JP2017181928A - Positive type radiation-sensitive resin composition, interlayer insulation film, method for forming interlayer insulation film, semiconductor element and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type radiation-sensitive resin composition excellent in sensitivity and resolution and capable of providing a cured film excellent in low dielectric property, transparency and heat resistance, an interlayer insulation film using the positive type radiation-sensitive resin composition, a formation method therefor, a semiconductor element and a display element.SOLUTION: There is provided a positive type radiation-sensitive resin composition containing a polymer component containing a first polymer containing a structural unit having a group represented by the formula (1-1) or the formula (1-2) and a radiation-sensitive compound. In the formulae (1-1) and (1-2), at least one of R, Rand Ris an alkoxy group having 1 to 6 carbon atoms or are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms or a phenyl group.SELECTED DRAWING: None

Description

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

  Generally, a cured film such as an interlayer insulating film, a spacer, a protective film, and a color filter coloring pattern is used for a display element such as a liquid crystal display element. The cured film such as the interlayer insulating film is required to have high hardness, low dielectric constant, and excellent transparency and heat resistance. As a material for forming such a cured film, a radiation-sensitive resin composition is widely used because the number of steps for forming a pattern is small and a high surface hardness is obtained.

  As a radiation sensitive resin composition for forming a cured film of a display element, for example, a radiation sensitive resin composition containing a copolymer containing a carboxy group and an epoxy group is known (Japanese Patent Laid-Open No. 2001-354822). reference). In such a radiation sensitive resin composition, it is comprised so that the surface hardness as a cured film may be obtained when a carboxy group and an epoxy group react. In addition, a radiation-sensitive resin composition using a copolymer obtained by further copolymerizing a silane monomer and a quinonediazide compound which is a kind of acid generator has been developed (see JP-A-2006-209112). ).

  These radiation-sensitive resin compositions have room for improvement in sensitivity and resolution. For example, when a copolymer obtained by copolymerizing the above-mentioned silane monomer and an acid generator are used, a siloxane bond is generated by a hydrolysis condensation reaction using an acid generated from the acid generator as a catalyst. In some cases, a positive pattern cannot be formed.

JP 2001-354822 A JP 2006-209112 A

  The present invention has been made based on the circumstances as described above, and its object is to provide a positive-type radiation-sensitive radiation that can provide a cured film excellent in sensitivity and resolution, and excellent in low dielectric properties, transparency, and heat resistance. It is providing the insulating resin composition, the interlayer insulation film using this positive radiation sensitive resin composition, its formation method, a semiconductor element, and a display element.

（式（１−１）中、Ｒ^１、Ｒ^２及びＲ^３は、それぞれ独立して、水素原子、ハロゲン原子、ヒドロキシ基、炭素数１〜１２のアルキル基、フェニル基、又は炭素数１〜６のアルコキシ基である。但し、Ｒ^１、Ｒ^２及びＲ^３の少なくとも１つは、炭素数１〜６のアルコキシ基である。Ａ^１は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、又は炭素数１〜６のアルコキシ基である。Ａ^１が複数の場合、複数のＡ^１は、それぞれ独立して上記定義を満たす。ｎ１は、０〜４の整数である。＊は、結合部位を示す。
式（１−２）中、Ｒ^１、Ｒ^２及びＲ^３は、上記式（１−１）と同義である。Ａ^２は、ハロゲン原子、ヒドロキシ基、炭素数１〜６のアルキル基、又は炭素数１〜６のアルコキシ基である。Ａ^２が複数の場合、複数のＡ^２は、それぞれ独立して上記定義を満たす。ｎ２は、０〜６の整数である。＊は、結合部位を示す。） The invention made to solve the above problems is also referred to as a first structural unit (hereinafter referred to as “structural unit (I)”) having a group represented by the following formula (1-1) or the following formula (1-2). .) Containing a polymer component (hereinafter also referred to as “[A] polymer component”) and a radiation sensitive compound (hereinafter also referred to as “[B] radiation sensitive compound”). It is a radiation resin composition.

(In formula (1-1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or 1 to 1 carbon atoms. 6, wherein at least one of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms, A ¹ is a halogen atom, a hydroxy group, or a carbon atom having 1 to 6 carbon atoms. An alkyl group or an alkoxy group having 1 to 6 carbon atoms, and when A ¹ is plural, the plural A ¹ independently satisfy the above definition, and n1 is an integer of 0 to 4. * is Indicates the binding site.
Wherein ^(1-2), R 1, ^{R 2} and ^{R 3} is as defined in the above formula (1-1). A ² is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. If A ² is plural, a plurality of A ² are each independently satisfy the above definition. n2 is an integer of 0-6. * Indicates a binding site. )

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

  Still another invention made in order to solve the above-mentioned problems is the step of forming a coating film on a substrate using the positive radiation sensitive resin composition, the step of irradiating a part of the coating film with radiation, It is a method for forming a cured film comprising a step of developing the coating film irradiated with the radiation and a step of heating the developed coating film.

  Yet another invention made to solve the above-described problems is a semiconductor element provided with the interlayer insulating film.

  Still another invention made to solve the above-described problems is a display element including the semiconductor element.

  The present invention is a positive radiation sensitive resin composition capable of obtaining a cured film excellent in sensitivity and resolution, and having excellent low dielectric properties, transparency and heat resistance, and an interlayer using this positive radiation sensitive resin composition. An insulating film, a method for forming the insulating film, a semiconductor element, and a display element can be provided. Therefore, the positive-type radiation-sensitive resin composition, the interlayer insulating film formed from the positive-type radiation-sensitive resin, the semiconductor element and the display element, and the method for forming the interlayer insulating film are flexible displays and the like. It can be used suitably for manufacturing processes of electronic devices and the like.

<Positive radiation sensitive resin composition>
The positive radiation sensitive resin composition according to an embodiment of the present invention contains [A] a polymer component and [B] a radiation sensitive compound. The positive radiation-sensitive resin composition is excellent in sensitivity and resolution, and it is not clear why a cured film excellent in low dielectric property, transparency and heat resistance can be obtained, but it exhibits good positive photosensitive properties. The possible reasons are as follows. [A] The structural unit (I) of the polymer component has an alkoxysilyl group bonded to an aromatic ring. When the coating film of such positive radiation sensitive resin composition is irradiated with radiation, [B] hydrolysis with water in the atmosphere or in the developer using an acid generated from the radiation sensitive compound as a catalyst By the reaction, a silanol group (Si—OH) is generated from the alkoxysilyl group. Since this silanol group is bonded to the aromatic ring, the condensation reaction of the silanol group is inhibited, and the silanol group can exist in a stabilized state. For this reason, it is presumed that the silanol group increases the solubility of the radiation-irradiated region in the alkaline developer, and expresses positive photosensitive characteristics. On the other hand, in the case of a structure in which an alkoxysilyl group (silanol group) is not bonded to an aromatic ring, the silanol group is unstable and condensation to siloxane occurs. For this reason, it is presumed that the radiation irradiation area is insolubilized (negative) and the positive photosensitive characteristics are not exhibited.

<[A] Polymer component>
[A] A polymer component is a component comprised from 1 type, or 2 or more types of polymers containing the polymer containing the said structural unit (I). [A] The polymer component is a second structural unit having a crosslinkable group in the same or different polymer as the polymer containing the structural unit (I) (hereinafter also referred to as “structural unit (II)”). It is preferable to contain. [A] The polymer component is also referred to as a third structural unit (hereinafter referred to as “structural unit (III)”) having an acidic group in the same or different polymer as the polymer containing the structural unit (I). ) Is preferably included. The structural unit (II) and the structural unit (III) can be present in the same or different polymers.

That is, as the form of the [A] polymer component,
A polymer comprising the structural unit (I),
A copolymer comprising structural unit (I) and structural unit (II),
A copolymer comprising the structural unit (I) and the structural unit (III),
A copolymer comprising structural unit (I), structural unit (II) and structural unit (III),
A mixture of a polymer containing the structural unit (I) and a polymer containing the structural unit (II);
A mixture of a polymer containing the structural unit (I) and a polymer containing the structural unit (III);
A mixture of a polymer comprising the structural unit (I) and a polymer comprising the structural unit (II) and the structural unit (III);
Examples thereof include a mixture of a polymer containing the structural unit (I), a polymer containing the structural unit (II), and a polymer containing the structural unit (III).

  Further, the same structural unit in different polymers such as a mixture of a copolymer containing the structural unit (I) and the structural unit (II) and a copolymer containing the structural unit (I) and the structural unit (III). May be included.

  [A] The polymer component preferably has all of the structural unit (I), the structural unit (II), and the structural unit (III). [A] As an aspect of the polymer component, the structural unit (I), the copolymer containing the structural unit (II) and the structural unit (III), the polymer containing the structural unit (I), and the structural unit (II And a polymer containing the structural unit (III). [A] Each of these polymers constituting the polymer component can have other structural units (IV) other than the structural units (I) to (III). Hereinafter, each structural unit will be described.

[Structural unit (I)]
The structural unit (I) is a structural unit having a group represented by the following formula (1-1) or the following formula (1-2). The structural unit (I) may be composed of a plurality of types of structural units. This structural unit (I) can exhibit good positive photosensitive characteristics as described above. Moreover, various characteristics, such as heat resistance of the cured film obtained, can be improved more by including an aromatic ring.

In formula (1-1), R ¹ , R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or 1 to 6 carbon atoms. Of the alkoxy group. However, at least one of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms. A ¹ is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. If A ¹ is plural, a plurality of A ¹ are each independently satisfy the above definition. n1 is an integer of 0-4. * Indicates a binding site with another site in the structural unit (I).

In formula (1-2), R ¹ , R ² and R ³ have the same meaning as in formula (1-1). A ² is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. If A ² is plural, a plurality of A ² are each independently satisfy the above definition. n2 is an integer of 0-6. * Indicates a binding site with another site in the structural unit (I).

Examples of the halogen atom represented by R ^{1 to} R ³ include a fluorine atom, a chlorine atom, and a bromine atom.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ^{1 to} R ³ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl. Group, t-butyl group and the like. Among these, a C1-C6 alkyl group is preferable, a C1-C3 alkyl group is more preferable, and a methyl group is further more preferable.

The alkoxy group having 1 to 6 carbon atoms represented by ^R 1 to R ^3, may be mentioned a methoxy group, an ethoxy group, n- propoxy group, an i- propoxy group. Among these, a C1-C3 alkoxy group is preferable, a methoxy group and an ethoxy group are more preferable, and a methoxy group is further more preferable.

At least one of the ^R 1 to R ³ is an alkoxy group having 1 to 6 carbon atoms, preferably at least two of the ^R 1 to R ³ is a alkoxy group having 1 to 6 carbon atoms, the ^{R 1} It is more preferable that all of R ³ are alkoxy groups having 1 to 6 carbon atoms. When R ^{1 to} R ³ are not an alkoxy group having 1 to 6 carbon atoms, the R ^{1 to} R ³ are preferably an alkyl group having 1 to 12 carbon atoms.

Examples of the halogen atom represented by A ¹ and A ² , the alkyl group having 1 to 6 carbon atoms, and the alkoxy group having 1 to 6 carbon atoms include those exemplified as R ^{1 to} R ^3. .

  N1 is preferably 0. Moreover, as said n2, 0 is preferable.

  Of the group represented by the formula (1-1) and the group represented by the formula (1-2), the group represented by the formula (1-1) is preferable.

  As said structural unit (I), the structural unit represented by following formula (3) can be mentioned.

In said formula (3), ^RA is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group, or a trifluoromethyl group. R ^B is a group represented by the above formula (1-1) or the formula (1-2). X is a single bond or a divalent organic group.

As said ^RA , a hydrogen atom and a methyl group are preferable.

  Examples of the divalent organic group represented by X include a divalent chain hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 to 20 carbon atoms. A divalent hydrocarbon group such as a divalent aromatic hydrocarbon group, an ester group (—COO—), a group formed by bonding the divalent hydrocarbon group and an oxy group (—O—), The group which combined these groups etc. can be mentioned.

As the X, a single bond and -COO - * (. * Is showing the binding position of ^{R B)} is more preferably a single bond.

  Examples of the structural unit (I) include structural units represented by the following formulas (I-1) to (I-16).

In the above formula, ^{R A} has the same meaning as ^{R A} in the above formula (3).

  Monomers that give structural unit (I) include styryltrimethoxysilane, styryltriethoxysilane, styryltripropoxysilane, styryldimethoxymethylsilane, styrylmethoxydimethylsilane, trimethoxysilylphenyl (meth) acrylate, and triethoxysilyl. Phenyl (meth) acrylate, dimethoxymethylsilylphenyl (meth) acrylate, methoxydimethylsilylphenyl (meth) acrylate, trimethoxysilylvinylnaphthalene, triethoxysilylvinylnaphthalene, dimethoxymethylsilylvinylnaphthalene, trimethoxysilylnaphthyl (meth) acrylate Etc.

  [A] As a minimum of the content rate of structural unit (I) with respect to all the structural units in a polymer component, 10 mass% is preferred, 20 mass% is more preferred, and 25 mass% is still more preferred. On the other hand, as this upper limit, 80 mass% is preferable, 60 mass% is more preferable, and 40 mass% is further more preferable. By making the content rate of structural unit (I) into the said range, the heat resistance of a cured film obtained, a low dielectric constant, etc. can be improved more, exhibiting a more favorable positive photosensitive characteristic. When this content ratio is less than the above lower limit, the positive photosensitive characteristics may be lowered, and the heat resistance, low dielectric constant, etc. of the resulting cured film may be lowered. Moreover, when this content rate exceeds the said upper limit, developability may fall at the time of pattern formation of a cured film. In general, the content ratio of each structural unit can be considered to be the same as the charging ratio of the corresponding monomer (the same applies hereinafter).

[Structural unit (II)]
The structural unit (II) is a structural unit having a crosslinkable group. The structural unit (II) may be composed of a plurality of types of structural units. The structural unit (II) can improve the curing reactivity, the heat resistance of the resulting cured film, and the like.

  The crosslinkable group refers to a group other than the group represented by the formula (1-1) or the formula (1-2) and an acidic group, and a group that can be covalently bonded to other groups. . Examples of the crosslinkable group include oxiranyl group (1,2-epoxy structure), oxetanyl group (1,3-epoxy structure), methylol group, vinyl group, (meth) acryloyl group, and cyclic carbonate group.

  Among the crosslinkable groups, an oxiranyl group (epoxy group), an oxetanyl group, a methylol group, and a combination thereof are preferable, an oxiranyl group and an oxetanyl group are more preferable, and an oxiranyl group is further preferable.

  Examples of the structural unit (II) containing an oxiranyl group include structural units represented by the following formulas (II-1) to (II-5). Examples of the structural unit (II) containing an oxetanyl group include structural units represented by the following formulas (II-6) to (II-9). Examples of the structural unit (II) containing a cyclic carbonate group include structural units represented by the following formulas (II-10) to (II-14). Examples of the structural unit (II) containing a methylol group include a structural unit represented by the following formula (II-15).

In the above formula, R ^C represents a hydrogen atom, a methyl group or a trifluoromethyl group.

  Examples of the monomer that gives the structural unit (II) represented by the above formulas (II-1) to (II-15) include glycidyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meta ) Acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxynorbornyl (meth) acrylate and other (meth) acrylates having a crosslinkable group, p-vinylbenzylglycidyl ether, etc. Examples thereof include substituted styrene monomers having a crosslinkable group.

As the structural unit (II) containing a (meth) acryloyl group, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene di ( (Meth) acrylate, tripropylene di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl Di (meth) acrylate compounds such as 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, pentaerythritol tri (meth) acrylate;
Tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate;
And structural units derived from monomers such as penta (meth) acrylate compounds such as dipentaerythritol penta (meth) acrylate.

  The structural unit (II) containing a (meth) acryloyl group or vinyl group is a compound having a group reacting with the specific group and a (meth) acryloyl group or vinyl group in a specific group of the structural unit in the polymer. It can also be obtained by reacting. For example, (1) a method in which an epoxy group-containing unsaturated compound is reacted with a polymer having a carboxy group, (2) a method in which (meth) acrylic acid is reacted with a polymer having an epoxy group, (3) a hydroxy group (Meth) acrylic acid ester having an isocyanate group or a vinyl compound is reacted with a polymer having an isocyanate group, (4) (meth) acrylic acid is reacted with a polymer having an acid anhydride moiety, etc. ) Structural units (II) containing acryloyl groups or vinyl groups can be introduced.

  [A] As a minimum of the content rate of structural unit (II) to all the structural units in a polymer ingredient, 5 mass% is preferred, 10 mass% is more preferred, and 20 mass% is still more preferred. On the other hand, as this upper limit, 50 mass% is preferable and 40 mass% is more preferable. By making the content rate of structural unit (II) into the said range, the photosensitive characteristic and various characteristics of the cured film obtained can be improved with a sufficient balance.

[Structural unit (III)]
The structural unit (III) is a structural unit having an acidic group. The structural unit (III) may be composed of a plurality of types of structural units. With the structural unit (III), the solubility of the [A] polymer component in the developer can be increased, and the curing reactivity can be increased.

  Examples of the acidic group include a carboxy group, a sulfo group, a phenolic hydroxyl group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, a sulfonamide group, and a hydroxyalkyl in which a hydrogen atom bonded to a carbon atom is substituted with an electron withdrawing group. Groups and the like. Examples of the electron withdrawing group include halogen atoms such as fluorine and chlorine, nitro groups, cyano groups, and the like. As the acidic group, a carboxy group, a sulfo group, a phenolic hydroxyl group, a fluorine-containing alcoholic hydroxyl group (hydroxyfluorinated alkyl group), a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, and a combination thereof are preferable. More preferred is a hydroxyl group. By such an acidic group, the effect of the present invention can be exhibited more effectively.

  As said fluorine-containing alcoholic hydroxyl group, group represented by following formula (2) is preferable. The group represented by the following formula (2) can exhibit particularly good developability and good crosslinking reactivity with the crosslinkable group of the structural unit (II).

In formula (2), R ⁴ is a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. R ⁵ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group having 1 to 4 carbon atoms.

Examples of the fluorinated alkyl group having 1 to 4 carbon atoms represented by R ⁴ include a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, and perfluoro. Ethyl group, 2,2,3,3-tetrafluoropropyl group, perfluoroethylmethyl group, perfluoropropyl group, 2,2,3,3,4,4-hexafluorobutyl group, perfluorobutyl group, etc. Can be mentioned.

R ⁴ is preferably a fluorinated alkyl group, more preferably a perfluoroalkyl group, and even more preferably a trifluoromethyl group (perfluoromethyl group).

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁵ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t -A butyl group etc. can be mentioned. Examples of the fluorinated alkyl group having 1 to 4 carbon atoms represented by R ⁵ include those exemplified in the description of R ⁴ .

R ⁵ is preferably a hydrogen atom, a fluorine atom and a fluorinated alkyl group, more preferably a hydrogen atom and a fluorinated alkyl group, still more preferably a perfluoroalkyl group, and particularly preferably a trifluoromethyl group.

Furthermore, both R ⁴ and R ⁵ are preferably fluorinated alkyl groups, more preferably perfluoroalkyl groups, and even more preferably both trifluoromethyl groups. When R ⁴ and R ⁵ are such groups, they are suitable acidic groups, so that a good cross-linking reaction occurs, and various properties of the obtained cured film such as chemical resistance can be further enhanced.

  As the structural unit (III), a structural unit represented by the following formula (2-1), a structural unit represented by the following formula (2-2), a structural unit derived from (meth) acrylic acid, vinyl sulfonic acid And the like, structural units having a phosphonic acid group, structural units having a phenolic hydroxyl group, and the like.

In the above formula (2-1) and (2-2), ^{R 4} and ^{R 5} have the same meanings as ^{R 4} and ^{R 5} in the formula (2). R ⁶ and R ⁷ are each independently an (n + 1) -valent organic group. However, R ⁷ excludes those having a main chain side terminal having an ester structure (—COO—). Each R is independently a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group or a trifluoromethyl group. n is an integer of 1-5 each independently. When n is 2 or more, the plurality of R ⁴ and R ⁶ may be the same or different from each other.

Examples of the (n + 1) -valent organic group represented by R ⁶ and R ⁷ include a hydrocarbon group having (n + 1) -valent chain hydrocarbon group having 1 to 20 carbon atoms, 3 to 20 carbon atoms ( n + 1) -valent alicyclic hydrocarbon group, (n + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, or (n + 1) -valent group obtained by combining two or more of these groups. It is done. However, one part or all part of the hydrogen atom which these groups have may be substituted.

As the R ⁸ and R ^9, preferably a hydrocarbon group, an aromatic hydrocarbon group is more preferable. Examples of the aromatic hydrocarbon group include a phenylene group and a naphthylene group when n is 1, and a phenylene group is particularly preferable. When R ⁶ and R ⁷ are aromatic hydrocarbon groups, heat resistance and the like can be further improved.

  As R in the formulas (2-1) and (2-2), a hydrogen atom and a methyl group are preferable.

  As n in the formulas (2-1) and (2-2), 1 and 2 are preferable, and 1 is more preferable.

  Examples of the structural unit represented by the formula (2-1) include structural units represented by the following formulas (III-1) to (III-6). Moreover, as a structural unit represented by the said Formula (2-2), the structural unit respectively represented by following formula (III-7)-(III-8) can be mentioned.

In said formula, R is synonymous with R in said formula (2-1) and (2-2). Among these, structural units containing an aromatic hydrocarbon group represented by the formulas (III-3), (III-7) and (III-8) are preferable, and the formulas (III-3) and (III-7) A structural unit represented by the formula ( ₁ ) in which a group represented by —C (CF ₃ ) ₂ OH as an acidic group is substituted on an aromatic hydrocarbon group is more preferred.

  Among these, the structural unit (III) is derived from the structural unit represented by the above formula (2-1), the structural unit represented by the above formula (2-2), and (meth) acrylic acid. Structural units are preferred. Furthermore, as the structural unit (III), the structural unit represented by the above formula (2-1) or the structural unit represented by the above formula (2-2) and a structural unit derived from (meth) acrylic acid. It is preferable to use together with a structural unit having a carboxy group such as. Moreover, the structural unit represented by the said Formula (2-2) is preferable in the structural unit represented by the said Formula (2-1) and the structural unit represented by the said Formula (2-2). When the structural unit (III) has such a configuration, the photosensitive characteristics and various characteristics of the obtained cured film can be further enhanced.

  [A] As a minimum of the content rate of structural unit (III) to all the structural units in a polymer ingredient, 5 mass% is preferred, 15 mass% is more preferred, and 25 mass% is still more preferred. On the other hand, as this upper limit, 70 mass% is preferable, 60 mass% is more preferable, and 50 mass% is further more preferable. By making the content rate of structural unit (III) into the said range, a photosensitive characteristic, various characteristics of the cured film obtained, etc. can be improved more.

  Among the structural units (III), the lower limit of the content ratio of structural units having a fluorine-containing alcoholic hydroxyl group such as the structural units represented by the above formulas (2-1) and (2-2) is [A ] 5 mass% is preferable with respect to all structural units constituting the polymer component, 10 mass% is more preferable, and 20 mass% is still more preferable. On the other hand, as this upper limit, 50 mass% is preferable and 40 mass% is more preferable.

  Among the structural units (III), as the lower limit of the content ratio of structural units having a carboxy group, such as structural units derived from (meth) acrylic acid, [A] with respect to all structural units constituting the polymer component 3 mass% is preferable and 5 mass% is more preferable. On the other hand, as this upper limit, 30 mass% is preferable, 20 mass% is more preferable, and 15 mass% is further more preferable.

[Structural unit (IV)]
The structural unit (IV) is a structural unit other than the structural units (I) to (III). The structural unit (IV) may be composed of a plurality of types of structural units. [A] The polymer component has the structural unit (IV), thereby adjusting the glass transition temperature of the resin and improving the melt flow property at the time of thermosetting, the mechanical strength and chemical resistance of the resulting cured film. Etc.

  Examples of the structural unit (IV) include structural units represented by the following formulas (IV-1) to (IV-10).

In the above formula, R ^D is a hydrogen atom, a methyl group or a trifluoromethyl group. R ^M is a hydrogen atom or a methyl group. s is an integer of 1-10. R ¹⁰ is an alkyl group having 1 to 4 carbon atoms. t is an integer of 0-5. Among these, as the structural unit (IV), structural units represented by the formulas (IV-1) to (IV-6) and (IV-10) are preferable.

  Examples of the monomer compound that gives the structural unit (IV) include (meth) acrylic acid chain alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid diester, Saturated compounds, maleimide compounds, unsaturated aromatic compounds and conjugated diene compounds, and unsaturated compounds having a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, or a skeleton represented by the following formula (4), and other unsaturated compounds Examples include structural units derived from compounds and the like.

In the formula (4), ^{R M} and s have the same meanings as ^{R M} and s in the formula (IV-9).

Examples of the (meth) acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, Acrylic acid chain alkyl esters such as n-lauryl acrylate, tridecyl acrylate, and n-stearyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-methacrylate Examples include methacrylic acid chain alkyl esters such as stearyl.

Examples of the (meth) acrylic acid cyclic alkyl ester include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, and tricyclo [5 acrylate]. .2.1.0 ^2,6 ] decan-8-yloxyethyl, acrylic acid cyclic alkyl esters such as isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8 methacrylate -Methacrylic acid cyclic alkyl esters such as yloxyethyl and isobornyl methacrylate.

Examples of the (meth) acrylic acid aryl ester include phenyl acrylate. Acrylic acid aryl esters such as benzyl acrylate;
And methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate.

  Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.

  Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 5-ethylbicyclo [2.2.1]. ] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2. 2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [ 2.2.1] Hep 2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] hept-2- Ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di ( 2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [ 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, and the like.

  Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate. N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

  Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, vinyltoluene, p-methoxystyrene, α-methyl-p-hydroxystyrene, and the like.

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

  Examples of the unsaturated compound having a tetrahydrofuran skeleton include 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, and tetrahydrofurfuryl (meth) acrylate.

  Examples of the unsaturated compound having a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3-ene. 2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2 -Yl-hex-1-en-3-one, acrylic acid-2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one Etc.

  Examples of the unsaturated compound containing the tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-ene-3- ON, 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one and the like.

  Examples of the unsaturated compound having a pyran skeleton include 4- (1,4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyran and 4- (1,5-dioxa-6-oxo. -7-octenyl) -6-methyl-2-pyran and the like.

  Examples of the other unsaturated compounds include (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, and vinyl acetate.

Among these, as the monomer compound giving the structural unit (IV), methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, maleimide compound, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, the above formula The unsaturated compound, unsaturated aromatic compound and acrylic acid cyclic alkyl ester having a skeleton represented by (4) are preferred, and styrene, vinyltoluene, methyl methacrylate, methacrylic acid t- Butyl, n-lauryl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide , Tetrahydrofur (meth) acrylic acid Furyl, polyethylene glycol (n = 2 to 10) mono (meth) acrylate and 3- (meth) acryloyloxy-2-one is more preferred.

  [A] When the polymer component has a structural unit (IV), the lower limit of the content ratio of the structural unit (IV) to the total structural unit in the [A] polymer component is preferably 5% by mass, and preferably 10% by mass. More preferred. On the other hand, as this upper limit, 50 mass% is preferable and 30 mass% is more preferable. Chemical resistance etc. can be improved effectively by making the content rate of structural unit (IV) into the said range. Further, the upper limit of the content ratio of the structural unit (IV) may be 20% by mass, 10% by mass, 5% by mass, or 1% by mass. . In some cases, the structural unit (IV) may not be contained in the [A] polymer component.

<[A] Polymer component synthesis method>
[A] The polymer component can be produced, for example, by polymerizing monomers corresponding to predetermined respective structural units in a suitable solvent using a radical initiator. In general, the blending ratio of each monomer during polymerization coincides with the content ratio of the corresponding structural unit in the obtained [A] polymer component. Moreover, the preferable compounding ratio (preparation ratio) of each monomer is the same as the preferable content rate of the corresponding structural unit mentioned above.

  As a specific synthesis method, (1) a method in which a solution containing a monomer and a radical initiator is dropped into a reaction solvent or a solution containing a monomer to cause a polymerization reaction; A method in which a solution containing a radical initiator and a solution containing a radical initiator are separately dropped into a reaction solvent or a solution containing a monomer to cause a polymerization reaction; (3) a plurality of types each containing a monomer; It is preferable to synthesize the solution and a solution containing a radical initiator separately by a method such as a method of dropping them into a reaction solvent or a solution containing a monomer to cause a polymerization reaction.

  In addition, as the [A] polymer component, a plurality of types of polymers can be synthesized, and then the plurality of types of polymers can be mixed and used.

  What is necessary is just to determine the reaction temperature in these methods suitably with initiator seed | species. Usually, it can be set to 30 ° C. to 180 ° C. The dropping time varies depending on the reaction temperature, the type of initiator, the monomer to be reacted, etc., but is usually 30 minutes to 8 hours. Further, the total reaction time including the dropping time varies depending on the conditions similarly to the dropping time, but is usually 30 minutes to 8 hours.

  Examples of the radical initiator used in the polymerization include azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2 -Cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile) and the like. These initiators may be used alone or in combination of two or more.

  The polymerization solvent is not limited as long as it is a solvent other than a solvent that inhibits polymerization (nitrobenzene having a polymerization inhibiting effect, mercapto compound having a chain transfer effect, etc.) and can dissolve the monomer. Examples of the polymerization solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester / lactone solvents, nitrile solvents, and the like. These solvents may be used alone or in combination of two or more.

  The polymer obtained by the polymerization reaction can be recovered by a reprecipitation method. That is, after completion of the polymerization reaction, the polymer is recovered as a powder by putting the polymer solution into a reprecipitation solvent. As the reprecipitation solvent, alcohols or alkanes can be used alone or in admixture of two or more. In addition to the reprecipitation method, the polymer can be recovered by removing low-molecular components such as monomers and oligomers by a liquid separation operation, a column operation, an ultrafiltration operation, or the like. In addition, when the polymerization solvent is the same as the solvent of the radiation sensitive resin composition to be prepared, the radiation sensitive resin composition can be obtained by using the obtained polymer solution as it is or by adding a solvent to the obtained polymer solution. You may use for preparation of.

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

  [A] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer component is not particularly limited, but is preferably 1,000 or more and 30,000 or less. [A] The ratio (Mw / Mn) of Mw of the polymer to the number average molecular weight (Mn) in terms of polystyrene by GPC is preferably 1 or more and 3 or less.

  The content of the [A] polymer component in the positive radiation sensitive resin composition is not particularly limited, but the lower limit of the content of the [A] polymer in the total solid content is preferably 50% by mass, 70 mass% is more preferable, and 90 mass% is further more preferable. On the other hand, the upper limit is preferably 99% by mass, and more preferably 97% by mass. By making content of [A] polymer component in the said positive type radiation sensitive resin composition into the said range, the photosensitive characteristic and various characteristics of the cured film obtained can be improved more effectively.

<[B] Radiation sensitive compound>
The positive radiation sensitive resin composition contains [B] a radiation sensitive compound (photosensitive agent). For this reason, in the said radiation sensitive resin composition, the alkoxy silyl in the group represented by the said Formula (1-1) or (1-2) by irradiation of a radiation (visible light, an ultraviolet-ray, far ultraviolet rays, etc.). The group hydrolysis proceeds, and a positive pattern can be formed as described above. [B] Examples of radiation sensitive compounds include [B1] acid generators, [B2] base generators, and [B1] acid generators are preferred. [B] The acid or base generated from the radiation-sensitive compound functions effectively as a catalyst for the hydrolysis reaction. These [B] radiation sensitive compounds can be used singly or in combination of two or more.

<[B1] Acid generator>
[B1] The acid generator (radiation sensitive acid generator) is a compound that generates an acid in response to radiation. [B1] Examples of the acid generator include oxime sulfonate compounds, onium salts, sulfonimide compounds, sulfonic acid ester compounds, quinone diazide compounds, halogen-containing compounds, diazomethane compounds, and carboxylic acid ester compounds. These [B1] acid generators may be used alone or in admixture of two or more.

  As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the following formula (5) is preferable.

In the above formula (5), R ^a is an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 4 to 12 carbon atoms, or an aryl having 6 to 20 carbon atoms. It is a group. Some or all of the hydrogen atoms of these alkyl groups, alicyclic hydrocarbon groups and aryl groups may be substituted with substituents.

  Specific examples of the oxime sulfonate compound include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophen-2-yl). Ylidene)-(2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2- Examples include ylidene)-(2-methylphenyl) acetonitrile, 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile, and the like, which are commercially available.

  Examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, tetrahydrothiophenium salt, and benzylsulfonium salt. As the onium salt, a tetrahydrothiophenium salt and a sulfonium salt are preferable.

  Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy). ) Succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N -(2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenyl monomer Imides, 4-methylphenyl sulfonyloxy) diphenyl maleimide, trifluoromethanesulfonic acid 1,8-naphthalimide and the like.

  Examples of the sulfonic acid ester compound include haloalkyl sulfonic acid esters and the like, and N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester is preferable.

  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 or 1,2-naphthoquinonediazidesulfonic acid amide is used. be able to.

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

  As the 1,2-naphthoquinonediazidesulfonic acid halide, 1,2-naphthoquinonediazidesulfonic acid chloride is preferable, and 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2-naphthoquinonediazide-5-sulfonic acid chloride are preferable. More preferred is 1,2-naphthoquinonediazide-5-sulfonic acid chloride.

  As the 1,2-naphthoquinonediazide sulfonic acid amide, 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid amide is preferable.

  In the condensation reaction between a phenolic compound or an alcoholic compound (mother nucleus) and 1,2-naphthoquinone diazide sulfonic acid halide or 1,2-naphthoquinone diazide sulfonic acid amide, it is preferable for the number of OH groups in the mother nucleus. 1,2-naphthoquinone diazide sulfonic acid halide or 1,2-naphthoquinone diazide sulfonic acid amide corresponding to 30 mol% or more and 85 mol% or less is preferably used. In addition, the said condensation reaction can be implemented by a well-known method.

  [B1] As the acid generator, oxime sulfonate compounds, onium salts, sulfonimide compounds, sulfonate ester compounds, halogen-containing compounds, diazomethane compounds, and carboxylic acid ester compounds are preferable, and oxime sulfonate compounds, onium salts, sulfonimide compounds. And sulfonic acid ester compounds are more preferred, and sulfonimide compounds are more preferred. Moreover, these preferable acid generators and quinonediazide compounds can be used in combination.

  [B1] The lower limit of the content of the acid generator is preferably 0.1 parts by mass, more preferably 0.3 parts by mass, and 0.5 parts by mass with respect to 100 parts by mass of the polymer component [A]. Further preferred. On the other hand, as this upper limit, 40 mass parts is preferable, 30 mass parts is more preferable, 15 mass parts may be sufficient, 5 mass parts may be sufficient, and 3 mass parts may be sufficient. [B1] When the acid generator is an oxime sulfonate compound, an onium salt, a sulfonimide compound, a sulfonic acid ester compound, a halogen-containing compound, a diazomethane compound, or a carboxylic acid ester compound, the lower limit of the content of these acid generators As for [A] polymer component 100 mass parts, 0.1 mass part is preferred, 0.3 mass part is more preferred, and 0.5 mass part is still more preferred. On the other hand, as this upper limit, 5 mass parts is preferable and 3 mass parts is more preferable. Moreover, when using a quinonediazide compound as a [B1] acid generator, as a minimum of content of a quinonediazide compound, 2 mass parts is preferable with respect to 100 mass parts of [A] polymer components, and 5 mass parts is more preferable. On the other hand, as this upper limit, 50 mass parts is preferable and 30 mass parts is more preferable. [B1] By setting the content of the acid generator within the above range, it is possible to optimize sensitivity and the like and to form a cured film that is superior in various properties.

<[B2] Base generator>
[B2] The base generator (radiation sensitive base generator) is a compound that generates a base in response to radiation. [B2] Examples of the base generator include [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, 2-nitrobenzylcyclohexylcarbamate, N- (2-nitrobenzyloxycarbonyl) pyrrolidine, bis [[( 2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyloxime, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoethane, (4 -Morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, hexaamminecobalt (III) tris (triphenylmethylborate) and the like. Can be mentioned.

  [B] The lower limit of the content of the radiation sensitive compound is preferably 0.1 parts by weight, more preferably 0.3 parts by weight, and 0.5 parts by weight with respect to 100 parts by weight of the polymer component [A]. Is more preferable. On the other hand, as this upper limit, 20 mass parts is preferable, 15 mass parts is more preferable, 10 mass parts may be sufficient, 5 mass parts may be sufficient, and 3 mass parts may be sufficient. [B] By setting the content of the radiation-sensitive compound within the above range, the sensitivity and the like can be optimized, and a cured film having better properties can be formed.

<Other ingredients>
The positive radiation sensitive resin composition may further contain other components in addition to the above-described [A] polymer component and [B] radiation sensitive compound. Examples of such other components include [C] adhesion assistant, [D] antioxidant, [E] surfactant, crosslinkable compound, polymerization initiator and the like in addition to the solvent described later. In addition, the said positive type radiation sensitive resin composition may use said each component individually or in combination of 2 or more types. However, in the positive-type radiation-sensitive resin composition, the upper limit of the content of components other than the above-mentioned [A] polymer component, [B] radiation-sensitive compound and [C] adhesion assistant in the total solid content 20 mass% may be preferable, 5 mass% or less may be preferable, and 1 mass% or less may be preferable. When the content of other components is large, the photosensitive characteristics and the performance of the cured film obtained may be affected.

<[C] Adhesion aid>
[C] The adhesion assistant is a component that improves the adhesion between the obtained cured film and the substrate. [C] The adhesion assistant is preferably a functional silane coupling agent having a reactive functional group such as a carboxy group, a methacryloyl group, a vinyl group, an isocyanate group, or an oxiranyl group.

  Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and 3-glycidyloxypropyl. Examples include trimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  [C] The content of the adhesion assistant is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymer component [A].

<[D] Antioxidant>
[D] The antioxidant is a component capable of decomposing a peroxide and the like generated by the oxidation and preventing the bond breakage of the polymer molecule. As a result, the obtained cured film is prevented from oxidative deterioration over time, and for example, changes in the film thickness of the cured film can be suppressed.

  [D] 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. In these, as a [D] antioxidant, the compound which has a hindered phenol structure is preferable.

  [D] As content of antioxidant, 0.001 mass part or more and 5 mass parts or less are preferable with respect to 100 mass parts of [A] polymer components. [D] By making content of antioxidant into the said range, the oxidative deterioration with time of the cured film obtained can be suppressed effectively.

<[E] surfactant>
[E] Surfactant is a component that improves film-forming properties. [E] Examples of the surfactant include a fluorine-based surfactant, a silicone-based surfactant, and other surfactants.

  As such a surfactant, surfactants described in JP2011-133498A, JP2012-37814A, and the like can be used.

  [E] As content of surfactant, 0.01 mass part or more and 3 mass parts or less are preferable with respect to 100 mass parts of [A] polymer components. [E] By making the content of the surfactant within the above range, the film forming property can be effectively improved.

<Method for preparing positive-type radiation-sensitive resin composition>
The positive-type radiation-sensitive resin composition is prepared by mixing [A] polymer, [B] radiation-sensitive compound and other components as required in a predetermined ratio, and preferably dissolving in a suitable solvent. it can. The prepared radiation-sensitive resin composition is preferably filtered through, for example, a filter having a pore diameter of about 0.2 μm.

  As the [F] solvent used for the preparation of the positive type radiation sensitive resin composition, those components which the positive type radiation sensitive resin composition contains are uniformly dissolved or dispersed and do not react with the above components. Is used.

[F] Examples of the solvent include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and octanol;
Esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate;
Ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene diglycol monomethyl ether, ethylene diglycol ethyl methyl ether;
Amides such as dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone;
Aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene can be used. [F] A solvent can be used 1 type or in mixture of 2 or more types.

  As solid content concentration of the said positive type radiation sensitive resin composition, it can be 10 mass% or more and 50 mass% or less, for example.

<Use of positive-type radiation-sensitive resin composition>
The positive radiation-sensitive resin composition can provide a cured film that is excellent in sensitivity and resolution, and excellent in low dielectric properties, transparency, and heat resistance. Therefore, the positive radiation sensitive resin composition can be suitably used as a cured film for display elements such as an interlayer insulating film, a spacer, a protective film, and a color filter coloring pattern, particularly as a material for forming an interlayer insulating film.

<Interlayer insulation film>
The interlayer insulation film which concerns on one Embodiment of this invention is formed from the said radiation sensitive resin composition. The method for forming the interlayer insulating film is not particularly limited, but it can be preferably formed by using the method for forming the interlayer insulating film described later. Since the interlayer insulating film is formed from the positive radiation sensitive resin composition, it is excellent in low dielectric properties, transparency, heat resistance, and the like. Since the interlayer insulating film has the above characteristics, it is suitable as an interlayer insulating film of a display element, for example.

<Method for forming interlayer insulating film>
A method for forming an interlayer insulating film according to an embodiment of the present invention includes:
(1) Using the positive radiation sensitive resin composition, a step of forming a coating film on a substrate (hereinafter, also referred to as “step (1)”),
(2) A step of irradiating a part of the coating film (hereinafter also referred to as “step (2)”),
(3) a step of developing the coating film irradiated with the radiation (hereinafter also referred to as “step (3)”), and (4) a step of heating the developed coating film (hereinafter referred to as “step (4)”). Is also called)
Is provided.

  Since the positive-type radiation-sensitive resin composition has the above-described properties, the interlayer insulating film excellent in low dielectric property, transparency, heat resistance, and the like is excellent according to the method for forming the interlayer insulating film. It can be formed with sensitivity and resolution. Hereinafter, each process is explained in full detail.

[Step (1)]
In this step, a coating film is formed on the substrate using the positive radiation sensitive resin composition. Specifically, the positive radiation sensitive resin composition in the form of a solution is applied to the surface of the substrate, and preferably a prebake is performed to remove the solvent and form a coating film. Examples of the substrate include a glass substrate, a silicon substrate, a plastic substrate, and a substrate on which various metal thin films are formed. Examples of the plastic substrate include a resin substrate made of plastic such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethersulfone, polycarbonate, polyimide, and the like.

  As a coating method, 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, or an ink jet method can be employed. Of these, spin coating, bar coating, and slit die coating are preferred as the coating method. The pre-baking conditions may vary depending on the type of each component, the usage ratio, and the like, but may be, for example, 60 ° C. to 130 ° C. for 30 seconds to 10 minutes. The film thickness of the coating film to be formed is preferably 0.1 μm or more and 8 μm or less as a value after pre-baking.

[Step (2)]
In this step, a 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, X-rays, and charged particle beams.

Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet light include KrF excimer laser light. 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, h-line and / or i-line is more preferable. The exposure amount of radiation, 0.1 J / ^{m 2} or more 10,000 J / ^{m 2} or less.

[Step (3)]
In this step, the coating film irradiated with the radiation is developed. Specifically, the coating film irradiated with radiation in the step (2) is developed with a developer to remove the radiation irradiated portion. The developer is usually an alkali developer such as 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 (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7- Examples include aqueous solutions of alkalis (basic compounds) such as undecene and 1,5-diazabicyclo [4,3,0] -5-nonane. Also, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent or surfactant such as methanol or ethanol to the aqueous alkali solution, or an alkaline aqueous solution containing a small amount of various organic solvents capable of dissolving the positive-type radiation-sensitive resin composition. You may use as a developing solution.

As a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, or a shower method can be employed. 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 development step, the patterned coating film is rinsed with running water, and then exposed to a whole surface 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 this post-exposure is preferably 2,000 J / m ² or more and 5,000 J / m ² or less.

[Step (4)]
In this step, the developed coating film is heated. Although it does not specifically limit as a heating method, For example, it can heat using heating apparatuses, such as oven and a hotplate. As heating temperature in this process, it can be set as 120 to 250 degreeC, for example. The heating time varies depending on the type of heating equipment, but for example, when heat treatment is performed on a hot plate, it is 5 minutes to 40 minutes, and when heat treatment is performed in an oven, it is 30 minutes to 80 minutes. be able to. In this way, a desired interlayer insulating film can be formed on the substrate.

<Semiconductor element>
A semiconductor element according to an embodiment of the present invention includes the interlayer insulating film. This interlayer insulating film functions as a film that insulates the wirings in the semiconductor element. The semiconductor element can be formed using a known method. Since the semiconductor element includes the interlayer insulating film, the semiconductor element can be suitably used for electronic devices such as display elements, LEDs, and solar cells.

<Display element>
A display element according to an embodiment of the present invention includes the semiconductor element. Since the display element includes a semiconductor element having the interlayer insulating film, the display element satisfies general characteristics required for practical use as a display element. Examples of the display element include a liquid crystal display element. In the liquid crystal display element, for example, two TFT array substrates having a liquid crystal alignment film formed on the surface thereof are arranged facing each other on the liquid crystal alignment film side through a sealant provided at the periphery of the TFT array substrate. The liquid crystal is filled between these two TFT array substrates. The TFT array substrate has wirings arranged in layers, and the wirings are insulated by the interlayer insulating film.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. The measuring method of each physical property value is shown below.

[Weight average molecular weight (Mw) and number average molecular weight (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.
Equipment: GPC-101 from Showa Denko
GPC column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 manufactured by Shimadzu GL Corp. Combined mobile phase: Tetrahydrofuran Column temperature: 40 ° C.
Flow rate: 1.0 mL / min Sample concentration: 1.0 mass%
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<[A] Synthesis of polymer component>
[Synthesis Example 1] (Synthesis of polymer (A-1))
A flask equipped with a condenser and a stirrer was charged with 10 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether. Subsequently, 30 parts by mass of styryltrimethoxysilane, 30 parts by mass of glycidyl methacrylate, 10 parts by mass of methacrylic acid, 1,1,1,3,3,3-hexafluoro- (4-vinylphenyl) -propan-2-ol 30 The polymer (A-1), which is an alkali-soluble resin, is prepared by raising the temperature of the solution to 70 ° C. while gently stirring, and then polymerizing while maintaining this temperature for 5 hours. A polymer solution containing was obtained. The solid content concentration of this polymer solution was 33.4% by mass, the Mw of the polymer (A-1) was 10,000, and the molecular weight distribution (Mw / Mn) was 2.2. In addition, solid content concentration means the ratio of the copolymer mass to the total mass of a polymer solution, and is defined similarly in the following.

[Synthesis Examples 2 to 15 and Comparative Synthesis Examples 1 to 4] (Synthesis of Polymers (A-2) to (A-15) and (A′-1) to (A′-4))
The solid content concentration, molecular weight, and molecular weight distribution equivalent to those of the polymer (A-1) were obtained in the same manner as in Synthesis Example 1 except that the components of the types and blending amounts (parts by mass) shown in Table 1 were used. Polymer solutions containing the polymers (A-2) to (A-15) and (A′-1) to (A′-4) were obtained. In Table 1, “-” indicates that the corresponding component was not used.

Abbreviations in Table 1 indicate the following monomers.
(Monomer giving structural unit (I))
STMS: styryltrimethoxysilane SDMS: styryldimethoxymethylsilane STES: styryltriethoxysilane TMSPhMA: trimethoxysilylphenyl methacrylate DMSPhMA: dimethoxymethylsilylphenyl methacrylate NTMS: trimethoxysilylvinylnaphthalene NDMS: dimethoxymethylsilylvinylnaphthalene body)
APTMS: acryloyltrimethoxysilane APTMS: acryloyltriethoxysilane STM: styryltrimethylsilane (monomer giving structural unit (II))
OXMA: (3-ethyloxetane-3-yl) methyl methacrylate GMA: glycidyl methacrylate VBG: p-vinylbenzylglycidyl ether ECHMA: 3,4-epoxycyclohexylmethyl methacrylate ENMA: 3,4-epoxynorbornyl methacrylate (structural unit) Monomer that gives (III))
MA: methacrylic acid HFAS: 1,1,1,3,3,3-hexafluoro- (2-vinylphenyl) -propan-2-ol (monomer giving structural unit (IV))
MMA: Methyl methacrylate ST: Styrene

<Preparation of radiation-sensitive resin composition>
The [A] polymer component, [B] radiation sensitive compound, [C] adhesion assistant and [F] solvent used for the preparation of the radiation sensitive resin compositions of Examples and Comparative Examples are shown below.
[A] Polymer components A-1 to A-15, A′-1 to A′-4: Polymers (A-1) to (A-15) synthesized in Synthesis Examples 1 to 15 and Comparative Synthesis Example 1 Polymers (A′-1) to (A′-4) synthesized in
[B] Radiation sensitive compound (acid generator)
B-1: trifluoromethanesulfonic acid-1,8-naphthalimide B-2: p-tolylsulfonic acid-1,8-naphthalimide B-3: 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-4: 1 , 1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) condensate [C] adhesion assistant C- 1: 3-glycidyloxypropyltrimethoxysilane C-2: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane [F] solvent F-1: propylene glycol monomethyl ether Acetate (PGMEA)
F-2: Ethylene diglycol methyl ethyl ether (EDM)

<Preparation of radiation-sensitive resin composition>
[Example 1]
For the amount corresponding to 100 parts by mass (solid content) of the polymer (A-1), 1 part by mass of the radiation sensitive compound (B-1) and 3 parts by mass of the adhesion assistant (C-1) are mixed, After dissolving in a solvent (F-1) so that solid content concentration might be 30 mass%, it filtered with the membrane filter with the hole diameter of 0.2 micrometer, and prepared the radiation sensitive resin composition.

[Examples 2 to 16 and Comparative Examples 1 to 4]
Except having used each component of the kind shown in following Table 2 with the compounding quantity shown in Table 2, it operated like Example 1 and the radiation sensitive resin composition of Examples 2-16 and Comparative Examples 1-4 was used. Prepared. In addition, when two types of polymers were used as [A] polymer component, 50 mass parts was mix | blended respectively. Moreover, about [B] radiation sensitive compound, as shown in Table 2, about 1 mass part, radiation sensitive compound (B-3) or about radiation sensitive compound (B-1) or (B-2), or About (B-4), 20 mass parts was mix | blended, and when using the radiation sensitive compound (B-1) and (B-2) together, 0.5 mass part was mix | blended each.

<Evaluation>
The cured film (insulating film) was formed from the radiation sensitive resin composition of Examples 1-16 and Comparative Examples 1-4, and the following item was evaluated by the method demonstrated below. The evaluation results are shown in Table 2.

[Radiation sensitivity (minimum exposure)]
Using a spinner, a radiation sensitive resin composition was applied on a silicon substrate that had been subjected to HMDS treatment at 60 ° C. for 60 seconds, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having an average film thickness of 3.0 μm. Formed. This 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, and then washed with running ultrapure water for 1 minute. At this time, the minimum exposure amount capable of forming a line and space pattern having a width of 10 μm was measured. When this measured value is less than 300 J / m ² , the sensitivity is good, and when it is 300 J / m ² or more, it can be evaluated as defective.

[Low dielectric property (dielectric constant)]
After applying the radiation sensitive resin composition on the SUS substrate using a spinner, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having an average film thickness of 3.0 μm. Using an exposure machine (Canon "MPA-600FA"), the total irradiation amount is exposing the coating film so as to 9,000J / ^{m 2,} 30 minutes at 200 ° C. The exposed substrate in a clean oven An insulating film was formed on the SUS substrate by heating. Next, a Pt / Pd electrode pattern was formed on the insulating film by vapor deposition to produce a dielectric constant measurement sample. For the substrate having this electrode pattern, an electrode (Yokogawa Hewlett Packard's “HP16451B”) and a precision LCR meter (Yokogawa Hewlett Packard's “HP4284A”) are used. Measurements were made. At this time, if the dielectric constant is 3.3 or less, if the low dielectric property is good, it can be evaluated that the low dielectric property is poor if it exceeds 3.3.

[Transparency (Transmittance)]
Using a spinner, a radiation sensitive resin composition was applied on a silicon substrate that had been subjected to HMDS treatment at 60 ° C. for 60 seconds, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having an average film thickness of 3.0 μm. Formed. Using an exposure machine (Canon "MPA-600FA"), the total irradiation amount is exposing the coating film so as to 9,000J / ^{m 2,} 30 minutes at 200 ° C. The exposed substrate in a clean oven By heating, an insulating film was formed on the silicon substrate. An ultraviolet-visible light transmission spectrum of the substrate was collected, and transmittance at a wavelength of 400 nm was measured. At this time, when the transmittance is 95% or more, it can be evaluated that the transparency is good, and when it is less than 95%, the transparency is poor.

[Heat resistance (5% weight loss temperature)]
Using a spinner, a radiation sensitive resin composition was applied on a silicon substrate that had been subjected to HMDS treatment at 60 ° C. for 60 seconds, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having an average film thickness of 3.0 μm. Formed. Using an exposure machine (Canon "MPA-600FA"), the total irradiation amount is exposing the coating film so as to 9,000J / ^{m 2,} 30 minutes at 200 ° C. The exposed substrate in a clean oven By heating, an insulating film was formed on the silicon substrate. The coating film on the substrate was scraped off, and the temperature change was measured at 10 ° C./min using a thermogravimetry apparatus (EXSTAR TG / DTA7300 manufactured by SII Nanotechnology Co., Ltd.) in a nitrogen atmosphere, and the change in weight was measured. At this time, it can be evaluated that the heat resistance is good when the 5% weight loss temperature is 300 ° C. or higher and the heat resistance is poor when the temperature is less than 300 ° C.

[Minimum resolution]
Using a spinner, a radiation sensitive resin composition was applied on a silicon substrate that had been subjected to HMDS treatment at 60 ° C. for 60 seconds, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having an average film thickness of 3.0 μm. Formed. This coating film was irradiated with a predetermined amount of ultraviolet rays by a mercury lamp through a pattern mask having a square pattern of 1 to 10 μm on a side. 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, and then washed with running ultrapure water for 1 minute. At this time, the minimum mask size capable of forming a square pattern was measured. When this measured value is 4 μm or less, the resolution is good, and when it is 5 μm or more, it can be evaluated as defective.

  As shown in Table 2, each of the radiation-sensitive resin compositions of Examples has good sensitivity and resolution as a positive photosensitive material, and the obtained cured film has low dielectric constant, transparency, and heat resistance. It can be seen that all of the properties are good. On the other hand, in the radiation sensitive resin composition of the comparative example, the sensitivity and the resolution were not good, and none of the obtained cured films had all the characteristics of low dielectric property, transparency and heat resistance. In particular, in the radiation sensitive resin compositions of Comparative Examples 1 and 2, a negative pattern was formed and could not be used as a positive radiation sensitive resin composition.

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

Claims (10)

A positive radiation sensitive resin composition comprising a polymer component containing a first structural unit having a group represented by the following formula (1-1) or the following formula (1-2), and a radiation sensitive compound.

(In formula (1-1), R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or 1 to 1 carbon atoms. 6, wherein at least one of R ¹ , R ² and R ³ is an alkoxy group having 1 to 6 carbon atoms, A ¹ is a halogen atom, a hydroxy group, or a carbon atom having 1 to 6 carbon atoms. An alkyl group or an alkoxy group having 1 to 6 carbon atoms, and when A ¹ is plural, the plural A ¹ independently satisfy the above definition, and n1 is an integer of 0 to 4. * is Indicates the binding site.
In formula (1-2), R ¹ , R ² and R ³ have the same meaning as in formula (1-1). A ² is a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. If A ² is plural, a plurality of A ² are each independently satisfy the above definition. n2 is an integer of 0-6. * Indicates a binding site. )   2. The positive radiation-sensitive resin composition according to claim 1, wherein the polymer component further includes a second structural unit having a crosslinkable group in the same or different polymer as the polymer including the first structural unit. .   The positive radiation sensitive resin composition according to claim 2, wherein the crosslinkable group is an oxiranyl group, an oxetanyl group, a methylol group, or a combination thereof.   The positive electrode according to claim 1, 2 or 3, wherein the polymer component further comprises a third structural unit having an acidic group in the same or different polymer as the polymer containing the first structural unit. Type radiation sensitive resin composition.   The positive radiation-sensitive resin according to claim 4, wherein the acidic group is a carboxy group, a sulfo group, a phenolic hydroxyl group, a fluorine-containing alcoholic hydroxyl group, a phosphoric acid group, a phosphonic acid group, a phosphinic acid group, or a combination thereof. Composition. The positive radiation-sensitive resin composition according to claim 5, wherein the acidic group is represented by the following formula (2).

(In the above formula (2), R ⁴ is a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. R ⁵ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom. -4 fluorinated alkyl groups.)   The interlayer insulation film formed from the positive radiation sensitive resin composition of any one of Claims 1-6. A step of forming a coating film on a substrate using the positive radiation sensitive resin composition according to any one of claims 1 to 6,
Irradiating a part of the coating film with radiation,
A method for forming an interlayer insulating film, comprising: developing a coating film irradiated with the radiation; and heating the developed coating film.   A semiconductor device comprising the interlayer insulating film according to claim 7.   A display element comprising the semiconductor element according to claim 9.