TW202330668A - Method for producing lens, radiation-sensitive composition for producing lens, lens, imaging element, imaging device, display element, and display device - Google Patents

Abstract

A lens is produced by a method comprising: a step for applying a radiation-sensitive composition onto a base material to form a coating film; a step for irradiating a portion of the coating film with a radioactive ray to generate an acid in an exposed portion; a step for developing the coating film that has been irradiated with the radioactive ray to form a pattern; a step for irradiating the pattern with a radioactive ray; and a step for heating the pattern after the irradiation of the pattern with the radioactive ray to form a lens. The radiation-sensitive composition comprises at least one polymer (A), a radiation-sensitive acid generator (B) and a solvent(C), in which the polymer (A) contains, in a single molecule or different molecules, a structural unit (a1) having a hydroxyl group bound to an aromatic ring and a structural unit (a2) having such a configuration that an acid-dissociating group is detached by the action of an acid to generate a carboxyl group.

Description

Method for producing lens, radiation-sensitive composition for lens production, lens, imaging element, imaging device, display element, and display device

[CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims priority based on Japanese Patent Application No. 2022-005909 filed on January 18, 2022, the entirety of which is incorporated herein by reference. The disclosure relates to a manufacturing method of a lens, a radiation-sensitive composition for lens manufacturing, a lens, an imaging element, an imaging device, a display element, and a display device.

Various image sensors such as Charge-Coupled Device (CCD) image sensors and Complementary Metal-Oxide-Semiconductor (CMOS) image sensors are being used in imaging devices such as cameras solid-state imaging elements. In a solid-state imaging device, tiny condenser lenses (hereinafter, also referred to as "microlenses") are regularly arranged to condense light into a light-receiving element (photodiode) to increase the sensitivity of the sensor. improve. In addition, in display elements such as organic electroluminescent (organic EL (electroluminescence)) elements, in order to improve light extraction efficiency, a structure in which microlenses are provided on the light emission side of each pixel is also adopted.

As one of the methods of forming microlenses, a thermal flow method is known. In this heat flow method, a radiation-sensitive composition is used to form a pattern corresponding to a microlens on the upper part of a light-receiving element or a light-emitting element. Fluidization is performed by heat treatment to form a hemispherical microlens array (for example, refer to Patent Document 1). [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2020-101659

[Problem to be Solved by the Invention] For the radiation-sensitive composition used for forming the microlens pattern, it is required that a microlens with high radiation sensitivity, chemical resistance, and high transparency can be produced. In addition, in order to secure a manufacturing margin, a wide temperature range (hereinafter, also referred to as “flow margin”) in which a good microlens pattern can be formed is required.

This disclosure was made in view of the above-mentioned problems, and its main purpose is to provide a lens manufacturing method and a radiation-sensitive composition for lens manufacturing, which can obtain a lens with high radiation sensitivity, large flow margin, and excellent chemical resistance and transparency. lens. [Means to solve the problem]

According to the present disclosure, the following lens manufacturing method, radiation-sensitive composition for lens manufacturing, lens, imaging element, imaging device, display element, and display device are provided.

[1] A method of manufacturing a lens, comprising: a step of coating a radiation-sensitive composition on a base material to form a coating film; irradiating a part of the coating film with radiation, thereby generating acid in an exposed portion; a step of developing the coating film irradiated with radiation to form a pattern on the substrate; a step of irradiating the pattern with radiation; and heating the pattern after irradiating the pattern, whereby the The step of forming a lens on the base material, the radiation-sensitive composition contains a polymer (A), a radiation-sensitive acid generator (B), and a solvent (C), and the polymer (A) is in the same molecule Or different molecules include a structural unit (a1) and a structural unit (a2), the structural unit (a1) has a hydroxyl group bonded to an aromatic ring, and the structural unit (a2) is acid-dissociable by the action of an acid detach, thereby generating a carboxyl group.

[2] A radiation-sensitive composition for lens production, comprising: a polymer (A); a radiation-sensitive acid generator (B); and a solvent (C), the polymers (A) being in the same molecule or different The molecule contains a structural unit (a1) and a structural unit (a2), the structural unit (a1) has a hydroxyl group bonded to an aromatic ring, and the structural unit (a2) is detached from an acid dissociative group by the action of an acid, resulting in a carboxyl group.

[3] A lens formed using the radiation-sensitive composition for lens production of the above [2]. [4] An imaging device including the lens of [3]. [5] An imaging device including the imaging element of [4]. [6] A display element including the lens of [3]. [7] A display device including the display element of [6]. [Effect of the invention]

According to the production method of the present disclosure, a coating film is formed on a base material using a radiation-sensitive composition containing the polymer (A), a radiation-sensitive acid generator (B) and a solvent (C), and the coating film is formed after exposure. After development, exposure and heating are further performed, thereby increasing the flow margin and forming a lens with high chemical resistance and transparency. In addition, the radiation-sensitive composition for lens production of the present disclosure has high sensitivity to radiation, and can form a lens with a good shape with a small amount of irradiation.

Hereinafter, matters related to the embodiment will be described in detail. In addition, in this specification, the numerical range described using "-" is the meaning which includes the numerical value described before and after "-" as a lower limit and an upper limit. The term "structural unit" refers to a structural unit that mainly constitutes the main chain structure and includes at least two or more chemical structures in the main chain structure.

"How to Make a Lens" The manufacturing method of the present disclosure is to manufacture tiny light concentrators, i.e. lenses ( Hereinafter, also referred to as "microlens") method, more specifically, a method based on heat flow. The manufacturing method disclosed herein includes the following steps (I) to (V). (I) Step of forming a coating film by coating a radiation-sensitive composition for lens production on a base material (II) A step of irradiating a part of the coating film with radiation to generate acid in the exposed portion (first exposure step) (III) Process of developing the coating film irradiated with radiation to form a pattern on the substrate (IV) A step of irradiating the pattern obtained by the step (III) with radiation (second exposure step) (V) A step of forming a lens on a base material by irradiating the pattern with radiation in the above step (IV) and then heating the pattern Hereinafter, first, the radiation-sensitive composition for lens production used in the production method of the present disclosure will be described, and then each step included in the production method of the present disclosure will be described.

[Radiation sensitive composition for lens manufacturing] The radiation-sensitive composition for lens production of the present disclosure (hereinafter also simply referred to as “this composition”) contains a polymer (A), a radiation-sensitive acid generator (B), and a solvent (C). In addition, unless otherwise specified, each component may be used individually by 1 type, and may use it in combination of 2 or more types.

Here, in this specification, a "hydrocarbon group" has the meaning including a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The term "chain hydrocarbon group" refers to a linear hydrocarbon group and a branched hydrocarbon group that do not contain a cyclic structure in the main chain but only consist of a chain structure. Among them, the chain hydrocarbon group may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group including only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure. Among them, the alicyclic hydrocarbon group does not need to consist only of the alicyclic hydrocarbon structure, and includes those having a chain structure in a part thereof. The "aromatic hydrocarbon group" refers to a hydrocarbon group including an aromatic ring structure as a ring structure. Among them, the aromatic hydrocarbon group does not need to consist only of an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure in a part thereof. In addition, the ring structure which an alicyclic hydrocarbon group and an aromatic hydrocarbon group have may have the substituent which contains a hydrocarbon structure.

In addition, in this specification, "(meth)acryl" is the meaning which includes "acryl" and "methacryl". "(Meth)acryl" is meant to include "acryl" and "methacryl". In this specification, an "epoxy group" including an oxiranyl group and an oxetanyl group is also called.

＜Polymer (A)＞ The polymer (A) includes one or both of a structural unit (a1) and a structural unit (a2), the structural unit (a1) has a hydroxyl group bonded to an aromatic ring, and the structural unit (a2) is The acid dissociative group is removed by the action of acid, thereby generating a carboxyl group. Among them, the polymer (A) contains the structural unit (a1) and the structural unit (a2) in the same molecule or in different molecules. As long as it contains the structural unit (a1) and the structural unit (a2), the polymer (A) may contain one kind of polymer or two or more kinds of polymers.

Specific examples of the polymer (A) include the following (I) and (II). (I) A polymer having a structural unit (a1) and a structural unit (a2) in one molecule. (II) A mixture of a first polymer having the structural unit (a1), and a second polymer having the structural unit (a2) and being different from the first polymer. This composition is preferable in terms of reducing the number of components constituting the composition as much as possible, while obtaining the sensitivity of the composition or a large flow margin, and improving the chemical resistance of the obtained hardened product. The polymer (A) is a polymer including a structural unit (a1) and a structural unit (a2) in the same molecule.

· Structural unit (a1) By including the structural unit (a1) in the polymer (A), the solubility of the polymer (A) to an alkali developing solution (alkali solubility) can be improved while ensuring the transparency of the microlens formed from the composition, or Improve hardening reactivity. In addition, in this specification, "alkali-soluble" means to dissolve in the aqueous alkali solution, such as the tetramethylammonium hydroxide aqueous solution of 2.38 mass % concentration, at room temperature.

As an aromatic ring which a structural unit (a1) has, a benzene ring, a naphthalene ring, an anthracene ring, etc. are mentioned, for example. Among these, a benzene ring or a naphthalene ring is preferable, and a benzene ring is more preferable from the viewpoint of the permeability of the obtained cured product. In the structural unit (a1), the number of hydroxyl groups bonded to the aromatic ring is not particularly limited. The number of hydroxyl groups bonded to the aromatic ring is preferably from 1 to 3, more preferably 1 or 2. A substituent other than a hydroxyl group may also be introduced into the aromatic ring of the structural unit (a1). Examples of such substituents include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), alkyl groups having 1 to 4 carbons, alkoxy groups having 1 to 4 carbons, and alkoxy groups having 1 to 4 carbons. Fluorinated alkyl, etc.

The structural unit (a1) is preferably a structural unit derived from a monomer having a structure in which a hydroxyl group and an aromatic ring are bonded and a polymerizable unsaturated bond (hereinafter also referred to as "monomer (M1)"). In terms of obtaining good patternability and resolution, among them, the monomer (M1) is preferably selected from (meth)acrylate compounds, (meth)acrylamide compounds, compounds having a styrene structure and at least one of the group consisting of compounds having a maleimide structure. Specifically, the structural unit (a1) is preferably at least one selected from the group consisting of compounds represented by the following formula (a1-1) and compounds represented by the following formula (a1-2) structural unit.

[chemical 1] (In formula (a1-1), R ¹ is a hydrogen atom, a halogen atom, an alkyl group with 1 to 4 carbons, or a fluorinated alkyl group with 1 to 4 carbons; R ² is a single bond, * ¹ -C(= O)-O- or * ¹ -C(=O)-NH-; "* ¹ "represents a bond to the carbon atom to which R ¹ is bonded; R ³ is a halogen atom, an alkane with 1 to 4 carbons group, an alkoxy group with 1 to 4 carbons or a fluorinated alkyl group with 1 to 4 carbons; m1 is an integer of 0 to 4; m2 is 1 or 2; among them, m1+m2≦5; m1 is 2 or more In the case of , multiple R ³ are the same or different; In formula (a1-2), R ⁴ is a halogen atom, an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, or an alkoxy group with 1 to 4 carbons fluorinated alkyl; n1 is an integer from 0 to 4; n2 is 1 or 2; wherein, n1+n2≦5; when n1 is 2 or more, multiple R ⁴ are the same or different)

In the formula (a1-1) and the formula (a1-2), examples of the halogen atom represented by R ¹ , R ³ and R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl group having 1 to 4 carbons may be linear or branched, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, isobutyl, tertiary butyl. Examples of the alkoxy group having 1 to 4 carbon atoms include groups in which each of the groups exemplified as the alkyl group having 1 to 4 carbon atoms is bonded to an oxygen atom. Examples of the fluorinated alkyl group having 1 to 4 carbon atoms include groups in which at least one hydrogen atom of each group exemplified as the alkyl group having 1 to 4 carbon atoms is substituted with a fluorine atom.

R ¹ is preferably a hydrogen atom or a methyl group from the viewpoint of copolymerizability of the monomer providing the structural unit (a1). R ² is preferably a single bond or * ¹ -C(=O)-O-. m1 and n1 are preferably 0-2, more preferably 0 or 1, respectively.

Specific examples of the structural unit (a1) include structural units represented by the following formulas (1-1) to (1-13), respectively. [Chem 2] (In formulas (1-1) to (1-10), R ^A1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbons, or a fluorinated alkyl group having 1 to 4 carbons) [Chem. 3]

In the polymer (A), from the viewpoint of imparting good solubility in an alkaline developer to the polymer (A), the content of the structural unit (a1) relative to all the structural units constituting the polymer (A) is The ratio is preferably at least 10 mol%, more preferably at least 15 mol%, and still more preferably at least 25 mol%. On the other hand, if the content ratio of the structural unit (a1) is too large, the difference in solubility in an alkali developing solution between the exposed part and the unexposed part becomes small, and it may be difficult to obtain a favorable pattern shape. From this point of view, the content ratio of the structural unit (a1) is preferably at most 90 mol %, more preferably at most 85 mol %, and still more preferably at most 80 mol %, relative to all structural units constituting the polymer (A). Ear % below. In addition, when the polymer (A) contains two or more polymers, the content ratio of the structural unit (a1) refers to the ratio of the structural unit (a1) in the two or more polymers constituting the polymer (A). The total amount (the same is true for the following structural units).

· Structural unit (a2) The structural unit (a2) is a structural unit in which an acid dissociative group is detached from an acid generated by irradiating the composition with radiation to generate a carboxyl group. When the polymer (A) contains the structural unit (a2), the solubility of the polymer (A) in the developer can be changed by irradiation with radiation. Thereby, a patterned hardened product can be obtained. Here, the "acid dissociative group" refers to a group that substitutes a hydrogen atom of an acid group such as a carboxyl group and dissociates by the action of an acid.

In particular, in this composition, by irradiating the composition with radiation, carboxyl groups are generated as acid groups in the side chain portion of the polymer (A) in the region irradiated with radiation. It is considered that by utilizing this reaction, further exposure treatment in step (IV) and heat treatment in step (V) are performed after image development, a crosslinking reaction involving carboxyl groups proceeds in the presence of an acid. It is considered that the cross-linking reaction involving carboxyl groups proceeds in this way to accelerate hardening, and as a result, this composition can realize good chemical resistance and a large fluidity margin. Furthermore, it is considered that through the further exposure treatment in step (IV) and the heat treatment in step (V), in the structural unit (a1), for example, a crosslinking reaction based on the etherification of aromatic rings will also proceed. .

Examples of monomers constituting the structural unit (a2) include structural units derived from protected unsaturated carboxylic acids. As unsaturated carboxylic acid, an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated acid anhydride, an unsaturated polyhydric carboxylic acid, etc. are mentioned, for example.

As specific examples of these, unsaturated monocarboxylic acids include: (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2-(meth)acryloxyethyl-succinic acid, 2- (Meth)acryloxyethyl hexahydrophthalic acid, 2-(meth)acryloxyethyl-phthalic acid, 2-carboxyethyl (meth)acrylate, 4- Vinyl benzoic acid, etc. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, and citraconic acid. Examples of unsaturated acid anhydrides include maleic anhydride, itaconic anhydride, and citraconic anhydride. As the unsaturated polyhydric carboxylic acid, ω-carboxypolycaprolactone mono(meth)acrylate and the like are exemplified.

As the acid dissociative group which the structural unit (a2) has, a tertiary alkyl group, an acetal type functional group, a tertiary alkyl carbonate group etc. are mentioned, for example. Among these, a tertiary alkyl group or an acetal-based functional group is preferable at the point that it is easily dissociated by an acid. In the case where the acid-dissociative group is an acetal-based functional group, the step of postexposure bake (PEB) can be omitted, and the steps can be simplified. Furthermore, the PEB step is a heating step performed after the exposure by the step (II) and before the development by the step (III), preferably after the heat treatment by the step (V). at low temperature.

The structural unit (a2) is preferably a structural unit derived from a monomer (hereinafter, also referred to as "monomer (M2)") having a carboxyl group that is detached from an acid-dissociable group by an acid. structure and polymeric unsaturated bonds. Among them, the structural unit (a2) is preferably derived from a compound represented by the following formula (a2-1) and the following formula (a2-2) A structural unit of at least one of the group consisting of compounds represented by (a2-2). [chemical 4] (In formula (a2-1), R ⁵ is a hydrogen atom, a halogen atom, an alkyl group with 1 to 4 carbons, or a fluorinated alkyl group with 1 to 4 carbons; R ⁶ is a single bond, substituted or unsubstituted phenylene group, or * ² -C(=O)-OR ¹⁵ -; "* ² "represents the bonding bond with the carbon atom to which R ⁵ is bonded; R ¹⁵ is a substituted or unsubstituted divalent Hydrocarbon group; R ⁷ is a monovalent aliphatic hydrocarbon group; R ⁸ and R ⁹ are each independently a monovalent aliphatic hydrocarbon group, or it means that R ⁸ and R ⁹ are combined with each other and form together with the carbon atom to which R ⁸ and R ⁹ are bonded alicyclic structure; in formula (a2-2), R ¹⁰ is a hydrogen atom, a halogen atom, an alkyl group with 1 to 4 carbons, or a fluorinated alkyl group with 1 to 4 carbons; R ¹¹ is a single bond, Substituted or unsubstituted phenylene, or * ³ -C(=O)-OR ¹⁶ -; "* ³ "represents the bond to the carbon atom to which R ¹⁰ is bonded; R ¹⁶ is substituted or unsubstituted A substituted divalent hydrocarbon group; R ¹² is a hydrogen atom or a monovalent aliphatic hydrocarbon group; Regarding R ¹³ and R ¹⁴ , R ¹³ is a monovalent aliphatic hydrocarbon group, and R ¹⁴ is a monovalent aliphatic hydrocarbon group, an aralkyl group or a substituted Aralkyl group, or R ¹³ and R ¹⁴ represent a cyclic ether structure in which R ¹³ and R ¹⁴ are combined with each other and the carbon atom to which R ¹³ is bonded and the oxygen atom to which R ¹⁴ is bonded)

In formula (a2-1) and formula (a2-2), specific examples of R ⁵ and R ¹⁰ include groups exemplified in the description of R ¹ . R ⁵ and R ¹⁰ are preferably a hydrogen atom or a methyl group from the viewpoint of the copolymerizability of the monomer providing the structural unit (a2).

Regarding R ⁶ and R ¹¹ , divalent hydrocarbon groups represented by R ¹⁵ and R ¹⁶ include alkanediyl groups having 1 to 5 carbon atoms, cycloalkanediyl groups having 3 to 10 carbon atoms, and phenylene groups. Examples of the substituent introduced into the phenylene group when R ⁶ and R ¹¹ are substituted phenylene groups, and the substituents when R ¹⁵ and R ¹⁶ have substituents include: halogen atoms, carbon atoms of 1 to Alkyl group having 4, alkoxy group having 1 to 4 carbons, fluorinated alkyl group having 1 to 4 carbons, etc. Specific examples of these include groups exemplified in the description of R ¹ .

Examples of the monovalent aliphatic hydrocarbon groups represented by R ⁷ to R ⁹ in formula (a2-1) and R ¹² to R ¹⁴ in formula (a2-2) include monovalent alkyl groups having 1 to 10 carbon atoms, A monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms.

Among R ⁷ to R ⁹ and R ¹² to R ¹⁴ , the alkyl group having 1 to 10 carbons may be linear or branched. Specific examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl base, n-hexyl, n-heptyl, etc.

Among R ⁷ to R ⁹ and R ¹² to R ¹⁴ , the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms includes a group obtained by removing one hydrogen atom from a monocyclic or polycyclic saturated alicyclic hydrocarbon. As specific examples of saturated alicyclic hydrocarbons, monocyclic alicyclic hydrocarbons include cyclopentane, cyclohexane, cycloheptane, and cyclooctane. Examples of polycyclic alicyclic hydrocarbons include: bicyclo[2.2.1]heptane (norbornane), bicyclo[2.2.2]octane, tricyclo[3.3.1.1 ^3,7 ]decane (adamantane ), tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]decane, etc.

The substituted or unsubstituted aralkyl group represented by ^R14 includes: an aralkyl group having 7 to 20 carbon atoms, at least one hydrogen atom of the aralkyl group via a halogen atom, an alkane group having 1 to 4 carbon atoms. A group, an alkoxy group having 1 to 4 carbons, a group substituted with a fluorinated alkyl group having 1 to 4 carbons. Specific examples of the aralkyl group include benzyl group, phenethyl group, naphthylmethyl group, anthracenylmethyl group, methylphenylmethyl group and the like.

Examples of the alicyclic structure in which R ⁸ and R ⁹ are bonded to each other and constitute the carbon atoms to which R ⁸ and R ⁹ are bonded include monocyclic or polycyclic alicyclic hydrocarbons having 3 to 20 carbon atoms. A group obtained by removing two hydrogen atoms from the same carbon atom (hereinafter also referred to as "divalent alicyclic group"). When the divalent alicyclic group is a polycyclic hydrocarbon group, the polycyclic hydrocarbon group may be any of a bridged alicyclic hydrocarbon group and a condensed alicyclic hydrocarbon group. In addition, the condensed alicyclic hydrocarbon group refers to a polycyclic alicyclic hydrocarbon group constituted such that a plurality of aliphatic rings share a side (a bond between two adjacent carbon atoms). The so-called bridged ring alicyclic hydrocarbon group refers to a polycyclic alicyclic hydrocarbon group formed by bonding between two carbon atoms that are not adjacent to each other among the carbon atoms that constitute the aliphatic ring by using a bond chain that contains more than one carbon atom. Hydrocarbyl.

In the case where R ⁸ and R ⁹ are combined to form a divalent alicyclic group, the divalent alicyclic group is preferable in terms of improving the solubility of the exposed portion with respect to an alkaline developing solution. to contain saturated hydrocarbons. Specifically, as a monocyclic alicyclic hydrocarbon group, a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, a cyclooctanediyl group, etc. are mentioned. In addition, the polycyclic alicyclic hydrocarbon group is preferably bridged alicyclic saturated hydrocarbon group, and is preferably bicyclo[2.2.1]heptane-2,2-diyl, bicyclo[2.2.2]octane-2 ,2-diyl or tricyclo[3.3.1.1 ^3,7 ]decane-2,2-diyl.

From the viewpoint of improving the solubility of the exposed portion with respect to an alkaline developer, R ⁸ and R ⁹ preferably represent an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, or R ⁸ and R 9 ⁹ are combined with each other and form a monocyclic or polycyclic alicyclic structure with 3 to 12 carbons together with the carbon atoms to which R ⁸ and R ⁹ are bonded, more preferably an alkyl group or carbon with 1 to 4 carbons A cycloalkyl group with a number of 3 to 8, or a monocyclic saturated alicyclic structure composed of R ⁸ and R ⁹ bonded to each other and the carbon atoms to which R ⁸ and R ⁹ are bonded.

The cyclic ether structure formed by combining R ¹³ and R ¹⁴ with each other preferably has 5 or more ring members, more preferably 5-12 ring members. Specifically, a tetrahydrofuran ring structure, a tetrahydropyran ring structure, etc. are mentioned, for example. When R ¹³ and R ¹⁴ combine with each other to form a cyclic ether structure, R ¹² is preferably a hydrogen atom, methyl or ethyl group, more preferably a hydrogen atom, in terms of being easily dissociated by acid.

As a specific example of a structural unit (a2), the structural unit etc. which are represented by the following formula are mentioned, for example. [chemical 5] [chemical 6] (In the formula, R ^A1 is a hydrogen atom, a halogen atom, an alkyl group with 1 to 4 carbons, or a fluorinated alkyl group with 1 to 4 carbons) [Chemical 7] (In the formula, R ^A1 is a hydrogen atom, a halogen atom, an alkyl group with 1 to 4 carbons or a fluorinated alkyl group with 1 to 4 carbons)

The content ratio of the structural unit (a2) is preferably at least 5 mol %, more preferably at least 10 mol %, further preferably at least 15 mol %, and still more preferably at least 15 mol %, relative to all structural units constituting the polymer (A). Preferably it is more than 20 mol%. In addition, the content of the structural unit (a2) is preferably at most 60 mol%, more preferably at most 55 mol%, and still more preferably at most 50 mol%, based on all structural units constituting the polymer (A). By setting the content ratio of a structural unit (a2) into the said range, the pattern formation ability of this composition can be improved further.

The total content ratio of the structural unit (a1) and the structural unit (a2) in the polymer (A) is preferably at least 50 mol%, more preferably 55 mol%, relative to all the structural units constituting the polymer (A). % or more, more preferably 60 mol% or more, more preferably 65 mol% or more, and more preferably 70 mol% or more. When the total content ratio of the structural unit (a1) and the structural unit (a2) in the polymer (A) is within the above-mentioned range, the sensitivity of the present composition to radiation and a large flow margin can be sufficiently ensured, and the composition can be sufficiently An effect of improving the chemical resistance of the obtained cured product is obtained.

·Other structural units The polymer (A) may further include a structural unit different from the structural unit (a1) and the structural unit (a2) in addition to the structural unit (a1) and the structural unit (a2) (hereinafter also referred to as "other structural units") ).

Examples of other structural units include structural units having an oxetanyl group or an oxiranyl group (hereinafter also referred to as "structural unit (a3)").

• Structural unit (a3) The structural unit (a3) is not particularly limited as long as it has an epoxy group. The structural unit (a3) includes, for example, a structural unit derived from a monomer having a polymerizable carbon-carbon unsaturated bond and an epoxy group (hereinafter also referred to as “monomer (M3)”). Specifically, the structural unit (a3) includes a structural unit represented by the following formula (3). [chemical 8] (In formula (3), R ³¹ is a monovalent group with an oxetane structure or an oxirane structure; R ³² is a hydrogen atom or a methyl group; X ³ is a single bond or a divalent linking group)

In the formula (3), examples of R ³¹ include oxiranyl, oxetanyl, 3,4-epoxycyclohexyl, 3,4-epoxytricyclo[5.2.1.0 ^{2 ,6} ] Decyl, 3-ethyl oxetanyl and so on. Among these, R ³¹ is preferably a monovalent group having an oxirane structure in terms of high photoreactivity. Examples of the divalent linking group of ^X3 include alkanediyl groups such as methylene, ethylene, and 1,3-propanediyl.

Specific examples of the third monomer include, for example, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (methyl) ) acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate, (3-methyloxetan-3-yl)methyl(meth)acrylate, (3-ethyloxetan-3-yl)(meth)acrylate, (oxetane butane-3-yl)methyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, and the like.

When the polymer (A) contains the structural unit (a3), the epoxy group contained in the structural unit (a3) functions as a crosslinkable group, whereby the resolution of the film obtained by using this composition can be improved And chemical resistance of hardened products. On the other hand, when the polymer (A) contains the structural unit (a3), acid cannot be sufficiently generated in the exposed portion in the exposure step before development, so the radiation sensitivity of the present composition may decrease or the pattern forming ability may decrease. concerns. Therefore, the polymer (A) preferably does not contain the structural unit (a3), or contains a relatively small amount of the structural unit (a3).

Specifically, the content ratio of the structural unit (a3) in the polymer (A) is preferably from 0 mol % to 15 mol % with respect to all the structural units constituting the polymer (A), more preferably 0 mol% to 10 mol%, more preferably 0 mol% to 5 mol%, still more preferably 0 mol% to 1 mol%. By setting the content ratio of the structural unit (a3) within the above-mentioned range, acid can be sufficiently generated in the exposed portion by radiation irradiation before development, and a hardened product having a good pattern shape can be obtained by subsequent development treatment. .

Examples of monomers constituting other structural units include alkyl (meth)acrylates, (meth)acrylates having an alicyclic structure, and (meth)acrylic acid having an aromatic ring structure in addition to the above. Esters, aromatic vinyl compounds, N-substituted maleimide compounds, monomers with hydroxyl groups (excluding phenolic hydroxyl groups), monomers with cyclic ether structures (including oxirane structures and oxetane Monomers other than alkane structures, monomers with cyclic carbonate structures, etc.

Specific examples of the above-mentioned monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and (meth)acrylic acid. Isopropyl ester, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, etc. Among these, from the viewpoint of securing the heat resistance of the polymer (A), the alkyl group constituting the alkyl ester moiety has preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

Examples of (meth)acrylates having an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 (meth)acrylate, ^2,6 ]decane-8-yl ester, tricyclo[5.2.1.0 ^2,5 ]decane-8-yloxyethyl (meth)acrylate, isobornyl (meth)acrylate, etc.

Examples of (meth)acrylates having an aromatic ring structure include: phenyl (meth)acrylate, benzyl (meth)acrylate, naphthylmethyl (meth)acrylate, naphthylethyl (meth)acrylate ester, phenoxyethyl (meth)acrylate, m-phenoxyphenylmethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, etc.

Examples of aromatic vinyl compounds include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, and 2,4-dimethylstyrene , 2,4-diisopropylstyrene, 5-tert-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, tertiary butoxystyrene, vinylbenzyl dimethyl amine, (4-vinylbenzyl) dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2- Ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, vinyl naphthalene, Vinylpyridine, etc.

Examples of N-substituted maleimide compounds include: N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide , N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-(2,6-dimethylcyclohexyl)maleimide Amine, N-norbornylmaleimide, N-tricyclodecanylmaleimide, N-adamantylmaleimide, N-phenylmaleimide, N-(2 -Methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6 -Dimethylphenyl)maleimide, N-benzylmaleimide, N-naphthylmaleimide, etc.

As a monomer having a hydroxyl group (except for a phenolic hydroxyl group), hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ( 3-Hydroxypropyl methacrylate, 2-Hydroxybutyl (meth)acrylate, 4-Hydroxybutyl (meth)acrylate, 5-Hydroxypentyl (meth)acrylate, 6-Hydroxy (meth)acrylate Hydroxyhexyl Ester, Glycerol Mono(Meth)acrylate, N-(Hydroxymethyl)Maleimide, N-(2-Hydroxyethyl)Maleimide, N-(3-Hydroxypropane base) maleimide, etc.

Examples of monomers having a cyclic ether structure (except for the oxirane structure and the oxetane structure) include: tetrahydrofurfuryl (meth)acrylate, tetrahydropyranyl (meth)acrylate , 5-ethyl-1,3-dioxan-5-ylmethyl (meth)acrylate, 1,3-dioxan-5-ylmethyl (meth)acrylate, (meth)acrylic acid 5-Methyl-1,3-dioxolan-5-ylmethyl ester, (meth)acrylic acid (2-methyl-2-ethyl-1,3-dioxolan-4-yl) Methyl ester, (2,2-dimethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, (2,2-dimethyl-1-(meth)acrylate ,3-dioxolan-4-yl)ethyl ester, 2-(meth)acryloxymethyl-1,4,6-trioxaspiro[4.6]undecane, 2- (Meth)acryloxymethyl-1,4,6-trioxaspiro[4.4]nonane, 2-(meth)acryloxymethyl-1,4,6-trioxy Heterospiro[4.5]decane, etc. As a monomer which has a cyclic carbonate structure, glycerol carbonate (meth)acrylate etc. are mentioned, for example.

Examples of monomers constituting other structural units further include unsaturated dicarboxylic acid dialkyl ester compounds such as diethyl itaconate; conjugated diene compounds such as 1,3-butadiene and isoprene; Nitrogen-containing vinyl compounds such as (meth)acrylonitrile and (meth)acrylamide; vinyl chloride, vinylidene chloride, vinyl acetate, etc.

In the polymer (A), the content ratio of other structural units can be suitably set within the range which does not impair the effect of this indication. The ratio of the other structural units to all the structural units constituting the polymer (A) can be, for example, 0 mol % to 45 mol %, preferably 40 mol % or less, more preferably 35 mol % % or less, and preferably less than 30 mole %. In addition, the content ratio of each structural unit is normally equivalent to the ratio of the monomer used at the time of manufacture of a polymer (A).

As monomers constituting other structural units, in terms of improving solubility in alkaline developing solutions, or adjusting a large flow margin in a balanced manner, chemical resistance of the obtained hardened product, etc., among the above, more can be used. It is preferable to use at least one monomer selected from the group consisting of alkyl (meth)acrylates, (meth)acrylates having an alicyclic structure, and (meth)acrylates having an aromatic ring structure ( Hereinafter, it is also referred to as "(meth)acrylate"). The content ratio of the structural unit derived from (meth)acrylate is, for example, not less than 0 mol % and not more than 45 mol %, more preferably not more than 40 mol %, relative to all the structural units constituting the polymer (A), More preferably, it is 35 mol% or less, and still more preferably, it is 30 mol% or less.

In the polymer (A), the polystyrene-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography (Gel Permeation Chromatography, GPC) is preferably 2,000 or more. When Mw is 2000 or more, heat resistance and chemical resistance are sufficiently high, and the hardened|cured material which shows favorable developability can be obtained, and it is preferable in this point. Mw is more preferably at least 5000, further preferably at least 6000. In addition, from the viewpoint of improving film-forming properties, Mw is preferably at most 50,000, more preferably at most 30,000, still more preferably at most 20,000, and even more preferably at most 18,000.

In the polymer (A), the molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 4.0 or less, more preferably 3.0 or less. Furthermore, when the polymer (A) contains two or more polymers, it is preferable that Mw and Mw/Mn of each polymer satisfy the above-mentioned ranges respectively.

The content ratio of the polymer (A) is preferably 20% by mass relative to the total amount of solid components contained in the present composition (that is, the total mass of components other than the solvent (C) in the radiation-sensitive composition). % or more, more preferably 40 mass % or more, and more preferably 50 mass % or more. In addition, the content of the polymer (A) is preferably at most 99% by mass, more preferably at most 97% by mass, based on the total amount of solids contained in the present composition. By setting the content ratio of a polymer (A) into the said range, heat resistance and chemical resistance are high enough, and the hardened|cured material which shows favorable developability and transparency can be obtained.

The method for synthesizing the polymer (A) is not particularly limited. The polymer (A) can be produced, for example, by a known method such as radical polymerization in an appropriate polymerization medium in the presence of a polymerization initiator or the like using a monomer capable of introducing each of the above structural units. In the case of utilizing radical polymerization, examples of the polymerization initiator used include: 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethyl valeronitrile), 2,2'-azobis(isobutyrate) dimethyl ester and other azo compounds. It is preferable that the usage ratio of a polymerization initiator is 0.01 mass part - 30 mass parts with respect to 100 mass parts of total amounts of the monomer used for reaction. Examples of the polymerization solvent include organic solvents such as alcohols, ethers, ketones, esters, and hydrocarbons.

In the polymerization reaction, the reaction temperature is usually 30°C to 180°C. The reaction time varies depending on the types of the polymerization initiator and the monomer, or the reaction temperature, but is usually 0.5 to 10 hours. The amount of the polymerization solvent used is preferably such that the total amount of the monomers used in the reaction becomes 0.1% by mass to 60% by mass relative to the entire amount of the reaction solution. The polymer obtained by the polymerization reaction can be separated using, for example, the following known separation methods: a method of drying the precipitate obtained by injecting the reaction solution into a large amount of poor solvent under reduced pressure; using an evaporator to A method for removing the reaction solution by distillation under reduced pressure, etc.

＜Radiation sensitive acid generator (B)＞ As the radiation-sensitive acid generator (B) contained in this composition (hereinafter, also simply referred to as "acid generator (B)"), as long as it generates an acid by irradiation with radiation, the components in the composition The acid-dissociative group which it has is detached. Specifically, a compound that generates an acid in response to radiation having a wavelength of 300 nm or more (preferably 300 nm to 450 nm) can be preferably used. When using an acid generator that is not directly sensitive to radiation with a wavelength of 300 nm or more as the acid generator (B), it is possible to generate an acid by being sensitive to radiation with a wavelength of 300 nm or more by using it in combination with a sensitizer. The acid generator (B) may further generate an acid by heating. As the acid generator (B), a compound that generates an acid having an acid dissociation constant (pKa) of 4.0 or less can be preferably used. In addition, in this specification, "radiation" is a concept including a visible ray, an ultraviolet-ray, a deep ultraviolet-ray, an X-ray, and a charged particle beam.

As the acid generator (B), known compounds that generate acid in response to radiation can be used. Specific examples of the acid generator (B) include oxime sulfonate compounds, sulfonimide compounds, onium salts, halogen-containing compounds (trichloromethyl-s-triazine compounds, etc.), diazomethane Compounds, Sulfonate Compounds, Sulfonate Compounds, Carboxylate Compounds, etc.

Specific examples of these include, for example, oxime sulfonate compounds: (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (5-Octylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, (camphorsulfonyloxyimino-5H-thiophene-2 -ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile, ( 2-[2-(4-methylphenylsulfonyloxyimino)]-2,3-dihydrothiophen-3-ylidene]-2-(2-methylphenyl)acetonitrile), 2-(Octylsulfonyloxyimino)-2-(4-methoxyphenyl)acetonitrile, derivatives thereof, compounds described in International Publication No. 2016/124493, and the like. As a commercial item of an oxime sulfonate compound, Irgacure PAG121 by BASF Corporation etc. are mentioned.

Specific examples of sulfonyl imide compounds include: N-(trifluoromethylsulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, N-(4 -Methylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(4-fluorophenylsulfonyloxy) base) succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(camphorsulfonyloxy)phthalimide, N-(2 -Trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalimide, N-(trifluoromethyl Sulfonyloxy)diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, (4-methylphenylsulfonyloxy)diphenyl Maleimide, trifluoromethanesulfonic acid-18-naphthalimide, and derivatives thereof.

Examples of onium salts include diphenyliodonium salts, triphenylconium salts, percite salts, quaternary ammonium salts, benzothiazolium salts, and tetrahydrothiophenium salts. As specific examples of these, diphenyliodonium salts include, for example, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, etc.; Fluoromethanesulfonate, Triphenylpermellium camphorsulfonate, Triphenylpermedium tetrafluoroborate, Triphenylpermedium trifluoroacetate, Triphenylpermedium p-toluenesulfonate, Triphenylpermedium butyl trifluoromethanesulfonate (2,6-difluorophenyl) borate, etc.

In addition, examples of permeic salts include benzyl permeic salts, dibenzyl permeic salts, substituted benzyl permeic salts, and the like. Alkyl percited salts include, for example, alkyl permedium salts such as 4-acetyloxyphenyldimethylconium hexafluoroantimonate and 4-acetyloxyphenyldimethylconium hexafluoroarsenate; Benzyl-4-hydroxyphenylmethylpercited hexafluoroantimonate, benzyl-4-hydroxyphenylmethylpercited hexafluorophosphate and other benzyl percited salts; dibenzyl-4-hydroxyphenyl percite hexafluorophosphate and other dibenzyl percite salts; -Hydroxyphenylmethyl percite hexafluoroantimonate and other substituted benzyl percite salts and the like.

Examples of benzothiazolium salts include: 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate , 3-(p-methoxybenzyl)benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5-chlorobenzene And thiazolium hexafluoroantimonate, etc.

Examples of tetrahydrothiophenium salts include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate, 4,7-di-n-butoxynaphthyltetrahydrothiophenium -10-Camphorsulfonate, etc. In addition, as the onium salt, onium salts described in JP-A-2014-174235, JP-A-2016-87486, JP-A-2014-157252, JP-A-2015-18131, etc. Salts can also be used as acid generators (B).

In addition, as specific examples of oxime sulfonate compounds, sulfonimide compounds, onium salts, halogen-containing compounds, diazomethane compounds, sulfonate compounds, sulfonate compounds, and carboxylate compounds, Japanese Patent Laid-Open Compounds described in paragraphs 0078 to 0106 of Publication No. 2014-157252, compounds described in International Publication No. 2016/124493, and the like. As the acid generator (B), a compound known as an ionic photoacid generating type or a nonionic photoacid generating type photocationic polymerization initiator can also be used. As the acid generator (B), at least one selected from the group consisting of oxime sulfonate compounds, sulfonimide compounds, and onium salts can be preferably used from the viewpoint of radiation sensitivity.

In this composition, the content ratio of the acid generator (B) is preferably at least 0.5 parts by mass, more preferably at least 1 part by mass, and still more preferably at least 2 parts by mass, based on 100 parts by mass of the polymer (A). servings or more. In addition, the content of the acid generator (B) is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less, based on 100 parts by mass of the polymer (A). If the content ratio of the acid generator (B) is set to 0.5 parts by mass or more, the acid is sufficiently generated by irradiation with radiation, and the difference in solubility of the portion irradiated with radiation and the portion not irradiated with respect to the alkali developer can be sufficiently increased. . Thereby, good patterning can be performed. In addition, the amount of the acid involved in the reaction with the polymer (A) in the step (V) can be increased, and a lens having better heat resistance and chemical resistance can be obtained. On the other hand, if the content ratio of the acid generator (B) is set to 30 parts by mass or less, the amount of unreacted acid generator (B) in the portion irradiated with radiation can be sufficiently reduced during the developing step, and the Decrease in developability due to residual acid generator (B).

<Solvent (C)> This composition is preferably a liquid composition in which a polymer (A), an acid generator (B), and other components prepared as necessary are dissolved or dispersed in a solvent (C). The solvent (C) is preferably an organic solvent that dissolves the components formulated in the present composition and does not react with the components.

Specific examples of the solvent (C) include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol mono Methyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxymethyl propionate, 3-ethoxy ethyl propionate and other esters; ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethyl Diethylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, dimethyl glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether and other ethers; dimethyl Formamide, N,N-dimethylacetamide, N-methylpyrrolidone and other amides; Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; Benzene , toluene, xylene, ethylbenzene and other aromatic hydrocarbons. Among them, the solvent (C) preferably contains at least one selected from the group consisting of ethers and esters, more preferably selected from the group consisting of ethylene glycol alkyl ether acetate, diethylene glycol, At least one selected from the group consisting of propylene glycol monoalkyl ether and propylene glycol monoalkyl ether acetate.

＜Other ingredients＞ The present composition may further contain components other than these (hereinafter also referred to as “other components”) in addition to the above-mentioned polymer (A), acid generator (B) and solvent (C). Examples of other components include a nitrogen-containing basic compound (D), a polyfunctional reactive compound (E), a surfactant, an adhesive agent, and the like.

・Nitrogen-containing basic compound (D) The nitrogen-containing basic compound (D) (hereinafter, also simply referred to as "basic compound (D)") is formulated in the present composition as an acid diffusion control agent that reacts to the generation of acid by exposure. The diffusion length of the acid produced by agent (B) is controlled. By containing the nitrogen-containing basic compound (D) in this composition, the diffusion length of an acid can be moderately controlled, and a pattern shape can be made favorable.

As the nitrogen-containing basic compound (D), for example, arbitrarily selected from compounds used as acid diffusion control agents in chemically amplified resists can be used. Specifically, examples of the nitrogen-containing basic compound (D) include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, carboxylic acid quaternary ammonium salts, and the like. Specific examples of the nitrogen-containing basic compound (D) include compounds described in paragraphs 0128 to 0147 of JP-A-2011-232632 , and the like. As the nitrogen-containing basic compound (D), at least one selected from the group consisting of aromatic amines and heterocyclic amines can be preferably used.

Examples of aromatic amines and heterocyclic amines include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N,N-dimethylaniline, 2-methylaniline, 3 -Methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline , 2,6-dinitroaniline, 3,5-dinitroaniline, N,N-dimethyltoluidine and other aniline derivatives; imidazole, 4-methylimidazole, 4-methyl-2-phenyl Imidazole, benzimidazole, 2-phenylbenzimidazole, triphenylimidazole, N-tert-butoxycarbonyl-2-phenylbenzimidazole and other imidazole derivatives; pyrrole, 2H-pyrrole, 1-methyl Pyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, N-methylpyrrole and other pyrrole derivatives; pyridine, picoline, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl)pyridine, lutidine, collidine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 3-methyl-4-phenylpyridine , 4-tertiary butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinylpyridine , 1-methyl-4-phenylpyridine, 2-(1-ethylpropyl)pyridine, aminopyridine, dimethylaminopyridine, nicotine and other pyridine derivatives; N-acetylmorpholine, etc. Morpholine derivatives; other compounds described in JP-A-2011-232632.

In the case where the present composition contains a nitrogen-containing basic compound (D), from the viewpoint of sufficiently improving the pattern-forming ability of the present composition by formulating the nitrogen-containing basic compound (D), relative to the polymer (A ) 100 parts by mass, the content of the nitrogen-containing basic compound (D) is preferably at least 0.005 parts by mass, more preferably at least 0.01 parts by mass. In addition, the content of the nitrogen-containing basic compound (D) is preferably at most 10 parts by mass, more preferably at most 5 parts by mass, based on 100 parts by mass of the polymer (A).

・Polyfunctional reactive compound (E) The polyfunctional reactive compound (E) (hereinafter, also referred to as "reactive compound (E)") has two or more functional groups capable of reacting with the polymer (A) by stimulation (preferably heat). compound. By further including the reactive compound (E) in the present composition, the fluid margin can be further increased, and the chemical resistance of the obtained cured product can be further improved. In addition, the reactive compound (E) is a different component from the polymer (A).

It is preferable that the functional group which a reactive compound (E) has is a group which reacts with the functional group which a polymer (A) has by applying heat, and forms a crosslinked structure. Examples of the functional group included in the reactive compound (E) include: oxirane group, oxetanyl group, (meth)acryl group, formyl group, acetyl group, vinyl group, isopropene group A group, an alkoxymethyl group, a methylol group, etc. can be suitably selected according to the functional group which a polymer (A) has. As the reactive compound (E), among them, polyfunctional oxirane compounds, polyfunctional At least one of the group consisting of oxetane compounds, polyfunctional melamine compounds and polyfunctional alkoxymethyl compounds.

Specific examples of the reactive compound (E) include, for example, polyfunctional oxirane compounds: bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A Polyglycidyl ethers of bisphenols such as diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol Alcohol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and other polyol polyglycidyl ethers; Aliphatic polyglycidyl ethers of polyether polyols obtained by adding one or more than two alkylene oxides to aliphatic polyols such as ethylene glycol, propylene glycol, and glycerin; 3,4-epoxycyclohexyl Methyl(3,4-epoxy)cyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m - Compounds having two or more 3,4-epoxycyclohexyl groups in the molecule, such as dioxane; phenol novolac epoxy resins such as bisphenol A novolac epoxy resins; cresol novolac epoxy resins ; Polyphenol epoxy resin; Cyclic aliphatic epoxy resin; Diglycidyl esters of aliphatic long-chain dibasic acids; Glycidyl esters of higher fatty acids; Epoxidized soybean oil, epoxidized linseed oil, etc.

Examples of polyfunctional oxetane compounds include: 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,4-bis[(3-ethyl-3- Oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl -3-oxetanylmethoxy)methyl]propane, bis[1-ethyl(3-oxetanyl)]methyl ether, bis(3-ethyl-3-oxetanylmethyl)ether , Ethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, triethylene glycol bis (3-ethyl-3-oxetanyl methyl) ether, tetraethylene glycol bis (3- Ethyl-3-oxetanylmethyl)ether, 1,3-bis(3-ethyl-3-oxetanylmethoxy)propane, 1,4-bis(3-ethyl-3-oxa Cyclobutylmethoxy)butane, 1,4-bis(3-ethyl-3-oxetanylmethoxymethyl)benzene, 1,3-bis(3-ethyl-3-oxetanylmethoxy 1,2-bis(3-ethyl-3-oxetanylmethoxymethyl)benzene, 4,4'-bis[(3-ethyl-3-oxetanyl) )methoxymethyl]biphenyl, 2,2'-bis(3-ethyl-3-oxetanylmethoxymethyl)biphenyl, 1,6-bis((3-methyloxetane Butane-3-yl)methoxy)hexane, 1,6-bis((3-ethyloxetan-3-yl)methoxy)hexane, 3-ethyl-3{[ (3-ethyloxetan-3-yl)methoxy]methyl}oxetane and the like.

Examples of polyfunctional melamine compounds include hexamethoxymethylmelamine (2,4,6-tris[bis(methoxymethyl)amino]-1,3,5-triazine), hexaethoxy Methylmelamine, hexapropoxymethylmelamine, hexabutoxymethylmelamine, hexapentyloxymethylmelamine, etc.

As a polyfunctional alkoxymethyl compound, the reaction product of a polyhydric phenol compound and formaldehyde is mentioned. Specific examples of polyfunctional phenolic compounds include: 4-(1-{4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl}-1-methylethyl)phenol, 1 , 1,1-tris(4-hydroxyphenyl)ethane, 4,4'-dihydroxybiphenyl, etc. In addition, examples of commercially available polyfunctional alkoxymethyl compounds include: HMOM-TPHAP (manufactured by Honshu Chemical Co., Ltd.), Nikalac (Nikalac) Mw-100LM, Nikalac (Nikalac) Mx-750LM, Nikalac Nikalac Mx-270, Nikalac Mx-280 (manufactured by Sanwa Chemical Co., Ltd. above), etc.

When blending the reactive compound (E) in this composition, from the viewpoint of securing a large fluidity margin, the reactive compound is The content of (E) is preferably at least 0.05 parts by mass, more preferably at least 0.1 parts by mass. In addition, from the viewpoint of suppressing the decrease in sensitivity, or from the viewpoint of sufficiently generating acid in the exposed portion by radiation irradiation in step (II) to obtain a microlens with a good pattern shape, compared to the The total amount of the polymers (A) is 100 parts by mass, and the content of the reactive compound (E) is preferably at most 5 parts by mass, more preferably at most 4 parts by mass, still more preferably at most 2 parts by mass.

·Surfactant Surfactants can be used to improve the coatability of the composition (wet spread or reduce uneven coating). As a surfactant, a fluorine-type surfactant, a silicone-type surfactant, and a nonionic surfactant are mentioned, for example.

As specific examples of surfactants, fluorine-based surfactants can include surfactants with the following trade names: Megafac F-171, Megafac F-172, Megafac F-173, Megafac F-251, Megafac F-430, F-554, F-563 (manufactured by DIC); Fluorad FC430, Fluorad FC431 (Manufactured by Sumitomo 3M); Asahi Guard AG710, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon ( Surflon) SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106, Surflon S-611 (AGC Qingmei Chemical ( AGC Seimi Chemical Co.); Polyflow No.75, Polyflow No.95 (Kyoeisha Chemical Co.); FTX-218 (Neos Co., Ltd. ); Ai Futuo (Eftop) EF301, Ai Futuo (Eftop) EF303, Ai Futuo (Eftop) EF352 (manufactured by Shin Akita Chemical Co., Ltd.), etc.

Examples of silicone-based surfactants include the following trade names: SH200-100cs, SH-28PA, SH-30PA, SH-89PA, SH-190, SH-8400, FLUID, SH-193, SZ-6032, SF-8428, DC-57, DC-190, Painted (PAINTAD) 19, FZ-2101, FZ-77, FZ-2118, L-7001, L-7002 (East Toray Dow Corning Silicone (manufactured by Toray Dow Corning Silicone); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-300, BYK-306, BYK -310, BYK-330, BYK-335, BYK-341, BYK-344, BYK-370, BYK-340 , BYK-345 (manufactured by BYK-Chemie Japan), etc.

Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonyl ether, and polyoxyethylene n-octyl phenyl ether. Phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, etc.

When blending a surfactant in this composition, the content ratio of the surfactant is preferably 0.01 to 1.5 parts by mass with respect to 100 parts by mass of the total amount of polymers (A) contained in this composition. , more preferably 0.02 to 1.2 parts by mass, more preferably 0.05 to 1.0 parts by mass.

· Adhesives Adhesive additives are components that improve the adhesion between the cured product formed using this composition and the base material. As an adhesive auxiliary agent, a functional silane coupling agent having a reactive functional group can be preferably used. As a reactive functional group which a functional silane coupling agent has, a carboxyl group, a (meth)acryl group, an epoxy group, a vinyl group, an isocyanate group etc. are mentioned.

Specific examples of functional silane coupling agents include, for example, trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2 -(3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxy silane, vinyltriacetoxysilane, vinyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, etc.

When the present composition contains an adhesive auxiliary agent, the content ratio of the adhesive auxiliary agent is preferably 0.01 mass parts or more and 4 mass parts or less with respect to 100 mass parts of the polymer (A) contained in the present composition. Preferably, it is 0.1 mass part or more and 2 mass parts or less.

·About epoxy group-containing compounds This composition preferably does not contain a compound having an oxirane group or an oxetanyl group (hereinafter, also referred to as an "epoxy group-containing compound") as another component, or when containing an epoxy group-containing compound The content of the epoxy group-containing compound is relatively small. Thereby, acid can be sufficiently generated in the exposed portion by irradiation of radiation in step (II), and a cured product having a good pattern shape can be obtained by developing, exposing, and heating treatments performed later.

The epoxy group-containing compound includes monofunctional compounds and polyfunctional compounds. As an example of a monofunctional compound, the compound which has an epoxy group among the compounds illustrated as an adhesive auxiliary agent is mentioned. Moreover, as an example of a polyfunctional compound, the compound illustrated as a polyfunctional oxirane compound and a polyfunctional oxetane compound in description of a polyfunctional reactive compound (E) is mentioned.

The content of the epoxy group-containing compound in the composition is preferably at least 0% by mass and at most 5% by mass, more preferably at least 0% by mass, based on the total amount of the polymer (A) contained in the composition. And 4 mass % or less, More preferably, it is 0 mass % or more and 2 mass % or less, More preferably, it is 0 mass % or more and 1 mass % or less. If the content of the epoxy group-containing compound is within the above-mentioned range, acid can be sufficiently generated in the exposed portion by the radiation irradiation in step (II), and a microlens having a favorable pattern shape can be formed.

Examples of other components other than the above include antioxidants, sensitizers, photodegradable bases, softeners, plasticizers, reaction initiators (photoradical polymerization initiators, etc.), polymerization inhibitors , chain transfer agent, etc. The compounding ratio of these components can be suitably selected according to each component in the range which does not impair the effect of this indication.

This composition can be obtained by mixing a polymer (A), an acid generator (B), a solvent (C), and other optional components in a predetermined ratio. The composition obtained by mixing the components can be filtered, for example, with a filter having a pore size of 0.5 μm or less.

The solid content concentration of this composition (that is, the ratio of the total mass of the components other than the solvent (C) in the radiation-sensitive composition to the total mass of the radiation-sensitive composition) may take viscosity or volatility into consideration. etc. are suitably selected, and it is preferable that it is the range of 1 mass % - 60 mass %. When the solid content concentration is 1% by mass or more, the film thickness of the coating film can be sufficiently secured when the present composition is applied on the substrate, which is preferable. In addition, if the solid content concentration is 60% by mass or less, the film thickness of the coating film will not become too large, and the viscosity of the present composition can be moderately increased to ensure good applicability. good. The solid content concentration in this composition is more preferably 2 mass % - 50 mass %, More preferably, it is 5 mass % - 40 mass %.

[manufacturing method of lens] By using the radiation-sensitive composition prepared as described above and applying the thermal flow method, microlenses can be produced. This composition is particularly suitable as a positive pattern forming material for forming a microlens by forming a pattern using an alkali developing solution. Hereinafter, each step (step (I) to step (V)) included in the manufacturing method of the microlens of the present disclosure will be described.

<Step (I): Coating step> Step (I) is a step of forming a coating film on the substrate by applying the present composition on the substrate. Examples of the base material include glass substrates, silicon wafers, plastic substrates, and substrates on which colored resists, overcoats, antireflection films, and various metal thin films are formed. Examples of plastic substrates include polyethylene terephthalate (polyethylene terephthalate, PET), polybutylene terephthalate (polybutylene terephthalate, PBT), polyether foil, polycarbonate, polyimide and other plastic resin substrates. Various elements (for example, light-receiving elements such as photodiodes and light-emitting elements such as organic light-emitting diodes) may be provided in advance on these substrates.

As the coating method of this composition, suitable methods, such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, and an inkjet method, can be employ|adopted, for example. As a coating method, among these, a spin coating method, a bar coating method, or a slit die coating method is preferable.

After the composition is applied on the substrate, the composition may be preheated (prebaked) for the purpose of preventing dripping or the like. The prebaking conditions also vary depending on the type of each component, the usage ratio, and the like, but can be set, for example, at 60° C. to 130° C. for about 30 seconds to 10 minutes. The film thickness of the formed coating film is preferably from 0.1 μm to 8 μm, more preferably from 0.2 μm to 5 μm, and still more preferably from 0.4 μm to 3 μm, as a value after prebaking.

<Step (II): First Exposure Step> Step (II) is a step of generating acid in the exposed portion by irradiating a part of the coating film formed in step (I) with radiation. In the step (II), radiation irradiation to the coating film is carried out through a mask having a pattern (for example, a dot pattern) for obtaining microlenses having a desired shape. The mask can also be a multi-grayscale mask such as a halftone mask or a gray tone mask.

As radiation irradiated to a coating film, an ultraviolet-ray, an extreme ultraviolet-ray, X-ray, a charged particle beam, etc. are mentioned, for example. Examples of ultraviolet rays include g-rays (wavelength: 436 nm), i-rays (wavelength: 365 nm), KrF excimer laser light (wavelength: 248 nm), and the like. Examples of X-rays include synchrotron radiation and the like. As the charged particle beam, an electron beam and the like are exemplified. Among these, the radiation irradiated to the coating film is preferably ultraviolet rays, more preferably ultraviolet rays having a wavelength of 200 nm or more and 380 nm or less. Examples of the light source used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, and excimer lasers. The amount of radiation exposure is preferably 1,000 J/m ² to 20,000 J/m ² .

Furthermore, in the production method of the present disclosure, post-exposure baking may also be performed for the purpose of promoting the deprotection of the acid-dissociative group possessed by the polymer (A) after the exposure in the step (II). (PEB). The temperature of PEB is, for example, 60°C to 130°C, preferably 70°C to 120°C.

<Step (III): Developing step> Step (III) is a step of forming a pattern on the substrate by developing the coating film irradiated with radiation in step (II). By this development process, the exposed part in the coating film formed on a base material can be removed, and the pattern containing an unexposed part can be formed on a base material.

Examples of developers include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine , triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazepine Aqueous solutions of bases (basic compounds) such as heterobicyclo[5.4.0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonane, etc. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant, or a small amount of various organic solvents capable of dissolving the composition to an aqueous alkali solution can also be used as a developer.

As an image development method, suitable methods, such as the flooding method, the dipping method, the shaking dipping method, and the shower method, can be employ|adopted, for example. The developing time can be appropriately adjusted according to the composition of this composition, and can be set to, for example, 30 seconds to 120 seconds.

<Step (IV): Second exposure step> Step (IV) is a step of further irradiating at least a part of the developed coating film with radiation. It is preferred to irradiate the entire surface of the developed coating film (that is, the unexposed portion in the step (II)) with the radiation in the step (IV) (hereinafter also referred to as “post-exposure”). Since the acid generator (B) remains in the pattern, it is considered that the acid can function as a cross-linking catalyst by generating an acid in the pattern by post-exposure and heating in the next step (V). crosslinking reaction. Regarding the type of radiation and exposure conditions in the post-exposure, the same conditions as in step (II) can be employed. In addition, conditions, such as the wavelength, irradiation amount, and light source of the irradiation light at the time of post-exposure, may be the same as that of step (II), and may be different.

<Step (V): Heating step> Step (V) is a step of heating the post-exposed pattern. By the heat treatment in the step (V), the present composition is hardened while flowing heat to the pattern obtained in the steps (I) to (IV) (for example, a pattern with a substantially rectangular cross-section). Thereby, a microlens array in which hemispherical minute cured products are regularly arranged on a substrate can be obtained. The heat treatment can be performed, for example, using a heating device such as an oven or a hot plate.

The heating temperature in step (V) is preferably at least 80°C, more preferably at least 100°C, and still more preferably at least 120°C, from the viewpoint of obtaining microlenses with high heat resistance and chemical resistance and good shape. , and more preferably at least 140°C. In addition, the heating temperature in step (V) is preferably not higher than 240°C, more preferably not higher than 220°C, and still more preferably not higher than 200°C. The heating time can be appropriately set according to the type of heating device and the like. For example, in the case of heating with a hot plate, the heating time is, for example, 5 minutes to 30 minutes. Moreover, when heating with an oven, heating time is 10 minutes - 90 minutes, for example. In step (V), a step bake method in which heat treatment is performed multiple times may also be used.

The microlenses thus obtained have good lens shape. The diameter of the microlens is, for example, not less than 1 μm and not more than 100 μm. In addition, the microlenses obtained from this composition are excellent in chemical resistance and have high transparency. Therefore, the microlens of the present disclosure can be suitably used as a microlens for solid-state imaging elements included in imaging devices such as cameras, or various display elements such as organic EL elements or liquid crystal display elements included in various display devices.

According to the present disclosure described above, the following means can be provided.

[Means 1] A radiation-sensitive composition for lens production, comprising a polymer (A), a radiation-sensitive acid generator (B), and a solvent (C), the polymers (A) being in the same molecule or different The molecule contains a structural unit (a1) and a structural unit (a2), the structural unit (a1) has a hydroxyl group bonded to an aromatic ring, and the structural unit (a2) is detached from an acid dissociative group by the action of an acid, resulting in a carboxyl group. [Means 2] The radiation-sensitive composition for lens production according to [Means 1], wherein the structural unit (a1) is equal to the structural unit of all structural units constituting the polymer (A). The total content of (a2) is 50 mol% or more. [Means 3] The radiation-sensitive composition for lens production according to [Means 1] or [Means 2], wherein the structural unit (a1) is derived from the group represented by the formula (a1-1) A structural unit of at least one of the group consisting of compounds represented by the formula (a1-2). [Means 4] The radiation-sensitive composition for lens production according to any one of [Means 1] to [Means 3], wherein the structural unit (a2) is derived from the formula (a2- 1) A structural unit of at least one of the group consisting of the compound represented by the formula (a2-2) and the compound represented by the formula (a2-2). [Means 5] The radiation-sensitive composition for lens production according to any one of [Means 1] to [Means 4], wherein the polymerization The content rate of the structural unit (a3) which has an oxirane group or an oxetanyl group in a substance (A) is 0 mol% or more and 15 mol% or less. [Means 6] The radiation-sensitive composition for lens production according to any one of [Means 1] to [Means 5], further comprising a nitrogen-containing basic compound (D). [Means 7] The radiation-sensitive composition for lens production according to any one of [Means 1] to [Means 6], which is 5 parts by mass relative to 100 parts by mass of the total amount of the polymer (A) The polyfunctional reactive compound (except the polymer (A) mentioned above) is contained in the proportion of less than one part. [Means 8] The radiation-sensitive composition for lens production according to [Means 7], wherein the polyfunctional reactive compound is selected from polyfunctional oxirane compounds, polyfunctional oxetane compounds, At least one of the group consisting of multifunctional melamine compounds and multifunctional alkoxymethyl compounds. [Means 9] A method for manufacturing a lens, comprising: coating a substrate with the radiation-sensitive composition for lens manufacture described in any one of [Means 1] to [Means 8] to form a coating film; A step of irradiating a part of the coating film with radiation to generate acid in the exposed portion; a step of developing the coating film irradiated with radiation to form a pattern on the substrate; irradiating the pattern with radiation steps; and a step of heating the pattern after irradiating the pattern with radiation, thereby forming a lens on the base material. [Means 10] A lens formed using the radiation-sensitive composition for lens production according to any one of [Means 1] to [Means 8]. [Means 11] An imaging device including the lens described in [Means 10]. [Means 12] An imaging device including the imaging element described in [Means 11]. [Means 13] A display element including the lens as described in [Means 10]. [Means 14] A display device including the display element as described in [Means 13]. [Example]

Hereinafter, the present disclosure will be specifically described with examples, but the present disclosure is not limited to these examples. In addition, "part" and "%" in an Example and a comparative example are a mass standard unless otherwise indicated.

In this example, the weight average molecular weight (Mw) of a polymer was measured by the following method. Determination method: gel permeation chromatography (GPC) method ・Device: Showa Denko GPC-101 GPC column: combine GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 of Shimadzu GLC ·Mobile phase: tetrahydrofuran ·Column temperature: 40℃ ·Flow rate: 1.0 mL/min ・Sample concentration: 1.0% by mass ・Sample injection volume: 100 μL Detector: differential refractometer ·Standard material: monodisperse polystyrene

＜Preparation of radiation-sensitive resin composition＞ The polymer (A), acid generator (B), solvent (C), basic compound (D) and reactive compound (E) used to prepare each radiation-sensitive resin composition are shown below.

"Polymer (A)" (A-1): Resin represented by the following formula (A-1) (weight average molecular weight: 10,000, x=55, y=45) [Chemical 9]

(A-2): Resin represented by the following formula (A-2) (weight average molecular weight 12000, x=45, y=10, z=45) [Chem. 10]

(A-3): Resin represented by the following formula (A-3) (weight average molecular weight: 10,000, x=70, y=30) [Chem. 11]

(A-4): Resin represented by the following formula (A-4) (weight average molecular weight 8000, w=30, x=30, y=10, z=30) [Chem. 12]

(A-5): Resin represented by the following formula (A-5) (weight average molecular weight: 10,000, x=55, y=45) [Chem. 13]

In addition, in the above-mentioned formulas representing (A-1) to (A-5), the subscripts (w, x, y, and z) attached to each structural unit are relative to each structural unit constituting each resin. Ratio of total structural units (mole %).

《Acid Generator (B)》 (B-1): "SP-606" manufactured by ADEKA (B-2): Triphenylcaldium trifluoromethanesulfonate

"Solvent (C)" (C-1): Propylene glycol monomethyl ether acetate (C-2): Propylene glycol monomethyl ether (C-3): Methyl 3-methoxypropionate

"Basic Compounds (D)" (D-1): N-tert-butoxycarbonyl-2-phenylbenzimidazole (D-2): N-Acetylmorpholine

《Reactive compound (E)》 (E-1): 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl (E-2): Reaction product of 4-(1-{4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl}-1-methylethyl)phenol and formaldehyde

[Example 1] A polymer solution containing 100 parts by mass (solid content) of (A-1) as the polymer (A), 4 parts by mass of (B-1) as the acid generator (B), and a basic compound (D) (D-1) 0.8 parts by mass, adhesive agent (3-glycidoxypropyltrimethoxysilane) 0.5 parts by mass, and surfactant ("FTX-218" manufactured by Neos Corporation) ) in 0.2 parts by mass, and further adding (C-1) as a solvent (C) so that the solid content concentration becomes 12 mass %, and then stirring and dissolving. Next, the mixture was filtered through a membrane filter with a pore size of 0.2 μm, thereby preparing the radiation-sensitive resin composition of Example 1.

[Example 2 to Example 8 and Comparative Example 1 to Comparative Example 2] Except for the types and compounding amounts (parts by mass) of the polymer (A), acid generator (B), solvent (C), basic compound (D) and reactive compound (E) as shown in Table 1 , Each radiation-sensitive resin composition of Examples 2 to 8, Comparative Example 1, and Comparative Example 2 was prepared in the same manner as in Example 1. In addition, in Table 1, the compounding quantity of a polymer (A) is 100 mass parts. The numerical values of acid generator (B), basic compound (D) and reactive compound (E) represent the compounding of each compound used in the preparation of each radiation-sensitive resin composition with respect to 100 parts by mass of polymer (A) Ratio (parts by mass). The numerical value of the solvent (C) represents the ratio (mass %) of each compound used in the preparation of each radiation-sensitive resin composition to the total amount of the solvent.

[Table 1] Polymer (A) Acid generator (B) Basic compound (D) Reactive compound (E) solvent (C) B-1 B-2 D-1 D-2 E-1 E-2 C-1 C-2 C-3 Example 1 A-1 4 0.8 100 Example 2 A-1 4 0.8 60 40 Example 3 A-1 4 0.6 3 60 40 Example 4 A-2 4 0.6 100 Example 5 A-2 8 0.6 2 100 Example 6 A-3 4 0.8 60 40 Example 7 A-3 4 0.6 3 60 40 Example 8 A-4 6 0.6 60 40 Comparative example 1 A-5 4 0.8 100 Comparative example 2 A-5 4 0.8 6 100

＜Evaluation＞ Using each radiation sensitive resin composition, it evaluated according to the following evaluation method. The evaluation results are shown in Table 2.

[Sensitivity] Each radiation-sensitive resin composition of Examples 1 to 8, Comparative Example 1, and Comparative Example 2 was coated on a silicon substrate on which an antireflection film was formed using a Clean Track. Then, prebaking was performed at 90° C. for 90 seconds to form a coating film with a film thickness of 0.6 μm. Next, using the "NSR2205EX12B" reduction projection exposure machine (numerical aperture (NA) = 0.55, λ = 248 nm) manufactured by Nikon Corporation, the exposure time was changed and the interval was 0.2 μm space and 0.9 μm point The patterned mask exposes the coating film. After exposure, the substrate was subjected to PEB treatment at 90° C. for 90 seconds using a hot plate, and then developed at 25° C. for 1 minute by a flooding method using a tetramethylammonium hydroxide aqueous solution (developing solution). After the development process, the coating film is rinsed with water and dried to form a pattern on the wafer. In this exposure and development process, the minimum exposure dose required to form 0.2 μm spaces and 0.9 μm dots is taken as the sensitivity (mJ/cm ² ). Under the above conditions, those whose sensitivity is less than 100 mJ/cm ² are marked as "◎", those with a sensitivity of more than 100 mJ/cm ² and less than 130 mJ/cm ² are marked "○", and those with a sensitivity of 130 mJ/cm 2 Those with cm ² or more were marked as "×".

[Fluidity] For Examples 1 to 8, Comparative Example 1, and Comparative Example 2, the "PLA-501F" exposure machine (ultra-high pressure mercury lamp) manufactured by Canon was used to evaluate the sensitivity. The 0.2 μm space and 0.9 μm dot pattern were further exposed to make the cumulative irradiation dose 500 mJ/cm ² . Next, post-baking was performed at each temperature of 130° C. to 220° C. for 300 seconds using a hot plate, and the cross section of the resist pattern was observed with a scanning electron microscope (SEM). The minimum temperature T1 at which an appropriate microlens pattern is formed without contacting the bottom edge portions of adjacent microlens patterns by the post-baking process, and the bottom of adjacent microlens patterns are obtained. The minimum temperature T2 when the edge parts are in contact. The temperature difference (T2-T1) between the lowest temperature T1 and the lowest temperature T2 was used as the flow margin, and the following criteria were used for evaluation. Under these conditions, a flow margin of 10°C or higher was rated as "⊚", a flow margin of less than 10°C and 5°C or higher was rated as "◯", and a flow margin of less than 5°C was rated as "×".

[Chemical Resistance] After coating the radiation-sensitive resin compositions of Examples 1 to 8, Comparative Example 1, and Comparative Example 2 on a silicon substrate using a spinner, the coating was carried out on a hot plate at 90°C. Pre-bake for 90 seconds to form a coating film with a film thickness of 0.6 μm. The obtained coating film was irradiated with ultraviolet rays by a mercury lamp so that the cumulative irradiation dose became 500 mJ/cm ² . Next, the silicon substrate on which the coating film was formed was post-baked at 180° C. for 300 seconds using a hot plate to obtain a cured film. The film thickness (H1 [μm]) of the obtained cured film was measured. Next, the silicon substrate on which this cured film was formed was immersed in acetone for 5 minutes. The film thickness (H2 [μm]) of the cured film after immersion in acetone was measured, and the film thickness change rate was calculated from the following formula, which was used as an index of chemical resistance. Film thickness change rate={(H2-H1)/H1}×100 (%) When the absolute value of the film thickness change rate obtained by the above formula is less than 5.0%, it is judged as "○". When the absolute value of the film thickness change rate was 5.0% or more, it was judged as "x".

[transparency] Except having used a glass substrate, the cured film was produced by the same method as evaluation of chemical resistance. The transmittance of the obtained cured film was measured using the ultraviolet-visible spectrophotometer ("V-630" by JASCO Corporation). At this time, the case where the transmittance of light with a wavelength of 400 nm is 97% or more is judged as "⊚", and the case where the transmittance is 95% or more and less than 97% is judged as "◯". The case of less than 95% was judged as "×".

[Table 2] Sensitivity fluidity Chemical Resistance transparency Example 1 ◎ ○ ○ ◎ Example 2 ◎ ○ ○ ◎ Example 3 ○ ◎ ○ ◎ Example 4 ◎ ○ ○ ◎ Example 5 ○ ◎ ○ ○ Example 6 ◎ ○ ○ ◎ Example 7 ○ ◎ ○ ◎ Example 8 ○ ◎ ○ ○ Comparative example 1 ○ x x ○ Comparative example 2 x ○ ○ ○

As shown in Table 2, the radiation-sensitive resin compositions of Examples 1 to 8 exhibit good radiation sensitivity, and also have good fluidity, chemical resistance, and transparency. On the other hand, in the radiation-sensitive comparative example 1 having the same composition as that of Example 1 except that the polymer (A-5) having a protected hydroxyl group was used instead of the polymer (A-1) having a protected carboxyl group, Among the permanent resin compositions, the fluidity and chemical resistance were evaluated as "×". In addition, Comparative Example 2 in which 6 parts by mass of (E-1) as a reactive compound (E) was blended with respect to 100 parts by mass of polymer (A-5) in the radiation-sensitive resin composition of Comparative Example 1 In the radiation-sensitive resin composition, the fluidity and chemical resistance were improved, but the radiation sensitivity was evaluated as "×".

From the above results, it is clear that the radiation-sensitive composition containing the polymer (A) including the structural unit (a1) and the structural unit (a2) can exhibit high radiation sensitivity in a balanced manner and secure a large Various characteristics required for a radiation-sensitive composition for microlens production, such as sufficient flow, good chemical resistance and transparency of the obtained cured product.

none

Claims (21)

A method of manufacturing a lens, comprising: A step of coating a radiation-sensitive composition on a substrate to form a coating film; a step of irradiating a part of the coating film with radiation, thereby generating an acid in the exposed portion; A step of developing the coating film irradiated with radiation to form a pattern on the substrate; a step of irradiating the pattern; and a step of forming lenses on the substrate by heating the pattern after irradiating the pattern with radiation, The radiation-sensitive composition contains a polymer (A), a radiation-sensitive acid generator (B), and a solvent (C), The polymer (A) contains a structural unit (a1) and a structural unit (a2) in the same molecule or in different molecules, the structural unit (a1) has a hydroxyl group bonded to an aromatic ring, and the structural unit (a2 ) is detached from the acid dissociative group by the action of an acid, thereby generating a carboxyl group. The method for producing a lens according to claim 1, wherein the total content ratio of the structural unit (a1) to the structural unit (a2) is 50 relative to all structural units constituting the polymer (A). More than mole%. The method for producing a lens according to claim 1 or claim 2, wherein the structural unit (a1) is derived from a compound represented by the following formula (a1-1) and the following formula (a1-2 ) is a structural unit of at least one of the group of compounds represented by , (In formula (a1-1), R ¹ is a hydrogen atom, a halogen atom, an alkyl group with 1 to 4 carbons, or a fluorinated alkyl group with 1 to 4 carbons; R ² is a single bond, * ¹ -C(= O)-O- or * ¹ -C(=O)-NH-; "* ¹ "represents a bond to the carbon atom to which R ¹ is bonded; R ³ is a halogen atom, an alkane with 1 to 4 carbons group, an alkoxy group with 1 to 4 carbons or a fluorinated alkyl group with 1 to 4 carbons; m1 is an integer of 0 to 4; m2 is 1 or 2; among them, m1+m2≦5; m1 is 2 or more In the case of , multiple R ³ are the same or different; In formula (a1-2), R ⁴ is a halogen atom, an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, or an alkoxy group with 1 to 4 carbons fluorinated alkyl; n1 is an integer of 0 to 4; n2 is 1 or 2; wherein, n1+n2≦5; when n1 is 2 or more, multiple R ⁴ are the same or different). The method for producing a lens according to claim 1 or claim 2, wherein the structural unit (a2) is derived from a compound represented by the following formula (a2-1) and the following formula (a2-2 ) is a structural unit of at least one of the group of compounds represented by , (In formula (a2-1), R ⁵ is a hydrogen atom, a halogen atom, an alkyl group with 1 to 4 carbons, or a fluorinated alkyl group with 1 to 4 carbons; R ⁶ is a single bond, substituted or unsubstituted phenylene group, or * ² -C(=O)-OR ¹⁵ -; "* ² "represents the bonding bond with the carbon atom to which R ⁵ is bonded; R ¹⁵ is a substituted or unsubstituted divalent Hydrocarbon group; R ⁷ is a monovalent aliphatic hydrocarbon group; R ⁸ and R ⁹ are each independently a monovalent aliphatic hydrocarbon group, or it means that R ⁸ and R ⁹ are combined with each other and form together with the carbon atom to which R ⁸ and R ⁹ are bonded alicyclic structure; in formula (a2-2), R ¹⁰ is a hydrogen atom, a halogen atom, an alkyl group with 1 to 4 carbons, or a fluorinated alkyl group with 1 to 4 carbons; R ¹¹ is a single bond, Substituted or unsubstituted phenylene, or * ³ -C(=O)-OR ¹⁶ -; "* ³ "represents the bond to the carbon atom to which R ¹⁰ is bonded; R ¹⁶ is substituted or unsubstituted A substituted divalent hydrocarbon group; R ¹² is a hydrogen atom or a monovalent aliphatic hydrocarbon group; Regarding R ¹³ and R ¹⁴ , R ¹³ is a monovalent aliphatic hydrocarbon group, and R ¹⁴ is a monovalent aliphatic hydrocarbon group, an aralkyl group or a substituted Aralkyl, or R ¹³ and R ¹⁴ represent a cyclic ether structure in which R ¹³ and R ¹⁴ are combined with each other and the carbon atom to which R ¹³ is bonded and the oxygen atom to which R ¹⁴ is bonded). The method for producing a lens according to claim 1 or claim 2, wherein, relative to all structural units constituting the polymer (A), the polymer (A) has an oxirane group or an oxygen The content rate of the structural unit (a3) of a heterocyclobutyl group is 0 mol% or more and 15 mol% or less. The method for manufacturing a lens according to Claim 1 or Claim 2, wherein the radiation-sensitive composition further contains a nitrogen-containing basic compound (D). The method for producing a lens according to claim 1 or claim 2, wherein the radiation-sensitive composition is contained in a ratio of 5 parts by mass or less with respect to 100 parts by mass of the total amount of the polymer (A). A polyfunctional reactive compound (E) (wherein the polymer (A) is excluded). The method for manufacturing a lens according to claim 7, wherein the polyfunctional reactive compound (E) is selected from polyfunctional oxirane compounds, polyfunctional oxetane compounds, polyfunctional melamine compounds, and polyfunctional At least one of the group consisting of functional alkoxymethyl compounds. A radiation-sensitive composition for lens manufacture, comprising: a polymer (A); Radiation-sensitive acid generators (B); and solvent (C), The polymer (A) contains a structural unit (a1) and a structural unit (a2) in the same molecule or in different molecules, the structural unit (a1) has a hydroxyl group bonded to an aromatic ring, and the structural unit (a2 ) The acid dissociative group is detached by the action of acid, thereby generating a carboxyl group. The radiation-sensitive composition for lens production according to Claim 9, wherein the total of the structural unit (a1) and the structural unit (a2) relative to all structural units constituting the polymer (A) is The content is more than 50 mol%. The radiation-sensitive composition for lens production according to claim 9, wherein the structural unit (a1) is derived from a compound represented by the following formula (a1-1) and the following formula (a1-2 ) is a structural unit of at least one of the group of compounds represented by , (In formula (a1-1), R ¹ is a hydrogen atom, a halogen atom, an alkyl group with 1 to 4 carbons, or a fluorinated alkyl group with 1 to 4 carbons; R ² is a single bond, * ¹ -C(= O)-O- or * ¹ -C(=O)-NH-; "* ¹ "represents a bond to the carbon atom to which R ¹ is bonded; R ³ is a halogen atom, an alkane with 1 to 4 carbons group, an alkoxy group with 1 to 4 carbons or a fluorinated alkyl group with 1 to 4 carbons; m1 is an integer of 0 to 4; m2 is 1 or 2; among them, m1+m2≦5; m1 is 2 or more In the case of , multiple R ³ are the same or different; In formula (a1-2), R ⁴ is a halogen atom, an alkyl group with 1 to 4 carbons, an alkoxy group with 1 to 4 carbons, or an alkoxy group with 1 to 4 carbons fluorinated alkyl; n1 is an integer of 0 to 4; n2 is 1 or 2; wherein, n1+n2≦5; when n1 is 2 or more, multiple R ⁴ are the same or different). The radiation-sensitive composition for lens production according to Claim 9, wherein the structural unit (a2) is derived from a compound represented by the following formula (a2-1) and the following formula (a2-2 ) is a structural unit of at least one of the group of compounds represented by , (In formula (a2-1), R ⁵ is a hydrogen atom, a halogen atom, an alkyl group with 1 to 4 carbons, or a fluorinated alkyl group with 1 to 4 carbons; R ⁶ is a single bond, substituted or unsubstituted phenylene group, or * ² -C(=O)-OR ¹⁵ -; "* ² "represents the bonding bond with the carbon atom to which R ⁵ is bonded; R ¹⁵ is a substituted or unsubstituted divalent Hydrocarbon group; R ⁷ is a monovalent aliphatic hydrocarbon group; R ⁸ and R ⁹ are each independently a monovalent aliphatic hydrocarbon group, or it means that R ⁸ and R ⁹ are combined with each other and form together with the carbon atom to which R ⁸ and R ⁹ are bonded alicyclic structure; in formula (a2-2), R ¹⁰ is a hydrogen atom, a halogen atom, an alkyl group with 1 to 4 carbons, or a fluorinated alkyl group with 1 to 4 carbons; R ¹¹ is a single bond, Substituted or unsubstituted phenylene, or * ³ -C(=O)-OR ¹⁶ -; "* ³ "represents the bond to the carbon atom to which R ¹⁰ is bonded; R ¹⁶ is substituted or unsubstituted A substituted divalent hydrocarbon group; R ¹² is a hydrogen atom or a monovalent aliphatic hydrocarbon group; Regarding R ¹³ and R ¹⁴ , R ¹³ is a monovalent aliphatic hydrocarbon group, and R ¹⁴ is a monovalent aliphatic hydrocarbon group, an aralkyl group or a substituted Aralkyl, or R ¹³ and R ¹⁴ represent a cyclic ether structure in which R ¹³ and R ¹⁴ are combined with each other and the carbon atom to which R ¹³ is bonded and the oxygen atom to which R ¹⁴ is bonded). The radiation-sensitive composition for lens production according to claim 9, wherein, relative to all structural units constituting the polymer (A), the polymer (A) has an oxirane group or an oxygen The content rate of the structural unit (a3) of a heterocyclobutyl group is 0 mol% or more and 15 mol% or less. The radiation-sensitive composition for lens production according to Claim 9 further contains a nitrogen-containing basic compound (D). The radiation-sensitive composition for lens production according to Claim 9, wherein the polyfunctional reactive compound (wherein , except the polymer (A)). The radiation-sensitive composition for lens manufacture according to claim 15, wherein the polyfunctional reactive compound is selected from polyfunctional oxirane compounds, polyfunctional oxetane compounds, polyfunctional melamine compounds and At least one of the group consisting of polyfunctional alkoxymethyl compounds. A lens formed by using the radiation-sensitive composition for lens production according to any one of Claim 9 to Claim 16. An imaging element, comprising the lens as claimed in claim 17. An imaging device, comprising the imaging element described in claim 18. A display element, comprising the lens as claimed in claim 17. A display device, comprising the display element described in Claim 20.