JP6750213B2 - Radiation-sensitive resin composition, method for forming cured film, cured film, semiconductor element and display element - Google Patents

Description

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

In recent years, flexible displays such as electronic paper have received attention, and plastic substrates using polyethylene terephthalate or the like have been investigated as flexible display substrates. Since this substrate expands or contracts when heated, lowering the temperature of the manufacturing process is being studied. Above all, there is a demand for lowering the firing temperature in the step of forming a cured film such as an interlayer insulating film, which has the highest temperature in the manufacturing process.

As a material for the cured film capable of lowering the baking temperature, a radiation-sensitive resin composition having a small number of steps in pattern formation and high surface hardness is used, and for example, a carboxy group and an epoxy group are used. A radiation-sensitive resin composition containing a copolymer containing the same is known (see JP 2001-354822 A). In such a radiation-sensitive resin composition, the surface hardness as a cured film is obtained by reacting a carboxy group and an epoxy group. However, in the radiation-sensitive resin composition containing the above-mentioned copolymer, even when the radiation-sensitive resin composition is stored, the carboxy group and the epoxy group react with each other to increase the viscosity, that is, storage stability. It may cause deterioration of sex.

Therefore, curing that can sufficiently satisfy general characteristics such as surface hardness, chemical resistance, heat resistance, transparency (high light transmittance), low dielectric property (low relative dielectric constant), and development adhesion. There is a need for a radiation-sensitive resin composition that can form a film and is excellent in storage stability. As such a material, a composition containing a copolymer having a fluorinated alkyl alcohol structure and a crosslinkable group is known (see JP-A-2014-152192). In this composition, the fluorinated alkyl alcohol structure and a crosslinkable group such as an epoxy group react with each other to cure. However, in this composition, since the reactivity between the fluorinated alkyl alcohol structure and the epoxy group is slightly inferior to the reactivity between the carboxy group and the epoxy group, the heat resistance and chemical resistance of the obtained cured film are high. It may cause deterioration of sex.

JP 2001-354822A JP, 2014-152192, A

The present invention has been made based on the above circumstances, and an object thereof is to obtain a cured film having excellent heat resistance, chemical resistance, surface hardness, development adhesion, transparency and low dielectric property. Provided are a radiation-sensitive resin composition which is capable of satisfying characteristics such as storage stability and sensitivity, and a method for forming a cured film using the radiation-sensitive resin composition, a cured film, a semiconductor element and a display element. It is to be.

（上記式（１）中、Ｒ^１は、水素原子、ハロゲン原子、ヒドロキシ基又は炭素数１〜６のアルコキシ基である。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１〜６のアルコキシ基、炭素数１〜１０のアルキル基又はフェニル基である。） The invention made to solve the above problems includes a first structural unit having a group represented by the following formula (1), and the content ratio of the structural unit to all structural units is 20% by mass or more and 90% by mass or less. A first polymer (hereinafter, also referred to as “[A] polymer”), an epoxy compound having an epoxy group (hereinafter, also referred to as “[B] epoxy compound”), and a radiation-sensitive compound (hereinafter, A radiation-sensitive resin composition containing "[C] radiation-sensitive compound").

(In the above formula (1), R ¹ is a hydrogen atom, a halogen atom, a hydroxy group or an alkoxy group having 1 to 6 carbon atoms. R ² and R ³ are each independently a hydrogen atom, a halogen atom, It is a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.)

Another invention made to solve the above problems is to use the radiation-sensitive resin composition to form a coating film on a substrate, irradiating a part of the coating film with radiation, and the radiation is It is a method of forming a cured film, which comprises a step of developing an irradiated coating film and a step of heating the developed coating film.

Yet another invention made to solve the above problems is a cured film formed from the radiation-sensitive resin composition.

Still another invention made to solve the above problems is a semiconductor element including the cured film.

Yet another invention made to solve the above problems is a display device including the semiconductor device.

INDUSTRIAL APPLICABILITY The present invention can provide a cured film having excellent heat resistance, chemical resistance, surface hardness, development adhesiveness, transparency and low dielectric constant, and is also radiation-sensitive to satisfy the characteristics such as storage stability and sensitivity. A resin composition, a method for forming a cured film using the radiation-sensitive resin composition, a cured film, a semiconductor element and a display element can be provided. Therefore, the radiation-sensitive resin composition, the cured film formed from the radiation-sensitive resin, the semiconductor element and the display element, and the method for forming the cured film are the manufacturing process of electronic devices such as flexible displays. Can be suitably used.

<Radiation-sensitive resin composition>
The radiation-sensitive resin composition according to one embodiment of the present invention contains a [A] polymer, a [B] epoxy compound, and a [C] radiation-sensitive compound. The radiation-sensitive resin composition contains the [A] polymer, the [B] epoxy compound, and the [C] radiation-sensitive compound, and is excellent in film formation while suppressing the reactivity during storage. It can exhibit excellent curing reactivity. The reason why such an effect occurs is not clear, but it is presumed that it is caused by the presence of the group represented by the following formula (1) and the epoxy group in different compounds. More specifically, for example, in a solution, the distance between the reaction points of the group represented by the following formula (1) present in different compounds and the epoxy group becomes appropriate due to the presence of the solvent. It is presumed that the cause is. Therefore, according to the radiation-sensitive resin composition, a cured film having excellent heat resistance, chemical resistance, surface hardness, development adhesion, transparency and low dielectric property can be obtained, and storage stability and storage stability can be improved. The characteristics such as sensitivity can be fully satisfied. The radiation-sensitive resin composition can be used as either a positive-type or negative-type radiation-sensitive resin composition.

<[A] polymer>
[Structural unit (I)]
The polymer [A] contains a first structural unit having a group represented by the following formula (1) (hereinafter, also referred to as “structural unit (I)”). The structural unit (I) may be composed of a plurality of types of structural units.

In the above formula (1), R ¹ is a hydrogen atom, a halogen atom, a hydroxy group or an alkoxy group having 1 to 6 carbon atoms. R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.

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 alkoxy group having 1 to 6 carbon atoms represented by R ^{1 to} R ³ include a methoxy group, an ethoxy group, an n-propoxy group, and an i-propoxy group.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ² and 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.

As the R ^1, preferably an alkoxy group having 1 to 6 carbon atoms, more preferably a methoxy group and an ethoxy group, a methoxy group is more preferred.

As R ² and R ³ , an alkoxy group having 1 to 6 carbon atoms is preferable, a methoxy group and an ethoxy group are more preferable, and a methoxy group is still more preferable.

The structural unit (I) preferably has at least one group selected from the group represented by the following formula (2-1) and the group represented by the following formula (2-2).

In the above formula (2-1), R ¹ , R ² and R ³ have the same meaning as in the above formula (1). A ¹ is a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms or an alkyl 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.

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

When the above structural unit (I) has a group represented by the above formula (2-1) or (2-2), the heat resistance and the like of the obtained cured film can be further enhanced, and the storage stability is high. Can also be increased. Among the above groups, the group represented by the above formula (2-1) is more preferable. Of the above formula (2-1) and (2-2) ^in, specific examples and preferred groups for R 1 to R ³ are the same as ^R 1 to R ³ in the formula (1). The bonding position of the silicon atom on the aromatic ring may be any position with respect to the linking group, but in the case of the benzene ring, it is preferably the para position.

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

0 is preferable as n1. Moreover, 0 is preferable as n2.

Examples of the structural unit (I) include a structural unit represented by the following formula (3-1) and a structural unit represented by the following formula (3-2).

In the above formula (3-1) and ^(3-2), R 1 to R ³ have the same meanings as ^R 1 to R ³ in the formula (1). R ⁴ and R ⁵ are each independently a divalent organic group. However, in R ⁵ , those having an ester structure (—COO—) at the main chain side terminal are excluded. R ^A's are each independently a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group or a trifluoromethyl group.

Examples of the divalent organic group represented by R ⁴ and R ⁵ include hydrocarbon groups such as a divalent chain hydrocarbon group having 1 to 20 carbon atoms and a divalent alicyclic group having 3 to 20 carbon atoms. Examples thereof include a formula hydrocarbon group, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a divalent group obtained by combining two or more of these groups. However, some or all of the hydrogen atoms contained in these groups may be substituted with a substituent. Examples of the substituent include the groups represented by A ¹ and A ² .

Examples of the divalent chain hydrocarbon group having 1 to 20 carbon atoms include alkanediyl groups such as methanediyl group, ethanediyl group, propanediyl group, hexanediyl group and decandiyl group, alkenediyl groups such as ethenediyl group and propenediyl group, Examples thereof include alkynediyl groups such as ethynediyl group. Among these, an alkanediyl group is preferable, an alkanediyl group having 1 to 5 carbon atoms is more preferable, a propanediyl group is further preferable, and a propane-1,3-diyl group is particularly preferable.

Examples of the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cyclooctanediyl group, norbornanediyl group and adamantanediyl group. Can be mentioned.

Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenylene group (benzenediyl group) and a naphthylene group (naphthalenediyl group). Phenylene group and naphthylene group are preferable, and p- A phenylene group is more preferred.

As R ⁴ and R ⁵ , a divalent chain hydrocarbon group and a divalent aromatic hydrocarbon group are preferable, and a divalent aromatic hydrocarbon group is more preferable. When R ⁴ and R ⁵ are aromatic hydrocarbon groups, various properties such as heat resistance, chemical resistance and hardness of the obtained cured film can be further enhanced.

As R ^A , a hydrogen atom and a methyl group are preferable.

Examples of the structural unit represented by the above formula (3-1) include structural units represented by the following formulas (3-1-1) to (3-1-2). Examples of the structural unit represented by the above formula (3-2) include structural units represented by the following formulas (3-2-1) to (3-2-2).

In the above formula, ^{R A} has the same meaning as ^{R A} in the above formula (3-1) and (3-2). Among these, the structural unit represented by the formula (3-2-1) is preferable from the viewpoint of heat resistance and the like.

The lower limit of the content of the structural unit (I) in the polymer [A] is 20% by mass, preferably 30% by mass, and more preferably 40% by mass, based on all structural units constituting the polymer [A]. More preferred. On the other hand, the upper limit is 90% by mass, preferably 80% by mass, and more preferably 60% by mass. By setting the content ratio of the structural unit (I) within the above range, it is possible to improve the heat resistance and low dielectric property of the obtained cured film. When this content ratio is less than 20% by mass, the heat resistance of the obtained cured film tends to decrease and the dielectric constant tends to increase. Further, when the content ratio exceeds 90% by mass, the developability tends to decrease during pattern formation of the cured film.

[Structural unit (II)]
The polymer [A] preferably further has a structural unit having an acidic group (hereinafter, also referred to as “structural unit (II)”). The structural unit (II) may be composed of a plurality of types of structural units. By the above structural unit (II), the solubility or insolubility of the polymer [A] in a developing solution can be enhanced, or the curing reactivity can be enhanced.

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. A group etc. can be mentioned. Examples of the electron-withdrawing group include a halogen atom such as fluorine and chlorine, a nitro group and a cyano group. The acidic group is preferably 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 or a combination thereof, and a fluorine-containing alcohol. Of a hydroxyl group is more preferable. The effect of the present invention can be more effectively exhibited by such an acidic group.

The fluorine-containing alcoholic hydroxyl group is preferably a group represented by the following formula (4). The group represented by the following formula (4) can exhibit good cross-linking reactivity with the group represented by the formula (1) of the structural unit (I).

In the formula (4), R ⁶ is a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. R ⁷ 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 ⁶ include difluoromethyl group, trifluoromethyl group, 2,2-difluoroethyl group, 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.

As R ⁶ , a fluorinated alkyl group is preferable, a perfluoroalkyl group is more preferable, and a trifluoromethyl group (perfluoromethyl group) is further preferable.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁷ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, and t. A butyl group and the like. Examples of the fluorinated alkyl group having 1 to 4 carbon atoms represented by R ⁷ include those exemplified in the description of R ⁶ .

As R ⁷ , a hydrogen atom, a fluorine atom and a fluorinated alkyl group are preferable, a hydrogen atom and a fluorinated alkyl group are more preferable, a perfluoroalkyl group is further preferable, and a trifluoromethyl group is particularly preferable.

Further, both R ⁶ and R ⁷ are preferably a fluorinated alkyl group, more preferably both a perfluoroalkyl group, and even more preferably a trifluoromethyl group. When R ⁶ and R ⁷ are such groups, they serve as a suitable acidic group, so that a favorable cross-linking reaction occurs, and various properties of the obtained cured film such as chemical resistance can be further enhanced.

As the structural unit (II), a structural unit represented by the following formula (5-1), a structural unit represented by the following formula (5-2), a structural unit represented by the following formula (6), and others, Examples thereof include structural units derived from (meth)acrylic acid, structural units derived from vinyl sulfonic acid, and structural units having a phosphonic acid group.

In the above formula (5-1) and (5-2), ^{R 6} and ^{R 7} have the same meanings as ^{R 6} and ^{R 7} in the formula (4). R ⁸ and R ⁹ are each independently a (n+1)-valent organic group. However, R ⁹ excludes those having an ester structure (-COO-) at the main chain side terminal. 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, a plurality of R ⁶ and R ⁷ may be the same or different.

Examples of the (n+1)-valent organic group represented by R ⁸ and R ⁹ include, for example, a hydrocarbon group having a (n+1)-valent chain hydrocarbon group having 1 to 20 carbon atoms and a 3 to 20 carbon atom ( Examples thereof include an (n+1)-valent alicyclic hydrocarbon group, a (n+1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a (n+1)-valent group obtained by combining two or more of these groups. To be However, some or all of the hydrogen atoms contained in these groups may be substituted.

Examples of the (n+1)-valent chain hydrocarbon group having 1 to 20 carbon atoms include a group in which n hydrogen atoms have been removed from a linear or branched alkyl group having 1 to 20 carbon atoms. Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methyl group. Examples thereof include propyl group and t-butyl group.

Examples of the (n+1)-valent alicyclic hydrocarbon group having 3 to 20 carbon atoms include groups obtained by removing n hydrogen atoms from a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, norbornyl group, adamantyl group and the like.

Examples of the (n+1)-valent aromatic hydrocarbon group having 6 to 20 carbon atoms include groups in which n hydrogen atoms have been removed from a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, tolyl group and naphthyl group.

As the above R ⁸ and R ⁹ ,
Methylene group, ethylene group, propylene group (1,3-propylene group, 1,2-propylene group, etc.), tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group. , Undecamethylene group, dodecamethylene group, tridecamethylene group, tetradecamethylene group, pentadecamethylene group, hexadecamethylene group, heptadecamethylene group, octadecamethylene group, nonadecamethylene group, insalen group, 1- Methyl-1,3-propylene group, 2-methyl-1,3-propylene group, 2-methyl-1,2-propylene group, 1-methyl-1,4-butylene group, 2-methyl-1,4- Saturated chain hydrocarbon groups such as butylene group, methylidene group, ethylidene group, propylidene group, 2-propylidene group;
Cyclobutylene group such as 1,3-cyclobutylene group, cyclopentylene group such as 1,3-cyclopentylene group, cyclohexylene group such as 1,4-cyclohexylene group, 1,5-cyclooctylene group, etc. A monocyclic hydrocarbon ring group such as a cycloalkylene group such as a cyclooctylene group;
Norbornylene group (1,4-norbornylene group, 2,5-norbornylene group, etc.), adamantylene group (1,5-adamantylene group, 2,6-adamantylene group, etc.), cyclohexanetriyl group (1,3,3) 5-cyclohexanetriyl group) and other polycyclic hydrocarbon groups;
Aromatic hydrocarbon groups such as 1,3-phenylene group and 1,4-phenylene group;
And groups combining these are preferred.

R ⁸ is more preferably a methylene group, an ethylene group, a 1,2-propylene group, a 2,5-norbornylene group, a 1,4-phenylene group or a 1,3,5-cyclohexanetriyl group. As R ⁸ , an (n+1)-valent aromatic hydrocarbon group is more preferable. When R ⁸ is an aromatic hydrocarbon group, heat resistance and the like can be further improved.

Further, R ⁹ is more preferably a (n+1)-valent aromatic hydrocarbon group such as a 1,3-phenylene group or a 1,4-phenylene group, and further preferably a 1,4-phenylene group. When R ⁹ is an aromatic hydrocarbon group, heat resistance and the like can be further improved.

As R above, a hydrogen atom and a methyl group are preferable.

The above n is preferably 1 or 2.

Examples of the structural unit represented by the above formula (5-1) include structural units represented by the following formulas (5-1-1) to (5-1-6). Examples of the structural unit represented by the above formula (5-2) include structural units represented by the following formulas (5-2-1) to (5-2-2).

In the above formula, R has the same meaning as R in the above formulas (5-1) and (5-2). Among these, structural units containing an aromatic hydrocarbon group represented by the formulas (5-1-3), (5-2-1) and (5-2-2) are preferable, and the structural unit represented by the formula (5-1- The structural unit in which the group represented by —C(CF ₃ ) ₂ OH as an acidic group is substituted on the aromatic hydrocarbon group represented by 3) and (5-2-1) is more preferable.

In the above formula (6), R′ is a hydrogen atom, a methyl group or a trifluoromethyl group. R ^{L1 to} R ^L5 are each independently a hydrogen atom, a hydroxy group or an alkyl group having 1 to 4 carbon atoms. Y is a single bond, -COO- or -CONH-. p is an integer of 0-3. However, at least one of R ^{L1 to} R ^L5 is a hydroxy group.

The alkyl group having 1 to 4 carbon atoms represented by R ^{L1 to} R ^L5 has 1 carbon atom among the groups exemplified as the alkyl group having 1 to 10 carbon atoms represented by R ² and R ^3. ~4 alkyl groups can be mentioned.

Examples of the structural unit represented by the above formula (6) include structural units represented by the following formulas (6-1) to (6-8).

In the above formula, R'and p have the same meanings as R'and p in the above formula (6), respectively. Among these, the structural units represented by formulas (6-1), (6-4) and (6-7) are preferable.

Among these, the structural unit (II) is preferably the structural unit represented by the above formula (5-1) or the structural unit represented by the above formula (5-2). Furthermore, as the structural unit (II), the structural unit represented by the formula (5-1) or the structural unit represented by the formula (5-2) 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 When the structural unit (II) has such a constitution, various properties such as chemical resistance of the obtained cured film can be further enhanced.

As a minimum of the content rate of structural unit (II) in a [A] polymer, 5 mass% is preferred to all the structural units which constitute a [A] polymer, 10 mass% is more preferred, and 15 mass%. Is more preferable. On the other hand, the upper limit is preferably 60% by mass, more preferably 40% by mass, and further preferably 30% by mass. By setting the content ratio of the structural unit (II) within the above range, storage stability and various properties of the obtained cured film can be further improved.

Among the structural units (II), the lower limit of the content ratio of the structural units having a fluorine-containing alcoholic hydroxyl group, such as the structural units represented by the formulas (5-1) and (5-2), is [A ] 3 mass% is preferable with respect to all the structural units which comprise a polymer, and 5 mass% is more preferable. On the other hand, the upper limit is preferably 30% by mass, more preferably 15% by mass.

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

[Structural unit (III)]
The polymer [A] preferably further has a structural unit having a crosslinkable group (hereinafter, also referred to as “structural unit (III)”). The structural unit (III) may be composed of a plurality of types of structural units. The structural unit (III) can enhance the curing reactivity.

The crosslinkable group refers to a group other than the group represented by the above formula (1) and the acidic group, which is capable of forming a covalent bond with another group or the like. Examples of the crosslinkable group include an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3-epoxy structure), a vinyl group, a (meth)acryloyl group, a hydroxymethylphenyl group, a cyclic carbonate group, and the like. To be Among these, an oxiranyl group, an oxetanyl group, a vinyl group, a (meth)acryloyl group, a hydroxymethylphenyl group and a combination thereof are preferable, and an oxetanyl group is more preferable. When it is an oxetanyl group, it is possible to further improve the heat resistance and the like of the obtained cured film while suppressing the decrease in storage stability.

Examples of the structural unit (III) containing an oxiranyl group include structural units represented by the following formulas (7-1) to (7-5). Examples of the structural unit (III) containing an oxetanyl group include structural units represented by the following formulas (7-6) to (7-9). Examples of the structural unit (III) containing a cyclic carbonate group include structural units represented by the following formulas (7-10) to (7-14). Examples of the structural unit (III) containing a hydroxymethylphenyl group include structural units represented by the following formula (7-15) and the like.

In the above formula, R ^B is a hydrogen atom, a methyl group or a trifluoromethyl group.

Examples of the structural unit (III) containing a (meth)acryloyl group include 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;
Structural units derived from a monomer compound such as a penta(meth)acrylate compound such as dipentaerythritol penta(meth)acrylate may be mentioned.

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

As a minimum of the content rate of structural unit (III) in a [A] polymer, 5 mass% is preferred to all the structural units which constitute a [A] polymer, and 10 mass% is more preferred. On the other hand, the upper limit is preferably 50% by mass, more preferably 30% by mass. By setting the content ratio of the structural unit (III) in the above range, various properties of the obtained cured film can be further enhanced while maintaining high storage stability.

[Structural Unit (IV)]
The above-mentioned [A] polymer may have a structural unit other than the structural units (I) to (III) (hereinafter, also referred to as “structural unit (IV)”). When the polymer [A] has the structural unit (IV), the glass transition temperature of the resin can be adjusted to improve the melt flow property during thermosetting, the mechanical strength of the obtained cured film, and the chemical resistance. it can.

Examples of the structural unit (IV) include structural units represented by the following formulas (8-1) to (8-10).

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 to 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 (V), structural units represented by formulas (8-1), (8-6) to (8-8) and (8-10) are preferable.

Examples of the monomer compound providing 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, and bicyclo 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 (9), and other unsaturated compounds Structural units derived from compounds and the like can be mentioned.

In the above formula (9), ^{R M} and s have the same meanings as ^{R M} and s in the formula (8-9).

Examples of the chain alkyl ester of (meth)acrylic acid include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, Acrylic 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 thereof 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 ]decane-8-yl acrylate, tricyclo[5]acrylic acid. 2.2.1.0 ^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 Examples include 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;
Examples thereof include 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]Hept-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- Examples thereof include hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene and 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene.

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, and 2,3-dimethyl-1,3-butadiene.

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

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 a tetrahydropyran skeleton include (tetrahydropyran-2-yl)methyl methacrylate and 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 can be mentioned.

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 can be mentioned.

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

Among these, as the monomer compound that gives 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 An unsaturated compound having a skeleton represented by (9), an unsaturated aromatic compound, and a cyclic alkyl ester of acrylic acid are preferable, and styrene, vinyltoluene, methyl methacrylate, and t-methacrylic acid are preferable from the viewpoint of copolymerization reactivity. Butyl, n-lauryl methacrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide More preferred are tetrahydrofurfuryl (meth)acrylate, polyethylene glycol (n=2 to 10) mono(meth)acrylate and 3-(meth)acryloyloxytetrahydrofuran-2-one.

As a minimum of the content rate of structural unit (IV) in a polymer [A], 5 mass% is preferred to all the structural units which constitute a polymer [A], and 10 mass% is more preferred. On the other hand, the upper limit is preferably 50% by mass, more preferably 30% by mass. By setting the content ratio of the structural unit (IV) within the above range, chemical resistance and the like can be effectively improved.

<Method of synthesizing [A] polymer>
The polymer [A] can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical initiator. In addition, usually, the compounding ratio of each monomer at the time of polymerization corresponds to the content ratio of the corresponding structural unit in the obtained [A] polymer. As a specific synthesis method, (1) a method of dropping a solution containing a monomer and a radical initiator into a reaction solvent or a solution containing a monomer to cause a polymerization reaction, and (2) using a monomer A method of carrying out a polymerization reaction by separately adding a solution containing and a solution containing a radical initiator to a reaction solvent or a solution containing a monomer, and (3) a plurality of kinds containing each monomer. It is preferable that the solution and the solution containing a radical initiator are separately added to a reaction solvent or a solution containing a monomer to carry out a polymerization reaction.

The reaction temperature in these methods may be appropriately determined depending on the initiator species. Usually, it can be set to 30°C to 180°C. The dropping time varies depending on the reaction temperature, the type of the initiator, the monomer to be reacted and the like, but is usually 30 minutes to 8 hours. Further, the total reaction time including the dropping time also 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 above 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. You may use these initiators individually or in combination of 2 or more types.

The polymerization solvent is not limited as long as it is a solvent other than a solvent that inhibits polymerization (such as nitrobenzene having a polymerization inhibiting effect and a mercapto compound having a chain transfer effect), 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. You may use these solvent individually or in combination of 2 or more types.

The polymer obtained by the polymerization reaction can be recovered by the reprecipitation method. That is, after the completion of the polymerization reaction, the polymer solution is added to the reprecipitation solvent to recover the target polymer as powder. As the reprecipitation solvent, alcohols, alkanes and the like can be used alone or in combination 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 liquid separation operation, column operation, ultrafiltration operation, or the like. When the polymerization solvent is the same as the solvent of the radiation-sensitive resin composition to be prepared, the obtained polymer solution may be used as it is, or a solvent may be added to the obtained polymer solution to give a radiation-sensitive resin composition. May be used for preparation.

In the polymerization reaction for producing the polymer [A], 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; dimethyl. Xanthogens such as xanthogen sulfide and diisopropyl xanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

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

The content of the [A] polymer in the 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 30% by mass, and 40% by mass. Is more preferable. On the other hand, the upper limit is preferably 70% by mass, more preferably 60% by mass. By setting the content of the polymer [A] in the radiation-sensitive resin composition within the above range, various properties of the obtained cured film can be more effectively enhanced.

<[B] Epoxy compound>
The [B] epoxy compound is not particularly limited as long as it is a compound having an epoxy group. The epoxy group is a group having a cyclic ether structure. Examples of the epoxy group include an oxiranyl group having a three-membered ring (1,2-epoxy structure) and an oxetanyl group having a four-membered ring (1,3-epoxy structure). The [B] epoxy compound may be a second polymer containing the above structural unit having an epoxy group (hereinafter, also referred to as "[B1] polymer"), or a compound having another epoxy group ( Hereinafter, it may be "[B2] other epoxy compound" or "[B2] compound"). However, the polymer having the structural unit (I) is not included in the [B1] polymer.

<[B1] polymer>
The polymer [B1] is a polymer containing a structural unit having an epoxy group (structural unit (III′)).

[Structural unit (III')]
Examples of the structural unit (III′) having an epoxy group in the [B1] polymer include those having an epoxy group in the structural unit (III) having a crosslinkable group of the [A] polymer. Specifically, the structural units represented by the above formulas (7-1) to (7-9) and the like exemplified as the structural unit (III) of the polymer [A] can be exemplified. The structural unit (III′) may be composed of a plurality of types of structural units. As the structural unit (III′) of the polymer [B1], a structural unit having an oxiranyl group and a structural unit having an oxetanyl group are preferable, and a structural unit having an oxiranyl group is more preferable.

As a minimum of the content rate of structural unit (III') in a [B1] polymer, 20 mass% is preferred to all the structural units which constitute a [B1] polymer, and 40 mass% is more preferred. On the other hand, the upper limit is preferably 80% by mass, more preferably 70% by mass. By setting the content ratio of the structural unit (III) in the above range, various properties of the obtained cured film can be further enhanced while maintaining high storage stability.

[Structural unit (II)]
The above-mentioned [B1] polymer preferably further contains a structural unit (II) having an acidic group. The structural unit (II) may be composed of a plurality of types of structural units. By the above structural unit (II), the solubility or insolubility of the [B1] polymer in a developing solution can be enhanced, or the curing reactivity can be enhanced.

As the acidic group contained in the structural unit (II) of the polymer [B1], the same acidic groups as those contained in the structural unit (II) of the polymer [A] can be exemplified, and a carboxy group, a sulfo group, Phenolic hydroxyl group, fluorine-containing alcoholic hydroxyl group (hydroxyfluorinated alkyl group), phosphoric acid group, phosphonic acid group, phosphinic acid group and combinations thereof are preferable, and carboxy group, phenolic hydroxyl group and fluorine-containing alcoholic hydroxyl group are more preferable. ..

As the structural unit (II) of the polymer [B1], the same structural unit as the structural unit (II) of the polymer [A] can be exemplified.

The structural unit (II) of the polymer [B1] is represented by the structural unit represented by the above formula (5-1), the structural unit represented by the above formula (5-2), or the above formula (6). And a structural unit having a carboxy group are preferred. More preferable structure among the structural unit represented by the above formula (5-1), the structural unit represented by the above formula (5-2), and the structural unit represented by the above formula (6) is A] It is the same as the preferable structure described in the structural unit (II) of the polymer. As the structural unit having a carboxy group, a structural unit derived from (meth)acrylic acid is preferable.

As a minimum of the content rate of structural unit (II) in a [B1] polymer, 5 mass% is preferred to all the structural units which constitute a [B1] polymer, 10 mass% is more preferred, and 15 mass%. Is more preferable. On the other hand, the upper limit is preferably 50% by mass, more preferably 40% by mass, and further preferably 30% by mass. By setting the content ratio of the structural unit (II) within the above range, the storage stability and various properties of the obtained cured film can be further improved.

[Structural Unit (IV)]
The above-mentioned [B1] polymer may have a structural unit (IV) other than the structural units (III) and (II) (however, the structural unit (I) is excluded). When the polymer [B1] has the structural unit (IV), the glass transition temperature of the resin can be adjusted, and the melt flow property during thermosetting, the mechanical strength of the obtained cured film, and the chemical resistance can be improved. it can. Specific examples and preferable structures of the structural unit (IV) include the same as the structural unit (IV) of the polymer [A].

As a minimum of the content rate of structural unit (IV) in a [B1] polymer, 5 mass% is preferred to all the structural units which constitute a [A] polymer, and 10 mass% is more preferred. On the other hand, the upper limit is preferably 50% by mass, more preferably 30% by mass. By setting the content ratio of the structural unit (IV) within the above range, chemical resistance and the like can be effectively improved.

<Method for synthesizing [B1] polymer>
The [B1] polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical initiator. That is, the [B1] polymer can be produced according to the above-mentioned method for synthesizing the [A] polymer.

The polystyrene-equivalent weight average molecular weight (Mw) of the polymer [B1] by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1,000 or more and 30,000 or less. The ratio (Mw/Mn) of the Mw of the polymer [A] to the polystyrene reduced number average molecular weight (Mn) measured by GPC is preferably 1 or more and 3 or less.

The content of the [B1] polymer in the radiation-sensitive resin composition is not particularly limited, but the lower limit relative to 100 parts by mass of the [A] polymer is preferably 50 parts by mass, and more preferably 75 parts by mass. On the other hand, the upper limit is preferably 200 parts by mass, more preferably 150 parts by mass. By setting the content of the [B1] polymer in the radiation-sensitive resin composition in the above range, various properties of the obtained cured film can be more effectively enhanced.

<[B2] compound (other epoxy compound)>
As the [B2] compound, a compound having a plurality of the above epoxy groups in the molecule is preferably used. As the compound [B2], a compound having two or more oxiranyl groups or oxetanyl groups in the molecule can be preferably used.

Examples of the compound having two or more oxiranyl groups in the molecule include bisphenol type diglycidyl ethers such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, Hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, etc.;
As polyglycidyl ethers of polyhydric alcohol, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether etc.;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
Epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin and polyphenol type epoxy resin;
Diglycidyl esters of aliphatic long-chain dibasic acids;
Glycidyl esters of higher fatty acids;
Aliphatic polyglycidyl ethers;
Examples include epoxidized soybean oil and epoxidized linseed oil.

Examples of the compound having two or more oxetanyl groups in the molecule include 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene and di[1-ethyl-(3-oxetanyl)methyl]ether. (Alias: bis(3-ethyl-3-oxetanylmethyl)ether), 3,7-bis(3-oxetanyl)-5-oxa-nonane, 3,3′-[1,3-(2-methylenyl)pro Pandiylbis(oxymethylene)]bis-(3-ethyloxetane), 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanyl) Methoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ) Ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ) Ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, xylenebisoxetane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, pentaerythritol tris(3-ethyl-3) -Oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis(3-ethyl-3-oxetanylmethyl) ) Ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-) Oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-) 3-oxetanylmethyl) ether, PO-modified bisphenol A bis(3-E Cyl-3-oxetanylmethyl)ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO-modified bisphenol F(3-ethyl-3-oxetanylmethyl)ether and the like can be mentioned.

The content of the [B2] compound in the radiation-sensitive resin composition is not particularly limited, but the lower limit relative to 100 parts by mass of the [A] polymer is preferably 10 parts by mass, and more preferably 50 parts by mass. On the other hand, the upper limit is preferably 200 parts by mass, more preferably 150 parts by mass. By setting the content of the [B2] compound in the radiation-sensitive resin composition within the above range, various properties of the cured film obtained can be more effectively enhanced.

<[C] Radiation-sensitive compound>
Since the radiation-sensitive compound (C) contains the radiation-sensitive compound (photosensitizer) in the radiation-sensitive resin composition, the radiation-sensitive resin composition is exposed to radiation (visible light, ultraviolet ray, far ultraviolet ray, etc.). A positive or negative pattern can be formed. Examples of the [C] radiation-sensitive compound include a [C1] acid generator, a [C2] polymerization initiator, a [C3] base generator, and the like, and a [C1] acid generator and a [C2] polymerization initiator. And combinations thereof are preferred. These may be used alone or in combination of two or more. When a [C1] acid generator or a [C3] base generator is used as the [C] radiation-sensitive compound, the solubility of the exposed area in a developer changes to form a positive or negative pattern. Can be formed. Further, when the [C1] acid generator or the [C3] base generator functions as a curing catalyst to accelerate the curing of the exposed portion, a negative pattern can be formed. On the other hand, when a [C2] polymerization initiator is used as the [C] radiation-sensitive compound, it may react with a compound having a vinyl group or a (meth)acryloyl group (eg, [D] crosslinkable compound described later). The curing of the exposed portion is promoted, and a negative pattern can be formed.

<[C1] acid generator>
The [C1] acid generator (radiation-sensitive acid generator) is a compound that generates an acid in response to radiation. Examples of the [C1] acid generator include an oxime sulfonate compound, an onium salt, a sulfonimide compound, a sulfonic acid ester compound, a quinonediazide compound, a halogen-containing compound, a diazomethane compound and a carboxylic acid ester compound. These [C1] acid generators may be used alone or in combination of two or more.

The oxime sulfonate compound is preferably a compound containing an oxime sulfonate group represented by the following formula (10).

In the above formula (10), ^{R a} is an alkyl group having 1 to 12 carbon atoms, fluoroalkyl group having 1 to 12 carbon atoms, alicyclic hydrocarbon group or an aryl having 6 to 20 carbon atoms having 4 to 12 carbon atoms It is a base. Some or all of the hydrogen atoms contained in these alkyl group, alicyclic hydrocarbon group and aryl group may be substituted with a substituent.

Specific examples of the oxime sulfonate compound include (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile and (5-octylsulfonyloxyimino-5H-thiophene-2-). (Ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-) Ylidene)-(2-methylphenyl)acetonitrile, 2-(octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile and the like can be mentioned, and these can be obtained as commercial products.

Examples of onium salts include diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, benzothiazonium salts, tetrahydrothiophenium salts, and benzylsulfonium salts. 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, and 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)diphenylmaleimide, 4-methylphenylsulfonyloxy)diphenylmaleimide,trifluoromethanesulfonic acid-1, 8-naphthalimide and the like can be mentioned.

Examples of the sulfonic acid ester compound include haloalkyl sulfonic acid ester 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 a 1,2-naphthoquinonediazidesulfonic acid halide or a 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.

Specific examples of the mother nucleus include, for example, trihydroxybenzophenone such as 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone.
As tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,3,4 , 2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone and the like;
As pentahydroxybenzophenone, 2,3,4,2′,6′-pentahydroxybenzophenone and the like;
As hexahydroxybenzophenone, 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxybenzophenone and the like;
As (polyhydroxyphenyl)alkane, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1,1-tris(p-hydroxyphenyl) Ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl-4-) Hydroxyphenyl)-3-phenylpropane, 4,4′-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, bis(2,5-dimethyl-4) -Hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-1,1'-spirobiindene-5,6,7,5',6',7'-hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan and the like;
Can be mentioned.

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

Among these, as the mother nucleus, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris(p-hydroxyphenyl)ethane, and 4,4'-[1-[4- [1-[4-Hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol is preferred.

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 More preferred is 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and further preferred.

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 of the phenolic compound or the alcoholic compound (mother nucleus) with the 1,2-naphthoquinonediazidesulfonic acid halide or the 1,2-naphthoquinonediazidesulfonic acid amide, the number of OH groups in the mother nucleus is preferable. It is preferable to use 1,2-naphthoquinonediazidesulfonic acid halide or 1,2-naphthoquinonediazidesulfonic acid amide corresponding to 30 mol% or more and 85 mol% or less. The condensation reaction can be carried out by a known method.

As the [C1] acid generator, a quinonediazide compound is preferable when the radiation-sensitive resin composition is a positive type. On the other hand, when the radiation-sensitive resin composition is a negative type, acid generators other than quinonediazide compounds are preferable, and onium salts and sulfonimide compounds are more preferable. By using the above compound as the [C1] acid generator, the sensitivity and the like can be further improved.

The lower limit of the content of the [C1] acid generator is preferably 1 part by mass, more preferably 3 parts by mass, and even more preferably 5 parts by mass, relative to 100 parts by mass of the [A] polymer. On the other hand, the upper limit is preferably 50 parts by mass, more preferably 30 parts by mass. By setting the content of the [C1] acid generator within the above range, it is possible to optimize the sensitivity and form a cured film having more excellent characteristics.

<[C2] Polymerization initiator>
The [C2] polymerization initiator (radiation-sensitive radical polymerization initiator) is a compound capable of initiating polymerization by generating radicals in response to radiation. Examples of the [C2] polymerization initiator include O-acyl oxime compounds, acetophenone compounds, and biimidazole compounds. These compounds may be used alone or in combination of two or more.

Examples of the O-acyl oxime compound include 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)] and ethanone-1-[9-ethyl-6-(2-methylbenzoyl). )-9H-carbazol-3-yl]-1-(O-acetyloxime), 1-(9-ethyl-6-benzoyl-9.H.-carbazol-3-yl)-octan-1-one oxime-O. -Acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9. H. -Carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9. H. -Carbazol-3-yl]-ethan-1-one oxime-O-benzoate, ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9. H. -Carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9. H. -Carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9. H. -Carbazol-3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl }-9. H. -Carbazol-3-yl]-1-(O-acetyloxime) and the like.

Of these, 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-1-(O-acetyloxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9. H. -Carbazol-3-yl]-1-(O-acetyloxime) and ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl }-9. H. -Carbazol-3-yl]-1-(O-acetyloxime) is preferred.

Examples of the acetophenone compound include α-aminoketone compounds and α-hydroxyketone compounds.

Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one and 2-dimethylamino-2-(4-methylbenzyl)-1-(4 -Morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one and the like can be mentioned.

Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone and the like can be mentioned.

As the acetophenone compound, an α-aminoketone compound is preferable, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)- More preferred are 1-(4-morpholin-4-yl-phenyl)-butan-1-one and 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis(2,4). -Dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5 Examples include'-tetraphenyl-1,2'-biimidazole and the like. Among these, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole is preferable.

Among these, as the [C2] polymerization initiator, an O-acyl oxime compound is preferable, and a polymerization initiator having a carbazole skeleton in the molecule is particularly preferable. For example, ethanone 1-[9-ethyl-6-(2-methyl Benzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) and the like are preferable.

The [C2] polymerization initiators may be used alone or in combination of two or more. The lower limit of the content of the [C2] polymerization initiator is preferably 1 part by mass, more preferably 5 parts by mass, and even more preferably 15 parts by mass with respect to 100 parts by mass of the [A] polymer. On the other hand, the upper limit is preferably 40 parts by mass, more preferably 20 parts by mass. By setting the content ratio of the [C2] polymerization initiator within the above range, good curability and the like can be exhibited.

<[C3] base generator>
The [C3] base generator (radiation-sensitive base generator) is a compound that generates a base in response to radiation. Examples of the [C3] 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), etc. Can be mentioned.

<Other ingredients>
The radiation-sensitive resin composition may further contain other components in addition to the above-mentioned [A] polymer, [B] epoxy compound and [C] radiation-sensitive compound. Examples of such other components include a solvent described below, a [D] crosslinkable compound, an [E] antioxidant, a [F] surfactant, and a [G] adhesion aid. In addition, the said radiation sensitive resin composition may use each said component individually or in combination of 2 or more types.

<[D] Crosslinkable compound>
The [D] crosslinkable compound is usually a compound having a plurality of crosslinkable groups. However, the [D] crosslinking compound does not include the above-mentioned [A] polymer and [B] epoxy compound. Examples of the crosslinkable group include a vinyl group, a (meth)acryloyl group and a hydroxymethylphenyl group. Among these, vinyl groups and (meth)acryloyl groups are preferable. By using the [D] crosslinkable compound having such a crosslinkable group together with the [C2] polymerization initiator, curing of the exposed area is promoted and a negative pattern can be efficiently formed.

Examples of the crosslinkable compound [D] include polyfunctional (meth)acrylic acid esters such as bifunctional (meth)acrylic acid esters and trifunctional or higher functional (meth)acrylic acid esters.

Examples of the bifunctional (meth)acrylic acid ester include ethylene glycol di(meth)acrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetra Examples thereof include ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, and 1,9-nonanediol dimethacrylate.

Examples of trifunctional or higher functional (meth)acrylic acid esters include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate. Acrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, tri(2-acryloyloxy) Ethyl)phosphate, tri(2-methacryloyloxyethyl)phosphate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, a linear alkylene group and an alicyclic structure, and 2 A compound having at least one isocyanate group and a compound having at least one hydroxy group in the molecule and having three, four or five (meth)acryloyloxy groups Examples include functional urethane acrylate compounds.

The crosslinkable compound [D] may be a polymer. Examples of such a polymer include a polymer containing a structural unit having a (meth)acryloyl group or a vinyl group. Examples of the structural unit having a (meth)acryloyl group or a vinyl group include those exemplified in the structural unit (III) of the polymer [A]. As the method of introducing the (meth)acryloyl group or vinyl group into a specific structural unit of the polymer, the method described in the structural unit (III) of the polymer [A] can be used.

The content of the [D] crosslinkable compound in the radiation-sensitive resin composition is not particularly limited, but the lower limit relative to 100 parts by mass of the [A] polymer is preferably 10 parts by mass, and more preferably 50 parts by mass. On the other hand, the upper limit is preferably 200 parts by mass, more preferably 150 parts by mass. By setting the content of the [D] crosslinkable compound in the radiation-sensitive resin composition within the above range, various properties of the obtained cured film can be more effectively enhanced.
<[E] Antioxidant>
[E] The antioxidant is a component capable of decomposing radicals generated by exposure or heating or peroxide generated by oxidation to prevent the cleavage of the bond of the polymer molecule. As a result, the obtained cured film is prevented from oxidative deterioration over time, and, for example, a change in the thickness of the cured film can be suppressed.

Examples of the [E] antioxidants include compounds having a hindered phenol structure, compounds having a hindered amine structure, compounds having an alkyl phosphite structure, compounds having a thioether structure, and the like. Among these, as the [E] antioxidant, compounds having a hindered phenol structure are preferable.

Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and thiodiethylenebis[3-(3,5-di-). tert-Butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris-(3,5-di-t-butyl-4-hydroxy) Benzyl)-isocyanurate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N′-hexane-1,6 -Diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenylpropionamide), 3,3',3',5',5'-hexa-tert-butyl-a,a',a '-(Mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, 4,6-bis(dodecylthiomethyl)-o-cresol, ethylene Bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate, hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] , 1,3,5-Tris[(4-tert-butyl-3-hydroxy-2,6-xylyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)- Trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamine)phenol, 1,3,5-trimethyl-2,4. 6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 2,6-di-t-butyl-4-cresol and the like can be mentioned.

Examples of commercially available compounds having the hindered phenol structure include, for example, Adeka Stub AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, AO-330 (above, ADEKA), sumilizerGM, GS, MDP-S, BBM-S, WX-R, GA-80 (above, Sumitomo Chemical Co., Ltd.), IRGANOX1010, 1035, 1076. , 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 565, IRGAMOD295 (above, BASF), Yoshinox BHT, BB, 2246G, 425. , Ibid 250, ibid 930, iSS, iTT, ibid 917, ibid 314 (above, AP Corporation).

Among the compounds having a hindered phenol structure, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-Di-t-butyl-4-hydroxybenzyl)benzene and 2,6-di-t-butyl-4-cresol are more preferred.

The content of the [E] antioxidant is preferably 0.001 part by mass or more and 5 parts by mass or less based on 100 parts by mass of the [A] polymer. By setting the content of the [E] antioxidant in the above range, it is possible to effectively suppress oxidative deterioration of the obtained cured film over time.

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

The above-mentioned fluorine-based surfactant is preferably a compound having a fluoroalkyl group and/or a fluoroalkylene group at at least one of the terminal, main chain and side chain sites, for example 1,1,2,2-tetrafluoro-n. -Octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di(1,1,2,2) 2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di(1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di(1,1,2,2,3,3) 3-hexafluoro-n-pentyl) ether, octapropylene glycol di(1,1,2,2-tetrafluoro-n-butyl) ether, sodium perfluoro-n-dodecanesulfonate, 1,1,2,2,3,3. 3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, fluoroalkylcarboxylic acid Sodium acid, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylates, carboxylic acid fluoro Examples thereof include alkyl esters.

Examples of commercially available products of the above-mentioned fluorine-based surfactant include BM-1000, BM-1100 (above, BM CHEMIE), Megafac F142D, the same F172, the same F173, the same F183, the same F178, the same F191, the same F471, The same F476 (above, Dainippon Ink and Chemicals, Inc.), Florard FC-170C, the same -171, the same -430, the same -431 (above, Sumitomo 3M Co., Ltd.), Surflon S-112, the same -113, the same -131, Same-141, Same-145, Same-382, Surflon SC-101, Same-102, Same-103, Same-104, Same-105, Same-106 (above Asahi Glass Co., Ltd.), Ftop EF301, Same 303, 352 (above, Shin-Akita Chemical Co., Ltd.), Futgent FT-100, same-110, same-140A, same-150, same-250, same-251, same-300, same-310, same-400S, FTX. -218, the same -251 (above, Neos company) etc. are mentioned.

Examples of commercially available products of the above silicone-based surfactants include Toray silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (above, Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 ( As mentioned above, GE Toshiba Silicone Co., Ltd., organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned.

Examples of the other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n. And polyoxyethylene aryl ethers such as nonyl phenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; and the like.

Examples of commercially available products of the above-mentioned other surfactants include (meth)acrylic acid-based copolymer Polyflow No. 57, same No. 57. 95 (above, Kyoeisha Chemical Co., Ltd.) and the like.

The content of the [F] surfactant is preferably 0.01 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the [A] polymer. By setting the content of the [F] surfactant within the above range, the film formability can be effectively improved.

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

Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxy. Examples thereof include propyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

The content of the adhesion promoter [G] is preferably 0.01 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the polymer [A].

<Method for preparing radiation-sensitive resin composition>
The radiation-sensitive resin composition is prepared by mixing the [A] polymer, the [B] epoxy compound, the [C] radiation-sensitive compound and, if necessary, other components in a predetermined ratio, and preferably in a suitable solvent. It can be prepared by dissolving. The prepared radiation-sensitive resin composition is preferably filtered, for example, with a filter having a pore size of about 0.2 μm.

As the solvent used for the preparation of the radiation-sensitive resin composition, those that uniformly dissolve or disperse each component contained in the radiation-sensitive resin composition and do not react with the above-mentioned components are used. Examples of such a solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents and the like.

Examples of the alcohol solvent include, as monoalcohol solvents, methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, tert-butanol, n-pentanol, i-pen. Tanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n. -Octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-hepta Decyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, etc.;
As the polyhydric alcohol solvent, ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2 , 4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and the like;
As a polyhydric alcohol partial ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Examples include monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and the like.

Examples of the ether solvent include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and the like.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n. -Hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone and the like.

Examples of the amide solvent include N,N′-dimethylimidazolidinone, N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide. , N-methylpropionamide, N-methylpyrrolidone and the like.

Examples of the ester solvent include methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, acetic acid. 3-methoxybutyl, 3-methyl-3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, acetoacetic acid Ethyl acetate ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n acetate -Propyl ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoacetate Ethyl ether, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate , N-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate and the like.

Examples of the above-mentioned hydrocarbon solvent include, as aliphatic hydrocarbon solvents, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, methylcyclohexane and the like;
As aromatic hydrocarbon solvents, benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene , N-amylnaphthalene and the like.

Further, the solvent may further contain a high boiling point solvent such as caproic acid, caprylic acid, ethylene carbonate, propylene carbonate.

<Cured film forming method>
A method for forming a cured film according to an embodiment of the present invention,
(1) A step of forming a coating film on a substrate using the radiation-sensitive resin composition (hereinafter, also referred to as “step (1)”),
(2) A step of irradiating a part of the coating film with radiation (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, "step (4)" Also called)
Equipped with.

Since the radiation-sensitive resin composition has the above-mentioned properties, according to the method for forming the cured film, heat resistance, chemical resistance, surface hardness, development adhesion, low dielectric property, transparency, etc. It is possible to form a cured film sufficiently satisfying the general characteristics of. Further, according to the method for forming the cured film, it is possible to perform development with good sensitivity. Hereinafter, each step will be described in detail.

[Step (1)]
In this step, a coating film is formed on the substrate using the radiation sensitive resin composition. Specifically, the radiation-sensitive resin composition in the form of a solution is applied to the surface of the substrate and preferably prebaked to remove the solvent to form a coating film. Examples of the substrate include a glass substrate, a silicon substrate, a plastic substrate, and a substrate having various metal thin films formed on the surface thereof. Examples of the plastic substrate include resin substrates made of plastic such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyether sulfone, polycarbonate and polyimide.

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

[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, charged particle beams, and the like.

Examples of the ultraviolet rays include g-line (wavelength 436 nm) and i-line (wavelength 365 nm). Examples of the far ultraviolet rays include KrF excimer laser light. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam and the like. Among these radiations, ultraviolet rays are preferable, and among the ultraviolet rays, radiations including g rays, h rays and/or i rays are 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 the radiation in the step (2) is developed with a developing solution to remove the irradiation portion of the radiation. Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyl. Diethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo Examples include an aqueous solution of an alkali (basic compound) such as [4,3,0]-5-nonane. Further, an aqueous solution prepared by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous alkali solution, or an alkaline aqueous solution containing a small amount of various organic solvents capable of dissolving the radiation-sensitive resin composition is used as a developing solution. You may use as.

As a developing method, for example, a suitable method such as a puddle method, a dipping method, a rocking dipping method, and a shower method can be adopted. The developing time varies depending on the composition of the radiation-sensitive resin composition, but can be, for example, 30 seconds or more and 120 seconds or less. After the development step, the patterned coating film is rinsed with running water, and then the entire surface is irradiated with radiation from a high-pressure mercury lamp or the like (post-exposure), so that the coating film remains in the coating film [C ] It is preferable to decompose 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. The heating method is not particularly limited, but heating can be performed using a heating device such as an oven or a hot plate. The heating temperature in this step is preferably 200° C. or lower. Since heating at such a low temperature is possible, the method for forming a cured film can be preferably used for forming a cured film such as an interlayer insulating film on a plastic substrate of a flexible display. The lower limit of the heating temperature is preferably 120°C. The heating time varies depending on the type of heating equipment, but is, for example, 5 minutes or more and 40 minutes or less when performing heat treatment on a hot plate, and 30 minutes or more and 80 minutes or less when performing heat treatment in an oven. be able to. In this way, a target cured film such as an interlayer insulating film can be formed on the substrate.

<Cured film>
The cured film according to one embodiment of the present invention is formed from the radiation sensitive resin composition. The method for forming the cured film is not particularly limited, but preferably the above-described method for forming the cured film can be used. Since the cured film is formed from the radiation-sensitive resin composition, it has excellent heat resistance, chemical resistance, surface hardness, development adhesion, low dielectric property, transparency and the like. Since the cured film has the above characteristics, it is suitable as, for example, an interlayer insulating film of a display element, a spacer, a protective film, a colored pattern for a color filter, or the like.

<Semiconductor element>
A semiconductor device according to an embodiment of the present invention includes the cured film. This cured film is used, for example, as an interlayer insulating film for insulating between wirings in the semiconductor element, a spacer, a protective film, a colored pattern for a color filter, and the like. The semiconductor element can be formed using a known method. Since the semiconductor element has the cured film, it 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 the semiconductor element having the cured film, the display element satisfies general characteristics practically required as the display element. Examples of the display element include a liquid crystal display element. In the above liquid crystal display device, for example, two TFT array substrates having a liquid crystal alignment film formed on the surface thereof are arranged to face each other on the liquid crystal alignment film side via a sealant provided in the peripheral portion 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 cured film as an interlayer insulating film.

Hereinafter, the present invention will be specifically described based on Examples, but the present 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: Showa Denko GPC-101
GPC column: Shimadzu GLC GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined. Mobile phase: Tetrahydrofuran column temperature: 40°C.
Flow rate: 1.0 mL/min Sample concentration: 1.0 mass%
Sample injection volume: 100 μL
Detector: Differential refractometer Standard substance: Monodisperse polystyrene

[Measurement of Structural Unit Content of Polymer]
¹ H-NMR (analytical instrument: "ECX400P" by JEOL Ltd.), ¹³ C-NMR (analytical instrument: "ECX400P" by JEOL Ltd.), FT-IR (analytical instrument: "Nexus 470" by Nicolet Ltd.) and heat. Decomposition gas chromatography-mass spectrometry (analytical instrument: "JPS330" (Py) from Japan Analytical Industry Co., "GC6890A" (GC) from Agilent, "5973Inert" (MS) from Agilent) The content (content ratio) was determined.

<Synthesis of [A] Polymer>
The monomer compounds used for synthesizing the polymers of Examples and Comparative Examples are shown below. The following monomer compounds (1) to (4) are compounds that give the structural unit (I), and monomer compounds (5) to (10) are compounds that give the structural unit (II), The monomer compounds (11) to (14) are compounds which give the structural units (III) and (III′), and the monomer compounds (15) to (16) are compounds which give the structural unit (IV). ..

[Synthesis Example 1] (Synthesis of Polymer (A-1))
A flask equipped with a cooling tube and a stirrer was charged with 7 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether. Then, 60 parts by mass of the monomer compound (1), 10 parts by mass of the monomer compound (5), 10 parts by mass of the monomer compound (9), and 20 parts by mass of the monomer compound (15) were charged, and nitrogen was added. Replaced. Next, while gently stirring, the temperature of the solution was raised to 70° C., and this temperature was maintained for 4 hours to carry out polymerization to obtain a polymer solution containing the polymer (A-1). The solid content concentration of this polymer solution was 30.4% by mass, the Mw of the polymer (A-1) was 8,000, and the molecular weight distribution (Mw/Mn) was 2.3. The content ratio of each structural unit of the polymer (A-1) was the same as the charging ratio of the corresponding monomer compound.

[Synthesis Examples 2 to 31, Comparative Synthesis Examples 1 to 4] (Polymers (A-2) to (A-19), Polymers (B1-1) to (B1-12) and Polymers (P1) to (( Synthesis of P4))
Polymer (A-2) to (A-19) and polymer (B1-1) were operated in the same manner as in Synthesis Example 1 except that the types and amounts of the monomer compounds shown in Table 1 below were used. ~ (B1-12) and polymers (P1) to (P4) were synthesized. The solid content concentration of each of the obtained polymer solutions, and the Mw and Mw/Mn of each polymer were the same as those of the polymer (A-1). The content ratio of each structural unit of each polymer was the same as the charging ratio of the corresponding monomer compound. The blank column in Table 1 indicates that the corresponding monomer compound was not mixed.

[Synthesis Example 32] (Synthesis of Polymer (D-1))
In a container equipped with a stirrer, 5 parts by mass of 2,2′-azobisisobutyronitrile and 250 parts by mass of propylene glycol monomethyl ether acetate were charged, followed by 18 parts by mass of methyl methacrylate and tricyclomethacrylate [5.2]. .1.0 ^2,6 ]Decan-8-yl (25 parts by mass), methacrylic acid 2-hydroxyethyl ester (30 parts by mass) and benzyl methacrylate (22 parts by mass) were charged, and the atmosphere was replaced with nitrogen. Then, the temperature of the solution was raised to 70° C. with gentle stirring, and the temperature was maintained for 5 hours to carry out polymerization to obtain a copolymer (α) solution having a solid content concentration of 29.2%. ..

Then, 30 parts by mass of 2-methacryloyloxyethyl isocyanate (Karenzu MOI of Showa Denko KK) and 0.2 parts by mass of 4-methoxyphenol were added to the copolymer (α) solution, and then at 40° C. for 1 hour. Further, the mixture was reacted at 60° C. for 2 hours with stirring. The progress of the reaction between the isocyanate group and the hydroxy group of the copolymer (α) was confirmed by IR (infrared absorption) spectrum. After 1 hour at 40° C. and further after reacting at 60° C. for 2 hours, the IR spectra of the respective solutions confirmed that the peak near 2270 cm ⁻¹ derived from the isocyanate group was decreasing. By completing the above reaction, a solution of the polymer (B1-13) having a solid content concentration of 31.0% was obtained. The weight average molecular weight (Mw) of the obtained polymer (D-1) was 14,000.

<Preparation of radiation-sensitive resin composition>
The components used in the preparation of the radiation-sensitive resin composition other than the polymers synthesized as the polymer [A] and the polymer [B1] which is the epoxy compound [B] are shown below.
[B2] Compound B2-1: Bisphenol A type epoxy resin (“jER1009” manufactured by Mitsubishi Chemical Corporation)
B2-2: Bisphenol A type epoxy resin (“jER1004” by Mitsubishi Chemical Corporation)
B2-3: Bisphenol A type epoxy resin (“jER4010P” manufactured by Mitsubishi Chemical Corporation)
B2-4: Tetrakis(hydroxyphenyl)ethane type epoxy resin (“jER1031S” from Mitsubishi Chemical Corporation)
B2-5: Biphenyl type epoxy resin (“jERYX4000H” manufactured by Mitsubishi Chemical Corporation)
B2-6: Bisphenol F-type epoxy resin (“YDF-2004” by Nippon Steel & Sumikin Chemical Co., Ltd.)
B2-7: o-cresol novolac type epoxy resin (“YDCN-704A” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
B2-8: Crystalline epoxy resin (“YDC-1312” by Nippon Steel & Sumikin Chemical Co., Ltd.)
B2-9: Crystalline epoxy resin (“YSLV-80XY” of Nippon Steel & Sumikin Chemical Co., Ltd.)
B2-10: Crystalline epoxy resin (“YSLV-120TE” of Nippon Steel & Sumikin Chemical Co., Ltd.)
B2-11: Naphthylene ether type epoxy resin (“HP-6000” manufactured by DIC)
B2-12: Naphthalene type epoxy resin (“HP-4710” manufactured by DIC)
B2-13: Dicyclopentadienyl diphenol type epoxy resin ("HPC-8000-65T" manufactured by DIC)

[C1] Acid Generator (C1-1) Acid Generator for Positive-Type Radiation-sensitive Resin Composition C1-1-1:1,4'-[1-[4-[1-[4-hydroxyphenyl] Condensation product of -1-methylethyl]phenyl]ethylidene]bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) C1-1-2:1,1, Condensate (C1-2) negative radiation-sensitive resin of 1-tri(p-hydroxyphenyl)ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) Acid generator C1-2-1 for composition: trifluoromethanesulfonic acid-1,8-naphthalimide (Aldrich)
C1-2-2: Aromatic sulfonium salt (“San-Aid SI-110” from Sanshin Chemical Industry Co., Ltd.)

[C2] Polymerization initiator C2-1: 1,2-octanedione 1-[4-(phenylthio)-2-(O-benzoyloxime)] ("IRGACURE OXE01" manufactured by BASF)
C2-2: Ethanone 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) ("IRGACURE OXE02" manufactured by BASF).
C2-3: "NCI-831" of ADEKA
C2-4: "NCI-930" of ADEKA

[D] Crosslinkable compound D-1: Polymer synthesized in Synthesis Example 32 (D-1)
D-2: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.)
D-3: 12 mol ethylene oxide modified dipentaerythritol hexaacrylate ("KAYARAD DPEA-12" manufactured by Nippon Kayaku Co., Ltd.)
D-4: Dipentaerythritol pentaacrylate modified with succinic acid ("Aronix M-520" manufactured by Toagosei Co., Ltd.)
D-5: Carboxyl group-containing polybasic acid-modified acrylic oligomer (“Aronix M-510” manufactured by Toagosei Co., Ltd.)

[Example 1]
[A] A polymer solution containing 100 parts by mass (solid content) of the polymer (A-1) as a polymer, and [B] 100 parts by mass (solid content) of the polymer (B1-1) as an epoxy compound. Polymer solution to be contained, 10 parts by mass of acid generator (C1-1-1) as [C] radiation-sensitive compound, 5 parts by mass of adhesion aid (γ-glycidoxypropyltrimethoxysilane), surfactant (Neos "FTX-218") 0.5 parts by mass and an antioxidant (BASF "IRGANOX1010") 0.1 parts by mass are mixed, and a solvent is added so that the solid content concentration is 30% by mass. Was added as diethylene glycol methyl ethyl ether. Then, a positive type radiation sensitive resin composition was prepared by filtering with a membrane filter having a pore size of 0.2 μm.

[Examples 2 to 60 and Comparative Examples 1 to 10]
[A] polymer, [B] epoxy compound ([B1] polymer and [B2] compound), [C] radiation-sensitive compound ([C1] acid generator and [C2] polymerization initiator) and [D] Negative and positive radiation-sensitive resin compositions were prepared in the same manner as in Example 1 except that the type of crosslinking compound shown in Table 2 was used.

<Evaluation>
The negative and positive radiation-sensitive resin compositions thus prepared were used and evaluated according to the following evaluation methods. The evaluation results are also shown in Table 2.

[Storage stability]
The viscosity (V ₁ ) of each radiation-sensitive resin composition was measured, and each radiation-sensitive resin composition was left in an oven at 40°C for 1 week. The viscosity (V ₂ ) after heating was measured, and the viscosity change rate (%) was calculated from the following formula, which was used as an index of storage stability.
Viscosity change rate _{(%) = {(V 2} -V 1) / V 1} × 100 (%)
Viscosity change rate is divided into A: viscosity change rate of less than 5%, B: viscosity change rate of 5% or more and less than 10%, C: viscosity change rate of 10% or more and less than 15%, D: viscosity change rate of 15% or more, In the case of A or B, the storage stability was evaluated as good, and in the case of C or D, the storage stability was evaluated as poor. The viscosity was measured at 25° C. using an E-type viscometer (“VISCONIC ELD.R” manufactured by Toki Sangyo Co., Ltd.).

[sensitivity]
Each radiation-sensitive resin composition was applied on a silicon substrate using a spinner and then prebaked at 90° C. for 2 minutes on a hot plate to form a coating film having a film thickness of 3.0 μm. The obtained coating film was irradiated with a predetermined amount of ultraviolet rays from a mercury lamp through a pattern mask having a line-and-space pattern with a width of 10 μm. Next, a developing solution containing a 2.38 mass% tetramethylammonium hydroxide solution was used for development treatment at 25° C. for 60 seconds, followed by washing with running ultrapure water for 1 minute. At this time, the minimum ultraviolet ray irradiation amount capable of forming a line-and-space pattern having a width of 10 μm was measured. In the positive type radiation sensitive resin composition, the sensitivity was evaluated as good when the measured value was less than 250 J/m ^2, and in the negative type radiation sensitive resin composition, the measured value was 100 J/m 2. ^When it was less than ² , the sensitivity was evaluated as good.

[Development adhesion]
Each radiation-sensitive resin composition was applied on a silicon substrate using a spinner and then prebaked at 90° C. for 2 minutes on a hot plate to form a coating film having a film thickness of 3.0 μm. The obtained coating film was irradiated with 1,000 J/m ² of ultraviolet rays by a mercury lamp through a pattern mask having a line-and-space pattern with a width of 10 μm. Next, a developing solution containing a 2.38 mass% tetramethylammonium hydroxide solution was used for development treatment at 25° C. for 60 seconds, followed by washing with running ultrapure water for 1 minute. Then, the presence or absence of peeling of the line-and-space pattern having a width of 10 μm was observed with a microscope to determine the development adhesion. At this time, depending on the degree of peeling, A: no peeling, B: slight peeling, C: partial peeling, D: whole peeling are classified. In the case of A or B, the development adhesion is good, C Or, in the case of D, it was evaluated as defective.

[chemical resistance]
Each radiation-sensitive resin composition was applied on a silicon substrate using a spinner and then prebaked at 90° C. for 2 minutes on a hot plate to form a coating film having a film thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the integrated irradiation amount would be 3,000 J/m ² . Next, this silicon substrate was heated on a hot plate at 200° C. for 30 minutes, and the film thickness (T1) of the obtained cured film was measured. Then, the silicon substrate on which the cured film was formed was immersed in dimethyl sulfoxide whose temperature was controlled at 70° C. for 20 minutes, and then the film thickness (t1) of the cured film after the immersion was measured. The rate of change in film thickness was calculated from the following formula, which was used as an index of chemical resistance.
Film thickness change rate={(t1-T1)/T1}×100(%)
When the absolute value of this value was less than 3%, the chemical resistance was evaluated as good, and when it was 3% or more, it was evaluated as poor.

[Heat-resistant]
Each radiation-sensitive resin composition was applied on a silicon substrate using a spinner and then prebaked at 90° C. for 2 minutes on a hot plate to form a coating film having a film thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the integrated irradiation amount would be 3,000 J/m ² . Next, this silicon substrate was heated on a hot plate at 200° C. for 30 minutes to obtain a cured film. The 5% weight loss temperature of the obtained cured film was measured under air using a measuring device (“TG/DTA220U” manufactured by SII Nanotechnology Inc.) and used as an index of heat resistance. At this time, when the 5% weight loss temperature was 300°C or higher, the heat resistance was evaluated as good, and when it was less than 300°C, the heat resistance was evaluated as poor.

[Transmittance (transparency)]
Each radiation-sensitive resin composition was applied onto a glass substrate using a spinner, and then prebaked at 90° C. for 2 minutes on a hot plate to form a coating film having a thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the integrated irradiation amount would be 3,000 J/m ² . Next, this glass substrate was heated on a hot plate at 200° C. for 30 minutes to obtain a cured film. The transmittance of the obtained cured film was measured using an ultraviolet-visible spectrophotometer (“V-630” manufactured by JASCO Corporation). In the positive-type radiation-sensitive resin composition, a transmittance of light having a wavelength of 400 nm of 95% or more was evaluated as good (transparency is good), and a transmittance of less than 95% was evaluated as poor (poor transparency). .. In the negative radiation-sensitive resin composition, when the transmittance of light having a wavelength of 400 nm was 97% or more, it was evaluated as good (transparency was good), and when it was less than 97%, it was evaluated as bad (poor transparency). ..

[surface hardness]
Each radiation-sensitive resin composition was applied on a silicon substrate using a spinner and then prebaked at 90° C. for 2 minutes on a hot plate to form a coating film having a film thickness of 3.0 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the integrated irradiation amount would be 3,000 J/m ² . Then, this silicon substrate was heated on a hot plate at 200° C. for 30 minutes to obtain a cured film. Then, for the substrate on which the cured film was formed, the pencil hardness of the cured film was measured by the JIS-K-5400-1990 8.4.1 pencil scratch test, and this was used as an index of the surface hardness. When the pencil hardness was 3H or more, the surface hardness of the cured film was evaluated as good (having sufficient curability), and when it was 2H or less, it was evaluated as poor.

[Specific permittivity (low dielectric property)]
Each radiation-sensitive resin composition was applied onto a SUS substrate using a spinner and then prebaked at 90° C. for 2 minutes on a hot plate to form a coating film having a thickness of 3.0 μm. Using an exposure machine (“MPA-600FA” manufactured by Canon Inc.), the above coating film was exposed so that the integrated irradiation amount was 9,000 J/m ^2, and the exposed substrate was kept in a clean oven at 200° C. for 30 minutes. A cured film was formed on the SUS substrate by heating. Then, a Pt/Pd electrode pattern was formed on the cured film by a vapor deposition method to prepare a dielectric constant measurement sample. For a substrate having this electrode pattern, a relative dielectric constant was measured by a CV method at a frequency of 10 kHz using an electrode (“HP16451B” manufactured by Yokogawa-Hewlett-Packard Co.) and a precision LCR meter (“HP4284A” manufactured by Yokogawa-Hewlett-Packard Co.). The measurement was performed. At this time, a relative dielectric constant of 3.6 or less was evaluated as good, and a relative dielectric constant of more than 3.6 was evaluated as bad.

INDUSTRIAL APPLICABILITY The present invention can provide a cured film having excellent heat resistance, chemical resistance, surface hardness, development adhesiveness, transparency and low dielectric constant, and is also radiation-sensitive to satisfy the characteristics such as storage stability and sensitivity. A resin composition, a method for forming a cured film using the radiation-sensitive resin composition, a cured film, a semiconductor element and a display element can be provided. Therefore, the radiation-sensitive resin composition, the cured film formed from the radiation-sensitive resin, the semiconductor element and the display element, and the method for forming the cured film are the manufacturing process for electronic devices such as flexible displays. Can be suitably used.

Claims (10)

A structural unit containing a structural unit having at least one group selected from the group represented by the following formula (2-1) and the group represented by the following formula (2-2), and the content ratio of the above structural unit to all structural units. Is 30 mass% or more and 90 mass% or less, the first polymer,
A radiation-sensitive resin composition containing an epoxy compound having an epoxy group (however, the first polymer is not included in the epoxy compound), and a radiation-sensitive compound.

(In the formulas (2-1) and (2-2), R ¹ is a hydrogen atom, a halogen atom, a hydroxy group or an alkoxy group having 1 to 6 carbon atoms. R ² and R ³ are each independently. And a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.
In the formula (2-1), A ¹ is a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms or an alkyl 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.
In the above formula (2-2), A ² is a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms. When A ² is plural, the plural A ² independently satisfy the above definition. n2 is an integer of 0-6. * Indicates a binding site. ) The radiation-sensitive resin composition according to claim 1, wherein the first polymer further contains a structural unit having an acidic group. The radiation-sensitive resin composition according to claim 2, 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. .. The radiation-sensitive resin composition according to claim 1, 2 or 3, wherein the epoxy compound is a second polymer containing the structural unit having the epoxy group. The radiation-sensitive resin composition according to claim 4, wherein the second polymer further contains a structural unit having an acidic group. The radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the radiation-sensitive compound is an acid generator, a polymerization initiator or a combination thereof. A step of forming a coating film on a substrate using the radiation-sensitive resin composition according to any one of claims 1 to 6 ;
Irradiating a part of the coating film with radiation,
A method of 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. A cured film formed from the radiation-sensitive resin composition according to any one of claims 1 to 6 . A semiconductor device comprising the cured film according to claim 8 . A display device comprising the semiconductor device according to claim 9 .