KR20200014679A - Radiation-sensitive composition and uses thereof - Google Patents

Abstract

The present invention relates to a radiation-sensitive composition having excellent storage stability and high PCD and PED margin. Provided is a radiation-sensitive composition capable of forming a hardening film having low relative permittivity. The radiation-sensitive composition includes: a polymer component (A) having, in the same or different polymers, a structural unit (I) derived from maleimide and a structural unit (II) containing a group represented by an equation (II-1); and a radiation-sensitive compound (B). R^1, R^2, and R^3 are each independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, an aryl group, a group in which a part or whole of hydrogen atoms included in the preceding groups is substituted with a substituent group, or -SiR^A_3. R^A are each independently a C1-C10 alkyl group, and Q^1 is an ester bond or a divalent group represented by -Ar^1-O-, wherein Ar^1 is an arylene group or a group in which a part or whole of hydrogen atoms included in the arylene group is substituted with a substituent group.

Description

Radiation-sensitive composition and its use {RADIATION-SENSITIVE COMPOSITION AND USES THEREOF}

The present invention relates to a radiation sensitive composition and its use.

The radiation sensitive composition is conventionally used for forming the cured film which has a pattern shape, such as an interlayer insulation film, a protective film, and a spacer, as a cured film which a display element has (for example, refer patent document 1).

Japanese Laid-Open Patent Publication No. 2012-159601

With high performance of the display element, since the display element requires a large amount of current, low dielectric properties are required for the cured film. In addition, from the viewpoint of workability at the time of forming a cured film, the radiation-sensitive composition has a small decrease in radiation sensitivity after storage and excellent storage stability, Post Coating Delay (PCD) margin and Post Exposure Delay (PED). A large margin is desired.

That is, an object of the present invention is to provide a radiation-sensitive composition which is excellent in storage stability and has a high radiation-sensitive composition having a high PCD and PED margin, and can form a cured film having a low relative dielectric constant.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to solve the said subject. As a result, it discovered that the said subject can be solved by the radiation sensitive composition which has the following structures, and came to complete this invention. This invention relates to the following [1]-[9], for example.

[1] A polymer component (A) having a structural unit (II) containing a structural unit (I) derived from maleimide and a group represented by the following formula (II-1) in the same or different polymer, and a radiation-sensitive compound A radiation sensitive composition containing (B).

[In formula (II-1), R <^1> , R <^2> and R <^3> are respectively independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, an aryl group, group in which one part or all part of the hydrogen atom which these groups have substituted by the substituent. Or -SiR ^A ₃ , R ^A is each independently an alkyl group having 1 to 10 carbon atoms, and Q ¹ is a divalent group represented by an ester bond or -Ar ¹ -O- (Ar ¹ is an arylene group, or Some or all of the hydrogen atoms of the arylene group are substituted with substituents.

[2] The structural unit, wherein the polymer component (A) contains a crosslinkable group in the same or different polymer as the polymer having at least one structural unit selected from the structural unit (I) and the structural unit (II). The radiation sensitive composition as described in said [1] which further has (III).

[3] The radiation-sensitive composition according to the above [2], wherein the crosslinkable group is at least one group selected from an oxiranyl group, an oxetanyl group, and a (meth) acryloyl group.

[4] The radiation of any of the above-mentioned [1] to [3], wherein R ¹ , R ^2, and R ³ are each independently a C1-C20 alkyl group in the group represented by the formula (II-1). Sex composition.

[5] The radiation sensitive compound according to any one of the above [1] to [4], wherein the radiation sensitive compound (B) is a radiation sensitive acid generator (B1) or a radiation sensitive base generator (B2). Composition.

[6] The radiation sensitive compound (B) according to any one of the above [1] to [4], wherein the radiation sensitive compound (B) is at least one radiation sensitive acid generator selected from an oxime sulfonate compound and a sulfonimide compound. Radiation-sensitive composition.

[7] A cured film formed of the radiation sensitive composition according to any one of [1] to [6].

[8] step [1] of forming a coating film of the radiation-sensitive composition according to any one of the above [1] to [6] on a substrate, a step of irradiating at least a portion of the coating film with radiation [2], and And a process [3] of developing the said coating film irradiated with radiation, and a process [4] of heating the developed said coating film.

[9] A display element comprising the cured film according to the above [7].

ADVANTAGE OF THE INVENTION According to this invention, the radiation sensitive composition which can form the cured film with low relative dielectric constant as a radiation sensitive composition excellent in storage stability and high in PCD and PED margin can be provided.

(Form to carry out invention)

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated.

Although the upper limit and the lower limit which are preferable in the content rate of each component etc. are described in this specification, respectively, the numerical range prescribed | regulated from any combination of the upper limit and the lower limit described shall also be described in this specification.

[Radiation Composition]

The radiation sensitive composition of this invention (it is also called "the composition of this invention" simply) contains the polymer component (A) and the radiation sensitive compound (B) demonstrated below.

<Polymer component (A)>

The polymer component (A) has a structural unit (II) including the structural unit (I) derived from maleimide and the group shown by Formula (II-1) mentioned later in the same or different polymer.

In addition, a polymer component (A) can have a structural unit (III) mentioned later in the same or different polymer as the polymer which has at least 1 sort (s) of structural unit chosen from a structural unit (I) and a structural unit (II). .

In addition, a polymer component (A) can have a structural unit (IV) mentioned later in the same or different polymer as the polymer which has at least 1 sort (s) of structural unit chosen from structural unit (I)-(III).

The detail of these structural units is demonstrated below.

Structural Unit (Ⅰ)

Structural unit (I) is a structural unit derived from maleimide. The structural unit derived from maleimide is a structural unit derived from unsubstituted maleimide shown by Formula (I-1).

By using the polymer component (A) which has a structural unit (I) with a structural unit (II), the coating film which consists of a composition of this invention becomes large in Post Coating Delay (PCD) margin and Post Exposure Delay (PED) margin. Here, PCD and PED margins are indicative of the manufacturing process, which means that the higher the productivity of the final product. On the other hand, in the case of the polymer component having structural unit (II) but no structural unit (I), PCD and PED margins are small. In addition, a polymer component (A) can improve the solubility to a developing solution or the heat resistance of the obtained cured film by having a structural unit (I). Moreover, the composition of this invention containing the polymer component (A) which has a structural unit (I) with a structural unit (II) is small in the fall of the radiation sensitivity after storage, and is excellent in storage stability.

Structural Unit (II)

Structural unit (II) contains the group shown by Formula (II-1).

In formula (II-1), each of R ¹ , R ² and R ³ independently represents a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, an aryl group, a group in which part or all of the hydrogen atoms of these groups are substituted with a substituent, Or -SiR ^A ₃ . R ^A is each independently an alkyl group having 1 to 10 carbon atoms. Q ¹ is an ester bond (-COO-) or a divalent group represented by -Ar ¹ -O- (Ar ¹ is an arylene group or a group in which part or all of hydrogen atoms of an arylene group are substituted with a substituent) . Here, the ester bond is bonded and -SiR ¹ R ² R ³ to ^{be, -COO-SiR 1 R 2 R} 3. In addition, the -Ar ¹ -O- is bonded with -SiR ¹ R ² R ³ to be -Ar ¹ -O-SiR ¹ R ² R ³ .

The structural unit (II) may be one type of structural unit or a plurality of types of structural units.

By action of a component such as an acid or a base generated from the radiation-sensitive compound (B) by irradiation with radiation, the group represented by the formula (II-1) is decomposed, that is, -SiR ¹ R ² R ³ dissociates, A carboxyl group or phenolic hydroxyl group is considered to generate | occur | produce. Here, -SiR ¹ R ² R ³ is an protecting group of a carboxyl group or a phenolic hydroxyl group as an acid or base dissociable group. Therefore, in the irradiation part of the coating film which consists of a composition of this invention, the group shown by Formula (II-1) decomposes | generates, a carboxyl group or a phenolic hydroxyl group is generated, and this part becomes soluble in a developing solution. Therefore, the composition of this invention can be used suitably as a positive radiation sensitive composition. By having a structural unit (II), a polymer component (A) can improve the solubility to a developing solution, or can improve heat resistance.

As an alkyl group in R <^1> , R <^2> and R <^3> , For example, linear alkyl groups, such as a methyl group, an ethyl group, n-propyl group, n-butyl group; And branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, t-butyl group and n-hexyl group. Carbon number of the said alkyl group becomes like this. Preferably it is 1-20, More preferably, it is 1-10. Examples of the alkyl group for R ^A include the groups exemplified above.

As alicyclic hydrocarbon group in R <^1> , R <^2> and R <^3> , For example, Monocyclic alicyclic hydrocarbon groups, such as a cyclopentyl group and a cyclohexyl group; Polycyclic alicyclic hydrocarbon groups, such as an adamantyl group, norbornyl group, and a tricyclo decanyl group, are mentioned. Carbon number of the said alicyclic hydrocarbon group becomes like this. Preferably it is 3-20.

As an aryl group in R <^1> , R <^2> and R <^3> , a phenyl group, a tolyl group, a dimethylphenyl group, a 2,4, 6- trimethylphenyl group, a naphthyl group is mentioned, for example. Carbon number of the said aryl group becomes like this. Preferably it is 6-20, More preferably, it is 6-10.

As an arylene group in Ar <^1> , a benzenediyl group, toluenediyl group, xylenediyl group, naphthalenediyl group is mentioned, for example. Carbon number of the said arylene group becomes like this. Preferably it is C6-C20, More preferably, it is 6-10.

As said substituent represented by description of R <^1> , R <^2> and R <^3> and Ar <^1> , it is an alkyl group, an alicyclic hydrocarbon group, an aryl group, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, a cyan, for example. Anger is mentioned.

It is preferable that R <^1> , R <^2> and R <^3> are respectively independently C1-C20 alkyl groups from a viewpoint of obtaining the said favorable dissociation property by the action of an acid or a base.

Examples of —SiR ¹ R ² R ³ include, for example, trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, diethylisopropylsilyl group, triisopropylsilyl group, dimethylhexylsilyl group and t-butyl A diphenyl silyl group, a dimethylphenyl silyl group, a triphenyl silyl group, and the tris (trimethyl silyl) silyl group are mentioned. Among these, trimethylsilyl group, triethylsilyl group, triisopropylsilyl group and t-butyldimethylsilyl group are preferable.

Structural unit (II) is a structural unit represented by Formula (II-2), for example, Preferably it is a structural unit represented by Formula (II-2-1) or Formula (II-2-2).

In formulas (II-2), (II-2-1) and (II-2-2), R ¹ to R ³ and Q ¹ are the same as the same symbols in formula (II-1), respectively. , R ⁴ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ^B is an alkyl group, an alicyclic hydrocarbon group, an aryl group, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group or a cyano group. n is an integer of 0-4. When R ^B is to be at least 2, even if each of the same may be different.

Structural Unit (Ⅲ)

The polymer component (A) has a structural unit (III) containing a crosslinkable group in the same or different polymer as the polymer having at least one structural unit selected from the structural unit (I) and the structural unit (II). desirable. Structural unit (III) can raise the hardening reactivity of the composition of this invention, and the heat resistance of the cured film obtained.

The structural unit (III) may be one type of structural unit or a plurality of types of structural units.

In this specification, a crosslinkable group means group which can form covalent bonds, for example by reacting groups of the same kind (for example, epoxy groups) under heating conditions. As a crosslinkable group, For example, epoxy groups, such as an oxiranyl group (1, 2- epoxy structure) and an oxetanyl group (1, 3- epoxy structure); Polymerizable carbon-carbon double bond-containing groups such as a (meth) acryloyl group and a vinyl group; A cyclic carbonate group and a methylol group are mentioned. Among these, an oxiranyl group, an oxetanyl group, and a (meth) acryloyl group are preferable, and an oxiranyl group and an oxetanyl group are more preferable.

Structural unit (III), Preferably it is represented by Formula (III-1).

In formula (III-1), R ⁵ is a single bond or an alkanediyl group. R ⁶ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. Q ² is formed by combining two or more selected from an oxygen atom, an ester bond, an amide bond, an arylene group, an alkanediyl group, or these (that is, an oxygen atom, an ester bond, an amide bond, an arylene group, an alkanediyl group) Qi. Examples of the combination of the above groups include, for example, an aryleneoxy group (-Ar ² -O-; Ar ² is an arylene group), an aralkyleneoxy group (-Ar ³ -RO-; Ar ³ is an arylene group, and R is an alkanedi Diary). As for Q <^2> , an ester bond is preferable. A is group containing the above-mentioned crosslinkable group or the said crosslinkable group.

Alkanediyl group in R <^5> and Q <^2> , Preferably it is a C1-C10, More preferably, it is a C1-C5 alkanediyl group, For example, methanediyl group, ethane-1,2-di Diary, propane-1,3-diyl group. The arylene group in Q ² is preferably an arylene group having 6 to 10 carbon atoms, and examples thereof include a benzenediyl group, a toluenediyl group, and a naphthalenediyl group. As a group containing a crosslinkable group, polycyclic alicyclic hydrocarbon groups, such as monocyclic alicyclic hydrocarbon groups, such as a cyclopentyl group and a cyclohexyl group, an adamantyl group, a norbornyl group, and a tricyclo decanyl group, are epoxidized, for example. Or cyclic carbonated rings.

As a structural unit containing an oxiranyl group, the structural unit represented by Formula (III-1)-(III-7), (III-18) is mentioned, for example. As a structural unit containing an oxetanyl group, the structural unit represented by Formula (III-8)-(III-11) is mentioned, for example. As a structural unit containing a cyclic carbonate group, the structural unit represented by following formula (III-12)-(III-16) is mentioned, for example. As a structural unit containing a methylol group, the structural unit represented by Formula (III-17) is mentioned, for example.

In formulas (III-1) to (III-18), R ⁶ is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

As a structural unit containing a (meth) acryloyl group, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and propylene glycol di ( Meta) acrylate, dipropylene di (meth) acrylate, tripropylene di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanedioldi (meth) acrylate, 1 Di (meth) acrylate compounds such as 6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and tripropylene glycol diacrylate; Tri (meth) acrylate compounds such as tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate; Tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate; Structural units derived from monomers, such as penta (meth) acrylate compounds, such as dipentaerythritol penta (meth) acrylate, are mentioned.

As a structural unit containing a (meth) acryloyl group or a vinyl group, for example, (meth) acrylic acid is reacted with the structural unit obtained by making an epoxy group containing unsaturated compound react with the structural unit containing a carboxyl group, and the structural unit containing an epoxy group. Structural unit obtained by making (meth) acrylic acid react with the structural unit obtained by making the structural unit obtained by making the (meth) acrylic acid ester or vinyl compound containing an isocyanate group react with the structural unit containing a hydroxyl group, and the structural unit containing an acid anhydride Also can be mentioned.

Structural Unit (IV)

The polymer component (A) is a structural unit (IV) other than the structural units (I) to (III) in the same or different polymer as the polymer having at least one structural unit selected from the structural units (I) to (III). You may have By structural unit (IV), the radiation sensitive characteristic of a polymer component (A), the dielectric constant of a cured film, and heat resistance can be improved.

The structural unit (IV) may be one type of structural unit or a plurality of types of structural units.

As a monomer which gives a structural unit (IV), the monomer which has acidic functional groups, such as a carboxyl group, an acid anhydride group, a phenolic hydroxyl group, and a fluorinated hydroxyalkyl group, is mentioned, for example. As a monomer which has an acidic functional group, For example, (meth) acrylic-acid hydroxyaryl esters, such as unsaturated carboxylic acid, its anhydride, and (meth) acrylic-acid hydroxyphenyl; And fluorinated hydroxyalkyl group-containing compounds such as 4- (1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl) styrene.

As unsaturated carbonic acid and its anhydride, For example, unsaturated monocarboxylic acids, such as (meth) acrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid; Unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, itaconic acid, citraconic acid, fumaric acid and mesaconic acid; Mono [(meth) acryloyloxyalkyl] ester of bivalent or more polyvalent carbonic acid, such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Can be mentioned.

As a monomer which gives a structural unit (IV), besides the monomer which has an acidic functional group, it is a (meth) acrylic-acid chain alkyl ester, an alicyclic containing (meth) acrylic acid ester, an aromatic ring containing (meth) acrylic acid ester, and hydroxyl group containing ( Meta) acrylic acid esters, alkoxy group-containing (meth) acrylic acid esters, N-substituted maleimide compounds, unsaturated dicarboxylic acid diesters, vinyl group-containing aromatic compounds, and other bicyclounsaturated compounds, tetrahydrofuran skeletons, And unsaturated compounds having a furan skeleton, tetrahydropyran skeleton or pyran skeleton, and other unsaturated compounds.

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

As an alicyclic containing (meth) acrylic acid ester, For example, (meth) acrylic-acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, (meth) acrylic-acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, (Meth) acrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl and isobornyl (meth) acrylic acid are mentioned.

As an aromatic ring containing (meth) acrylic acid ester, For example, (meth) acrylic-acid aryl ester, such as (meth) acrylic-acid phenyl; (Meth) acrylic-acid aralkyl ester, such as benzyl (meth) acrylic acid, is mentioned.

As the hydroxyl group-containing (meth) acrylic acid ester, for example, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 4-hydroxy butyl, (meth) acrylic acid 6-hydroxy (Meth) acrylic-acid hydroxyalkyl, such as oxyhexyl, is mentioned.

As an alkoxy-group containing (meth) acrylic acid ester, (meth) acrylic-acid alkoxy alkyl, such as (meth) acrylic-acid methoxymethyl, (meth) acrylic-ethoxymethyl, (meth) acrylic-acid ethoxyethyl, is mentioned, for example.

As an N-substituted maleimide compound, For example, N-alkyl-group substituted maleimide, such as N-methyl maleimide, N-ethyl maleimide, N-tert- butyl maleimide; N-cycloalkyl group substituted maleimide, such as N-cyclohexyl maleimide; N-aromatic ring containing group substituted maleimide, such as N-phenylmaleimide, N-benzyl maleimide, N- (9-acridinyl) maleimide, and N-hydroxyphenyl maleimide.

As unsaturated dicarboxylic acid diester, diethyl maleate, diethyl fumarate, diethyl itaconic acid is mentioned, for example.

As a vinyl group containing aromatic compound, styrene, (alpha) -methylstyrene, vinyltoluene, p-methoxy styrene, (alpha) -methyl- p-hydroxy styrene is mentioned, for example.

As another unsaturated compound, (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, and vinyl acetate are mentioned, for example.

Among these, as the structural unit (IV), an unsaturated carboxylic acid, a fluorinated hydroxyalkyl group-containing compound, a (meth) acrylic acid chain alkyl ester, an alicyclic-containing (meth) acrylic acid ester, an aromatic ring-containing (meth) acrylic acid ester, a hydroxyl group-containing (meth) ) At least one structural unit derived from an acrylic acid ester, an alkoxy group-containing (meth) acrylic acid ester, an N-substituted maleimide compound, or a vinyl group-containing aromatic compound is preferable.

<< content rate of each structural unit >>

The lower limit of the content ratio of the structural unit (I) to the total structural units in the polymer component (A) is preferably 3% by mass, more preferably 5% by mass, still more preferably 10% by mass; This upper limit becomes like this. Preferably it is 60 mass%, More preferably, it is 50 mass%, More preferably, it is 40 mass%. In such an aspect, the cured film obtained tends to have better relative dielectric constant and adhesion to the substrate while the composition of the present invention exhibits better radiation-sensitive characteristics and storage stability.

The lower limit of the content ratio of the structural unit (II) to the total structural units in the polymer component (A) is preferably 5% by mass, more preferably 10% by mass, still more preferably 15% by mass; This upper limit becomes like this. Preferably it is 75 mass%, More preferably, it is 65 mass%, More preferably, it is 55 mass%. In such an aspect, the cured film obtained tends to have a low dielectric constant while the composition of the present invention exhibits better radiation-sensitive characteristics, PCD margin and PED margin.

When a polymer component (A) has a structural unit (III), the lower limit of the content rate of the structural unit (III) with respect to all the structural units in a polymer component (A) becomes like this. Preferably it is 5 mass%, More preferably, Is 8% by mass, more preferably 10% by mass; This upper limit becomes like this. Preferably it is 60 mass%, More preferably, it is 50 mass%, More preferably, it is 40 mass%. In such an aspect, the cured film obtained tends to have better heat resistance and adhesion to the substrate while the composition of the present invention exhibits better PCD margin and PED margin.

When a polymer component (A) has a structural unit (IV), the lower limit of the content rate of the structural unit (IV) with respect to the whole structural unit in a polymer component (A) becomes like this. Preferably it is 3 mass%, More preferably, Is 5% by mass; This upper limit becomes like this. Preferably it is 70 mass%, More preferably, it is 50 mass%, More preferably, it is 40 mass%. If it is such an aspect, the composition of this invention will become more radiation sensitive.

The content rate of each structural unit of a polymer component (A) is a value in all the structural units which comprise a polymer component (A), and can be measured by NMR analysis, for example.

The polymer component (A) may be composed of, for example, one polymer or two or more polymers. When it consists of two or more types of polymers (blend material), if it can be confirmed that the whole blend has structural unit (I) and structural unit (II), for example by NMR analysis, a structural unit ( The polymer which does not have I) or (II) may be contained. The said blend is a mixture of the polymer which has a structural unit (I), and the polymer which has a structural unit (II), for example.

As for the polymer component (A), the copolymer which has a structural unit (I) and a structural unit (II) in the same polymer is preferable. When the polymer component (A) further has structural units (III) and / or (IV), the polymer component (A) is a structural unit (I), a structural unit (II) and a structural unit (III) in the same polymer. And / or copolymers having (IV) are preferred.

<< Synthesis method of a polymer component (A) >>

A polymer component (A) can be manufactured by superposing | polymerizing the monomer corresponding to each predetermined structural unit in a suitable polymerization solvent using radical polymerization initiators, such as an azo compound and an organic peroxide, for example. In addition, the compounding ratio of each monomer at the time of superposition | polymerization generally corresponds with the content rate of the corresponding structural unit in the polymer component (A) obtained. In addition, as a polymer component (A), you may synthesize | combine plural types of polymers, respectively, and may mix and use these plural types of polymers after that.

<< physical property of a polymer component (A), content rate >>

The lower limit of the weight average molecular weight (Mw) of polystyrene conversion by the gel permeation chromatography (GPC) method of a polymer component (A) becomes like this. Preferably it is 1,000, More preferably, it is 3,000; This upper limit becomes like this. Preferably it is 50,000, More preferably, it is 30,000. Moreover, the upper limit of ratio (Mw / Mn) of the number average molecular weight (Mn) of polystyrene conversion by Mw of a polymer component (A) by GPC method becomes like this. Preferably it is 3.0; Although the lower limit is not specifically limited, 1.1 may be sufficient.

The lower limit of the content rate of the polymer component (A) which occupies for the total solid of the composition of this invention becomes like this. Preferably it is 50 mass%, More preferably, it is 70 mass%, More preferably, it is 85 mass%; This upper limit becomes like this. Preferably it is 99 mass%, More preferably, it is 97 mass%. If it is such an aspect, a radiation sensitive characteristic and the agent characteristic (for example, radiation sensitivity, heat resistance) of the cured film obtained can be raised more effectively. In addition, all solid content means all components other than an organic solvent.

<Radiation Compound (B)>

The composition of this invention contains a radiation sensitive compound (B) with a polymer component (A). Therefore, the composition of this invention can form the film (henceforth a "patterned film") which has a pattern shape by radiation irradiation and a development process. As a radiation sensitive compound (B), a radiation sensitive acid generator (B1) and a radiation sensitive base generator (B2) are mentioned, for example.

In the composition of this invention, the lower limit of content of a radiation sensitive compound (B) with respect to 100 mass parts of polymer components (A) is 1 mass part normally, Preferably it is 2 mass parts, More preferably, it is 3 mass parts. Wealth; This upper limit is 30 mass parts normally, Preferably it is 20 mass parts, More preferably, it is 10 mass parts.

`` Radiation Acid Generator (B1) ''

A radiation sensitive acid generator (B1) (henceforth "component (B1)") is a compound which generate | occur | produces an acid by irradiation. Examples of the radiation include ultraviolet rays, far ultraviolet rays, visible rays, X rays, and electron beams.

By the irradiation process with respect to the coating film formed from the composition of this invention, an acid generate | occur | produces in a irradiation part based on component (B1), and the solubility of the polymer component (A) to alkaline developing solution changes based on the action | action of this acid.

Examples of the component (B1) include 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 a quinone diazide compound. Can be mentioned.

As a specific example of 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, and a carboxylic acid ester compound, For example, Unexamined-Japanese-Patent No. 2014-157252 And the compounds described in paragraphs [0078] to [0106], and these acid generators are described herein.

As a component (B1), at least 1 sort (s) of compound chosen from an oxime sulfonate compound and a sulfonimide compound is preferable from a radiation sensitivity viewpoint.

It is preferable that an oxime sulfonate compound is a compound which has an oxime sulfonate group shown by Formula (B1-1).

In formula (B1-1), R ^b1 is an alkyl group, an alicyclic containing hydrocarbon group, an aromatic ring containing hydrocarbon group, or a group in which part or all of the hydrogen atoms of these groups are substituted with a substituent.

As an alkyl group, a C1-C20, Preferably C1-C12 linear or branched alkyl group is preferable. As an alicyclic containing hydrocarbon group, the hydrocarbon group which has a C4-C12 alicyclic ring is preferable. As an aromatic ring containing hydrocarbon group, a C6-C20 aryl group is preferable and a phenyl group, a naphthyl group, a tolyl group, and a xylyl group are more preferable. As said substituent, a C1-C5 alkyl group, an alkoxy group, an oxo group, and a halogen atom are mentioned, for example.

Illustrative examples of the oxime sulfonate compound include, for example, (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino -5H-thiophene-2-ylidene)-(2-methylphenyl) acetonitrile, (5-camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl) acetonitrile, (5 -p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, 4-methylphenylsulfonyloxyimino-α- (4-methoxyphenyl) acetonitrile is mentioned.

As the sulfonimide compound, an N-sulfonyloxyimide compound is preferable, and for example, N- (trifluoromethylsulfonyloxy) succinimide, N- (campsulsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoro Romethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy ) Phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, (4-methylphenylsulfonyloxy) diphenylmaleimide, N- ( Trifluoromethylsulfonyloxy) naphthalimide is mentioned.

As a quinone diazide compound, a naphthoquinone diazide compound is mentioned, for example, The compound which has one or more phenolic hydroxyl groups, 1,2-naphthoquinone diazide sulfonic-acid halide, or 1,2-naphtho Condensate of quinonediazidesulfonic acid amide. As a specific example of a quinone diazide compound, 4,4'- dihydroxy diphenylmethane, 2,3,4,2 ', 4'- pentahydroxy benzophenone, a tris (4-hydroxyphenyl), for example. Methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl ] Benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [1- (4-hydroxyphenyl) -1-methylethyl] -1, Compound selected from 3-dihydroxybenzene and 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, and 1,2- And ester compounds of naphthoquinone diazide-4-sulfonic acid chloride or 1,2-naphthoquinone diazide-5-sulfonic acid chloride.

A component (B1) can be used individually or in combination of 2 or more types.

`` Radiation Base Generator (B2) ''

A radiation sensitive base generator (B2) (henceforth "component (B2)") is a compound which generate | occur | produces a base by irradiation. As the component (B2), for example, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, 2-nitrobenzylcyclohexyl carbamate, N- (2-nitrobenzyloxycarbonyl) pi Lolidine, bis [[(2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyl oxime, 4- (methylthio Benzoyl) -1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanol and hexaammine cobalt (III) tris (triphenylmethyl borate) are mentioned.

A component (B2) can be used individually or in combination of 2 or more types.

Antioxidant (C)

By containing antioxidant (C), the composition of this invention can suppress antipyretic deterioration of the polymer molecule in the cured film formed from the said composition, and can improve light resistance etc.

As antioxidant (C), the compound which has a hindered phenol structure, the compound which has a hindered amine structure, the compound which has an alkyl phosphite structure, and the compound which has a thioether structure are mentioned, for example.

Examples of the compound having a hindered phenol structure include tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and pentaerythritol tetrakis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate] and the hindered phenol-type antioxidant of Unexamined-Japanese-Patent No. 2008-208319. As a compound which has a hindered amine structure, the hindered amine light stabilizer of Unexamined-Japanese-Patent No. 2008-208319 is mentioned, for example. As a compound which has an alkyl phosphite structure, the phosphorus antioxidant of Unexamined-Japanese-Patent No. 2002-30264 is mentioned, for example. As a compound which has a thioether structure, di (tridecyl) 3,3'- thiodipropionate is mentioned, for example.

When using antioxidant (C), in the composition of this invention, the lower limit of content of antioxidant (C) is 0.1 mass part normally with respect to 100 mass parts of polymer components (A), Preferably it is 0.2 mass part. ego; This upper limit is 15 mass parts normally, Preferably it is 10 mass parts, More preferably, it is 5 mass parts. By making content of antioxidant (C) into the said range, antipyretic deterioration of the polymer molecule in the cured film formed from the composition of this invention can be suppressed more effectively.

<Acid Diffusion Control Agent (D)>

By containing the acid diffusion control agent (D), the composition of the present invention can appropriately control the diffusion length of the acid generated from the radiation-sensitive acid generator (B1) by irradiation with radiation, and improve the pattern developability. Can be. As an acid diffusion control agent (D), the acid diffusion control agent of Unexamined-Japanese-Patent No. 2011-232632 can be used, for example.

When using an acid diffusion control agent (D), in the composition of this invention, the lower limit of content of an acid diffusion control agent (D) is 0.001 mass part normally with respect to 100 mass parts of polymer components (A). Is 0.005 parts by mass; This upper limit is 2 mass parts normally, Preferably it is 1 mass part, More preferably, it is 0.2 mass part. By making content of an acid diffusion control agent (D) into the said range, pattern developability improves more.

<Other components (E)>

The composition of this invention can contain other component (E) in addition to the component mentioned above. As another component (E), a crosslinkable compound, an adhesion | attachment adjuvant, surfactant is mentioned, for example.

As a crosslinkable compound, the compound which has 2 or more of polymerizable carbon-carbon double bonds is mentioned, for example, Preferably it is a polyfunctional (meth) acrylate which has 2 or more of (meth) acryloyloxy groups. More preferably, it is polyfunctional (meth) acrylate which has 2-6 (meth) acryloyloxy groups.

As said polyfunctional (meth) acrylate, For example, alkylene glycol, such as ethylene glycol di (meth) acrylate, polyethyleneglycol di (meth) acrylate, and 1, 6- hexanediol di (meth) acrylate Or (meth) acrylic acid diesters of polyalkylene glycols; (Meth) acrylic acid diesters of mono or polycycloalkanedimethanol, such as cyclohexanedimethanol di (meth) acrylate and tricyclodecane dimethanol di (meth) acrylate; Of trivalent or higher polyhydric alcohols such as trimethylolpropanepoly (meth) acrylate, ditrimethylolpropanepoly (meth) acrylate, pentaerythritol poly (meth) acrylate, dipentaerythritol poly (meth) acrylate (Meth) acrylic acid polyester; AO modification or caprolactone of a trivalent or higher polyhydric alcohol such as pentaerythritol AO-modified poly (meth) acrylate, trimethylolpropane AO-modified poly (meth) acrylate, dipentaerythritol AO-modified poly (meth) acrylate (Meth) acrylic acid polyester of a modified product is mentioned. Poly here means di, tri, tetra, penta, hexa, or more. In the present specification, AO modification means alkylene oxide (AO) modification such as ethylene oxide (EO) modification and propylene oxide (PO) modification.

When using a crosslinkable compound, in the composition of this invention, with respect to 100 mass parts of polymer components (A), the lower limit of content of a crosslinkable compound is 1 mass part normally, Preferably it is 3 mass parts; This upper limit is 20 mass parts normally, Preferably it is 15 mass parts.

In the composition of this invention, 20 mass% may be preferable and the upper limit of the total content rate of components other than a polymer component (A) and a radiation sensitive compound (B) which occupies for total solid content may be preferable, and 15 mass% is preferable. In some cases, 10 mass% may be preferable.

<Organic solvent>

The composition of this invention can contain an organic solvent. As an organic solvent, the organic solvent which melt | dissolves or disperse | distributes each component which the composition of this invention contains uniformly and does not react with said each component is used.

Examples of the organic solvent include alcohol solvents such as isopropyl alcohol, butanol, isoamyl alcohol, octanol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and propylene glycol monomethyl ether; Ester solvents such as butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropionate methyl and 3-ethoxypropionate; Ether solvents such as ethylene glycol ethyl methyl ether and diethylene glycol methyl ethyl ether; Amide solvents such as N, N-dimethylacetoamide and N-methylpyrrolidone; Ketone solvents such as methyl isobutyl ketone and cyclohexanone; Aromatic hydrocarbon solvent, such as toluene and xylene, is mentioned.

An organic solvent can be used individually or in combination of 2 or more types.

The lower limit of the content rate of the organic solvent in the composition of this invention becomes like this. Preferably it is 10 mass%, More preferably, it is 20 mass%, More preferably, it is 30 mass%; This upper limit becomes like this. Preferably it is 95 mass%, More preferably, it is 90 mass%, More preferably, it is 85 mass%.

The composition of this invention demonstrated above can be used suitably as a formation material of the cured film which display elements, such as an interlayer insulation film, a protective film, and a spacer, especially an insulation film.

Cured Film and Its Manufacturing Method

The cured film of this invention is formed from the composition of this invention, and usually has a pattern shape. The shape of the pattern is not particularly limited as long as it has a concave-convex structure, and examples thereof include line and space patterns, dot patterns, hole patterns, and lattice patterns.

Although the film thickness of a cured film is not specifically limited, For example, it is 0.1-10 micrometers.

The manufacturing method of the cured film of this invention is a process [1] of forming the coating film of the composition of this invention on a board | substrate, the process [2] of irradiating at least one part of the said coating film, and the said coating film irradiated with radiation Developing step [3] and heating the developed coating film [4].

<Step [1]>

In process [1], the coating film which consists of a composition of this invention is formed on a board | substrate. Specifically, the composition in solution is applied to the surface of the substrate, and preferably, prebaking is performed to remove the organic solvent to form a coating film.

As a board | substrate, a glass substrate, a silicon substrate, a plastic substrate, and the board | substrate with which various metal thin films were formed in these surfaces are mentioned, for example. As a plastic substrate, the resin substrate which consists of plastics, such as a polyethylene terephthalate, a polybutylene terephthalate, a polyether sulfone, a polycarbonate, and a polyimide, is mentioned, for example. In order to improve the adhesiveness with a coating film, the board | substrate may be hydrophobized surface treatment, such as hexamethyldisilazane (HMDS) process.

As a coating method, the spray method, the roll coating method, the rotary coating method (spin coating method), the slit die coating method, the bar coating method, and the inkjet method are mentioned, for example.

As conditions of prebaking, although it changes also with the kind, content rate, etc. of each containing component in the composition of this invention, it can be made into about 30 second-10 minutes at 60-130 degreeC, for example. As for the film thickness of the coating film formed, 0.1-10 micrometers is preferable as a value after prebaking.

<Step [2]>

In step [2], at least part of the coating film is irradiated with radiation. Specifically, the coating film formed in step [1] is irradiated with radiation through a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, visible rays, X rays, and electron beams. As ultraviolet rays, ArF laser (193 nm), KrF laser (248 nm), g line (wavelength 436 nm), h line (wavelength 405 nm), i line | wire (wavelength 365 nm) are mentioned, for example. Among these radiations, ultraviolet rays are preferable, and among ultraviolet rays, radiation containing any one or more of g-rays, h-rays, and i-rays is more preferable. As an irradiation amount of radiation, 10-500mJ / cm <2> is preferable. For high sensitivity, the coating film may be wetted with a liquid such as water before irradiation.

<Process [3]>

In step [3], the coating film irradiated with radiation is developed. Specifically, the coating film irradiated with radiation in step [2] is developed using a developing solution to remove the radiation portion. For high sensitivity, the coating film may be wetted with a liquid such as water before development.

A developing solution is usually an alkaline developing solution, for example, the aqueous solution of a basic compound is mentioned. Examples of the basic compound 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 and 1,5-diazabicyclo [4.3.0] -5-nonane. The density | concentration of the basic compound in the said aqueous solution is 0.1-10 mass%, for example. You may use as aqueous solution the aqueous solution which added a suitable amount of water-soluble organic solvents, such as methanol and ethanol, and surfactant to the said aqueous solution, or the aqueous alkali solution containing the small amount of various organic solvents which can melt a radiation sensitive composition.

As a developing method, the puddle method, the dipping method, the oscillation dipping method, and the shower method are mentioned, for example. As image development temperature and image development time, it can be set as 20-30 degreeC and 30-120 second, respectively, for example.

Moreover, it is preferable to perform the rinse process by running water washing and / or the air drying process using compressed air or compressed nitrogen with respect to the film | membrane which has the obtained pattern shape after image development. Moreover, you may perform the decomposition | disassembly process of the radiation sensitive compound (B) which remain | survives in the said film by irradiating (post-exposure) the radiation by high pressure mercury lamp etc. to the whole surface.

<Process [4]>

In step [4], the developed coating film (film having a pattern shape) is heated. Thereby, hardening reaction of the component derived from a polymer component (A) can be accelerated | stimulated, and a cured film can be formed. As a heating method, the method of heating using heating apparatuses, such as an oven and a hotplate, is mentioned, for example. Heating temperature is 120-250 degreeC, for example. Although heating time changes with kinds of a heating apparatus, it is 5 to 40 minutes when heat processing on a hotplate, and 10 to 80 minutes when heat processing in oven.

As mentioned above, the target cured film, especially an insulating film, can be formed on a board | substrate.

[Display element]

The display element of this invention is equipped with the said cured film, Preferably the said insulating film. The said insulating film functions as a film | membrane which insulates the wiring in a display element. The display element of this invention can be manufactured using a well-known method. Since the display element of this invention is equipped with the said cured film, it can use suitably for display apparatuses, such as a liquid crystal display device, a light emitting diode (LED), and a TFT array.

The display apparatus which is one Embodiment is equipped with the said display element. As said display apparatus, a liquid crystal display device and an organic electroluminescent (EL) display apparatus are mentioned, for example.

(Example)

Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. Unless otherwise specified, "part" means "part by mass".

[Polymer component]

<Weight average molecular weight (Mw)>

The weight average molecular weight (Mw) of the polymer component was measured by the gel permeation chromatography (GPC) method under the following conditions.

Device: Showa Denko's `` GPC-101 ''

Column: Combines GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 from Shimadzu Corporation

Mobile phase: tetrahydrofuran

Column temperature: 40 ℃

Flow rate: 1.0mL / min

Sample concentration: 1.0 mass%

Sample injection volume: 100 μL

Detector: parallax refractometer

Standard material: monodisperse polystyrene

<Monomer>

The monomer used for the synthesis | combination of a polymer component is shown below.

<< Monomer which gives structural unit (I) >>

M-1 maleimide

<< Monomer which gives structural unit (II) >>

M-2 methacrylate trimethylsilyl

M-3 triethylsilyl methacrylate

M-4 'methacrylate triisopropylsilyl

M-5 'methacrylate t-butyldimethylsilyl

<< monomer which gives structural unit (III) >>

M-6 methacrylate glycidyl

M-7 3,4-Epoxycyclohexylmethyl methacrylate

M-8'3-Methylacryloyloxymethyl-3-ethyloxetane

Monomers Confer Structural Unit (IV)

M-9 'methacrylate 1-ethoxyethyl

M-10 styrene

M-11 cyclohexylmaleimide

M-12 benzyl methacrylate

M-13 2-hydroxyethyl methacrylate

M-14 methacrylic acid

M-15 4- (1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl) styrene

Synthesis Example 1 (Synthesis of Polymer Component (A-1))

In a flask equipped with a cooling tube and a stirrer, 5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of methyl-3-methoxypropionate were placed. In this flask, 10 parts of monomer (M-1): maleimide, 20 parts of monomer (M-2): trimethylsilyl methacrylate and 70 parts of monomer (M-9): 1-ethoxyethyl methacrylate After input and nitrogen replacement, stirring was slowly started. The polymer solution containing the polymer component (A-1) was obtained by raising the temperature of the solution in a flask to 70 degreeC, and hold | maintaining this temperature for 6 hours. Solid content concentration of this polymer solution was 32.5 mass%. The weight average molecular weight (Mw) of polystyrene conversion of the polymer component (A-1) was 12,000.

Synthesis Examples 2 to 20

The same procedures as in Synthesis Example 1 were conducted except that the components shown in Table 1 and the amounts used were used, and polymer components (A-2) to (A-18) and polymer components (cA-19) to (cA-) for comparison. 20) was prepared. Mw of these polymers is shown in Table 1.

[Preparation of radiation sensitive composition]

The radiation sensitive acid generator (B1), antioxidant (C), acid diffusion control agent (D), and other component (E) used for preparation of a radiation sensitive composition are shown below.

<Radiation Acid Generator (B1)>

B-1: (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile ("IRGACURE PAG 103" of BASF Corporation)

B-2: (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile ("IRGACURE PAG 121" of BASF Corporation)

B-3: 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile ("CGI-725" of BASF Corporation)

B-4: (5-camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile ("CGI-1380" of BASF Corporation)

B-5: 4-methylphenylsulfonyloxyimino-α- (4-methoxyphenyl) acetonitrile ("PAI-101" of Midorigaku Corporation)

B-6: N- (trifluoromethylsulfonyloxy) naphthalimide

Antioxidant (C)

C-1: tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate (ADEKA STUB AO-20 by ADEKA Corporation)

C-2: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (ADEKA STUB AO-60)

<Acid Diffusion Control Agent (D)>

D-1: 4-dimethylaminopyridine

D-2: 2-phenylbenzoimidazole

<Other components (E)>

E-1: dipentaerythritol penta / hexaacrylate ("aronix M-402" of Toagosei Co., Ltd.)

Example 1

(B-1) 3 as a radiation sensitive acid generator (B1) to the polymer solution (amount equivalent to (A-1) 100 parts (solid content)) containing (A-1) as a polymer component (A) 2 parts of (C-1) as an antioxidant (C) and 0.1 part of (D-1) as an acid diffusion control agent (D) were mixed, and propylene glycol monomethyl ether was added so that solid content concentration might be 20 mass%, , The radiation sensitive composition of Example 1 was prepared.

[Examples 2 to 22 and Comparative Examples 1 and 2]

Except having used the component of the kind and compounding quantity shown in Table 2, it carried out similarly to Example 1, and prepared the radiation sensitive composition of Examples 2-22 and Comparative Examples 1-2.

[evaluation]

The following evaluation was performed using the radiation sensitive composition of Examples 1-22 and Comparative Examples 1-2. The evaluation results are shown in Table 2.

<Radiation sensitivity>

After applying the radiation sensitive composition using a spinner on a silicon substrate treated with HMDS (1,1,1,3,3,3-hexamethyldisilazane) at 60 ° C. for 60 seconds, (1a) 90 Prebaking at 2 degreeC on a hotplate for 2 minute (s) forms a coating film with an average film thickness of 3.0 micrometers, (2a) Line and end is used for this coating film using the exposure machine ("MPA-600FA" (ghi line mixing) of Canon Corporation) Irradiation with a variable exposure dose through a mask having a pattern of space (60 μm: 6 μm to 10 μm: 1 μm), and (3a) tetramethylammonium at a concentration of 2.38% by mass to the coating film after irradiation. After developing by the puddle method at 23 degreeC in the hydroxide aqueous solution for 80 second, the flowing water wash | cleaned with ultrapure water for 1 minute, and after that, the patterned film was formed. At this time, the minimum exposure amount required in order for the exposure part corresponding to the 4 micrometer space of a line and space (40 micrometer: 4 micrometers) to melt | dissolve completely was investigated. When the value of this exposure amount was 150 mJ / cm <2> or less, radiation sensitivity was made into the outstanding thing, and when the value of this exposure amount exceeded 150mJ / cm <2>, the radiation sensitivity was evaluated as favorable.

<Dielectric constant>

After apply | coating the said radiation sensitive composition on the board | substrate made from SUS304 which grind | polished by the sisal buff (smooth buff) and smoothed the surface, after setting the reaching pressure to 100 Pa, removing a solvent under vacuum, it added further. Prebaked at 90 degreeC for 2 minutes, and formed the coating film of 3.0 micrometers of average film thicknesses. The obtained coating film was exposed by an exposure machine ("MPA-600FA made by Canon") so as to have an integrated irradiation amount of 9,000 J / m 2, and the substrate having the coated film after exposure was heated at 220 ° C. for 1 hour in a clean oven. An insulating film was formed in the. The Pt / Pd electrode pattern was formed on this insulating film by the vapor deposition method, and the sample for dielectric constant measurement was produced. About the board | substrate which has this electrode pattern, the dielectric constant was measured by CV method at the frequency of 10 kHz using the HP16451B electrode by the Yokogawa Hewlett-Packard company, and the HP4284A fresh LCR meter. When this value was 3.5 or less, "A" and the case exceeding 3.5 and the case below 3.9 "B" and the case exceeding 3.9 were determined as "C". In the case of A or B, the relative dielectric constant was good, and in the case of C, the relative dielectric constant was evaluated as poor.

<Evaluation of PCD and PED Margin>

Evaluation of PCD margin and PED margin was performed similarly to said <radiation sensitivity>. In the case of post coating delay (PCD) margin evaluation, after (1a), before (2a), and after PED (Post Exposure Delay) margin evaluation, after (2a), Before, the process of leaving the said coating film for 20 minutes at room temperature was added. At this time, the minimum exposure amount required in order for the exposure part corresponding to the 4 micrometer space of a line and space (40 micrometer: 4 micrometers) to melt | dissolve completely was investigated. Compare this measured value with the measured value of <radiation sensitivity>, and the case where the increase rate of minimum exposure amount is less than 10% is "A", and the case where it is 10% or more and less than 20% is "B" and the case where 20% or more is "C". Judging. In the case of A or B, the PCD and PED margins can be evaluated as good, and in the case of C, the PCD and PED margins can be evaluated as defective.

<Heat Resistance of Curing Film>

After forming a coating film similarly to the said evaluation of <radiation sensitivity>, the said coating film was heated for 30 minutes using the oven heated at 230 degreeC, and the cured film was formed. When the cured film was heated at 10 ° C / min using a thermogravimetric measuring device (EXSTAR TG / DTA7300 manufactured by SII Nanotechnology, Inc.) under a nitrogen atmosphere, the case where the film thickness change rate was less than 5% was "A". When the thickness change rate is 5% or more and less than 10%, "B" and the case where the film thickness change rate is 10% or more are called "C", and heat resistance is good in the case of A or B, and heat resistance is bad in the case of C did. The film thickness was measured at 25 degreeC using the optical interference type film thickness measuring apparatus ("Lamda Ace VM-1010" of Dainippon Screen Corporation).

<Evaluation of Preservation Stability>

The prepared radiation sensitive composition was enclosed in the light-shielding and airtight container. After 7 days had elapsed at 25 ° C, the container was opened, the <radiation sensitivity> was measured, and the increase rate of the minimum exposure amount before and after storage for 7 days was calculated. The case where this value was less than 5% was determined as "C" and the case where it was "B" and the case where it was 20% or more was "C" when it was "A" and 5% or more and less than 20%. In the case of A or B, the storage stability was good, and in the case of C, the storage stability was evaluated as poor.

Claims (9)

Polymer component (A) which has structural unit (II) containing the structural unit (I) derived from maleimide, and group shown by following formula (II-1) in the same or different polymer, and
Radiation-sensitive compound (B)
A radiation sensitive composition containing:

[In formula (II-1), R <^1> , R <^2> and R <^3> are respectively independently a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, an aryl group, group in which one part or all part of the hydrogen atom which these groups have substituted by the substituent. Or -SiR ^A ₃ , R ^A is each independently an alkyl group having 1 to 10 carbon atoms, and Q ¹ is a divalent group represented by an ester bond or -Ar ¹ -O- (Ar ¹ is an arylene group, or Some or all of the hydrogen atoms of the arylene group are substituted with substituents. The method of claim 1,
Structural unit (III) in which the said polymer component (A) contains a crosslinkable group in the same or different polymer as the polymer which has at least 1 sort (s) of structural unit chosen from the said structural unit (I) and the said structural unit (II). A radiation sensitive composition further having. The method of claim 2,
The radiation-sensitive composition in which at least 1 sort (s) of said crosslinkable group is chosen from an oxiranyl group, an oxetanyl group, and a (meth) acryloyl group. The method of claim 1,
In the group represented by the formula (II-1), each of R ¹ , R ^2, and R ³ independently represents a C 1-20 alkyl group. The method of claim 1,
The radiation sensitive composition whose said radiation sensitive compound (B) is a radiation sensitive acid generator (B1) or a radiation sensitive base generator (B2). The method of claim 1,
A radiation sensitive composition, wherein said radiation sensitive compound (B) is at least one radiation sensitive acid generator selected from an oxime sulfonate compound and a sulfonimide compound. The cured film formed from the radiation sensitive composition in any one of Claims 1-6. Step [1] of forming the coating film of the radiation sensitive composition of any one of Claims 1-6 on a board | substrate,
Irradiating at least a portion of the coating film with radiation [2];
Developing the coating film irradiated with radiation [3];
Heating the developed coating film [4]
The manufacturing method of the cured film which has. The display element provided with the cured film of Claim 7.