JP5803635B2 - Positive radiation-sensitive composition, cured film, and method for forming cured film - Google Patents

Description

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

  A color TFT liquid crystal display element or the like is formed by overlapping a color filter substrate and a TFT array substrate. The TFT array substrate is generally provided with an interlayer insulating film for insulating between wirings arranged in layers. As a material for forming this interlayer insulating film, a positive radiation sensitive composition is widely used because it has a small number of steps for obtaining a required pattern shape and preferably has sufficient flatness. Yes.

  As a component of such a radiation-sensitive composition for forming an interlayer insulating film, an acrylic resin is mainly used (see JP 2001-354822 A). 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 2006-178436 A, JP 2006-2006 A). 276598 and JP-A 2006-293337). The siloxane polymer used in the conventional polysiloxane-based radiation sensitive composition can be obtained by hydrolytic condensation of a silane compound. As the silane compound, phenyltrimethoxysilane is widely used for reasons such as excellent compatibility with a quinonediazide compound that is a photosensitizer. However, a positive-type radiation-sensitive composition containing a siloxane polymer synthesized using phenyltrimethoxysilane tends to cause film loss due to heating of the resulting cured film, and does not sufficiently satisfy heat resistance. Furthermore, the positive radiation-sensitive composition has a problem of toxicity to the central nervous system, hematopoietic system, respiratory system, etc., particularly carcinogenicity, and is harmful to the human body in the heating step in forming a cured film. There is a disadvantage that benzene is generated as outgas.

  Under such circumstances, the surface hardness, refractive index, light transmittance, resist stripping solution resistance, dry etching resistance, low dielectric constant, etc. required for cured films such as interlayer insulating films are sufficiently satisfied, and excellent heat resistance Development of a positive-type radiation-sensitive composition that can form a cured film having the property and can reduce generation of outgas such as benzene harmful to the human body in the heating step in forming the cured film is strongly desired.

JP 2001-354822 A JP 2006-178436 A JP 2006-276598 A JP 2006-293337 A

  The present invention has been made based on the above-described circumstances, and its purpose is to provide general characteristics required for a cured film, such as surface hardness, refractive index, light transmittance, resist stripping solution resistance, and dry resistance. It can sufficiently satisfy etching properties, low dielectric constant, etc., can form a cured film with excellent heat resistance, and can reduce generation of outgas such as benzene harmful to human body in the heating process when forming the cured film It is to provide a positive radiation sensitive composition, a cured film formed from the positive radiation sensitive composition, and a method of forming the cured film.

（式（ｉ）中、Ｒ^１は、炭素数６〜１５のアリール基である。但し、このアリール基の水素原子の一部又は全部は置換されていてもよい。Ｙは、単結合又はヘテロ原子を含む２価の連結基である。Ｘは、メチレン基又は炭素数２〜１０のアルキレン基である。但し、Ｒ^１とＸとが互いに結合して環構造を形成してもよい。） The invention made to solve the above problems is
[A] A siloxane polymer having a structure in which a group represented by the following formula (i) is bonded to a silicon atom (hereinafter also referred to as [A] siloxane polymer), and [B] a positive radiation sensitive material containing a quinonediazide compound. It is a composition.

(In formula (i), R ¹ is an aryl group having 6 to 15 carbon atoms, provided that part or all of the hydrogen atoms of the aryl group may be substituted. Y is a single bond or hetero A divalent linking group containing an atom, X is a methylene group or an alkylene group having 2 to 10 carbon atoms, provided that R ¹ and X may be bonded to each other to form a ring structure.

  The positive radiation-sensitive composition contains a [A] siloxane polymer having a structure in which the group represented by the formula (i) is bonded to a silicon atom, so that a cured film having excellent heat resistance can be formed. And the generation of outgas in the heating process in forming the cured film can be reduced. Moreover, because the group represented by the formula (i) has an aryl group, the [A] siloxane polymer is excellent in compatibility with the [B] quinonediazide compound. Furthermore, the cured film formed from the positive radiation sensitive composition also satisfies general characteristics such as surface hardness.

（式（１）中、Ｒ^１、Ｙ及びＸは上記式（ｉ）と同義である。Ｒ^２は、炭素数１〜６のアルキル基又は炭素数３〜３０の１価の脂環式炭化水素基である。Ｚは、ハロゲン原子又はＯＲ^３である。但し、Ｒ^３は、水素原子、炭素数１〜６のアシル基又は炭素数１〜６のアルキル基である。ａは、１から３の整数である。ｂは、０から２の整数である。但し、ａ＋ｂ≦３を満たす。Ｒ^１、Ｙ、Ｘ、Ｒ^２、Ｚ及びＲ^３がそれぞれ複数の場合、複数のＲ^１、Ｙ、Ｘ、Ｒ^２、Ｚ及びＲ^３は、それぞれ同一でも異なっていてもよい。） The [A] siloxane polymer of the positive radiation sensitive composition is a hydrolysis condensate of a compound containing a hydrolyzable silane compound represented by the following formula (1) (hereinafter also referred to as “compound (I)”). It is preferable that

(In the formula ^(1), .R ^{2 R} 1, Y and X are as defined in the above formula (i) is a monovalent alicyclic hydrocarbon alkyl or C3-30 from 1 to 6 carbon atoms Z is a halogen atom or OR ³ , where R ³ is a hydrogen atom, an acyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. B is an integer of 0 to 2, provided that a + b ≦ 3 is satisfied, and when there are a plurality of R ¹ , Y, X, R ² , Z, and R ³ , a plurality of R ¹ , Y, X, R ² , Z and R ³ may be the same or different.

  Thus, by using the hydrolysis condensate of the compound containing the compound (I) as the [A] siloxane polymer, the positive radiation sensitive composition can form a cured film having more excellent heat resistance, And generation | occurrence | production of the outgas in the heating process in the case of cured film formation can be reduced more. Moreover, the compatibility of a [A] siloxane polymer and a [B] quinonediazide compound can be improved more by using the hydrolysis condensate of a compound containing compound (I) as a [A] siloxane polymer.

Preferably, R ¹ is a phenyl group, Y is an imino group, an amide group, an ether group or a carbonyl group, and X is a methylene group or an alkylene group having 2 to 6 carbon atoms. By containing the [A] siloxane polymer having such a specific structure, the positive radiation-sensitive composition can form a cured film having further excellent heat resistance, and at the time of forming the cured film. Generation of outgas in the heating process can be further reduced. Moreover, the compatibility of a [A] siloxane polymer and a [B] quinonediazide compound can further be improved by containing the [A] siloxane polymer which has such a specific structure.

  [A] The siloxane polymer is a hydrolytic condensate of the compound containing the compound (I), and the content ratio of the structural unit derived from the compound (I) in the [A] siloxane polymer is 5 mol% or more and 60 mol% or less. It is preferable that [A] When the content ratio of the structural unit derived from the compound (I) in the siloxane polymer is 5 mol% or less, the compatibility between the [A] siloxane polymer and the [B] quinonediazide compound is reduced, and foreign matter in the liquid is There is a tendency to increase. On the other hand, when the content ratio of the structural unit derived from the compound (I) in the [A] siloxane polymer is 60 mol% or more, the amount of outgas generated in the heating step during the formation of the cured film tends to increase.

  The positive radiation-sensitive composition preferably further contains a [C] heat-sensitive acid generator or a heat-sensitive base generator (hereinafter also referred to as “[C] component”). Thus, by containing [C] a heat-sensitive acid generator or a heat-sensitive base generator, a condensation reaction of [A] siloxane polymer or the like in the heating step after development of the positive radiation-sensitive composition can be achieved. It is promoted and a cured film having further excellent surface hardness and heat resistance can be formed.

  The positive radiation sensitive composition of the present invention is suitably used for forming a cured film. The positive radiation-sensitive composition can form a cured film having excellent heat resistance. Moreover, the cured film formed from the positive radiation-sensitive composition sufficiently satisfies general characteristics such as surface hardness.

In addition, 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), and (4) a step of heating the coating film developed in step (3).

  In the formation method, since the positive radiation-sensitive composition of the present invention is used, a cured film having excellent heat resistance can be formed, and generation of outgas in the heating process during the formation of the cured film can be reduced. . Moreover, the cured film formed by the forming method sufficiently satisfies general characteristics such as surface hardness.

  The present invention includes a cured film formed using the positive radiation sensitive composition. Since the cured film of the present invention is formed using the positive radiation-sensitive composition, general properties such as surface hardness are sufficiently satisfied and heat resistance is excellent.

  Here, the “organic group” refers to a group containing at least one carbon atom.

  The positive radiation sensitive composition of the present invention sufficiently satisfies the general properties required for a cured film, such as surface hardness, refractive index, light transmittance, resist stripping solution resistance, dry etching resistance, and low dielectric constant. In addition, a cured film having excellent heat resistance can be formed, and generation of outgas in the heating process during the formation of the cured film can be reduced. Therefore, the positive radiation-sensitive composition is suitably used for forming a cured film such as a color TFT liquid crystal display element, an organic EL element, a flexible display such as electronic paper.

<Positive radiation sensitive composition>
The positive radiation sensitive composition of the present invention contains [A] siloxane polymer and [B] quinonediazide compound. In addition, the positive radiation-sensitive composition may include [C] a heat-sensitive acid generator or a heat-sensitive base generator as a suitable component, and other optional components as long as the effects of the present invention are not impaired. You may contain. 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 of a compound having a structure in which the group represented by the above formula (i) is bonded to a silicon atom and a siloxane bond. [A] The siloxane polymer is condensed to form a cured film such as an interlayer insulating film in a coating film forming process (pre-baking process) and a heating process (post-baking process) for forming a cured film. In addition, when the preferred component [C] heat-sensitive acid generator or heat-sensitive base generator is added to the positive radiation-sensitive composition, an acidic active substance or a basic active substance is generated in the heating step, It becomes a catalyst to further accelerate the condensation of the [A] siloxane polymer.

  [A] Since the group represented by the above formula (i) has an aryl group, the [A] siloxane polymer is excellent in compatibility with the [B] quinonediazide compound. In addition, since the aryl group is not directly bonded to the silicon atom, the positive radiation-sensitive composition can suppress the generation of outgas derived from the aromatic group in the heating step in forming the cured film. And a cured film having excellent heat resistance can be formed. Furthermore, the positive radiation sensitive composition is excellent in radiation sensitivity, and the cured film formed from the positive radiation sensitive composition also satisfies general characteristics such as surface hardness.

In formula (i), R ¹ is an aryl group having 6 to 15 carbon atoms. However, some or all of the hydrogen atoms of this aryl group may be substituted. Y is a divalent linking group containing a single bond or a hetero atom. X is a methylene group or an alkylene group having 2 to 10 carbon atoms. However, R ¹ and X may be bonded to each other to form a ring structure.

Examples of the aryl group having 6 to 15 carbon atoms represented by R ¹ include a phenyl group, a benzyl group, a phenethyl group, a naphthyl group, and an anthracenyl group. Of these, a phenyl group, a benzyl group, a phenethyl group, and a naphthyl group are preferable. The aryl group is a concept including an aralkyl group.

  Examples of the group that may substitute part or all of the hydrogen atoms of the aryl group include a methyl group, an ethyl group, a methoxy group, an ethoxy group, and a nitro group. Of these, a methyl group, a methoxy group, and a nitro group are preferable.

  Examples of the divalent linking group containing a hetero atom represented by Y include an imino group, an amide group, an ether group, a carbonyl group, a carbonate group, a carbamate group, and a urea group.

  Y is preferably a single bond, imino group, amide group, carbonyl group or carbamate group, more preferably a single bond or imino group.

  Examples of the alkylene group having 2 to 10 carbon atoms represented by X include an ethylene group, a propylene group, a butylene group, and a pentylene group.

  As said X, a methylene group and a C2-C6 alkylene group are preferable, and a methylene group, ethylene group, and a propylene group are more preferable.

Examples of the ring structure that R ¹ and X may be bonded to each other include alicyclic structures such as a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cyclooctane structure, and a cyclodecane structure. . Of these, a cyclopentane structure is preferred.

  Examples of the group represented by the above formula (i) include groups represented by the following formulas (i-1) to (i-12).

  Of these, groups represented by (i-1) to (i-7) are preferable.

  [A] A preferred form of the siloxane polymer is a siloxane polymer that is a hydrolytic condensate of a compound containing the compound (I). [A] Since the siloxane polymer is a hydrolysis condensate of a compound containing the compound (I) having an aryl group, the compatibility with the [B] quinonediazide compound is excellent. In addition, since the aryl group is not directly bonded to a silicon atom, the positive radiation-sensitive composition can suppress the occurrence of outgas derived from an aromatic group in the heating step in forming a cured film. A cured film having more excellent heat resistance can be formed. Furthermore, the cured film formed from the positive radiation sensitive composition also satisfies general characteristics such as surface hardness.

  Here, the "hydrolyzable condensate of hydrolyzable silane compound" is a hydrolytic condensation in which some silanol groups of the hydrolyzed silane compound of the compound represented by the above formula (1) are reacted and condensed with each other. Or a part of silanol group of the hydrolyzed silane compound of the compound represented by the above formula (1) and a part of silanol group of the hydrolyzed silane compound of “other hydrolyzable silane compound” described later It means a hydrolysis-condensation product in which a group has reacted and condensed. The “other hydrolyzable silane compound” is not particularly limited as long as it is a compound other than the compound (I) and is hydrolyzed to generate a silanol group.

[Compound (I)]
In said formula (1), R < ¹ >, Y and X are synonymous with the said formula (i). R ² is an alkyl group having 1 to 6 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms. Z is a halogen atom or OR ³ . However, R < ³ > is a hydrogen atom, a C1-C6 acyl group, or a C1-C6 alkyl group. a is an integer of 1 to 3. b is an integer of 0 to 2. However, a + b ≦ 3 is satisfied. ^{R 1, Y, X, R} 2, when Z and ^{R 3} are a plurality of each of the plurality of ^{R 1, Y, X, R} 2, Z and ^{R 3} may each be the same or different.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ² include a methyl group and an ethyl group.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms represented by R ² include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, and cyclododecyl group. Can be mentioned.

  Examples of the halogen atom represented by Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom is preferable from the viewpoint of the reactivity of hydrolysis condensation.

As a C1-C6 acyl group represented by said R < ³ >, a formyl group, an acetyl group, a propionyl group, a benzoyl group etc. are mentioned, for example.

As a C1-C6 alkyl group represented by said R < ³ >, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group etc. are mentioned, for example.

  As said a, 1 or 2 is preferable and 1 is more preferable.

  The b is preferably 0.

  Examples of compound (I) include compounds (I-1) to (I-17) represented by the following formulas.

  Of the above compounds, compounds (I-1) to (I-7) are preferred.

  [A] The content of the structural unit derived from the compound (I) in the siloxane polymer is preferably 5 mol% or more and 60 mol% or less, more preferably 10 mol% or more and 55 mol% or less, and 15 mol% or more and 50 mol% or less. The following is more preferable. [A] When the content ratio of the structural unit derived from the compound (I) in the siloxane polymer is 5 mol% or less, the compatibility between the [A] siloxane polymer and the [B] quinonediazide compound is reduced, and foreign matter in the liquid is There is a tendency to increase. On the other hand, when the content ratio of the structural unit derived from the compound (I) in the [A] siloxane polymer is 60 mol% or more, the amount of outgas generated in the heating step during the formation of the cured film tends to increase. Moreover, the positive type radiation sensitive composition can form the cured film which is more excellent in heat resistance by making the content rate of the structural unit derived from the compound (I) in a [A] siloxane polymer into the said range. it can.

<[A] Synthesis of Siloxane Polymer>
The conditions for hydrolytic condensation of the hydrolyzable silane compound including the compound (I) and other hydrolyzable silane compounds are such that at least a part of the hydrolyzable silane compound such as the compound (I) is hydrolyzed and hydrolyzed. Although it does not specifically limit as long as it decomposes | disassembles a group (-OR < ³ >) etc. into a silanol group and causes a condensation reaction, it can implement as follows as an example.

  The “other hydrolyzable silane compound” is not particularly limited, and examples thereof include tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, and methyltributoxysilane. As other hydrolyzable silane compounds, those having no aryl group are preferable, and methyltrimethoxysilane is particularly preferable.

  The water used for the hydrolytic condensation of the hydrolyzable 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 from 0.1 mol to 3 mol, more preferably from 0.3 mol to 2 mol, based on 1 mol of the total amount of hydrolyzable groups of the hydrolyzable silane compound, More preferably, mol to 1.5 mol. By using an amount of water in the above range, the reaction rate of hydrolysis / condensation can be optimized.

  The solvent that can be used for the hydrolytic condensation of the hydrolyzable silane compound is not particularly limited, but is usually the same as the solvent used for the preparation of the positive radiation sensitive composition described later. Can be used. 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. Of these, 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, 4-hydroxy-4-methyl-2-pentanone (diacetone Alcohol) is preferred.

  The hydrolysis / condensation reaction of the hydrolyzable 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; Carbonate such as potassium carbonate; carboxylate such as sodium acetate; various Lewis bases], or alkoxide (eg, zirconium alkoxide, titanium alkoxide, aluminum alkoxide) is used in the presence of a catalyst. As the aluminum alkoxide, for example, tri-i-propoxyaluminum can be used. The amount of the catalyst used is preferably 0.2 mol or less, more preferably 0.00001 or more and 0.1 mol or less, with respect to 1 mol of the monomer of the hydrolyzable silane compound, from the viewpoint of promoting the hydrolysis condensation reaction. preferable.

  The reaction temperature and reaction time in the hydrolytic condensation of the hydrolyzable silane compound are appropriately set. For example, the following conditions can be adopted. The reaction temperature is preferably 40 ° C. or higher and 200 ° C. or lower, and more preferably 50 ° C. or higher and 150 ° C. or lower. The reaction time is preferably from 30 minutes to 24 hours, more preferably from 1 hour to 12 hours. By setting such reaction temperature and reaction time, the hydrolysis condensation reaction can be performed most efficiently. In this hydrolysis condensation, the reaction may be carried out in one step by adding the hydrolyzable silane compound, water and catalyst to the reaction system at one time, or the hydrolyzable silane compound, water and catalyst may be added in several steps. The hydrolysis condensation reaction may be carried out in multiple stages by adding it to the reaction system in batches. 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. The dehydrating agent used at this stage is generally added to the positive-type radiation-sensitive composition because excess water is adsorbed or included so that the dehydrating capacity is completely consumed or removed by evaporation. It shall not fall within the category of dehydrating agents described later.

  [A] The molecular weight of the siloxane polymer can be measured as a weight average molecular weight in terms of polystyrene using GPC (gel permeation chromatography) using tetrahydrofuran as a mobile phase. [A] The weight average molecular weight of the siloxane polymer is preferably 500 or more and 10,000 or less, and more preferably 1,000 or more and 5,000 or less. [A] By setting the value of the weight average molecular weight of the siloxane polymer within the above range, the film-forming property of the coating film of the positive radiation-sensitive composition can be improved, and the decrease in radiation sensitivity is prevented. be able to.

<[B] quinonediazide compound>
[B] A quinonediazide compound is a 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. The “radiation” of the “radiation-sensitive composition” in the present specification is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like.

  [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 a hydrogen atom or a substituent represented by the following formula (2).

（式（２）中、Ｒ^４、Ｒ^５及びＲ^６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、Ｒ^４、Ｒ^５及びＲ^６のうち２つ以上が結合して環構造を形成してもよい。）

(In formula (2), R ⁴ , R ⁵ and R ⁶ are each independently an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group or a substituted phenyl group, provided that R ⁴ , R ⁵ And two or more of R ⁶ may combine to form a ring structure.)

In the substituent represented by the above formula (2), when R ⁴ , R ⁵ and R ⁶ are alkyl groups having 1 to 10 carbon atoms, a part or all of the hydrogen atoms of the alkyl group are substituted. It may be. Examples of such an alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, and n-heptyl. Group, n-octyl group, trifluoromethyl group, 2-carboxyethyl group and the like. Moreover, a hydroxyl group etc. are mentioned as a substituent of a substituted phenyl group. Examples of the ring structure formed by R ⁴ , R ^5, and R ⁶ include a cyclopentane structure, a cyclohexane structure, an adamantane structure, and a fluorene structure.

  Examples of the compound having a phenolic hydroxyl group include a compound group represented by the following formula.

  As the naphthoquinone diazide sulfonic acid halide, 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. Examples of particularly preferred quinonediazide compounds include 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2 -Condensation product with naphthoquinonediazide-5-sulfonic acid chloride (3.0 mol), 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5 Mention may be made of condensates with sulphonic acid chloride (3.0 mol).

  [B] The molecular weight of the quinonediazide compound is preferably 300 to 1,500, and more preferably 350 to 1,200. By setting the molecular weight of the quinonediazide compound to 300 or more, the transparency of the formed cured film for display element 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 content of the [B] quinonediazide compound in the positive radiation sensitive composition is preferably 2 parts by mass or more and 50 parts by mass or less, and 3 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the [A] siloxane polymer. Is more preferable. [B] By making content of a quinonediazide compound into the said range, the difference of the solubility of the irradiation part with respect to the alkaline aqueous solution used as a developing solution and an unirradiated part becomes large, and patterning performance becomes favorable.

<[C] heat-sensitive acid generator or heat-sensitive base generator>
[C] The heat-sensitive acid generator or the heat-sensitive base generator can release an acidic active substance or a basic active substance that acts as a catalyst when the [A] siloxane polymer is condensed and cured by heating. Defined as a compound. By using such a compound of [C] component, the condensation reaction of [A] siloxane polymer in the heating step after development of the positive radiation sensitive composition is promoted, so that the surface hardness and heat resistance are further improved. An excellent cured film can be formed. The heat-sensitive acid generator or heat-sensitive base generator of the component [C] is acidic during prebaking at a relatively low temperature (for example, 70 ° C. to 120 ° C.) in the coating film forming step of the positive radiation sensitive composition. Those which do not release an active substance or a basic active substance and have a property of releasing an acidic active substance or a basic active substance during post-baking at a relatively high temperature (for example, 120 ° C. to 250 ° C.) in a heating step after development are preferable. .

  The heat-sensitive acid generator as the component [C] includes an ionic heat-sensitive acid generator and a nonionic heat-sensitive acid generator.

  As the ionic compound, those containing no heavy metal or halogen ion are preferable.

  Examples of the ionic thermosensitive acid generator include triphenylsulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, 1-dimethylthio-4,7-dihydroxynaphthalene, 4-hydroxyphenyldimethylsulfonium, benzyl. Methanesulfonates such as -4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium , Trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, hexafluorophosphonate and the like. Moreover, as a commercial item of benzylsulfonium salt, for example, SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-80L, SI-100L, SI-110L, SI- 145L, SI-150L, SI-160L, SI-180L (manufactured by Sanshin Chemical Industry) and the like.

  Examples of nonionic heat-sensitive acid generators include halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, phosphoric acid ester compounds, sulfonimide compounds, and sulfonebenzotriazole compounds. .

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Of these, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-naphthyl-4,6-bis (Trichloromethyl) -s-triazine is preferred.

  Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, and bis (2,4-xylylsulfonyl) diazomethane. Bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane Etc.

  Examples of the sulfone compound include β-ketosulfone compounds, β-sulfonylsulfone compounds, diaryldisulfone compounds, and the like. Of these, 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, and 4-chlorophenyl-4-methylphenyldisulfone compounds are preferred.

  Examples of the sulfonic acid ester compound include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Of these, benzoin tosylate, pyrogallol trimesylate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, and 2,6-dinitrobenzylbenzenesulfonate are preferred. Examples of commercially available products of iminosulfonate include PAI-101 (manufactured by Midori Kagaku), PAI-106 (manufactured by Midori Chemical), CGI-1311 (manufactured by Ciba Specialty Chemicals), and the like.

  Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide (trade name “SI-105” (manufactured by Midori Chemical)), N- (camphorsulfonyloxy) succinimide (trade name “SI-106” (midori) Chemical)), N- (4-methylphenylsulfonyloxy) succinimide (trade name “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- (trifluoromethylsulfonyloxy) diphenylmaleimide (trade name “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 (trade name “NDI-100” (manufactured by Midori Chemical)), N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] Hept-5-e -2,3-dicarboxylimide (trade name “NDI-101” (manufactured by Midori Chemical)), N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-di Carboxylimide (trade name “NDI-105” (manufactured by Midori Chemical)), N- (nonafluorobutanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide (trade name) “NDI-109” (manufactured by Midori Chemical)), N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide (trade name “NDI-106” (Midori Chemical)), N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoro Methylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept- 5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane- 5,6-oxy-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (4 Fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-105” (Manufactured by Midori Kagaku)), N- (camphorsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-106” (manufactured by Midori Chemical)), N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide (trade name) “NAI-101” (manufactured by Midori Kagaku)), N- (phenylsulfonyloxy) naphthyl dicarboxylimide (trade name “NAI-100” (manufactured by Midori Kagaku)), N- (2-trifluoromethylphenylsulfonyloxy) Naphthyl dicarboxylimide, N- (4-fluorophenyl Sulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyloxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide ( Trade name “NAI-109” (manufactured by Midori Chemical)), N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (butylsulfonyloxy) naphthyl dicarboxylimide ( Trade name “NAI-1004” (manufactured by Midori Chemical)), N- (pentylsulfonyloxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) naphthyl dicarboxylimide, - (heptyloxy sulfonyloxy) naphthyl dicarboxyl imide, N- (octyl sulfonyloxy) naphthyl dicarboxyl imide, N- (nonyl sulfonyloxy) naphthyl dicarboxylic imide and the like.

  Other examples of heat sensitive acid generators include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophene. And tetrahydrothiophenium salts such as nitrotrifluoromethanesulfonate.

  Examples of the heat-sensitive base generator of component [C] include transition metal complexes such as cobalt; orthonitrobenzyl carbamates; α, α-dimethyl-3,5-dimethoxybenzyl carbamates; acyloxyiminos and the like. .

  Examples of the transition metal complex include bromopentammonium cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonia cobalt perchlorate, and hexamethylamine cobalt perchlorate. Examples include chlorate and hexapropylamine cobalt perchlorate.

  Examples of the orthonitrobenzyl carbamates include [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, and [[(2-nitrobenzyl) oxy]. Carbonyl] hexylamine, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl] aniline, [[(2-nitrobenzyl) oxy] carbonyl] piperidine, bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] toluenediamine, bis [[ (2-Nitrobenzyl) Oki ] Carbonyl] diaminodiphenylmethane, bis [[(2-nitrobenzyl) oxy] carbonyl] piperazine, [[(2,6-dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] Carbonyl] propylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2,6-dinitrobenzyl) oxy ] Carbonyl] aniline, [[(2,6-dinitrobenzyl) oxy] carbonyl] piperidine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2,6-dinitrobenzyl ) Oxy] carbonyl] phenylenediamine, bis [(2,6-dinitrobenzyl) oxy] carbonyl] toluenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine Etc.

  Examples of the α, α-dimethyl-3,5-dimethoxybenzylcarbamate include [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] methylamine, [[(α, α-dimethyl). −3,5-dimethoxybenzyl) oxy] carbonyl] propylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] hexylamine, [[(α, α-dimethyl-3,5 -Dimethoxybenzyl) oxy] carbonyl] cyclohexylamine, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] aniline, [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy ] Carbonyl] piperidine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] Xamethylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] phenylenediamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] toluene Diamine, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(α, α-dimethyl-3,5-dimethoxybenzyl) oxy] carbonyl] piperazine, etc. Can be mentioned.

  Examples of the acyloxyiminos include propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoyl benzophenone oxime, adipoyl Acetone oxime, acryloyl acetophenone oxime, acryloyl benzophenone oxime, acryloyl acetone oxime and the like can be mentioned.

  Other examples of the heat-sensitive base generator include 2-nitrobenzyl cyclohexyl carbamate, O-carbamoylhydroxyamide and the like.

  Of the heat-sensitive acid generators and heat-sensitive base generators mentioned so far, [A] benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 2-nitro from the viewpoint of the catalytic action of the condensation / curing reaction of the siloxane polymer. Benzylcyclohexyl carbamate, 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate, and N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide are preferred.

  As the component [C], either a heat-sensitive acid generator or a heat-sensitive base generator is used, and one kind may be used alone, or two or more kinds may be used in combination. [C] As a content when using a component, 0.01 mass part or more and 10 mass parts or less are preferable with respect to 100 mass parts of [A] component, and 0.1 mass part or more and 5 mass parts or less are more. preferable. By making the usage-amount of a [C] component into the said range, the radiation sensitivity of a positive radiation sensitive composition can be optimized, and the cured film excellent in surface hardness can be formed, maintaining transparency.

<Heat crosslinkable compound>
The thermally crosslinkable compound acts as a crosslinking component such as [A] siloxane polymer during thermal curing in a heating step (post-baking step) when forming a cured film. By using such a heat-crosslinkable compound, the cured film that further promotes the condensation (crosslinking) of the [A] siloxane polymer in the heating step after the development of the positive radiation-sensitive composition, and is superior in surface hardness and heat resistance. Can be formed.

  The heat crosslinkable compound is not particularly limited as long as it is a compound that crosslinks a siloxane polymer or the like at the time of thermosetting, but two or more reactive groups such as epoxy group (oxiranyl group, oxetanyl group), vinyl group, acrylic group, methacrylic group. A compound having a group, a methylol group, an alkoxymethyl group, or a silanol group can be used. Among these compounds, a compound having two or more groups represented by the following formula (3), a compound represented by the following formula (4), a compound represented by the following formula (5), and 2 oxetane groups. Compounds selected from the group consisting of one or more compounds are preferred. In addition, since the compound represented by the following formula (4) has a common structure with the silane compound of the above formula (1) constituting the [A] siloxane polymer, the compatibility with such a siloxane polymer is good. In addition, a cured film having high transparency can be obtained.

（式（３）中、Ｒ^７は、水素原子又は炭素数１〜１０のアルキル基である。）

(In Formula (3), R ⁷ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)

（式（４）中、Ｒ^８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。これらの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^９は、水素原子、炭素数１〜６のアルキル基、炭素数１〜６のアシル基又は炭素数６〜１５のアリール基である。これらの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。ｍは０から２の整数である。但し、Ｒ^８及びＲ^９がそれぞれ複数の場合、複数のＲ^８及びＲ^９は、それぞれ同一でも異なっていてもよい。）

(In the formula (4), ^{R 8} represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group an alkenyl group or a C6-15 C2-10. Hydrogen atoms with these groups R ⁹ may be a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 15 carbon atoms. the good .m also some or all of the hydrogen atoms have been replaced the group has an integer from 0 to 2. However, in the case of multiple R ⁸ and R ⁹ are each, a plurality of R ⁸ and R ⁹ Each may be the same or different.)

（式（５）中、Ｒ^１０、Ｒ^１１及びＲ^１２は、それぞれ独立して、炭素数１〜４のアルキル基であり、ｃ、ｄ及びｅは、それぞれ独立して、１〜６の整数である。）

(In Formula (5), R < ¹⁰ >, R < ¹¹ > and R < ¹² > are respectively independently a C1-C4 alkyl group, and c, d, and e are respectively independently the integers of 1-6. .)

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁷ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, an n-hexyl group, An n-decyl group etc. are mentioned.

  Examples of the compound having two or more groups represented by the above formula (3) include compound groups represented by the following formulas such as the following melamine derivatives, urea derivatives, and phenolic compounds.

  The compound having two or more groups represented by the above formula (3) not only improves the surface hardness and heat resistance of the cured film as a thermally crosslinkable compound, but also [A] siloxane in a positive radiation sensitive composition. The solubility of the polymer can also be improved, and as a result, radiation sensitivity can be improved and scum can be reduced during development. Among these compounds, 1,3,4,6-tetrakis (methoxymethyl) glycoluril (for example, “Nicalac MX-270”, manufactured by Sanwa Chemical Co., Ltd.) is preferable from the viewpoint of the effect of promoting dissolution.

The alkyl group represented by ^{R 8,} for example a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, t- butyl group, n- hexyl, n- decyl group, tri Fluoromethyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 3-aminopropyl group, 3-mercaptopropyl group, 3- An isocyanate propyl group etc. are mentioned.

Examples of the alkenyl group represented by R ⁸ include a vinyl group, a 3-acryloxypropyl group, and a 3-methacryloxypropyl group.

Examples of the aryl group represented by R ⁸ include a phenyl group, a tolyl group, a p-hydroxyphenyl group, a 1- (p-hydroxyphenyl) ethyl group, a 2- (p-hydroxyphenyl) ethyl group, and a 4-hydroxy group. Examples include -5- (p-hydroxyphenylcarbonyloxy) pentyl group and naphthyl group.

Examples of the alkyl group represented by R ⁹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a t-butyl group.

Examples of the acyl group represented by R ⁹ include a formyl group, an acetyl group, a propionyl group, and a benzoyl group.

Examples of the aryl group represented by R ⁹ include the same groups as the aryl group exemplified for R ⁸ .

  Examples of the compound represented by the above formula (4) include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetraphenoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri i-propoxysilane, and methyltrin-butoxy. Silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri i-propoxysilane, ethyltri n-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxy Silane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloxypropyltrimethoxy Lan, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 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, 3-glycidoxyp Pyrtrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and other dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi Examples include acetoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane, and (3-glycidoxypropyl) methyldiethoxysilane.

Examples of the alkyl group represented by R ¹⁰ , R ¹¹ and R ¹² include a methyl group, an ethyl group, a propyl group, and a butyl group. Moreover, it is preferable that c, d, and e in Formula (5) are an integer of 1-3 from a reactive viewpoint and compatibility with a [A] siloxane polymer.

  Examples of the compound represented by the above formula (5) include tris- (3-trimethoxysilylmethyl) isocyanurate, tris- (3-triethoxysilylmethyl) isocyanurate, tris- (3-trimethoxysilylethyl). Examples include isocyanurate, tris- (3-triethoxysilylethyl) isocyanurate, tris- (3-trimethoxysilylpropyl) isocyanurate, and tris- (3-triethoxysilylpropyl) isocyanurate.

  Examples of the compounds having two or more oxetane groups include commercially available products such as OXT-121, OXT-221, OXT-191, OX-SQ-H, PNOX-1009, RSOX (manufactured by Toagosei), etanacol OXBP, etanacol OXTP. (Manufactured by Ube Industries).

  Among these thermally crosslinkable compounds, N, N, N, N-tetra (methoxymethyl) glycoluril, 3-glycidoxypropyltrimethoxysilane are used from the viewpoint of increasing the surface hardness and heat resistance of the cured film to be formed. Tris- (3-trimethoxysilylpropyl) isocyanurate is preferred.

  Two or more heat crosslinkable compounds may be used in combination. As content when using a heat-crosslinkable compound, 0 to 20 mass parts is preferable with respect to 100 mass parts of [A] siloxane polymer, and 0.1 to 10 mass parts is more preferable. . By making the usage-amount of a heat-crosslinkable compound into the said range, the radiation sensitivity of positive type radiation sensitive composition can be improved more, and the cured film which is excellent in surface hardness can be formed, preventing the fall of transparency.

<Other optional components>
The positive radiation sensitive composition of the present invention has the effects of the present invention in addition to the above [A] siloxane polymer and [B] quinonediazide compound, and the [C] component and the thermally crosslinkable compound as suitable optional components. Other optional components such as a dehydrating agent and a surfactant can be contained as needed as long as they are not impaired.

[Dehydrating agent]
A dehydrating agent is defined as a substance that can convert water to a substance other than water by a chemical reaction or trap water by physical adsorption or inclusion. As a result of the condensation of [A] siloxane polymer in the heating step after the development of the positive type radiation sensitive composition, moisture entering from the environment by arbitrarily adding a dehydrating agent to the positive type radiation sensitive composition The generated moisture can be reduced. Therefore, by using a dehydrating agent, it is possible to reduce moisture in the composition, and as a result, it is possible to improve the storage stability of the composition. Furthermore, it is considered that the condensation reactivity of the [A] siloxane polymer can be increased. As such a dehydrating agent, at least one compound selected from the group consisting of carboxylic acid esters, acetals (including ketals), and carboxylic acid anhydrides is preferable.

  Examples of the carboxylic acid esters include orthocarboxylic acid esters and carboxylic acid silyl esters. 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. Of these, methyl orthoformate is preferred. Examples of the carboxylic acid silyl ester include trimethylsilyl acetate, tributylsilyl acetate, trimethylsilyl formate, and trimethylsilyl oxalate.

  Examples of the acetals include a reaction product of a ketone and an alcohol, a reaction product of a ketone and a dialcohol, and a ketene silyl acetal. 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, acetic acid benzoic anhydride, and the like. Of these, acetic anhydride and succinic anhydride are preferred in view of the dehydration effect.

  The amount when the dehydrating agent is used is preferably 0.1 parts by mass or more and 50 parts by mass or less, more preferably 0.5 parts by mass or more and 30 parts by mass or less, with respect to 100 parts by mass of the [A] siloxane polymer. Particularly preferred is from 10 to 10 parts by weight. By making the usage-amount of a dehydrating agent into the said range, the storage stability of the said positive type radiation sensitive composition can be optimized.

[Surfactant]
The surfactant can be added to improve the coating property of the positive radiation-sensitive composition, reduce coating unevenness, and improve the developability of the radiation irradiated portion. Examples of such surfactants include nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether;
Polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether;
Polyethylene glycol dialkyl esters such as polyethylene glycol dilaurate and polyethylene glycol distearate;
Polyflow No. 57, no. (Meth) acrylic acid copolymers such as 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, Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,1) 2,2-tetrafluorobutyl) ether, fluoroethers such as hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether;
Sodium perfluorododecyl sulfonate; fluoroalkanes such as 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane Kind;
Sodium fluoroalkylbenzenesulfonates;
Fluoroalkyloxyethylene ethers;
Fluoroalkylammonium iodides;
Fluoroalkyl polyoxyethylene ethers;
Perfluoroalkyl polyoxyethanols;
Perfluoroalkyl alkoxylates;
Fluorine alkyl esters and the like can be mentioned.

  Examples of commercially available fluorosurfactants include F-top EF301, 303, and 352 (manufactured by Shin-Akita Kasei), MegaFuck F171, 172, and 173 (manufactured by Dainippon Ink), and Florard FC430 and 431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC-101, 102, 103, 104, 105, 106 (Asahi Glass), FTX-218 (Neos), and the like.

  Examples of the silicone surfactant include SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH8400FLUID (manufactured by Toray Dow Corning Silicone), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

  As content when using the said surfactant, 0.01 mass part or more and 10 mass parts or less are preferable with respect to 100 mass parts of [A] siloxane polymers, and 0.05 mass part or more and 5 mass parts or less are preferable. More preferred. By making content of surfactant into the said range, the applicability | paintability of the said positive type radiation sensitive composition can be optimized.

<Preparation method of positive radiation sensitive composition>
The positive radiation-sensitive composition of the present invention contains, for example, [A] siloxane polymer, [B] quinonediazide compound, [C] component, thermally crosslinkable compound and other optional components as required in a predetermined ratio in a solvent. It is prepared by mixing with. The positive radiation sensitive composition is preferably prepared and used in a state dissolved or dispersed in a suitable solvent.

  As the solvent that can be used for the preparation of the positive radiation-sensitive composition, a solvent that can uniformly dissolve or disperse each component and does not react with each component is preferably used. Examples of such solvents include ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, aromatics. Examples thereof include hydrocarbons, ketones, esters and the like. In addition, these solvents can use 2 or more types together.

Examples of ethers include tetrahydrofuran and the like;
Examples of diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;
Examples of ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;
Examples of propylene glycol monoalkyl ether acetates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate;
Examples of propylene glycol monoalkyl ether propionates include propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like;

Examples of aromatic hydrocarbons include toluene and xylene;
Examples of ketones include methyl ethyl ketone, methyl-i-butyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol) and the like;
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 Examples include -propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, and the like.

  Among these solvents, from the viewpoint of excellent solubility or dispersibility, non-reactivity with each component, and ease of coating film formation, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, Propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters are preferred, especially diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclo Xanone, 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.

  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 the positive radiation sensitive composition is prepared as a solution or dispersion, the proportion of components other than the solvent in the liquid (that is, the total amount of [A] siloxane polymer and [B] quinonediazide compound and optional components) is Depending on the purpose of use and desired film thickness, etc., it can be arbitrarily set, but is preferably 5% by mass or more and 50% by mass or less, more preferably 10% by mass or more and 40% by mass or less, and more preferably 15% by mass or more and 35% by mass. % Or less is more preferable.

<Method for forming 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), and (4) a step of heating the coating film developed in step (3). According to the method for forming a cured film, since the positive radiation sensitive composition of the present invention is used, a cured film having excellent heat resistance can be formed, and outgassing in the heating step during the formation of the cured film can be performed. Generation can be reduced. Moreover, the cured film formed by the forming method sufficiently satisfies general characteristics such as surface hardness. Hereinafter, each process is explained in full detail.

[Step (1)]
In this step, after the positive radiation-sensitive composition 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 substrate materials 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 a cyclic olefin, and a hydrogenated product thereof.

  The application method of the positive radiation sensitive composition is not particularly limited, and for example, a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or the like is adopted. be able to. Of these, spin coating or slit die coating is preferred. Prebaking (PB) conditions vary depending on the type of each component, the blending ratio, and the like, but the PB temperature is preferably 70 ° C to 120 ° C. The PB time is preferably about 1 to 10 minutes.

[Step (2)]
In this step, at least a part of the coating film formed in step (1) is exposed. In this case, when exposing to a part of coating film, it exposes normally through the photomask which has a predetermined pattern. Examples of radiation used for exposure include visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Of these, radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable.

The exposure amount in this step is preferably 100 J / m ² or more and 10,000 J / m ² or less 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.). / M ² or more and 6,000 J / m ² or less is more preferable.

[Step (3)]
In this step, the coating film exposed in step (2) is developed to remove unnecessary portions (radiation irradiated portions) and form a predetermined pattern. As the developer used in the development step, an aqueous alkali (basic compound) solution is preferable. 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 (TMAH) and tetraethylammonium hydroxide Is mentioned.

  In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline aqueous solution. The concentration of alkali in the aqueous alkali 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.

[Step (4)]
In this step, the thin film patterned in step (3) is heated using a heating device such as a hot plate or an oven, thereby promoting the condensation reaction of the [A] siloxane polymer and obtaining a cured product. . In particular, when the heat-sensitive acid generator or heat-sensitive base generator of the component [C] is used, an acidic active substance or a basic active substance is generated in the heating step, and this is used as a catalyst for the [A] siloxane polymer. It is thought that the condensation reaction is further promoted. The heating temperature in this step is usually 120 ° C to 250 ° C. The heating time varies depending on the type of the heating device. For example, when the heating process is performed on a hot plate, the heating time is 5 to 30 minutes, and when the heating process is performed in an oven, the heating time is 30 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. The thickness of the cured film thus formed is preferably from 0.1 μm to 8 μm, more preferably from 0.1 μm to 6 μm, and even more preferably from 0.1 μm to 5 μm.

<Curing film>
Since the cured film of the present invention is formed using the positive radiation-sensitive composition described above, general properties such as surface hardness are sufficiently satisfied and heat resistance is excellent. Therefore, the cured film of the present invention is suitably used for color TFT liquid crystal display elements, organic EL elements, flexible displays such as electronic paper, and the like.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly to this Example. The measuring method of various physical property values is shown below.

^[1 H-NMR analysis and FT-IR Analysis
¹ H-NMR analysis was performed using AVANCE 500 (manufactured by Bruker), and FT-IR analysis was performed using FT-720 (manufactured by Horiba).

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 (manufactured by Showa Denko) combined Mobile phase: Tetrahydrofuran

<[A] Synthesis of Siloxane Polymer>
[Synthesis Example 1]
In a container equipped with a stirrer, 90.3 g of propylene glycol monomethyl ether was charged, followed by 7.6 g (0.03 mol) of the compound represented by the above formula (I-1) and 132.1 g of methyltrimethoxysilane. (0.97 mol) was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., an aqueous phosphoric acid solution in which 0.28 g of phosphoric acid was dissolved in 54 g of ion-exchanged water was dropped, heated to 75 ° C., and held for 3 hours. Subsequently, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. The siloxane polymer (A-1) which is a hydrolysis condensate was synthesize | combined by the above. The solid content concentration of the siloxane polymer (A-1) was 40.0% by mass, the number average molecular weight (Mn) was 1,800, and the molecular weight distribution (Mw / Mn) was 1.9. In the present specification, the “solid content” means a residue obtained by drying a sample on a hot plate at 175 ° C. for 1 hour to remove volatile substances. The content ratios of the structural unit derived from the compound (I-1) and the structural unit derived from methyltrimethoxysilane determined from ¹ H-NMR and FT-IR were 3 mol% and 97 mol%, respectively.

[Synthesis Example 2]
In a container equipped with a stirrer, 90.3 g of propylene glycol monomethyl ether was charged, followed by 178.1 g (0.70 mol) of the compound represented by the above formula (I-1), 40.9 g of methyltrimethoxysilane. (0.30 mol) was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., an aqueous phosphoric acid solution in which 0.28 g of phosphoric acid was dissolved in 54 g of ion-exchanged water was dropped, heated to 75 ° C., and held for 3 hours. Subsequently, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. The siloxane polymer (A-2) which is a hydrolysis-condensation product was synthesize | combined by the above. The solid content concentration of the siloxane polymer (A-2) was 40.0% by mass, the number average molecular weight (Mn) was 1,800, and the molecular weight distribution (Mw / Mn) was 1.9. The content ratios of the structural unit derived from the compound (I-1) and the structural unit derived from methyltrimethoxysilane determined from ¹ H-NMR and FT-IR were 69 mol% and 31 mol%, respectively.

[Synthesis Example 3]
In a container equipped with a stirrer, 90.3 g of propylene glycol monomethyl ether was charged, followed by 128.9 g (0.35 mol) of the compound represented by the above formula (I-1) and 88.5 g of methyltrimethoxysilane. (0.65 mol) was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., an aqueous phosphoric acid solution in which 0.28 g of phosphoric acid was dissolved in 54 g of ion-exchanged water was dropped, heated to 75 ° C., and held for 3 hours. Subsequently, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. The siloxane polymer (A-3) which is a hydrolysis-condensation product was synthesize | combined by the above. The solid content concentration of the siloxane polymer (A-3) was 40.3% by mass, the number average molecular weight (Mn) was 1,500, and the molecular weight distribution (Mw / Mn) was 2.1. The content ratios of the structural unit derived from the compound (I-1) and the structural unit derived from methyltrimethoxysilane determined from ¹ H-NMR and FT-IR were 34 mol% and 66 mol%, respectively.

[Synthesis Example 4]
In a container equipped with a stirrer, 74.0 g of propylene glycol monomethyl ether was charged, followed by 79.2 g (0.35 mol) of the compound represented by the above formula (I-2) and 88.5 g of methyltrimethoxysilane. (0.65 mol) was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., an aqueous phosphoric acid solution in which 0.23 g of phosphoric acid was dissolved in 54 g of ion-exchanged water was dropped, heated to 75 ° C., and held for 3 hours. Subsequently, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. As described above, a siloxane polymer (A-4) which is a hydrolysis-condensation product was synthesized. The solid content concentration of the siloxane polymer (A-4) was 39.9% by mass, the number average molecular weight (Mn) was 1,400, and the molecular weight distribution (Mw / Mn) was 2.0. The content ratios of the structural unit derived from the compound (I-2) and the structural unit derived from methyltrimethoxysilane determined from ¹ H-NMR and FT-IR were 34 mol% and 66 mol%, respectively.

[Synthesis Example 5]
In a container equipped with a stirrer, 90.3 g of propylene glycol monomethyl ether was charged, followed by 100.9 g (0.35 mol) of the compound represented by the above formula (I-3), and 88.5 g of methyltrimethoxysilane. (0.65 mol) was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., an aqueous phosphoric acid solution in which 0.28 g of phosphoric acid was dissolved in 54 g of ion-exchanged water was added dropwise, heated to 75 ° C. and held for 3 hours. Subsequently, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. As described above, a siloxane polymer (A-5), which is a hydrolysis-condensation product, was synthesized. The solid content concentration of the siloxane polymer (A-5) was 40.1% by mass, the number average molecular weight (Mn) was 1,350, and the molecular weight distribution (Mw / Mn) was 1.9. The content ratios of the structural unit derived from the compound (I-3) and the structural unit derived from methyltrimethoxysilane, determined from ¹ H-NMR and FT-IR, were 35 mol% and 65 mol%, respectively.

[Synthesis Example 6]
In a container equipped with a stirrer, 108.7 g of propylene glycol monomethyl ether was charged, followed by 140.2 g (0.35 mol) of the compound represented by the above formula (I-4) and 88.5 g of methyltrimethoxysilane. (0.65 mol) was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., an aqueous phosphoric acid solution in which 0.34 g of phosphoric acid was dissolved in 54 g of ion-exchanged water was dropped, heated to 75 ° C., and held for 3 hours. Subsequently, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, a siloxane polymer (A-6), which is a hydrolysis-condensation product, was synthesized. The solid content concentration of the siloxane polymer (A-6) was 40.1% by mass, the number average molecular weight (Mn) was 1,550, and the molecular weight distribution (Mw / Mn) was 2.0. The content ratios of the structural unit derived from the compound (I-4) and the structural unit derived from methyltrimethoxysilane determined from ¹ H-NMR and FT-IR were 34 mol% and 66 mol%, respectively.

[Synthesis Example 7]
In a container equipped with a stirrer, 92.7 g of propylene glycol monomethyl ether was charged, followed by 104.1 g (0.35 mol) of the compound represented by the above formula (I-5) and 88.5 g of methyltrimethoxysilane. (0.65 mol) was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., an aqueous phosphoric acid solution in which 0.29 g of phosphoric acid was dissolved in 54 g of ion-exchanged water was dropped, heated to 75 ° C., and held for 3 hours. Subsequently, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, a siloxane polymer (A-7), which is a hydrolysis-condensation product, was synthesized. The solid content concentration of the siloxane polymer (A-7) was 40.1% by mass, the number average molecular weight (Mn) was 1,350, and the molecular weight distribution (Mw / Mn) was 2.2. The content ratios of the structural unit derived from the compound (I-5) and the structural unit derived from methyltrimethoxysilane determined from ¹ H-NMR and FT-IR were 34 mol% and 66 mol%, respectively.

[Synthesis Example 8]
In a container equipped with a stirrer, 81.6 g of propylene glycol monomethyl ether was charged, followed by 89.4 g (0.35 mol) of the compound represented by the above formula (I-6) and 88.5 g of methyltrimethoxysilane. (0.65 mol) was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., an aqueous phosphoric acid solution in which 0.26 g of phosphoric acid was dissolved in 54 g of ion-exchanged water was dropped, heated to 75 ° C., and held for 3 hours. Subsequently, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. As described above, a siloxane polymer (A-8), which is a hydrolysis-condensation product, was synthesized. The solid content concentration of the siloxane polymer (A-8) was 40.1% by mass, the number average molecular weight (Mn) was 1,400, and the molecular weight distribution (Mw / Mn) was 2.0. The content ratios of the structural unit derived from the compound (I-6) and the structural unit derived from methyltrimethoxysilane determined from ¹ H-NMR and FT-IR were 34 mol% and 66 mol%, respectively.

[Synthesis Example 9]
In a container equipped with a stirrer, 78.2 g of propylene glycol monomethyl ether was charged, followed by 84.8 g (0.35 mol) of the compound represented by the above formula (I-7) and 88.5 g of methyltrimethoxysilane. (0.65 mol) was charged and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., an aqueous phosphoric acid solution in which 0.25 g of phosphoric acid was dissolved in 54 g of ion-exchanged water was dropped, heated to 75 ° C., and held for 3 hours. Subsequently, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, a siloxane polymer (A-9), which is a hydrolysis-condensation product, was synthesized. The solid content concentration of the siloxane polymer (A-9) was 40.1% by mass, the number average molecular weight (Mn) was 1,450, and the molecular weight distribution (Mw / Mn) was 2.0. The content ratios of the structural unit derived from the compound (I-7) and the structural unit derived from methyltrimethoxysilane determined from ¹ H-NMR and FT-IR were 34 mol% and 66 mol%, respectively.

[Synthesis Example 10]
In a container equipped with a stirrer, 66.6 g of propylene glycol monomethyl ether is charged, followed by 69.4 g (0.35 mol) of phenyltrimethoxysilane and 88.5 g (0.65 mol) of methyltrimethoxysilane. The solution was heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., an aqueous phosphoric acid solution in which 0.21 g of phosphoric acid was dissolved in 54 g of ion-exchanged water was dropped, heated to 75 ° C., and held for 3 hours. Subsequently, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. As described above, a siloxane polymer (A-10), which was a hydrolysis-condensation product, was synthesized. The solid content concentration of the siloxane polymer (A-10) was 40.1% by mass, the number average molecular weight (Mn) was 1,600, and the molecular weight distribution (Mw / Mn) was 2.1. The content ratios of the structural unit derived from phenyltrimethoxysilane and the structural unit derived from methyltrimethoxysilane determined from ¹ H-NMR and FT-IR were 34 mol% and 66 mol%, respectively.

[Synthesis Example 11]
In a container equipped with a stirrer, 66.6 g of propylene glycol monomethyl ether was charged, followed by 101.6 g (0.35 mol) of 3-methacryloxypropyltrimethoxysilane and 88.5 g (0.65 of methyltrimethoxysilane). Mol) and heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., an aqueous phosphoric acid solution in which 0.21 g of phosphoric acid was dissolved in 54 g of ion-exchanged water was dropped, heated to 75 ° C., and held for 3 hours. Subsequently, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. Thus, a siloxane polymer (A-11), which is a hydrolysis-condensation product, was synthesized. The solid content concentration of the siloxane polymer (A-11) was 40.1% by mass, the number average molecular weight (Mn) was 1,600, and the molecular weight distribution (Mw / Mn) was 2.1. The content ratios of the structural unit derived from 3-methacryloxypropyltrimethoxysilane and the structural unit derived from methyltrimethoxysilane determined from ¹ H-NMR and FT-IR were 34 mol% and 66 mol%, respectively. .

<Preparation of radiation-sensitive composition>
Each component used for preparation of each radiation sensitive composition is shown below.

<[B] quinonediazide compound>
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] component>
C-1: benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate C-2: 2-nitrobenzylcyclohexylcarbamate C-3: 1- (4,7-dibutoxy-1-naphthalenyl) tetrahydrothiophenium trifluoromethanesulfonate C-4: N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide (NAI-105 (manufactured by Midori Chemical))

[Example 1]
[A] (B-1) 7 as a quinonediazide compound in a solution containing (A-1) as a siloxane polymer (amount corresponding to 100 parts by mass (solid content) of siloxane polymer (A-1)) Part by weight, 2 parts by weight of (C-1) as component [C], and 0.1 parts by weight of a fluorosurfactant (FTX-218, manufactured by Neos) as a surfactant are added, and the solid content concentration is 25. Propylene glycol monomethyl ether was added so as to have a mass% to prepare a positive radiation sensitive composition.

[Examples 2 to 14 and Comparative Examples 1 and 2]
Each positive-type radiation-sensitive composition was prepared in the same manner as in Example 1 except that the components having the types and contents shown in Table 1 were mixed.

<Physical property evaluation>
The positive radiation sensitive composition prepared as described above was used, and various properties as the composition, cured film and liquid crystal cell were evaluated as follows.

[Evaluation of radiation sensitivity of positive radiation-sensitive composition]
Each positive radiation sensitive composition was applied onto a silicon substrate using a spinner and then prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 4.0 μm. Using the PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon, the exposure time is changed through a mask having a 3.0 μm line and space (10 to 1) pattern. After exposure, the film was developed with a 2.38 mass% TMAH 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 0.30 μm was measured. This minimum exposure amount is shown in Table 1 as radiation sensitivity. When the minimum exposure amount is 200 (mJ / m ² ) or less, it can be said that the radiation sensitivity is good.

[Evaluation of pencil hardness (surface hardness) of cured film]
A coating film was formed in the same manner as in the above [Evaluation of Radiation Sensitivity of Positive Radiation Sensitive Composition] except that the film was not exposed, and post-baked at 220 ° C. for 1 hour in a clean oven. Thereafter, a cured film was formed on the silicon substrate. The pencil hardness (surface hardness) of the cured film was measured by the 8.4.1 pencil scratch test of JIS K-5400-1990. The results are shown in Table 1. When this value is 3H or larger, it can be said that the surface hardness of the cured film is good.

[Evaluation of refractive index of cured film]
In the same manner as in the above [Evaluation of pencil hardness (surface hardness) of cured film], a cured film is formed on a silicon substrate, and the refractive index of the obtained cured film is set to Auto EL IV NIR III (manufactured by Rudolf Research) Ellipso. Measurement was performed at 633 nm using a meter. When this value is 1.50 or more, it can be said that the refractive index of the interlayer insulating film is at a level that causes no problem in practice.

[Evaluation of heat resistance of cured film (1)]
In the same manner as in [Evaluation of pencil hardness (surface hardness) of cured film], a cured film was formed on a silicon substrate, and the film thickness (T2) of the obtained cured film was measured. Next, the silicon substrate on which the cured film is formed is additionally baked in a clean oven at 240 ° C. for 1 hour, and then the thickness (t2) of the cured film is measured, and the rate of change in film thickness due to the additional baking {| t2−T2 | / T2} × 100 [%] was calculated. The results are shown in Table 1. When this value is 3% or less, it can be said that the heat resistance is good.

[Evaluation of heat resistance of cured film (2)]
In the same manner as described above [Evaluation of pencil hardness (surface hardness) of cured film], a cured film was formed on a silicon substrate, and the obtained cured film was pulverized and weighed to obtain a sample. Subsequently, using a Hi-Res TGA2950 type Thermogravimetric Analyzer (manufactured by TA Instruments), the sample was heated from room temperature to 400 ° C at a rate of 10 ° C / min at 10 ° C / min, and the weight loss at that time was measured. did. If the temperature at 5% weight change is 350 ° C. or higher, it can be said that the heat resistance is good.

[Evaluation of light transmittance of cured film]
A coating film was formed on a glass substrate in the same manner as described above [Evaluation of radiation sensitivity of positive radiation-sensitive composition]. Each of the obtained coating films was exposed using a Canon PLA-501F exposure machine (extra-high pressure mercury lamp) so that the integrated irradiation amount was 3,000 J / m ^2, and then in a clean oven. A cured film was obtained by heating at 220 ° C. for 1 hour. The light transmittance of the glass substrate having this cured film was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam” (manufactured by Hitachi, Ltd.). Table 1 shows the values of the minimum light transmittance at that time. When the minimum light transmittance is 95% or more, it can be said that the light transmittance is good.

[Evaluation of foreign matter in the positive-type radiation-sensitive composition]
Using a light scattering type in-liquid particle detector (“KS-28B” manufactured by Rion), a solid foreign substance having a size of 0.5 μm or more in the liquid of the positive radiation sensitive composition stored at 5 ° C. for 7 days. It was measured. When the compatibility between the [A] siloxane polymer and the [B] quinonediazide compound is low, the [B] quinonediazide compound is likely to precipitate as a solid foreign matter, and the foreign matter in the liquid tends to increase over time. When a cured film is formed using such a positive radiation-sensitive composition in which solid foreign matters tend to increase, solid foreign matters are scattered in the cured film, so that the entire cured film becomes cloudy. Therefore, the evaluation of foreign matter in the liquid over time is a judgment index of the compatibility between the [A] siloxane polymer and the [B] quinonediazide compound and the level of suppression of whitening of the cured film. After storage at 5 ° C. for 7 days, when the solid foreign matter having a size of 0.5 μm or more in the liquid of the positive radiation sensitive composition is 80 / ml or less, [A] siloxane polymer and [B] quinonediazide It can be judged that the compatibility with the compound is good.

[Evaluation of resist stripping solution resistance of cured film]
The resist stripping solution resistance of the cured film was evaluated in the following steps.

(1) Formation of cured film A cured film was formed on a silicon substrate in the same manner as described above [Evaluation of pencil hardness (surface hardness) of cured film].

(2) Formation of ITO film on cured film ITO target (ITO filling rate 95% or more, In ₂ O ₃ / SnO ₂ = 90/10 mass ratio) with high speed sputtering apparatus SH-550-C12 manufactured by Nippon Vacuum Technology Was used to perform ITO sputtering at 60 ° C. At this time, the degree of decompression was 1.0 × 10 ⁻⁵ Pa, the Ar gas flow rate was 3.12 × 10 ⁻³ m ³ / Hr, and the O ₂ gas flow rate was 1.2 × 10 ⁻⁵ m ³ / Hr. . The substrate after sputtering was heated at 240 ° C. for 60 minutes in the above-mentioned clean oven and annealed.

(3) Formation of resist pattern on ITO film Next, the substrate was set on a spinner, and a JSR G-line positive resist PFR3650-21cp was dropped onto the substrate and applied at 3,500 rpm × 30 seconds. The substrate was heated on a hot plate at 90 ° C. for 2 minutes to remove the solvent. After that, using an exposure machine Canon PLA501F (made by Canon), an exposure dose of illuminance of 23 mW / m ² and 25 mJ / m ² in terms of i-line, and a ghi line (wavelength 436 nm, 405 nm, 365 nm) through a 10 μm / 10 μm pattern mask Intensity ratio = 2.7: 2.5: 4.8). Subsequently, it was immersed and developed for 60 seconds using a 2.4% TMAH aqueous solution at room temperature, rinsed with ultrapure water for 60 seconds, and then air-dried. Thus, a 10 μm / 10 μm line and space pattern was formed.

(4) Etching of ITO film As an etchant, a mixture of nitric acid / hydrochloric acid at a weight ratio of 1/3 was used. The substrate prepared in the above (3) was immersed in an etchant for 60 seconds, and the ITO film where there was no resist pattern was etched.

(5) Resist stripping The substrate obtained by etching the ITO film in (4) above is immersed in a resist stripping solution TOK-106 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) heated to 70 ° C. for 10 minutes, washed with water, and further in an oven. And dried at 210 ° C. for 15 minutes to remove the resist.

  Through the above steps, the film thickness when the ITO film is formed on the cured film of (2) above and the film thickness after (5) resist removal are measured, and the film thickness change of the latter with respect to the former is 5 If it is less than%, the swelling of the cured film by the resist stripping solution is small, and it can be said that the resist stripping solution resistance is good. If the film thickness change is less than 10%, the resist stripping solution resistance is slightly good, and if the film thickness change is 10% or more, it can be determined that the resist stripping solution resistance is poor. When the film thickness change of the cured film was less than 5%, it was evaluated as (◯), when it was less than 10% (Δ), and when it was 10% or more, it was evaluated as (×). The results are listed in Table 1.

[Evaluation of dry etching resistance of cured film]
In the same manner as described above [Evaluation of pencil hardness (surface hardness) of cured film], a cured film is formed on a silicon substrate, and a dry etching apparatus CDE-80N (manufactured by Shibaura Mechatronics) is used, and etching gas CF _{4 is} 50 ml / min. , Dry etching was performed under the conditions of O ₂ 10 ml / min, output 400 mW, and etching time 90 seconds, and the film thickness was measured before and after the treatment. The results are shown in Table 1. When the thickness reduction is less than 1.0 μm, it can be said that the dry etching resistance is good.

[Evaluation of relative permittivity of cured film]
Each composition was applied onto a polished SUS304 substrate using a spinner and then prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. 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 relative dielectric constant in the frequency of 10 kHz was measured by CV method using the HP16451B electrode and HP4284A precision LCR meter by Yokogawa-Hewlett Packard. The results are shown in Table 1. 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.

[Evaluation of voltage holding ratio of liquid crystal cell]
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% TMAH 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 (manufactured by Merck) was injected, and then the liquid crystal injection port was sealed to prepare a liquid crystal cell.

  This liquid crystal cell is placed in a constant temperature layer of 60 ° C., and the voltage of the liquid crystal cell is set to a square wave of 5.5 V with a liquid crystal voltage holding ratio measurement system VHR-1A type (manufactured by Toyo Technica), the measurement frequency is 60 Hz. Retention was measured. The results are shown in Table 1. Here, the voltage holding ratio is a value obtained by the following formula. 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, it can be said that 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.

  Voltage holding ratio (%) = (liquid crystal cell potential difference after 16.7 milliseconds from the reference time) / (voltage applied at 0 milliseconds [reference time]) × 100

[Evaluation of the amount of outgas components derived from aromatic groups]
Each positive-type radiation-sensitive composition solution was applied onto a silicon substrate with a spinner to form a coating film having a coating thickness of 6.0 μm. About this coating film, head space gas chromatography / mass spectrometry (head space sampler; manufactured by Nippon Analytical Industry, JHS-100A, gas chromatography / mass spectrometer, JEOL JMS-AX505W type mass spectrometer; manufactured by JEOL Ltd.) The analysis was performed. The purge area was set to 100 ° C./10 min, and the peak area A related to the generation of components derived from aromatic groups in the cured film was determined. Using n-octane (specific gravity: 0.701, injection amount: 0.02 μL) as a standard substance, and generation of components derived from aromatic groups in the cured film in terms of n-octane based on the peak area based on the peak area The amount (μg) was calculated.
Generation amount of component derived from aromatic group of cured film (μg) = A × (amount of n-octane) / (peak area of n-octane)
When this value is low, it can be judged that the generation amount of the aromatic group-derived component of the cured film is small and the generation of the aromatic group-derived outgas component of the cured film is low.

  As is clear from the results in Table 1, when the positive radiation sensitive compositions of Examples 1 to 14 were used, the amount of outgas generated in the heating process was higher than that of the positive radiation sensitive composition of Comparative Example 1. It was significantly reduced and it was found that the cured film formed had good heat resistance. In addition, the positive radiation sensitive compositions of Examples 1 to 14 were less in the liquid than the positive radiation sensitive composition of Comparative Example 2, and [A] siloxane polymer and [B] quinonediazide compound. It was found that the compatibility was excellent and the heat resistance was good. In addition, the cured films formed from the positive radiation sensitive compositions of Examples 1 to 14 have general surface hardness, refractive index, light transmittance, resist stripping solution resistance, dry etching resistance, low dielectric constant, and the like. It was found that the required characteristics were well balanced.

  The positive radiation sensitive composition of the present invention sufficiently satisfies the general properties required for a cured film, such as surface hardness, refractive index, light transmittance, resist stripping solution resistance, dry etching resistance, and low dielectric constant. In addition, a cured film having excellent heat resistance can be formed, and generation of outgas in the heating process during the formation of the cured film can be reduced. Therefore, the positive radiation-sensitive composition is suitably used for forming a cured film such as a color TFT liquid crystal display element, an organic EL element, a flexible display such as electronic paper.

Claims (7)

[A] A positive radiation-sensitive composition containing a siloxane polymer having a structure in which a group represented by the following formula (i) is bonded to a silicon atom, and [B] a quinonediazide compound.

(In the formula (i), R ¹ is a phenyl group. Y is an imino group, an amide group, an ether group or a carbonyl group. X is a methylene group or an alkylene group having 2 to 6 carbon atoms. ) [A] The positive radiation sensitive composition according to claim 1, wherein the siloxane polymer is a hydrolysis condensate of a compound containing a hydrolyzable silane compound represented by the following formula (1).

(In the formula ^(1), .R ^{2 R} 1, Y and X are as defined in the above formula (i) is a monovalent alicyclic hydrocarbon alkyl or C3-30 from 1 to 6 carbon atoms Z is a halogen atom or OR ³ , where R ³ is a hydrogen atom, an acyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. B is an integer of 0 to 2, provided that a + b ≦ 3 is satisfied, and when there are a plurality of R ¹ , Y, X, R ² , Z, and R ³ , a plurality of R ¹ , Y, X, R ² , Z and R ³ may be the same or different. [A] The positive radiation sensitive composition according to claim 2, wherein the content ratio of the structural unit derived from the compound represented by the formula (1) in the siloxane polymer is 5 mol% or more and 60 mol% or less. [C] The positive radiation-sensitive composition according to any one of claims 1 to 3 , further comprising a heat-sensitive acid generator or a heat-sensitive base generator. 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 5 on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) A method of forming a cured film, including a step of developing the coating film irradiated with radiation in step (2), and (4) a step of heating the coating film developed in step (3). A cured film formed from the positive radiation-sensitive composition according to claim 5 .