mass for the polymerizable compound (c2), and 5 to 45% by mass for the polymerizable compound (c3). is there.

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

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

  The copolymer [C] has a mass average molecular weight (Mw) of 5,000 to 25,000, preferably 10,000 to 25,000, and preferably 15,000 to 25,000. Particularly preferred. The molecular weight distribution (Mw / Mn) of the copolymer [C] (ratio of Mw to the number average molecular weight Mn) is preferably 1 to 10, more preferably 2 to 4.

  The method for producing the copolymer [C] is not particularly limited, and is based on a known method, for example, a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, or an anionic polymerization method, a solution polymerization method, a bulk polymerization method, an emulsion polymerization method. Etc. can be manufactured. Among these production methods, the radical polymerization method in a solution is simple and industrially preferable.

  Examples of the polymerization initiator used in producing the copolymer [C] include peroxides such as benzoyl peroxide and diacyl peroxide; 2,2′-azobisisobutyronitrile, phenylazotriphenylmethane An azo compound such as

  The copolymer [C] can be produced in the presence or absence of a solvent, but it is preferably carried out in the presence of a solvent from the viewpoint of workability. 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, and other polar solvents. .

Examples of these solvents include
Examples of the alcohol include ethanol, isopropyl alcohol, n-butanol, iso-butanol, tert-butanol and the like;
Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl amino ketone.
Examples of the alkyl ester of monocarboxylic acid include, for example, methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, butyl lactate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, Butyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate and the like;
Examples of the ether include methyl cellosolve, cellosolve, butyl cellosolve, butyl carbitol, ethyl cellosolve acetate, tetrahydrofuran, dioxane and the like;
Examples of the propylene glycol and esters thereof include propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate and the like;
Examples of the halogenated hydrocarbon include 1,1,1-trichloroethane, chloroform and the like;
Examples of the aromatic hydrocarbon include benzene, toluene, xylene and the like;
Examples of the fluorinated inert liquid include perfluorooctane and perfluorotri-n-butylamine;
Examples of the other polar solvent include dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone and the like.
One kind of these solvents may be used alone, or two or more kinds may be appropriately mixed and used.

  In production of the copolymer [C], a chain transfer agent such as lauryl mercaptan, 2-mercaptoethanol, ethylthioglycolic acid, octylthioglycolic acid or the like may be used as necessary.

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

<Other optional components>
In addition to the components [A] to [C] described above, the positive radiation-sensitive composition of the present invention includes [D] an adhesion assistant and [E] base as necessary within a range not impairing the intended effect. Other optional components such as a functional compound can be contained.

<[D] Adhesion aid>
In the positive-type radiation-sensitive resin composition, in order to improve the adhesion between an inorganic material serving as a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, or aluminum, and an insulating film The adhesion assistant as component [D] can be used. As such an adhesion assistant, a functional silane coupling agent is preferably used. Examples of functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, epoxy groups (preferably oxiranyl groups), thiol groups, and the like.

  Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxy Examples include propyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. . Among these, γ-glycidoxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane are preferable.

  In the positive radiation-sensitive resin composition, such an adhesion assistant is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more with respect to 100 parts by mass of the polymer [A]. It is used in an amount of 10 parts by mass or less. By setting the amount of the adhesion assistant in the above range, the adhesion between the formed interlayer insulating film and the substrate is improved.

<[E] basic compound>
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples of the basic compound include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, carboxylic acid quaternary ammonium salts, and the like. By including a basic compound in the positive radiation-sensitive composition, the diffusion length of the acid generated from the photoacid generator by exposure can be appropriately controlled, and the pattern developability should be good. Can do.

  Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and dicyclohexylamine. , Dicyclohexylmethylamine and the like.

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

  Examples of the heterocyclic amine include 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, nicotinamide, 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 etc. are mentioned.

  Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.

  Examples of the carboxylic acid quaternary ammonium salt include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

  It is preferable that content of the basic compound in the said positive radiation sensitive composition shall be 0.001-1 mass part with respect to 100 mass parts of polymers [A], and 0.005-0.2 mass. More preferably, it is a part. Pattern developability becomes favorable by making content of a basic compound into the said range.

<Positive radiation sensitive composition>
The positive radiation-sensitive composition of the present invention includes the above-mentioned [A] polymer, [B] photoacid generator, [C] a copolymer formed from a monomer having a specific structure, and, if necessary, Prepared by mixing optional ingredients. Usually, the positive radiation-sensitive composition is preferably prepared and used in a state dissolved or dispersed in an appropriate [F] solvent. For example, a positive radiation-sensitive composition can be prepared by mixing [A], [B] and [C] components, and optional components in a solvent in a predetermined ratio.

<[F] solvent>
As the [F] solvent that can be used for the preparation of the positive radiation sensitive composition, those that uniformly dissolve or disperse each component and do not react with each component are preferably used. Examples of such solvents include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionate. , Aromatic hydrocarbons, ketones, esters and the like.

These solvents include
Examples of alcohols include benzyl alcohol and diacetone alcohol;
Examples of ethers include dialkyl ethers such as tetrahydrofuran, diisopropyl ether, di n-butyl ether, di n-pentyl ether, diisopentyl ether, and di n-hexyl ether;
Examples of diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;
Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;
Examples of propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate;
Examples of propylene glycol monoalkyl ether propionates include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like;

Examples of aromatic hydrocarbons include toluene and xylene;
Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone, etc.
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionic acid Ethyl, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, protyl 3-hydroxypropionate, 3-hydroxy Butyl propionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, ethoxy Butyl acetate, methyl propoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2 Examples thereof include propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate and the like.

  Among these solvents, from the viewpoint of excellent solubility or dispersibility, non-reactivity with each component, and ease of coating film formation, ethers such as dialkyl ethers, diethylene glycol alkyl ethers, Ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters are preferred, especially diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene Glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol Noethyl ether acetate, cyclohexanone, propyl acetate, i-propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl lactate, Ethyl lactate, propyl lactate, butyl lactate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate are preferred. These solvents can be used alone or in combination.

  Among these solvents, ethers such as diisopropyl ether such as diisopropyl ether, di n-butyl ether, di n-pentyl ether, diisopentyl ether and di n-hexyl ether are preferable, and diisopentyl ether is most preferable. . By using such a solvent, when applying the radiation-sensitive composition to a large glass substrate by the slit coating method, the drying process time is shortened, and at the same time, the coating property is further improved (coating unevenness is suppressed). Is possible.

  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, caproic acid, caprylic acid, 1-octanol, 1-octanol High-boiling solvents such as nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, carbitol acetate and the like can also be used in combination.

  When preparing a positive radiation sensitive composition in a solution or dispersion state, components other than the [F] solvent in the solution (that is, the sum of the components [A], [B] and [C] and other optional components) The ratio of (amount) can be arbitrarily set according to the purpose of use, desired film thickness, etc., but is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and still more preferably 15 to 35% by mass. %.

<Formation of interlayer insulating film>
Next, a method for forming a cured film of an interlayer insulating film on a substrate using the positive radiation sensitive composition will be described. The method includes the following steps in the order described below.
(1) The process of forming the coating film of the said positive type radiation sensitive composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A step of developing the coating film irradiated with radiation in the step (2), and (4) A step of heating the coating film developed in the step (3).

<(1) Step of forming a coating film of positive radiation sensitive composition on substrate>
In the step (1), after applying the solution or dispersion of the positive radiation sensitive composition on the substrate, the coating surface is preferably removed by heating (pre-baking) the coated surface. Form. Examples of the substrate that can be used include glass, quartz, silicon, and resin. Specific examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of cyclic olefin, and hydrogenated products thereof.

  The coating method of the composition solution or dispersion is not particularly limited, and an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or the like is employed. be able to. Among these coating methods, a spin coating method or a slit die coating method is preferable, and a slit die coating method is particularly preferable. Prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but are preferably 70 to 120 ° C. for about 1 to 10 minutes.

<(2) Step of irradiating radiation to at least part of coating film>
In the step (2), at least a part of the formed coating film is exposed. In this case, when a part of the coating film is exposed, it is usually exposed through a photomask having a predetermined pattern. As the radiation used for exposure, the radiation used for the photoacid generator is suitable. Among these radiations, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation including ultraviolet light of 365 nm is particularly preferable.

The exposure amount in this step is preferably 500 to 6,000 J / m ² , more preferably 1, as a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.). it is a 500~1,800J / ^{m 2.}

<(3) Development process>
In the step (3), by developing the exposed coating film, unnecessary portions (radiation irradiated portions) are removed to form a predetermined pattern. As the developer used in the development step, an alkaline aqueous solution is preferable. Examples of alkalis include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. be able to.

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to such an alkaline aqueous solution. The concentration of the alkali in the alkaline aqueous solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. As a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the positive radiation-sensitive composition, but is preferably about 10 to 180 seconds. Following such development processing, for example, after washing with running water for 30 to 90 seconds, a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

<(4) Heating process>
In the process (4), the patterned thin film is heated by using a heating device such as a hot plate or an oven to accelerate the curing reaction of the [A] component and the [C] component, and a cured product is obtained. Obtainable. The heating temperature in this step is, for example, 120 to 250 ° C. Although heating time changes with kinds of heating apparatus, for example, when performing a heating process on a hotplate, it can be set to 30 to 90 minutes when performing a heating process in an oven. The step baking method etc. which perform a heating process 2 times or more 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 insulating film thus formed is preferably 0.1 to 8 μm, more preferably 0.1 to 6 μm, and still more preferably 0.1 to 4 μm.

  The interlayer insulating film formed from the positive-type radiation-sensitive composition of the present invention satisfies the general required characteristics of heat resistance and transparency in a well-balanced manner, as will be apparent from the following examples. High flatness without unevenness. Therefore, the interlayer insulating film is suitably used for display elements.

  The present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.

Below, the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer were measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<Synthesis Example of Polymer [A]>
[Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. 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 3 parts by mass of α-methylstyrene dimer were charged. After that, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-1). The polystyrene equivalent mass average molecular weight (Mw) of the polymer (A-1) was 9,000. Further, the solid content concentration of the polymer solution obtained here (referring to the ratio of the mass of the polymer contained in the polymer solution to the total mass of the polymer solution; the same shall apply hereinafter) is 32.1% by mass. there were.

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 5 parts by weight of methacrylic acid, 40 parts by weight of tetrahydro-2H-pyran-2-yl methacrylate, 5 parts by weight of styrene, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate and 3 parts by weight of α-methylstyrene dimer Was added, and the mixture was purged with nitrogen. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-2). The polymer (A-2) had a polystyrene equivalent mass average molecular weight (Mw) of 9,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.3 mass%.

[Synthesis Example 3]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 67 parts by mass of 1-n-butoxyethyl methacrylate, 23 parts by mass of benzyl methacrylate, and 10 parts by mass of methacrylic acid were charged and purged with nitrogen, and then gently stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-1). The polystyrene equivalent mass average molecular weight (Mw) of the polymer (a-1) was 9,000. Moreover, the solid content concentration of the polymer solution obtained here was 30.3% by mass.

[Synthesis Example 4]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 90 parts by mass of 1-benzyloxyethyl methacrylate, 6 parts by mass of 2-hydroxyethyl methacrylate, and 4 parts by mass of methacrylic acid were charged and purged with nitrogen, and then gently stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-2). The polymer (a-2) had a polystyrene-reduced mass average molecular weight (Mw) of 9,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.2 mass%.

[Synthesis Example 5]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 85 parts by mass of tetrahydro-2H-pyran-2-yl methacrylate, 7 parts by mass of 2-hydroxyethyl methacrylate, and 8 parts by mass of methacrylic acid were charged and replaced with nitrogen, and then gently stirred. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (a-3). The polymer (a-3) had a polystyrene equivalent mass average molecular weight (Mw) of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 29.2 mass%.

[Synthesis Example 6]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, after 52 parts by mass of glycidyl methacrylate and 48 parts by mass of benzyl methacrylate were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (aa-1). The polymer (aa-1) had a polystyrene-reduced mass average molecular weight (Mw) of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.3 mass%.

[Synthesis Example 7]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 45 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate, 45 parts by mass of benzyl methacrylate, and 10 parts by mass of methacrylic acid were charged and purged with nitrogen, and then gently agitated. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (aa-2). The polymer (aa-2) had a weight average molecular weight (Mw) in terms of polystyrene of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 33.2 mass%.

[Synthesis Example 8]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 35 parts by mass of 1-n-butoxyethyl methacrylate, 35 parts by mass of benzyl methacrylate, and 30 parts by mass of glycidyl methacrylate were charged and purged with nitrogen, and then gently stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (aa-3). The polymer (aa-3) had a polystyrene equivalent mass average molecular weight (Mw) of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.3 mass%.

<Synthesis of Copolymer [C]>
[Synthesis Example 9]
In a glass flask equipped with a stirrer, a condenser and a thermometer, 28.4 parts by mass of the compound represented by the above formula (c1-1) as the (c1) compound and (c2) manufactured by Shin-Nakamura Chemical Co., Ltd. “NK-ester M-90G” 20.7 parts by mass, (c3) 18.1 parts by mass of a compound represented by the following formula (c3-1-1-1) as a compound, (c4) methyl methacrylate as a compound 5. 9 parts by mass and 23.5 parts by mass of 2-ethylhexyl acrylate, 3.4 parts by mass of a compound obtained by methacrylateating both ends of tetramethylene glycol as the compound (c5), and 414 parts by mass of isopropyl alcohol as a solvent were charged with a nitrogen gas stream Medium, under reflux, 0.7 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator and a chain transfer agent After adding 4 parts by mass of lauryl mercaptan, the solution was refluxed at 75 ° C. for 8 hours to carry out copolymerization to obtain a solution containing the copolymer (C-1). Then, the copolymer (C-1) was isolated by removing a solvent on 70 degreeC or less heating conditions using an 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.

（式中、Ｍｅはメチル基である。）

(In the formula, Me is a methyl group.)

[Synthesis Example 10]
A copolymer (C-2) was obtained in the same manner as in Synthesis Example 3 except that the addition amount of lauryl mercaptan 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 3 except that lauryl mercaptan as a chain transfer agent was not used and the copolymerization temperature and time were 73 ° C. and 10 hours, respectively. . 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 a glass flask equipped with a stirrer, a condenser and a thermometer, (1) 31.8 parts by mass of the compound represented by the above formula (c1-3) as the (c1) compound and (c2) manufactured by Shin-Nakamura Chemical Co., Ltd. 31.6 parts by mass of “NK-ester M-90G”, 29.0 parts by mass of the compound represented by the above formula (c3-1-1-1) and 414 parts by mass of isopropyl alcohol as (c3) compound, In a gas stream, under reflux, 0.7 parts by weight of AIBN as a polymerization initiator and 4 parts by weight of lauryl mercaptan as a chain transfer agent were added and refluxed at 75 ° C. for 8 hours to carry out copolymerization. A solution containing the coalescence (C-4) was obtained. Then, the copolymer (C-4) was isolated by removing a solvent on 70 degreeC or less heating conditions using an 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. The molecular weight distribution (Mw / Mn) was 2.0.

[Synthesis Example 13]
In a glass flask equipped with a stirrer, a condenser and a thermometer, (2) parts by mass of the compound represented by the above formula (c1-5) as (c1) compound and (c2) manufactured by Shin-Nakamura Chemical Co., Ltd. "NK-ester M-90G" 20.7 parts by mass, (c3) 21.5 parts by mass of the compound represented by the above formula (c3-1-1-1) as the compound, (c4) n-butyl methacrylate as the compound 29.4 parts by mass and 414 parts by mass of isopropyl alcohol were charged, and after adding 0.7 parts by mass of AIBN as a polymerization initiator and 4 parts by mass of lauryl mercaptan as a chain transfer agent under reflux in a nitrogen gas stream, 75 The solution was refluxed at 0 ° C. for 8 hours for copolymerization to obtain a solution containing the copolymer (C-5). Then, the copolymer (C-5) was isolated by removing a solvent on 70 degreeC or less heating conditions using an evaporator. The number average molecular weight Mn of the obtained copolymer (C-5) was 3,500, and the mass average molecular weight Mw was 6,000. Moreover, molecular weight distribution (Mw / Mn) was 1.7.

[Synthesis Example 14]
In a glass flask equipped with a stirrer, a condenser and a thermometer, 16.6 parts by mass of the compound represented by the above formula (c1-7) as the compound (c1) and Shin Nakamura Chemical Co., Ltd. as the compound (c2) "NK-ester M-90G" 20.7 parts by mass, (c3) 21.5 parts by mass of the compound represented by the above formula (c3-1-1-1) as the compound, (c4) n-butyl methacrylate as the compound 29.4 parts by mass and 414 parts by mass of isopropyl alcohol were charged, and after adding 0.7 parts by mass of AIBN as a polymerization initiator and 4 parts by mass of lauryl mercaptan as a chain transfer agent under reflux in a nitrogen gas stream, 75 The solution was refluxed at 0 ° C. for 8 hours for copolymerization to obtain a solution containing the copolymer (C-5). Then, the copolymer (C-6) was isolated by removing a solvent on 70 degreeC or less heating conditions using an evaporator. The number average molecular weight Mn of the obtained copolymer (C-5) was 4,000, and the mass average molecular weight Mw was 7,000. The molecular weight distribution (Mw / Mn) was 1.8.

<Preparation of positive radiation sensitive composition>
[Example 1]
In a solution containing the polymer (A-1) obtained in Synthesis Example 1 (an amount corresponding to 100 parts by mass (solid content) of the polymer (A-1)), IRGACURE PAG 103 (Ciba Special) (Made by Tea Chemicals Co., Ltd.) 3 parts by weight and 0.50 part by weight of the copolymer (C-1) obtained in Synthesis Example 9 as the [C] component are mixed, and the solid content concentration is further 25% by weight. After adding diethylene glycol ethyl methyl ether as a solvent, a positive radiation sensitive composition (S-1) was prepared by filtering through a membrane filter having a diameter of 0.2 μm.

[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 types and amounts of each component were as shown in Table 1. In addition, the component used by each Example and the comparative example is as follows.

(Photoacid generator: B component)
B-1: Compound (i) above ("IRGACURE PAG 103" manufactured by Ciba Specialty Chemicals)
B-2: Compound (ii) ("IRGACURE PAG 108" manufactured by Ciba Specialty Chemicals)
B-3: Compound (iii) (“CGI 1380” manufactured by Ciba Specialty Chemicals)
B-4: The above compound (iv) (“IRGACURE PAG 121” manufactured by Ciba Specialty Chemicals)
B-5: Compound (v) (“CGI 725” manufactured by Ciba Specialty Chemicals)
(Surfactant)
c-1 (Comparative Example 1): Silicone surfactant ("SH-193" manufactured by Toray Dow Corning Silicone Co., Ltd.)
c-2 (Comparative Example 2): Fluorosurfactant ("Florard F-430" manufactured by 3M Co., Ltd.)
(Adhesion aid: 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

<Physical property evaluation>
Each positive radiation sensitive composition prepared as described above was used, and the composition and various properties as a coating film or an interlayer insulating film were evaluated as follows.

(1) Appearance evaluation of coating film On a 550 × 650 mm chromium-deposited glass, the radiation-sensitive composition prepared as described above is a slit die coater (manufactured by Tokyo Ohka Kogyo Co., Ltd., model “TR6321055-CL”). Then, the ultimate pressure was set to 100 Pa and the solvent was removed under vacuum, followed by prebaking at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Under the sodium lamp, the appearance of the coating film was observed with the naked eye. At this time, the appearance state was investigated, assuming that the haze-like unevenness generated in the entire coating film was “moy unevenness” and the unevenness derived from the proxy pin of the pre-baking furnace was “pin unevenness”. If none of these unevennesses are visible, it is evaluated as “Good (Good)”, if any of these unevennesses is a little visible, “△ (Slightly bad)”, and clearly visible as “Good (Good)” did. 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 described above was measured using a needle contact type measuring instrument (AS200 manufactured by KLA Tencor). The uniformity was calculated from the film thickness at nine measurement points. The nine measurement points are (X [mm], Y [mm]), 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 uniformity calculation formula is expressed by the following formula. In the following formula, FT (X, Y) max is the maximum value in the film thickness at 9 measurement points, FT (X, Y) min is the minimum value in the film thickness at 9 measurement points, and FT (X, Y) avg . Is an average value in the film thickness at nine measurement points. When the uniformity is 2% or less, it can be judged that the film thickness uniformity is good. The evaluation results are shown in Table 1.
(Uniformity calculation formula)
Uniformity (%) = {FT (X, Y) max−FT (X, Y) min} × 100 / {2 × FT (X, Y) avg. }

(3) Evaluation of high-speed application property It apply | coats on a 550 mm x 650 mm non-alkali glass substrate using a slit coater, and as application conditions, the distance between the base and the nozzle (GAP) is 150 μm, and the film thickness after exposure is 2.5 μm. The coating liquid is discharged from the nozzle so that the nozzle moving speed is 120 mm / sec. -220 mm / sec. The maximum speed at which streaky unevenness due to liquid breakage does not occur was determined. At this time, 180 mm / sec. If streaky unevenness does not occur even at the above speed, it can be determined that high-speed application is possible. The evaluation results are shown in Table 1.

(4) Evaluation of Radiation Sensitivity of Radiation Sensitive Composition Hexamethyldisilazane (HMDS) was applied on a 550 × 650 mm chromium film and heated at 60 ° C. for 1 minute (HMDS treatment). The radiation-sensitive composition prepared as described above is applied onto the chromium-deposited glass after the HMDS treatment using a slit die coater “TR6322105-CL”, the ultimate pressure is set to 100 Pa, and the solvent is removed under vacuum. Then, the film was further pre-baked at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Subsequently, using an MPA-600FA exposure machine manufactured by Canon Inc., the coating film was irradiated with radiation through the mask having a 60 μm line and space (10 to 1) pattern with the exposure amount as a variable. Then, the film was developed by a puddle method at 25 ° C. with an aqueous tetramethylammonium hydroxide solution having the concentration shown in Table 1. Here, the development time was 80 seconds when a developer having a tetramethylammonium hydroxide concentration of 0.40% by mass was used, and 50 seconds when a 2.38% by mass developer was used. Next, the substrate was washed with ultrapure water for 1 minute and then dried to form a pattern on the chromium-deposited glass substrate after the HMDS treatment. At this time, the exposure amount necessary for completely dissolving the 6 μm space pattern was examined. This value is shown in Table 1 as radiation sensitivity. It can be said that the sensitivity is good when this value is 500 J / m ² or less.

(5) Evaluation of heat resistance of interlayer insulating film On the chromium film-forming glass (4-inch glass wafer), the radiation-sensitive composition prepared as described above was applied using a spin coater, and further at 90 ° C. for 3 minutes. Pre-baked to form a coating film. Next, this coating film was heated in a clean oven at 220 ° C. for 1 hour to form a cured film on the chromium film-forming glass. The film thickness (T2) of the cured film obtained here was measured. Next, the chromium film-formed glass substrate on which this cured film was formed was subjected to additional heating at 240 ° C. for 1 hour in a clean oven, and then the thickness (t2) of the cured film was measured again, and additional heating was performed. The film thickness change rate was calculated by the following formula. When this value is 5% or less, it can be said that the heat resistance is good. 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 Transparency of Interlayer Insulating Film The above [Interlayer insulating film] except that a 550 × 650 mm glass substrate (“NA35” manufactured by NH Techno Glass Co., Ltd.) was used instead of the chromium film-forming glass substrate. A cured film was formed on a glass substrate in the same manner as in the case of [Evaluation of heat resistance of film]. Using a spectrophotometer "150-20 type double beam (manufactured by Hitachi, Ltd.)", the light transmittance of the glass substrate on which the cured film is formed is 400 to 400 with reference to the glass substrate having no cured film. Measurements were made at a wavelength in the range of 800 nm. The values of the minimum light transmittance at that time are shown in Table 1. When this value is 90% or more, it can be said that the transparency is good.

  As is clear from the results in Table 1, the positive radiation sensitive compositions of Examples 1 to 12 containing the [A], [B] and [C] components were compared to Comparative Examples 1 to 1 containing no [C] component. Compared with No. 3 positive type radiation sensitive composition, it turned out that it is remarkably excellent also about the coating nonuniformity in the external appearance of a coating film, and the flatness of an interlayer insulation film even if it is high-speed coating. In addition, the positive-type radiation-sensitive compositions of these examples have a high radiation sensitivity and can form an interlayer insulating film that sufficiently satisfies the general required characteristics of heat resistance and transparency. I understood.

  As described above, the positive radiation-sensitive composition of the present invention can be applied at high speed, has high radiation sensitivity, and has excellent flatness in addition to sufficient heat resistance and transparency. Can be formed. Therefore, the positive radiation sensitive composition is suitably used for forming an interlayer insulating film for a display element.

Claims (6)

[A] a polymer having a structural unit containing a group represented by the following formula (1) and an epoxy group-containing structural unit in the same or different polymer molecules;
[B] a photoacid generator, and [C] (c1) a polymerizable compound represented by the following formula ( 6 ),
(C2) a polymerizable compound represented by the following formula ( 7 ) ,
( C3) a polymerizable compound having a group represented by the following formula (4) ,
(C4) a polymerizable compound having an unsubstituted alkyl ester group having 1 to 8 carbon atoms, and
(C5) containing a copolymer having at least a structural unit derived from a polymerizable compound having two or more unsaturated bonds in one molecule ;
[C] The copolymer is based on the total amount of the polymerizable compounds (c1) to (c5).
Polymerizable compound (c1) 25-35% by mass,
Polymerizable compound (c2) 20-30% by mass,
Polymerizable compound (c3) 15-20% by mass,
Polymerizable compound (c4) 25-35% by mass, and
1-5 mass% of polymeric compounds (c5)
A positive radiation sensitive composition comprising a composition comprising:

(In Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and a part of the hydrogen atoms of these alkyl group, cycloalkyl group or aryl group) Alternatively, all may be substituted with a substituent (provided that R ¹ and R ² are not both hydrogen atoms) R ³ represents an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or —M (R ^3m ) is a group represented by ₃ (M is Si, Ge or Sn, R ^3m is an alkyl group), and some or all of these hydrogen atoms are substituted with substituents. R ¹ and R ³ may be linked to form a cyclic ether.)

(In formula ( 6 ), R ⁴ is a hydrogen atom or a methyl group. Β is an integer of 1-8 .)

(In the formula (7), ^{R 5} is .R ⁶ is a hydrogen atom or a methyl group is .a the number of structural units is an alkyl group having 1 to 12 carbon atoms, the number average value thereof is 4-12 .)

(In Formula (4), R < ⁷ >, R < ⁸ >, R <^9> , R < ¹⁰ > and R < ¹¹ > are each independently represented by a C1-C20 alkyl group, a phenyl group, or the following formula (5). And b is an integer of 0 to 3.)

(In Formula (5), R <^12> , R <^13> and R < ¹⁴ > are respectively independently a C1-C20 alkyl group or a phenyl group. C is an integer of 0-3.) [D] The positive type radiation-sensitive composition of claim 1 which further contains an adhesion aid. [E] The positive radiation-sensitive composition according to claim 1 or 2 , further comprising a basic compound. The positive radiation-sensitive composition according to claim 1 , 2 or 3 , which is used for forming an interlayer insulating film of a display element. (1) The process of forming the coating film of the positive radiation sensitive composition of Claim 4 on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A step of developing the coating film irradiated with radiation in step (2), and (4) a step of heating the coating film developed in step (3). The interlayer insulation film of the display element formed from the positive radiation sensitive composition of Claim 4 .