JP6750233B2 - Radiation-sensitive resin composition for forming cured film, cured film, method for forming the same, and electronic device - Google Patents

Description

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

Electronic components such as thin film transistor type liquid crystal display elements are generally provided with an interlayer insulating film to insulate between wirings arranged in layers, and the organic electroluminescence element also flattens the upper part of the semiconductor element, The flattening film is provided to stack 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 on the transparent electrode film. Therefore, the interlayer insulating film is exposed to high temperature conditions in the process of forming the transparent electrode film and is exposed to the stripping solution of the resist used for forming the pattern of the electrode. Solventity is required.

As a conventional interlayer insulating film for a liquid crystal display device, a positive type radiation sensitive resin composition using an acid generator such as naphthoquinonediazide is used from the viewpoint of patterning performance (for example, JP 2001-354822 A). See the bulletin).
In recent years, for the purpose of forming a cured film for a display device with higher sensitivity than a positive-type radiation-sensitive resin composition using an acid generator such as naphthoquinonediazide, for example, JP 2004-4669 A discloses. The cross-linking agent, the acid generator, and itself are insoluble or sparingly soluble in an alkaline aqueous solution, but have a protective group that can be cleaved by the action of an acid, and after the protective group is cleaved, it is soluble in an alkaline aqueous solution. A positive-type chemical amplification material characterized by containing the following resin has been proposed. Further, JP-A-2004-264623, JP-A-2008-304902, and the like contain a resin containing an acetal structure and/or a ketal structure and an epoxy group, and an acid generator, which is a positive type impression. Radioactive compositions have been proposed.

However, when these radiation-sensitive resin compositions are used, the solvent resistance of the obtained cured film is insufficient, and the alignment process is performed during the etching process or alignment film formation of the transparent electrode formed on the interlayer insulating film. There is a problem that the organic solvent contained in the agent deteriorates the interlayer insulating film.

Furthermore, in the interlayer insulating film, there has been a particular demand for a lower dielectric constant (higher insulation) and a higher refractive index. For example, in the IPS mode liquid crystal display element, the number of constituent members arranged on the array substrate increases, and the electrode structure and the wiring arrangement structure on the array substrate are more complicated than those of other liquid crystal modes such as the TN mode. Will be things. For this reason, lowering the power consumption of the panel is achieved by lowering the dielectric constant of the interlayer insulating film, etc., and by increasing the refractive index of the interlayer insulating film and making it closer to the refractive index of the transparent electrode, increasing the pixel transmittance. Is required to do.

JP 2001-354822A JP 2004-4669 A JP, 2004-264623, A JP, 2008-304902, A JP 2012-133091A JP2012-163937A

The present invention has been made based on the above circumstances, and an object thereof is to provide a radiation-sensitive resin composition for forming a cured film capable of sufficiently satisfying general characteristics such as sensitivity and achieving solvent resistance. And a cured film formed from the radiation-sensitive resin composition for forming a cured film can achieve a low dielectric constant and a high refractive index, and an electronic device including the cured film is provided.

The invention made to solve the above 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 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, 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.)
Another invention made to solve the above problems is achieved by a cured film formed from the radiation-sensitive resin composition and an electronic device including the cured film.
including.

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

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

<Radiation-sensitive resin composition>
The radiation-sensitive resin composition of the present invention contains a polymer component [A] and a radiation-sensitive acid generator [B]. Further, the radiation-sensitive resin composition may contain other optional components as long as the effects of the present invention are not impaired. Hereinafter, each component will be described in detail.

<[A] polymer component>
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.
Since the polymer component [A] has the above structural unit, the radiation-sensitive resin composition has excellent sensitivity and can suppress the change in film thickness of the unexposed portion after the development step or the post-baking step. .. Moreover, the polymer component [A] may have other structural units within a range that does not impair the effects of the present invention. The second structural unit is mainly a structural unit having a crosslinkable group, and by containing the structural unit having a crosslinkable group, the cured film formed from the radiation-sensitive resin composition has heat resistance and solvent resistance. It is possible to improve the physical properties of the cured film such as.
Further, the polymer component [A] may have a third structural unit containing an acid dissociable group, if necessary. By further containing 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.

Examples of the polymer component [A] include, for example,
(1) A polymer component containing a polymer having a first structural unit, a second structural unit and a third structural unit;
(2) A polymer component containing a polymer having a first structural unit and a polymer having a first structural unit and a third structural unit;
(3) A polymer component containing a polymer having a second structural unit and a polymer having a first structural unit and a third structural unit;
(4) A polymer component containing a polymer having a third structural unit and a polymer having a first structural unit and a second structural unit; and the like.

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 contains a crosslinkable group. The cured film formed from the radiation-sensitive resin composition is such that the [A] polymer component has a second structural unit containing a crosslinkable group, and thus the polymers constituting the [A] polymer component or [ The strength can be increased by cross-linking the polymer constituting the A] polymer component with the [D] cyclic ether compound described below.
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 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 Indicates 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.

In formulas (1) and (2), when A ¹ is an oxygen atom, m1 is 1 to represent a group having an oxirane ring, m1 is 2 to represent a group having an oxetane ring, and m 1 is 3 A group having an oxolane ring is shown. When A ¹ is a sulfur atom, when m1 is 1, it represents a group having a thiirane ring, when m1 is 2, it represents a group having a thietan ring, and when m1 is 3, it represents a group having a thiolane ring.
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).

Unsaturated double bond compounds (a-4), (a-18), (a-22) and the like which 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, more preferably 1 mol% or more and 60 mol% or less, based on all structural units constituting the [A] polymer component. It is more preferably 10 mol% or more and 40 mol% or less.
[Second structural unit]
The polymer component [A] has a structural unit 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 the monomer that provides another structural unit include unsaturated monocarboxylic acid, (meth)acrylic acid ester having a hydroxyl group, (meth)acrylic acid chain alkyl ester, (meth)acrylic acid cyclic alkyl ester, ( A (meth)acrylic acid aryl ester, an unsaturated aromatic compound, a conjugated diene, an unsaturated compound having a tetrahydrofuran skeleton, or the like, 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 It is ^one kind selected from the group of groups represented by the following formula (5-3): X ¹ is a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms, and Y ¹ is a single bond, oxygen. An atom, a sulfur atom or an imino group.In formula (5-3), R ¹³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and * represents a bonding site.)

Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, and the like. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like. Examples of the unsaturated dicarboxylic acid anhydrides include anhydrides of the compounds exemplified as the above dicarboxylic acids. Examples of mono[(meth)acryloyloxyalkyl]esters of polyvalent carboxylic acids include succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], and hexa. Examples include mono-2-(methacryloyloxy)ethyl hydrophthalate and the like. Examples of the polymer mono(meth)acrylate 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, anhydrides of monocarboxylic acids and dicarboxylic acids are preferable, and (meth)acrylic acid and maleic anhydride are more preferable from the viewpoint of copolymerization reactivity, solubility in an alkaline aqueous solution, and easy 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 methacrycryl. Examples thereof include 2-hydroxyethyl acid, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate.

Examples of the chain alkyl ester of (meth)acrylic acid 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]decane-8-yl methacrylate, tricyclo[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, etc. are mentioned.

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

Examples of unsaturated aromatic compounds include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-tolyl. Maleimide, N-naphthyl maleimide, N-ethyl maleimide, N-hexyl maleimide, N-benzyl maleimide, etc. are 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 having a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth)acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, and 3-(meth)acryloyloxytetrahydrofuran-2-one.
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, an oxiranyl group or an oxetanyl group is preferable, a monomer containing an oxiranyl group or an oxetanyl group is more preferable, and glycidyl methacrylate, 3- Methacryloyloxymethyl-3-ethyloxetane, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate are more preferable.

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

In the radiation-sensitive resin composition, since the polymer component [A] has the first structural unit, it is possible to achieve high radiation sensitivity and improve 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 possessed by this hydrocarbon group is a hydroxyl group, a halogen atom, or It is a group substituted with a cyano group. However, there is no case where both R ¹ and R ² are hydrogen atoms. R ³ is a hydrocarbon group having 1 to 30 carbon atoms, a group containing an oxygen atom at the carbon-carbon or terminal end on the bond side of the carbon-hydrogen group, or at least a part of hydrogen atoms contained in these groups is a hydroxyl group or halogen. A group substituted with 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, a 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 formulas (3-1) to (3-10), R ¹⁷ represents a hydrogen atom or a methyl group.

Examples of the monomer that provides the structural units represented by the formulas (3-1) to (3-10) of the third structural unit include 1-ethoxyethyl methacrylate, 1-butoxyethyl methacrylate, and 1-methacrylic acid. -(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 formulas (4-1) to (4-5), R ²⁰ represents a hydrogen atom or a methyl group.

Tetrahydro-2H-pyran-2-yl methacrylate (4-3) is preferable as the monomer that provides the structural unit represented by the above formula (4).

The content ratio of the third structural unit is preferably 0.1 mol% or more and 80 mol% or less, more preferably 1 mol% or more and 60 mol% or less, based on all structural units constituting the polymer component [A]. It is more preferably 10 mol% or more and 40 mol% or less.
<Method of synthesizing polymer component [A]>
The polymer component [A] 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 in which a solution containing a monomer and a radical initiator is dropped 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 conducting a polymerization reaction by dropping into a solution containing a reaction solvent or a monomer, a plurality of types of solutions containing each monomer, and a solution containing a radical initiator separately, It is preferable to synthesize by a method such as a method of dropping into a solution containing a reaction solvent or a monomer to cause a polymerization reaction.

Examples of the solvent used in the polymerization reaction of the polymer component [A] 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), 2,2′-azobis(methyl 2-methylpropionate) and other azo compounds; benzoyl Organic peroxides such as peroxides, lauroyl peroxide, t-butylperoxypivalate, and 1,1′-bis-(t-butylperoxy)cyclohexane; hydrogen peroxide and the like.

In the polymerization reaction of the polymer component [A], 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 include xanthogens such as dimethylxanthogen sulfide and diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

The polystyrene-equivalent weight average molecular weight (Mw) of the polymer [A] by gel permeation chromatography (GPC) is preferably 2.0×10 ³ or more and 1.0×10 ⁵ or less, and 5.0×10 ³ or more. It is more preferably 5.0×10 ⁴ or less. By setting the Mw of the polymer component [A] within the above range, the sensitivity and alkali developability of the radiation-sensitive resin composition can be enhanced.

The polystyrene reduced number average molecular weight (Mn) of the polymer component [A] by GPC 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 are more preferable. By setting the Mn of the polymer [A] in the above range, the curing reactivity at the time of curing the coating film of the radiation-sensitive resin composition can be improved.

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

The (B1) acid generator is not particularly limited as long as it is a compound that generates an acid (for example, carboxylic acid, sulfonic acid, etc.) upon irradiation with radiation. Examples of the acid generator (B1) include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, quinonediazide compounds, and the like. Of these, quinonediazide compounds are preferred.
(Quinonediazide compound)
The 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 a 1,2-naphthoquinonediazidesulfonic acid halide can be used.

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

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

Examples of the tetrahydroxybenzophenone include 2,2′,4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, and 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, and 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'-spirobiindene-5,6,7,5',6',7'- Hexanol, 2,2,4-trimethyl-7,2′,4′-trihydroxyflavan and the like can be mentioned.

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.

Among these mother nuclei, (polyhydroxyphenyl)alkane is preferable, and 1,1,1-tri(p-hydroxyphenyl)ethane and 4,4′-[1-[4-[1-[4-hydroxyphenyl] ]-1-Methylethyl]phenyl]ethylidene]bisphenol is more preferred. The sensitivity and the like can be particularly enhanced by using 1,1,1-tri(p-hydroxyphenyl)ethane as the mother nucleus. Further, by using 4,4′-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol or the like as the mother nucleus, chemical resistance is particularly enhanced. be able to.

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

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

Further, as the quinonediazide compound, 1,2-naphthoquinonediazide sulfonic acid amides in which the ester bond of the mother nucleus illustrated above is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide -4-sulfonic acid amide and the like are also preferably used.

These quinonediazide compounds may 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]
The oxime sulfonate compound is preferably a compound containing an oxime sulfonate group represented by the following formula (6).

In the above formula (6), R ¹⁴ is 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 group having 6 to 20 carbon atoms. A group or a group in which some or all of the hydrogen atoms of the alkyl group, alicyclic hydrocarbon group and aryl group thereof 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, and 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, a halogen atom and the like. ..

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, a halogen atom and the like.

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 in the formula (6). In the formulas (6-1) and (6-2), R ¹⁹ is an alkyl group having 1 to 12 carbon atoms or a fluoroalkyl group having 1 to 12 carbon atoms.
In formula (6-3), X is 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 above is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group represented by X above 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 (6-3) include compounds represented by the following formulas (6-4) to (6-8). The compound etc. which are represented are mentioned.

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

The lower limit of the content of the (B1) acid generator in the radiation-sensitive resin composition is preferably 5 parts by mass, more preferably 10 parts by mass, and 15 parts by mass with respect to 100 parts by mass of the [A] polymer. Is more preferable. On the other hand, the upper limit is preferably 60 parts by mass, more preferably 40 parts by mass, and further preferably 30 parts by mass. By setting the content of the (B1) acid generator in the above range, it is possible to increase the difference in solubility between the portion irradiated with the radiation and the portion not irradiated with the radiation in the developing solution and improve the patterning performance. In addition, the solvent resistance of the insulating film can be improved.
((B2) Polymerization initiator)
The (B2) polymerization initiator is a component which produces an active species capable of initiating the polymerization of a compound having a polymerizing property in response to radiation. By including the (B2) polymerization initiator, the pattern forming resin composition can exhibit a negative radiation-sensitive property with respect to, for example, an alkali developing solution. Examples of the (B2) polymerization initiator include a photo radical polymerization initiator. Examples of the photo radical polymerization initiator include O-acyl oxime compounds, acetophenone compounds, and biimidazole compounds. These compounds may be used alone or in combination of two or more.
(O-acyl oxime compound)
Examples of the O-acyl oxime compound include 1-[4-(phenylthio)-2-(O-benzoyloxime)] and 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]-octan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9. H. -Carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9. H. -Carbazol-3-yl]-ethan-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. -Carbazol-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 the acetophenone compound 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 and 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 can be mentioned.
(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 and 1-hydroxycyclohexylphenylketone are mentioned.
(Biimidazole compound)
Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and 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 and the like.

The lower limit of the content of the (B2) polymerization initiator in the radiation-sensitive resin composition is, for example, preferably 5 parts by mass, more preferably 10 parts by mass, and 15 parts by mass with respect to 100 parts by mass of the [A] polymer. Is more preferable. On the other hand, the upper limit is preferably 60 parts by mass, more preferably 40 parts by mass, and further preferably 30 parts by mass. By setting the content of the (B2) polymerization initiator in such a range, the radiation-sensitive resin composition can form an insulating film having high solvent resistance, hardness and adhesion even at a low exposure amount. It can be formed.

<Other optional ingredients>
The radiation-sensitive resin composition is a compound having an antioxidant, a polyfunctional acrylate, a surfactant, an adhesion aid, inorganic oxide particles, a cyclic ether group, if necessary, within a range that does not impair the effects of the present invention. Other components such as an acid diffusion control agent and a solvent may be contained. The other optional components may be used alone or in combination of two or more.
Examples of the antioxidant include phenol-based antioxidants, sulfur-based antioxidants, amine-based antioxidants, and the like, and phenol-based antioxidants are particularly preferable. The 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 with respect to 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 insulating film formed from the radiation sensitive resin composition can be further enhanced.
As the antioxidant, the antioxidants described in JP 2011-227106 A and the like 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, and more preferably 0.5 parts by mass or more and 50 parts by mass or less. It is more preferably 1 part by mass or more and 25 parts by mass or less. By using within this range, the heat resistance and solvent resistance of the interlayer insulating film formed from the radiation sensitive resin composition can be further enhanced.
As the polyfunctional acrylate, the polyfunctional acrylate described in JP-A-2005-227525 can be used.

The surfactant is a component that enhances the film forming property of the radiation sensitive resin composition. The radiation-sensitive resin composition can improve the surface smoothness of the coating film by containing the surfactant, and as a result, the film thickness uniformity of the cured film formed from the radiation-sensitive resin composition can be improved. You can improve more.

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

As the adhesion aid, a functional silane coupling agent is preferable.
As the inorganic oxide particles, inorganic oxide particles that are oxides 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. The inorganic oxide particles described in JP2011-128385A can be used.
<Compound Having Cyclic Ether Group>
The compound having a cyclic ether group is a compound having a cyclic ether group and different from the polymer contained in the polymer component [A]. By containing a compound having a cyclic ether group, the radiation-sensitive resin composition accelerates the crosslinking of the polymer component [A] due to the thermal reactivity of the compound having a cyclic ether group, and thus the radiation-sensitive resin composition. The hardness of the cured film formed from the composition can be further increased, and the radiation sensitivity of the radiation-sensitive resin composition can be increased.

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 the compound having an epoxy group as the compound having a cyclic ether group, the compounds described in JP2011-257537A 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, and bis[(3-ethyloxetan-3-yl)methyl]isophthalate, 1,4- Bis[(3-ethyloxetan-3-yl)methoxymethyl]benzene, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (EHPE3150( Daicel Chemical Industries, Ltd.)) is more preferable.

The content of the compound having a cyclic ether group is usually 150 parts by mass or less, preferably 0.5 parts by mass or more and 100 parts by mass or less, and preferably 1 part by mass or more with respect to 100 parts by mass of the polymer component [A]. The amount is preferably 50 parts by mass or less, more preferably 10 parts by mass or more and 25 parts by mass or less. By setting the content of the compound having a cyclic ether group in the above range, the hardness of the cured film formed from the radiation sensitive resin composition can be further increased.

The acid diffusion control agent can be arbitrarily selected from those used in chemically amplified resists. When the radiation-sensitive resin composition contains an acid diffusion controller, the diffusion length of the acid generated from the radiation-sensitive acid generator upon exposure can be appropriately controlled, and the pattern developability can be improved. As the acid diffusion controlling agent, the acid diffusion controlling agent described in JP2011-232632A can be used.

The content of the acid diffusion control agent is usually 2 parts by mass or less, preferably 0.001 parts by mass or more and 1 part by mass or less, and 0.005 parts by mass or more with respect to 100 parts by mass of the polymer component [A]. It is more preferably 0.2 parts by mass or less. By setting the content of the acid diffusion controller within the above range, the pattern developability is further improved.
<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. Is prepared. For example, the radiation-sensitive resin composition can be prepared by mixing the respective components in a solvent at a predetermined ratio.
<Solvent>
As the solvent, a solvent that uniformly dissolves or disperses the other components in the radiation-sensitive resin composition and does not react with the other components is preferably used. Examples of such a solvent 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, Examples thereof include aromatic hydrocarbons, ketones, and other esters. As the solvent, the solvents described in JP2011-232632A can be used.
<Polymer composition>
The polymer composition of the present invention contains a first structural unit which is a structural unit represented by the general formula (1) or general formula (2), a second structural unit containing a crosslinkable group and the like and an acid dissociable group. It contains a polymer component having a structural unit selected from the group consisting of the third structural unit. This polymer component is the same as the polymer component [A] of the radiation-sensitive resin composition. Even if the polymer component contains the first structural unit, the second structural unit, and the third structural unit and/or other structural unit in the same polymer, the first structural unit in a different polymer. It may contain a unit, a second structural unit, and a third structural unit and/or another structural unit. Since the polymer composition contains the same polymer component as the polymer component [A], it can be suitably used for the preparation of the radiation-sensitive resin composition.
<Cured film>
The cured film of the present invention is formed from the radiation sensitive resin composition. Since the cured film is formed from the radiation-sensitive resin composition, it has excellent water repellency, coating film appearance characteristics, and film thickness uniformity. The cured film having such characteristics is, for example, a bank (partition wall) that defines a region for forming an interlayer insulating film, a planarizing film, and a light emitting layer of an electronic device such as a display element, a spacer, a protective film, and a collar. It can be used as a coloring pattern for filters. The method for forming the cured film is not particularly limited, but it is preferable to apply the method for forming the cured film described below.
<Cured film forming method>
The radiation-sensitive resin composition can be suitably used for forming a cured film.

The method for forming a cured film of the present invention comprises 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 with radiation (hereinafter, also referred to as "step (2)"), a step of developing a coating film with irradiation of 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 a highly stable pattern shape can be formed. Further, since the amount of change in the film thickness of the unexposed portion can be suppressed, as a result, the production process margin can be improved and the yield can be improved. Further, a cured film having a fine and delicate pattern can be easily formed by forming a pattern by exposing, developing, 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 radiation-sensitive resin composition contains a solvent, it is preferable to remove the solvent by prebaking the coated surface.

Examples of the substrate include glass, quartz, silicone, resin, and the like. Examples of the above-mentioned resin include polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide, ring-opening polymers of cyclic olefins and hydrogenated products thereof. The pre-baking condition is usually 70° C. to 120° C. and 1 minute to 10 minutes, although it varies depending on the type of each component, the mixing ratio, and the like.
[Step (2)]
In this step, at least a part of the coating film is irradiated with radiation to be exposed. At the time of exposure, it is usually exposed through a photomask having a predetermined pattern. The radiation used for the exposure is preferably radiation having a wavelength in the range of 190 nm to 450 nm, more preferably radiation containing ultraviolet light of 365 nm. 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 coating 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. To be As the developing solution, an organic solvent such as a ketone organic solvent or an alcohol organic solvent can be used.

A suitable amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline aqueous solution before use. The concentration of alkali in the alkaline aqueous solution is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of obtaining suitable developability.

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

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

The rate of change in film thickness after development with respect to the film thickness of the coating film before development is preferably 90% or more. As described above, according to the forming method using the radiation-sensitive resin composition, the amount of change in film thickness of the unexposed portion with respect to the development time can be suppressed, and the film thickness after development is 90 times that before development. % Or more can be maintained.
[Step (4)]
In this step, the developed coating film is heated. A heating device such as a hot plate or an oven is used for heating, and the patterned thin film is heated to accelerate the curing reaction of the polymer component [A] to form a cured film. The heating temperature is, for example, about 120°C to 250°C. The heating time varies depending on the type of heating device, but is, for example, about 5 minutes to 30 minutes for the hot plate and about 30 minutes to 90 minutes for the oven. Further, a step baking method or the like in which a heating process is performed twice 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, 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 this liquid crystal display element is provided with the cured film, it is excellent in reliability such as heat resistance.

As a method of manufacturing a liquid crystal display element, first, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one surface is prepared, and the radiation-sensitive resin composition is applied onto the transparent conductive film of one of the substrates. The material is used to form an interlayer insulating film, a spacer or a protective film, or both according to the method described in the above “<Cured film forming method>”. Then, an alignment film having a liquid crystal alignment ability is formed on the transparent conductive film and the spacer or the protective film of these substrates. These substrates are arranged facing each other with a certain gap (cell gap) so that the liquid crystal alignment directions of the respective alignment films are orthogonal or antiparallel, with the surface on the side where the alignment film is formed being inside. 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 form a liquid crystal cell. Then, a polarizing plate is attached to both outer surfaces of the liquid crystal cell so that the polarization direction thereof coincides with or is orthogonal to the liquid crystal alignment direction of the alignment film formed on the one surface of the substrate, whereby the electronic device of the present invention is obtained. The liquid crystal display element of is 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 or 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 curing sealant is applied using a dispenser, and then liquid crystal is dripped into fine liquid droplets using a liquid crystal dispenser, and both substrates are bonded together under vacuum. To do. Then, the above sealing agent portion is irradiated with ultraviolet rays using a high pressure mercury lamp to seal both substrates. Finally, a polarizing plate is attached to both outer surfaces of the liquid crystal cell to obtain a liquid crystal display element as an electronic device of the present invention.

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. Further, as a polarizing plate used on the outside of the liquid crystal cell, a polarizing film in which a polarizing film called "H film" in which polyvinyl alcohol is stretched and aligned while absorbing iodine is sandwiched between cellulose acetate protective films, or an H film is used. Examples thereof include a polarizing plate made of itself.

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

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples. The weight average molecular weight (Mw) of the polymer component [A] was measured by the following method.
[Weight average molecular weight (Mw)]
It was measured by gel permeation chromatography (GPC) under the following conditions.

Equipment: Showa Denko's "GPC-101"
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are bonded Mobile phase: Tetrahydrofuran Column temperature: 40°C
Flow rate: 1.0 mL/min Sample concentration: 1.0 mass%
Sample injection volume: 100 μL
Detector: Differential refractometer Standard substance: Monodisperse polystyrene <Synthesis of polymer component [A]>
[Synthesis Example 1] (Synthesis of Polymer (P-1))
A flask equipped with a cooling tube 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) as a monomer giving the second structural unit, and methyl methacrylate ( Hereafter, also referred to as MMA) 50 parts by mass were charged, the atmosphere was replaced with nitrogen, and then gently stirring was started. 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 reduced 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 of the polymerizable monomers (Table 1), a resin was prepared in the same manner as in the synthesis example of P-1. The symbol-in Table 1 indicates that it is not contained. The polystyrene reduced weight average molecular weight (Mw) of the obtained polymer is shown in (Table 1).

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

a-2: compound represented by the following formula

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

ca-2: a compound represented by the following formula

ca-3: a compound represented by the following formula

ca-4: a compound represented by the following formula

[Synthesis Example 2] (Synthesis of Polymer (P-9))
A flask equipped with a cooling tube 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 a compound giving the first structural unit: ), methyl methacrylate (40 mol %) as a compound giving the second structural unit was charged, and the atmosphere was replaced with nitrogen. Then, gentle stirring was started. 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 the polymer (P-9).
The polystyrene reduced 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 cooling tube 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-ylmethacrylate (b-2) (30 mol %) as a compound giving the third structural unit, and a compound represented by the following formula (a-2) as a compound giving the first structural unit ( (30 mol %), methyl methacrylate (40 mol %) as a compound giving the second structural unit was charged and the atmosphere was replaced with nitrogen, and then gently stirring was started. 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 the polymer (P-10). The polystyrene reduced weight average molecular weight (Mw) of the polymer (P-10) was 12,000.
<Preparation of radiation-sensitive resin composition>
[Example 1]
A polymer solution containing (P-1) as a polymer component (A) (amount corresponding to 100 parts by mass (solid content) of (P-1)) is added to (B-) as a radiation-sensitive compound. 1) 20 parts by mass were mixed and filtered with a membrane filter having a pore size of 0.2 μm to prepare a radiation-sensitive resin composition.

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 radiation-sensitive resin compositions (CS-1) to (CS-8) of Comparative Examples were used.
Radiation-sensitive resin compositions (S-1) to (S-28,) Radiation-sensitive resin compositions (CS-1) to (CS-4) of Comparative Examples are positive-type radiation-sensitive resin compositions. The compositions and evaluation results are shown in Tables 2, 4, and 6. 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 radiation-sensitive resin compositions. The composition and evaluation results are shown in Tables 3 and 5.

In addition, "-" in the table indicates that the corresponding component was not blended.
(Radiation-sensitive compound)
B-1: 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensation product with sulfonic acid chloride (2.0 mol) B-2: (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile ("CGI" manufactured by BASF). -1311")
B-3: 4-methylphenylsulfonyloxyimino-α-(4-methoxyphenyl)acetonitrile (“PAI-101” manufactured by Midori Kagaku Co., Ltd.)
B-4: O-acyl oxime compound (“IRGACURE OXE01” manufactured by BASF)
B-5: O-acyl oxime 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 Chemicals 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]
The radiation-sensitive resin composition was applied onto a silicon substrate using a spinner, and then prebaked at 90° C. for 2 minutes on a hot plate to form a coating film having a thickness of 3.0 μm. Then, using an exposure machine (“MPA-600FA” (mixed by ghi ray) manufactured by Canon Inc.), the exposure amount for the coating film was passed through a mask having a pattern of 60 μm line-and-space (10:1). Was irradiated as a variable. Then, it was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 23° C. for 80 seconds by a puddle method. Next, a pattern was formed by washing with running ultrapure water for 1 minute and then drying. At this time, the exposure amount required for completely dissolving the 5 μm space pattern was examined. When the value of this exposure amount is 80 mJ/cm ² or less, it can be judged 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 and 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 [Fabrication of electrical property evaluation substrate]
Using the radiation-sensitive resin compositions described in Examples and Comparative Examples, each was coated 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 90° C. on a hot plate. Was pre-baked for 2 minutes and the organic solvent was evaporated to form each coating film. Next, as an electrode extraction site for measuring electrical characteristics, a part of the edge of the substrate coated with the radiation-sensitive resin composition was wiped with acetone to expose the underlying ITO. After that, it was heated (post-baked) at 230° C. for 30 minutes in an oven and cured to form an insulating film on the ITO substrate.
[Measurement of dielectric constant]
An Al (aluminum) electrode for measuring capacitance is provided on the insulating film of each electrical property evaluation substrate manufactured by the method described in [Production of electrical property evaluation substrate] described above by a vacuum evaporation apparatus (JEOL VACUUM). It was prepared using EVAPOATOR JEE-420). Next, a lead wire for electrode connection is soldered to the ITO portion which has been exposed in advance, and the lead wire and an Al electrode produced by a vacuum evaporation apparatus are respectively added to the plus terminal of an LCR meter (HEWLETT PACKARD 4284A PRECISION LCR METER). And the negative terminal were connected, and the electrostatic 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 measured capacitance C, the area S(m ² ) of the Al electrode, and the film thickness d(m) of the cured film were substituted into the following formula to obtain the value of the dielectric constant ε.
Dielectric constant ε = Capacitance C × Film thickness d(m) of cured film ÷ Electrode area S(m ² )
The evaluation criteria are shown below.

A: less than 3.0,
B: 3.0 or more and less than 3.2,
C: 3.2 or more and 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 with a stripping solution. The radiation sensitive resin composition was applied onto a silicon substrate using a spinner, and then prebaked at 90° C. for 2 minutes on a hot plate 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 the immersion was determined, which was used as an index of chemical resistance. The film thickness change rate is 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%. As described above, 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 poor. 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]
Using a spinner on a glass substrate, one of the radiation-sensitive resin compositions prepared as Examples and Comparative Examples was applied, and then prebaked at 90° C. for 2 minutes on a hot plate to give 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 integrated irradiation amount would be 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 Metrocon. The refractive index (nD) was measured at a wavelength of 633 nm, and 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. It was 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 have excellent radiation sensitivity, and cured films formed from these radiation-sensitive resin compositions have dielectric constants and chemical resistances. It was excellent.

On the other hand, it was found that the radiation-sensitive resin compositions of Comparative Examples 1 to 4 were excellent in radiation sensitivity but inferior in dielectric constant and refractive index.
As is clear 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 dielectric constants and chemical resistances. It had excellent properties and refractive index.

On the other hand, it was found that the radiation-sensitive resin compositions of Comparative Examples 5 to 8 were excellent in radiation sensitivity but inferior in dielectric constant and refractive index.

<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]
The curability was evaluated using the dissolution in the stripping solution as an index. The radiation sensitive resin composition was applied onto a silicon substrate using a spinner, and then prebaked at 90° C. for 2 minutes on a hot plate to form a coating film having a thickness of 3.0 μm. Subsequently, after using a proximity exposure machine (“MA-1200” (Canon Inc., ghi ray mixing) manufactured by Canon Inc.) to irradiate the entire surface of the substrate with 300 mJ of light, post-baking was performed for 30 minutes using a hot plate with temperature as a variable. A cured film was formed at each temperature. These films were immersed in a N-methylpyrrolidone solvent heated to 40° C. for 6 minutes, and the substrate after the immersion was baked for 15 minutes on a hot plate at the same temperature as the post-baking temperature to reduce the film thickness before and after the immersion. (%) was determined and used as an index of low temperature curability. The film thickness reduction rate is ◯: the film thickness reduction rate is less than 2%, Δ: the film thickness reduction rate is 2% or more and less than 10%, x: the film thickness reduction rate is 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 radiation sensitivity of Examples 52 to 54 and 56. The radioactive resin composition was excellent in curing performance at 180° C. or higher.

On the other hand, the radiation sensitive resin compositions of Comparative Examples 9 to 12 were inferior in low temperature curing performance as compared with Examples 49 to 72.

Claims (12)

Forming a cured film for forming a cured film of at least one of an interlayer insulating film of an electronic device, a flattening film, a bank defining a region for forming a light emitting layer, a spacer, a protective film, and a colored pattern for a color filter. A radiation-sensitive resin composition for use,
[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] contains a radiation-sensitive compound ,
Further, the polymer component (A) has a third structural unit containing an acid dissociable group as a structural unit other than the first structural unit and the second structural unit, and is a radiation sensitive resin for forming a cured film. Composition.
(In the formulas (1) and (2), A ¹ represents 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, 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.) Formation of a cured film for forming a cured film of at least one of an interlayer insulating film of an electronic device, a flattening film, a bank defining a region for forming a light emitting layer, a spacer, a protective film, and a colored pattern for a color filter. A radiation-sensitive resin composition for use,
[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] contains a radiation-sensitive compound ,
Further, the polymer component (A) has a third structural unit containing an acid dissociable group as a structural unit other than the first structural unit and the second structural unit, and is a radiation sensitive resin for forming a cured film. Composition.
(In the 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, m1 represents 1, m2 represents an integer of 0 to 4, and m3 represents an integer of 0 to 6.) The group containing an acid dissociable group is represented by the following formula (3) or the following formula (4), The radiation sensitive resin composition for forming a cured film according to claim 1 or 2 .
(In the 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 hydrogen atoms contained in 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, and the carbon-carbon of this carbon-hydrogen group A group containing an oxygen atom at the terminal of the space or the bond or a group in which at least a part of the hydrogen atoms of these groups are 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, a plurality of R ⁷ and R ⁸ may be the same or different. * Indicates a binding site. ) The said 2nd structural unit is represented by following formula (5), The radiation sensitive resin composition for hardened film formation of any one of Claim 1 to 3 characterized by the above-mentioned.
(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 It is ^one kind selected from the group of groups represented by the following formula (5-3): X ¹ is a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms, and Y ¹ is a single bond, oxygen. An atom, a sulfur atom or an imino group.In formula (5-3), R ¹³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and * represents a bonding site.)
Forming a cured film for forming a cured film of at least one of an interlayer insulating film of an electronic device, a flattening film, a bank defining a region for forming a light emitting layer, a spacer, a protective film, and a colored pattern for a color filter. A radiation-sensitive resin composition for use,
[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] contains a radiation-sensitive compound ,
The radiation sensitive resin composition for forming a cured film , wherein the second structural unit is represented by the following formula (5) .
(In the formulas (1) and (2), A ¹ represents 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, 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 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 It is ^one selected from the group of groups represented by the following formula (5-3): X ¹ is a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms, and Y ¹ is a single bond, oxygen. An atom, a sulfur atom or an imino group.In formula (5-3), R ¹³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and * represents a bonding site.)
Forming a cured film for forming a cured film of at least one of an interlayer insulating film of an electronic device, a flattening film, a bank defining a region for forming a light emitting layer, a spacer, a protective film, and a colored pattern for a color filter. A radiation-sensitive resin composition for use,
[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] contains a radiation-sensitive compound ,
The radiation sensitive resin composition for forming a cured film , wherein the second structural unit is represented by the following formula (5) .
(In the 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, m1 represents 1, m2 represents an integer of 0 to 4, and m3 represents an integer of 0 to 6.)
(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 It is ^one kind selected from the group of groups represented by the following formula (5-3): X ¹ is a single bond, a methylene group or an alkylene group having 2 to 12 carbon atoms, and Y ¹ is a single bond, oxygen. An atom, a sulfur atom or an imino group.In formula (5-3), R ¹³ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and * represents a bonding site.)
The radiation-sensitive resin composition for forming a cured film according to any one of claims 1 to 6 , wherein the radiation-sensitive compound is an acid generator, a polymerization initiator, or a combination thereof. Forming a cured film for forming a cured film of at least one of an interlayer insulating film of an electronic device, a flattening film, a bank defining a region for forming a light emitting layer, a spacer, a protective film, and a colored pattern for a color filter. A radiation-sensitive resin composition for use,
[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] contains a radiation-sensitive compound ,
The radiation-sensitive compound contains an acid generator,
The radiation-sensitive resin composition for forming a cured film , wherein the acid generator contains an oxime sulfonate group represented by the following formula (6) .
(In the formulas (1) and (2), A ¹ represents 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, 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 the 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 are substituted with a substituent. Indicates the binding site.) Forming a cured film for forming a cured film of at least one of an interlayer insulating film of an electronic device, a flattening film, a bank defining a region for forming a light emitting layer, a spacer, a protective film, and a colored pattern for a color filter. A radiation-sensitive resin composition for use,
[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] contains a radiation-sensitive compound ,
The radiation-sensitive compound contains an acid generator,
The radiation-sensitive resin composition for forming a cured film , wherein the acid generator contains an oxime sulfonate group represented by the following formula (6) .
(In the 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, m1 represents 1, m2 represents an integer of 0 to 4, and m3 represents an integer of 0 to 6.)
(In the 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 are substituted with a substituent. Indicates the binding site.) A cured film formed from the radiation-sensitive resin composition for forming a cured film according to any one of claims 1 to 9 . The method comprises the steps of forming a coating film on a substrate, irradiating at least a part of the coating film with radiation, developing the coating film irradiated with the radiation, and heating the developed coating film. A method of forming a cured film, comprising:
Method for forming a cured film formed using the coating film cured film-forming radiation-sensitive resin composition according to any one of claims 1 to 9. An electronic device comprising the cured film according to claim 10 .