JP2016109855A - Radiation-sensitive resin composition, insulation film, method for forming the same film and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition that forms an insulation film excellent in low dielectric property, adhesion and optical transparency in a laminated state and is excellent in storage stability, to provide an insulation film formed from the radiation-sensitive resin composition, to provide a method for forming the insulation film and to provide a display element having the insulation film.SOLUTION: The radiation-sensitive resin composition includes a polymer having a structural unit represented by formula (1) and a radiation-sensitive compound. In formula (1), Wis a divalent aromatic ring group having at least an electron-withdrawing group or a divalent group formed by coupling a plurality of divalent aromatic ring groups which may have a substituent through an electron-withdrawing coupling group; Wis a divalent aromatic ring group which may have a substituent or a divalent group formed by coupling a plurality of divalent aromatic ring groups which may have a substituent through a coupling group; and Yand Yare each independently an oxygen atom or a sulfur atom.SELECTED DRAWING: None

Description

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

  The display element is provided with an insulating film such as an interlayer insulating film that insulates wirings arranged in layers. As a material for forming an insulating film such as an interlayer insulating film, a radiation-sensitive resin composition that has a small number of steps for obtaining a required pattern shape and can obtain high surface hardness is widely used.

  The interlayer insulating film or the like needs to have low dielectric properties (insulating properties), adhesion to the substrate, and the like. For example, if the adhesion to the substrate is low, the developer soaks between the substrate and the insulating film during pattern formation, and the wiring pattern provided on the substrate is corroded.

  Further, for example, in an IPS (In-Plane Switching) type liquid crystal display element, a transparent electrode or the like is formed on an interlayer insulating film. The interlayer insulating film used in such a liquid crystal display element is required to have chemical resistance (solvent) resistance, light transmittance, and the like when patterning the transparent electrode. In particular, high light transmittance (high lamination transmittance) in a laminated state laminated with a transparent electrode or the like is important.

  On the other hand, the radiation sensitive resin composition used for forming such an insulating film includes a radiation sensitive resin containing a copolymer composed of an unsaturated carboxylic acid and / or an anhydride thereof, an epoxy group-containing unsaturated compound, and the like. Resin compositions are known. This radiation-sensitive resin composition is configured to obtain a surface hardness as an insulating film by a reaction between a carboxyl group and an epoxy group (see JP-A-2001-354822).

  However, the low dielectric properties, adhesion, light transmittance, etc. of the insulating film obtained using the conventional radiation sensitive resin composition, the storage stability of the radiation sensitive resin composition itself, etc. are not necessarily sufficient. Needless to say, there is a need for a radiation-sensitive resin composition with better performance.

JP 2001-354822 A

  The present invention has been made based on the circumstances as described above, and the object thereof is to form an insulating film excellent in low dielectric property, adhesion, and light transmission in a laminated state, and storage stability. It is providing the radiation sensitive resin composition which is excellent also in, the insulating film formed from this radiation sensitive resin composition, the formation method of this insulating film, and a display element provided with this insulating film.

（式（１）中、Ｗ^１は、電子吸引性基を少なくとも有する２価の芳香環基、又は置換基を有していてもよい複数の２価の芳香環基が電子吸引性の連結基で連結されてなる２価の基である。Ｗ^２は、置換基を有していてもよい２価の芳香環基、又は置換基を有していてもよい複数の２価の芳香環基が連結基で連結されてなる２価の基である。Ｙ^１及びＹ^２は、それぞれ独立して、酸素原子又は硫黄原子である。） The invention made in order to solve the above problems includes a polymer having a structural unit represented by the following formula (1) (hereinafter referred to as “[A] polymer”), and a radiation sensitive compound (hereinafter referred to as “ It is a radiation sensitive resin composition containing [B] a radiation sensitive compound.

(In Formula (1), W ¹ is a divalent aromatic ring group having at least an electron-withdrawing group, or a plurality of divalent aromatic ring groups which may have a substituent are electron-withdrawing linking groups. W ² is a divalent aromatic ring group which may have a substituent, or a plurality of divalent aromatic ring groups which may have a substituent. Is a divalent group formed by linking with a linking group, and Y ¹ and Y ² are each independently an oxygen atom or a sulfur atom.)

  Another invention made to solve the above problems is an insulating film formed from the radiation-sensitive resin composition.

  Still another invention made in order to solve the above-described problems includes a step of forming a coating film on a substrate, a step of irradiating at least a part of the coating film, and a coating film irradiated with the radiation. An insulating film forming method comprising a step and a step of heating the developed coating film, wherein the radiation-sensitive resin composition is used for forming the coating film.

  Yet another invention made to solve the above problems is a display element including the insulating film.

  Here, the aromatic ring group refers to a group composed of an aromatic ring, and the n-valent aromatic ring group refers to a group in which n hydrogen atoms on the aromatic ring are removed from the aromatic ring. The aromatic ring group having a substituent refers to a group in which one or more hydrogen atoms on the aromatic ring of the aromatic ring group are substituted with the substituent. An organic group refers to a group containing at least one carbon atom.

  According to the radiation-sensitive resin composition of the present invention, it is possible to form an insulating film having excellent low dielectric properties, adhesion, and light transmission in a laminated state, and excellent storage stability. The insulating film of the present invention is excellent in low dielectric property, adhesion, and light transmittance in a stacked state, and a display element including the insulating film can have high reliability and the like. Further, according to the method for forming an insulating film of the present invention, such an insulating film can be formed.

<Radiation sensitive resin composition>
The radiation sensitive resin composition of the present invention contains [A] a polymer and [B] a radiation sensitive compound. The radiation-sensitive resin composition can form an insulating film excellent in low dielectric properties, adhesion, and light transmission in a laminated state, and is excellent in storage stability. Moreover, the said radiation sensitive resin composition can also express high photorefractive property, chemical resistance, developability, etc. The radiation-sensitive resin composition can contain other components in addition to the [A] polymer and the [B] radiation-sensitive compound. Hereinafter, each component etc. are demonstrated.

<[A] polymer>
[A] The polymer has a structural unit represented by the following formula (1). [A] The polymer is a so-called aromatic poly (thio) ether.

In Formula (1), W ¹ is a divalent aromatic ring group having at least an electron-withdrawing group, or a plurality of divalent aromatic ring groups which may have a substituent are electron-withdrawing linking groups. A divalent group connected by W ² is a divalent aromatic ring group that may have a substituent, or a divalent group in which a plurality of divalent aromatic ring groups that may have a substituent are connected by a linking group. It is. Y ¹ and Y ² are each independently an oxygen atom or a sulfur atom.

(W ¹ )
Examples of the divalent aromatic ring group in W ¹ include a benzenediyl group, a naphthalenediyl group, and an anthracenediyl group, and a benzenediyl group is preferable.

Examples of the electron-withdrawing group possessed by the divalent aromatic ring group in W ¹ include acyl groups such as cyano group, nitro group, trifluoromethyl group, carboxy group and acetyl group, alkylsulfonyl groups such as methylsulfonyl group, and dicyano. Examples thereof include a vinyl group, a tricyanovinyl group, a halogen atom such as a fluorine atom and a chlorine atom. Of these, a cyano group, a nitro group, a fluorine atom and a chlorine atom are preferable, and a cyano group and a nitro group are more preferable.

Examples of the electron-withdrawing linking group for W ¹ include a carbonyl group, a sulfonyl group, a difluoromethylene group, and the like, and a carbonyl group and a sulfonyl group are preferable.

As the substituent that the divalent aromatic ring group in W ¹ may have, in addition to the electron-withdrawing group, a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a hydroxyl group, and a mercapto group , An amino group, an acidic group, a group in which an acidic group is generated by a decomposition reaction, and the like.

  Examples of the hydrocarbon group having 1 to 12 carbon atoms include a monovalent chain hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and 6 to 12 carbon atoms. And monovalent aromatic hydrocarbon groups.

Examples of the monovalent chain hydrocarbon group having 1 to 12 carbon atoms include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, and an i-propyl group,
An alkenyl group such as an ethenyl group or a propenyl group,
Examples thereof include alkynyl groups such as ethynyl group and propynyl group.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkyl groups such as a cyclopropyl group, a cyclohexyl group, and a norbornyl group,
Examples thereof include cycloalkenyl groups such as cyclopropenyl group, cyclohexenyl group and norbornenyl group.

  Examples of the monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a tolyl group and a benzyl group in addition to an aromatic ring group such as a phenyl group and a naphthyl group.

  As said C1-C12 alkoxy group, a methoxy group, an ethoxy group, etc. can be mentioned.

Examples of the acidic group include a sulfo group (—SO ₃ H), a carboxy group (—COOH), a phosphoric acid group (—O—P (═O) (OH) ₂ ), and a phosphonic acid group (—P (═O). (OH) ₂ ) and oxo acid groups such as phosphinic acid groups (> P (═O) (OH)). Moreover, as said acidic group, a C1-C12 alkyl group etc. which have these oxo acid groups as a substituent may be sufficient, for example.

“Decomposition” in a group in which an acidic group is generated by the decomposition means decomposition generated in response to heat, radiation, acid, base, etc. in addition to hydrolysis. Examples of the group that generates an acidic group by the decomposition reaction include a group containing an ester bond derived from the acidic group, a group containing an amide bond derived from the acidic group, and the like, and an ester bond derived from the acidic group A group containing is preferred. Examples of the group containing an ester bond derived from the acidic group include a sulfonate ester bond (—SO ₂ —O—), a carboxylic acid ester bond (—COO—), and a phosphate ester bond (—O—P (═O). (-O-) ₂ ), phosphonic acid ester bonds (—P (═O) (— O—) ₂ ), phosphinic acid ester bonds (> P (═O) (— O—)), etc. be able to. Specific examples of the monovalent group that generates an acidic group by a decomposition reaction include alkyl ester groups such as a methyl ester group (—COOCH ₃ ) and aryl ester groups such as a phenyl ester group (—COOC ₆ H ₅ ). be able to.

  In addition, the group that generates an acidic group by the decomposition reaction may be a group having a cyclic structure (cyclic ester structure). Examples of such groups include groups exemplified by the following formula.

W ¹ is preferably a group represented by the following formula (2) or formula (3).

(Group represented by Formula (2))
In formula (2), X is an electron withdrawing group. R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a mercapto group, a halogen atom, an acidic group, or a group in which an acidic group is generated by a decomposition reaction. . n ¹ is an integer of 0 to 3. When n ¹ is 2 or more, the plurality of R ¹ may be the same or different.

Specific examples and preferred groups of the electron-withdrawing group represented by X include those described above as the electron-withdrawing group possessed by the divalent aromatic ring group in W ¹ .

Examples of the hydrocarbon group having 1 to 12 carbon atoms represented by R ¹ , an alkoxy group having 1 to 12 carbon atoms, an acidic group, and a group in which an acidic group is generated by a decomposition reaction include a divalent aromatic ring group in W ¹ . Examples of the substituent that may be used include those described above.

R ¹ is preferably a cyano group, a nitro group, and a halogen atom, and more preferably a cyano group and a nitro group.

(Group represented by Formula (3))
In formula (3), Z is a carbonyl group or a sulfonyl group. R ² and R ³ are each independently a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a mercapto group, a halogen atom, an acidic group, or a decomposition reaction. Thus, an acidic group is generated. n ² and ^{n 3} are each independently an integer of 0 to 4. When n ² is 2 or more, the plurality of R ² may be the same or different. When n ³ is 2 or more, the plurality of R ³ may be the same or different.

Examples of the hydrocarbon group having 1 to 12 carbon atoms represented by R ² and R ³ , an alkoxy group having 1 to 12 carbon atoms, an acidic group, and a group in which an acidic group is generated by a decomposition reaction include a divalent aromatic ring in W ¹ . What was mentioned above can be mentioned as a substituent which group may have.

R ² and R ³ are preferably a cyano group, a nitro group and a halogen atom, and more preferably a nitro group.

n ² and n ³ are each independently an integer of 0 to 4, preferably 0 to 2, and more preferably 0 and 2.

(W ² )
Specific examples and preferred groups of divalent aromatic ring group in W ² may be mentioned those described above as the divalent aromatic group in W ^1.

Specific examples of the substituent that the divalent aromatic ring group in W ² may have include those described above as the substituent that the aromatic ring group in W ¹ may have. As the substituent that the divalent aromatic hydrocarbon group in W ² may have, an acidic group and a group in which an acidic group is generated by a decomposition reaction are preferable, and a carboxyl group and a group having a cyclic ester structure are more preferable. A group having a cyclic structure containing a carboxy group and a phosphinic ester bond is more preferred.

Examples of the linking group in W ² include an oxygen atom, a sulfur atom, a sulfonyl group, an imino group, and other divalent organic groups.

  Examples of the divalent organic group include a carbonyl group, a carbonyloxy group, an amide group (-CONH-, etc.), a substituted or unsubstituted divalent hydrocarbon group having 1 to 20 carbon atoms, or a combination thereof. The group can be mentioned.

  Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a carbon number. Examples thereof include 6 to 20 divalent aromatic hydrocarbon groups.

Examples of the divalent chain hydrocarbon group having 1 to 20 carbon atoms include methanediyl group (methylene group), ethanediyl group, propane-2,2-diyl group (isopropylidene group), butane-2,2-diyl. Alkanediyl groups such as
Alkenediyl groups such as ethenediyl group and propenediyl group,
Examples include alkynediyl groups such as ethynediyl group and propynediyl group.

Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cycloalkanediyl groups such as cyclopropanediyl group and norbornanediyl group,
Examples thereof include cycloalkenediyl groups such as cyclopropene diyl group and norbornene diyl group.

  Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include benzenediyl group, toluenediyl group, naphthalenediyl group, 1-phenyl-ethane-2,2-diyl group and the like. Moreover, as a C6-C20 bivalent aromatic hydrocarbon group, the group containing the condensed ring of an aromatic ring and an alicyclic ring may be sufficient. Examples of such a group include a fluorene-9,9-diyl group represented by the following formula (a) and a 3-phenyl-indan-1,1-diyl group represented by the following formula (b). be able to.

  The divalent hydrocarbon group having 1 to 20 carbon atoms is preferably a divalent chain hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

Examples of the substituent that the divalent hydrocarbon group having 1 to 20 carbon atoms can have include those exemplified as the substituent that the divalent aromatic ring group in W ¹ can have.

Examples of the linking group in W ² include a divalent group having a cyclic ester structure as a group that generates an acidic group by a decomposition reaction. Examples of such groups include groups exemplified by the following formula.

Examples of the linking group in W ² include a sulfur atom, a sulfonyl group, a carbonyl group, an unsubstituted chain hydrocarbon group, an unsubstituted aromatic hydrocarbon group, an acidic group as a substituent, or a group that generates an acidic group by a decomposition reaction. A chain hydrocarbon group, an aromatic group (including a phenolic hydroxyl group) as a substituent, an aromatic hydrocarbon group having a group that generates an acidic group by a decomposition reaction, and a divalent group having a cyclic ester structure are preferable.

W ² is preferably a group represented by the following formula (4), formula (5) or formula (6).

(Group represented by Formula (4))
In Formula (4), A is an oxygen atom, a sulfur atom, a sulfonyl group, or a divalent organic group that may have an acidic group or a group that generates an acidic group by a decomposition reaction. R ⁴ and R ⁵ are each independently a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a mercapto group, a halogen atom, an acidic group, or a decomposition reaction. Thus, an acidic group is generated. n ⁴ and ^{n 5} are each independently an integer of 0 to 4. When n ⁴ is 2 or more, the plurality of R ⁴ may be the same or different. When n ⁵ is 2 or more, the plurality of R ⁵ may be the same or different. m ¹ and m ² are each independently 1 or 2.

Specific examples of the divalent organic group in A include an acidic group exemplified as the linking group in W ² or a divalent organic group which may have a group capable of generating an acidic group by a decomposition reaction.

  A includes a sulfur atom, a sulfonyl group, a carbonyl group, an unsubstituted chain hydrocarbon group, an unsubstituted aromatic hydrocarbon group, a chain carbon having an acidic group as a substituent or a group that generates an acidic group by a decomposition reaction. A hydrogen group, an acidic group (including a phenolic hydroxyl group) as a substituent, an aromatic hydrocarbon group having a group that generates an acidic group by a decomposition reaction, and a divalent group having a cyclic ester structure are preferable.

Examples of the hydrocarbon group having 1 to 12 carbon atoms represented by R ⁴ and R ⁵ , an alkoxy group having 1 to 12 carbon atoms, an acidic group, and a group in which an acidic group is generated by a decomposition reaction include a divalent aromatic ring in W ¹ . What was mentioned above can be mentioned as a substituent which group may have.

R ⁴ and R ⁵ preferably include an acidic group and a group that generates an acidic group by a decomposition reaction, more preferably include an acidic group, and further preferably include a carboxy group.

n ⁴ and n ⁵ are each independently an integer of 0 to 4, with 0 and 1 being preferred.

(Group represented by Formula (5))
In formula (5), R ⁶ is a single bond, an oxygen atom, a sulfur atom, a methylene group or an imino group. R ⁷ and R ⁸ are each independently a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a mercapto group, a halogen atom, an acidic group, or a decomposition reaction. Thus, an acidic group is generated. n ⁷ and n ⁸ are each independently an integer of 0 to 4. When n ⁷ is 2 or more, the plurality of R ⁷ may be the same or different. When n ⁸ is 2 or more, the plurality of R ⁸ may be the same or different.

Examples of the hydrocarbon group having 1 to 12 carbon atoms represented by R ⁷ and R ⁸ , an alkoxy group having 1 to 12 carbon atoms, an acidic group, and a group in which an acidic group is generated by a decomposition reaction include a divalent aromatic ring in W ¹ . What was mentioned above can be mentioned as a substituent which group may have. R ⁷ and R ⁸ preferably include an acidic group and a group that generates an acidic group by a decomposition reaction.

(Group represented by Formula (6))
In the formula (6), R ⁹ is acidic by a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a mercapto group, a halogen atom, an acidic group, or a decomposition reaction. A group from which a group is formed. n ⁹ is an integer of 0 to 4. When n ⁹ is 2 or more, the plurality of R ⁹ may be the same or different.

Examples of the hydrocarbon group having 1 to 12 carbon atoms represented by R ⁹ , an alkoxy group having 1 to 12 carbon atoms, an acidic group, and a group in which an acidic group is generated by a decomposition reaction include a divalent aromatic ring group in W ¹ . Examples of the substituent that may be used include those described above. R ⁹ preferably includes an acidic group and a group that generates an acidic group by a decomposition reaction.

n ⁹ is an integer of 0 to 4, but 1 is preferable.

(Acid group or group in which acidic group is generated by decomposition reaction)
It is preferable that at least one of W ¹ and W ^{2 in} Formula (1) has an acidic group or a group that generates an acidic group by a decomposition reaction, and W ² has an acidic group or a group that generates an acidic group by a decomposition reaction. Is more preferable. Thus, when the structural unit of the polymer [A] has an acidic group or a group that generates an acidic group by a decomposition reaction, the radiation-sensitive resin composition can effectively exhibit alkali developability. .

Examples of the acidic group and the group that generates an acidic group by a decomposition reaction include those described above as the substituent that the divalent aromatic ring group in W ¹ may have. As the acidic group, a carboxyl group and a group containing a carboxyl group are preferable. As the group that generates an acidic group by a decomposition reaction, a group having a cyclic ester structure is preferable, a group having a carboxylic acid ester bond and a group having a phosphinic acid ester bond are also preferable, and a cyclic group including a carboxylic acid ester bond or a phosphinic acid ester bond A group having a structure is more preferred.

Note that when at least one of W ¹ and W ² has an acidic group, the optical refractive index of the obtained insulating film can be further increased. In addition, when at least one of W ¹ and W ² has a group that generates an acidic group by a decomposition reaction, the substrate adhesion of the obtained insulating film can be further improved.

(Y ¹ and Y ² )
Y ¹ and Y ² are each independently an oxygen atom or a sulfur atom, preferably an oxygen atom.

(Other structural units, etc.)
[A] The polymer may have a structural unit other than the structural unit represented by the formula (1). Other structural units include a structural unit derived from a monomer containing the monomer (3) described later, a structural unit derived from a monomer containing a diol (polyhydric alcohol, etc.) that does not have an aromatic ring, etc. Can be mentioned.

  [A] As a minimum of the content rate of the structural unit represented by the said Formula (1) in a polymer, 50 mol% is preferable with respect to all the structural units which comprise a [A] polymer, and 80 mol% is More preferred is 90 mol%.

([A] Polymer Synthesis Method)
[A] The polymer can be obtained, for example, by reacting the monomer (1) represented by the following formula (7) with the monomer (2) represented by the following formula (8). .

S ¹ -W ¹ -S ¹ (7)
In the above formula (7), two S ¹ are each independently a halogen atom. As this halogen atom, a fluorine atom and a chlorine atom are preferable. W ¹ has the same meaning as ^{W 1} in formula (1).

^{T 2 -W 2 -T 2 (8} )
In the above formula (8), two T ² are each independently a hydroxyl group or a mercapto group. W ² has the same meaning as ^{W 2} in the formula (1).

A structure corresponding to W ¹ in the structural unit represented by the formula (1) is formed from the monomer (1), and corresponds to W ² in the structural unit represented by the formula (1) from the monomer (2). A structure is formed. The monomer (1) and the monomer (2) can be used alone or in combination of two or more.

  Although it does not specifically limit as ratio of the usage-amount of a monomer (1) and a monomer (2), For example, it is as follows. The lower limit of the equivalents of all the halogen atoms substituted on the aromatic ring in the monomer (1) relative to 1 equivalent of all the hydroxyl groups and mercapto groups substituted on the aromatic ring in the monomer (2) is 1 equivalent. Preferably, 1.5 equivalent is more preferable. Moreover, as this upper limit, 3 equivalent is preferable and 2 equivalent is more preferable.

As the monomer (2), W ² are all substituted to the aromatic ring of the case, all of the monomer (2) using a monomer having a group which the acidic group is caused by acidic or decomposition reactions (2a) The lower limit of the equivalents of all the hydroxyl groups and mercapto groups substituted on the aromatic ring in the monomer (2a) with respect to 1 equivalent of the hydroxyl group and mercapto group is preferably 0.2 equivalent, more preferably 0.3 equivalent.

  In addition to the monomer (1) and the monomer (2), another monomer may be further added to synthesize the [A] polymer.

  As another monomer, the monomer (3) represented, for example by following formula (9) can be mentioned. The monomer (3) includes an aromatic ring having both a hydroxyl group or a mercapto group and an acidic group or a group that generates an acidic group by a decomposition reaction. By using the [A] polymer synthesized by further using the monomer (3), the radiation sensitivity of the radiation-sensitive resin composition can be increased.

W ³ -U ³ (9)
In the above formula (9), ^{U 3} is a hydroxyl group or a mercapto group. W ³ has at least a monovalent aromatic ring group having at least an acidic group or a group that generates an acidic group by a decomposition reaction, or an acidic group or a group that generates an acidic group by a decomposition reaction, and a plurality of aromatic rings are linking groups or It is a monovalent group connected by a single bond.

Examples of the monovalent aromatic ring group in W ³ include a phenyl group and a naphthyl group, and a phenyl group is preferable. Examples of the linking group in W ³ include those described above as the linking group in W ² . Examples of the monovalent group in which a plurality of aromatic rings in W ³ are linked by a linking group or a single bond include a biphenyl group.

Examples of the acidic group in W ³ or the group in which an acidic group is generated by a decomposition reaction include those exemplified as the acidic group in W ¹ or a group in which an acidic group is generated by a decomposition reaction, and a carboxy group is preferable. The number of acidic groups that a monovalent aromatic ring group or a monovalent group in which a plurality of aromatic rings are connected by a linking group or a single bond in W ³ or the number of groups that generate an acidic group by a decomposition reaction is 1 and 2. Is preferred.

  The amount of the monomer (3) used is, for example, that the aromatic ring in the monomer (3) is substituted for 1 equivalent of all hydroxyl groups and mercapto groups substituted in the aromatic ring in the monomer (2). As the lower limit of the equivalent of all hydroxyl groups and mercapto groups, 0.01 equivalent is preferable, and 0.05 equivalent is more preferable. Moreover, as this upper limit, 0.3 equivalent is preferable and 0.15 equivalent is more preferable.

  [A] Specifically, the polymer can be synthesized, for example, by the method shown below. In an organic solvent, the monomer (2) and, if necessary, the monomer (3) are reacted with an alkali metal or an alkali metal compound to obtain an alkali metal salt such as the monomer (2). The alkali metal salt such as the monomer (2) and the monomer (1) are polymerized to obtain the [A] polymer. In addition, reaction of a monomer (2) etc. and an alkali metal or an alkali metal compound can also be performed in presence of a monomer (1). That is, the monomer (2) and the monomer (1) can be polymerized in the presence of an alkali metal or an alkali metal compound.

  Examples of the alkali metal or alkali metal compound include alkali metals such as lithium, potassium, and sodium, alkali metals such as lithium hydroxide, potassium hydroxide, and sodium hydroxide, and alkali metals such as lithium carbonate, potassium carbonate, and sodium carbonate. Examples thereof include alkali metal hydrogen carbonates such as carbonate, lithium hydrogen carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate. These can be used alone or in combination of two or more.

  Examples of the organic solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, sulfolane, dimethyl sulfoxide, diethyl Polar solvents such as sulfoxide, dimethylsulfone, diethylsulfone, diisopropylsulfone, diphenylsulfone, diphenylether, benzophenone, dialkoxybenzene (alkoxy group having 1 to 4 carbon atoms), trialkoxybenzene (alkoxy group having 1 to 4 carbon atoms), etc. Can be mentioned. Among these, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenylsulfone and dimethylsulfoxide are preferable as polar solvents having a high dielectric constant. These organic solvents can be used alone or in combination of two or more.

  As said organic solvent, in addition to the said polar solvent, the organic solvent azeotroped with water, such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole, and phenetole, can also be used. These can be used alone or in combination of two or more.

  As a minimum of reaction temperature in superposition | polymerization, 60 degreeC is preferable and 80 degreeC is more preferable. On the other hand, as this upper limit, 250 degreeC is preferable and 200 degreeC is more preferable. Moreover, as a minimum of reaction time, 15 minutes are preferable and 1 hour is more preferable. On the other hand, the upper limit is preferably 100 hours, and more preferably 24 hours.

  [A] As a minimum of polystyrene conversion weight average molecular weight (Mw) by GPC (gel permeation chromatography) of a polymer, 4,000 is preferred and 8,000 is more preferred. On the other hand, the upper limit is preferably 50,000, and more preferably 30,000.

  [A] The upper limit of the molecular weight distribution (Mw / Mn) of the polymer is preferably 4, and more preferably 3. The lower limit is, for example, 1.5 and may be 2. “Mn” is the number average molecular weight in terms of polystyrene by GPC.

<[B] Radiation sensitive compound>
[B] The radiation-sensitive compound imparts radiation-sensitive properties to the radiation-sensitive 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. [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.

  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, 20 mass parts Is more preferable. On the other hand, as this upper limit, 80 mass parts is preferable, 60 mass parts is more preferable, and 40 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 said radiation sensitive resin composition can exhibit the negative radiation sensitive characteristic with respect to an alkali developing solution, for example by containing (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-benzoyloxime). )], 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 content of (B2) polymerization initiator in the said radiation sensitive resin composition, it is 1 mass part or more and 40 mass parts or less with respect to 100 mass parts of [A] polymers, for example. (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 ingredients>
In addition to the [A] polymer and the [B] radiation sensitive compound, the radiation sensitive resin composition includes, for example, [C] antioxidants, [D] adhesion assistants, [E] surfactants, other heavy compounds. A coalescence, a polyfunctional acrylate, metal oxide particles, a heat-sensitive acid generator, etc. can be contained.

<[C] Antioxidant>
[C] Antioxidant is a component that suppresses the breakage of the bond of polymer molecules by capturing radicals generated by exposure or heating, or by decomposing a peroxide generated by oxidation. When the radiation sensitive resin composition contains the [C] antioxidant, the degradation of the polymer molecules in the insulating film to be formed is suppressed, and durability and the like can be improved. [C] Antioxidants may be used alone or in combination of two or more.

  [C] Examples of the antioxidant include a compound having a hindered phenol structure, a compound having a hindered amine structure, a compound having an alkyl phosphite structure, and a compound having a thioether structure. Among these, it is preferable that [D] antioxidant is a compound which has a hindered phenol structure.

  Examples of the compound having a hindered phenol structure (hindered phenol compound) include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di- tert-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N '-Hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxy Phenylpropionamide), 3,3 ′, 3 ′, 5 ′, 5′-hexa-tert-butyl-a, a ′, a ′-(mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy -M-tolyl) propionate, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris [(4-tert-butyl-3-hydroxy -2,6-xylyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6- Scan (octylthio) -1,3,5-triazin-2-ylamine) phenol, and the like.

  Examples of commercially available compounds having a hindered phenol structure include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, and AO-80. AO-330 (above, manufactured by ADEKA), sumizer GM, GS, MDP-S, BBM-S, WX-R, GA-80 (above, manufactured by Sumitomo Chemical), IRGANOX 1010, 1035, 1076, Same 1098, Same 1135, Same 1330, Same 1726, Same 1425 WL, Same 1520L, Same 245, Same 259, Same 3114, Same 565, IRGAMOD295 (above, manufactured by BASF), Yoshinox BHT, Same BB, Same 2246G, Same 425, 250, 930, SS, TT, 917, 314 (above, API Corporation) ), And the like.

  As a minimum of content of [C] antioxidant in the said radiation sensitive resin composition, 0.01 mass part is preferable with respect to 100 mass parts of [A] polymers, and 0.05 mass part is more preferable. . On the other hand, as this upper limit, 3 mass parts is preferable, 1 mass part is more preferable, and 0.3 mass part is further more preferable.

<[D] Adhesion aid>
[D] The adhesion assistant improves the adhesion between the insulating film formed from the radiation-sensitive resin composition and the substrate. As such an adhesion assistant, a functional silane coupling agent is preferable. Examples of the functional silane coupling agent include those having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. Examples of such functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-glycid. Examples include xylpropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. [D] The adhesion assistant may be used alone or in combination of two or more.

  As a minimum of content of [D] adhesion assistant in the radiation sensitive resin composition, 0.1 mass part is preferred to 100 mass parts of [A] polymer, and 1 mass part is more preferred. On the other hand, as this upper limit, 20 mass parts is preferable and 10 mass parts is more preferable. [D] By setting the content of the adhesion assistant in the above range, it is possible to sufficiently suppress the occurrence of development residue in the development process while sufficiently improving adhesion.

<[E] surfactant>
[E] Surfactant can improve the applicability of the radiation-sensitive resin composition. [E] Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant, and a fluorine-based surfactant is preferable. [E] Surfactant can be used 1 type or in mixture of 2 or more types.

  Examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octa Ethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2, , 2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8 , 9, 9, 10, 10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc., Sodium Le Oro alkylbenzenesulfonate; fluoroalkyl polyoxyethylene ethers; fluoroalkyl ammonium iodide, fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethylene ethanol; perfluoroalkyl alkoxylate; fluorine-based alkyl esters.

  Commercially available fluorosurfactants include, for example, “BM-1000” and “BM-1100” from BM CHEMIE, “Megafac F142D”, “Same F172” and “Same F173” from Dainippon Ink & Chemicals, Inc. "F183", "F178", "F191", "F471", "F476", "Florard FC-170C", "FC-171", "FC-430" of Sumitomo 3M Limited. , “Same FC-431”, “Surflon S-112”, “S-113”, “S-131”, “S-141”, “S-145”, “S-145” of Asahi Glass Co., Ltd. 382 ”,“ SC-101 ”,“ SC-102 ”,“ SC-103 ”,“ SC-104 ”,“ SC-105 ”,“ SC-106 ”, Shin-Akita Kasei Co., Ltd. "F Top EF301", "Same "F303", "Same EF352", Neos' "Factent FT-100", "Same FT-110", "Same FT-140A", "Same FT-150", "Same FT-250", "Same FT" -251 "," FT-300 "," FT-310 "," FT-400S "," FTX-218 "," FT-251 ", and the like.

  As a minimum of content of [E] surfactant in the said radiation sensitive resin composition, 0.1 mass part is preferable with respect to 100 mass parts of [A] polymers, and 0.3 mass part is more preferable. . On the other hand, as this upper limit, 5 mass parts is preferable and 2 mass parts is more preferable. [E] By setting the content of the surfactant in the above range, it is possible to improve the coatability and to suppress the occurrence of film defects in the obtained insulating film.

<Other polymers>
The other polymer is a polymer other than the [A] polymer. Examples of other polymers include epoxy resins and other alkali-soluble resins.

  Epoxy resins improve properties such as heat resistance and surface hardness of an insulating film formed from the radiation-sensitive resin composition. The epoxy resin is not particularly limited as long as the compatibility with the [A] polymer is not affected. Examples of the epoxy resin include phenol novolac type epoxy resin, bisphenol A type epoxy resin, cresol novolac type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin, glycidyl methacrylate. (Co) polymerized resin and the like.

<Multifunctional acrylate>
A polyfunctional acrylate is a compound having an ethylenically unsaturated bond. By containing the polyfunctional acrylate, the radiation-sensitive composition can form an insulating film having excellent surface hardness by irradiation with radiation and having sufficient surface hardness even at a low exposure amount.

  The polyfunctional acrylate is not particularly limited as long as it is a polymerizable compound having an ethylenically unsaturated bond. For example, ω-carboxypolycaprolactone mono (meth) acrylate, 2- (2′-vinyloxyethoxy) ethyl (meth) Monofunctional (meth) acrylate compounds such as acrylate; ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) Acrylate, tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, dimethylol tricyclo Candi (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, succinic acid modified di Pentaerythritol pentaacrylate, a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and one or more in the molecule And a polyfunctional (meth) acrylate compound such as a urethane (meth) acrylate compound obtained by reacting with a compound having a hydroxyl group of 3 to 5 (meth) acryloyloxy groups. These polyfunctional acrylates can be used alone or in combination of two or more.

<Metal oxide particles>
The metal oxide particles control the increase in the dielectric constant while maintaining the electrical insulation of the insulating film formed from the radiation sensitive resin composition. The metal oxide particles can also be used for the purpose of controlling the refractive index of the insulating film, controlling the transparency of the insulating film, suppressing cracks by alleviating curing shrinkage, and improving the surface hardness of the insulating film.

  The metal oxide particles are, for example, oxide particles of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium, and hafnium. These oxide particles may be used alone or in combination of two or more, and may be single oxide particles or composite oxide particles.

  Examples of the single oxide include silica, alumina, zirconia, titania, and ceria.

  Examples of the composite oxide include barium titanate, strontium titanate, ATO (antimoy-tin oxide), ITO (indium-tin oxide), and IZO (indium-zinc oxide).

Among these, oxide particles of silicon, zirconium, titanium, zinc, and barium are preferable, and silica particles, zirconia particles, titania particles, and barium titanate (BaTiO ₃ ) are more preferable. As a commercial item of metal oxide particles, for example, “Nanotech (registered trademark)” manufactured by CI Kasei Co., Ltd. can be used.

  The shape of the metal oxide particles is not particularly limited, and may be spherical or indeterminate, and may be hollow particles, porous particles, core / shell particles, or the like.

  The volume average particle diameter of the metal oxide particles is a value determined by a dynamic light scattering method and is preferably from 5 nm to 200 nm. If the volume average particle diameter of the metal oxide particles is less than 5 nm, the hardness of the insulating film obtained using the radiation-sensitive resin composition may be lowered, or the intended relative dielectric constant may not be expressed. On the other hand, if the volume average particle diameter exceeds 200 nm, the haze of the insulating film may increase and the transmittance may decrease, and the smoothness of the insulating film may deteriorate.

<Heat-sensitive acid generator>
The heat-sensitive acid generator improves properties such as heat resistance and hardness of an insulating film formed from the radiation-sensitive resin composition. Examples of the heat-sensitive acid generator include onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts.

<Method for preparing radiation-sensitive resin composition>
The said radiation sensitive resin composition is prepared by mixing a [A] polymer and a [B] radiation sensitive compound, and another component as needed uniformly. The radiation-sensitive resin composition is preferably used in the form of a solution after being dissolved in an appropriate solvent.

  As the solvent, a solvent that uniformly dissolves the contained component and does not react with the contained component is used. As such a solvent, what was illustrated as a solvent used for the synthesis | combination of a [A] polymer can be mentioned, for example. These solvents can be used alone or in combination of two or more.

  Examples of the solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol acetate from the viewpoints of solubility, dispersibility of solids, and coating properties of the composition. Monoethyl ether, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3 -Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, Acid n- butyl acetate i- butyl, formic acid n- amyl acetate, i- amyl, propionic acid n- butyl, ethyl butyrate, i- propyl, butyric acid n- butyl and ethyl pyruvate preferred.

  Further, together with the above solvents, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination. The said high boiling point solvent can be used 1 type or in mixture of 2 or more types.

  Although the solid content concentration in the said radiation sensitive resin composition is not specifically limited, As a minimum, 5 mass% is preferable, 10 mass% is more preferable, and 20 mass% is further more preferable. On the other hand, as this upper limit, 50 mass% is preferable and 40 mass% is more preferable. By making solid content concentration into the said range, the applicability | paintability, stability, etc. of the said radiation sensitive resin composition can be made more favorable.

<Insulating film>
The insulating film (cured film) of the present invention is formed from the radiation-sensitive resin composition. The insulating film can be preferably used as an insulating film for a display element. Examples of the insulating film for the display element include an interlayer insulating film, a protective film, and a planarizing film. Since the said insulating film is formed from the said radiation sensitive resin composition, it is excellent in low dielectric property, adhesiveness, and the light transmittance in a laminated state. Note that a method for forming the insulating film is not particularly limited, but an insulating film forming method described below is preferably applied.

  Note that the insulating film may be a non-patterned flat film. Such an insulating film can be obtained through a step of forming a coating film on the substrate using the radiation-sensitive resin composition, a step of irradiating the entire surface of the coating film, and a step of heating the coating film. . Each of these steps can be performed with reference to step (1), step (2), and step (4) described later.

<Method for forming insulating film>
The method for forming an insulating film of the present invention includes:
(1) forming a coating film on the substrate;
(2) A step of irradiating at least a part of the coating film with radiation,
(3) The process of developing the coating film irradiated with radiation, and (4) The process of heating the developed coating film is provided.

[Step (1)]
In the step (1), a coating film is formed by applying a solution of the radiation-sensitive resin composition to the substrate surface and removing the solvent, preferably by pre-baking. Examples of the substrate used in the step (1) include a glass substrate, a silicon wafer, a plastic substrate, and a substrate on which various metals are formed. Examples of the plastic substrate include a substrate mainly composed of a plastic such as polyethylene terephthalate (PET), polybutylene terephthalate, polyethersulfone, polycarbonate, and polyimide.

  As a coating method of the radiation sensitive resin composition, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method, or the like may be adopted. Can do. Among these coating methods, spin coating, bar coating, and slit die coating are preferable. The pre-baking conditions vary depending on the types and contents of the components contained in the radiation-sensitive resin composition, but may be, for example, 60 ° C. or higher and 100 ° C. or lower for 30 seconds to 10 minutes. The film thickness of the coating film is preferably 0.1 μm as the lower limit after pre-baking. Moreover, as this upper limit, 8 micrometers is preferable, 6 micrometers is more preferable, and 4 micrometers is further more preferable.

[(2) Process]
In step (2), the coating film formed in step (1) is irradiated with radiation through a mask having a predetermined pattern. Examples of radiation at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.

Examples of ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet light include a KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam. Among these radiations, ultraviolet rays are preferable, and among the ultraviolet rays, radiation containing g-line and / or i-line is particularly preferable. The exposure dose is preferably, for example, 100 J / m ² or more and 10,000 J / m ² or less.

[Step (3)]
In the step (3), the coating film irradiated with the radiation in the step (2) is developed to remove the irradiated portion, and a desired pattern can be formed. As the developer used for the development treatment, an alkaline aqueous solution (alkaline developer) can be used. Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3, 0] -5-nonane and the like. As the developer, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution, or a solution containing a small amount of various organic solvents that dissolve the radiation-sensitive resin composition. Can be used. Moreover, you may use an organic solvent as a developing solution. Furthermore, as a developing method, for example, a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time varies depending on the composition of the radiation-sensitive resin composition, but can be, for example, 30 seconds or longer and 120 seconds or shorter.

After the step (3), the patterned coating film is rinsed with running water, and subsequently irradiated with a high-pressure mercury lamp or the like (post-exposure) to remain in the coating film [ B] It is preferable to perform a decomposition treatment of the radiation-sensitive compound. The exposure amount in the post-exposure is preferably about 2,000 J / m ² or more and 5,000 J / m ² or less.

[Step (4)]
In step (4), the coating film is heated and baked (post-baked) by using a heating device such as a hot plate or oven for baking the coating film developed in step (3). Curing is performed. Moreover, as a minimum of the calcination temperature in a process (4), 120 degreeC is preferable. On the other hand, as this upper limit, 200 degreeC is preferable, 180 degreeC is more preferable, and 150 degreeC is further more preferable. The firing time varies depending on the type of heating device, but for example, 5 to 40 minutes when heat treatment is performed on a hot plate, and 30 to 80 minutes when heat treatment is performed in an oven. be able to. Particularly preferably, it is 30 minutes or less when heat treatment is performed on a hot plate, and 60 minutes or less when heat treatment is performed in an oven.

  According to the manufacturing method, since the pattern is formed by exposure, development and heating using the radiation sensitivity of the radiation sensitive resin composition, a fine and elaborate pattern can be easily formed.

<Display element>
The display element of the present invention includes the insulating film. That is, the insulating film can be suitably used for a display element. Examples of the display element include a liquid crystal display element and an organic EL element. Examples of such an insulating film for a display element include an interlayer insulating film, a protective film, and a planarizing film.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)>
Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions. The molecular weight distribution (Mw / Mn) was calculated from the obtained Mw and Mn.

Apparatus: GPC-101 (Showa Denko)
GPC column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined (Shimadzu GC)
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

  The chemical formula of the monomer used in the synthesis example is shown below. Monomers represented by formulas (1-1) to (1-13) are monomers (1), and monomers represented by formulas (2-1) to (2-11) are monomers. (2) The monomer represented by the formulas (3-1) to (3-3) is the monomer (3).

<[A] Synthesis of polymer>
[Synthesis Example 1] Synthesis of Polymer (A-1) In a flask equipped with a condenser, a Dean Stark and a stirrer, 1.1 equivalents of the compound represented by the formula (1-1) as the monomer (1) , 1 equivalent of the compound represented by the formula (2-1) as the monomer (2), 2.2 equivalent of potassium carbonate as the base (alkali metal compound), 100 equivalents of N, N-dimethylacetamide as the solvent, and 25 equivalents of toluene were added. Each equivalent is a molar ratio based on the number of moles of all hydroxyl groups and mercapto groups substituted on the aromatic ring in monomer (2) (1 equivalent). Vacuuming and nitrogen replacement were repeated to remove water in the flask. Thereafter, the reaction system was pressurized with nitrogen, and the temperature of the solution was raised to 130 ° C. while gently stirring. A solution containing the polymer (A-1) was obtained by polymerization while maintaining this temperature for 4 hours. The obtained polymer solution was filtered, and the solid content was washed with N, N-dimethylacetamide. Then, the solution was recovered, and an ion exchange resin was added to this solution, followed by stirring for 4 hours and filtration. The obtained resin was reprecipitated with methanol to obtain the desired resin. Mw of the polymer (A-1) was 10,000, and the molecular weight distribution (Mw / Mn) was 2.1.

[Synthesis Example 2] Synthesis of Polymer (A-2) 1.7 equivalents of a compound represented by Formula (1-1) as a monomer (1) in a flask equipped with a condenser, a Dean Stark and a stirrer , 0.5 equivalent of the compound represented by the formula (2-1) as the monomer (2) and 0.5 equivalent of the compound represented by the formula (2-7), and potassium carbonate as the base (alkali metal compound) 2.2 equivalents were charged, and 100 equivalents of N, N-dimethylacetamide and 25 equivalents of toluene were added as a solvent. Vacuuming and nitrogen replacement were repeated to remove water in the flask. Thereafter, the reaction system was pressurized with nitrogen, and the temperature of the solution was raised to 130 ° C. while gently stirring. A solution containing the polymer (A-2) was obtained by polymerization while maintaining this temperature for 4 hours. An ion exchange resin was added to the resulting polymer solution, and the mixture was stirred for 4 hours and filtered. The polymer solution was filtered, the solid content was washed with N, N-dimethylacetamide, the solution was recovered, and the resulting solution was reprecipitated with water to obtain the desired resin. Mw of the polymer (A-2) was 12,000, and the molecular weight distribution (Mw / Mn) was 2.5.

[Synthesis Example 3] Synthesis of Polymer (A-3) 1.7 equivalents of a compound represented by Formula (1-1) as a monomer (1) in a flask equipped with a condenser, a Dean Stark and a stirrer Monomer (2) 0.5 equivalent of the compound represented by formula (2-1) and 0.5 equivalent of the compound represented by formula (2-7), monomer (3) as formula (3- 0.09 equivalent of the compound represented by 1) and 2.2 equivalent of potassium carbonate as a base (alkali metal compound) were charged, and 100 equivalent of N, N-dimethylacetamide and 25 equivalent of toluene were added as a solvent. Vacuuming and nitrogen replacement were repeated to remove water in the flask. Thereafter, the reaction system was pressurized with nitrogen, and the temperature of the solution was raised to 130 ° C. while gently stirring. A solution containing the polymer (A-3) was obtained by polymerization while maintaining this temperature for 4 hours. An ion exchange resin was added to the resulting polymer solution, and the mixture was stirred for 4 hours and filtered. The polymer solution was filtered, the solid content was washed with N, N-dimethylacetamide, the solution was recovered, and the resulting solution was reprecipitated with water to obtain the desired resin. Mw of the polymer (A-3) was 12,500, and the molecular weight distribution (Mw / Mn) was 2.8.

[Synthesis Examples 4 to 48] Synthesis of Polymers (A-4) to (A-46) Synthesis Example 1 except that monomers of the types and amounts shown in Table 1 were used. Polymers (A-4) to (A-46) were synthesized in the same manner. Mw and molecular weight distribution of the polymers (A-4) to (A-46) were the same as those of the polymer (A-1).

[Comparative Synthesis Example 1] Synthesis of polymer (a-1) In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and diethylene glycol methyl ethyl ether 220 The mass part was charged. Next, 60 parts by mass of styrene, 18 parts by mass of methacrylic acid, and 22 parts by mass of glycidyl methacrylate were charged, purged with nitrogen, and the temperature of the solution was raised to 70 ° C. while gently stirring. A polymer solution containing the copolymer (a-1) was obtained by polymerization while maintaining this temperature for 4 hours. The solid content concentration of this polymer solution was 30.4% by mass, the Mw of the copolymer (a-1) was 8,000, and the molecular weight distribution (Mw / Mn) was 2.3.

[Comparative Synthesis Example 2] Synthesis of polymer (a-2) In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and diethylene glycol methyl ethyl ether 220 were used. The mass part was charged. Next, 60 parts by mass of styrene, 15 parts by mass of methacrylic acid, 20 parts by mass of glycidyl methacrylate, and 5 parts by mass of methyl methacrylate were charged, and the temperature of the solution was raised to 70 ° C. while gently replacing the nitrogen. A polymer solution containing the polymer (a-2) was obtained by polymerization while maintaining this temperature for 4 hours. The solid content concentration of the polymer solution was 30.4% by mass, the Mw of the polymer (a-2) was 8,000, and the molecular weight distribution (Mw / Mn) was 2.3.

[Comparative Synthesis Example 3] Synthesis of Polymer (a-3) In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and diethylene glycol methyl ethyl ether 220 were used. The mass part was charged. Next, 60 parts by mass of styrene, 15 parts by mass of methacrylic acid, 20 parts by mass of glycidyl methacrylate, and 5 parts by mass of tricyclodecyl methacrylate were charged, and the temperature of the solution was increased to 70 ° C. while gently stirring. A polymer solution containing the polymer (a-3) was obtained by polymerization while maintaining this temperature for 4 hours. The solid content concentration of this polymer solution was 30.4% by mass, the Mw of the polymer (a-3) was 8,000, and the molecular weight distribution (Mw / Mn) was 2.3.

[Comparative Synthesis Example 4] Synthesis of polymer (a-4) In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and diethylene glycol methyl ethyl ether 220 The mass part was charged. Next, 30 parts by mass of styrene, 18 parts by mass of methacrylic acid, 22 parts by mass of glycidyl methacrylate, and 30 parts by mass of tricyclodecyl methacrylate were charged, and the temperature of the solution was increased to 70 ° C. while gently stirring. A polymer solution containing the polymer (a-4) was obtained by polymerization while maintaining this temperature for 4 hours. The solid content concentration of this polymer solution was 30.4% by mass, the Mw of the polymer (a-4) was 8,000, and the molecular weight distribution (Mw / Mn) was 2.3.

<Preparation of radiation-sensitive resin composition>
[A] polymer and [B] radiation sensitive compound used for preparation of the radiation sensitive resin composition of an Example and a comparative example are shown below.
[A] Polymers A-1 to A-46, a-1 to a-5: Polymers (A-1) to Polymers (A-46) synthesized in Synthesis Examples 1 to 48 and Comparative Synthesis Examples 1 to 5 ) And polymer (a-1) to polymer (a-4)
[B] 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-sulfonic acid chloride (2.0 mol) B-2: 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinonediazide-5-sulfone Condensate with acid chloride (2.0 mol)

[Example 1]
An amount corresponding to 100 parts by mass (solid content) of the polymer (A-1), [B] (B-1) 30 parts by mass as a radiation sensitive compound, and γ-glycol as an adhesion assistant Sidoxypropyltrimethoxysilane 5 parts by mass, fluorosurfactant (“FTX-218” manufactured by Neos) 0.5 part by mass, antioxidant (IRGANOX1010 manufactured by BASF) ) 0.1 part by mass was mixed. Furthermore, after adding diethylene glycol methyl ethyl ether as a solvent so that a solid content concentration might be 30 mass%, the radiation sensitive resin composition was prepared by filtering with a membrane filter with the hole diameter of 0.2 micrometer.

[Examples 2-48, Comparative Examples 1-5]
The radiation sensitive resins of Examples 2 to 48 and Comparative Examples 1 to 5 were the same as Example 1 except that the types and amounts of polymers and radiation sensitive compounds shown in Table 2 and Table 3 below were used. A composition was prepared.

<Evaluation>
The following evaluation was performed about the prepared radiation sensitive resin composition and the cured | curing material formed below. The results are shown in Tables 2 and 3.

[Storage stability]
The obtained radiation-sensitive resin composition was left in an oven at 40 ° C. for 1 week, and the viscosity before and after heating was measured to determine the rate of change in viscosity (%). At this time, the viscosity change rate was regarded as storage stability, and the storage stability was evaluated according to the following criteria. A: Viscosity change rate less than 5%, B: Viscosity change rate 5-10%, C: Viscosity change rate 10-15%, D: Viscosity change rate 15% or more. B and higher were judged to have good storage stability. The viscosity was measured at 25 ° C. using an E-type viscometer (VISCONIC ELD.R, Toki Sangyo Co., Ltd.).

[sensitivity]
After applying any of the radiation-sensitive resin compositions prepared as examples and comparative examples on a silicon substrate using a spinner, pre-baking on a hot plate at 90 ° C. for 2 minutes and an average film thickness of 3.0 μm The coating film was formed. The obtained coating film was irradiated with a predetermined amount of ultraviolet rays by a mercury lamp through a pattern mask having a line and space pattern having a width of 10 μm. Next, using a developer composed of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development processing was carried out at 25 ° C. for 60 seconds, followed by washing with ultrapure water for 1 minute. At this time, the minimum ultraviolet irradiation amount capable of forming a line and space pattern having a width of 10 μm was measured. When this value was less than 500 J / m ² , it was judged that the sensitivity was good.
In addition, "-" in a table | surface shows that this evaluation is not performed.

[Development adhesion]
After applying any of the radiation-sensitive resin compositions prepared as examples and comparative examples on a silicon substrate using a spinner, pre-baking on a hot plate at 90 ° C. for 2 minutes and an average film thickness of 3.0 μm The coating film was formed. The obtained coating film was irradiated with 500 J / m ² of ultraviolet rays by a mercury lamp through a pattern mask having a line and space pattern having a width of 10 μm. Next, using a developer composed of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development processing was carried out at 25 ° C. for 60 seconds, followed by washing with ultrapure water for 1 minute. At this time, the presence or absence of peeling of the 10 μm-wide line and space pattern was observed with a microscope, and the development adhesion was evaluated according to the following criteria. A: No peeling, B: Slight peeling, C: Partial peeling, D: Whole peeling. B or higher was judged to have good adhesion.

[Board adhesion]
“JIS K-5400-1990, 8.5.3 Adhesive cross-cut tape method” was performed to determine the number of cross-cuts remaining in 100 cross-cuts, and the substrate adhesion of the film was evaluated. When the number of grids remaining in 100 grids is 80 or less, the substrate adhesion is poor (B), and when more than 80 and 95 or less, the substrate adhesion is good (A), more than 95 In this case, the substrate adhesion was judged to be particularly good (AA).

[Chemical resistance (solvent resistance)]
After applying any of the radiation-sensitive resin compositions prepared as examples and comparative examples on a silicon substrate using a spinner, pre-baking on a hot plate at 90 ° C. for 2 minutes and an average film thickness of 3.0 μm The coating film was formed. The obtained coating film was irradiated with ultraviolet rays with a mercury lamp so that the cumulative irradiation amount was 3,000 J / m ² . Next, this silicon substrate was heated at 150 ° C. for 30 minutes for Examples 1-48 and Comparative Examples 1-2 on a hot plate. Comparative Examples 3 and 4 were heated at 150 ° C. for 60 minutes, and Comparative Example 5 was heated at 230 ° C. for 30 minutes. The average film thickness (T1) of the obtained cured film was measured. And after immersing the silicon substrate in which this cured film was formed in dimethyl sulfoxide temperature-controlled at 70 degreeC for 20 minutes, the average film thickness (t1) of the said cured film was measured, and film thickness change rate was calculated | required Calculated from the following formula, this was defined as chemical resistance.
Film thickness change rate = {(t1-T1) / T1} × 100 (%)
When the absolute value of this value was 6% or less, the chemical resistance was good, and when it was less than 5%, the chemical resistance was judged to be excellent.

[Heat-resistant]
After applying any of the radiation-sensitive resin compositions prepared as examples and comparative examples on a silicon substrate using a spinner, pre-baking on a hot plate at 90 ° C. for 2 minutes and an average film thickness of 3.0 μm The coating film was formed. The obtained coating film was irradiated with ultraviolet rays with a mercury lamp so that the cumulative irradiation amount was 3,000 J / m ² . Next, this silicon substrate was heated on a hot plate at 200 ° C. for 60 minutes. The 5% thermal weight loss temperature of the obtained cured film was measured under air using “TG / DTA220U” manufactured by SII Nanotechnology. The heat resistance was judged to be excellent when the 5% mass reduction temperature was 300 ° C. or higher.

[Transmissivity]
After applying any of the radiation-sensitive resin compositions prepared as examples and comparative examples on a glass substrate using a spinner, pre-baking on a hot plate at 90 ° C. for 2 minutes and an average film thickness of 3.0 μm The coating film was formed. The obtained coating film was irradiated with ultraviolet rays with 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 200 ° C. for 60 minutes. The transmittance of the obtained cured film was measured with an ultraviolet-visible spectrophotometer (“V-630” manufactured by JASCO Corporation). It was judged that the transparency was excellent when the transmittance of 400 nm light was 94% or more, and the transparency was particularly excellent when the transmittance was 95% or more.

[Laminated transmittance]
On the glass substrate, it laminated | stacked so that it might become a SiNx film | membrane (average film thickness 200nm) / cured film | membrane (average film thickness 3 micrometers) / ITO film | membrane (Indium Tin Oxide: average film thickness 50um). The cured film was prepared in the same procedure as the evaluation of the transmittance using any of the radiation-sensitive resin compositions prepared as examples and comparative examples. The transmittance from the back surface (glass substrate side) was measured with an ultraviolet-visible spectrophotometer (“V-630” manufactured by JASCO Corporation). When the transmittance of 400 nm light was 75% or more, it was judged that the transparency in the laminated state was excellent.

[Pencil hardness (surface hardness)]
About the board | substrate which has a cured film formed by evaluation of solvent resistance, the pencil hardness of the cured film was measured by 8.4.1 pencil scratch test of JIS-K-5400-1990, and this was made into surface hardness. When this value was 3H or more, the surface hardness as a cured film was good, and the radiation-sensitive resin composition used to form the cured film was judged to have sufficient curability.

[Relative permittivity]
After applying any of the radiation-sensitive resin compositions prepared as examples and comparative examples on a SUS substrate using a spinner, pre-baking on a hot plate at 90 ° C. for 2 minutes and an average film thickness of 3.0 μm The coating film was formed. Using an exposure machine (“MPA-600FA” manufactured by Canon Inc.), the resulting coating film was exposed so that the integrated dose was 9,000 J / m ^2, and this substrate was 150 ° C. in a clean oven. For 30 minutes to form a cured film on the SUS substrate. A dielectric constant measurement sample was prepared by forming a Pt / Pd electrode pattern on the cured film by vapor deposition. The substrate having this electrode pattern was measured for relative dielectric constant by the CV method at a frequency of 10 kHz using “HP16451B electrode” and “HP4284A precision LCR meter” manufactured by Yokogawa-Hewlett-Packard. When this value was 3.9 or less, it was judged that the low dielectric property (insulating property) was good.

[Refractive index (nD)]
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 with 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 200 ° C. for 60 minutes. The refractive index of the obtained cured film was measured by “Prism Coupler Model 2010” manufactured by Metricon. The refractive index was measured at three wavelengths of 408 nm, 633 nm, and 828 nm, and the refractive index (nD) at the D line (589 nm) was determined using the Cauchy equation. The refractive index of F line (486 nm) and C line (656 nm) was determined in the same manner, and the Abbe number (νD) was calculated. The refractive index (nD) was evaluated as “A” when the refractive index was 1.640 or more, and “B” when the refractive index was less than 1.640.

  As is clear from the results of Tables 2 and 3, the radiation-sensitive resin compositions and cured films (insulating films) of Examples 1 to 48 have storage stability, low dielectric properties, adhesion, and light in a laminated state. It was excellent in permeability. In addition, other evaluation items were sufficiently high.

  The radiation sensitive resin composition of the present invention can be suitably used as a material for forming an insulating film for a display element.

Claims (10)

The radiation sensitive resin composition containing the polymer which has a structural unit represented by following formula (1), and a radiation sensitive compound.

(In Formula (1), W ¹ is a divalent aromatic ring group having at least an electron-withdrawing group, or a plurality of divalent aromatic ring groups which may have a substituent are electron-withdrawing linking groups. W ² is a divalent aromatic ring group which may have a substituent, or a plurality of divalent aromatic ring groups which may have a substituent. Is a divalent group formed by linking with a linking group, and Y ¹ and Y ² are each independently an oxygen atom or a sulfur atom.) The radiation-sensitive resin composition according to claim 1, wherein W ¹ in the formula (1) is represented by the following formula (2) or formula (3).

(In formula (2), X is an electron-withdrawing group. R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cyano group, a nitro group, a hydroxyl group, or a mercapto group. , A halogen atom, an acidic group or a group in which an acidic group is generated by a decomposition reaction, n ¹ is an integer of 0 to 3. When n ¹ is 2 or more, a plurality of R ¹ may be the same or different. .
In formula (3), Z is a carbonyl group or a sulfonyl group. R ² and R ³ are each independently a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a mercapto group, a halogen atom, an acidic group, or a decomposition reaction. Thus, an acidic group is generated. n ² and ^{n 3} are each independently an integer of 0 to 4. When n ² is 2 or more, the plurality of R ² may be the same or different. When n ³ is 2 or more, the plurality of R ³ may be the same or different. ) The radiation-sensitive resin composition according to claim 1 or ² , wherein W ² in the formula (1) is represented by the following formula (4), formula (5), or formula (6).

(In Formula (4), A is an oxygen atom, a sulfur atom, a sulfonyl group, or a divalent organic group that may have an acidic group or a group that generates an acidic group by a decomposition reaction. R ⁴ and R ⁵ independently represents a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a mercapto group, a halogen atom, an acidic group or an acidic group by a decomposition reaction. the .n ⁴ and ^{n 5} is caused group, each independently, for .n ⁴ is 2 or more is an integer of 0 to 4, a plurality of ^{R 4} is good .n ⁵ be the same or different 2 In the above case, the plurality of R ⁵ may be the same or different, and m ¹ and m ² are each independently 1 or 2.
In formula (5), R ⁶ is a single bond, an oxygen atom, a sulfur atom, a methylene group or an imino group. R ⁷ and R ⁸ are each independently a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a mercapto group, a halogen atom, an acidic group, or a decomposition reaction. Thus, an acidic group is generated. n ⁷ and n ⁸ are each independently an integer of 0 to 4. When n ⁷ is 2 or more, the plurality of R ⁷ may be the same or different. When n ⁸ is 2 or more, the plurality of R ⁸ may be the same or different.
In the formula (6), R ⁹ is acidic by a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a cyano group, a nitro group, a hydroxyl group, a mercapto group, a halogen atom, an acidic group, or a decomposition reaction. A group from which a group is formed. n ⁹ is an integer of 0 to 4. When n ⁹ is 2 or more, the plurality of R ⁹ may be the same or different. The radiation-sensitive resin composition according to claim 1, wherein at least one of W ¹ and W ² in the formula (1) has an acidic group or a group that generates an acidic group by a decomposition reaction. .   5. The acidic group or a group in which an acidic group is generated by a decomposition reaction is a sulfo group, a carboxy group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, or a group containing an ester bond derived from these groups. Radiation sensitive resin composition.   The radiation sensitive resin composition according to any one of claims 1 to 5, wherein the radiation sensitive compound is an acid generator, a polymerization initiator, or a combination thereof.   The radiation sensitive resin composition according to any one of claims 1 to 6, further comprising an antioxidant.   The insulating film formed from the radiation sensitive resin composition of any one of Claims 1-7. Forming a coating film on the substrate;
Irradiating at least a part of the coating film with radiation,
A method of forming an insulating film comprising: developing a coating film irradiated with the radiation; and heating the developed coating film,
The formation method of the insulating film which uses the radiation sensitive resin composition of any one of Claims 1-7 for formation of the said coating film.   A display element comprising the insulating film according to claim 8.