JP5659714B2 - Positive radiation-sensitive composition, interlayer insulating film and method for forming the same - Google Patents

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 a material for forming an interlayer insulating film, a radiation-sensitive composition is widely used because a material having a small number of steps for obtaining a necessary pattern shape and having sufficient flatness is preferable.

  In addition, the interlayer insulating film of the display element needs to form a contact hole pattern for wiring. Since it is difficult to form a contact hole having a hole diameter that can be used practically with a negative composition, a positive radiation sensitive composition is widely used for forming an interlayer insulating film of a display element. (See JP 2001-354822 A).

  As a component of such a radiation sensitive composition for forming an interlayer insulating film, an acrylic resin is mainly used. On the other hand, an attempt has been made to use a polysiloxane material, which is superior in heat resistance and transparency as compared to an acrylic resin, as a component of the radiation-sensitive composition (Japanese Patent Laid-Open Nos. 2000-1648 and 2006). 178436).

  On the other hand, a display element such as a TFT type liquid crystal display element using an interlayer insulating film is manufactured through a process of forming a transparent electrode film on the interlayer insulating film and further forming a liquid crystal alignment film thereon. In this case, the interlayer insulating film is exposed to high temperature conditions in the transparent electrode film forming process or exposed to a resist stripping solution used for electrode pattern formation. It becomes. In addition, in the development process of the manufacturing process of the interlayer insulating film, if the development time is slightly longer than the optimal time, the developer tends to penetrate between the pattern and the substrate, so that the development tends to occur. It needs to be strictly controlled. In recent years, display devices using display elements such as TFT-type liquid crystal display elements have been in the trend of larger screens, higher brightness, higher definition, faster response, and thinner thickness. The high radiation sensitivity of the radiation-sensitive composition for forming and the low dielectric constant and high transmittance of the formed interlayer insulating film are required to have higher performance than before.

  With the recent widespread use of large-screen televisions and demands for reducing manufacturing costs, the size of substrate glass used for manufacturing substrates with color filters tends to increase. For this reason, it has become difficult to adopt a spin coating method that has been widely used in the coating process of a radiation-sensitive composition when forming an interlayer insulating film on a substrate. Therefore, a so-called slit coating method in which a radiation-sensitive composition is applied by discharging from a slit-like nozzle instead of such a spin coating method has been adopted for coating on a large glass substrate. . This slit coating method has an advantage that the amount of the radiation-sensitive composition required for coating can be reduced as compared with the spin coating method, and contributes to a reduction in manufacturing cost of the display element. Such a slit coating method is performed by bringing the substrate into close contact with the coating stage by vacuum suction, and sweeping the coating nozzle in a certain direction to form a coating film on the substrate. After the coating film is formed, the support pins stored in the vacuum suction holes are raised, whereby the substrate is lifted from the coating stage and transported to the next step. In this series of steps, the coating film may have unevenness due to minute irregularities caused by holes for vacuum adsorption, and to achieve the high level of flatness required as the characteristics of the interlayer insulating film Has become an obstacle.

  Under such circumstances, the heat resistance, transparency, solvent resistance and low dielectric properties generally required as an interlayer insulating film are excellent, and high flatness (film thickness uniformity) without coating unevenness is achieved. Development of a polysiloxane-based positive radiation-sensitive composition that can form an interlayer insulating film having high radiation sensitivity and a large development margin (allowable development time for forming a good pattern) is strong It is desired.

JP 2001-354822 A JP 2000-1648 A JP 2006-178436 A

  The present invention has been made based on the above circumstances, and its purpose is to satisfy the general required characteristics of heat resistance, transparency, solvent resistance and low dielectric constant in a well-balanced manner, and to prevent uneven coating. Polysiloxane-based positive-type radiation-sensitive composition capable of forming an interlayer insulating film having a high degree of flatness (film thickness uniformity) and having excellent radiation sensitivity and development margin, and formed from the composition And providing a method for forming the interlayer insulating film.

（式（１）中、Ｒ^１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（２）中、Ｒ^２は、水素原子又はメチル基である。Ｒ^３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、その数平均値は１〜３０である。）

（式（３）中、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８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（４）で表される基である。ｂは、０〜３の整数である。但し、Ｒ^５及びＲ^６がそれぞれ複数ある場合、複数のＲ^５及びＲ^６は、それぞれ同一であっても異なっていてもよい。）

（式（４）中、Ｒ^９、Ｒ^１０及びＲ^１１は、それぞれ独立して炭素数１〜２０のアルキル基又はフェニル基である。ｃは、０〜３の整数である。但し、Ｒ^１０及びＲ^１１がそれぞれ複数ある場合、複数のＲ^１０及びＲ^１１は、それぞれ同一であっても異なっていてもよい。） The invention made to solve the above problems is
[A] siloxane polymer,
[B] a quinonediazide compound, and [C] (c1) a polymerizable compound represented by the following formula (1) (hereinafter also referred to as “(c1) compound”),
(C2) a polymerizable compound represented by the following formula (2) (hereinafter also referred to as “(c2) compound”), and (c3) a polymerizable compound having a group represented by the following formula (3) (hereinafter, Also referred to as “(c3) compound”)
A copolymer having a structural unit derived from (hereinafter also referred to as “[C] copolymer”)
Is a positive radiation sensitive composition.

(In formula (1), R ¹ 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 (2), R ² is a hydrogen atom or a methyl group. R ³ is an alkyl group having 1 to 12 carbon atoms. Γ is 2 or 3. a is the number of structural units. Yes, the number average value is 1-30.)

(In formula (3), R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a group represented by the following formula (4). .b it is an integer of 0 to 3. However, ^{if R 5} and ^{R 6} are a plurality each of the plurality of ^{R 5} and ^{R 6} may each be the same or different.)

(In the formula ^(4), R ^{9, R 10} and ^{R 11} are each independently an alkyl group or a phenyl group having 1 to 20 carbon atoms .c is an integer of 0 to 3. ^{However, R 10} And when there are a plurality of R ^{11 s} , the plurality of R ¹⁰ and R ¹¹ may be the same or different.)

  The positive-type radiation-sensitive composition has positive-type radiation-sensitive properties, and is formed from a polymerizable compound having a specific structure in addition to [A] siloxane polymer and [B] quinonediazide compound. The copolymer functions as a surfactant with high surface tension reduction performance, satisfying the general required properties of heat resistance, transparency, solvent resistance, and low dielectric properties in a well-balanced manner, and without coating unevenness. An interlayer insulating film having flatness (film thickness uniformity) can be formed. Further, the positive radiation sensitive composition has excellent radiation sensitivity and development margin.

  The positive radiation-sensitive composition further has a structural unit derived from (c4) a polymerizable compound having an unsubstituted alkyl ester group having 1 to 8 carbon atoms (hereinafter also referred to as “(c4) compound”). Is preferred. Since the [C] copolymer further has a structural unit derived from the compound (c4), the affinity of the [C] copolymer for other components and solvents can be improved, and the film thickness of the resulting interlayer insulating layer Uniformity can be further improved.

  In the positive radiation sensitive composition, the [C] copolymer is further converted into (c5) a polymerizable compound having two or more unsaturated bonds in one molecule (hereinafter also referred to as “(c5) compound”). It is preferable to have a derived structural unit. In addition to the structural unit derived from the compound (c4), the copolymer [C] further includes the structural unit derived from the compound (c5), thereby increasing the strength together with the film thickness uniformity of the obtained interlayer insulating film. And general properties such as heat resistance can be improved.

（式（５）中、Ｒ^１は上記式（１）と同義である。βは、１〜８の整数である。）

（式（６）中、Ｒ^２及びＲ^３は、上記式（２）と同義である。ａの数平均値は、４〜１２である。） In the positive radiation sensitive composition,
(C1) The compound is a polymerizable compound represented by the following formula (5),
(C2) The compound is a polymerizable compound represented by the following formula (6), and [C] copolymer is:
(C1) 25% by mass or more and 35% by mass or less of the compound,
(C2) 20% by mass or more and 30% by mass or less of the compound,
(C3) 15% by mass or more and 20% by mass or less of the compound,
(C4) It is preferably synthesized from a composition containing 25% by mass or more and 35% by mass or less of compound, and (c5) 1% by mass or more and 5% by mass or less of compound.

(In formula (5), ^{R 1} has the same meaning as the above formula (1) .Beta is an integer from 1 to 8.)

(In the formula (6), ^{R 2} and ^{R 3,} the number average value of .a as defined in the above formula (2) 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.

（式（７）中、Ｒ^１２は、炭素数１〜２０の非加水分解性の有機基である。Ｒ^１３は、炭素数１〜４のアルキル基である。ｘは、０〜３の整数である。但し、Ｒ^１２及びＲ^１３がそれぞれ複数ある場合、複数のＲ^１２及びＲ^１３は、それぞれ同一であっても異なっていてもよい。） The [A] siloxane polymer of the positive radiation sensitive composition is preferably a hydrolysis condensate of a hydrolyzable silane compound represented by the following formula (7).

(In the formula ^{(7), R 12} is ^{.R 13} is a non-hydrolyzable organic group having 1 to 20 carbon atoms, the .x is an alkyl group having 1 to 4 carbon atoms, an integer of 0 to 3 it is. ^{However, if R 12} and ^{R 13} are a plurality each of a plurality of ^{R 12} and ^{R 13} may each be the same or different.)

  In the positive radiation sensitive composition, the radiation sensitivity and the development margin can be further increased by using a hydrolysis condensate of a specific silane compound as the [A] siloxane polymer.

  The positive radiation-sensitive composition preferably further contains [D] a heat-sensitive acid generator or a heat-sensitive base generator. By using such a heat-sensitive acid or base generator, the condensation reaction of the [A] siloxane polymer in the heating step after development of the positive radiation-sensitive composition is further promoted, and the heat resistance of the resulting interlayer insulating film is increased. Property and solvent resistance can be further improved.

  The positive radiation sensitive composition preferably further contains [E] a dehydrating agent. Thus, it becomes possible to improve the storage stability of the positive radiation sensitive composition by further containing a dehydrating agent.

The method for forming an interlayer insulating film for a display element according to 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 with radiation,
(3) a step of developing the coating film irradiated with the radiation, and (4) a step of heating the developed coating film.

  In the formation method, the above-mentioned positive radiation-sensitive composition having excellent radiation sensitivity and development margin is used, and a pattern is formed by exposure, development, and heating using radiation sensitivity, thereby easily and finely and elaborately. An interlayer insulating film for a display element having a simple pattern can be formed. Furthermore, the interlayer insulating film formed in this way is excellent in a good balance of general required characteristics, that is, heat resistance, transparency, solvent resistance and low dielectric properties, and has high flatness without uneven coating. Have

  As described above, the positive-type radiation-sensitive composition of the present invention satisfies the general required characteristics of heat resistance, transparency, solvent resistance, and low dielectric constant in a well-balanced manner and is highly flat without coating unevenness. An interlayer insulating film having the property (film thickness uniformity) can be formed. Further, the positive radiation sensitive composition has excellent radiation sensitivity and development margin.

  The positive radiation sensitive composition of the present invention contains [A] siloxane polymer, [B] quinonediazide compound, and [C] copolymer. Furthermore, you may contain another arbitrary component in the range which does not impair the effect of this invention. Hereinafter, each component will be described in detail.

<[A] Siloxane polymer>
[A] The siloxane polymer is not particularly limited as long as it is a polymer having a siloxane bond. [A] A siloxane polymer forms a cured product by hydrolytic condensation. When an optional component [D] heat-sensitive acid generator or heat-sensitive base generator described below is added to the positive radiation-sensitive composition, acid or base is generated by applying heat, and this serves as a catalyst. [A] Hydrolytic condensation of the siloxane polymer is further promoted.

  [A] The siloxane polymer is preferably a hydrolytic condensate of a hydrolyzable silane compound represented by the above formula (7) (hereinafter also referred to as “specific silane compound”). The “hydrolyzable silane compound” in the present application is usually a silanol group that is hydrolyzed by heating in the temperature range of room temperature (about 25 ° C.) to about 100 ° C. in the presence of non-catalyst and excess water. It refers to a silane compound having a hydrolyzable group capable of forming a silane compound having a hydrolyzable group capable of forming a siloxane condensate. In contrast, a “non-hydrolyzable group” refers to a group that does not undergo hydrolysis or condensation and exists stably under such hydrolysis conditions.

  In the hydrolysis reaction of the specific silane compound, some hydrolyzable groups may remain in an unhydrolyzed state. The “hydrolyzable condensate of hydrolyzable silane compound” referred to here means a hydrolyzed condensate obtained by reacting and condensing some silanol groups of the hydrolyzed silane compound.

The non-hydrolyzable organic group having 1 to 20 carbon atoms represented by R ¹² is an alkyl group having 1 to 12 carbon atoms substituted with one or more unsubstituted, (meth) acryloyl groups or epoxy groups. Group, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a vinyl group. These may be linear, branched or cyclic. R ¹² may contain a structural unit having a hetero atom. Examples of such a structural unit include ether, ester, sulfide and the like.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹³ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a butyl group. Among these R ¹³ , a methyl group and an ethyl group are preferable from the viewpoint of easy hydrolysis. X is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. When x is an integer of 0 to 2, the hydrolysis condensation reaction proceeds more easily, and as a result, the speed of the curing reaction due to the self-condensation of the [A] siloxane polymer is further increased. Heat resistance and solvent resistance can be further improved.

  As the specific silane compound, a silane compound substituted with four hydrolyzable groups, a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups, and two non-hydrolyzed groups And a silane compound substituted with two non-hydrolyzable groups and one hydrolyzable group, or a mixture thereof.

  Examples of the silane compound substituted with four hydrolyzable groups include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, tetra-n-propoxysilane, and tetra-i-propoxy. Silane etc. are mentioned.

  Examples of the silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups include methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n -Propoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, γ-glycy Trimethoxysilane, .gamma.-glycidoxypropyl triethoxy silane, beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

  Examples of the silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups include dimethyldimethoxysilane, diphenyldimethoxysilane, dibutyldimethoxysilane and the like.

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

  Of these specific silane compounds, silane compounds substituted with four hydrolyzable groups and silane compounds substituted with one non-hydrolyzable group and three hydrolyzable groups are preferred. A silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups is particularly preferred. Specific examples of preferable hydrolyzable silane compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane. Examples include ethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane. . Such hydrolyzable silane compounds may be used alone or in combination of two or more.

  Conditions for hydrolytic condensation of the specific silane compound are particularly limited as long as at least a part of the specific silane compound is hydrolyzed to convert the hydrolyzable group into a silanol group and cause a condensation reaction. However, it can be implemented as follows as an example.

The water used for the hydrolytic condensation of the specific silane compound is preferably water purified by a method such as reverse osmosis membrane treatment, ion exchange treatment or distillation. By using such purified water, side reactions can be suppressed and the reactivity of hydrolysis can be improved. The amount of water used is preferably 0.1 mol to 3 mol, more preferably 0.3 mol to 2 mol, in particular, with respect to 1 mol of the total amount of hydrolyzable groups (—OR ¹³ ) of the specific silane compound. The amount is preferably 0.5 mol to 1.5 mol. By using such an amount of water, the reaction rate of the hydrolysis condensation can be optimized.

  The solvent that can be used for the hydrolytic condensation of the specific silane compound is not particularly limited, but usually the same solvent as that used for the preparation of the positive radiation sensitive composition described later is used. be able to. Preferable examples of such a solvent include ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid esters. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, or methyl 3-methoxypropionate is particularly preferable.

  The hydrolytic condensation reaction of the specific silane compound is preferably an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resin, various Lewis acids. ), Basic catalysts (for example, ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing compounds such as pyridine; basic ion exchange resins; hydroxides such as sodium hydroxide; potassium carbonate, etc. Carboxylate; carboxylate such as sodium acetate; various Lewis bases] or alkoxide (for example, zirconium alkoxide, titanium alkoxide, aluminum alkoxide) and the like. As the aluminum alkoxide, for example, tri-i-propoxyaluminum can be used. The amount of the catalyst to be used is preferably 0.2 mol or less, more preferably 0.00001 mol to 0.001 mol per mol of the hydrolyzable silane compound monomer from the viewpoint of promoting the hydrolysis condensation reaction. 1 mole.

  The reaction temperature and reaction time in the hydrolytic condensation of the specific silane compound are appropriately set. For example, the following conditions can be adopted. The reaction temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 150 ° C. The reaction time is preferably 30 minutes to 24 hours, more preferably 1 hour to 12 hours. By setting it as such reaction temperature and reaction time, a hydrolysis condensation reaction can be performed most efficiently. In this hydrolysis condensation, the reaction may be carried out in a single stage by adding the hydrolyzable silane compound, water and catalyst to the reaction system at once, or the hydrolyzable silane compound, water and catalyst may be added several times. The hydrolysis and condensation reaction may be carried out in multiple stages by adding them separately in the reaction system. After the hydrolysis condensation reaction, water and the produced alcohol can be removed from the reaction system by adding a dehydrating agent and then subjecting it to evaporation. However, since the dehydrating agent used at this stage generally adsorbs or includes excess water and the dehydrating ability is completely consumed or removed by evaporation, the positive radiation sensitive composition It does not fall into the category of [E] dehydrating agent added later.

The molecular weight of the hydrolyzed condensate of the specific silane compound can be measured as a number average molecular weight in terms of polystyrene using GPC (gel permeation chromatography) using tetrahydrofuran as a mobile phase. The hydrolysis condensation number average molecular weight, is usually preferably ^{5.0 × 10 2 ~1.0 × 10 4} , more preferably ^{1.0 × 10 3 ~5.0 × 10 3} . By setting the value of the number average molecular weight of the hydrolysis-condensation product to 5.0 × 10 ² or more, the film formability of the coating film of the positive radiation sensitive composition can be improved. On the other hand, when the value of the number average molecular weight of the hydrolysis-condensation product is 1.0 × 10 ⁴ or less, it is possible to prevent the radiation sensitivity of the positive radiation-sensitive composition from being lowered.

<[B] quinonediazide compound>
[B] A quinonediazide compound is a quinonediazide compound that generates a carboxylic acid upon irradiation with radiation. The positive radiation sensitive composition containing such a quinonediazide compound has positive radiation sensitive characteristics in which an exposed portion in the radiation irradiation process is removed in the development process. [B] As the quinonediazide compound, it is preferable to use a compound obtained by esterifying a compound having a phenolic hydroxyl group constituting the mother nucleus and a naphthoquinonediazidesulfonic acid halide. Examples of the compound having a phenolic hydroxyl group include compounds in which the ortho position and the para position of the phenolic hydroxyl group are each independently a hydrogen atom or a substituent represented by the following formula (8).

（式（８）中、Ｒ^１４、Ｒ^１５及びＲ^１６は、それぞれ独立して炭素数１〜１０のアルキル基、カルボキシル基、フェニル基又は置換フェニル基である。但し、上記炭素数１〜１０のアルキル基が有する水素原子の一部又は全部は、置換されていてもよい。また、Ｒ^１４及びＲ^１５、又はＲ^１４、Ｒ^１５及びＲ^１６は、それぞれが結合している炭素原子と共に環構造を形成してもよい。）

(In Formula (8), R <^14> , R <^15> and R < ¹⁶ > are respectively independently a C1-C10 alkyl group, a carboxyl group, a phenyl group, or a substituted phenyl group. However, the said C1-C10 Some or all of the hydrogen atoms of the alkyl group may be substituted, and R ¹⁴ and R ¹⁵ , or R ¹⁴ , R ^15, and R ¹⁶ , together with the carbon atom to which each is bonded, A structure may be formed.)

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹⁴ , R ¹⁵ and R ¹⁶ include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t- A butyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, trifluoromethyl group, 2-carboxyethyl group and the like can be mentioned. Examples of the substituent of the substituted phenyl group include a hydroxyl group. ^Moreover, the ^{R 14} and ^{R 15} are, or the ^{R 14} and ^{R 15} and ^{R 16} are as ring structure which may be formed together with the carbon atom bonded to each other, such as cyclopentane ring, cyclohexane ring, adamantane Ring, fluorene ring and the like.

  Examples of the compound having a phenolic hydroxyl group include compounds represented by the following formulas (9) and (10).

  As other compounds having a phenolic hydroxyl group, for example, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, 1,1,1- And tri (p-hydroxyphenyl) ethane.

  As the naphthoquinone diazide sulfonic acid halide, for example, 4-naphthoquinone diazide sulfonic acid halide or 5-naphthoquinone diazide sulfonic acid halide can be used. An ester compound (quinonediazide compound) obtained from 4-naphthoquinonediazidesulfonic acid halide is suitable for i-line exposure because it has absorption in the i-line (wavelength 365 nm) region. In addition, an ester compound (quinonediazide compound) obtained from 5-naphthoquinonediazidesulfonic acid halide is suitable for exposure in a wide range of wavelengths because absorption exists in a wide range of wavelengths. It is preferable to select an ester compound obtained from 4-naphthoquinone diazide sulfonic acid halide or an ester compound obtained from 5-naphthoquinone diazide sulfonic acid halide depending on the wavelength to be exposed. Particularly preferred quinonediazide compounds include 4,4 ′-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene] bisphenol (1.0 mol) and 1,2-naphtho. Examples thereof include condensates with quinonediazide-5-sulfonic acid chloride (2.0 mol).

  [B] The molecular weight of the quinonediazide compound is preferably 300 to 1,500, more preferably 350 to 1,200. By setting the molecular weight of the quinonediazide compound to 300 or more, the transparency of the formed interlayer insulating film can be maintained high. On the other hand, when the molecular weight of the quinonediazide compound is 1,500 or less, it is possible to suppress a decrease in the pattern forming ability of the positive radiation-sensitive composition.

  These [B] quinonediazide compounds can be used alone or in combination of two or more. The amount of the [B] quinonediazide compound used in the positive radiation sensitive composition is preferably 5 parts by mass to 100 parts by mass, more preferably 10 parts by mass to 50 parts by mass with respect to 100 parts by mass of the [A] siloxane polymer. Part. [B] By using the quinonediazide compound in an amount of 5 parts by mass to 100 parts by mass, the difference in solubility between the irradiated part and the non-irradiated part with respect to the alkaline aqueous solution used as the developer is large, and the patterning performance is improved. Moreover, the solvent resistance of the obtained interlayer insulating film is also improved.

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

  In the positive radiation sensitive composition, the [C] copolymer preferably has a structural unit derived from the compound (c4), and in addition to the structural unit derived from the compound (c4), the compound (c5) It is more preferable to have a structural unit derived from.

[(C1) Compound]
(C1) The compound is a polymerizable compound represented by the above formula (1). In formula (1), R ¹ is a hydrogen atom or a methyl group. α is an integer of 0-6. β is an integer of 1-20.

The group —C _α H _2α — in the above formula (1) 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.

_-C β F 2β _{+ 1} in the formula (1) 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. —C _β F _{2β + 1} is preferably a linear fluoroalkyl group.

  As the compound (c1) in the present invention, a compound represented by the above formula (5) is preferable. Examples of the compound (c1) include compounds represented by the following formulas (c1-1) to (c1-8).

[(C2) Compound]
(C2) The compound is a polymerizable compound represented by the above formula (2). In formula (2), R ² is a hydrogen atom or a methyl group. R ³ is an alkyl group having 1 to 12 carbon atoms. γ is 2 or 3. a is the number of structural units, and the number average value thereof is 1-30.

Group -C _gamma H _{2 [gamma} in the above equation (2) - is a linear or branched alkylene group. _-C γ H 2γ - when is asymmetrical, regardless the direction of its bond. Examples of —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 number of structural units a in the above formula (2). The number average value of a is 1-30, preferably 2-20, more preferably 4-12. 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 with respect to 1 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 the compound (c2), and the moles of ethylene oxide or propylene oxide introduced per mole of (meth) acrylic acid. A value that is the number average molecular weight obtained above is calculated from the number and obtained.

  (C2) As a compound, a commercial item can be used conveniently. Examples of commercially available products include NK-ester M-40G, NK-ester M-90G, and AM-90G manufactured by Shin-Nakamura Chemical Co., Ltd .; NOF Bremer PME-200, PME-400, and PME-550. .

[(C3) Compound]
(C3) The compound is a polymerizable compound represented by the above formula (3). In formula (3), R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a group represented by the above formula (4). is there. b is an integer of 0-3. However, if R ⁵ and R ⁶ are a plurality each of the plurality of R ⁵ and R ⁶ may each be the same or different. In formula (4), R <^9> , R < ¹⁰ > and R < ¹¹ > are respectively independently a C1-C20 alkyl group or a phenyl group. c is an integer of 0-3.

(C3) As a compound, in said formula (3), R < ⁴ >, R < ⁵ > and R < ⁶ > are respectively a C1-C20 alkyl group or a phenyl group, and R < ⁷ > and R <^8> are respectively the said formula. A polymerizable unsaturated compound having a group represented by (4) is preferred.

  As the compound (c3), a compound represented by the following formula (c3-1) is preferable.

（式（ｃ３−１）中、Ｒ^Ｓｉは、上記式（３）で表される基である。Ｒ^１７は、水素原子又はメチル基である。ｄは、１〜３の整数である。）

(In formula (c3-1), R ^Si is a group represented by the above formula (3). R ¹⁷ is a hydrogen atom or a methyl group. D is an integer of 1 to 3.)

  Examples of the compound (c3-1) include compounds represented by the following formulas (c3-1-1), (c3-1-2), and (c3-1-3).

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

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

（式（ｃ３−１−２）中、Ｍｅ、ｒ、ｓ及びｔは、上記式（ｃ３−１−１）と同義である。）

(In the formula (c3-1-2), Me, r, s, and t have the same meanings as the above formula (c3-1-1).)

（式（ｃ３−１−３）中、Ｍｅ、ｒ、ｓ及びｔは、上記式（ｃ３−１−１）と同義である。Ｐｈは、フェニル基である。）

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

[(C4) Compound]
(C4) The compound is a polymerizable compound having an unsubstituted alkyl ester group having 1 to 8 carbon atoms. Examples of the compound (c4) include alkyl (meth) acrylates having an unsubstituted alkyl ester group having 1 to 8 carbon atoms. Examples of the (c4) compound include n-butyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate and the like.

[(C5) Compound]
(C5) The compound is a polymerizable compound having two or more unsaturated bonds in one molecule. Examples of the compound (c5) include compounds in which both ends are methacrylated, 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), commercially available products can be suitably used, and examples thereof include NK ester 1G, 2G, 3G, 4G, 9G and 14G manufactured by Shin-Nakamura Chemical Co., Ltd.

  [C] When the copolymer has structural units derived from the compound (c1), the compound (c2) and the compound (c3) as described above, the use ratio of each polymerizable compound with respect to the total amount of these polymerizable compounds is (C1) 10 mass% to 55 mass% per compound, (c2) 10 mass% to 50 mass% per compound, and (c3) 5 mass% to 45 mass% per compound.

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

  [C] When the copolymer further has a structural unit derived from the compound (c5), the use ratio of each polymerizable compound relative to the total amount of the polymerizable unsaturated compound is 25% by mass to 35% by mass per compound (c1). (C2) 20% to 30% by weight per compound, (c3) 15% to 20% by weight per compound, (c4) 25% to 35% by weight per compound, and (C5) 1% by mass to 5% by mass per compound. [C] Each of the compounds (c1) to (c5) for forming the copolymer may be used alone, or a plurality of types may be mixed and used.

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

<Method for Producing [C] Copolymer>
[C] The method for producing the copolymer 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, a radical polymerization method in a solution is preferable because it is simple.

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

  [C] The copolymer can be produced in the presence or absence of a solvent, but 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 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 the production of the [C] copolymer, 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 the [C] copolymer used in the positive radiation-sensitive composition is preferably 0.01 parts by mass to 3 parts by mass, more preferably 0 with respect to 100 parts by mass of the [A] copolymer. .05 parts by mass to 2 parts by mass. By using the [C] copolymer in such a ratio, an interlayer insulating film having high flatness without coating unevenness can be formed.

<Other optional components>
The positive radiation-sensitive composition of the present invention is [D] a heat-sensitive acid generator or a heat-sensitive material as necessary, in addition to the above-mentioned components [A] to [C], as long as the desired effect is not impaired. Other optional components such as a base generator and [E] dehydrating agent can be contained.

[[D] heat-sensitive acid generator or heat-sensitive base generator]
[D] The heat-sensitive acid generator or the heat-sensitive base generator acts as a catalyst for self-condensation curing of the [A] siloxane polymer (preferably a hydrolysis condensate of a specific silane compound) by applying heat. Is defined as a compound capable of releasing an acid or a base. By using such a [D] heat-sensitive acid generator or heat-sensitive base generator, the heat resistance and solvent resistance of the resulting interlayer insulating film can be further improved. [D] As the heat-sensitive acid generator or heat-sensitive base generator, an acid or salt is used at the time of pre-baking at a relatively low temperature (for example, 70 ° C. to 120 ° C.) in the coating forming process of the positive radiation sensitive composition. Those which do not release and have a property of releasing acid or base at the time of post-baking at a relatively high temperature (for example, 120 ° C. to 250 ° C.) in the heating step after development are preferable.

  [D] Examples of the heat-sensitive acid generator include diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, benzothiazonium salts, ammonium salts, phosphonium salts, onium salts such as tetrahydrothiophenium salts, sulfonimide compounds, and the like. Can be mentioned.

  Examples of the diphenyliodonium salt 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-butylphenyl) iodonium hexafluoroarsenate Bis (4-t-butylphenyl) iodonium trifluorome Sulphonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonic acid, etc. .

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

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

  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 and the like can be mentioned.

  Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenyl. Methylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenyl Examples include methylsulfonium hexafluorophosphate.

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

  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 the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, and 3- (p-methoxybenzyl). ) Benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

  Examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nona. Fluoro-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) tetrahydride Thiophenium-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.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide (SI-105, manufactured by Midori Chemical), N- (camphorsulfonyloxy) succinimide (SI-106, manufactured by Midori Chemical), N- (4- Methylphenylsulfonyloxy) succinimide (SI-101, manufactured by Midori Chemical), N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) ) Phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoro) Tylsulfonyloxy) diphenylmaleimide (PI-105, manufactured by Midori Chemical), N- (camphorsulfonyloxy) diphenylmaleimide, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2, 3-dicarboxylimide (NDI-100, manufactured by Midori Chemical), N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (NDI-101) , Green Manufactured), N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (NDI-105, manufactured by Midori Chemical), N- (nonafluorobutanesulfonyloxy) ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (NDI-109, manufactured by Midori Chemical), N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboxylimide (NDI-106, manufactured by Midori Chemical), N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-di Carboxylimide, 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-dicarboxyl Imido, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxa Cyclo [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-5,6-oxy-2, 3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyl N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide (NAI-105, manufactured by Midori Kagaku), N- (camphorsulfonyloxy) naphthyl dicarboxylimide (NAI-106, manufactured by Midori Chemical), N- (4 -Methylphenylsulfonyloxy) naphthyl dicarboxylimide (NAI-101, manufactured by Midori Chemical), N- (phenylsulfonyloxy) naphthyl dicarboxylimide (NAI-100, manufactured by Midori Chemical), N- (2-trifluoromethylphenyl) Sulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropyl sulphonyl) Phosphonyloxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide (NAI-109, manufactured by Midori Chemical), N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl Dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide (NAI-1004, manufactured by Midori Chemical), N- (pentylsulfonyloxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) naphthyl dicarboxylimide, N -(Heptylsulfonyloxy) naphthyl dicarboxylimide, N- (octylsulfonyloxy) naphthyl dicarboxylimide, N- (nonylsulfonyloxy) naphthyl dicarboxylimide De, and the like.

  Among these heat-sensitive acid generators, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, and tetrahydrothiophenium salt are preferable from the viewpoint of improving the heat resistance and solvent resistance of the obtained interlayer insulating film. 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- (4,7-dibutoxy-1 Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylic imide are preferable.

  [D] Examples of the heat-sensitive base generator include 2-nitrobenzylcyclohexyl carbamate, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, bis [ [(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyloxime, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, hexaamminecobalt (III) tris (triphenylmethylborate) Etc. . Of these [D] heat-sensitive base generators, 2-nitrobenzylcyclohexyl carbamate and O-carbamoylhydroxyamide are particularly preferred from the viewpoint of improving the heat resistance and solvent resistance of the resulting interlayer insulating film.

  [D] As the heat-sensitive acid generator or the heat-sensitive base generator, either an acid or a base is used, and one kind may be used alone, or two or more kinds may be used in combination. Good. [D] The amount of the heat-sensitive acid generator or the heat-sensitive base generator used is preferably 0.1 to 20 parts by mass, more preferably 1 to 100 parts by mass of the [A] siloxane polymer. Parts by mass to 10 parts by mass. [D] By using the heat-sensitive acid generator or the heat-sensitive base generator in an amount of 0.1 to 20 parts by mass, the positive type having excellent heat resistance and solvent resistance of the formed interlayer insulating film A radiation-sensitive composition can be obtained, and generation of precipitates can be prevented in the coating film forming step, thereby facilitating coating film formation.

[[E] Dehydrating agent]
[E] A dehydrating agent is defined as a substance that can convert water into a substance other than water by a chemical reaction or trap water by physical adsorption or inclusion. By allowing the positive radiation sensitive composition to optionally contain [E] a dehydrating agent, it is possible to reduce moisture entering from the external environment. Therefore, by using the [E] dehydrating agent, it is possible to reduce the moisture in the composition, and as a result, the storage stability of the composition can be improved. As such [E] dehydrating agent, at least one compound selected from the group consisting of carboxylic acid esters, acetals (including ketals), and carboxylic acid anhydrides can be preferably used.

  As the carboxylic acid ester, orthocarboxylic acid ester and carboxylic acid silyl ester are preferable. Examples of the orthocarboxylic acid ester include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, propyl orthoacetate, butyl orthoacetate, methyl orthopropionate, ethyl orthopropionate, etc. Is mentioned. Of these orthocarboxylic acid esters, orthoformate such as methyl orthoformate is more preferable. Examples of the carboxylic acid silyl ester include trimethylsilyl acetate, tributylsilyl acetate, trimethylsilyl formate, and trimethylsilyl oxalate.

  As acetals, the reaction product of ketones and alcohol, the reaction product of ketones and dialcohol, and ketene silyl acetals are preferable. Examples of the reaction product of ketones and alcohol include dimethyl acetal, diethyl acetal, dipropyl acetal, and the like.

  As the carboxylic anhydride, formic anhydride, acetic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and acetic acid benzoic anhydride are preferable. Among these carboxylic acid anhydrides, acetic anhydride and succinic anhydride are more preferable from the viewpoint of dehydration effect.

  [E] The amount of the dehydrating agent used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the [A] siloxane polymer. Especially preferably, it is 0.03 mass part-1 mass part. [E] By making the usage-amount of a dehydrating agent into 0.001 mass part-10 mass parts, the storage stability of a positive radiation sensitive composition can be improved.

<Positive radiation sensitive composition>
The positive radiation sensitive composition of the present invention is prepared by mixing the above [A] siloxane polymer, [B] quinonediazide compound, [C] copolymer, and other optional components as required. . 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 is prepared by mixing [A] siloxane polymer, [B quinonediazide compound] and [C] copolymer, and other optional components in a predetermined ratio in a solvent. Can do.

[[F] solvent]
[F] As the solvent, a solvent in which each component is uniformly dissolved or dispersed and does not react with each component is 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 propionates. , Aromatic hydrocarbons, ketones, esters and the like.

  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 the 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, propylene glycol monobutyl ether and the like.

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

  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, and 4-hydroxy-4-methyl-2-pentanone.

  Examples of the 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 -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, 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 monoethyl 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 dialkyl ethers 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 more 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 the form of a solution or dispersion, the total proportion of components other than the [F] solvent in the solution should be arbitrarily set according to the purpose of use, desired film thickness, etc. However, it is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 15 to 35% by mass.

<Method for forming interlayer insulating film>
The method for forming the 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 with radiation,
(3) a step of developing the coating film irradiated with the radiation, and (4) a step of heating the developed coating film.

  In the formation method, the above-mentioned positive radiation-sensitive composition having excellent radiation sensitivity and development margin is used, and a pattern is formed by exposure, development, and heating using radiation sensitivity, thereby easily and finely and elaborately. An interlayer insulating film for a display element having a simple pattern can be formed. Furthermore, the interlayer insulating film formed in this way is excellent in a good balance of general required characteristics, that is, heat resistance, transparency, solvent resistance and low dielectric properties, and has high flatness without uneven coating. Have

[(1) Step of forming coating film of positive radiation-sensitive composition on substrate]
In this step, after the positive radiation-sensitive composition solution or dispersion is applied on the substrate, the coating surface is preferably removed by heating (pre-baking) the coating surface to form a coating film. 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 a hydrogenated product thereof.

  As a method for applying the composition solution or the dispersion, 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 can be employed. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable. The prebaking conditions vary depending on the type of each component, the blending ratio, and the like, but can be preferably about 70 to 120 ° C. for 1 to 10 minutes.

[(2) Step of irradiating at least part of coating film with radiation]
In this step, 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 radiation used for exposure, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used, for example. Among these radiations, radiation having a wavelength in the range of 190 nm 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 J / m ^{2 to} 6,000 J / m ² , more preferably 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.). Is 1,500 J / m ^{2 to} 1,800 J / m ² .

[(3) Process of developing the coating film irradiated with radiation]
In this step, the exposed coating film is developed to remove unnecessary portions (radiation irradiated portions) and form a predetermined pattern. The developer used in the development step is preferably an aqueous solution of an alkali (basic compound). Examples of the alkali 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. .

  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 filling 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 seconds to 180 seconds. Subsequent to such development processing, for example, after washing with running water for 30 seconds to 90 seconds, a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

[(4) Step of heating the developed coating film]
In this step, by heating the patterned thin film using a heating device such as a hot plate or oven, the hydrolysis condensation reaction of the [A] siloxane polymer and the curing reaction of the [C] copolymer are promoted, A cured product can be obtained. In particular, when [D] a heat-sensitive acid generator or heat-sensitive base generator is used, an acid or a base is generated in the heating step, and this serves as a catalyst to further accelerate the condensation reaction of [A] siloxane polymer. it is conceivable that. The heating temperature in the said process is 120 to 250 degreeC, for example. The heating time varies depending on the type of the heating device, but for example, when the heating process is performed on a hot plate, it may be 5 minutes to 30 minutes, and when the heating process is performed in an oven, it may be 30 minutes to 90 minutes. it can. 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 μm to 8 μm, more preferably 0.1 to 6 μm, and particularly preferably 0.1 μm to 4 μm.

  The interlayer insulating film formed from the positive radiation-sensitive composition of the present invention has general requirements of heat resistance, transparency, solvent resistance and low dielectric property, as will be apparent from the following examples. It satisfies the characteristics in a well-balanced manner and has a high level of flatness without application 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.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the hydrolyzable silane compound hydrolyzable silane compound and [C] copolymer obtained from each of the following synthesis examples are as follows. Measured by gel permeation chromatography (GPC) according to specifications.
Apparatus: GPC-101 (made by Showa Denko)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (manufactured by Showa Denko) combined Mobile phase: Tetrahydrofuran

<[A] Synthesis of Siloxane Polymer>
[Synthesis Example 1]
In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, and then 30 parts by mass of methyltrimethoxysilane, 23 parts by mass of phenyltrimethoxysilane, and 0.1 parts by mass of tri-i-propoxyaluminum were charged. The solution was heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 18 parts by mass of ion-exchanged water was charged, heated to 75 ° C. and held for 3 hours. Next, 28 parts by mass of methyl orthoformate was added as a dehydrating agent and stirred for 1 hour. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining the temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, a hydrolysis-condensation product (A-1) was obtained. The solid content concentration of the hydrolysis condensate (A-1) is 40.5% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 1,500, and the molecular weight distribution (Mw / Mn) is 2. Met.

[Synthesis Example 2]
In a vessel equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 22 parts by mass of methyltrimethoxysilane, 12 parts by mass of γ-glycidoxypropyltrimethoxysilane, 20 parts by mass of phenyltrimethoxysilane, And 0.1 mass part of tri-i-propoxyaluminum was prepared, and the hydrolysis-condensation product (A-2) was obtained by the method similar to the synthesis example 1. The solid content concentration of the hydrolysis condensate (A-2) is 39.8% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 1,600, and the molecular weight distribution (Mw / Mn) is 2. Met.

<Synthesis of [C] copolymer>
[Synthesis Example 3]
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 compound (c1) and “NK-” manufactured by Shin-Nakamura Chemical Co., Ltd. as the compound (c2) Ester M-90G "20.7 parts by mass, 18.1 parts by mass of the compound represented by the following formula (c3-1-1-1) as the (c3) compound, and 5.9 parts by mass of methyl methacrylate as the (c4) compound And 23.5 parts by mass of 2-ethylhexyl acrylate, 3.4 parts by mass of a compound obtained by methacrylate formation of both ends of tetramethylene glycol as (c5) compound, and 414 parts by mass of isopropyl alcohol as a solvent were refluxed in a nitrogen gas stream. Below, 0.7 part by mass of 2,2′-azobisisobutyronitrile as a polymerization initiator and lauryl mercapta as a chain transfer agent After adding 4 parts by mass of the solution, the mixture 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 degrees C or less heating conditions using an evaporator. The number average molecular weight Mn of the obtained copolymer (C-1) was 2,800, the weight average molecular weight Mw was 5,300, and the molecular weight distribution (Mw / Mn) was 1.9.

（式（ｃ３−１−１−１）中、Ｍｅは、メチル基である。）

(In the formula (c3-1-1-1), Me is a methyl group.)

[Synthesis Example 4]
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 weight average molecular weight Mw was 11,000, and the molecular weight distribution (Mw / Mn) was 2.3.

[Synthesis Example 5]
The copolymer (C-3) was prepared 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. Obtained. The number average molecular weight Mn of the obtained copolymer (C-3) was 5,600, the weight average molecular weight Mw was 21,000, and the molecular weight distribution (Mw / Mn) was 3.8.

[Synthesis Example 6]
In a glass flask equipped with a stirrer, a condenser and a thermometer, 39.4 parts by mass of the compound represented by the above formula (c1-3) as the compound (c1) and “NK-” manufactured by Shin-Nakamura Chemical Co., Ltd. as the compound (c2) Ester M-90G "31.6 parts by mass, (c3) 29.0 parts by mass of the compound represented by the formula (c3-1-1-1) and 414 parts by mass of isopropyl alcohol were charged as a compound, and in a nitrogen gas stream Then, 0.72 parts by mass of 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator and 4 parts by mass of lauryl mercaptan as a chain transfer agent were added under reflux, and then at 75 ° C. for 8 hours. The solution was refluxed for copolymerization to obtain a solution containing the copolymer (C-4). 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 3,000, and the weight average molecular weight Mw was 6,000. The molecular weight distribution (Mw / Mn) was 2.0.

[Synthesis Example 7]
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 (c1-5) as the compound (c1) and “NK-” manufactured by Shin-Nakamura Chemical Co., Ltd. as the compound (c2) 20.7 parts by mass of “ester M-90G”, 21.5 parts by mass of the compound represented by the above formula (c3-1-1-1) as the compound (c3), and 29.4 parts of n-butyl methacrylate as the compound (c4) 1 part by weight and 414 parts by weight of isopropyl alcohol were charged under reflux in a nitrogen gas stream, 0.7 part by weight of 2,2′-azobisisobutyronitrile (AIBN) as a polymerization initiator, and lauryl mercaptan as a chain transfer agent After adding 4 parts by mass, the mixture was refluxed at 75 ° 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 2,600, and the weight average molecular weight Mw was 5,000. The molecular weight distribution (Mw / Mn) was 1.9.

<Preparation of positive radiation sensitive composition>
[Example 1]
As a solution containing the hydrolysis condensate (A-1) obtained in Synthesis Example 1 (an amount corresponding to 100 parts by mass (solid content) of the hydrolysis condensate (A-1)), 4 as [B] quinonediazide compound. , 4 ′-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride ( 2.0 mol) of the condensate (B-1) 30 parts by mass, [C] the copolymer (C-1) 0.50 part by mass obtained in Synthesis Example 3 as a copolymer, Diethylene glycol ethyl methyl ether was added as a solvent so that the solid content concentration was 25% by mass, and then filtered through a membrane filter having a pore size of 0.2 μm to prepare a positive radiation sensitive composition.

[Examples 2-7 and Comparative Examples 1-3]
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 described in Table 1. In Comparative Examples 1 and 2, the following surfactants were used in place of the [C] copolymer.
c-1: Silicone surfactant (made by Toray Dow Corning Silicone, SH-193)
c-2: Fluorine-based surfactant (manufactured by Neos, Aftergent 222F)

<Evaluation>
Each positive radiation sensitive composition prepared as described above was used, and various properties as the composition and its coating film or interlayer insulating film were evaluated as follows. The evaluation results are shown in Table 1.

[Appearance of coating film]
The radiation sensitive composition prepared as described above was applied onto a 550 × 650 mm chromium film using a slit die coater (manufactured by Tokyo Ohka Kogyo Co., Ltd., TR6322105-CL), and the ultimate pressure was set to 100 Pa. After removing the solvent under vacuum, it was further pre-baked 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”. The case where almost none of these unevennesses were visible was determined as “A”, the case where any of these unevennesses was slightly visible was determined as “B”, and the case where they were clearly visible was determined as “C”.

[Radiation sensitivity]
Hexamethyldisilazane (HMDS) was applied onto 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 “TR6321055-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, after using a Canon MPA-600FA exposure machine and irradiating the coating film with a variable exposure amount through a mask having a 6 μm line-and-space (one-to-one) pattern, Development was carried out 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, washing with running ultrapure water for 1 minute was performed, followed by drying to form a pattern on the chromium-deposited glass substrate after the HMDS treatment. At this time, the exposure amount required for completely dissolving the 6 μm line-and-space (one-to-one) space pattern was examined. When this value was 700 J / m ² or less, the sensitivity was judged good.

[Development margin]
The HMDS process of the chromium film-forming glass (4-inch glass wafer) was performed in the same manner as in the evaluation of the radiation sensitivity. On the chromium-deposited glass after the HMDS treatment, the radiation-sensitive composition prepared as described above was applied using a spin coater, the ultimate pressure was set to 100 Pa, and the solvent was removed by vacuum drying. By prebaking at 2 ° C. for 2 minutes, a coating film having a thickness of 3.0 μm was formed. Subsequently, using a Canon MPA-600FA exposure machine, the radiation examined by the above-described evaluation of radiation sensitivity with respect to the coating film through a mask having a 6 μm line-and-space (one-to-one) pattern. Exposure was performed at an exposure amount corresponding to the sensitivity value, and then development was performed by a puddle method at 25 ° C. using a tetramethylammonium hydroxide aqueous solution having a concentration shown in Table 1 with a development time as a variable. Next, washing with running ultrapure water for 1 minute was performed, followed by drying to form a pattern on the chromium-deposited glass substrate after the HMDS treatment. At this time, the development time necessary for the line width to be 6 μm is shown in Table 1 as the optimum development time. Further, when the development was further continued from the optimum development time, the time until the 6 μm line pattern was peeled was measured. When this value was 30 seconds or more, the development margin was judged to be good.

[Solvent resistance]
After applying the radiation-sensitive composition prepared as described above onto a chromium film-forming glass (4 inch glass wafer) using a spin coater, setting the ultimate pressure to 100 Pa and removing the solvent under vacuum, Furthermore, it prebaked at 90 ° C. for 2 minutes to form a coating film. By exposing the coated film to an accumulated dose of 9,000 J / m ² using a Canon MPA-600FA exposure machine, and then heating at 220 ° C. for 1 hour in a clean oven, An interlayer insulating film was formed on the chromium film-forming glass. The film thickness (T1) of the interlayer insulating film obtained here was measured. And after immersing the chromium film-forming glass substrate on which this interlayer insulating film was formed in dimethyl sulfoxide whose temperature was controlled at 70 ° C. for 20 minutes, the film thickness (t1) of the interlayer insulating film was measured again, and the immersion The film thickness change rate was calculated from the following formula.
{| T1-T1 | / T1} × 100 (%)
When this value was 5% or less, it was judged that the solvent resistance was good.

[Heat-resistant]
An interlayer insulating film was formed on the chromium-deposited glass in the same manner as in the evaluation of the solvent resistance. The film thickness (T2) of the interlayer insulating film obtained here was measured. Next, the chromium film-formed glass substrate on which the interlayer insulating film is formed is heated for one hour at 240 ° C. in a clean oven, and then the thickness (t2) of the interlayer insulating film is measured again. The film thickness change rate {| t2-T2 | / T2} × 100 [%] by heating was calculated. When this value was 5% or less, it was judged that the heat resistance was good.

[transparency]
An interlayer insulating film is formed on the glass substrate in the same manner as in the evaluation of the solvent resistance except that a 550 × 650 mm glass substrate (“NA35” manufactured by NH Techno Glass) is used instead of the chromium film-formed glass substrate. Formed. Using a spectrophotometer “150-20 type double beam (manufactured by Hitachi, Ltd.)”, the light transmittance of the formed glass substrate having an interlayer insulating film is determined to be 400 nm to 800 nm with the glass substrate having no interlayer insulating film as a reference side. Measured at a wavelength in the range of. When this value was 90% or more, it was judged that the transparency was good.

[Thickness uniformity (flatness)]
An interlayer insulating film was formed on the glass substrate by operating in the same manner as the evaluation of the transparency. About this interlayer insulation film, the film thickness was measured at 20 measurement points, and the film thickness uniformity was calculated by the following formula.
Uniformity of film thickness (%) = (maximum value of film thickness of interlayer insulating film−minimum value) × 100 / ((average of coating film thickness of 20 points) × 2)
If the uniformity of the film thickness of the interlayer insulating film calculated in this way is 1% or less, it can be said that the film thickness uniformity is good. The 20 measurement points were determined as follows. That is, an inner region (450 × 550 mm) excluding a range of 5 cm from each end of the long side and the short side of the substrate (550 × 650 mm) is set as a measurement region, and the long side direction and the short side direction are within the region. Ten points (20 points in total) were determined every 4 cm on a straight line, and these were used as measurement points.

[Relative permittivity]
The radiation-sensitive composition prepared as described above was applied by spin coating on a SUS304 substrate that had been polished by sisal buffing and smoothed, and the ultimate pressure was set to 100 Pa under vacuum. After removing the solvent, it was further pre-baked at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film is exposed with a Canon MPA-600FA exposure machine so that the integrated dose is 9,000 J / m ^2, and this substrate is heated at 220 ° C. for 1 hour in a clean oven. Thus, an interlayer insulating film was formed on the substrate. On this interlayer insulating film, a Pt / Pd electrode pattern was formed by vapor deposition to prepare a dielectric constant measurement sample. Using the HP16451B electrode and HP4284A Precision LCR meter manufactured by Yokogawa-Hewlett-Packard, the relative dielectric constant of the substrate having this electrode pattern was measured by the CV method at a frequency of 10 kHz. When this value was 3.9 or less, it was judged that the relative dielectric constant (low dielectric constant) was good.

  As is clear from the results in Table 1, the positive radiation sensitive compositions of Examples 1 to 7 containing [A] siloxane polymer, [B] quinonediazide compound and [C] copolymer were obtained from [C] copolymer. Compared with the positive radiation sensitive compositions of Comparative Examples 1 to 3 which do not contain coalescence, it was found that the coating unevenness in the appearance of the coating film and the flatness of the interlayer insulating film were superior. In addition, the positive-type radiation-sensitive compositions of these examples have high radiation sensitivity and development margin, and sufficiently satisfy the general required characteristics of heat resistance, transparency, solvent resistance and low dielectric properties. It was found that an interlayer insulating film can be formed.

  As described above, the positive radiation-sensitive composition of the present invention has excellent radiation sensitivity and development margin, and has excellent flatness in addition to sufficient heat resistance, transparency, solvent resistance and low dielectric property. It is possible to form an interlayer insulating film having properties. Therefore, the positive radiation sensitive composition is suitably used for forming an interlayer insulating film for a display element.

Claims (10)

[A] siloxane polymer,
[B] quinonediazide compound, and [C] (c1) a polymerizable compound represented by the following formula (1),
(C2) A positive compound containing a polymerizable compound represented by the following formula (2), and (c3) a copolymer having a structural unit derived from a polymerizable compound having a group represented by the following formula (3) Radiation sensitive composition.

(In formula (1), R ¹ 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 (2), R ² is a hydrogen atom or a methyl group. R ³ is an alkyl group having 1 to 12 carbon atoms. Γ is 2 or 3. a is the number of structural units. Yes, the number average value is 1-30.)

(In formula (3), R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a group represented by the following formula (4). .b it is an integer of 0 to 3. However, ^{if R 5} and ^{R 6} are a plurality each of the plurality of ^{R 5} and ^{R 6} may each be the same or different.)

(In the formula ^(4), R ^{9, R 10} and ^{R 11} are each independently an alkyl group or a phenyl group having 1 to 20 carbon atoms .c is an integer of 0 to 3. ^{However, R 10} And when there are a plurality of R ^{11 s} , the plurality of R ¹⁰ and R ¹¹ may be the same or different.)   The positive radiation sensitive composition according to claim 1, wherein the [C] copolymer further comprises (c4) a structural unit derived from a polymerizable compound having an unsubstituted alkyl ester group having 1 to 8 carbon atoms.   The positive radiation sensitive composition according to claim 2, wherein the [C] copolymer further comprises (c5) a structural unit derived from a polymerizable compound having two or more unsaturated bonds in one molecule. (C1) The compound is a polymerizable compound represented by the following formula (5),
(C2) The compound is a polymerizable compound represented by the following formula (6), and [C] copolymer is:
(C1) 25% by mass or more and 35% by mass or less of the compound,
(C2) 20% by mass or more and 30% by mass or less of the compound,
(C3) 15% by mass or more and 20% by mass or less of the compound,
The positive radiation-sensitive composition according to claim 3, which is synthesized from a composition containing (c4) 25% by mass to 35% by mass of the compound and (c5) 1% by mass to 5% by mass of the compound.

(In formula (5), ^{R 1} is .Beta as defined in the above formula (1) is an integer of 1 to 8.)

(In the formula (6), ^{R 2} and ^{R 3,} the number average value of .a as defined in the above formula (2) is 4-12.)
[A] The positive radiation sensitive composition according to any one of claims 1 to 4, wherein the siloxane polymer is a hydrolysis condensate of a hydrolyzable silane compound represented by the following formula (7).

(In the formula ^{(7), R 12} is ^{.R 13} is a non-hydrolyzable organic group having 1 to 20 carbon atoms, the .x is an alkyl group having 1 to 4 carbon atoms, an integer of 0 to 3 it is. ^{However, if R 12} and ^{R 13} are a plurality each of a plurality of ^{R 12} and ^{R 13} may each be the same or different.)   [D] The positive radiation sensitive composition according to any one of claims 1 to 5, further comprising a heat sensitive acid generator or a heat sensitive base generator.   [E] The positive radiation sensitive composition according to any one of claims 1 to 6, further comprising a dehydrating agent.   The positive radiation sensitive composition according to any one of claims 1 to 7, 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 8 on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) A step of developing the coating film irradiated with the radiation, and (4) A method for forming an interlayer insulating film for a display element, comprising the step of heating the developed coating film.   The interlayer insulation film of the display element formed from the positive radiation sensitive composition of Claim 8.