KR20170067649A - Radiation-sensitive resin composition, method for forming cured film, cured film, semiconductor device, and display device - Google Patents

Abstract

A radiation-sensitive resin composition capable of obtaining a cured film having excellent heat resistance, chemical resistance, surface hardness, developing adhesion, transparency and low dielectric properties, satisfying properties such as storage stability and sensitivity, A method of forming a cured film using the resin composition, a cured film, a semiconductor element, and a display element.
(Solution) The radiation sensitive resin composition of the present invention comprises a first structural unit having a group represented by the following formula (1), wherein the content of the first structural unit with respect to the total structural unit is 20 mass% or more and 90 % By mass or less, an epoxy compound having an epoxy group, and a radiation-sensitive resin composition. In the formula (1), R ¹ is a hydrogen atom, a halogen atom, a hydroxyl 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 hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or the like.

Description

TECHNICAL FIELD [0001] The present invention relates to a radiation-sensitive resin composition, a method of forming a cured film, a cured film, a semiconductor device and a display device,

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

2. Description of the Related Art In recent years, a flexible display such as an electronic paper has received attention, and a substrate made of plastic using polyethylene terephthalate or the like has been studied as a substrate of a flexible display. Since this substrate causes elongation or shrinkage upon heating, the lowering of the manufacturing process has been studied. In particular, in the manufacturing process, it is required to lower the firing temperature in the process of forming a cured film such as an interlayer insulating film which becomes the highest temperature.

As the material of the cured film capable of lowering the sintering temperature, there is used a radiation-sensitive resin composition in which the number of processes at the time of forming a pattern is small and a high surface hardness can be obtained. For example, a radiation-curable resin composition containing a copolymer containing a carboxyl group and an epoxy group Sensitive radiation-sensitive resin composition is known (see JP-A-2001-354822). In such a radiation sensitive resin composition, the surface hardness of the cured film is obtained by reacting the carboxyl group and the epoxy group. However, in the radiation-sensitive resin composition containing the above-mentioned copolymer, there is a fear that the storage stability may deteriorate in that when the radiation-sensitive resin composition is stored, the carboxyl group and the epoxy group react with each other to increase the viscosity .

Therefore, it is possible to form a cured film which can sufficiently satisfy general characteristics such as surface hardness, chemical resistance, heat resistance, transparency (light transmittance is high), low dielectric constant (low relative dielectric constant) Further, a radiation-sensitive resin composition having excellent storage stability is required. As such a material, a composition containing a copolymer containing 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 the crosslinkable group such as an epoxy group react with each other to cure. However, in this composition, 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, and there is a possibility that heat resistance and chemical resistance of the resulting cured film are lowered.

Japanese Patent Application Laid-Open No. 2001-354822 Japanese Laid-Open Patent Publication No. 2014-152192

The object of the present invention is to provide a cured film having excellent heat resistance, chemical resistance, surface hardness, developing adhesion, transparency and low dielectric constant, and has characteristics such as storage stability and sensitivity And a method of forming a cured film using the radiation sensitive resin composition, a cured film, a semiconductor element, and a display element.

The present invention for solving the above problems is characterized in that it comprises a first structural unit having a group represented by the following formula (1), wherein the content of the first structural unit with respect to the total structural unit is 20 mass% or more and 90 mass% (Hereinafter also referred to as " [C] radiation-sensitive compound "), an epoxy compound having an epoxy group Quot;). ≪ / RTI >

(1), R ¹ is a hydrogen atom, a halogen atom, a hydroxyl 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, 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 provide a method for manufacturing a radiation sensitive resin composition which comprises a step of forming a coating film on a substrate using the radiation sensitive resin composition, a step of irradiating a part of the coating film with radiation, And a step of heating the developed coating film.

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

Another invention made to solve the above problems is a semiconductor device having the cured film.

Another invention made to solve the above problems is a display device comprising the semiconductor device.

The present invention relates to a radiation-sensitive resin composition capable of obtaining a cured film having excellent heat resistance, chemical resistance, surface hardness, developing adhesion, transparency and low dielectric constant, and satisfying characteristics such as storage stability and sensitivity, A method of forming a cured film using the resin composition, a cured film, a semiconductor element, and a display element can be provided. Accordingly, the radiation sensitive resin composition, the cured film formed of the radiation sensitive resin, the semiconductor element and the display element, and the method of forming the cured film can be suitably used for a manufacturing process of an electronic device such as a flexible display .

(Mode for carrying out the invention)

<Radiation-Resistant Resin Composition>

The radiation-sensitive resin composition according to one embodiment of the present invention contains the [A] polymer, the [B] epoxy compound and the [C] radiation-sensitive compound. By containing the [A] polymer, the [B] epoxy compound and the [C] radiation-sensitive compound, the radiation sensitive resin composition can exert excellent curing reactivity at the time of film formation while suppressing the reactivity at the time of storage . The reason why such an effect occurs is not clear, but it is presumed that the epoxy group is present in a different compound from the group represented by the following formula (1). More specifically, it is presumed that, for example, in the solution, the distance between the reaction point of the epoxy group and the groups represented by the following formula (1) existing in different compounds becomes an appropriate distance due to the presence of the solvent. Therefore, according to the radiation sensitive resin composition, a cured film having excellent heat resistance, chemical resistance, surface hardness, developing adhesion, transparency and low dielectric property can be obtained, and properties such as storage stability and sensitivity can be satisfactorily satisfied. The radiation sensitive resin composition of the present invention can be used as either a positive or negative radiation sensitive resin composition.

<[A] Polymer>

[Structural unit (I)]

The polymer [A] includes 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 plural kinds of structural units.

In the formula (1), R ¹ is a hydrogen atom, a halogen atom, a hydroxyl 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 hydroxyl 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, ethoxy group, n-propoxy group and i-propoxy group.

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ² and R ³ include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, .

As R ¹ , 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 more preferable.

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 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 formula (2-1), R ¹ , R ² and R ³ have the same meanings as in the formula (1). A ¹ is a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms. When A ¹ is plural, plural A ¹ each independently satisfy the above definition. n1 is an integer of 0 to 4; * Represents a binding site.

In the formula (2-2), R ¹ , R ² and R ³ have the same meanings as in the formula (1). A ² is a halogen atom, a hydroxyl 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, plural A ² each independently satisfy the above definition. n2 is an integer of 0 to 6; * Represents a binding site.

When the structural unit (I) has a group represented by the formula (2-1) or (2-2), the heat resistance and the like of the resulting cured film can be further improved and the storage stability can be enhanced. Among these groups, the group represented by the formula (2-1) is more preferred. The formula (2-1) and (2-2) of, specific examples of R ¹ ~R ³ Examples and preferred group is the same as R ¹ ~R ³ in the above formula (1). The bonding position of the silicon atom on the aromatic ring may be any position relative to the linking group, but in the case of a benzene ring, it is preferably a 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 above as R ¹ to R ³ .

As n1, 0 is preferable. In addition, as n2, 0 is preferable.

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 formula (3-1) and (3-2), R ¹ ~R ³ is the above equation (1) means the same as in R ¹ ~R ^3. R ⁴ and R ⁵ are each independently a divalent organic group. However, in the case of R ⁵ , an ester structure (-COO-) is excluded at the main chain terminal end. R ^A each independently represents 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 a hydrocarbon group having 1 to 20 carbon atoms, a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 6 to 20 carbon atoms A divalent group obtained by combining two or more of these groups, and the like. Provided that some or all of the hydrogen atoms of these groups may be substituted by a substituent. Examples of the substituent include groups represented by A ¹ and A ^{2 described} above.

Examples of the divalent straight chain hydrocarbon group having 1 to 20 carbon atoms include alkandiyl groups such as an alkanediyl group such as a methanediyl group, an ethanediyl group, a propanediyl group, a hexanediyl group and a decanediyl group, an ethanediyl group, , Ethynediyl groups such as ethynediyl groups, and the like. Among them, an alkanediyl group is preferable, an alkanediyl group having 1 to 5 carbon atoms is more preferable, a propanediyl group is more 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, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, cyclooctanediyl, norbornanediyl, adamantanediyl, and the like. .

Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenylene group (benzene diyl group), a naphthylene group (naphthalene diyl group), a phenylene group and a naphthylene group are preferable, and a p- desirable.

As R ⁴ and R ⁵ , a divalent straight 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 resulting cured film can be further enhanced.

As R &lt; ^A &gt;, a hydrogen atom and a methyl group are preferable.

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

In the formula, R ^A has the same meaning as R ^A in the formulas (3-1) and (3-2). Among them, a structural unit represented by the formula (3-2-1) is preferable from the standpoint of heat resistance and the like.

The lower limit of the content ratio of the structural unit (I) in the polymer [A] is preferably 20% by mass, preferably 30% by mass, more preferably 40% by mass, based on the total structural units constituting the polymer [A] Do. On the other hand, the upper limit is 90 mass%, preferably 80 mass%, more preferably 60 mass%. By setting the content ratio of the structural unit (I) within the above range, the heat resistance and low dielectric constant of the resulting cured film can be improved. When the content is less than 20 mass%, the heat resistance of the resulting cured film is lowered, and the dielectric constant tends to increase. When the content is more than 90% by mass, the developability tends to decrease at the time of pattern formation of the cured film.

[Structural unit (II)]

The polymer [A] preferably further has a second structural unit having an acidic group (hereinafter also referred to as &quot; structural unit (II) &quot;). The structural unit (II) may be composed of plural kinds of structural units. By the structural unit (II), the solubility or the inferior solubility of the polymer [A] to the developer can be increased, or the curing reactivity can be enhanced.

Examples of the acidic group include a carboxyl 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 group substituted with an electron withdrawing group . Examples of the electronic bulb popularity 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 (hydroxy fluorinated alkyl group), a phosphoric acid group, a phosphonic acid group, a phosphinic acid group and a combination thereof and more preferably a fluorine-containing alcoholic hydroxyl group Do. By this acid group, the effect of the present invention can be exerted more effectively.

As the fluorine-containing alcoholic hydroxyl group, a group represented by the following formula (4) is preferable. The group represented by the following formula (4) can exhibit good crosslinking reactivity with the group represented by the formula (1) of the structural unit (I), and the like.

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 a difluoromethyl group, a trifluoromethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a perfluoroethyl group, a 2 , A 2,3,3-tetrafluoropropyl group, a perfluoroethylmethyl group, a perfluoropropyl group, a 2,2,3,3,4,4-hexafluorobutyl group, a perfluorobutyl group and the like, .

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

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁷ include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec- have. 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 more preferable, and a trifluoromethyl group is particularly preferable.

It is preferable that R ⁶ and R ⁷ together are a fluorinated alkyl group, more preferably a perfluoroalkyl group, and more preferably a trifluoromethyl group. When R &lt; ⁶ &gt; and R &lt; ⁷ &gt; are such groups, a suitable crosslinking reaction occurs due to a suitable acidic group, thereby further improving the properties of the cured film in which chemical resistance and the like are obtained.

Examples of the structural unit (II) include 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) , A structural unit derived from vinylsulfonic acid, and a structural unit having a phosphonic acid group.

In the formulas (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 an (n + 1) -valent organic group. However, in R ⁹ , except that the main chain terminal end is an ester structure (-COO-). Each R independently represents a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group or a trifluoromethyl group. n is, independently of each other, an integer of 1 to 5; 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 a hydrocarbon group having 1 to 20 carbon atoms, a chain hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, (N + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms, or an (n + 1) -valent group obtained by combining two or more of these groups. However, some or all of the hydrogen atoms of these groups may be substituted.

Examples of the (n + 1) th chain hydrocarbon group having 1 to 20 carbon atoms include groups obtained by removing n hydrogen atoms 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 a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, Butyl group and the like.

Examples of the (n + 1) -valent alicyclic hydrocarbon group having 3 to 20 carbon atoms include groups in which n hydrogen atoms have been removed 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 a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a norbornyl group and an adamantyl group.

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 a phenyl group, a tolyl group, and a naphthyl group.

Examples of the R ⁸ and R ^9,

A methylene group, an ethylene group, a propylene group (e.g., a 1,3-propylene group and a 1,2-propylene group), a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, And examples thereof include a methylene group, an undecamethylene group, a dodecamethylene group, a tridecamethylene group, a tetradecamethylene group, a pentadecamethylene group, a hexadecamethylene group, an heptadecamethylene group, an octadecamethylene group, Propylene group, a 2-methyl-1,2-propylene group, a 1-methyl-1,4-butylene group, a 2-methyl- , A saturated chain hydrocarbon group such as a 4-butylene group, a methylidene group, an ethylidene group, a propylidene group and a 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 and the like Monocyclic hydrocarbon groups such as cycloalkylene groups such as cyclooctylene group;

Norbornylene group, 2,5-norbornylene group, etc.), adamantylene group (1,5-adamantylene group, 2,6-adamantylene group, etc.) Polycyclic hydrocarbon groups such as cyclohexanetriyl group (1,3,5-cyclohexanetriyl group and the like);

Aromatic hydrocarbon groups such as a 1,3-phenylene group and a 1,4-phenylene group;

And groups obtained by combining these groups are preferable.

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

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

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

As n, 1 and 2 are preferable.

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

In the above formulas, R is the same as R in the formulas (5-1) and (5-2). Among them, structural units containing an aromatic hydrocarbon group represented by formulas (5-1-3), (5-2-1) and (5-2-2) are preferable, and structural units represented by formulas (5-1-3) and 5-2-1), more preferably a structural unit substituted with a group represented by -C (CF ₃ ) ₂ OH as an acidic group in the aromatic hydrocarbon group.

In the above formula (6), R 'is a hydrogen atom, a methyl group or a trifluoromethyl group. Each of R ^L1 to R ^L5 independently represents a hydrogen atom, a hydroxyl 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 to 3; Provided that at least one of R ^L1 to R ^L5 is a hydroxyl group.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ^L1 to R ^L5 include alkyl groups having 1 to 4 carbon atoms among the groups exemplified as the alkyl group having 1 to 10 carbon atoms and represented by R ² and R ³ above.

Examples of the structural unit represented by the 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 formula (6), respectively. Of these, structural units represented by formulas (6-1), (6-4) and (6-7) are preferred.

As the structural unit (II), among them, a structural unit represented by the formula (5-1) and a structural unit represented by the formula (5-2) are preferable. Examples of the structural unit (II) include a structure having a carboxy group such as a structural unit represented by the formula (5-1) or a structural unit derived from (meth) acrylic acid and a structural unit represented by the formula (5-2) Unit is preferably used in combination. By employing such a constitutional unit (II), it is possible to further improve the properties of the resulting cured film such as chemical resistance.

The lower limit of the content ratio of the structural unit (II) in the polymer [A] is preferably 5% by mass, more preferably 10% by mass, and more preferably 15% by mass based on the total structural units constituting the polymer [A] Is more preferable. On the other hand, the upper limit is preferably 60 mass%, more preferably 40 mass%, still more preferably 30 mass%. By setting the content ratio of the structural unit (II) within the above range, the storage stability and the properties of the resulting 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 structural units represented by the formulas (5-1) and (5-2) Is preferably 3 mass%, more preferably 5 mass%, based on the total structural units. On the other hand, the upper limit is preferably 30% by mass, more preferably 15% by mass.

Among the above structural units (II), the lower limit of the content ratio of the structural unit having a carboxyl group such as a structural unit derived from (meth) acrylic acid is preferably 3% by mass based on the total structural units constituting the polymer [A] , And 5 mass% are 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 third structural unit having a crosslinkable group (hereinafter also referred to as &quot; structural unit (III) &quot;). The structural unit (III) may be composed of plural kinds of structural units. The curing reactivity can be enhanced by the structural unit (III).

The crosslinkable group means a group other than the group represented by the formula (1) and the acidic group, which can be covalently bonded 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, And the like. Among them, 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. In the case of an oxetanyl group, it is possible to improve the heat resistance and the like of the resulting cured film while suppressing deterioration of the 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 a structural unit represented by the following formula (7-15).

Wherein R ^B is a hydrogen atom, a methyl group or a trifluoromethyl group.

As the structural unit (III) containing a (meth) acryloyl group, for example,

(Meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Di (meth) acrylate compounds such as di (meth) acrylate and tripropylene glycol diacrylate;

Tri (meth) acrylate compounds such as tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate;

Tetra (meth) acrylate compounds such as pentaerythritol tetra (meth) acrylate;

And a penta (meth) acrylate compound such as dipentaerythritol penta (meth) acrylate.

The structural unit (III) containing a (meth) acryloyl group or a vinyl group is obtained by reacting a specific group of structural units in the polymer with a group which reacts with the specific group and a compound having a (meth) acryloyl group or a vinyl group You can get it. (2) a method in which a polymer having an epoxy group is reacted with (meth) acrylic acid or the like; (3) a method in which a polymer having a hydroxy group is reacted with an isocyanate (Meth) acryloyl group or vinyl group by a method of reacting a (meth) acrylic acid ester or a vinyl compound having a (meth) acryloyl group or a vinyl group with a polymer having an acid anhydride moiety, (III) can be introduced.

The lower limit of the content ratio of the structural unit (III) in the polymer [A] is preferably 5% by mass, more preferably 10% by mass, based on the total structural units constituting the polymer [A]. 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) within the above range, it is possible to further improve the properties of the resulting cured film while maintaining high storage stability.

[Structural unit (IV)]

The above-mentioned [A] polymer may have other structural units (hereinafter also referred to as "structural units (IV)") other than the structural units (I) to (III). 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 at the time of thermal curing and the mechanical strength and chemical resistance of the resulting cured film.

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

Wherein 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 to 5. Among them, the structural unit represented by the formula (8-1), (8-6) to (8-8) and (8-10) is preferable as the structural unit (IV).

Examples of the monomer compound giving 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, bicyclo unsaturated compound, Derived structural units such as unsaturated compounds having a skeleton represented by the following formula (9) or other unsaturated compounds, such as a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton or the following formula .

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

As the (meth) acrylic acid chain alkyl ester, for example,

Acrylic acid such as methyl acrylate, ethyl acrylate, n-butyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, Alkyl esters;

Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n- Methacrylic acid chain alkyl esters such as lauryl, tridecyl methacrylate, n-stearyl methacrylate, and the like.

As the (meth) acrylic acid cyclic alkyl ester, for example,

Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, acrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl acrylate, Cyclic alkyl esters such as acrylic acid;

Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8 And methacrylic acid cyclic alkyl esters such as isobutyl, isobutyl, sec-butyl, isobutyl, sec-butyl,

As the (meth) acrylic acid aryl esters, for example,

Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate;

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 bicyclounsaturated compound include bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] 2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dimethoxybicyclo [2.2. 2.2.1] hept-2-ene, 5-t-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5- 2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) (Cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] 2-ene, 5,6-di (2'-hydroxyethyl) bis 2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] 2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene and the like.

Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) Maleimidobenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-mal (9-acridinyl) maleimide, and the like.

Examples of the unsaturated aromatic compound include styrene,? -Methylstyrene, vinyltoluene, p-methoxystyrene,? -Methyl-p-hydroxystyrene, and the like.

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

Examples of the unsaturated compound having the tetrahydrofuran skeleton include 2-methacryloyloxypropionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydrofuran-2-one, tetramethyl (meth) acrylate, And hydrofurfuryl.

Examples of the unsaturated compound having a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, Methyl-1-hexen-3-one, 6-furan-2-one, Methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-ene- And the like.

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

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

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

Among them, examples of the monomer compound giving the structural unit (IV) include a methacrylic acid chain alkyl ester, a methacrylic acid cyclic alkyl ester, a maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, Unsaturated aromatic compounds and acrylic acid cyclic alkyl esters having a skeleton represented by the formula (9) are preferable, and styrene, vinyl toluene, methyl methacrylate, t-butyl methacrylate, Methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decan-8-yl, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmale (Meth) acrylic acid tetrahydrofurfuryl, polyethylene glycol (n = 2-10) mono (meth) acrylate and 3- (meth) acryloyloxytetrahydrofuran- It is preferred.

The lower limit of the content ratio of the structural unit (IV) in the polymer [A] is preferably 5% by mass, more preferably 10% by mass, based on the total structural units constituting the polymer [A]. 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, the chemical resistance and the like can be effectively improved.

<Method of synthesizing [A] polymer>

The [A] polymer can be produced, for example, by polymerizing monomers corresponding to predetermined structural units in a suitable solvent using a radical initiator. In general, the blending ratio of each monomer at the time of polymerization is the same as the content ratio of the corresponding structural unit in the polymer [A] to be obtained. Specific synthetic methods include (1) a method in which a solution containing a monomer and a radical initiator is added dropwise to a solution containing a reaction solvent or a monomer to carry out a polymerization reaction, (2) a method in which a solution containing a monomer and a solution containing a radical initiator (3) a method in which a solution containing a plurality of kinds of monomers and a solution containing a radical initiator is separately added to a reaction solvent or a monomer Or a method in which the compound is added dropwise to a solution containing the compound of the present invention.

The reaction temperature in these methods may be appropriately determined depending on the initiator species (species). But it may be usually 30 ° C to 180 ° C. The dropping time varies depending on the conditions such as the reaction temperature, the kind of the initiator, and the monomer to be reacted, but is usually 30 minutes to 8 hours. The total reaction time including the dropping time is also from 30 minutes to 8 hours, though it differs depending on conditions like the dropping time.

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

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

The polymer obtained by the polymerization reaction can be recovered by the reprecipitation method. That is, after completion of the polymerization reaction, the polymer solution is put into a reprecipitation solvent to recover the objective polymer as a powder. As the re-precipitation solvent, alcohols, alkanes, etc. may be used alone or in admixture of two or more. In addition to the reprecipitation method, a polymer may be recovered by removing low-molecular components such as monomers and oligomers by a liquid separation operation, a column operation, an ultrafiltration operation or the like. 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 prepare the radiation sensitive resin composition.

In the polymerization reaction for producing the polymer [A], a molecular weight regulator may be used to adjust the molecular weight. Examples of the molecular weight regulator 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; Azetidine derivatives such as dimethylzantogen sulfide and diisopropylzantogen disulfide; Terpinolene, alpha -methylstyrene dimer, and the like.

The polystyrene-reduced 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. The ratio (Mw / Mn) of the Mw of the polymer [A] to the polystyrene reduced number average molecular weight (Mn) by GPC is preferably 1 or more and 3 or less.

The content of the polymer [A] in the radiation sensitive resin composition is not particularly limited, but the lower limit of the content of the polymer [A] in the total solid content is preferably 30% by mass, more preferably 40% by mass. On the other hand, the upper limit is preferably 70% by mass, more preferably 60% by mass. When the content of the polymer [A] in the radiation sensitive resin composition is within the above range, the properties of the resulting cured film can be improved more effectively.

<[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 3-membered ring (1,2-epoxy structure) and an oxetanyl group having a 4-membered ring (1,3-epoxy structure). As the epoxy compound [B], a second polymer containing a structural unit having an epoxy group (hereinafter also referred to as "[B1] polymer") may be used, and other compounds having an epoxy group (hereinafter referred to as "[B2] Compound &quot; or &quot; [B2] compound &quot;). However, the polymer having the structural unit (I) is not included in the [B1] polymer.

<[B1] Polymer>

The [B1] polymer 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 polymer (B1) include those having an epoxy group in the structural unit (III) having a crosslinkable group of the polymer [A]. Specifically, 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 plural kinds 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.

The lower limit of the content ratio of the structural unit (III ') in the [B1] polymer is preferably 20% by mass, more preferably 40% by mass, based on the total structural units constituting the [B1] polymer. On the other hand, as the upper limit, 80 mass% is preferable, and 70 mass% is more preferable. By setting the content ratio of the structural unit (III ') within the above range, it is possible to further improve the properties of the resulting cured film while maintaining high storage stability.

[Structural unit (II)]

The above-mentioned [B1] polymer preferably further comprises a structural unit (II) having an acidic group. The structural unit (II) may be composed of plural kinds of structural units. By the structural unit (II), the solubility or the inferior solubility of the [B1] polymer in a developer can be increased, or the curing reactivity can be enhanced.

Examples of the acidic group of the structural unit (II) of the polymer [B1] include the same ones as those of the structural unit (II) of the polymer [A], and examples thereof include a carboxy group, a sulfo group, a phenolic hydroxyl group, A hydroxyl group (hydroxy fluorinated alkyl group), a phosphoric acid group, a phosphonic acid group, a phosphinic acid group and a combination thereof are preferable, and a carboxy group, a phenolic hydroxyl group and a fluorine-containing alcoholic hydroxyl group are more preferable.

The structural unit (II) of the polymer [B1] may be the same structural unit as the structural unit (II) of the polymer [A].

Examples of the structural unit (II) of the polymer [B1] include a structural unit represented by the formula (5-1), a structural unit represented by the formula (5-2), a structural unit represented by the formula (6) Structural units are preferred. A more preferable structure in the structural unit represented by the formula (5-1), the structural unit represented by the formula (5-2), and the structural unit represented by the formula (6) ). &Lt; / RTI &gt; As the structural unit having a carboxy group, a structural unit derived from (meth) acrylic acid is preferable.

The lower limit of the content ratio of the structural unit (II) in the polymer [B1] is preferably 5% by mass, more preferably 10% by mass, and more preferably 15% by mass, based on the total structural units constituting the [B1] Is more preferable. On the other hand, the upper limit is preferably 50% by mass, more preferably 40% by mass, still more preferably 30% by mass. By setting the content of the structural unit (II) within the above range, the storage stability and the properties of the resulting cured film can be further enhanced.

[Structural unit (IV)]

The above-mentioned [B1] polymer may have other structural units (IV) other than the structural units (III ') and (II) (except for the structural unit (I)). When the [B1] polymer has the structural unit (IV), the glass transition temperature of the resin can be adjusted to improve the melt flow property at the time of thermal curing and the mechanical strength and chemical resistance of the resulting cured film. Specific examples of the structural unit (IV) and preferred structures include those similar to the structural unit (IV) of the polymer [A].

The lower limit of the content ratio of the structural unit (IV) in the polymer [B1] is preferably 5% by mass, more preferably 10% by mass, based on the total structural units constituting the polymer [A]. 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, the chemical resistance and the like can be effectively improved.

<Synthesis method of [B1] polymer>

The [B1] polymer can be produced, for example, by polymerizing a monomer corresponding to a given structural unit in a suitable solvent using a radical initiator. That is, the [B1] polymer can be produced in accordance with the above-described method for synthesizing the [A] polymer.

The polystyrene-reduced 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 number average molecular weight (Mn) converted to polystyrene 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 preferably 50 parts by mass, more preferably 75 parts by mass, per 100 parts by mass of the polymer [A]. 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 above-described radiation-sensitive resin composition within the above range, it is possible to improve the properties of the resulting cured film more effectively.

<[B2] Compound (other epoxy compound)>

As the [B2] compound, a compound having a plurality of the above epoxy groups in the molecule is suitably used. As the [B2] compound, a compound having two or more oxiranyl groups or oxetanyl groups in the molecule can be suitably used.

As the compound having two or more oxiranyl groups in the molecule, for example,

Examples of bisphenol diglycidyl ethers include bisphenol diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, Cydyl ether, hydrogenated bisphenol AD diglycidyl ether and the like;

Examples of polyglycidyl ethers of polyhydric alcohols include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether, polyethylene glycol Diglycidyl ether, polypropylene glycol diglycidyl ether and the like;

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 novolak type epoxy resin, cresol novolak 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;

Epoxidized soybean oil, and epoxidized flaxseed oil.

Examples of the compound having two or more oxetanyl groups in the molecule include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, di [1- (3-ethyl-3-oxetanylmethyl) ether), 3,7-bis (3-oxetanyl) Bis (3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,1-bis (3-ethylhexyl) (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis Ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4- Butane, xylene bisoxetane, 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 , Dipentaerythritol pentaquis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentaquis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis Ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis Ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F Cetanylmethyl) ether, and the like.

The content of the [B2] compound in the radiation-sensitive resin composition is not particularly limited, but the lower limit of 100 parts by mass of the polymer [A] is preferably 10 parts by mass, 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. When the content of the [B2] compound in the radiation sensitive resin composition is within the above range, the properties of the resulting cured film can be improved more effectively.

&Lt; [C] Radiation-sensitive compound >

When the radiation-sensitive resin composition contains [C] a radiation-sensitive compound (photosensitive agent), the radiation-sensitive resin composition can be positively or negatively charged by irradiation with radiation (visible light, ultraviolet light, Type pattern can be formed. Examples of the [C] radiation-sensitive compound include a [C1] acid generator, a [C2] polymerization initiator and a [C3] base generator. Examples of the [C1] acid generator, . These may be used singly or in combination of two or more. When the [C1] acid generator or the [C3] base generator is used as the [C] radiation-sensitive compound, the solubility of the exposed portion in the developer is changed, whereby a positive or negative pattern can be formed. In addition, when the [C1] acid generator or the [C3] base generating agent functions as a curing catalyst and curing of the exposed portion is promoted, a negative pattern may be formed. On the other hand, when a [C2] polymerization initiator is used as the [C] radiation-sensitive compound, by the reaction between a vinyl group and a compound having a (meth) acryloyl group (such as a [D] The negative curing is promoted, and a negative pattern can be formed.

<[C1] Acid generator>

[C1] The acid generator (radiation-sensitive acid generator) is a compound which generates an acid in response to radiation. As the acid generator, for example, an oxime sulfonate compound, an onium salt, a sulfonimide compound, a sulfonic acid ester compound, a quinone diazide compound, a halogen-containing compound, a diazomethane compound, . These [C1] acid generators may be used alone or in combination of two or more.

As the oxime sulfonate compound, a compound containing an oxime sulfonate group represented by the following formula (10) is preferable.

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

Specific examples of the oxime sulfonate compound include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene) - (2-methylphenyl) acetonitrile, (5-octylsulfonyloxyimino-5H-thiophene (2-methylphenyl) acetonitrile, (camphorsulfonyloxyimino-5H-thiophen-2-ylidene) - (2- methylphenyl) acetonitrile, (5-p-toluenesulfonyloxy 2-ylidene) - (2-methylphenyl) acetonitrile and 2- (octylsulfonyloxyimino) -2- (4-methoxyphenyl) acetonitrile. &Lt; / RTI &gt;

Examples of the onium salts include diphenyl iodonium 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 compounds include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (Camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (Methanesulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, trifluoromethanesulfonic acid-1,8- Meade and the like.

As the sulfonic acid ester compound, haloalkylsulfonic acid ester and the like can be mentioned, and N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester is preferable.

As the quinone diazide compound, for example, a phenolic compound or an alcoholic compound (hereinafter also referred to as a "mother nucleus"), a 1,2-naphthoquinone diazide sulfonic acid halide or a 1,2-naphthoquinonediamine Condensates of zidosulfonic acid amide can be used.

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

As specific examples of the above-mentioned mother cells, for example,

As the trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone and the like;

As the tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxy Benzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone and the like;

As the pentahydroxybenzophenone, 2,3,4,2 ', 6'-pentahydroxybenzophenone and the like;

As the hexahydroxybenzophenone, 2,4,6,3 ', 4', 5'-hexahydroxybenzophenone, 3,4,5,3 ', 4', 5'-hexahydroxybenzophenone and the like;

(P-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (dihydroxyphenyl) methane, (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris 4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] -1,2,4- (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ', 3'-tetramethyl-1,1'-spirobindene- 7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan and the like;

.

Examples of other parent nuclei include 2- [2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7- Methylethyl] -3- (1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) ) -1- methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) - dihydroxybenzene, and the like.

Among them, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane and 4,4 '- [ 1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferable.

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-naphthoquinone Diazide-5-sulfonic acid chloride is more preferable, and 1,2-naphthoquinonediazide-5-sulfonic acid chloride is more preferable.

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 a phenolic compound or an alcoholic compound (mother nucleus) with 1,2-naphthoquinonediazidesulfonic acid halide or 1,2-naphthoquinonediazide sulfonic acid amide, the number of OH groups in the mother nucleus is preferably Is preferably a 1,2-naphthoquinonediazide sulfonic acid halide or 1,2-naphthoquinonediazide sulfonic 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, when the radiation-sensitive resin composition is a positive type, a quinone diazide compound is preferable. On the other hand, when the radiation sensitive resin composition is a negative type, an acid generator other than a quinone diazide compound is preferable, and onium salts and a sulfonimide compound are more preferable. When the [C1] acid generator is used as the above-mentioned compound, the sensitivity and the like can be made better.

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

<[C2] Polymerization initiator>

[C2] A polymerization initiator (radiation-sensitive radical polymerization initiator) is a compound capable of generating a radical in response to radiation and initiating polymerization. Examples of the polymerization initiator [C2] include O-acyloxime compounds, acetophenone compounds, and imidazole compounds. These compounds may be used alone or in combination of two or more.

Examples of the O-acyloxime compound include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone- 1- [ (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -octan-1-one Oxal-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- -Benzoate, ethanone-1- [9-ethyl-6- (2-methylpiperazin-1-ylmethyl) Yl] -1- (O-acetyloxime), ethanone- 1- [9-ethyl-6- (2- (9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) - 9H-carbazol-3-yl] 3-yl] -1- (O-acetyloxime), ethanone- 1- [9-ethyl-6- {2-methyl- 4- (2,2- (4-fluorophenyl) isoxazol-4-yl) -9- ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) .

Among them, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone- 1- [ (9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole-3 -Yl] -1- (O-acetyloxime) and ethanone-1- [9-ethyl-6- {2-methyl- 4- (2,2- } -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

Examples of the acetophenone compound include an? -Amino ketone compound,? -Hydroxy ketone compound and the like.

Examples of the? -amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- 1- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one .

Examples of the? -hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4- 1-on, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone and the like.

As the acetophenone compound, an? -Amino ketone compound is preferable, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- More preferable.

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

As the polymerization initiator, an O-acyloxime compound is preferable, and a polymerization initiator having a carbazole skeleton in the molecule is preferable. For example, ethanone-1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime).

[C 2] The polymerization initiator may be used alone or in combination of two or more. The lower limit of the content of [C2] polymerization initiator is preferably 1 part by mass, more preferably 5 parts by mass, further preferably 15 parts by mass, per 100 parts by mass of the polymer [A]. On the other hand, the upper limit is preferably 40 parts by mass, more preferably 20 parts by mass. When the content of the [C2] polymerization initiator is within the above range, good curability and the like can be exhibited.

<[C3] Base generator>

[C3] Base generators (radiation-sensitive base generators) are compounds that generate bases in response to radiation. Examples of the [C3] nucleophilic agent include [(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, 2-nitrobenzylcyclohexylcarbamate, N- (2-nitrobenzyloxycarbonyl (2-nitrobenzyl) oxy] carbonyl] hexane-1,6-diamine, triphenylmethanol, O-carbamoylhydroxyamide, O-carbamoyloxime, 4- (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, 2-benzyl-2-dimethylamino- Polynophenyl) -butanone, and hexaanemine cobalt (III) tris (triphenylmethyl borate).

<Other components>

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 [D] a crosslinking compound, [E] an antioxidant, [F] a surfactant, and [G] an adhesion aid, in addition to the solvent described below. The above-mentioned radiation-sensitive resin composition may be used alone or in combination of two or more.

&Lt; [D] Crosslinkable compound >

[D] The crosslinkable compound is usually a compound having a plurality of crosslinkable groups. However, the [D] crosslinkable compound does not include the [A] polymer and the [B] epoxy compound. Examples of the crosslinkable group include a vinyl group, a (meth) acryloyl group, and a hydroxymethylphenyl group. Among them, a vinyl group and a (meth) acryloyl group are preferable. When the [D] crosslinking compound having such a crosslinkable group is used in combination with the [C2] polymerization initiator, the curing of the exposed area is promoted and a negative pattern can be efficiently formed.

Examples of the [D] crosslinkable compound include multifunctional (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 esters include ethylene glycol di (meth) acrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene Glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate 1,9-nonanediol dimethacrylate, and the like.

Examples of the (meth) acrylic ester having three or more functional groups include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, Pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate , Dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol Lithol triacrylate, succinic acid-modified dipentaerythritol pen Acrylate, a compound having two or more isocyanate groups and a straight chain alkylene group and an alicyclic structure, and a compound having at least one hydroxy group in the molecule and having three, four or five (meth) acryloyloxy groups And a polyfunctional urethane acrylate-based compound obtained by reacting the compound with a compound having a carboxyl group.

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

The content of the [D] crosslinkable compound in the radiation sensitive resin composition is not particularly limited, but preferably 10 parts by mass, more preferably 50 parts by mass, per 100 parts by mass of the polymer [A]. On the other hand, the upper limit is preferably 200 parts by mass, more preferably 150 parts by mass. When the content of the [D] crosslinkable compound in the radiation sensitive resin composition is within the above range, the properties of the resulting cured film can be improved more effectively.

<[E] Antioxidant>

[E] The antioxidant is a component capable of decomposing a radical generated by exposure or heating, or a peroxide generated by oxidation, and preventing the dissociation of bonding of polymer molecules. As a result, the resulting cured film is prevented from deterioration in oxidation over time and suppressed, for example, from changing the film thickness of the cured film.

[E] Examples of the antioxidant include a compound having a hindered phenol structure, a compound having a hindered amine structure, a compound having an alkyl phosphite structure, and a compound having a thioether structure. Among them, the [E] antioxidant is preferably a compound having a hindered phenol structure.

Examples of the compound having a hindered phenol structure include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- Di-t-butyl-4-hydroxybenzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5- Hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert- butyl-4-hydroxyphenylpropionamide)], 3,3 ' , 5 ', 5'-hexa-tert-butyl-a, a', a'- (mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylene bis (oxyethylene) bis 3- [5- (tert- butyl-4-hydroxy-m- tolyl) propionate ], Hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Tris [(4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5-triazine- 3H, 5H) -thione, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin- , 3,5-di-t-butyl-4-hydroxybenzyl) benzene, 2,6-di-t-butyl-4-cresol and the like.

Examples of commercial products of the compounds having the hindered phenol structure include adecastab AO-20, AO-30, AO-40, AO-50, AO-60, AO- 80, AO-330 (above, ADEKA), SumilizerGM, Copper GS, Copper MDP-S, Copper BBM-S Copper WX-R Copper GA-80 (Sumitomo Kagakusha) IRGANOX 1010 Copper 1035 (Available from BASF), Yoshinox BHT, Copper BB, Copper Copper, Copper Copper, Copper Copper, Copper Copper, Copper Copper, Copper Copper, 2246G, 425, 250, 930, SS, TT, 917, 314 (above, APIC Corporation).

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

The content of [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 polymer [A]. By setting the content of the [E] antioxidant within the above range, it is possible to effectively suppress the deterioration of oxidation of the cured film over time.

<[F] Surfactant>

[F] Surfactant is a component that improves film formability. Examples of the [F] surfactant include a fluorine-based surfactant, a silicon-based surfactant, and other surfactants.

As the fluorine-based surfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of a terminal, a main chain and a side chain is preferable, and for example, a 1,1,2,2-tetrafluoro- (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di Hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, perfluoro- Sodium dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n -Dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarbonate, diglycerin tetrakis Fluoroalkylammonium iodide, fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethanols, perfluoroalkyl alkoxylates, carbonic acid fluoro Alkyl esters and the like.

Examples of commercially available products of the above fluorinated surfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), Megafac F142D, Copper F172, Copper F173, Copper F183, Copper F178, Copper F191, Copper F471, Copper F476 S-112, S-113, S-131 (manufactured by Sumitomo 3M Ltd.), Florad FC-170C, S-171, 103, 104, 105, 106 (above, Asahi Glass Co., Ltd.), F-top EF301, 310, 352 (above, Shin Akita Kasei), Fotogen FT-100, -110, -140A, -150, -250, -251, -300, -310, 400S, FTX-218, and-251 (manufactured by Neos).

Examples of commercially available products of the above silicon surfactants include Torensilicon DC3PA, Copper DC7PA, Copper SH11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH-190, Copper SH-193, Copper SZ- TSF-4440, TSF-4440, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 (above, DC- GE Toshiba Silicones), and organosiloxane polymer KP341 (Shinetsu Kagakuko Co., Ltd.).

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

Commercially available products of the above other surfactants include, for example, (meth) acrylic acid-based copolymer polyphosphoric acid copolymers. 57, No. 95 (above, Kyoeishakagakusa), and the like.

The content of the [F] surfactant is preferably 0.01 part by mass or more and 3 parts by mass or less based on 100 parts by mass of the polymer [A]. When the content of the [F] surfactant is within the above range, the film formability can be effectively improved.

<[G] Adhesion preparation>

[G] Adhesion aid is a component that improves the adhesion between the resulting 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 or an oxiranyl group is preferable.

Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

The content of the [G] adhesion aid 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].

&Lt; Preparation method of 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, preferably in a suitable solvent, can do. The prepared radiation sensitive resin composition is preferably filtered with a filter having a pore size of about 0.2 mu m, for example.

As the solvent used for preparing the radiation sensitive resin composition, the components contained in the radiation sensitive resin composition are uniformly dissolved or dispersed, and those which do not react with the respective components are used. Examples of the solvent include an alcohol solvent, an ether solvent, a ketone solvent, an amide solvent, an ester solvent, a hydrocarbon solvent and the like.

As the alcohol-based solvent, for example,

As the monoalcohol-based solvent, it is preferable to use at least one solvent selected from the group consisting of methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, Heptanol, sec-heptanol, 3-heptanol, n-octanol, sec-hexanol, sec-hexanol, sec- Sec-octadecyl alcohol, sec-tetradecyl alcohol, sec-tetradecyl alcohol, sec-octadecanol, sec-octadecyl alcohol, Heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol and the like;

Examples of polyhydric alcohol solvents include polyhydric alcohols such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl- , 4-heptanediol, 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and the like;

Examples of the polyhydric alcohol partial ether solvent include 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- Diethyleneglycol monoethyl ether, diethyleneglycol monopropyl ether, diethyleneglycol monobutyl ether, diethyleneglycol monohexyl ether, propyleneglycol monomethyl ether, propyleneglycol monoethyl ether, diethyleneglycol monomethylether, diethyleneglycol monomethylether, , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether.

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, .

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, -Butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethyl nonane, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, Acetonyl acetone, acetophenone, and the like.

Examples of the amide solvent include N, N'-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, Amide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone and the like.

Examples of the ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec- 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate , Methyl acetoacetate, ethyl acetoacetate, acetic acid ethylene glycol monomethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid ethylene glycol mono-n-propyl ether, acetic acid ethylene glycol mono-n-butyl ether, acetic acid diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether acetate , Diethylene glycol mono-n-butyl acetate 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, di Butyl acetate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, ethyl lactate, propyleneglycol monomethyl ether, propyleneglycol monoethyl ether, diacetic acid glycol, methoxytriglycol acetate, , N-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate.

As the hydrocarbon-based solvent, for example,

Examples of the aliphatic hydrocarbon solvent include aliphatic hydrocarbons such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, Methylcyclohexane and the like;

Examples of the aromatic hydrocarbon solvent include aliphatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, -I-propylbenzene, and n-amylnaphthalene.

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

&Lt; Method of forming a cured film &

A method of forming a cured film according to an embodiment of the present invention,

(1) a step of forming a coating film on a substrate (hereinafter also referred to as &quot; step (1) &quot;) using the radiation sensitive resin composition,

(2) a step of irradiating a part of the coating film with radiation (hereinafter also referred to as &quot; step (2) &quot;),

(3) a step of developing the coating film irradiated with the radiation (hereinafter also referred to as &quot; step (3) &quot;),

(4) a step of heating the developed coating film (hereinafter also referred to as &quot; step (4) &quot;).

Since the radiation sensitive resin composition has the above-mentioned properties, according to the method of forming the cured film, a cured film sufficiently satisfying general characteristics such as heat resistance, chemical resistance, surface hardness, developing adhesion, low dielectric constant and transparency is formed can do. Further, according to the method of forming the cured film, development can be performed with good sensitivity. Each step will be described in detail below.

[Step (1)]

In this step, a coating film is formed on a substrate using the radiation-sensitive resin composition. Specifically, a solution-form, radiation-sensitive resin composition is coated on the surface of a substrate, preferably by prebaking 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 on which various metal thin films are formed. 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, a suitable method such as a spraying method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method and the like can be adopted. Of these, spin coating method, bar coating method and slit die coating method are preferable as a coating method. The conditions of the prebaking may vary depending on the kind of each component, the use ratio, and the like, for example, from 60 to 130 占 폚 for 30 seconds to 10 minutes. The film thickness of the formed coating film is preferably 0.1 m or more and 8 m or less as a value after pre-baking.

[Step (2)]

In this step, a part of the coating film is irradiated with radiation. Specifically, the coating film formed in the step (1) is irradiated with radiation through a mask having a predetermined pattern. Examples of the radiation used at this time include ultraviolet rays, deep ultraviolet rays, X-rays, charged particle rays, and the like.

Examples of the ultraviolet ray include g-line (wavelength: 436 nm) and i-line (wavelength: 365 nm). Examples of the far ultraviolet ray include KrF excimer laser light. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include electron beams and the like. Among these radiation, ultraviolet rays are preferable, and among the ultraviolet rays, radiation including g line, h line and / or i line is more preferable. The exposure dose of the radiation is preferably 0.1 J / m 2 or more and 10,000 J / m 2 or less.

[Step (3)]

In this step, the coated film irradiated with the radiation is developed. Specifically, the coating film irradiated with the radiation in the step (2) is developed with a developer to remove the irradiated portion of the radiation. Examples of the developer include aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, Such as ethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0 ] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane, and the like. An aqueous solution containing an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant, or an aqueous alkali solution containing a small amount of various organic solvents capable of dissolving the radiation-sensitive resin composition may be used as the developer.

As the developing method, suitable methods such as a puddle method, a dipping method, a swing dipping method, a shower method and the like can be adopted. The developing time varies depending on the composition of the radiation sensitive resin composition, but may be, for example, 30 seconds or longer and 120 seconds or shorter. After the development step, the patterned coating film is subjected to a rinsing treatment by running water washing, and then irradiated (post-exposure) with radiation from a high-pressure mercury lamp or the like to the entire surface, C] radiation-sensitive compound is preferably subjected to a decomposition treatment. The exposure amount in the subsequent 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 by using a heating device such as an oven or a hot plate. The heating temperature in this step is preferably 200 DEG C or less. By heating at such a low temperature, the method of forming the cured film can be suitably 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 占 폚. The heating time varies depending on the type of the heating apparatus, but it can be set to, for example, 5 minutes to 40 minutes when heat treatment is performed on a hot plate, and 30 minutes or more to 80 minutes or less when heat treatment is performed in an oven . In this way, a desired 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 of the radiation sensitive resin composition. The method of forming the cured film is not particularly limited, but it can be preferably formed by the above-mentioned method of forming a cured film. This cured film is excellent in heat resistance, chemical resistance, surface hardness, development adhesion, low dielectric constant, transparency and the like because it is formed of the radiation sensitive resin composition. Since the cured film has the above characteristics, it is suitable as an interlayer insulating film of a display element, a spacer, a protective film, a coloring pattern for a color filter, and the like.

<Semiconductor device>

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, a spacer, a protective film, a coloring pattern for a color filter, or the like which insulates wirings in the semiconductor device. The semiconductor device can be formed by a known method. Since the semiconductor device includes the cured film, the semiconductor device can be suitably used for an electronic device such as a display device, an LED, and a solar cell.

<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 the general characteristics required for practical use. Examples of the display element include a liquid crystal display element and the like. In the liquid crystal display element, for example, two TFT array substrates on which liquid crystal alignment films are formed on the surface are arranged opposite to each other on the liquid crystal alignment film side through a sealant formed on the periphery of the TFT array substrate. Liquid crystal is filled between the 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.

[Example]

Hereinafter, the present invention will be described concretely with reference to Examples, but the present invention is not limited to these Examples. A method of measuring each property value is described 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.

Device: GPC-101 of Showa Denko

GPC column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 of Shimadzu

Mobile phase: tetrahydrofuran

Column temperature: 40 DEG C

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection amount: 100 μL

Detector: differential refractometer

Standard material: monodisperse polystyrene

[Measurement of the content ratio of the structural unit of the polymer]

¹ H-NMR (analyzer: Nihon Denshi "ECX400P" of), ¹³ C-NMR (analyzing device Nippon Denshi of "ECX400P"), FT-IR (analysis apparatus: Nicolet's "Nexus470") and thermal decomposition The content of the structural units of the polymer was measured by gas chromatography mass spectrometry (Analytical instrument: "JPS330" (Py) of Nihon Bunshikiko, "GC6890A" (GC) of Agilent, and "5973 Inert" (MS) Content ratio).

<Synthesis of [A] Polymer>

The monomer compounds used in the synthesis of the polymers in each of the Examples and Comparative Examples are shown below. The following monomeric compounds (1) to (4) are compounds imparting the structural unit (I), and the monomeric compounds (5) to (10) are compounds imparting the structural unit (II) ) To (14) are compounds giving structural units (III) and (III '), and monomer compounds (15) to (16) are structural units (IV).

[Synthesis Example 1] (Synthesis of polymer (A-1)

7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether were fed into a flask equipped with a condenser and a stirrer. Subsequently, 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 replaced with nitrogen. Then, the temperature of the solution was raised to 70 占 폚 while stirring slowly, and this temperature was maintained for 4 hours to polymerize to obtain a polymer solution containing the polymer (A-1). The solid concentration of the polymer solution was 30.4 mass%, the polymer (A-1) had a Mw of 8,000 and a molecular weight distribution (Mw / Mn) of 2.3. The content ratio of each structural unit in the polymer (A-1) was the same as that of the corresponding monomer compound.

Synthesis Examples 2 to 31 and Comparative Synthesis Examples 1 to 4 Synthesis Examples 2 to 31 and Comparative Synthesis Examples 1 to 4 were obtained in the same manner as in Comparative Synthesis Examples 1 to 4 except that (Polymers (A-1) to synthesis)

Polymers (A-2) to (A-19), polymers (B1-1) to (B1-12) were obtained in the same manner as in Synthesis Example 1 except that monomer compounds having the kinds and amounts shown in Table 1 below were used. And polymers (P1) to (P4) were synthesized. The solid concentration of each polymer solution thus obtained 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 in each polymer was the same as that of the corresponding monomer compound. The blank in Table 1 indicates that the corresponding monomer compound was not blended.

[Synthesis Example 32] (Synthesis of polymer (D-1)

5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of propylene glycol monomethyl ether acetate were fed into a container equipped with a stirrer, and then 18 parts by mass of methyl methacrylate, 5.2 parts by mass of methacrylic acid tricyclo [5.2. 1.0 ^2,6 ] decan-8-yl, 30 parts by mass of 2-hydroxyethyl methacrylate and 22 parts by mass of benzyl methacrylate were charged and replaced with nitrogen. Subsequently, the temperature of the solution was raised to 70 占 폚 while stirring slowly, and this temperature was maintained for 5 hours to polymerize to obtain a copolymer (?) Solution having a solid content concentration of 29.2% by mass.

Then, 30 parts by mass of 2-methacryloyloxyethyl isocyanate (car lens MOI manufactured by Showa Denko Co., Ltd.) and 0.2 part by mass of 4-methoxyphenol were added to this copolymer (?) Solution, For 2 hours at 60 ° C. The progress of the reaction between the isocyanate group and the hydroxyl group of the copolymer (?) Was confirmed by IR (infrared absorption) spectrum. The IR spectrum of each of the solutions after 1 hour at 40 ° C and after 2 hours of reaction at 60 ° C showed that the peak near 2270 cm ^-1 derived from the isocyanate group was reduced. By completing the reaction, a solution of the polymer (D-1) having a solid concentration of 31.0% by mass was obtained. The polymer (D-1) thus obtained had a weight average molecular weight (Mw) of 14,000.

&Lt; Preparation of radiation-sensitive resin composition >

The respective components used in the preparation of the radiation-sensitive resin composition other than the polymer synthesized as the [A] polymer and the [B1] polymer as the [B] epoxy compound are shown below.

[B2] Compound

B2-1: Bisphenol A type epoxy resin ("jER1009" manufactured by Mitsubishi Kagaku Co., Ltd.)

B2-2: Bisphenol A type epoxy resin ("jER1004" manufactured by Mitsubishi Kagaku Co., Ltd.)

B2-3: bisphenol A type epoxy resin ("jER4010P" manufactured by Mitsubishi Kagaku Co., Ltd.)

B2-4: tetrakis (hydroxyphenyl) ethane type epoxy resin ("jER1031S" manufactured by Mitsubishi Kagaku Co., Ltd.)

B2-5: biphenyl-type epoxy resin ("jERYX4000H" of Mitsubishi Kagaku Co., Ltd.)

B2-6: Bisphenol F type epoxy resin ("YDF-2004" of Shinnitetsu Sumikin Kagaku Co., Ltd.)

B2-7: o-cresol novolak type epoxy resin ("YDCN-704A" of Shinnitetsu Sumikin Kagaku Co., Ltd.)

B2-8: Crystalline epoxy resin ("YDC-1312" manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.)

B2-9: Crystalline epoxy resin ("YSLV-80XY" of Shinnitetsu Sumikin Kagaku Co., Ltd.)

B2-10: Crystalline epoxy resin ("YSLV-120TE" of Shinnitetsu Sumikinka Chemical Co., Ltd.)

B2-11: naphthylene ether type epoxy resin ("HP-6000" manufactured by DIC Corporation)

B2-12: Naphthalene type epoxy resin ("HP-4710" manufactured by DIC Corporation)

B2-13: dicyclopentadienyldiphenol type epoxy resin ("HPC-8000-65T" manufactured by DIC Corporation)

[C1] Acid generator

(C1-1) Acid generator for positive-tone radiation-sensitive resin composition

C1-1-1: 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol 5-sulfonic acid chloride (2.0 mol) in acetonitrile

C1-1-2: A condensate of 1,1,1-tris (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol)

(C1-2) acid generator for negative-tone radiation-sensitive resin composition

C1-2-1: Trifluoromethanesulfonic acid-1,8-naphthalimide (Aldrich)

C1-2-2: Aromatic sulfonium salt ("SANEID SI-110" by Sanzinka Kakuko)

[C2] Polymerization initiator

C2-1: 1,2-Octanedione 1- [4- (Phenylthio) -2- (O-benzoyloxime)] ("IRGACURE OXE01"

(2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) ("IRGACURE OXE02"

C2-3: ADEKA's "NCI-831"

C2-4: ADEKA's "NCI-930"

[D] Crosslinkable compound

D-1: Polymer (D-1) synthesized in Synthesis Example 32

D-2: A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate ("KAYARAD DPHA" manufactured by Nippon Kayaku Co., Ltd.)

D-3: ethylene oxide 12 mol-modified dipentaerythritol hexaacrylate ("KAYARAD DPEA-12" manufactured by Nippon Kayaku Co., Ltd.)

D-4: succinic acid-modified dipentaerythritol pentaacrylate ("Aronix M-520" manufactured by Toagosei Co., Ltd.)

D-5: Polybasic acid-modified acrylic oligomer containing carboxyl group ("Aronix M-510" manufactured by Toagosei Co., Ltd.)

[Example 1]

(A) a polymer solution containing 100 parts by mass (solid content) of a polymer (A-1) as a polymer, 100 parts by mass (solid content) of a polymer (B1-1) as an epoxy compound, 10 parts by mass of an acid generator (C1-1-1) as a radiation-sensitive compound, 5 parts by mass of an adhesive aid (? -Glycidoxypropyltrimethoxysilane), 0.5 parts by mass of a surfactant ("FTX-218" And 0.1 part by mass of an antioxidant ("IRGANOX 1010" manufactured by BASF) were mixed, and diethylene glycol methyl ethyl ether was further added as a solvent so that the solid content concentration became 30% by mass. Thereafter, the resultant was filtered through a membrane filter having a pore size of 0.2 탆 to prepare a positive radiation-sensitive resin composition.

[Examples 2 to 60 and Comparative Examples 1 to 10]

(A) polymer, (B) an epoxy compound ([B1] polymer and [B2] compound), [C] a radiation- sensitive compound Were prepared in the same manner as in Example 1, except that the kind of the negative and positive radiation-sensitive resin compositions shown in Table 2 were used.

<Evaluation>

Each prepared positive and positive radiation-sensitive resin composition was evaluated according to the following evaluation method. The evaluation results are 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 allowed to stand in an oven at 40 ° C for 1 week. The viscosity (V ₂ ) after heating was measured, and the rate of change in viscosity (%) was calculated from the following formula and used as an index of storage stability.

Viscosity change rate (%) = {(V ₂ -V ₁ ) / V ₁ } × 100 (%)

C: Viscosity change rate is 10% or more and less than 15%, D: Viscosity change rate is 15% or more, and A or B is a viscosity change rate , Storage stability was good, and in the case of C or D, it was evaluated as defective. Viscosity was measured at 25 캜 using an E-type viscometer ("VISCONIC ELD.R" manufactured by Toray Industries, Inc.).

[Sensitivity]

Each of the radiation sensitive resin compositions was coated on a silicon substrate using a spinner and then prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a film thickness of 3.0 mu m. The obtained coating film was irradiated with a predetermined amount of ultraviolet rays through a mercury lamp through a pattern mask having a line-and-space pattern of width 10 mu m. Subsequently, development was carried out at 25 DEG C for 60 seconds using a developer consisting of 2.38% by mass aqueous solution of tetramethylammonium hydroxide, followed by water washing with ultrapure water for 1 minute. At this time, the minimum ultraviolet radiation amount capable of forming a line-and-space pattern having a width of 10 mu m was measured. In the positive type radiation sensitive resin composition, the sensitivity is evaluated as good when the measured value is less than 250 J / m &lt; 2 &gt;, and in the case of the negative type radiation sensitive resin composition, when the measured value is less than 100 J / Was evaluated as good.

[Developing adhesion]

Each of the radiation sensitive resin compositions was coated on a silicon substrate using a spinner and then prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a film thickness of 3.0 mu m. Ultraviolet rays of 1,000 J / m &lt; 2 &gt; were irradiated to the obtained coating film by a mercury lamp through a pattern mask having a line-and-space pattern having a width of 10 mu m. Subsequently, development was carried out at 25 DEG C for 60 seconds using a developer consisting of 2.38% by mass aqueous solution of tetramethylammonium hydroxide, followed by water washing with ultrapure water for 1 minute. Then, the presence or absence of peeling of the line-and-space pattern having a width of 10 mu m was observed with a microscope to obtain the developing adhesion. In the case of A or B, the developing adhesion is good, and C or D is good. In the case of A or B, the developing adhesion is good. , It was evaluated as defective.

[Chemical resistance]

Each of the radiation sensitive resin compositions was coated on a silicon substrate using a spinner and then prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a film thickness of 3.0 mu m. The obtained coating film was irradiated with ultraviolet rays so that the cumulative irradiation amount was 3,000 J / m 2 by a mercury lamp. Subsequently, the silicon substrate was heated on a hot plate at 200 DEG C for 30 minutes, and the film thickness (T1) of the cured film thus obtained was measured. Then, the silicon substrate on which the cured film was formed was immersed in dimethylsulfoxide controlled at a temperature of 70 占 폚 for 20 minutes, and then the film thickness (t1) of the cured film after the immersion was measured. The film thickness change rate was calculated from the following equation, and this was used as an index of chemical resistance.

Film thickness change rate = {(t1-T1) / T1} x100 (%)

When the absolute value of this value was less than 3%, the chemical resistance was good, and when it was 3% or more, it was evaluated as bad.

[Heat resistance]

Each of the radiation sensitive resin compositions was coated on a silicon substrate using a spinner and then prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a film thickness of 3.0 mu m. The obtained coating film was irradiated with ultraviolet rays so that the cumulative irradiation amount was 3,000 J / m 2 by a mercury lamp. Subsequently, this silicon substrate was heated on a hot plate at 200 DEG C for 30 minutes to obtain a cured film. The 5% weight reduction temperature of the obtained cured film was measured under air using a measuring device (&quot; TG / DTA220U &quot; manufactured by SII Ai Nanotechnology Co., Ltd.) to obtain an index of heat resistance. At this time, when the 5% weight reduction temperature was 300 ° C or higher, the heat resistance was good. When the weight reduction temperature was less than 300 ° C, the heat resistance was evaluated as poor.

[Transmittance (Transparency)]

Each of the radiation sensitive resin compositions was coated on a glass substrate using a spinner, and then prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a film thickness of 3.0 mu m. The obtained coating film was irradiated with ultraviolet rays so that the cumulative irradiation amount was 3,000 J / m 2 by a mercury lamp. Subsequently, this glass substrate was heated on a hot plate at 200 DEG C for 30 minutes to obtain a cured film. The transmittance of the resulting cured film was measured using an ultraviolet visible spectrophotometer (&quot; V-630 &quot; manufactured by Nippon Bunko). In the positive-tone radiation-sensitive resin composition, the case where the light transmittance at a wavelength of 400 nm was 95% or more was evaluated as good (excellent transparency), and the case of less than 95% was evaluated as poor (poor transparency). In the negative-tone radiation-sensitive resin composition, the light transmittance at a wavelength of 400 nm was evaluated as good (good transparency) when 97% or more, and poor (transparency poor) was evaluated when the transmittance was 97% or less.

[Surface hardness]

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

[Relative dielectric constant (low dielectric constant)]

Each of the radiation sensitive resin compositions was coated on an SUS substrate using a spinner, and then prebaked on a hot plate at 90 DEG C for 2 minutes to form a coating film having a film thickness of 3.0 mu m. The above coated film was exposed using an exposure machine ("MPA-600 FA" manufactured by Canon Inc.) so that the cumulative amount of irradiation was 9,000 J / m 2, and the exposed substrate was heated in a clean oven at 200 캜 for 30 minutes, Thereby forming a cured film. Subsequently, a Pt / Pd electrode pattern was formed on the cured film by a vapor deposition method to prepare a sample for measuring a dielectric constant. With respect to the substrate having this electrode pattern, an electrode (HP16451B manufactured by Yokogawa Hewlett-Packard Co., Ltd.) and a Precision LCR meter (HP4284A manufactured by Yokogawa Hewlett Packard Co., Ltd.) And the relative dielectric constant was measured. At this time, the case where the relative dielectric constant was 3.6 or less was evaluated as good and the case where the relative dielectric constant exceeded 3.6 was evaluated as defective.

The present invention relates to a radiation-sensitive resin composition capable of obtaining a cured film having excellent heat resistance, chemical resistance, surface hardness, developing adhesion, transparency and low dielectric constant, and satisfying characteristics such as storage stability and sensitivity, A method of forming a cured film using the resin composition, a cured film, a semiconductor element, and a display element can be provided. Accordingly, the radiation sensitive resin composition, the cured film formed of the radiation sensitive resin, the semiconductor element and the display element, and the method of forming the cured film can be suitably used for a manufacturing process of an electronic device such as a flexible display .

Claims (11)

A first polymer comprising a first structural unit having a group represented by the following formula (1) and having a content ratio of the first structural unit with respect to the total structural unit of 20 mass% or more and 90 mass%
An epoxy compound having an epoxy group,
Sensitizing radiation compound
Wherein the radiation-sensitive resin composition comprises:

(In the formula (1), R ¹ is a hydrogen atom, a halogen atom, a hydroxyl 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 hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. The method according to claim 1,
Wherein the first polymer further comprises a second structural unit having an acidic group. 3. The method of claim 2,
Wherein the acidic group is a carboxyl 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 method according to claim 1, 2, or 3,
Wherein the epoxy compound is a second polymer comprising a structural unit having the epoxy group. 5. The method of claim 4,
Wherein the second polymer further comprises a structural unit having an acidic group. 6. The method according to any one of claims 1 to 5,
Wherein the first structural unit having a group represented by the formula (1) is a radiation-sensitive resin composition 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) :

(The formula (2-1) of, R ^1, R ² and R ³ are, the formula (1), is defined as a; A ¹ is a halogen atom, a hydroxyl group, an alkoxy group having a carbon number of 1 to 6 carbon atoms or is an alkyl group of 1 to 6; when a ¹ is plural, a plurality of a ¹ are, each independently meets the above definition; n1 is an integer of 0 to 4, and; - is, represents the binding site;
In the formula (2-2), R ¹ , R ² and R ³ have the same meanings as in the formula (1); A ² is a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms; When A ² is in plurality, a plurality of A ² are, each independently meets the above definition; n2 is an integer of 0 to 6; * Indicates a binding site). 7. The method according to any one of claims 1 to 6,
Wherein the radiation-sensitive compound is an acid generator, a polymerization initiator, or a combination thereof. A process for producing a radiation sensitive resin composition comprising the steps of forming a coating film on a substrate using the radiation sensitive resin composition according to any one of claims 1 to 7,
A step of irradiating a part of the coating film with radiation,
A step of developing the coated film irradiated with the radiation,
A step of heating the developed coating film
Of the cured film. A cured film formed from the radiation sensitive resin composition according to any one of claims 1 to 7. A semiconductor device comprising the cured film according to claim 9. A display device comprising the semiconductor element according to claim 10.