JP2016194671A - Radiation-sensitive resin composition, cured film, method of forming the same, and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition that sufficiently satisfies general properties such as sensitivity and can also achieve solvent resistance, a cured film formed from the radiation-sensitive resin composition capable of achieving a low dielectric constant and a high refractive index, and provide an electronic device comprising the cured film.SOLUTION: The problem is solved by a radiation-sensitive resin composition comprising: a polymer component comprising a first structural unit that is at least one of structural units represented by general formula (1) and formula (2) and a second structural unit; and [B] a radiation-sensitive acid generator.SELECTED DRAWING: None

Description

  The present invention relates to a radiation-sensitive resin composition, a cured film, a method for forming the same, and a display element.

In an electronic component such as a thin film transistor type liquid crystal display element, an interlayer insulating film is generally provided to insulate between wirings arranged in layers, and the upper part of a semiconductor element is flattened in an organic electroluminescence element. A flattening film is provided for stacking the electrode and the light emitting layer on the flattening film.
For example, a thin film transistor type liquid crystal display element is manufactured through a process of forming a transparent electrode film on an interlayer insulating film and further forming a liquid crystal alignment film thereon. For this reason, the interlayer insulating film is exposed to high temperature conditions in the transparent electrode film formation process or to a resist stripping solution used for electrode pattern formation. Solvent properties are required.

As a conventional interlayer insulating film for liquid crystal display elements, a positive radiation sensitive resin composition using an acid generator such as naphthoquinonediazide is used from the viewpoint of patterning performance (for example, JP-A-2001-354822). See the official gazette).
Recently, for the purpose of forming a cured film for a display element with higher sensitivity than a positive radiation-sensitive resin composition using an acid generator such as naphthoquinonediazide, for example, JP-A-2004-4669, The crosslinking agent, acid generator, and itself are insoluble or hardly soluble in an aqueous alkali solution, but have a protecting group that can be cleaved by the action of an acid, and are soluble in an aqueous alkali solution after the protecting group is cleaved. There has been proposed a positive chemical amplification material characterized by containing a resin. In addition, JP 2004-264623 A, JP 2008-304902 A, and the like include an acetal structure and / or a ketal structure, a resin containing an epoxy group, and an acid generator. Radiation compositions have been proposed.

  However, when these radiation-sensitive resin compositions are used, the resulting cured film has insufficient solvent resistance, and is aligned during the etching process of the transparent electrode formed on the interlayer insulating film and the alignment film formation. There was a problem that the interlayer insulating film deteriorated due to the organic solvent contained in the agent.

  Furthermore, in the interlayer insulating film, low dielectric constant (high insulation) and high refractive index are particularly required. For example, in an IPS mode liquid crystal display element, the number of constituent members arranged on the array substrate increases, and the electrode structure and wiring arrangement structure on the array substrate are more complicated than those of other liquid crystal modes such as the TN mode. It will be a thing. For this reason, lower power consumption of the panel is achieved by lowering the dielectric constant of the interlayer insulating film, etc., increasing the refractive index of the interlayer insulating film, and increasing the pixel transmittance by bringing it closer to the refractive index of the transparent electrode. It is requested to do.

JP 2001-354822 A JP 2004-4669 A JP 2004-264623 A JP 2008-304902 A JP 2012-133091 A JP 2012-163937 A

  The present invention has been made based on the circumstances as described above, and its purpose is to provide a radiation-sensitive resin composition that sufficiently satisfies general properties such as sensitivity and can achieve solvent resistance, A cured film formed from this radiation-sensitive resin composition can achieve a low dielectric constant and a high refractive index, and an object thereof is to provide an electronic device including the cured film.

  The invention made to solve the above-mentioned problems has [A] at least one first structural unit selected from structural units represented by the following formulas (1) and (2), and a second structural unit. This is achieved by a radiation-sensitive resin composition containing a polymer component, [B] a radiation-sensitive acid generator.

(In the formula (1), (2), A 1 represents an oxygen atom or a sulfur atom, ^{A 2} represents a hydrogen atom, an alkyl group or alkoxyl group having 1 to 12 carbon atoms having 1 to 12 carbon atoms, ^{A 3} Represents a hydrogen atom or a methyl group, m1 represents an integer of 1 to 3, m2 represents an integer of 0 to 4, and m3 represents an integer of 0 to 6.)
Moreover, another invention made | formed in order to solve the said subject is achieved by the electronic device provided with the cured film formed from the said radiation sensitive resin composition, and the said cured film.
including.

Furthermore, a step of forming a coating film on the substrate, a step of irradiating at least a part of the coating film, a step of developing the coating film irradiated with the radiation, and a step of heating the developed coating film A cured film forming method comprising:
This is achieved by a method for forming a cured film in which the coating film is formed using the radiation-sensitive resin composition of the present invention.

The present invention has been made based on the circumstances as described above, and its purpose is to provide a radiation-sensitive resin composition that sufficiently satisfies general properties such as sensitivity and can achieve solvent resistance, A cured film formed from this radiation-sensitive resin composition can achieve a low dielectric constant and a high refractive index, and an object thereof is to provide an electronic device including the cured film.
A cured film formed from the radiation-sensitive resin composition, a method for forming the cured film, and a display element including the cured film can be provided. Therefore, the said radiation sensitive resin composition, the said cured film, its formation method, and the said display element can be used suitably for manufacturing processes, such as a liquid crystal display device and an organic electroluminescent display element.

<Radiation sensitive resin composition>
The radiation sensitive resin composition of the present invention contains [A] a polymer component and [B] a radiation sensitive acid generator. Furthermore, the said radiation sensitive resin composition may contain another arbitrary component in the range which does not impair the effect of this invention. Hereinafter, each component will be described in detail.

<[A] Polymer component>
It is a polymer component having at least one first structural unit selected from structural units represented by the following formulas (1) and (2), and a second structural unit.
[A] Since the polymer component has the above structural unit, the radiation-sensitive resin composition is excellent in sensitivity and can suppress a change in the film thickness of the unexposed portion after the development process or after the post-baking process. . Moreover, the [A] polymer component may have another structural unit in the range which does not impair the effect of this invention. The second structural unit is a structural unit mainly having a crosslinkable group. By including the structural unit having a crosslinkable group, the heat resistance and solvent resistance of the cured film formed from the radiation-sensitive resin composition are included. It is possible to improve the physical properties of the cured film.
Furthermore, the [A] polymer component may have a 3rd structural unit containing an acid dissociable group as needed. By further including the third structural unit containing an acid dissociable group, the sensitivity of the radiation sensitive resin composition can be further improved. You may have 2 or more types of each structural unit.

[A] As the polymer component, for example,
(1) a polymer component including a polymer having a first structural unit, a second structural unit, and a third structural unit;
(2) a polymer component comprising a polymer having a first structural unit and a polymer having a first structural unit and a third structural unit;
(3) a polymer component comprising a polymer having a second structural unit and a polymer having a first structural unit and a third structural unit;
(4) A polymer component including a polymer having a third structural unit and a polymer having a first structural unit and a second structural unit;

Hereinafter, the first structural unit, the second structural unit, the third structural unit, and other structural units will be described in detail.
[First structural unit]
The first structural unit is at least one first structural unit selected from structural units represented by the following formulas (1) and (2), and includes a crosslinkable group. The cured film formed from the radiation-sensitive resin composition has a second structural unit containing a crosslinkable group in the [A] polymer component, so that the polymers constituting the [A] polymer component or [ A] The strength can be increased by crosslinking the polymer constituting the polymer component with the [D] cyclic ether compound described later.
The structural units represented by the following formulas (1) and (2) have a phenyl group and a naphthyl group, respectively, so that the cured film formed from the radiation-sensitive resin composition has a low dielectric constant and a high refractive index. Can be achieved. A ¹ in the following formulas (1) and (2) is preferably a sulfur atom from the viewpoint of a high refractive index.

In formulas (1) and (2), A ¹ represents an oxygen atom or a sulfur atom, A ² represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms, and A ³ represents A hydrogen atom or a methyl group is shown. m1 represents an integer of 1 to 3, m2 represents an integer of 0 to 4, and m3 represents an integer of 0 to 6.

In formulas (1) and (2), when A ¹ is an oxygen atom, when m1 is 1, it represents a group having an oxirane ring, when m1 is 2, it represents a group having an oxetane ring, and when m1 is 3 A group having an oxolane ring is shown. When A ¹ is a sulfur atom, a group having a thiirane ring is shown when m1 is 1, a group having a thietan ring is shown when m1 is 2, and a group having a thiolane ring is shown when m1 is 3.
Examples of the alkyl group having 1 to 12 carbon atoms represented by A ² include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and a sec-butyl group. , T-butyl group, n-hexyl group, n-octyl group, butyl group represented by n-do and the like.

  Specific examples of the first structural unit include structural units formed by unsaturated double bond compounds represented by the following formulas (a-1) to (a-24).

  The unsaturated double bond compounds (a-4), (a-18), (a-22) and the like that give the structural unit represented by the above formula are preferred.

The content ratio of the first structural unit is preferably 0.1 mol% or more and 80 mol% or less, and more preferably 1 mol% or more and 60 mol% or less with respect to all the structural units constituting the [A] polymer component. 10 mol% or more and 40 mol% or less are more preferable.
[Second structural unit]
[A] The polymer component has other structural units other than the first structural unit, the third structural unit, and the third structural unit as long as the effects of the present invention are not impaired.
Examples of monomers that give other structural units include unsaturated monocarboxylic acids, (meth) acrylic acid esters having a hydroxyl group, (meth) acrylic acid chain alkyl esters, (meth) acrylic acid cyclic alkyl esters, ( A meta) acrylic acid aryl ester, an unsaturated aromatic compound, a conjugated diene, an unsaturated compound having a tetrahydrofuran skeleton, or a compound represented by the following formula (5).

(In the formula (5), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² represents an epoxy group, a 3,4-epoxycyclohexyl group, the following formula (5-1), the following formula (5-2) or X ¹ is a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms, Y ¹ is a single bond, oxygen, or a group selected from the group of groups represented by the following formula (5-3). An atom, a sulfur atom or an imino group, wherein R ¹³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms in formula (5-3), and * represents a bonding site.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like. As an anhydride of unsaturated dicarboxylic acid, the anhydride of the compound illustrated as said dicarboxylic acid etc. are mentioned, for example. Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include, for example, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], hexane. And mono- (methacryloyloxy) ethyl hydrophthalate. Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends include ω-carboxypolycaprolactone mono (meth) acrylate. Examples of unsaturated polycyclic compounds having a carboxyl group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hept-2-ene and 5,6-dicarboxybicyclo [2.2.1]. Hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5- Carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2. 2.1] hept-2-ene anhydride and the like.

  Of these, monocarboxylic acid and dicarboxylic acid anhydrides are preferred, and (meth) acrylic acid and maleic anhydride are more preferred from the viewpoints of copolymerization reactivity, solubility in alkaline aqueous solutions, and availability.

  Examples of the (meth) acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, and methacrylate. Examples include 2-hydroxyethyl acid, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, and the like.

  Examples of the (meth) acrylic acid chain alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, N-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, acrylic acid Examples include isodecyl, n-lauryl acrylate, tridecyl acrylate, and n-stearyl acrylate.

  Examples of the (meth) acrylic acid cyclic alkyl ester include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.02,6] decan-8-yl methacrylate, and tricyclomethacrylate [5. 2.1.02,6] decan-8-yloxyethyl, isobornyl methacrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.02,6] decan-8-yl acrylate, tricyclo [ 5.2.1.02,6] decan-8-yloxyethyl acrylate, isobornyl acrylate and the like.

  Examples of the (meth) acrylic acid aryl ester include phenyl methacrylate, benzyl methacrylate, phenyl acrylate, and benzyl acrylate.

  Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-tolyl. Maleimide, N-naphthylmaleimide, N-ethylmaleimide, N-hexylmaleimide, N-benzylmaleimide and the like can be mentioned.

  Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and the like.
The structural unit represented by the above formula (5) is preferably a structural unit represented by the following formula.

In the above formula, R ²⁹ is a hydrogen atom or a methyl group.

As the compound giving such a structural unit, a monomer containing a (meth) acryloyl group, oxiranyl group or oxetanyl group is preferred, a monomer containing an oxiranyl group or oxetanyl group is more preferred, glycidyl methacrylate, 3- More preferred are methacryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate.

As a content rate of another structural unit, Preferably it is 5 mol%-30 mol% with respect to all the structural units, More preferably, it is 10 mol%-25 mol%. By setting the content of other structural units to 5 mol% to 30 mol%, a radiation sensitive resin composition that optimizes solubility in an aqueous alkali solution and is excellent in radiation sensitivity can be obtained.
[Third structural unit]
The third structural unit has an acid dissociable group. This acid-dissociable group acts as a protecting group for protecting a carboxy group, a phenolic hydroxyl group and the like in the polymer. A polymer having such a protective group is usually insoluble or hardly soluble in an alkaline aqueous solution. Since this protecting group is an acid-dissociable group, this polymer becomes soluble in an alkaline aqueous solution when the protecting group is cleaved by the action of an acid.

  In the radiation-sensitive resin composition, the [A] polymer component has the first structural unit, thereby achieving high radiation sensitivity and improving the stability of the pattern shape obtained by development or the like. .

  As the third structural unit containing an acid dissociable group, a structural unit containing a group represented by the following formula (3) or the following formula (4) is preferable.

In Formula (3), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or at least a part of the hydrogen atoms of the hydrocarbon group is a hydroxyl group, a halogen atom or A group substituted with a cyano group. However, there is no case where R ¹ and R ² are both hydrogen atoms. R ³ represents a hydrocarbon group having 1 to 30 carbon atoms, a group containing an oxygen atom between carbon-carbon or a bond side terminal of the carbon hydrogen group, or at least a part of hydrogen atoms of these groups is a hydroxyl group, a halogen atom A group substituted by an atom or a cyano group.

In formula (4), R ^{4 to} R ¹⁰ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. n is 1 or 2. When n is 2, the plurality of R ⁷ and R ⁸ may be the same or different. * Indicates a binding site.

  Examples of the structural unit having a group represented by the above formula (3) include structural units represented by the following formulas (3-1) to (3-10).

In the above formulas (3-1) to (3-10), R ¹⁷ represents a hydrogen atom or a methyl group.

  Examples of the monomer that gives the structural unit represented by the formulas (3-1) to (3-10) of the third structural unit include 1-ethoxyethyl methacrylate, 1-butoxyethyl methacrylate, methacrylic acid 1 -(Tricyclodecanyloxy) ethyl, 1- (pentacyclopentadecanylmethyloxy) ethyl methacrylate, 1- (pentacyclopentadecanyloxy) ethyl methacrylate, 1- (tetracyclododecanylmethyloxy) methacrylate ) Ethyl, 1- (adamantyloxy) ethyl methacrylate and the like.

    Examples of the structural unit having a group represented by the above formula (4) include structural units represented by the following formulas (4-1) to (4-5).

In the above formulas (4-1) to (4-5), R ²⁰ represents a hydrogen atom or a methyl group.

  As a monomer which gives the structural unit represented by the above formula (4), tetrahydro-2H-pyran-2-yl methacrylate (4-3) is preferable.

The content ratio of the third structural unit is preferably 0.1 mol% or more and 80 mol% or less, and more preferably 1 mol% or more and 60 mol% or less with respect to all the structural units constituting the [A] polymer component. 10 mol% or more and 40 mol% or less are more preferable.
<[A] Polymer component synthesis method>
[A] The polymer component can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator. For example, a method of dropping a solution containing a monomer and a radical initiator into a reaction solvent or a solution containing the monomer to cause a polymerization reaction, a solution containing the monomer, and a solution containing the radical initiator Separately, a method of dropping a reaction solvent or a monomer-containing solution into a polymerization reaction, a plurality of types of solutions containing each monomer, and a solution containing a radical initiator, It is preferable to synthesize by a method such as a method of dropping it into a reaction solvent or a solution containing a monomer to cause a polymerization reaction.

  [A] Examples of the solvent used in the polymerization reaction of the polymer component include the solvents exemplified in the section of preparation of the radiation-sensitive resin composition described later.

  As the polymerization initiator used in the polymerization reaction, those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis ( 2,4-Dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), azo compounds such as 2,2′-azobis (methyl 2-methylpropionate); benzoyl Organic peroxides such as peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane; hydrogen peroxide and the like.

  [A] In the polymerization reaction of the polymer component, a molecular weight modifier may be used to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid; Examples thereof include xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; terpinolene and α-methylstyrene dimer.

[A] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is preferably 2.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, and preferably 5.0 × 10 ³ or more. 5.0 × 10 ⁴ or less is more preferable. [A] By making Mw of a polymer component into the said range, the sensitivity and alkali developability of the said radiation sensitive resin composition can be improved.

[A] The number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer component is preferably 2.0 × 10 ³ or more and 1.0 × 10 ⁵ or less, and 5.0 × 10 ³ or more and 5.0 × 10 ^4. The following is more preferable. [A] By making Mn of a polymer into the said range, the cure reactivity at the time of hardening of the coating film of the said radiation sensitive resin composition can be improved.

[A] The molecular weight distribution (Mw / Mn) of the polymer component is preferably 3.0 or less, and more preferably 2.6 or less. [A] By making Mw / Mn of a polymer component 3.0 or less, the developability of the obtained cured film can be improved.
<[B] Radiation sensitive compound>
[B] The radiation-sensitive compound imparts radiation-sensitive properties to the radiation-sensitive resin composition. This [B] radiation sensitive compound is a compound which produces a reactive active species upon exposure to radiation. Here, the radiation includes at least visible light, ultraviolet rays, far ultraviolet rays, electron beams (charged particle beams), and X-rays. As content of the [B] radiation sensitive compound in the said radiation sensitive resin composition, it is 5 to 60 mass parts with respect to 100 mass parts of [A] polymer components, for example. [B] The radiation sensitive compound is preferably (B1) an acid generator, (B2) a polymerization initiator, or a combination thereof.
((B1) acid generator)
(B1) The acid generator is a compound that generates an acid upon irradiation with radiation. The said radiation sensitive resin composition can exhibit the positive radiation sensitive characteristic with respect to an alkali developing solution, for example by containing (B1) acid generator.

(B1) The acid generator is not particularly limited as long as it is a compound that generates an acid (for example, carboxylic acid, sulfonic acid, etc.) by irradiation with radiation. Examples of (B1) acid generators include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and quinone diazide compounds. Of these, quinonediazide compounds are preferred.
(Quinonediazide compound)
A quinonediazide compound generates a carboxylic acid upon irradiation with radiation. As the quinonediazide compound, for example, a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

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

  Examples of trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone.

  Examples of tetrahydroxybenzophenone include 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3 , 4,2′-tetrahydroxy-4′-methylbenzophenone, 2,3,4,4′-tetrahydroxy-3′-methoxybenzophenone, and the like. Examples of pentahydroxybenzophenone include 2,3,4,2 ', 6'-pentahydroxybenzophenone. Examples of hexahydroxybenzophenone include 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone and 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone. Examples of the (polyhydroxyphenyl) alkane include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tri (p-hydroxy). Phenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-) 4-hydroxyphenyl) -3-phenylpropane, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl) -4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobiin Down -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', 4'-trihydroxy flavan like.

  As other mother nucleus, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- {3- (1- [4 -Hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] -3- [1- {3- (1- [4-hydroxyphenyl] -1-methylethyl) -4 , 6-dihydroxyphenyl} -1-methylethyl] benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene, and the like.

  Of these mother nuclei, (polyhydroxyphenyl) alkanes are preferred, 1,1,1-tri (p-hydroxyphenyl) ethane and 4,4 ′-[1- [4- [1- [4-hydroxyphenyl]. ] -1-methylethyl] phenyl] ethylidene] bisphenol is more preferred. Note that sensitivity and the like can be particularly improved by using 1,1,1-tri (p-hydroxyphenyl) ethane or the like as a mother nucleus. Further, by using 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol or the like as a mother nucleus, chemical resistance and the like are particularly improved. be able to.

  As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. Examples of 1,2-naphthoquinonediazide sulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferred.

  The synthesis of the quinonediazide compound can be performed by a known condensation reaction. In this condensation reaction, 1,2-naphthoquinone diazide sulfonic acid halide corresponding to preferably 30 mol% or more and 85 mol% or less can be used with respect to the number of OH groups in the phenolic compound or alcoholic compound.

  Examples of the quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide. -4-sulfonic acid amide and the like are also preferably used.

  These quinonediazide compounds can be used alone or in combination of two or more. The quinonediazide compound can also be used in combination with an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carboxylic acid ester compound, and the like.

[Oxime sulfonate compound]
As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the following formula (6) is preferable.

In the above formula (6), R ¹⁴ represents an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or an aryl having 6 to 20 carbon atoms. Or a group in which some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group and aryl group are substituted with a substituent. * Indicates a bonding position.

The alkyl group represented by R ¹⁴ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. The linear or branched alkyl group having 1 to 12 carbon atoms may be substituted with a substituent. Examples of the substituent include an alkoxy group having 1 to 10 carbon atoms and 7,7-dimethyl- Examples thereof include alicyclic groups containing a bridged alicyclic group such as a 2-oxonorbornyl group. Examples of the fluoroalkyl group having 1 to 12 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, and a heptylfluoropropyl group.

The alicyclic hydrocarbon group represented by R ¹⁴ is preferably an alicyclic hydrocarbon group having 4 to 12 carbon atoms. The alicyclic hydrocarbon group having 4 to 12 carbon atoms may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom. .

The aryl group represented by R ¹⁴ is preferably an aryl group having 6 to 20 carbon atoms, and more preferably a phenyl group, a naphthyl group, a tolyl group, or a xylyl group. The aryl group may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.

  Examples of the compound containing an oxime sulfonate group represented by the above formula (6) include oxime sulfonate compounds represented by the following formula (6-1), formula (6-2), and formula (6-3). Is mentioned.

In the formulas (6-1) and (6-2), in the formula (6-3), R ¹⁸ has the same meaning as the formula (6). In the above formulas (6-1) and (6-2), R ¹⁹ is an alkyl group having 1 to 12 carbon atoms and a fluoroalkyl group having 1 to 12 carbon atoms.
In formula (6-3), X represents an alkyl group, an alkoxy group, or a halogen atom. b is an integer of 0-3. However, when there are a plurality of Xs, the plurality of Xs may be the same or different.

The alkyl group represented by X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom. Examples of the oxime sulfonate compound represented by the above (6-3) include the following formulas (6-4) to (6-8). And the like.

  The compounds represented by the above formulas (6-4) to (6-8) are (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octyl), respectively. Sulphonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p-toluene) Sulphonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile and (5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile, which are commercially available.

As a minimum of content of the (B1) acid generator in the said radiation sensitive resin composition, 5 mass parts is preferable with respect to 100 mass parts of [A] polymers, 10 mass parts is more preferable, 15 mass parts Is more preferable. On the other hand, as this upper limit, 60 mass parts is preferable, 40 mass parts is more preferable, and 30 mass parts is further more preferable. (B1) By making content of an acid generator into the said range, the difference of the solubility of the irradiated part with respect to a developing solution and the unirradiated part can be enlarged, and patterning performance can be improved. In addition, the solvent resistance of the insulating film can be improved.
((B2) polymerization initiator)
(B2) The polymerization initiator is a component that generates an active species that can start polymerization of a compound having polymerizability in response to radiation. The pattern-forming resin composition can exhibit negative radiation sensitive characteristics with respect to, for example, an alkaline developer by including (B2) a polymerization initiator. (B2) As a polymerization initiator, radical photopolymerization initiator can be mentioned. Examples of the photo radical polymerization initiator include O-acyl oxime compounds, acetophenone compounds, biimidazole compounds, and the like. These compounds can be used alone or in combination of two or more.
(O-acyl oxime compound)
Examples of the O-acyloxime compound include 1- [4- (phenylthio) -2- (O-benzoyloxime)], 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyl). Oxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl] -9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.
(Acetophenone compound)
Examples of acetophenone compounds include α-aminoketone compounds and α-hydroxyketone compounds.
(Α-aminoketone compound)
Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4 -Morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and the like.
(Α-hydroxyketone compound)
Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone can be mentioned.
(Biimidazole compound)
Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 Examples include '-tetraphenyl-1,2'-biimidazole.

  As a minimum of content of the (B2) polymerization initiator in the said radiation sensitive resin composition, 5 mass parts is preferable with respect to 100 mass parts of [A] polymers, for example, 10 mass parts is more preferable, 15 mass parts Is more preferable. On the other hand, as this upper limit, 60 mass parts is preferable, 40 mass parts is more preferable, and 30 mass parts is further more preferable. (B2) By making content of a polymerization initiator into such a range, even if the said radiation sensitive resin composition is a low exposure amount, the insulating film which has high solvent resistance, hardness, and adhesiveness is used. Can be formed.

<Other optional components>
The radiation-sensitive resin composition is a compound having an antioxidant, a polyfunctional acrylate, a surfactant, an adhesion aid, inorganic oxide particles, and a cyclic ether group as necessary, as long as the effects of the present invention are not impaired. In addition, other optional components such as an acid diffusion controller and a solvent may be contained. Other optional components may be used alone or in combination of two or more.
Examples of the antioxidant include phenolic antioxidants, sulfur-based antioxidants, amine-based antioxidants, and the like, and phenolic antioxidants are particularly preferable. Antioxidants can be used alone or in combination of two or more. The content of the antioxidant is preferably 0.1 parts by mass to 10 parts by mass, particularly preferably 100 parts by mass in total of the [A] polymer component contained in the radiation-sensitive resin composition of the present embodiment. Is 0.2 to 5 parts by mass. By using in this range, the heat resistance of the interlayer insulation film formed from this radiation sensitive resin composition can be improved more.
As the antioxidant, an antioxidant described in JP 2011-227106 A can be used.
The polyfunctional acrylate is 100 parts by mass or less with respect to 100 parts by mass of the [A] polymer component, preferably 0.1 parts by mass or more and 80 parts by mass or less, more preferably 0.5 parts by mass or more and 50 parts by mass or less. 1 to 25 parts by mass is more preferable. By using in this range, the heat resistance and solvent resistance of the interlayer insulation film formed from this radiation sensitive resin composition can be improved more.
As the polyfunctional acrylate, polyfunctional acrylates described in JP-A-2005-227525 can be used.

  Surfactant is a component which improves the film-forming property of the said radiation sensitive resin composition. By containing the surfactant, the radiation sensitive resin composition can improve the surface smoothness of the coating film. As a result, the film thickness uniformity of the cured film formed from the radiation sensitive resin composition can be improved. It can be improved.

  The adhesion assistant is a component that improves the adhesion between the film formation target such as a substrate and the cured film. The adhesion assistant is particularly useful for improving the adhesion between the inorganic substrate and the cured film.

As the adhesion assistant, a functional silane coupling agent is preferable.
The inorganic oxide particle is an oxide containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium and hafnium. Can be used. Inorganic oxide particles described in JP2011-128385A can be used.
<Compound having a cyclic ether group>
The compound having a cyclic ether group is a compound having a cyclic ether group and different from the polymer of the [A] polymer component. The radiation-sensitive resin composition contains a compound having a cyclic ether group, thereby promoting cross-linking of the [A] polymer component or the like by the thermal reactivity of the compound having a cyclic ether group, and the radiation-sensitive resin. While the hardness of the cured film formed from a composition can be raised more, the radiation sensitivity of the said radiation sensitive resin composition can be improved.

  The compound having a cyclic ether group is preferably a compound having two or more epoxy groups (oxiranyl group, oxetanyl group) in the molecule. As a compound having an epoxy group as a compound having a cyclic ether group, a compound described in JP 2011-257537 A can be used.

  Among these, the compound having a cyclic ether group is preferably a compound having two or more oxetanyl groups in the molecule, such as bis [(3-ethyloxetane-3-yl) methyl] isophthalate, 1,4- 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of bis [(3-ethyloxetane-3-yl) methoxymethyl] benzene, 2,2-bis (hydroxymethyl) -1-butanol (EHPE3150 ( Daicel Chemical Co., Ltd.)) is more preferable.

  As content of the compound which has a cyclic ether group, it is 150 mass parts or less normally with respect to 100 mass parts of [A] polymer components, 0.5 mass part or more and 100 mass parts or less are preferable, and 1 mass part or more is preferable. 50 mass parts or less are more preferable, and 10 mass parts or more and 25 mass parts or less are still more preferable. The hardness of the cured film formed from the said radiation sensitive resin composition can be raised more by making content of the compound which has a cyclic ether group into the said range.

  The acid diffusion control agent can be arbitrarily selected from those used in chemically amplified resists. By containing the acid diffusion control agent, the radiation sensitive resin composition can appropriately control the diffusion length of the acid generated from the radiation sensitive acid generator by exposure, and the pattern developability can be improved. As the acid diffusion control agent, an acid diffusion control agent described in JP 2011-232632 A can be used.

The content of the acid diffusion controller is usually 2 parts by mass or less, preferably 0.001 part by mass or more and 1 part by mass or less, and 0.005 part by mass or more with respect to 100 parts by mass of the polymer component [A]. 0.2 parts by mass or less is more preferable. Pattern developability improves more by making content of an acid spreading | diffusion controlling agent into the said range.
<Method for preparing radiation-sensitive resin composition>
The radiation-sensitive resin composition is dissolved or dispersed by mixing the [A] polymer component and the [B] radiation-sensitive acid generator, a suitable component as necessary, and other optional components in a solvent. Prepared. For example, the said radiation sensitive resin composition can be prepared by mixing each component in a predetermined ratio in a solvent.
<Solvent>
As the solvent, a solvent that uniformly dissolves or disperses other components in the radiation-sensitive resin composition and does not react with the other components is preferably used. Examples of such solvents include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether propionates, Aromatic hydrocarbons, ketones, other esters and the like can be mentioned. As the solvent, the solvents described in JP2011-232632 can be used.
<Polymer composition>
The polymer composition of the present invention includes a first structural unit which is a structural unit represented by the general formula (1) or the general formula (2), a second structural unit including a crosslinkable group, and the like, and an acid dissociable group. A polymer component having a structural unit selected from the group consisting of third structural units is contained. This polymer component is the same as the [A] polymer component of the radiation-sensitive resin composition. Even if the polymer component includes the first structural unit, the second structural unit, and the third structural unit and / or other structural units in the same polymer, the first structural unit in a different polymer. It may include a unit, a second structural unit, a third structural unit, and / or other structural units. Since the said polymer composition contains the polymer component similar to a [A] polymer component, it can be used conveniently for preparation of the said radiation sensitive resin composition.
<Curing film>
The cured film of the present invention is formed from the radiation sensitive resin composition. Since the said cured film is formed from the said radiation sensitive resin composition, it has the outstanding water repellency, the external appearance characteristic of a coating film, and the uniformity of a film thickness. The cured film having such characteristics is, for example, an interlayer insulating film, a planarization film, a bank (partition wall) that defines a region for forming a light emitting layer, a spacer, a protective film, a color, for an electronic device such as a display element. It can be used for coloring patterns for filters. In addition, although it does not specifically limit as a formation method of the said cured film, It is preferable to apply the formation method of the cured film demonstrated below.
<Method for forming cured film>
The said radiation sensitive resin composition can be used suitably for formation of a cured film.

  The method for forming a cured film of the present invention includes a step of forming a coating film on a substrate using the radiation-sensitive resin composition (hereinafter also referred to as “step (1)”), and at least a part of the coating film. A step of irradiating radiation (hereinafter also referred to as “step (2)”), a step of developing a coating film irradiated with radiation (hereinafter also referred to as “step (3)”), and heating the developed coating film (Hereinafter, also referred to as “step (4)”).

According to the method for forming a cured film, a cured film having high pattern shape stability can be formed. Further, since the amount of change in the film thickness of the unexposed portion can be suppressed, the production process margin can be improved as a result, and the yield can be improved. Furthermore, a cured film having a fine and elaborate pattern can be easily formed by forming a pattern by exposure, development and heating utilizing photosensitivity.
[Step (1)]
In this step, the radiation-sensitive resin composition is used and applied onto a substrate to form a coating film. When the said radiation sensitive resin composition contains a solvent, it is preferable to remove a solvent by prebaking an application surface.

Examples of the substrate include glass, quartz, silicone, and resin. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of cyclic olefin, and a hydrogenated product thereof. The pre-baking conditions vary depending on the type of each component, the blending ratio, and the like, but are usually about 70 ° C. to 120 ° C. and about 1 minute to 10 minutes.
[Step (2)]
In this step, at least a part of the coating film is irradiated with radiation and exposed. When exposing, it exposes normally through the photomask which has a predetermined pattern. As the radiation used for exposure, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is more preferable. The exposure amount ^is preferably ^{500J / m 2 ~6,000J / m 2} , 1,500J / m 2 ~1,800J / m 2 is more preferable. This exposure amount is 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).
[Step (3)]
In this step, the coating film irradiated with radiation is developed. By developing the coated film after exposure, unnecessary portions (radiation irradiated portions) are removed to form a predetermined pattern.

  The developer used in this step is preferably an alkaline aqueous solution. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. It is done. As the developer, an organic solvent such as a ketone organic solvent or an alcohol organic solvent can be used.

  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. As a density | concentration of the alkali in aqueous alkali solution, from a viewpoint of obtaining suitable developability, 0.1 to 5 mass% is preferable.

  Examples of the developing method include a liquid piling method, a dipping method, a rocking dipping method, a shower method, and the like. The development time varies depending on the composition of the radiation sensitive resin composition, but is usually about 10 seconds to 180 seconds.

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

It is preferable that the film thickness change rate of the film thickness after development with respect to the film thickness of the coating film before development is 90% or more. As described above, according to the forming method using the radiation-sensitive resin composition, the amount of change in the film thickness of the unexposed portion with respect to the development time can be suppressed, and the film thickness after development is 90% of the film thickness before development. % Or more can be maintained.
[Step (4)]
In this step, the developed coating film is heated. For heating, the patterned thin film is heated using a heating device such as a hot plate or an oven, whereby the curing reaction of the polymer component [A] can be promoted to form a cured film. As heating temperature, it is about 120 to 250 degreeC, for example. The heating time varies depending on the type of the heating device, but is, for example, about 5 to 30 minutes for a hot plate and about 30 to 90 minutes for an oven. Moreover, 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 desired cured film can be formed on the surface of the substrate. The thickness of the cured film is preferably 0.1 μm to 8 μm, and more preferably 0.1 μm to 6 μm.
<Electronic device>
The electronic device of the present invention includes the cured film. The electronic device is, for example, a liquid crystal display element or an organic EL display element.

  The liquid crystal display element is composed of, for example, a liquid crystal cell, a polarizing plate, and the like. Since the liquid crystal display element includes the cured film, the liquid crystal display element has excellent reliability such as heat resistance.

  As a manufacturing method of a liquid crystal display element, first, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the radiation-sensitive resin composition is formed on the transparent conductive film of one of the substrates. In accordance with the method described in the above “<Method for forming cured film>”, an interlayer insulating film, a spacer, a protective film, or both are formed. Next, an alignment film having liquid crystal alignment ability is formed on the transparent conductive film and the spacer or protective film of these substrates. These substrates are arranged facing each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed inside. A liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to constitute a liquid crystal cell. And as an electronic device of the present invention, the polarizing plate is bonded to both outer surfaces of the liquid crystal cell so that the polarization direction thereof coincides with or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. The liquid crystal display element can be obtained.

  As another method for manufacturing a liquid crystal display element, a pair of transparent substrates on which a transparent conductive film, an interlayer insulating film, a protective film, a spacer, or both, and an alignment film are formed are prepared in the same manner as the above manufacturing method. After that, along the edge of one of the substrates, an ultraviolet curable sealant is applied using a dispenser, then the liquid crystal is dropped into a fine droplet using a liquid crystal dispenser, and the two substrates are bonded together under vacuum. Do. Then, both the substrates are sealed by irradiating the sealing agent part with ultraviolet rays using a high-pressure mercury lamp. Finally, a liquid crystal display element as an electronic device of the present invention is obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

  Examples of the liquid crystal used in the above-described method for manufacturing a liquid crystal display element include nematic liquid crystal and smectic liquid crystal. In addition, as a polarizing plate used outside the liquid crystal cell, a polarizing film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films, or an H film Examples thereof include a polarizing plate made of itself.

  On the other hand, in the organic electroluminescence element, the cured film formed from the radiation-sensitive resin composition can be used as a planarization film formed on the TFT element, a partition defining a light emitting site, or the like.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In addition, the weight average molecular weight (Mw) of [A] polymer component was measured with the following method.
[Weight average molecular weight (Mw)]
It measured by gel permeation chromatography (GPC) under the following conditions.

Equipment: “GPC-101” from Showa Denko
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene <Synthesis of [A] polymer component>
[Synthesis Example 1] (Synthesis of polymer (P-1))
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of methyl-3-methoxypropionate. Subsequently, 30 parts by mass of vinyl styrene oxide (a-1) as a monomer giving the first structural unit, 20 parts by mass of methacrylic acid (hereinafter also referred to as MA) and methyl methacrylate (as the monomer giving the second structural unit) (Hereinafter, also referred to as MMA) 50 parts by mass were charged with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (P-1). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (P-1) was 12,000.
(Synthesis examples of polymers (P-2 to 8), comparative synthesis examples 1 to 4)
Based on the composition of each polymerizable monomer (Table 1), a resin was prepared in the same manner as in the synthesis example of P-1. -In (Table 1) indicates that it is not contained. The polystyrene equivalent weight average molecular weight (Mw) of the obtained polymer is shown in Table 1.

In Table 1, compounds giving the first structural unit are shown below.
a-1: Compound represented by the following formula

a-2: Compound represented by the following formula

<Compound giving second structural unit>
AA: acrylic acid, MA: methacrylic acid, MMA: methyl methacrylate, ST: styrene are shown.
In Table 1, the compounds shown in Comparative Synthesis Examples are shown below.
ca-1: Compound represented by the following formula

ca-2: Compound represented by the following formula

ca-3: Compound represented by the following formula

ca-4: Compound represented by the following formula

[Synthesis Example 2] (Synthesis of polymer (P-9))
A flask equipped with a condenser and a stirrer was charged with 3.4 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 68 parts by mass of methyl-3-methoxypropionate. Subsequently, 1-ethoxyethyl methacrylate (b-1) (30 mol%) as a compound giving the third structural unit, and a compound represented by the following formula (a-1) (30 mol%) as the compound giving the first structural unit ), Methyl methacrylate (40 mol%) was charged as a compound giving the second structural unit, and the atmosphere was purged with nitrogen, followed by gentle stirring. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain 105 parts by mass of a polymer solution containing a polymer (P-9).
The polystyrene equivalent weight average molecular weight (Mw) of the polymer (P-9) was 12,000.
[Synthesis Example 3] (Synthesis of Polymer (P-10))
A flask equipped with a condenser and a stirrer was charged with 3.4 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 68 parts by mass of methyl-3-methoxypropionate. Subsequently, tetrahydro-2H-pyran-2-yl methacrylate (b-2) (30 mol%) as a compound giving a third structural unit, and a compound represented by the following formula (a-2) as a compound giving a first structural unit ( 30 mol%), methyl methacrylate (40 mol%) was charged as a compound giving the second structural unit, and after nitrogen substitution, the mixture was gently stirred. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain 105 parts by mass of a polymer solution containing a polymer (P-10). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (P-10) was 12,000.
<Preparation of radiation-sensitive resin composition>
[Example 1]
[A] To a polymer solution containing (P-1) as a polymer component (amount corresponding to 100 parts by mass (solid content) of (P-1)), [B] (B- 1) A radiation-sensitive resin composition was prepared by mixing 20 parts by mass and filtering through a membrane filter having a pore size of 0.2 μm.

The radiation-sensitive resin compositions of Examples 2 to 52 and Comparative Examples 1 to 8 were prepared in the same manner as in Example 1. The radiation sensitive resin compositions (S-1) to (S-52) were used, and the comparative radiation sensitive resin compositions (CS-1) to (CS-8) were used.
Radiation-sensitive resin compositions (S-1) to (S-28) The comparative radiation-sensitive resin compositions (CS-1) to (CS-4) are positive-type radiation-sensitive resin compositions. Tables 2, 4 and 6 show the compositions and evaluation results. Further, the radiation sensitive resin compositions (S-29) to (S-52) of the comparative radiation sensitive resin compositions (CS-5) to (CS-8) are negative-type radiation sensitive resin compositions. Tables 3 and 5 show the compositions and evaluation results.

In addition, "-" in a table | surface shows having not mix | blended the applicable component.
(Radiosensitive compounds)
B-1: 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate with sulfonic acid chloride (2.0 mol) B-2: (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (BAGI "CGI -1311 ")
B-3: 4-methylphenylsulfonyloxyimino-α- (4-methoxyphenyl) acetonitrile (“PAI-101” from Midori Chemical Co., Ltd.)
B-4: O-acyl oxime compound ("Irgacure OXE01" from BASF)
B-5: O-acyloxime compound (NCI-930 (manufactured by ADEKA)
(Acid diffusion control agent)
C-1: 2-phenylbenzimidazole (crosslinking agent)
D-1: Aronix M-402 (trade name, dipentaerythritol penta / hexaacrylate, manufactured by Toagosei Co., Ltd.)
D-2: TA-G (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.)
D-3: Divinyl adipate D-1: KBM-403 (trade name, 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.)

<Evaluation>
Using the radiation-sensitive resin compositions of Examples 1 to 52 and Comparative Examples 1 to 8, the radiation sensitivity, the dielectric constant of the cured film, the chemical resistance of the cured film, and the refractive index of the cured film were evaluated. The evaluation results are shown in Table 3.
[Evaluation of radiation sensitivity]
A radiation sensitive resin composition was applied onto a silicon substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Subsequently, using an exposure machine (Canon's “MPA-600FA” (ghi line mixing)), the exposure amount to the coating film through a mask having a 60 μm line and space (10 to 1) pattern. Was irradiated as a variable. Thereafter, the film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 80 seconds by a puddle method. Next, running water was washed with ultrapure water for 1 minute and then dried to form a pattern. At this time, the exposure amount necessary for completely dissolving the 5 μm space pattern was examined. When the exposure value is 80 mJ / cm ² or less, it can be determined that the radiation sensitivity is good.
The evaluation criteria are shown below.
A: Less than 40 mJ / cm ²
B: 40 mJ / cm ² or more, less than 80 mJ / cm ²
C: 80mJ / cm ² or more and less than 120mJ / cm ^2,
D: 120 mJ / cm ² or more [Preparation of electrical property evaluation board]
Using the radiation-sensitive resin compositions described in the Examples and Comparative Examples, each was applied on an ITO substrate, which is a glass substrate with an ITO film, with a spin coater to a film thickness of 3 μm, and then on a hot plate at 90 ° C. Each of the coating films was formed by pre-baking for 2 minutes and evaporating the organic solvent. Next, as an electrode extraction site for measuring electrical characteristics, a part of the end of the substrate coated with the radiation-sensitive resin composition was wiped with acetone to expose the underlying ITO. Thereafter, it was cured by heating (post-baking) at 230 ° C. for 30 minutes in an oven to form an insulating film on the ITO substrate.
[Measurement of dielectric constant]
An Al (aluminum) electrode for measuring the capacitance is formed on a vacuum deposition apparatus (JEOL VACUUM) on the insulating film of each electrical property evaluation substrate produced by the method described in [Production of electrical property evaluation substrate]. It was prepared using EVAPROTOR JEE-420). Next, a lead wire for electrode connection is soldered to the ITO portion exposed in advance, and the lead wire and the Al electrode produced by the vacuum deposition apparatus are respectively positive terminals of an LCR meter (HEWRET PACKARD 4284A PRECISION LCR METER) The capacitance C of the insulating film was measured under the conditions of an applied voltage of 100 mV and a frequency of 10 kHz. The value of the dielectric constant ε was obtained by substituting the measured value of the capacitance C, the area S (m ² ) of the Al electrode, and the film thickness d (m) of the cured film into the following equation.
Dielectric constant ε = capacitance C × cured film thickness d (m) ÷ electrode area S (m ² )
The evaluation criteria are shown below.

A: Less than 3.0,
B: 3.0 or more, less than 3.2,
C: 3.2 or more, less than 3.4,
D: 3.4 or more [Evaluation of chemical resistance of cured film]
The chemical resistance of the cured film was evaluated as swelling due to the stripping solution. A radiation sensitive resin composition was applied onto a silicon substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Then, it baked for 30 minutes using the oven heated at 230 degreeC, and formed the cured film. This film was immersed in an N-methylpyrrolidone solvent heated to 40 ° C. for 6 minutes, and the rate of change in film thickness (%) before and after immersion was obtained as an index of chemical resistance. The film thickness change rate is as follows: A: film thickness change rate of less than 5%, B: film thickness change rate of 5% or more and less than 10%, C: film thickness change rate of 10% or more and less than 15%, D: film thickness change rate of 15% In the case of A or B, the chemical resistance was evaluated as good, and in the case of C or D, it was evaluated as defective. The film thickness was measured at 25 ° C. using an optical interference type film thickness measuring device (Lambda Ace VM-1010).
[Refractive index of cured film]
After applying any of the radiation-sensitive resin compositions prepared as Examples and Comparative Examples on a glass substrate using a spinner, the film was pre-baked on a hot plate at 90 ° C. for 2 minutes to have a film thickness of 3.0 μm. A coating film was formed. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation amount was 3,000 J / m 2. Next, this glass substrate was heated on a hot plate at 230 ° C. for 30 minutes. The refractive index of the obtained cured film was measured by “Prism Coupler Model 2010” manufactured by Metricon. Refractive index (nD) is measured at a wavelength of 633 nm, A: 1.60 or more, B: 1.55 or more and less than 1.60, C: 1.50 or more and less than 1.55, D: less than 1.50 Classified and used as an index of refractive index.
As is clear from the results in Table 4, the radiation sensitive resin compositions of Examples 1 to 28 are excellent in radiation sensitivity, and the cured film formed from these radiation sensitive resin compositions has a dielectric constant and chemical resistance. It was excellent in nature.

On the other hand, although the radiation sensitive resin composition of Comparative Examples 1-4 was excellent in a radiation sensitivity, it turned out that a dielectric constant and a refractive index are inferior.
As is apparent from the results in Table 5, the radiation sensitive resin compositions of Examples 29 to 52 have excellent radiation sensitivity, and the cured films formed from these radiation sensitive resin compositions have a dielectric constant and chemical resistance. Excellent in properties and refractive index.

  On the other hand, although the radiation sensitive resin composition of Comparative Examples 5-8 was excellent in radiation sensitivity, it turned out that a dielectric constant and a refractive index are inferior.

<Evaluation of low-temperature curing performance>
Using the radiation-sensitive resin compositions described in Examples 49 to 72 and Comparative Examples 9 to 12, the curability of the low temperature cured film was evaluated. The evaluation results are shown in Table 6.
[Evaluation of curability]
Curability was evaluated using dissolution by a stripping solution as an index. A radiation sensitive resin composition was applied onto a silicon substrate using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Subsequently, the substrate was irradiated with 300 mJ light using a proximity exposure machine (Canon “MA-1200” (ghi ray mixing)), and then post-baked for 30 minutes using a hot plate with the temperature as a variable. A cured film at each temperature was formed. These films were immersed in an N-methylpyrrolidone solvent heated to 40 ° C. for 6 minutes, and the substrate after immersion was baked for 15 minutes on a hot plate having the same temperature as the post-bake temperature, and the film thickness reduction rate before and after the immersion (%) Was obtained and used as an index of low-temperature curability. The film thickness reduction rate is: ○: film thickness reduction rate of less than 2%, Δ: film thickness reduction rate of 2% or more and less than 10%, x: film thickness reduction rate of 10% or more. In the case of Δ or ×, it was evaluated as defective. The film thickness was measured at 25 ° C. using an optical interference type film thickness measuring device (Lambda Ace VM-1010).

As is clear from the results in Table 6, the radiation-sensitive resin compositions of Examples 49 to 51, 55, and 57 to 72 are excellent in curing performance at 150 ° C. or higher, and the feelings of Examples 52 to 54, and 56. The radiation resin composition was excellent in curing performance at 180 ° C. or higher.

  On the other hand, the radiation sensitive resin composition of Comparative Examples 9-12 was inferior to the low temperature curing performance compared with Examples 49-72.

Claims (9)

[A] a polymer component having at least one first structural unit selected from structural units represented by the following formulas (1) and (2), and a second structural unit;
[B] A radiation-sensitive resin composition containing a radiation-sensitive compound.

(In the formula (1), (2), A 1 represents an oxygen atom or a sulfur atom, ^{A 2} represents a hydrogen atom, an alkyl group or alkoxyl group having 1 to 12 carbon atoms having 1 to 12 carbon atoms, ^{A 3} Represents a hydrogen atom or a methyl group, m1 represents an integer of 1 to 3, m2 represents an integer of 0 to 4, and m3 represents an integer of 0 to 6.)   Furthermore, (A) The polymer component has the 3rd structural unit containing an acid dissociable group, The radiation sensitive resin composition of Claim 1 characterized by the above-mentioned. The group containing the acid dissociable group is represented by the following formula (3) or the following formula (4).

(In Formula (3), R ¹ and R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or at least a part of the hydrogen atoms of the hydrocarbon group is a hydroxyl group or a halogen atom. Or a group substituted with a cyano group, provided that R ¹ and R ² are not both hydrogen atoms, R ³ is a hydrocarbon group having 1 to 30 carbon atoms, carbon-carbon of this carbon hydrogen group Or a group containing an oxygen atom at the end of the bond side or at least part of the hydrogen atoms of these groups is a group substituted with a hydroxyl group, a halogen atom or a cyano group.
In formula (4), R ^{4 to} R ¹⁰ are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. n is 1 or 2. When n is 2, the plurality of R ⁷ and R ⁸ may be the same or different. * Indicates a binding site. ) The radiation sensitive resin composition according to any one of claims 1 to 3, wherein the second structural unit is represented by the following formula (5).

(In the formula (5), R ¹¹ represents a hydrogen atom or a methyl group. R ¹² represents an epoxy group, a 3,4-epoxycyclohexyl group, the following formula (5-1), the following formula (5-2) or X ¹ is a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms, Y ¹ is a single bond, oxygen, or a group selected from the group of groups represented by the following formula (5-3). An atom, a sulfur atom or an imino group, wherein R ¹³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms in formula (5-3), and * represents a bonding site.
  The radiation sensitive resin composition according to any one of claims 1 to 4, wherein the radiation sensitive compound is an acid generator, a polymerization initiator, or a combination thereof. The said acid generator contains the oxime sulfonate group represented by following formula (6), The radiation sensitive resin composition as described in any one of Claims 1-5 characterized by the above-mentioned.

(In Formula (6), R ¹⁴ is an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group, or a group in which at least a part of hydrogen atoms of these groups is substituted with a substituent. Indicates a binding site.)   The cured film formed from the radiation sensitive resin composition of any one of Claims 1-6. A step of forming a coating film on the substrate; a step of irradiating at least a part of the coating film; a step of developing the coating film irradiated with the radiation; and a step of heating the developed coating film. A method for forming a cured film, comprising:
The formation method of the cured film which forms the said coating film using the radiation sensitive resin composition of any one of Claims 1-6.   An electronic device comprising the cured film according to claim 7.