JPWO2011065215A1 - Positive radiation-sensitive composition, cured film and method for forming the same - Google Patents

Abstract

An object of the present invention is to use a cured film excellent in heat resistance, transparency, solvent resistance and low dielectric constant, and a liquid crystal cell having a high voltage holding ratio, and sufficient radiation sensitivity, and It is to provide a polysiloxane-based positive radiation sensitive composition excellent in melt flow resistance in a heating step after development, a cured film formed from the composition, and a method for forming the cured film. The present invention relates to [A] siloxane polymer, [B] quinonediazide compound, and positive radiation sensitivity containing a radiation sensitive acid generator having a maximum absorption wavelength shorter than the maximum absorption wavelength of [C] [B] quinonediazide compound. It is a composition.

Description

  The present invention relates to a positive radiation sensitive composition, a cured film, and a method for forming the same.

  A liquid crystal display element or the like is generally provided with an interlayer insulating film in order to insulate between wirings arranged in layers. As a material for forming such a cured film typified by an interlayer insulating film, a material having a small number of steps for obtaining a required pattern shape and having sufficient flatness is preferable. Things are widely used.

  Further, for example, in the interlayer insulating film of the liquid crystal display element, it is necessary to form a pattern of contact holes for wiring. In a negative composition, it is difficult to form a contact hole having a hole diameter of a practically usable level. Therefore, a positive radiation sensitive composition is used for forming a cured film such as an interlayer insulating film of a liquid crystal display element. Are widely used (see JP 2001-354822 A).

  As a component of the radiation sensitive composition for forming a cured 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 with an acrylic resin, as a component of the radiation-sensitive composition (JP 2000-1648 A, JP 2006-178436 A). No. publication). Regardless of which radiation sensitive composition is used, in the heating process (post-baking process) after radiation irradiation and development, the melt flow of the pattern formed (the pattern shape melts and deforms with heat). It is important from the viewpoint of preventing display defects of the liquid crystal display element.

  As a radiation-sensitive composition using the polysiloxane material, a photosensitive siloxane composition containing polysiloxane, a quinonediazide compound, and a thermally crosslinkable compound has been developed (see JP-A-2006-293337). By using such a photosensitive siloxane composition, a cured film having high heat resistance, high transparency, low dielectric constant, high chemical resistance, and high resolution can be formed. Yes. However, even when these photosensitive siloxane compositions are used, a practically sufficient level of melt flow resistance cannot be obtained as a material for forming a cured film, and the transmittance is lowered by the photoacid generator used. Trigger.

  Under such circumstances, it is possible to form a cured film excellent in heat resistance, transparency, solvent resistance and low dielectric property, which is generally required, and a liquid crystal cell having a high voltage holding ratio, and in addition to radiation sensitivity. Therefore, development of a polysiloxane-based positive radiation sensitive composition excellent in melt flow resistance in the heating step after development is strongly desired.

JP 2001-354822 A JP 2000-1648 A JP 2006-178436 A JP 2006-293337 A

  The present invention has been made based on the above circumstances, and its purpose is to form a cured film excellent in heat resistance, transparency, solvent resistance and low dielectric properties, and a liquid crystal cell having a high voltage holding ratio. A polysiloxane positive-type radiation-sensitive composition that is suitably used for the above-mentioned and has excellent radiation sensitivity and excellent melt flow resistance in a heating step after development, a cured film formed from the composition, and It is to provide a method for forming the cured film.

The invention made to solve the above problems is
[A] siloxane polymer,
[B] quinonediazide compound, and radiation sensitive acid generator having a maximum absorption wavelength shorter than the maximum absorption wavelength of [C] [B] quinonediazide compound (hereinafter sometimes referred to as [C] acid generator)
Is a positive radiation-sensitive composition containing

Since the positive radiation sensitive composition contains [C] acid generator in addition to [A] siloxane polymer and [B] quinonediazide compound, the radiation of [B] quinonediazide compound by exposure at the time of pattern formation. While forming a positive pattern by promoting absorption, the cross-linking reaction of [A] siloxane polymer is promoted by radiation absorption of the [C] acid generator during exposure after development at a shorter wavelength than during pattern formation. The structure can be strengthened. As a result, it is possible to form a cured film that satisfies the general required characteristics of heat resistance, transparency, solvent resistance, and low dielectric properties in a well-balanced manner, and a liquid crystal cell having a high voltage holding ratio. In addition to excellent radiation sensitivity, high melt flow resistance in the heating step after development can be achieved.
When the [B] quinonediazide compound and the [C] acid generator have a plurality of absorption maximums, the wavelength corresponding to the absorption maximum having the highest absorbance among the absorption maximums is referred to as the maximum absorption wavelength. When a plurality of absorption maximums show the same absorbance, the wavelength corresponding to the absorption maximum that is shorter than the maximum absorption wavelength of the [B] quinonediazide compound and is on the longest wavelength side is referred to as the maximum absorption wavelength.

（式（１）中、
Ｒ^１は、水酸基、炭素数１〜１２の直鎖状若しくは分岐状のアルキル基、炭素数６〜１２のアリール基又は炭素数１〜１２のアルコキシ基である。但し、上記アルキル基、アリール基及びアルコキシ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。
Ｒ^２は、水素原子、炭素数１〜７の直鎖状若しくは分岐状のアルキル基又は炭素数６〜１２のアリール基である。但し、上記アルキル基、アリール基及びアルコキシ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。
ａは、０〜７の整数である。ｂは、０〜１０の整数である。ｃは、０〜３の整数である。但し、Ｒ^１及びＲ^２がそれぞれ複数ある場合、複数のＲ^１及びＲ^２は、それぞれ同一であっても異なっていてもよい。また、Ｒ^２が複数ある場合、複数のＲ^２のうち、２つのＲ^２が相互に結合して環状構造を形成してもよい。
Ｘは、ＳｂＦ_６、（Ｃ_ｎＦ_２ｎ＋１）_ＹＰＦ_６−Ｙ又はＣ_ｎＦ_２ｎ＋１ＳＯ_３である。Ｙは、０〜６の整数である。ｎは、１〜６の整数である。
式（２）中、
Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立して水酸基、炭素数１〜１２の直鎖状若しくは分岐状のアルキル基又は炭素数６〜１５のアリール基である。但し、上記アルキル基及びアリー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。
ｄ、ｅ及びｆは、それぞれ独立して０〜５の整数である。
但し、Ｒ^３、Ｒ^４及びＲ^５がそれぞれ複数ある場合、複数のＲ^３、Ｒ^４及びＲ^５は、それぞれ同一であっても異なっていてもよい。
Ｘ^１は、ＳｂＦ_６、（Ｃ_ｎＦ_２ｎ＋１）_ＹＰＦ_６−Ｙ又はＣ_ｎＦ_２ｎ＋１ＳＯ_３である。Ｙは、０〜６の整数である。ｎは、１〜６の整数である。
式（３）中、
Ｒ^６及びＲ^７は、それぞれ独立して炭素数１〜１２のアルキル基、炭素数４〜２０の脂環式アルキル基又は炭素数６〜２０のアリール基である。但し、上記アリール基が有する水素原子の一部又は全部は、炭素数１〜１２のアルコキシ基で置換されていてもよい。）

（式（１−１）中、
Ｒ^８及びＲ^９は、それぞれ独立して水素原子、水酸基、炭素数１〜１２の直鎖状若しくは分岐状のアルキル基又は炭素数１〜１２のアルコキシ基である。
Ｘは、上記式（１）と同義である。
式（２−１）中、
Ｒ^１０は、フェニル基、ナフチル基、アントラニル基又はフェニルチオ基である。
Ｘ^１は、上記式（２）と同義である。）[C] The acid generator is preferably at least one compound selected from the group consisting of compounds represented by the following formulas (1), (2) and (3). The compound represented by 1) is represented by the following formula (1-1), and the compound represented by the following formula (2) is more preferably a compound represented by the following formula (2-1).

(In the formula (1),
R ¹ is a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. However, one part or all part of the hydrogen atom which the said alkyl group, aryl group, and alkoxy group have may be substituted.
R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, or an aryl group having 6 to 12 carbon atoms. However, one part or all part of the hydrogen atom which the said alkyl group, aryl group, and alkoxy group have may be substituted.
a is an integer of 0-7. b is an integer of 0-10. c is an integer of 0-3. However, if the R ¹ and R ² are a plurality each of the plurality of R ¹ and R ² may each be the same or different. Also, when R ² are a plurality, of the plurality of R ^2, 2 two R ² may form a cyclic structure bonded to each other.
X _is, SbF _6, a _{(C n F 2n + 1)} Y PF 6-Y or _{C n F 2n + 1 SO 3} . Y is an integer of 0-6. n is an integer of 1-6.
In formula (2),
R ³ , R ⁴ and R ⁵ are each independently a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 15 carbon atoms. However, one part or all part of the hydrogen atom which the said alkyl group and aryl group have may be substituted.
d, e, and f are each independently an integer of 0-5.
^However, if R 3, ^{R 4} and ^{R 5} are a plurality each of the plurality of ^R 3, ^{R 4} and ^{R 5} may each be the same or different.
X ¹ is SbF ₆ , (C _n F _{2n + 1} ) _Y PF _6-Y, or C _n F _{2n + 1} SO ₃ . Y is an integer of 0-6. n is an integer of 1-6.
In formula (3),
R ⁶ and R ⁷ are each independently an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 4 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. However, one part or all part of the hydrogen atom which the said aryl group has may be substituted by the C1-C12 alkoxy group. )

(In Formula (1-1),
R ⁸ and R ⁹ are each independently a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
X is synonymous with the above formula (1).
In formula (2-1),
R ¹⁰ is a phenyl group, a naphthyl group, an anthranyl group, or a phenylthio group.
X ¹ is synonymous with the above formula (2). )

  [C] By making an acid generator into the said specific compound, the hydrolysis condensation reaction of the [A] siloxane polymer in the exposure after image development can be accelerated | stimulated more. As a result, the cross-linked structure of the [A] siloxane polymer is strengthened, and the melt flow resistance in the heating process can be further improved.

（式（４）中、Ｒ^１１は、非加水分解性の基である。Ｒ^１２は、炭素数１〜４のアルキル基である。ｇは、０〜３の整数である。但し、Ｒ^１１及びＲ^１２がそれぞれ複数ある場合、複数のＲ^１１及びＲ^１２は、それぞれ同一であっても異なっていてもよい。）[A] The siloxane polymer is preferably a hydrolysis-condensation product of a hydrolyzable silane compound represented by the following formula (4).

(In Formula (4), R ¹¹ is a non-hydrolyzable group. R ¹² is an alkyl group having 1 to 4 carbon atoms. G is an integer of 0 to 3. However, R ^11. And when there are a plurality of R ^{12 s} , the plurality of R ¹¹ and R ¹² may be the same or different.)

  In the positive radiation sensitive composition, the above [C] acid generator is adopted, and the hydrolysis condensate of the hydrolyzable silane compound represented by the above formula (4) is used as the [A] siloxane polymer. Further, the radiation sensitivity and the melt flow resistance in the heating step after development can be further improved.

  The positive radiation-sensitive composition preferably further contains [D] a heat-crosslinkable compound. Furthermore, by containing the [D] heat crosslinkable compound, the crosslinking reaction of the [A] siloxane polymer in the heating step after development of the positive radiation sensitive composition is further promoted, and the melt flow resistance in the same step is improved. It can be improved further.

  The positive radiation sensitive composition is suitably used for forming a cured film.

The method for forming the cured film of the present invention is as follows.
(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),
(4) a step of irradiating the coating film developed in step (3) with radiation; and (5) a step of heating the coating film irradiated with radiation in step (4).

  In the formation method, a [B] quinonediazide compound having a predetermined radiation absorption region is irradiated with radiation to form a positive pattern, and after development, the [C] acid generator is irradiated with radiation to carry out a crosslinking reaction. By promoting, a coating film having high melt flow resistance can be formed in the subsequent heating step.

  The cured film of the present invention can be suitably formed from the positive radiation sensitive composition.

  As described above, the positive-type radiation-sensitive composition of the present invention efficiently forms a cured film that satisfies the general required characteristics of heat resistance, transparency, solvent resistance, and low dielectric properties in a well-balanced manner. Can do. Further, the positive radiation sensitive composition can exhibit excellent radiation sensitivity and high melt flow resistance.

  The positive radiation sensitive composition of the present invention contains [A] siloxane polymer, [B] quinonediazide compound and [C] acid generator, and may contain other optional components.

<[A] Siloxane polymer>
[A] The siloxane polymer is not particularly limited as long as it is a polymer of a compound having a siloxane bond. This [A] siloxane polymer forms a cured product by hydrolytic condensation. Further, since the positive radiation-sensitive composition contains a [C] acid generator, acid is generated upon irradiation with radiation, and this serves as a catalyst to further promote the self-condensation of the [A] siloxane polymer. The

  [A] The siloxane polymer is preferably a hydrolysis condensate of a hydrolyzable silane compound represented by the above formula (4).

  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. A silane compound having a hydrolyzable group that can form a siloxane condensate or a silane compound having a hydrolyzable group that can form a siloxane. 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 hydrolyzable silane compound represented by the above formula (4), 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.

Examples of the non-hydrolyzable group represented by R ¹¹ include an alkyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with an unsubstituted, (meth) acryloyl group or epoxy group, and 6 carbon atoms. -20 aryl groups, C7-20 aralkyl groups, or vinyl groups. These may be linear, branched, or cyclic, and may be a combination thereof when a plurality of R ¹¹ are present in the same molecule. R ¹¹ may include 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 ¹² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a butyl group. Among these R ¹¹ , a methyl group and an ethyl group are preferable from the viewpoint of easy hydrolysis. Moreover, although g is an integer of 0-3, Preferably it is an integer of 0-2, More preferably, it is 0 or 1, Especially preferably, it is 1. When g is an integer of 0 to 2, the progress of the hydrolytic condensation reaction is facilitated, and the heat resistance and solvent resistance of the resulting cured film can be further improved.

  The hydrolyzable silane compound represented by the above formula (4) is a silane compound substituted with four hydrolyzable groups, substituted with one non-hydrolyzable group and three hydrolyzable groups. Silane compound substituted with two non-hydrolyzable groups and two hydrolyzable groups, substituted with three non-hydrolyzable groups and one hydrolyzable group A silane compound or a mixture thereof may be mentioned.

  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 chlorotrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, and methyl. Tributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane Vinyltri-n-propoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltrie Kishishiran, .gamma.-glycidoxypropyltrimethoxysilane, .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 hydrolyzable silane compounds represented by the above formula (4), a silane compound substituted with four hydrolyzable groups, and one non-hydrolyzable group and three hydrolyzable groups And a silane compound substituted with one non-hydrolyzable group and three hydrolyzable groups is more preferred. Preferred hydrolyzable silane compounds include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Examples include ethyltri-i-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane. These hydrolyzable silane compounds may be used alone or in combination of two or more.

  The condition for hydrolyzing and condensing the hydrolyzable silane compound represented by the above formula (4) is that at least a part of the hydrolyzable silane compound represented by the above formula (4) is hydrolyzed to produce a hydrolyzable group. As long as it is converted into a silanol group to cause a condensation reaction, it is not particularly limited, but can be carried out as follows as an example.

The water used for the hydrolytic condensation of the hydrolyzable silane compound represented by the above formula (4) 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 from 0.1 to 3 mol, more preferably from 1 mol of the total amount of hydrolyzable groups (—OR ¹² ) of the hydrolyzable silane compound represented by the above formula (4). Is 0.3 to 2 mol, particularly preferably 0.5 to 1.5 mol. By using such an amount of water, the reaction rate of the hydrolysis condensation can be optimized.

  Although it does not specifically limit as a solvent which can be used for the hydrolytic condensation of the hydrolysable silane compound represented by the said Formula (4), Usually, preparation of the positive radiation sensitive composition mentioned later The same solvent as that used in the above can be used. As such a solvent, ethylene glycol monoalkyl ether acetate, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and propionic acid esters are preferable. 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 and diacetone alcohol are more preferable.

  The hydrolytic condensation reaction of the hydrolyzable silane compound represented by the above formula (4) is preferably performed using an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphorus Acids, acidic ion exchange resins, various Lewis acids, etc.), basic catalysts (eg, nitrogen-containing compounds such as ammonia, primary amines, secondary amines, tertiary amines, pyridine; basic ion exchange resins; hydroxylation) In the presence of a catalyst such as a hydroxide such as sodium; a carbonate such as potassium carbonate; a carboxylate such as sodium acetate; various Lewis bases; or an alkoxide (eg, zirconium alkoxide, titanium alkoxide, aluminum alkoxide, etc.) Done. Examples of the aluminum alkoxide include tri-i-propoxyaluminum. The amount of the catalyst used is preferably 0.2 mol or less, more preferably 0.00001 to 0.1, with respect to 1 mol of the hydrolyzable silane compound monomer from the viewpoint of promoting the hydrolysis condensation reaction. Is a mole.

  The reaction temperature and reaction time in the hydrolytic condensation of the hydrolyzable silane compound represented by the above formula (4) 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. In addition, after a hydrolysis condensation reaction, water and the produced | generated alcohol can be removed from a reaction system by adding a dehydrating agent and then evaporating. However, since the dehydrating agent used at this stage generally absorbs or includes excess water and the dehydrating ability is completely consumed or removed by evaporation, a positive radiation sensitive composition is used. It is not included in the category of [F] dehydrating agent to be optionally added to the above.

  The molecular weight of the hydrolysis condensate of the hydrolyzable silane compound represented by the above formula (4) is measured as a number average molecular weight in terms of polystyrene using GPC (gel permeation chromatography) using tetrahydrofuran as a mobile phase. be able to. As a number average molecular weight of a hydrolysis-condensation product, 500-10,000 are preferable normally and 1,000-5,000 are more preferable. By setting the number average molecular weight of the hydrolysis-condensation product to 500 or more, the film formability of the coating film of the positive radiation-sensitive composition can be improved. On the other hand, the fall of the radiation sensitivity of a positive type radiation sensitive composition can be prevented by making the value of the number average molecular weight of a hydrolysis-condensation product into 10,000 or less.

<[B] quinonediazide compound>
[B] A quinonediazide compound is a quinonediazide compound that generates a carboxylic acid upon irradiation with radiation. Such a positive radiation sensitive composition containing a quinonediazide compound has a positive radiation sensitive property in which an exposed portion in a radiation irradiation step for pattern formation is removed in a subsequent development step. [B] The quinonediazide compound is preferably a compound obtained by esterifying a compound having a phenolic hydroxyl group 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 hydrogen or a substituent represented by the following formula (5).

（式（５）中、Ｒ^１３、Ｒ^１４及びＲ^１５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^１３とＲ^１４とが、又はＲ^１３とＲ^１４とＲ^１５とが、相互に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 (5), R <^13> , R <^14> and R < ¹⁵ > are respectively independently a C1-C10 alkyl group, a carboxyl group, a phenyl group, or a substituted phenyl group. However, the said C1-C1 Part or all of the hydrogen atoms of the alkyl group 10 may be substituted, and R ¹³ and R ¹⁴ or R ¹³ , R ^14, and R ¹⁵ are bonded to each other. (A ring structure may be formed with a carbon atom.)

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹³ , R ¹⁴ and R ¹⁵ 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. ^{Also, R 13} and ^{R 14} is or ^{R 13} and ^{R 14} and ^{R 15} 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 (6) and (7).

  Other examples of compounds having a phenolic hydroxyl group include 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, 1,1,1 -Tri (p-hydroxyphenyl) ethane etc. are mentioned.

  Examples of the naphthoquinone diazide sulfonic acid halide include 4-naphthoquinone diazide sulfonic acid halide and 5-naphthoquinone diazide sulfonic acid halide. 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. More preferable quinonediazide compounds include 4,4 ′-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene] bisphenol (1.0 mol) and 1,2-naphtho. Condensate with quinonediazide-5-sulfonic acid chloride (3.0 mol), 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid And a condensate with chloride (3.0 mol).

  The molecular weight of the naphthoquinone diazide compound is preferably 300 to 1,500, more preferably 350 to 1,200. By setting the molecular weight of the naphthoquinone diazide compound to 300 or more, the transparency of the formed cured film can be maintained high. On the other hand, when the molecular weight of the naphthoquinone diazide 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 1 to 100 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the [A] siloxane polymer. . [B] By using the quinonediazide compound in an amount of 1 to 100 parts by mass, the difference in solubility between the irradiated part and the non-irradiated part in the alkaline aqueous solution used as the developer is large, and the patterning performance is improved. The solvent resistance of the cured film obtained is also good.

<[C] acid generator>
The [C] acid generator contained in the positive radiation-sensitive composition has a maximum absorption wavelength shorter than the maximum absorption wavelength of the [B] quinonediazide compound, and is preferably an acid upon irradiation with radiation having the absorption wavelength. Is a compound that generates a strong acid such as perfluorosulfonic acid. The positive radiation sensitive composition containing such a [C] acid generator is a condensation reaction between siloxane polymers by an acid generated from the radiation sensitive acid generator in an exposure step (post exposure step) after development. Is promoted. In addition, since this radiation sensitive acid generator has a radiation absorption region different from the radiation at the time of pattern formation, no acid is generated by the radiation at the time of pattern formation, or a very small amount even if generated. Thus, it is possible to prevent an undesirable reaction from occurring due to a mixture of positive and negative radiation sensitive characteristics.

  [C] The acid generator is not particularly limited as long as it is a compound that has a maximum absorption wavelength shorter than the maximum absorption wavelength of the [B] quinonediazide compound and generates an acid upon irradiation with radiation having the absorption wavelength. The wavelength difference between the maximum absorption wavelength of the [B] quinonediazide compound and the maximum absorption wavelength of the [C] acid generator is substantially selective for either one of the radiation absorptions by irradiation during pattern formation or post-exposure. Any value may be used as long as it is generated. The wavelength difference is preferably 10 nm to 200 nm, and more preferably 20 nm to 100 nm.

  [C] The acid generator is preferably at least one compound selected from the group consisting of compounds represented by the above formula (1), formula (2) and formula (3).

In formula (1), R ¹ is a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. However, one part or all part of the hydrogen atom which the said alkyl group, aryl group, and alkoxy group have may be substituted. R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, or an aryl group having 6 to 12 carbon atoms. However, one part or all part of the hydrogen atom which the said alkyl group, aryl group, and alkoxy group have may be substituted. a is an integer of 0-7. b is an integer of 0-10. c is an integer of 0-3. However, if the R ¹ and R ² are a plurality each of the plurality of R ¹ and R ² may each be the same or different. Also, when R ² are a plurality, of the plurality of R ^2, 2 two R ² may form a cyclic structure bonded to each other. X _is, SbF _6, a _{(C n F 2n + 1)} Y PF 6-Y or _{C n F 2n + 1 SO 3} . Y is an integer of 0-6. n is an integer of 1-6. In formula (2), R ³ , R ⁴ and R ⁵ are each independently a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 15 carbon atoms. However, one part or all part of the hydrogen atom which the said alkyl group and aryl group have may be substituted. d, e, and f are each independently an integer of 0-5. ^However, if R 3, ^{R 4} and ^{R 5} are a plurality each of the plurality of ^R 3, ^{R 4} and ^{R 5} may each be the same or different. X ¹ is SbF ₆ , (C _n F _{2n + 1} ) _Y PF _6-Y, or C _n F _{2n + 1} SO ₃ . Y is an integer of 0-6. n is an integer of 1-6. In Formula (3), R ⁶ and R ⁷ are each independently an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 4 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. However, one part or all part of the hydrogen atom which the said aryl group has may be substituted by the C1-C12 alkoxy group.

The compound represented by the above formula (1) is represented by the above formula (1-1), and the compound represented by the above formula (2) is a compound represented by the above formula (2-1). Is more preferable. In formula (1-1), R ⁸ and R ⁹ are each independently a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. . X is synonymous with the above formula (1). In formula (2-1), R ¹⁰ represents a phenyl group, a naphthyl group, an anthranyl group, or a phenylthio group. X ¹ is synonymous with the above formula (2).

  Examples of the compound represented by the formula (1-1) include 1- (4-hydroxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxy-1-naphthalenyl) tetrahydro. Thiophenium trifluoromethanesulfonate, 1- (4,7-diethoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfone Narate, 1- (4,7-dihydroxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4,7-dipropylhydroxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate, Naphthalenyl tetrahydrothiophenium salts such as-(4,7-dihydroxy-1-naphthalenyl) tetrahydrothiophenium hexafluorophosphate, 1- (4,7-dihydroxy-1-naphthalenyl) tetrahydrothiophenium hexafluorophosphate Compounds and the like. Among these, 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate and 1- (4,7-dihydroxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate are preferable.

  Examples of the compound represented by the above formula (2-1) include diphenyl (4- (phenylthio) phenyl) sulfonium trifluoromethanesulfonate, diphenyl (4- (phenylthio) phenyl) sulfonium hexafluorophosphate, diphenyl (4- ( Phenylthio) phenyl) sulfonium hexafluoroantimonate, diphenyl (4- (phenylthio) phenyl) sulfonium trifluorotrispentafluoroethyl phosphate, diphenyl (4- (phenyl) phenyl) sulfonium trifluorotrispentafluoroethyl phosphate, diphenyl (4- (Naphthyl) phenyl) sulfonium trifluorotrispentafluoroethyl phosphate, diphenyl (4- (anthranyl) phenyl) sulfonium Triarylsulfonium salt compounds such as fluoro tris pentafluoroethyl phosphate. Among these, diphenyl (4- (phenylthio) phenyl) sulfonium trifluorotrispentafluoroethyl phosphate and diphenyl (4- (phenyl) phenyl) sulfonium trifluorotrispentafluoroethyl phosphate are preferable.

  Examples of the compound represented by the above formula (3) include bis (t-butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (4- and diazodisulfone compounds such as t-butylbenzenesulfonyl) diazomethane, bis (naphthalenesulfonyl) diazomethane, and bis (anthracenesulfonyl) diazomethane. Among these, bis (cyclohexylsulfonyl) diazomethane and bis (p-toluenesulfonyl) diazomethane are preferable. These [C] acid generators can be used alone or in combination of two or more.

  The amount of the [C] acid generator used in the positive radiation-sensitive composition is not particularly limited as long as it can promote the condensation reaction of the [A] siloxane polymer during exposure and strengthen the cross-linked structure. [C] As for the specific usage-amount of an acid generator, 0.5-5 mass parts is preferable with respect to 100 mass parts of [A] siloxane polymers, and 1-4 mass parts is more preferable. [C] By making the usage-amount of an acid generator into the said range, the high melt flow resistance with respect to the heat | fever in a heating process can be exhibited. In addition, when using several types of compounds as a [C] acid generator, what is necessary is just to set so that those total amounts may fall in the said range.

<[D] Thermally crosslinkable compound>
The positive radiation-sensitive composition preferably further contains [D] a heat-crosslinkable compound. The [D] heat crosslinkable compound is a compound that crosslinks the [A] siloxane polymer during the heat curing in the heating step. By including such a [D] heat crosslinkable compound, the degree of crosslinking of the cured film is increased. As a result, the chemical resistance of the cured film is improved and the melt flow in the heating process is suppressed.

  [D] The heat-crosslinkable compound is not particularly limited as long as it is a compound that crosslinks the siloxane polymer at the time of thermosetting, and two or more reactive groups such as epoxy group, oxetane group, vinyl group, acrylic group, methacryl group, The compound which has a methylol group, an alkoxymethyl group, and a silanol group is mentioned. Among these compounds, preferably selected from the group consisting of a compound having two or more groups represented by the following formula (8), a compound represented by the following formula (9), and a compound having two or more oxetane groups. These thermally crosslinkable compounds may be used alone or in combination of two or more.

（式（８）中、Ｒ^１６は、水素原子又は炭素数１〜１０のアルキル基である。但し、Ｒ^１６が複数存在する場合、複数のＲ^１６は、それぞれ同一でも異なっていてもよい。）

(In the formula ^{(8), R 16} is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ^{However, if R 16} there are a plurality, a plurality of ^{R 16} may each be the same or different. )

（式（９）中、ｉは、０〜２の整数である。Ｒ^１７は水素原子、炭素数１〜１０のアルキル基、炭素数２〜１０のアルケニル基又は炭素数６〜１５のアリール基である。但し、Ｒ^１７が複数存在する場合、複数のＲ^１７は、同一でも異なっていてもよい。Ｒ^１８は水素原子、炭素数１〜６のアルキル基、炭素数２〜６のアシル基又は炭素数６〜１５のアリール基である。但し、Ｒ^１８が複数存在する場合、複数のＲ^１７は、同一でも異なっていてもよい。）

(In formula (9), i is an integer of 0 to 2. R ¹⁷ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms. is. ^{However, if R 17} there are a plurality, a plurality of ^{R 17} are optionally be the same or different ^{.R 18} is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 2 to 6 carbon atoms Or an aryl group having 6 to 15 carbon atoms, provided that when a plurality of R ¹⁸ are present, the plurality of R ¹⁷ may be the same or different.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ¹⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, and n-decyl. Groups and the like.

  Examples of the compound having two or more groups represented by the above formula (8) include melamine derivatives and urea derivatives (manufactured by Sanwa Chemical) represented by the following formulas (8-1) to (8-10), Examples thereof include phenolic compounds (manufactured by Honshu Chemical Industry). In addition, the compounds represented by the formulas (8-1) to (8-10) are, in order, by trade name, Nicarak MW-30HM, Nicarax MX-270, Nicarax MX-280, Nicarac MX-290, DML-PTBP, respectively. , DMOM-PTBP, TML-BPA, TMOM-BPA, TML-BPAF, and TMOM-BPAF.

  The compound having two or more groups represented by the above formula (8) may be used alone or in combination of two or more.

In R ¹⁷ in the above formula (9), the alkyl group, alkenyl group, and aryl group may be substituted, and can be selected according to the characteristics of the composition. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, n-decyl group, trifluoromethyl group, 3, 3, 3 -Trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl group, 3-isocyanatopropyl group and the like can be mentioned. Examples of the alkenyl group include a vinyl group, a 3-acryloxypropyl group, a 3-methacryloxypropyl group, and the like. Examples of the aryl group include phenyl group, tolyl group, p-hydroxyphenyl group, 1- (p-hydroxyphenyl) ethyl group, 2- (p-hydroxyphenyl) ethyl group, 4-hydroxy-5- (p-hydroxy). A phenylcarbonyloxy) pentyl group, a naphthyl group, and the like.

In R ¹⁸ of the above formula (9), the alkyl group, acyl group, and aryl group may be substituted and can be selected according to the characteristics of the composition. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Specific examples of the acyl group include an acetyl group. Specific examples of the aryl group include a phenyl group.

  Examples of the compound represented by the formula (9) include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and methyltrin-butoxy. Silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltrin-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxy Silane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloxypropyltrimethoxy Lan, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, p-hydroxyphenyltrimethoxysilane, 1- ( p-hydroxyphenyl) ethyltrimethoxysilane, 2- (p-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (p-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, tri Fluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- (3,4-epoxy Cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, Examples include di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, and (3-glycidoxypropyl) methyldiethoxysilane. In addition, these compounds may be used alone or in combination of two or more.

  The compound represented by the above formula (9) is an organosilane compound, and is a compound similar to the organosilane compound of the above formula (4) constituting the [A] siloxane polymer. Therefore, the compatibility with the siloxane polymer is good, and the high transparency of the cured film can be maintained.

  Examples of the compound having two or more oxetane groups include OXT-121, OXT-221, OXT-191, OX-SQ-H, PNOX-1009, RSOX (above, manufactured by Toagosei Co., Ltd.), etanacol OXBP, etanacol OXTP (above, Ube) Manufactured by Kosan Co., Ltd.).

  A compound having two or more oxetane groups acts as a crosslinking agent during thermosetting, but is a relatively stable compound at room temperature. Therefore, it is possible to improve the melt flow resistance and chemical resistance of the film obtained from the composition without impairing the storage stability.

  Furthermore, [D] As a heat-crosslinkable compound, the other silane compound represented by following formula (10) or (12) may be included. These components are condensed together with the above-mentioned [A] siloxane polymer (preferably a hydrolysis condensate of a hydrolyzable silane compound represented by the above formula (4)) to form a cured product.

（式（１０）中、Ｒ^１９及びＲ^２１は、それぞれ独立して、炭素数１〜４のアルキル基である。Ｒ^２０は、メチレン基、炭素数２〜６のアルキレン基、フェニレン基又は下記式（１１）で表される基である。）

(In Formula (10), R ¹⁹ and R ²¹ are each independently an alkyl group having 1 to 4 carbon atoms. R ²⁰ is a methylene group, an alkylene group having 2 to 6 carbon atoms, a phenylene group, or It is a group represented by the formula (11).)

（式（１１）中、ｋ及びｍは、それぞれ独立して１〜４の整数である。）

(In formula (11), k and m are each independently an integer of 1 to 4.)

（式（１２）中、Ｒ^２２、Ｒ^２３及びＲ^２４は、それぞれ独立して、炭素数１〜４のアルキル基である。ｐ、ｑ及びｒは、それぞれ独立して１〜６の整数である。）

(In Formula (12), R <^22> , R <^23> and R < ²⁴ > are respectively independently a C1-C4 alkyl group. P, q, and r are respectively independently the integers of 1-6. is there.)

As R <^19> and R < ²¹ > of the said Formula (10), a methyl group, an ethyl group, a propyl group, and a butyl group are preferable, and a methyl group and an ethyl group are more preferable. R ^{20 in} formula (10) is preferably a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, or a phenylene group. Among these groups, a methylene group, an ethylene group, and a phenylene group are more preferable. ^Further, when ^{R 20} is a group represented by the formula (11), the k and m in the formula (11), 1 or 2 are preferred. [D] The reactivity with [A] siloxane polymer is improved by using the silane compound of the above formula (10) having such a preferred structure as the thermally crosslinkable compound.

R ²² , R ²³ and R ^{24 in the} formula (12) are preferably a methyl group, an ethyl group, a propyl group and a butyl group from the viewpoint of reactivity with the [A] siloxane polymer. Among these alkyl groups, a methyl group is more preferable. Moreover, p, q, and r in Formula (12) are preferably integers of 1 to 3 from the viewpoint of reactivity and compatibility with the [A] siloxane polymer.

  When the positive radiation sensitive composition contains a silane compound as a [D] heat crosslinkable compound, the silane compounds may be used alone or in combination of two or more. Of the silane compounds of the formulas (10) and (12), a silane compound having an isocyanuric ring represented by the formula (12) is more preferable. Thus, by using a silane compound having an isocyanuric ring in which three trialkoxysilyl groups are bonded in one molecule, a positive radiation-sensitive composition showing high radiation sensitivity can be obtained and formed from the composition. The degree of cross-linking of the cured film can be improved. Furthermore, a positive radiation-sensitive composition containing such an isocyanuric ring-containing silane compound can exhibit high resistance to melt flow in the heating step after development.

  Examples of the silane compounds represented by the formulas (10) and (12) include bistriethoxysilylethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, and bis-1,2- (trimethoxysilyl) ethane. Bis-1,6- (trimethoxysilyl) hexane, bis-1,6- (triethoxysilyl) hexane, bis-1,4- (trimethoxysilyl) benzene, bis-1,4- (triethoxysilyl) ) Benzene, 1,4-bis (trimethoxysilylmethyl) benzene, 1,4-bis (trimethoxysilylethyl) benzene, 1,4-bis (triethoxysilylmethyl) benzene, 1,4-bis (triethoxy) Silylethyl) benzene, tris (3-trimethoxysilylmethyl) isocyanurate, tris (3-triethoxy) Rylmethyl) isocyanurate, tris (3-trimethoxysilylethyl) isocyanurate, tris (3-triethoxysilylethyl) isocyanurate, tris (3-trimethoxysilylpropyl) isocyanurate, tris (3-triethoxysilylpropyl) An isocyanurate etc. are mentioned. Of these, 1,4-bis (trimethoxysilylmethyl) benzene, bis (triethoxysilyl) ethane, tris (3-trimethoxy) from the viewpoint of improving radiation sensitivity and melt flow resistance in the heating step after development. Silylethyl) isocyanurate, tris (3-trimethoxysilylpropyl) isocyanurate, and tris (3-triethoxysilylpropyl) isocyanurate are preferred.

  When the positive radiation sensitive composition contains a [D] heat crosslinkable compound, the amount of the [D] heat crosslinkable compound used is preferably 1 part by mass or more with respect to 100 parts by mass of the [A] siloxane polymer. 70 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less. [D] A positive radiation sensitive composition having an excellent balance of radiation sensitivity and melt flow resistance in the heating step after development by using the heat crosslinkable compound in an amount of 1 part by weight or more and 70 parts by weight or less. Can be obtained. In addition, what is necessary is just to mix | blend so that each total amount may become the said range, when several types of thermally crosslinkable compounds are included as a [D] heat crosslinkable compound.

<Other optional components>
The positive radiation-sensitive composition of the present invention is an essential component in addition to the above-mentioned [A] to [C] components and a suitable component [D] heat-crosslinkable compound, as long as the desired effect is not impaired. Other optional components such as [E] surfactant and [F] dehydrating agent can be contained as required.

<[E] surfactant>
[E] Surfactant can be added in order to improve the coating property of the positive radiation-sensitive composition, to reduce coating unevenness, and to improve the developability of the radiation irradiated part. Examples of preferred surfactants include nonionic surfactants, fluorine surfactants, and silicone surfactants.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene aryl ethers; polyethylene glycol dialkyl esters such as polyethylene glycol dilaurate and polyethylene glycol distearate; (meth) acrylic acid copolymers and the like. Examples of (meth) acrylic acid copolymers include Polyflow No. 57, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octa Ethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2, , 2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether and other fluoroethers; sodium perfluorododecylsulfonate; 1,1,2, 2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexa Fluoroalkanes such as lurodecane; sodium fluoroalkylbenzenesulfonates; fluoroalkyloxyethylene ethers; fluoroalkylammonium iodides; fluoroalkylpolyoxyethylene ethers; perfluoroalkylpolyoxyethanols; perfluoroalkylalkoxylates And fluorine alkyl esters.

  As these fluorosurfactants, for example, Ftop EF301, 303, 352 (above, manufactured by Shin-Akita Kasei), MegaFuck F171, 172, 173 (above, manufactured by Dainippon Ink), Florard FC430, 431 (above, Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, 102, 103, 104, 105, 106 (above Asahi Glass), FTX-218 (above Neos) and the like.

  Examples of the silicone surfactant include SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH8400 FLUID (above, manufactured by Toray Dow Corning Silicone), organosiloxane polymer KP341 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

  [E] The amount of the surfactant used is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the [A] siloxane polymer. Or less. [E] By making the usage-amount of surfactant into 0.01 mass part or more and 10 mass parts or less, the applicability | paintability of a positive radiation sensitive composition can be optimized.

<[F] dehydrating agent>
[F] 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. When the positive radiation sensitive composition optionally contains [F] dehydrating agent, moisture entering from the environment or [A] siloxane polymers in the heating step after development of the positive radiation sensitive composition The moisture generated as a result of condensation by [A] siloxane polymer and [D] thermally crosslinkable compound can be reduced. Therefore, by using [F] dehydrating agent, it is possible to reduce the water content in the composition, and as a result, the storage stability of the composition can be improved. Furthermore, the [A] siloxane polymers and the [A] siloxane polymer and the [D] heat crosslinkable compound can be increased in condensation reactivity, and the melt flow resistance of the positive radiation sensitive composition can be improved. Conceivable. As such [F] 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, for example, 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.

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

  [F] The amount of dehydrating agent used is preferably 0.001 part by mass or more and 50 parts by mass or less, more preferably 0.01 part by mass or more, with respect to 100 parts by mass of [A] siloxane polymer. 30 parts by mass or less, particularly preferably 0.05 parts by mass or more and 10 parts by mass or less. [F] The storage stability of the positive radiation-sensitive composition can be optimized by using the dehydrating agent in an amount of 0.001 to 50 parts by mass.

<Preparation method of positive radiation sensitive composition>
The positive radiation sensitive composition of the present invention comprises the above [A] siloxane polymer, [B] quinonediazide compound and [C] acid generator, and optional components ([D] heat crosslinkable compound, [E] surface activity. And a dehydrating agent of the component [F], etc.). Usually, the positive radiation-sensitive composition is preferably prepared and used in a state dissolved or dispersed in a suitable solvent. For example, a positive radiation sensitive composition can be prepared by mixing [A], [B] and [C] acid generators and optional components in a solvent in a predetermined ratio.

  As the solvent that can be used for the preparation of the positive radiation-sensitive composition, a solvent that uniformly dissolves or disperses each component 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 propionate. , 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, More preferred are propyl lactate, butyl lactate, methyl 2-methoxypropionate and ethyl 2-methoxypropionate. These solvents can be used alone or in combination.

  Among the ethers, 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 the positive radiation-sensitive composition as a solution or dispersion, the proportion of components other than the solvent in the liquid can be arbitrarily set according to the purpose of use, desired film thickness, etc. Preferably it is 5-50 mass%, More preferably, it is 10-40 mass%, Most preferably, it is 15-35 mass%.

<Method for forming cured film>
The method for forming the cured film 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),
(4) a step of irradiating the coating film developed in step (3) with radiation; and (5) a step of heating the coating film irradiated with radiation in step (4).

  In the formation method, a [B] quinonediazide compound having a predetermined radiation absorption region is irradiated with radiation to form a positive pattern, and after development, the [C] acid generator is irradiated with radiation to carry out a crosslinking reaction. By promoting, a coating film having high melt flow resistance can be formed in the subsequent heating step.

[(1) Step of forming coating film of positive radiation-sensitive composition on substrate]
In this step, after the solution or dispersion of the positive radiation-sensitive composition of the present invention 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. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of cyclic olefin, and a hydrogenated product thereof.

  Examples of the coating method of the composition solution or the dispersion include a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, and a bar coating method. Among these coating methods, a spin coating method or a slit die coating method is 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 a part of the coating film formed in step (1)]
In this step, at least a part of the formed coating film is exposed. In this case, when exposing to a part of coating film, it exposes normally through the photomask which has a predetermined pattern. As radiation used for exposure, 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 to 450 nm is preferable, and the wavelength is preferably shorter than the maximum absorption wavelength of the [B] quinonediazide compound.

The amount of exposure in this step is preferably 100 to 10,000 J / m ² , more preferably 500 to 500, as a value measured with a luminometer (OAI model 356, manufactured by OAI Optical Associates Inc.) at a wavelength of 365 nm. 6,000 J / m ² .

[(3) Step of developing the coating film irradiated with radiation in step (2)]
In this step, the exposed coating 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. It is done.

  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 irradiating the coating film developed in step (3) with radiation]
In this step, the developed coating film is irradiated with radiation to generate an acid from the [C] acid generator and promote the condensation / crosslinking reaction of the siloxane polymer by the generated acid. As the radiation used for exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, laser emitted light, light emitting diode light and the like can be used. The wavelength of these radiations is not particularly limited as long as it is a maximum absorption wavelength shorter than the maximum absorption wavelength of the [B] quinonediazide compound, but radiation irradiation to the [B] quinonediazide compound that was not exposed in the above step (2) is also possible. In consideration, radiation in the range of 150 to 400 nm is preferable, and radiation including ultraviolet rays of 300 nm and 365 nm is particularly preferable.

The amount of exposure in this step is preferably 100 to 10,000 J / m ² , more preferably 500 to 500, as a value measured with a luminometer (OAI model 356, manufactured by OAI Optical Associates Inc.) at a wavelength of 365 nm. 6,000 J / m ² .

[(5) Step of heating the coating film irradiated with radiation in step (4)]
In this step, the patterned thin film is heated at a relatively high temperature using a heating device such as a hot plate or an oven, whereby the above [A] siloxane polymer alone or [A] siloxane polymer and [D] thermal crosslinkability are used. The condensation reaction of the compound is promoted, and a cured product can be obtained reliably. 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 cured film can be formed on the surface of the substrate.

<Curing film>
The thickness of the cured film thus formed is preferably 0.1 to 8 μm, more preferably 0.1 to 6 μm, and particularly preferably 0.1 to 4 μm.

  The cured film formed from the positive-type radiation-sensitive composition of the present invention balances the general required characteristics of heat resistance, transparency, solvent resistance and low dielectric properties, as will be apparent from the examples described later. A liquid crystal panel that satisfies the requirements and has a high voltage holding ratio can be formed. Therefore, the cured film is suitably used as an interlayer insulating film for liquid crystal display elements, a protective film, and the like.

  EXAMPLES The present invention will be specifically described below with reference to examples, but 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 hydrolysis condensate of the hydrolyzable silane compound obtained from each of the following synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.
Apparatus: GPC-101 (made by Showa Denko)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 (above, 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 is charged, followed by 30 parts by mass of methyltrimethoxysilane, 23 parts by mass of phenyltrimethoxysilane, and 0.1 part by mass of tri-i-propoxyaluminum. 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. The hydrolysis condensate (A-1) was obtained by the above procedure. 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 container equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 18 parts by mass of methyltrimethoxysilane, 15 parts by mass of tetraethoxysilane, 20 parts by mass of phenyltrimethoxysilane, and 0.5 parts of oxalic acid. A hydrolysis condensate (A-2) was obtained in the same manner as in Synthesis Example 1 by charging a mass part. The solid content concentration of the hydrolysis condensate (A-2) is 40.8% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 1,200, and the molecular weight distribution (Mw / Mn) is 2. Met.

[Synthesis Example 3]
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-3) was obtained by the method similar to the synthesis example 1. The solid content concentration of the hydrolysis condensate (A-3) 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 Example 4]
In a container 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 3-methacryloxypropyltrimethoxysilane, 20 parts by mass of phenyltrimethoxysilane, and 0.5 parts by mass of oxalic acid was charged, and a hydrolysis condensate (A-4) was obtained in the same manner as in Synthesis Example 1. The solid content concentration of the hydrolysis condensate (A-4) is 39.8% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 1,200, and the molecular weight distribution (Mw / Mn) is 2. Met.

[Synthesis Example 5]
In a vessel equipped with a stirrer, 139 parts by mass of diacetone alcohol was charged, and subsequently, 128 parts by mass of phenyltrimethoxysilane and 48 parts by mass of methyltrimethoxysilane were charged and stirred at room temperature. Next, an aqueous phosphoric acid solution in which 0.18 parts by mass of phosphoric acid was dissolved was dropped into 54 parts by mass of ion-exchanged water and heated until the solution temperature reached 75 ° C. After the solution temperature reached 75 ° C., it was held for 3 hours. Subsequently, 159 mass parts of methyl orthoformate was added as a dehydrating agent, and it stirred for 1 hour. Further, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing water and methanol generated by hydrolysis condensation. Thus, a hydrolysis-condensation product (A-5) was obtained. The solid content concentration of the hydrolysis condensate (A-5) is 40.5% by mass, the number average molecular weight (Mn) of the obtained hydrolysis condensate is 1,700, and the molecular weight distribution (Mw / Mn) is 2. Met.

[Synthesis Example 6]
In a container equipped with a stirrer, 25 parts by mass of propylene glycol monomethyl ether was charged, followed by 17 parts by mass of methyltrimethoxysilane, 15 parts by mass of tetraethoxysilane, 12 parts by mass of 3-methacryloxypropyltrimethoxysilane, phenyltrimethylsilane. 15 parts by mass of methoxysilane and 0.5 parts by mass of oxalic acid were charged, and a hydrolysis condensate (A-6) was obtained in the same manner as in Synthesis Example 1. The solid content concentration of the hydrolysis condensate (A-6) is 40.8% 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.

<Preparation of positive radiation sensitive composition>
[Example 1]
[A] A solution containing (A-1) as a siloxane polymer (amount corresponding to 100 parts by mass (solid content) of (A-1)) and (B-1) 1.0 described below as a [B] quinonediazide compound. 10 parts by mass of a condensate of mol and 3.0 mols of 1,2-naphthoquinonediazide-5-sulfonic acid chloride, (C-1) 2 parts by mass described later as an [C] acid generator, [E] surfactant As described later, (E-1) 0.1 part by mass was added to prepare a positive radiation sensitive composition.

[Examples 2 to 13 and Comparative Examples 1 to 6]
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.

  Abbreviations of [B] quinonediazide compound, [C] acid generator, [D] thermally crosslinkable compound, and [E] surfactant in Table 1 are as follows.

B-1: 4,4 ′-[1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate B-2 with sulfonic acid chloride (3.0 mol): 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid Condensate with chloride (3.0 mol) C-1: 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate C-2: 1- (4,7-dihydroxy-1 -Naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate C-3: diphenyl (4- (phenylthio) phenyl) sulfonium trifluorotrispentafluoro Roethyl phosphate C-4: Diphenyl (4- (phenyl) phenyl) sulfonium trifluorotrispentafluoroethyl phosphate C-5: Bis (cyclohexylsulfonyl) diazomethane C-6: Bis (p-toluenesulfonyl) diazomethane c-1: As a compound having a maximum absorption wavelength longer than 365 nm, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide (manufactured by Midori Chemical, NAI-105)
D-1: N, N ′, N ″, N ′ ″-tetra (methoxymethyl) glycoluril (manufactured by Sanwa Chemical Co., Ltd., Nicalak MX-270)
D-2: 3-glycidoxypropyltrimethoxysilane D-3: tris (3-trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd., X-12-965)
E-1: Silicone surfactant (manufactured by Toray Dow Corning, SH 8400 FLUID)

<Evaluation>
Using the prepared positive radiation sensitive composition, various characteristics as the positive radiation sensitive composition and cured film were evaluated as follows. The results are shown in Table 1.

[Radiation sensitivity]
About Examples 1-3 and 5-13 and Comparative Examples 1-6 on a silicon substrate, after apply | coating each composition using a spinner, it is a film | membrane by prebaking on a hotplate for 2 minutes at 100 degreeC. A coating film having a thickness of 4.0 μm was formed. For Example 4, after applying the composition using a slit die coater, the pressure was reduced to 0.5 Torr over 15 seconds at room temperature, the solvent was removed, and then prebaked on a hot plate at 100 ° C. for 2 minutes. As a result, a coating film having a film thickness of 4.0 μm was formed. The exposure time of the obtained coating film was measured through a mask having a 6.0 μm line-and-space (one-to-one) pattern using a Canon PLA-501F exposure machine (365 nm ultra-high pressure mercury lamp). After changing the exposure, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 80 seconds by a puddle method. Next, running water was washed with ultrapure water for 1 minute and dried to form a pattern on the silicon substrate. At this time, the minimum exposure amount necessary for the space line width (bottom) to be 6.0 μm was defined as radiation sensitivity. When the minimum exposure amount was 600 (J / m ² ) or less, the sensitivity was judged good.

[Melt flow resistance]
Similarly to the above “evaluation of radiation sensitivity”, a pattern having a space line width (bottom) of 6.0 μm was formed. The obtained pattern was exposed using a Canon PLA-501F exposure machine (365 nm ultra-high pressure mercury lamp), respectively, so that the integrated dose was 3,000 J / m ^2, and then placed in a clean oven. And post-baking was performed by heating at 220 ° C. for 1 hour. Furthermore, it heated at 230 degreeC for 10 minute (s), the pattern was made to melt flow, and the dimension of the pattern bottom part was measured with SEM (scanning electron microscope). At this time, when the dimension of the pattern bottom was less than 6.30 μm, the melt flow resistance was judged to be good. On the other hand, when the dimension of the pattern bottom was 6.30 μm or more, it was judged that the melt flow resistance was poor.

[Solvent resistance]
A coating film was formed on the silicon substrate in the same manner except that the exposure was not performed in the above "Evaluation of radiation sensitivity". Thereafter, the obtained coating film was exposed to a cumulative irradiation amount of 3,000 J / m ² using a Canon PLA-501F exposure machine (extra-high pressure mercury lamp), respectively, and then in a clean oven. The cured film was obtained by heating at 220 ° C. for 1 hour. The film thickness (T1) of the obtained cured film was measured. And after immersing the silicon substrate in which this cured film was formed in dimethyl sulfoxide temperature-controlled at 70 degreeC for 20 minutes, the film thickness (t1) of the said cured film was measured, and the film thickness change rate by immersion was shown below. Calculated from the formula.
(| T1-T1 | / T1) × 100 (%)
When the film thickness change rate was 4% or less, the solvent resistance was judged to be good. In the evaluation of solvent resistance, the patterning of the film to be formed is unnecessary, so the development process was omitted, and only the coating film forming process, the radiation irradiation process, and the heating process were performed for evaluation.

[Heat-resistant]
A cured film was formed on a silicon substrate in the same manner as in the above “evaluation of solvent resistance”, and the film thickness (T2) of the obtained cured film was measured. Next, the silicon substrate on which this cured film was formed was additionally baked in a clean oven at 240 ° C. for 1 hour, and then the film thickness (t2) of the cured film was measured. Calculated from the formula.
(| T2-T2 | / T2) × 100 (%)
When the film thickness change rate was less than 3%, the heat resistance was judged to be good.

[Evaluation of light transmittance (transparency)]
In the above “evaluation of solvent resistance”, a cured film was formed on a glass substrate in the same manner except that a glass substrate “Corning 7059” (manufactured by Corning) was used instead of the silicon substrate. The light transmittance of the glass substrate on which the cured film was formed was measured using a spectrophotometer (150-20 type double beam, Hitachi, Ltd.) at a wavelength in the range of 400 to 800 nm. When the minimum light transmittance was 95% or more, the light transmittance was judged to be good.

[Relative permittivity (low dielectric constant)]
For Examples 1 to 3 and 5 to 13 and Comparative Examples 1 to 6 on a polished SUS304 substrate, each composition was applied using a spinner and then pre-baked on a hot plate at 100 ° C. for 2 minutes. As a result, a coating film having a thickness of 3.0 μm was formed. For Example 4, after applying the composition using a slit die coater, the pressure was reduced to 0.5 Torr over 15 seconds at room temperature, the solvent was removed, and then prebaked on a hot plate at 100 ° C. for 2 minutes. As a result, a coating film having a thickness of 3.0 μm was formed. The obtained coating film was exposed to a cumulative irradiation amount of 3,000 J / m ² using a Canon PLA-501F exposure machine (extra-high pressure mercury lamp), and then 220 in a clean oven. A cured film was formed on the substrate by heating at 0 ° C. for 1 hour. On this cured film, a Pt / Pd electrode pattern was formed by vapor deposition to prepare a sample for measuring relative permittivity. About the obtained sample, the dielectric constant in the frequency of 10 kHz was measured by CV method using the HP16451B electrode and HP4284A precision LCR meter by Yokogawa and Hewlett-Packard. In the evaluation of the relative dielectric constant, since the patterning of the film to be formed is unnecessary, the development process was omitted, and only the coating film forming process, the radiation irradiation process, and the heating process were performed for evaluation.

[Voltage holding ratio]
Each composition described in Table 1 using a spinner on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed on a surface and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape. Was applied and prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 2.0 μm. Development was performed by a dip method at 25 ° C. for 80 seconds in a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an integrated dose of 3,000 J / m ² without using a photomask. Further, post-baking was performed at 220 ° C. for 1 hour to form a cured film. Next, after spraying a 5.5 μm diameter bead spacer on the substrate having the cured film, the liquid crystal injection port is placed in a state where this is opposed to a soda glass substrate on which the ITO electrode is deposited in a predetermined shape. The remaining four sides were bonded using a sealing agent mixed with 0.8 mm glass beads, and liquid crystal MLC6608 (trade name) manufactured by Merck was injected, and then the liquid crystal injection port was sealed to produce a liquid crystal cell. did. This liquid crystal cell is put in a constant temperature layer of 60 ° C., and a liquid crystal voltage holding ratio measurement system (VHR-1A type, manufactured by Toyo Technica Co., Ltd.) is used to set the applied voltage to a square wave of 5.5 V and the measurement frequency to 60 Hz. The voltage holding ratio was measured. Here, the voltage holding ratio is a value obtained by the following formula.
Voltage holding ratio (%) = (liquid crystal cell potential difference after 16.7 milliseconds from the reference time) / (voltage applied at 0 milliseconds [reference time]) × 100
The lower the value of the voltage holding ratio of the liquid crystal cell, the higher the possibility of causing a problem called “burn-in” when forming the liquid crystal panel. On the other hand, the higher the value of the voltage holding ratio, the lower the possibility of occurrence of “burn-in” and the higher the reliability of the liquid crystal panel.

  As is clear from the results in Table 1, the positive radiation sensitive compositions of Examples 1 to 13 included in the present invention were compared with the positive radiation sensitive compositions of Comparative Examples 1 to 6 after development. The melt flow resistance in the heating process was good. In addition, the positive radiation sensitive compositions of Examples 1 to 13 are excellent in radiation sensitivity, and all of general required characteristics such as heat resistance, transparency, solvent resistance, light transmittance, and low dielectric properties. It was found that a liquid crystal cell having a higher voltage holding ratio can be obtained.

  As described above, the positive radiation-sensitive composition of the present invention has good melt flow resistance, excellent radiation sensitivity, and satisfies all general required characteristics such as heat resistance and transparency. And a liquid crystal cell having a high voltage holding ratio can be obtained. Therefore, the positive-type radiation-sensitive composition is preferably used as a material for forming an interlayer insulating film of a liquid crystal display element (LCD), a resist underlayer film, a microlens, a light-emitting diode element sealing material, and the like. Can do.

Claims (8)

[A] siloxane polymer,
A positive-type radiation-sensitive composition comprising a [B] quinonediazide compound, and a radiation-sensitive acid generator having a maximum absorption wavelength shorter than the maximum absorption wavelength of the [C] [B] quinonediazide compound. [C] The positive electrode according to claim 1, wherein the acid generator is at least one compound selected from the group consisting of compounds represented by the following formulas (1), (2) and (3). Type radiation sensitive composition.

(In the formula (1),
R ¹ is a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. However, one part or all part of the hydrogen atom which the said alkyl group, aryl group, and alkoxy group have may be substituted.
R ² is a hydrogen atom, a linear or branched alkyl group having 1 to 7 carbon atoms, or an aryl group having 6 to 12 carbon atoms. However, one part or all part of the hydrogen atom which the said alkyl group, aryl group, and alkoxy group have may be substituted.
a is an integer of 0-7. b is an integer of 0-10. c is an integer of 0-3. However, if the R ¹ and R ² are a plurality each of the plurality of R ¹ and R ² may each be the same or different. Also, when R ² are a plurality, of the plurality of R ^2, 2 two R ² may form a cyclic structure bonded to each other.
X _is, SbF _6, a _{(C n F 2n + 1)} Y PF 6-Y or _{C n F 2n + 1 SO 3} . Y is an integer of 0-6. n is an integer of 1-6.
In formula (2),
R ³ , R ⁴ and R ⁵ are each independently a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 15 carbon atoms. However, one part or all part of the hydrogen atom which the said alkyl group and aryl group have may be substituted.
d, e, and f are each independently an integer of 0-5.
^However, if R 3, ^{R 4} and ^{R 5} are a plurality each of the plurality of ^R 3, ^{R 4} and ^{R 5} may each be the same or different.
X ¹ is SbF ₆ , (C _n F _{2n + 1} ) _Y PF _6-Y, or C _n F _{2n + 1} SO ₃ . Y is an integer of 0-6. n is an integer of 1-6.
In formula (3),
R ⁶ and R ⁷ are each independently an alkyl group having 1 to 12 carbon atoms, an alicyclic alkyl group having 4 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. However, one part or all part of the hydrogen atom which the said aryl group has may be substituted by the C1-C12 alkoxy group. ) The compound represented by the above formula (1) is represented by the following formula (1-1), and the compound represented by the above formula (2) is a compound represented by the following formula (2-1): The positive radiation sensitive composition as described in 1. above.

(In Formula (1-1),
R ⁸ and R ⁹ are each independently a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
X is synonymous with the above formula (1).
In formula (2-1),
R ¹⁰ is a phenyl group, a naphthyl group, an anthranyl group, or a phenylthio group.
X ¹ is synonymous with the above formula (2). ) [A] The positive radiation sensitive composition according to claim 1, 2 or 3, wherein the siloxane polymer is a hydrolysis condensate of a hydrolyzable silane compound represented by the following formula (4).

(In Formula (4), R ¹¹ is a non-hydrolyzable group. R ¹² is an alkyl group having 1 to 4 carbon atoms. G is an integer of 0 to 3. However, R ^11. And when there are a plurality of R ^{12 s} , the plurality of R ¹¹ and R ¹² may be the same or different.)   [D] The positive radiation sensitive composition according to claim 1, 2 or 3, further comprising a thermally crosslinkable compound.   The positive radiation-sensitive composition according to any one of claims 1 to 4, which is used for forming a cured film. (1) The process of forming the coating film of the positive radiation sensitive composition of Claim 6 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),
(4) A method for forming a cured film, comprising: irradiating the coating film developed in step (3) with radiation; and (5) heating the coating film irradiated with radiation in step (4).   A cured film formed from the positive radiation-sensitive composition according to claim 6.