Radiation-sensitive composition for manufacturing lenses, display element, display device, solid-state imaging element, and imaging device

Abstract

To provide a radiation-sensitive composition for manufacturing lenses, which allows lens shapes to be formed through fluidization by heating at low temperatures and that can yield lenses having high heat resistance and a high refractive index.SOLUTION: The present invention provides a radiation-sensitive composition for manufacturing lenses by a thermal flow process, which is used in a lens manufacturing method including steps of applying a radiation-sensitive composition onto a substrate to form a coating film, irradiating a portion of the coating film with radiation, developing the irradiated coating film with the radiation to form a pattern on the substrate, and heating the pattern at 100°C or lower to form a lens, where the composition contains a component (A): a compound represented by the formula (1), a component (B): a photopolymerization initiator, and a component (C): a compound having a polymerizable carbon-carbon unsaturated bond, the compound including a (meth)acrylic acid ester having three or more functional groups (excluding the component (A)).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a radiation-sensitive composition for lens production, a display element, a display device, a solid-state imaging device, and an imaging device.

Background Art

[0002] Various image sensors such as CCD (Charge-Coupled Device) image sensors and CMOS (Complementary Metal-Oxide-Semiconductor) image sensors are used as solid-state imaging devices in imaging devices such as cameras. In the solid-state imaging device, minute condenser lenses (hereinafter also referred to as "microlenses") are regularly arranged in order to collect light on a light-receiving element (photodiode) and improve sensor sensitivity. Further, in various display elements such as an organic electroluminescence (organic EL) element and a liquid crystal display element, a structure in which a microlens is provided on the light-emitting side for each pixel has been adopted for the purpose of improving light extraction efficiency and adjusting a viewing angle. In a self-luminous display such as an organic EL display device, attempts have been made to improve luminance and adjust a viewing angle by forming a microlens with a high refractive index material.

[0003] As one method for forming a microlens, a thermal flow method is known (see, for example, Patent Document 1). The thermal flow method uses a radiation-sensitive composition to form a pattern corresponding to the arrangement of microlenses on the upper part of a light-receiving element or a light-emitting element, and then performs a heat treatment on the pattern formed by the radiation-sensitive composition to cause fluidization in the pattern, thereby forming a hemispherical microlens array.

[0004] Conventionally, in an organic EL element and a liquid crystal display element, a radiation-sensitive composition is applied onto a substrate, a pattern is formed by exposure and development processes, and then a heat treatment is performed to form a flattening film with a high refractive index. (See, for example, Patent Document 2).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] As a method for forming a high refractive index material such as a microlens or a planarization film, a method using a high refractive index filler such as a metal oxide is known. However, the method using a metal oxide has demerits such as the cleaning of the production line becoming complicated in the manufacturing process of the high refractive index material and the apparatus being easily contaminated. Further, in the case of a material containing a high refractive index filler, the pattern after exposure and development is less likely to flow due to heat, and it is difficult to form a microlens by the thermal flow method.

[0007] Also, a method has been proposed in which a pattern made of a photosensitive resin layer is fluidized by heat treatment to form a lens shape without using a high refractive index filler such as a metal oxide. However, when forming a microlens by the thermal flow of the photosensitive resin layer, there is a concern that it is not compatible with a process that requires a low temperature, such as a high temperature process of 150°C or higher being required during the thermal flow. Particularly in an organic EL element, when a microlens is provided on the light emitting side for each pixel for the purpose of improving the light extraction efficiency and adjusting the viewing angle, in the manufacturing process of the organic EL element, considering that the organic light emitting material is easily deteriorated by heat, it is required that the microlens can be formed at a low temperature (for example, 100°C or lower). Further, in the planarization film for an organic EL element, if the pattern after the exposure and development process can be fluidized by heating at a low temperature, it can be said that a cured film with a high degree of planarization can be formed while protecting the organic light emitting material from heat.

[0008] On the other hand, when the pattern after exposure and development is heated at a low temperature, there is a concern that the curing is insufficient and the heat resistance of the obtained high refractive index material (i.e., lens or planarization film) is low. Considering the manufacturing processes of organic EL elements and liquid crystal display elements, it is required that the finally obtained cured product has sufficient heat resistance while generating appropriate heat flow by heating at a low temperature for the pattern after exposure and development.

[0009] The present invention has been made in view of the above problems, and one object thereof is to provide a radiation-sensitive composition for lens production that can be fluidized by heating at a low temperature and can obtain a cured product having high heat resistance and a high refractive index.

Means for Solving the Problems

[0010] According to the present invention, there are provided the following lens manufacturing method, radiation-sensitive composition, display element, display device, solid-state imaging device, imaging device, and compound.

[0011] [1] A step of applying a radiation-sensitive composition on a substrate to form a coating film, a step of irradiating a part of the coating film with radiation, a step of developing the coating film irradiated with radiation to form a pattern on the substrate, and a step of heating the pattern to form a lens, wherein the radiation-sensitive composition (A) component: a compound represented by the following formula (1), (B) component: a photoinitiator, and (C) component: a compound having a polymerizable carbon-carbon unsaturated bond (excluding the (A) component). A method for manufacturing a lens, which contains

Chemical formula

[0012] [2] (Component (A): The compound represented by the above formula (1), Component (B): A photopolymerization initiator, and Component (C): A compound having a polymerizable carbon-carbon unsaturated bond (excluding the above Component (A)).), A radiation-sensitive composition for lens production by a thermal flow method. [3] A display element comprising a lens formed using the radiation-sensitive composition for lens production described in [2] above. [4] A radiation-sensitive composition for forming a planarizing film, containing component (A): a compound represented by the above formula (1), component (B): a photopolymerization initiator, and component (C): a compound having a polymerizable carbon-carbon unsaturated bond (excluding the above component (A)). [5] A display device comprising the display element described in [3] above or a planarizing film formed using the radiation-sensitive composition for forming a planarizing film described in [4] above. [6] A solid-state imaging device comprising a lens formed using the radiation-sensitive composition for lens production described in [2] above. [7] An imaging device comprising the solid-state imaging device described in [6] above. [8] The compound represented by the above formula (1). [9] A method for producing a lens, including a step of inkjet-applying a radiation-sensitive composition onto a substrate to form a pattern, wherein the radiation-sensitive composition contains component (A): a compound represented by the above formula (1), component (B): a photopolymerization initiator, and component (C): a compound having a polymerizable carbon-carbon unsaturated bond (excluding the above component (A)). [Effect of the Invention]

[0013] According to the production method of the present invention, a coating film is formed on a substrate using the radiation-sensitive composition containing the above components (A), (B), and (C), and the pattern formed by exposure treatment and development treatment is heated, whereby the pattern on the substrate can be processed into a lens shape, for example, by thermal flow at a temperature of 100°C or lower. Further, according to the production method of the present invention, a lens having high heat resistance and a high refractive index can be produced. Furthermore, according to the radiation-sensitive composition of the present invention containing the above components (A), (B), and (C), fluidization can be caused by heating at a low temperature, and a cured product having high heat resistance and a high refractive index can be obtained. Such a radiation-sensitive composition of the present invention is suitable for use in lens production or for forming a planarizing film.

Brief Description of the Drawings

[0014]

Figure 1

Modes for Carrying Out the Invention

[0015] Hereinafter, matters related to the embodiments will be described in detail. In this specification, a numerical range described using "~" means that the numerical values described before and after "~" are included as the lower limit value and the upper limit value.

[0016] ≪Method for Manufacturing a Lens and Radiation-Sensitive Composition≫ The manufacturing method of the present disclosure is a method for manufacturing a micro-condenser (hereinafter, also referred to as a "microlens") provided in a solid-state imaging device (for example, a CCD image sensor, a CMOS image sensor) or a display element (for example, an organic EL element). The manufacturing method of the first lens of the present disclosure includes the following steps (I) to (IV). (I) Step of applying a radiation-sensitive composition on a substrate to form a coating film (II) Step of irradiating a part of the coating film with radiation (III) Step of developing the irradiated coating film to form a pattern on the substrate (IV) Step of heating the pattern to form a lens

[0017] The manufacturing method of the second lens of the present disclosure includes a step of forming a pattern by inkjet-applying a radiation-sensitive composition on a substrate.

[0018] First, the radiation-sensitive composition (that is, the radiation-sensitive composition for lens manufacturing) used in the lens manufacturing method of the present disclosure (the manufacturing method of the first lens and the manufacturing method of the second lens) will be described, then each step in the manufacturing method of the first lens of the present disclosure will be described, and further the manufacturing method of the second lens of the present disclosure will be described.

[0019] [Radiation-sensitive composition] The radiation-sensitive composition of the present disclosure (hereinafter, also simply referred to as "this composition") contains the following components (A), (B), and (C). Unless otherwise specified for each component, one kind may be used alone, or two or more kinds may be used in combination. Component (A): A compound represented by the following formula (1) Component (B): A photoinitiator Component (C): A compound having a polymerizable carbon-carbon unsaturated bond (however, excluding component (A)).

[0020] [Chemical formula] (In formula (1), Ar 1 and Ar 2 are each independently an aromatic ring group. R 1 and R 2 are each independently a monovalent substituent, or R 1 and R 2 are combined with each other to represent a condensed ring structure formed together with Ar 1 and Ar 2 . The condensed ring structure has a structure in which two aromatic rings are linked by a single bond, -O-, -S-, -NR 8 -, a methylene group or an ethylene group. R 8 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R 3 and R 4 are each independently a monovalent substituent. X 1 and X 2 are each independently a group represented by the following formula (1x). m1 and m2 are each independently an integer from 0 to 6. k1 and k2 are each independently an integer from 0 to 4. n1 and n2 are each independently an integer from 1 to 6. When there are a plurality of R 1 ~R 4 , X 1 , X 2 present, the plurality of R 1 ~R 4 , X 1 , X 2 are the same or different.)

[0021]

Chem.

[0022] Here, in this specification, "hydrocarbon group" means a group including a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. "Chain hydrocarbon group" means a straight-chain hydrocarbon group and a branched hydrocarbon group that do not contain a cyclic structure in the main chain and are composed only of a chain structure. However, it may be saturated or unsaturated. "Alicyclic hydrocarbon group" means a hydrocarbon group that includes only the structure of an alicyclic hydrocarbon as the ring structure and does not include an aromatic ring structure. However, it is not necessary to be composed only of the structure of an alicyclic hydrocarbon, and those having a chain structure in a part thereof are also included. "Aromatic hydrocarbon group" means a hydrocarbon group that includes an aromatic ring structure as the ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure. Further, the aromatic ring structure possessed by the aromatic hydrocarbon group may be a monocyclic ring or a condensed ring. In addition, the ring structures possessed by the alicyclic hydrocarbon group and the aromatic hydrocarbon group may have a substituent composed of a hydrocarbon structure.)

[0023] In the present specification, "(meth)acryl" means including "acryl" and "methacryl". The "(meth)acryloyl group" means including "acryloyl group" and "methacryloyl group". "Alkali-soluble" means being soluble or swellable in an aqueous solution of tetramethylammonium hydroxide with a concentration of 2.38% by mass at 25°C.

[0024] · Component (A): A compound represented by formula (1) The compound represented by the above formula (1) (hereinafter, also referred to as "compound (A)") is a compound having a fluorene skeleton, a (meth)acryloyl group, and a carboxy group. Compound (A) has a high refractive index and good alkali solubility and photopolymerizability (especially radical photopolymerizability). Further, compound (A) has a lower molecular weight than the polymer component blended as a base resin in a radiation-sensitive composition used for forming a high refractive index material such as a microlens or a planarizing film. By using such a compound (A) as a component of a radiation-sensitive composition for forming a high refractive index material, a negative pattern can be formed by contact with an alkali developer, and fluidization can be caused in the pattern after exposure and development by heating at a lower temperature. Further, by containing compound (A), a cured product having a high refractive index can be obtained.

[0025] In the above formula (1), Ar 1 The aromatic ring group represented by is a group obtained by removing (m1 + n1 + 1) hydrogen atoms from the aromatic ring. Ar 2 The aromatic ring group represented by is a group obtained by removing (m2 + n2 + 1) hydrogen atoms from the aromatic ring. Ar 1 And Ar 2 The aromatic ring possessed by may be a monocyclic ring or a condensed ring. Ar 1 And Ar 2 The aromatic ring possessed by is preferably an aromatic hydrocarbon ring, and examples thereof include a benzene ring, a naphthalene ring, an indene ring, an anthracene ring, and a phenanthrene ring. Among these, the aromatic ring possessed by Ar 1 And Ar 2 is preferably a benzene ring or a naphthalene ring. R 1 And R2 When it is a monovalent substituent, in terms of achieving a high refractive index and high heat resistance, Ar 1 and Ar 2 preferably has a condensed polycyclic aromatic hydrocarbon ring, and more preferably has a naphthalene ring.

[0026] R 1 and R 2 When they are monovalent substituents, examples of the monovalent substituent include a halogen atom (such as a fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 3 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an aralkyloxy group having 6 to 12 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkylthio group having 3 to 12 carbon atoms, an arylthio group having 6 to 12 carbon atoms, an aralkylthio group having 6 to 12 carbon atoms, a cyano group, a nitro group, a dialkylamino group, etc. Among these, the monovalent substituent represented by R 1 and R 2 is preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0027] R 1 and R 2 When they are combined with each other to represent a condensed ring structure formed together with Ar 1 and Ar 2 the condensed ring structure has a structure in which the aromatic ring in Ar 1 and the aromatic ring in Ar 2 are linked by a single bond, -O-, -S-, -NR 8 -, a methylene group or an ethylene group. R 1 and R 2Examples of the condensed ring structures formed by combining them with each other include a fluorene ring, a tetrahydroanthracene ring, a xanthene ring, a thioxanthene ring, etc. Among these, the xanthene ring is preferred.

[0028] m1 and m2 can be selected according to the types of Ar 1 and Ar 2 m1 and m2 are preferably 0 to 3, more preferably 0 or 1, and even more preferably 0.

[0029] R 3 and R 4 Examples of the monovalent substituents represented by include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 3 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an aralkyloxy group having 6 to 12 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a cycloalkylthio group having 3 to 12 carbon atoms, an arylthio group having 6 to 12 carbon atoms, an aralkylthio group having 6 to 12 carbon atoms, a cyano group, an acyl group, etc. R 3 and R 4 The monovalent substituents represented by are preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 6 to 12 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 12 carbon atoms.

[0030] k1 and k2 are preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0031] X 1 and X 2 are the groups represented by the above formula (1x). In formula (1x), R 5 The alkanediyl group having 2 to 4 carbon atoms represented by may be linear or branched. R 5Among these, a linear or branched alkanediyl group having 2 or 3 carbon atoms is preferred. p is preferably 0 to 2, more preferably 0 or 1. R 6 is preferably a hydrogen atom.

[0032] In “-C(=O)-R 7 -COOH”, the divalent organic group represented by R 7 may have a chain structure, a cyclic structure, or both a chain structure and a cyclic structure. When producing compound (A) by reacting an (meth)acrylic acid adduct of an epoxy group-containing compound having a fluorene skeleton with a carboxylic anhydride, R 7 corresponds to the partial structure excluding the acid anhydride group of the carboxylic anhydride (more specifically, the group formed by dehydration condensation of two carboxy groups in one molecule).

[0033] R 7 Specific examples of R 9 include a divalent hydrocarbon group, a divalent group containing -O-, -S-, -NR- (R is a monovalent hydrocarbon group) etc. between carbon-carbon bonds of a hydrocarbon group, a divalent group in which any hydrogen atom of a hydrocarbon group is replaced by a monovalent heteroatom-containing group (for example, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group etc.), a divalent group in which two hydrogen atoms bonded to the same carbon in a hydrocarbon group are removed and replaced by a group represented by “=P(R 9 )3” (the three Rs

[0034] R 7When it is a divalent group having a complex ring structure, examples of the divalent group include groups having a nitrogen-containing complex ring structure, a sulfur-containing complex ring structure, or an oxygen-containing complex ring structure. Specific examples of these complex ring structures include, as the nitrogen-containing complex ring structure, a pyridine ring structure, a pyrimidine ring structure, a pyridazine ring structure, a pyrazine ring structure, etc.; as the oxygen-containing complex ring structure, a furan ring structure, etc.; and as the sulfur-containing complex ring structure, a thiophene ring structure, a 2,3-dihydro-1,4-dithiin ring structure, etc.

[0035] From the viewpoint of achieving both a high refractive index of the obtained cured product and thermal flow at low temperature, R 7 is preferably a group having at least one heteroatom selected from the group consisting of a sulfur atom, a nitrogen atom, and a phosphorus atom, or a group having a monocyclic aromatic hydrocarbon ring, a condensed polycyclic aromatic hydrocarbon ring, or an aliphatic hydrocarbon ring.

[0036] More specifically, from the viewpoint of achieving a high refractive index of the obtained cured product, R 7 is preferably a group having at least one heteroatom selected from the group consisting of a sulfur atom, a nitrogen atom, and a phosphorus atom, or a group having a monocyclic aromatic hydrocarbon ring or a condensed polycyclic aromatic hydrocarbon ring. Also, from the viewpoint of suppressing the generation of outgas from the cured product, R 7 is preferably a group having an aliphatic hydrocarbon ring.

[0037] R 7 Preferred specific examples of include groups represented by the following formulas (y-1) to (y-4).

Chemical formula

[0038] In the above formula (y-1), the monocyclic aromatic hydrocarbon ring group represented by Ar 3 is a group obtained by removing (r + 2) hydrogen atoms from a monocyclic aromatic hydrocarbon ring. The monocyclic aromatic hydrocarbon ring is preferably a benzene ring. The condensed polycyclic aromatic hydrocarbon ring group is a group obtained by removing (r + 2) hydrogen atoms from a condensed polycyclic aromatic hydrocarbon ring. Examples of the condensed polycyclic aromatic hydrocarbon ring include a naphthalene ring, an indene ring, an anthracene ring, a phenanthrene ring, etc., and a naphthalene ring is preferred.

[0039] The nitrogen-containing heterocyclic group represented by Ar 3 is a group obtained by removing (r + 2) hydrogen atoms from a nitrogen-containing heterocyclic ring. Examples of the nitrogen-containing heterocyclic ring include a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, etc. Examples of the sulfur-containing heterocyclic group represented by Ar 3 include a group obtained by removing (r + 2) hydrogen atoms from a thiophene ring, a 2,3-dihydro-1,4-dithiin ring.

[0040] The aliphatic hydrocarbon ring group represented by Ar 3 is a group obtained by removing (r + 2) hydrogen atoms from a saturated or unsaturated aliphatic hydrocarbon ring. Ar 3The aliphatic hydrocarbon ring of the aliphatic hydrocarbon group represented by may be monocyclic or polycyclic such as a condensed aliphatic ring or a bridged aliphatic ring. Specific examples of the aliphatic hydrocarbon ring include saturated monocyclic aliphatic rings such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring; unsaturated monocyclic aliphatic rings such as a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, and a cycloheptene ring; condensed aliphatic rings such as decahydronaphthalene and octahydronaphthalene; bridged aliphatic rings such as bicyclo[2.2.2]oct-5-ene ring and norbornene ring (bicyclo[2.2.1]hept-5-ene ring); and the like. From the viewpoint of achieving a high refractive index of the resulting cured product, Ar 3 The aliphatic hydrocarbon group represented by is preferably a group obtained by removing (r + 2) hydrogen atoms from an unsaturated aliphatic hydrocarbon ring among the above, more preferably a group obtained by removing (r + 2) hydrogen atoms from an unsaturated bridged aliphatic hydrocarbon ring, and still more preferably a group having a bicyclo[2.2.2]oct-5-ene ring or a norbornene ring.

[0041] R 10 Examples of the monovalent substituent represented by include the same groups as those exemplified as specific examples when R 1 and R 2 are monovalent substituents, a hydroxy group, a carboxy group, an alkoxycarbonyl group, and the like. The monovalent substituent represented by R 10 is preferably a halogen atom, a hydroxy group, a carboxy group, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, or an arylthio group having 6 to 12 carbon atoms.

[0042] In the above formula (y - 2), examples of the nitrogen-containing heterocyclic group and sulfur-containing heterocyclic group represented by Ar 4 and Ar 5 include a group obtained by removing one hydrogen atom from a substituted or unsubstituted nitrogen-containing heterocyclic ring or sulfur-containing heterocyclic ring. Specific examples of the nitrogen-containing heterocyclic ring and sulfur-containing heterocyclic ring include Ar 3Examples similar to the nitrogen-containing heterocyclic ring and sulfur-containing heterocyclic ring exemplified as specific examples thereof can be mentioned. Examples of the substituent include an alkyl group having 1 to 3 carbon atoms. Ar 4 and Ar 5 Among these, a substituted or unsubstituted monovalent sulfur-containing aromatic heterocyclic group is preferable.

[0043] In the above formula (y-3), the monovalent hydrocarbon group represented by R 9 Examples thereof include a linear or branched alkyl group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. Note that the three Rs 9 present in the formula (y-3) may be the same as or different from each other. From the viewpoint of obtaining a cured product having a high refractive index, it is preferable that one or more of the three Rs 9 are a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms, and more preferably all of the three Rs 9 are a monovalent aromatic hydrocarbon group having 6 to 12 carbon atoms. R 9 is preferably a substituted or unsubstituted phenyl group.

[0044] In the formula (y-4), the alkanediyl group represented by R 11 and R 12 may be linear or branched. The alkanediyl group represented by R 11 and R 12 preferably has 1 to 5 carbon atoms, and more preferably 1 to 3 carbon atoms.

[0045] Note that one or more of the Ys 1 contained in the n1 Xs 2 and the n2 Xs 1 in the above formula (1) are a group represented by “-C(=O)-R 7 -COOH”. From the viewpoint of alkali solubility during development, the compound (A) preferably has 1 to 6 groups represented by “-C(=O)-R 7 -COOH”, and more preferably has 1 to 4 groups. n1 and n2 are preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.

[0046] Y 1 is "-C(=O)-R 7 -COOH", preferred specific examples of the group represented by the above formula (1x) include groups represented by each of the following formulas (x1-1) to (x1-25).

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0047] From the viewpoint of achieving a high refractive index of the cured product while ensuring sufficient thermal flow at low temperature, Y 1 is "-C(=O)-R 7 -COOH", the group represented by the above formula (1x) is preferably a group represented by each of the above formulas (x1-1) to (x1-3), (x1-7) to (x1-13), (x1-16), (x1-17) and (x1-22) to (x1-25).

[0048] Note that as the compound (A), a multimer (for example, dimer, trimer, etc.) of the compound represented by the above formula (1) may be used.

[0049] In the compound (A), the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) is preferably 600 or more. When Mw is 600 or more, it is preferable in terms of forming an organic film exhibiting good alkali developability and obtaining a cured product having sufficiently high heat resistance and chemical resistance. Mw is more preferably 700 or more, and still more preferably 800 or more. Also, Mw is preferably 2,000 or less, more preferably 1,500 or less, and still more preferably 1,200 or less from the viewpoints of sufficiently generating thermal flow at a low temperature and suppressing the viscosity of this composition from becoming too high.

[0050] The compound (A) can be produced, for example, by reacting an (meth)acrylic acid adduct of an epoxy group-containing compound having a fluorene skeleton (hereinafter also referred to as "precursor (A)") with a carboxylic anhydride. By modifying the precursor (A) with a carboxylic anhydride, alkali developability can be imparted to the precursor (A).

[0051] The precursor (A) is represented by the following formula (1A).

Chemical formula

Chemical formula

[0052] Examples of the carboxylic acid anhydride include a carboxylic acid anhydride obtained by intramolecular dehydration condensation of a polyvalent carboxylic acid having a chain hydrocarbon structure (hereinafter also referred to as "chain carboxylic acid anhydride"); a carboxylic acid anhydride obtained by intramolecular dehydration condensation of a polyvalent carboxylic acid having a cyclic hydrocarbon structure (hereinafter also referred to as "cyclic carboxylic acid anhydride"); and a carboxylic acid anhydride having at least one heteroatom selected from the group consisting of a sulfur atom, a nitrogen atom, and a phosphorus atom (hereinafter also referred to as "heteroatom-containing carboxylic acid anhydride").

[0053] Examples of the chain carboxylic acid anhydrides include succinic anhydride, itaconic anhydride, maleic anhydride, fumaric anhydride, 2-(2-carboxyethyl)-3-methylmaleic anhydride, and compounds in which any hydrogen atom in these carboxylic acid anhydrides is replaced with a substituent. Examples of the cyclic carboxylic acid anhydrides include tetrahydrophthalic anhydride (1,2,3,6-tetrahydrophthalic anhydride), 3,4,5,6-tetrahydrophthalic anhydride, methylcyclohexenetricarboxylic anhydride, hexahydrophthalic anhydride (1,2-cyclohexanedicarboxylic anhydride), 3-methylcyclohexane-1,2-dicarboxylic anhydride, 4-cyclohexene-1,2-dicarboxylic anhydride, 3-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, 4-methyl-4-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]oct-5-ene-2,3-dicarboxylic anhydride, norbornenedicarboxylic anhydride (bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride), methylnadic anhydride, and other carboxylic acid anhydrides having an aliphatic hydrocarbon ring structure; phthalic anhydride, trimellitic anhydride, 2,3-naphthalenedicarboxylic anhydride, and other carboxylic acid anhydrides having an aromatic hydrocarbon structure; and compounds in which any hydrogen atom in these carboxylic acid anhydrides is replaced with a substituent. Specific examples of the substituents in the chain carboxylic acid anhydrides and cyclic carboxylic acid anhydrides include a halogen atom, a hydroxy group, a carboxy group, an alkyl group, an alkoxycarbonyl group, a thioalkyl group, a thioaryl group, and the like. Further, as the carboxylic acid anhydride to be reacted with the precursor (A), a compound in which any methylene group in the above-exemplified carboxylic acid anhydride is replaced with -O- (for example, 7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, etc.) may be used.

[0054] Specific examples of the heteroatom-containing carboxylic acid anhydrides include compounds represented by each of the following formulas (1a-1) to (1a-9).

Chemical formula

[0055] From the viewpoint of achieving both high refractive index of the resulting cured product and thermal flow at low temperature, the carboxylic anhydride to be reacted with the precursor (A) is preferably a carboxylic anhydride having one or more heteroatoms selected from the group consisting of sulfur atoms, nitrogen atoms, and phosphorus atoms, or a carboxylic anhydride having a monocyclic aromatic hydrocarbon ring structure, a condensed polycyclic aromatic hydrocarbon ring structure, or an aliphatic hydrocarbon ring structure. In particular, from the viewpoint of increasing the refractive index of the resulting cured product, the carboxylic anhydride to be reacted with the precursor (A) is preferably, among others, a carboxylic anhydride having one or more heteroatoms selected from the group consisting of sulfur atoms, nitrogen atoms, and phosphorus atoms, or a carboxylic anhydride having a monocyclic aromatic hydrocarbon ring structure or a condensed polycyclic aromatic hydrocarbon ring structure. Further, from the viewpoint of suppressing the generation of outgas from the cured product, the carboxylic anhydride to be reacted with the precursor (A) is preferably a carboxylic anhydride having an aliphatic hydrocarbon ring structure.

[0056] The reaction between the precursor (A) and the carboxylic anhydride can be carried out in the presence of a solvent and a catalyst as necessary. The reaction may be carried out in air or in an inert atmosphere. The amount of the carboxylic anhydride used is, for example, 0.2 to 2.0 moles, preferably 0.5 to 1.0 mole, per mole of the hydroxy group in the precursor (A). As the catalyst, for example, tertiary amine compounds such as triethylamine and basic catalysts such as quaternary ammonium salts, and phosphorus-based catalysts such as triphenylphosphine can be used. Examples of the solvent include alcohols, esters, ethers, amides, ketones, hydrocarbons, and halogens. The reaction may be carried out in the presence of a polymerization inhibitor (for example, 4-methoxyphenol, etc.). The reaction temperature is, for example, 30 to 150 °C. The reaction time is, for example, 0.5 to 48 hours.

[0057] In this composition, the content of compound (A) is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, per 100 parts by mass of the solid content contained in this composition (that is, the components other than the solvent in the radiation-sensitive composition). Further, the content of compound (A) is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, per 100 parts by mass of the solid content contained in this composition. When the content of compound (A) is within the above range, a cured product having a high refractive index can be obtained, and the cured product can be fluidized at a relatively low temperature (for example, 100 °C or lower), and a microlens having a good lens shape can be obtained.

[0058] In the present specification, the "solid content" means the components other than the solvent arbitrarily blended in the radiation-sensitive composition. That is, the "solid content contained in this composition" is the combined components of compound (A), the photopolymerization initiator, compound (C), and the components other than (A) to (C). Therefore, even if it is a liquid additive component (for example, a surfactant, etc.), the additive component shall be included in the solid content.

[0059] · Component (B): Photopolymerization initiator As the photopolymerization initiator, a photo radical polymerization initiator that can generate radicals in response to radiation and initiate polymerization can be preferably used. The photopolymerization initiator used is not particularly limited. Examples of the photopolymerization initiator include O-acyl oxime compounds, acetophenone compounds, biimidazole compounds, acylphosphine oxide compounds, and the like.

[0060] Examples of the O-acyl oxime compound include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetoxime), 1-(9-ethyl-6-benzoyl-9H-carbazol-3-yl)-octan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9H-carbazol-3-yl]-ethan-1-one oxime-O-benzoate, ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetoxime), ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetoxime), ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetoxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetoxime), and the like.

[0061] Examples of the acetophenone compound include α-amino ketone compounds, α-hydroxy ketone compounds, etc. Specific examples thereof include, as the α-amino ketone compound, for example, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, etc. Examples of the α-hydroxy ketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-i-propylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenylketone, etc.

[0062] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc.

[0063] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, etc.

[0064] The content of the photopolymerization initiator in the composition is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the total amount of the polymerizable compounds (Compound (A) and Compound (C)) contained in the composition. Further, the content of the photopolymerization initiator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 12 parts by mass or less, based on 100 parts by mass of the total amount of the polymerizable compounds contained in the composition. By setting the content of the photopolymerization initiator within the above range, a radiation-sensitive composition exhibiting good curability and transparency can be obtained.

[0065] · Component (C): A compound having a polymerizable carbon-carbon unsaturated bond The compound having a polymerizable carbon-carbon unsaturated bond as Component (C) (hereinafter also referred to as "Compound (C)") is a component copolymerizable with Compound (A), and can form a polymer together with Compound (A) upon irradiation with radiation. Note that Compound (C) is a compound different from Compound (A). While Compound (A) exhibits a high refractive index, when attempting to form a pattern into an appropriate lens shape by thermal flow, for example, a high-temperature process of 120°C or higher is required. Further, when only Compound (A) is used as the polymerizable compound, a high exposure amount is required to obtain sufficient curability. In contrast, by using Compound (A) and Compound (C) in combination, for example, the fluidization of the pattern can be realized by a low-temperature process at 100°C or lower, and an appropriate lens shape can be obtained. Also, the curing rate is improved, and curing with a relatively low exposure amount becomes possible.

[0066] From the viewpoint of making the temperature during thermal flow as low as possible, the molecular weight of Compound (C) is preferably smaller than that of Compound (A). Specifically, the molecular weight of Compound (C) is preferably less than 600, more preferably 550 or less, still more preferably 500 or less, and particularly preferably 450 or less. Further, from the viewpoint of obtaining a cured product having a high refractive index and excellent reliability in solvent resistance and low volatility, etc., the molecular weight of Compound (C) is preferably 100 or more.

[0067] Examples of the compound (C) include (meth)acryloyl group-containing compounds, chain vinyl compounds, aromatic vinyl compounds, maleimide compounds, etc. These compounds can be preferably used in terms of their good copolymerizability with the compound (A) and relatively high plasticity.

[0068] The compound (C) may be either a monofunctional compound or a polyfunctional compound. Further, a monofunctional compound and a polyfunctional compound may be used in combination as the compound (C). Specific examples of the case where the compound (C) is a monofunctional compound include (meth)acrylic acid esters having a chain structure, (meth)acrylic acid esters having an alicyclic structure, (meth)acrylic acid esters having an aromatic ring structure, (meth)acrylamide compounds, chain vinyl compounds, aromatic vinyl compounds, maleimide compounds, etc. When the compound (C) is a monofunctional compound, a (meth)acryloyl group-containing compound can be preferably used as the compound (C), and at least one (meth)acrylic acid ester compound selected from the group consisting of (meth)acrylic acid esters having a chain structure, (meth)acrylic acid esters having an alicyclic structure, and (meth)acrylic acid esters having an aromatic ring structure can be more preferably used.

[0069] Specific examples of the above compounds include, as (meth)acrylic acid esters having a chain structure, alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, polyoxyalkylene (meth)acrylates, etc. Examples of alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, etc. Examples of hydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Examples of alkoxyalkyl (meth)acrylates include methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxyethyl (meth)acrylate, etc. Examples of polyoxyalkylene (meth)acrylates include methoxydiethylene glycol (meth)acrylate, methoxytetraethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, ethoxydipropylene glycol (meth)acrylate, 2-ethylhexyloxydiethylene glycol (meth)acrylate, etc.

[0070] Examples of (meth)acrylic acid esters having an alicyclic structure include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, 4-butylcyclohexyl (meth)acrylate, 4-hydroxymethylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 decane-8-yl, tricyclo[5.2.1.0 2,5Examples include decan-8-yloxyethyl, isobornyl (meth)acrylate, etc. Examples of (meth)acrylic acid esters having an aromatic ring structure include phenyl (meth)acrylate, benzyl (meth)acrylate, naphthylmethyl (meth)acrylate, naphthylethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenylthioethyl (meth)acrylate, m-phenoxyphenylmethyl (meth)acrylate, p-phenoxyphenylmethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, polyethyleneoxynonylphenyl (meth)acrylate, (1-naphthyl)methyl (meth)acrylate, (2-naphthyl)methyl (meth)acrylate, (1,1'-biphenyl-4-yl)methyl (meth)acrylate, etc.

[0071] Examples of (meth)acrylamide compounds include (meth)acryloylmorpholine, N-(2-hydroxyethyl)(meth)acrylamide, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, etc. Examples of chain vinyl compounds include propene, butene, pentene, hexene, etc. Examples of aromatic vinyl compounds include styrene, methylstyrene, α-methylstyrene, t-butoxystyrene, vinylnaphthalene, etc. Examples of maleimide compounds include N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-(p-methylphenyl)maleimide, etc.

[0072] Specific examples of the case where the compound (C) is a polyfunctional compound include polyfunctional (meth)acrylate esters, aromatic vinyl compounds, chain vinyl compounds, and the like. Examples of the polyfunctional (meth)acrylate esters include bifunctional (meth)acrylate esters and polyfunctional (meth)acrylate esters having three or more functional groups. Specific examples thereof include, as the bifunctional (meth)acrylate esters, for example, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, and the like.

[0073] Examples of the polyfunctional (meth)acrylate esters having three or more functional groups include, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, tri(2-(meth)acryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol tri(meth)acrylate, succinic acid-modified dipentaerythritol penta(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, carboxy group-containing polybasic acid-modified (meth)acrylic oligomers, and in addition, compounds having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and compounds having one or more hydroxy groups in the molecule and having three, four, or five (meth)acryloyloxy groups, and polyfunctional urethane acrylate compounds obtained by reacting them.

[0074] Examples of the polyfunctional aromatic vinyl compound include 1,3 - divinylbenzene, 1,4 - divinylbenzene, etc. Examples of the polyfunctional chain vinyl compound include 1,5 - hexadiene, 1,6 - heptadiene, 1,7 - octadiene, etc.

[0075] Preferred specific examples of the compound (C) include compounds represented by the following formulas (C1 - 1) to (C1 - 47), etc.

Chemical formula

Chemical formula

[0076]

Chemical formula

Chemical formula

[0077] From the viewpoint of forming an appropriate lens shape by thermal flow at low temperature and obtaining a cured product with high heat resistance, the content of the compound (C) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more with respect to 100 parts by mass of the total amount of the compound (A) contained in the present composition. Further, from the viewpoint of suppressing the decrease in the refractive index of the obtained cured product, the content of the compound (C) is preferably 100 parts by mass or less, more preferably 50 parts by mass or less with respect to 100 parts by mass of the total amount of the compound (A) contained in the present composition.

[0078] Compound (C) preferably contains a compound in which the number of polymerizable carbon-carbon unsaturated bonds in one molecule is 1 or 2 (hereinafter also referred to as "compound (C1)"). From the viewpoint of fluidizing the pattern at a low temperature (for example, a temperature of 100 °C or lower) and obtaining a microlens with a good shape, the content of compound (C1) is preferably 10% by mass or more, more preferably 25% by mass or more, still more preferably 40% by mass or more, and even more preferably 50% by mass or more with respect to the total amount (100% by mass) of compound (C) contained in the present composition. Further, the content of compound (C1) is preferably 95% by mass or less, more preferably 90% by mass or less with respect to the total amount of compound (C) contained in the present composition from the viewpoint of obtaining a cured product having excellent heat resistance and chemical resistance and high reliability.

[0079] In particular, when compound (C) is contained in an amount of 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the total amount of compound (A), and compound (C1) is contained in an amount of 10% by mass or more with respect to the total amount of compound (C), it is suitable in that an appropriate lens shape can be formed by thermal flow at a low temperature and a cured product having high heat resistance can be obtained. From such a viewpoint, the present composition preferably contains compound (C) in an amount of 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the total amount of compound (A), and compound (C1) is more preferably contained in an amount of 25% by mass or more, still more preferably 40% by mass or more, and even more preferably 50% by mass or more with respect to the total amount of compound (C).

[0080] <Other components> In addition to the above-described compound (A), photoinitiator, and compound (C), the present composition may further contain components other than these (hereinafter also referred to as "other components"). Examples of the other components include polymers having a molecular weight of 2,000 or more and 100,000 or less, solvents, and the like.

[0081] · Component (D): A polymer having a molecular weight of 2,000 or more and 100,000 or less The composition may further contain, as an additive component, a polymer having a molecular weight of 2,000 or more and 100,000 or less (hereinafter also referred to as "polymer (D)"). Blending the polymer (D) into the composition is suitable in that it can enhance the heat resistance of the resulting cured product and obtain a high refractive index material with better reliability.

[0082] Examples of the polymer (D) include alkali-soluble polymers, fluorene skeleton-containing photosensitive polymers, carboxy group-containing photosensitive polymers, etc. Examples of the alkali-soluble polymer include (meth)acrylic acid / methyl (meth)acrylate copolymer, (meth)acrylic acid / benzyl (meth)acrylate copolymer, (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate / benzyl (meth)acrylate copolymer, (meth)acrylic acid / styrene / isoprene / tricyclodecanyl (meth)acrylate / 2-mono(hexahydrophthaloyloxy)ethyl (meth)acrylate copolymer, methacryl-modified acrylic resin, acid anhydride-modified acrylic resin, etc.

[0083] Examples of the fluorene skeleton-containing photosensitive polymer include those described in International Publication No. 2009 / 119622. Examples of the carboxy group-containing photosensitive polymer include acid-modified epoxy acrylates such as bisphenol A type epoxy acrylate, bisphenol F type epoxy acrylate, cresol novolak type epoxy acrylate, biphenyl type epoxy acrylate, etc. Specific examples of the carboxy group-containing photosensitive polymer include those with the trade names CCR-1235, CCR-1291H, ZAR-1035, ZAR-2000, ZFR-1401H, ZFR-1491H, ZCR-1569H, ZCR-1798H (manufactured by Nippon Kayaku Co., Ltd.).

[0084] When the polymer (D) is blended in the composition, the content of the polymer (D) is preferably 50 parts by mass or less, more preferably 20 parts by mass or less, based on 100 parts by mass of the total amount of the compound (A) contained in the composition. By setting the content of the polymer (D) within the above range, an appropriate lens shape can be obtained by thermal flow at low temperature, and an effect of improving heat resistance can be obtained.

[0085] · Component (E): Solvent This composition is preferably a liquid composition in which the compound (A), the photopolymerization initiator, the compound (C), and other components optionally blended are dissolved or dispersed in a solvent. As the solvent, an organic solvent that dissolves each component blended in the composition and does not react with each component is preferred.

[0086] Specific examples of the solvent include, for example, alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, ethylene diglycol monomethyl ether, ethylene diglycol ethyl methyl ether, dimethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether; amides such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. Among these, the solvent preferably contains at least one selected from the group consisting of ethers, esters, and ketones.

[0087] As other components, in addition to the above, for example, polymerization inhibitors, surfactants, antioxidants, sensitizers, softeners, plasticizers, adhesion aids, ultraviolet absorbers, etc. can be mentioned. The blending ratios of these components are appropriately selected according to each component within the range that does not impair the effects of the present disclosure.

[0088] For example, the surfactant can be used to improve the coatability (wetting spreadability and reduction of coating unevenness) of the present composition. Examples of the surfactant include fluorosurfactants, silicone surfactants, and nonionic surfactants.

[0089] Specific examples of the surfactant include, as fluorosurfactants, under the following trade names, Megafac F-171, F-172, F-173, F-251, F-430, F-554, F-563 (manufactured by DIC Corporation); Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited); Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106, S-611 (manufactured by AGC Seimi Chemical Co., Ltd.); Polyflow No.75, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.); FTX-218 (manufactured by Neos Co., Ltd.); Eftop EF301, EF303, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), etc.

[0090] Examples of silicone surfactants include, under 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, PAINTAD19, FZ-2101, FZ-77, FZ-2118, L-7001, L-7002 (manufactured by Toray Dow Corning Silicone Co., Ltd.); Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); BYK-300, 306, 310, 330, 335, 341, 344, 370, 340, 345 (manufactured by BYK-Chemie Japan Co., Ltd.).

[0091] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and the like.

[0092] When a surfactant is incorporated into the present composition, the content of the surfactant is preferably 0.01 to 1.5 parts by mass, more preferably 0.02 to 1.2 parts by mass, and still more preferably 0.05 to 1.0 parts by mass, based on 100 parts by mass of the total amount of compound (A) contained in the present composition.

[0093] The adhesion aid is a component that improves the adhesion between the cured product formed using the present composition and the substrate and suppresses the peeling of the cured product in the development process. As the adhesion aid, a functional silane coupling agent having a reactive functional group can preferably be used. Examples of the reactive functional group of the functional silane coupling agent include a carboxy group, a (meth)acryloyl group, an epoxy group, a vinyl group, an isocyanate group, and the like.

[0094] Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, and the like.

[0095] When the present composition contains an adhesion aid, its content is preferably 0.01 part by mass or more and 4 parts by mass or less, and more preferably 0.1 part by mass or more and 2 parts by mass or less, based on 100 parts by mass of compound (A) contained in the present composition.

[0096] This composition can be obtained by mixing a compound (A), a photopolymerization initiator, a compound (C), and other optionally blended components in a predetermined ratio. The composition obtained by mixing each component may be filtered, for example, through a filter with a pore size of 0.5 μm or less.

[0097] The solid content concentration of this composition (that is, the proportion of the total mass of components other than the solvent in the radiation-sensitive composition to the total mass of the radiation-sensitive composition) is appropriately selected in consideration of viscosity, volatility, etc. The solid content concentration of this composition is preferably in the range of 1 to 60% by mass. When the solid content concentration is 1% by mass or more, it is preferable in that a sufficient film thickness of the coating film can be ensured when this composition is applied on a substrate. Also, when the solid content concentration is 60% by mass or less, it is preferable in that the film thickness of the coating film does not become too large, and furthermore, the viscosity of this composition can be moderately increased to ensure good coatability. The solid content concentration in this composition is more preferably 2 to 50% by mass, and still more preferably 5 to 40% by mass.

[0098] The content of the polymerizable compound in this composition (that is, the total amount of compound (A) and compound (C)) is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, and still more preferably 85 parts by mass or more with respect to 100 parts by mass of the total amount of the solid content (components other than the solvent) contained in this composition, from the viewpoints of improving sensitivity and obtaining a good lens shape by thermal flow.

[0099] [Method for manufacturing the first lens] A microlens can be manufactured by using the radiation-sensitive composition prepared as described above. In particular, this composition is suitable as a negative-type pattern-forming material in which a part of the organic film formed by the radiation-sensitive composition is exposed, and the unexposed part of the organic film after exposure is dissolved in an alkaline developer to form a pattern (that is, a cured product formed by the radiation-sensitive composition), and the pattern is fluidized by heat treatment to form a lens shape. Hereinafter, each step (steps (I) to (IV)) in the method for manufacturing the first lens of the present disclosure will be described.

[0100] <Process (I): Coating Process> Process (I) is a process of forming a coating film on a substrate by applying the present composition onto the substrate. Examples of the substrate include a glass substrate, a silicon wafer, a plastic substrate, a plastic film, and a substrate having a colored resist, an overcoat, an antireflection film, various metal thin films, a sealing film, etc. formed on the surface thereof. Examples of the plastic substrate and the plastic film include resin substrates and films made of plastics such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethersulfone, polycarbonate, and polyimide. Various elements (for example, a light-receiving element such as a photodiode or a light-emitting element such as an organic light-emitting diode) may be provided in advance on these substrates.

[0101] As a method for applying the present composition, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coat method), a slit die coating method, a bar coating method, an inkjet method, etc. can be adopted. Among these coating methods, the spin coat method, the bar coating method, and the slit die coating method are preferable.

[0102] After applying the present composition onto the substrate, a treatment (pre-baking) for pre-heating the present composition may be performed for the purpose of preventing liquid dripping, etc. The pre-baking conditions can be appropriately set according to the types and usage ratios of the respective components. The pre-baking conditions can be, for example, conditions of 60 to 130°C for about 30 seconds to 10 minutes. The film thickness of the formed coating film is preferably 0.1 to 20 μm, more preferably 0.2 to 15 μm, as the value after pre-baking.

[0103] <Process (II): Exposure Process> Step (II) is a step of irradiating part of the coating film formed in Step (I) with radiation. Due to this radiation irradiation, a curing reaction proceeds in the exposed part, and a cured product in which the exposed part is cured is obtained. The radiation irradiation on the coating film in Step (II) is carried out through a mask having a pattern (for example, a dot pattern) for obtaining a microlens having a desired shape. The mask may be a multi-tone mask such as a half-tone mask or a gray-tone mask.

[0104] Examples of the radiation irradiated on the coating film include ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, etc. Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), KrF excimer laser light (wavelength 248 nm), etc. Examples of the X-rays include synchrotron radiation, etc. Examples of the charged particle beams include electron beams, etc. Among these, the radiation irradiated on the coating film is preferably ultraviolet rays, and more preferably ultraviolet rays with a wavelength of 200 nm or more and 380 nm or less. Examples of the light source to be used include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. The exposure amount of the radiation is 500 J / m 2 ~50,000 J / m 2 (50~500 mJ / cm 2 ) is preferable.

[0105] <Step (III): Development 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 step, the unexposed part of the coating film formed on the substrate is removed, and a pattern in which the exposed part remains (more specifically, an uneven pattern formed by a large number of regularly arranged minute cured products) can be formed on the substrate. The minute cured products are, for example, substantially rectangular in cross section.

[0106] Examples of the developer include an aqueous solution of an alkali (basic compound). Examples of the aqueous solution of an alkali 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-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonane, and the like. Further, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of an alkali, or adding a small amount of various organic solvents capable of dissolving the present composition may be used as the developer.

[0107] As the developing method, for example, an appropriate method such as a puddle method, a dipping method, a rocking immersion method, or a shower method can be adopted. The developing time may be appropriately adjusted according to the composition of the present composition. The developing time is, for example, 20 seconds to 120 seconds.

[0108] <Step (IV): Heating step> Step (IV) is a step of heating the pattern after development to form the fine cured product on the substrate into a lens shape by thermal flow. By the heat treatment in Step (IV), for example, further curing of the present composition is performed while thermally flowing a pattern composed of fine cured products having a substantially rectangular cross section. Thereby, a microlens array in which hemispherical fine cured products are regularly arranged on the substrate can be obtained. The heat treatment can be performed using a heating device such as an oven or a hot plate.

[0109] From the perspective of making it applicable to the high refractive index material of the organic electroluminescence device, the heating temperature in step (IV) is preferably 100 °C or lower, more preferably 95 °C or lower, and still more preferably 90 °C or lower. Also, from the perspective of obtaining a microlens with high heat resistance, chemical resistance, and good shape, the heating temperature in step (IV) is preferably 60 °C or higher, more preferably 80 °C or higher. The heating time can be appropriately set according to the type of heating device and the like. For example, when heating is performed using a hot plate, the heating time is, for example, 5 to 60 minutes. Also, when heating is performed using an oven, the heating time is, for example, 10 to 90 minutes. In step (IV), a step-bake method in which multiple heat treatments are performed can also be used.

[0110] The manufacturing method of the present disclosure may further include the following step (V) as an optional step. (V) A step of irradiating the lens obtained by the step (IV) above with radiation (hereinafter, also referred to as the "post-exposure step")

[0111] <Step (V): Post-exposure step> Step (V) is a step of further irradiating at least a part of the developed coating film with radiation. By irradiating the radiation in step (V) (hereinafter, also referred to as "post-exposure"), heat resistance, chemical resistance, etc. can be further improved, and a highly reliable cured product can be obtained. Specific examples of post-exposure include (1) a method of irradiating radiation to the coating film after the development step and before the heating step (that is, the pattern before thermal flow), and (2) a method of irradiating radiation to the coating film after the heating step (that is, the lens after thermal flow). Among these, from the perspective of preferably realizing thermal flow at a low temperature, the method of (2), that is, irradiating radiation to the lens formed by heating the pattern, is preferable. Regarding the type of radiation and exposure conditions in post-exposure, the same conditions as in step (II) can be adopted. Note that the conditions such as the wavelength, irradiation amount, and light source of the irradiation light during post-exposure may be the same as or different from those in step (II).

[0112] The microlens thus obtained has a good lens shape. The diameter of the microlens is, for example, 1 μm or more and 100 μm or less. Further, the microlens obtained by the present composition is excellent in heat resistance and chemical resistance and also has high transparency. Therefore, the microlens of the present disclosure can be suitably used as the microlens of a solid-state imaging device provided in an imaging device such as a camera, or the microlens of various display elements such as an organic EL element and a liquid crystal display element. In particular, according to the present composition, a lens shape can be formed even when thermal flow is performed at a low temperature of 100° C. or lower. Therefore, it is particularly suitable for a microlens for manufacturing an organic EL element that requires application of a low-temperature process.

[0113] [Method for manufacturing the second lens] The method for manufacturing the second lens includes a step of forming a pattern by inkjet coating a radiation-sensitive composition on a substrate. In the method for manufacturing the second lens, a spherical lens-shaped pattern may be directly formed on the substrate by inkjet coating. Alternatively, a pattern may be formed on the substrate by inkjet coating, and then the pattern may be heated and melted in the same manner as in the method for manufacturing the first lens to form a lens shape. Specifically, for the latter method, instead of steps (I), (II), and (III) in the method for manufacturing the first lens, it includes a step of forming a pattern by inkjet coating, and by applying step (IV) in the method for manufacturing the first lens to the pattern formed by this step in the same manner, a hemisphere can be formed and the lens can be manufactured. That is, the method for manufacturing the second lens may include a step of forming a pattern by inkjet coating a radiation-sensitive composition on a substrate and a step of heating the pattern formed by inkjet coating to form a lens.

[0114] [Radiation-sensitive composition for forming a planarization film] The radiation-sensitive composition for forming a planarization film of the present disclosure is a curable composition containing the above-described components (A), (B), and (C). As described above, the cured product formed from the curable composition has a high refractive index and high reliability in terms of heat resistance and the like. Further, by heating the pattern after development at a low temperature, it can sufficiently flow thermally, and a cured film excellent in surface planarization can be obtained. Therefore, the radiation-sensitive composition of the present disclosure is suitable as a composition for forming a planarization film provided in an organic EL element or a liquid crystal display element. The above description applies to the types and contents of the components (A), (B), (C), and the components optionally blended included in the radiation-sensitive composition for forming a planarization film of the present disclosure. Further, the planarization film can be manufactured by a method including steps (I) to (IV) in the same manner as the method for manufacturing the first lens described above. The method may further include the above step (V). Further, the planarization film can also be manufactured by the same method as the method for manufacturing the second lens described above.

[0115] The above-described radiation-sensitive composition of the present disclosure is applied onto a substrate, and a coating film having a film thickness of 5.0 μm is obtained by performing preheating (pre-baking) at 85° C. for 2 minutes. After irradiating this coating film with radiation of 200 mJ / cm 2 in terms of i-line conversion, a cured product having a refractive index of 1.60 or more can be obtained by heating (post-baking) at 100° C. for 40 minutes. According to the radiation-sensitive composition of the present disclosure, under the above conditions, a cured film having a high refractive index, preferably 1.62 or more, more preferably 1.64 or more, can also be obtained.

[0116] According to the present disclosure shown above, the following means are provided.

[0117] [Means 1] A step of applying a radiation-sensitive composition onto a substrate to form a coating film, a step of irradiating a part of the coating film with radiation, a step of developing the coating film irradiated with radiation to form a pattern on the substrate, and a step of heating the pattern to form a lens, wherein the radiation-sensitive composition is (A) component: a compound represented by the above formula (1), (B) component: a photopolymerization initiator, and (C) Component: A method for manufacturing a lens, which contains a compound having a polymerizable carbon-carbon unsaturated bond (however, excluding the (A) component). [Means 2] The method for manufacturing a lens according to [Means 1], wherein the content of the (C) component is 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the (A) component. [Means 3] The method for manufacturing a lens according to [Means 1] or [Means 2], wherein the (C) component contains a compound (C1) having 1 or 2 polymerizable carbon-carbon unsaturated bonds in one molecule in an amount of 50% by mass or more based on the total amount of the (C) component. [Means 4] The above R 7 is a group having one or more heteroatoms selected from the group consisting of a sulfur atom, a nitrogen atom, and a phosphorus atom, or a group having a monocyclic aromatic hydrocarbon ring, a condensed polycyclic aromatic hydrocarbon ring, or an aliphatic hydrocarbon ring. The method for manufacturing a lens according to any one of [Means 1] to [Means 3]. [Means 5] The above R 7 is represented by the above formula (y-1), formula (y-2), formula (y-3), or formula (y-4). The method for manufacturing a lens according to any one of [Means 1] to [Means 4]. [Means 6] The method for manufacturing a lens according to any one of [Means 1] to [Means 5], wherein the temperature for heating the pattern is 100 °C or lower. [Means 7] The method for manufacturing a lens according to any one of [Means 1] to [Means 6], wherein the (C) component is a compound having a molecular weight of less than 600. [Means 8] The (A) component is such that Ar 1 and Ar 2 have a condensed polycyclic aromatic hydrocarbon ring, or R 1 and R 2 are combined with each other to form a condensed ring structure together with Ar 1 and Ar 2 The method for manufacturing a lens according to any one of [Means 1] to [Means 7]. [Means 9] The method for manufacturing a lens according to any one of [Means 1] to [Means 8], further including a step of irradiating radiation to the lens formed by heating the pattern. [Means 10] A method for manufacturing a lens according to any one of [Means 1] to [Means 9], further containing a polymer having a molecular weight of 2,000 or more and 100,000 or less as the (D) component. [Means 11] A method for manufacturing a lens according to [Means 10], wherein the content of the (D) component is 50 parts by mass or less with respect to 100 parts by mass of the (A) component. [Means 12] (A) component: A compound represented by the above formula (1), (B) component: A photoinitiator, and (C) component: A radiation-sensitive composition for lens production by a thermal flow method, containing a compound having a polymerizable carbon-carbon unsaturated bond (excluding the (A) component). [Means 13] A display element including a lens formed using the radiation-sensitive composition for lens production according to [Means 12]. [Means 14] (A) component: A compound represented by the above formula (1), (B) component: A photoinitiator, and (C) component: A radiation-sensitive composition for planarization film formation, containing a compound having a polymerizable carbon-carbon unsaturated bond (excluding the (A) component). [Means 15] A display device including the display element according to [Means 13] or a planarization film formed using the radiation-sensitive composition for planarization film formation according to [Means 14]. [Means 16] A solid-state imaging device including a lens formed using the radiation-sensitive composition for lens production according to [Means 12]. [Means 17] An imaging device including the solid-state imaging device according to [Means 16]. [Means 18] A compound represented by the above formula (1). [Means 19] A method for manufacturing a lens, including a step of inkjet-applying a radiation-sensitive composition onto a substrate to form a pattern, wherein the radiation-sensitive composition (A) component: A compound represented by the above formula (1), (B) component: A photoinitiator, and (C) component: A radiation-sensitive composition for lens production, containing a compound having a polymerizable carbon-carbon unsaturated bond (excluding the (A) component).

Example

[0118] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples. In the examples and comparative examples, "parts" and "%" are based on mass unless otherwise specified. The weight average molecular weight (Mw) of the compound was a polystyrene conversion value measured by gel permeation chromatography (GPC) under the following conditions. Column: TSKgel GRC XLII manufactured by Tosoh Corporation Solvent: Tetrahydrofuran Temperature: 40 °C Pressure: 68 kgf / cm 2

[0119] The abbreviations of the compounds used in the examples and comparative examples are as follows. BNFGA: Acrylic acid adduct of 9,9-bis(6-glycidyloxy-2-naphthyl)fluorene, a compound obtained by synthesis according to the description in Patent No. 6175259 (molecular weight = 706.79) PGMEA: Propylene glycol monomethyl ether acetate CPN: Cyclopentanone TPP: Triphenylphosphine (3-1) to (3-16): Compounds represented by the following formulas (3-1) to (3-16)

Chemical formula

Chemical formula

Chemical formula

[0120] 1. Synthesis of compounds <Synthesis of BHXFGA> BHXFGA was synthesized according to the following scheme.

Chemical formula

[0121] ·Synthesis of BHXFG Dissolve 54 g (0.1 mol) of BHXF in 73.3 g (0.8 mol) of chloromethyloxirane, add 1.7 g of benzyltriethylammonium chloride, and stir at 60 °C for 1 hour. Next, while under reduced pressure (650 mmHg), add 25 g of a 40% aqueous sodium hydroxide solution dropwise over 1.5 hours at 45 °C. During this time, the water generated was removed from the system by azeotropy with chloromethyloxirane, and the distilled chloromethyloxirane was returned to the system. After the dropping was completed, the reaction was continued for another 3 hours. Then, the salt formed was removed by filtration, washed with water, and then chloromethyloxirane was distilled off until the solid content reached 50%. Then, 250 g of methanol was added. The precipitated crystals were filtered off and dried to obtain BHXFG as a white powder.

[0122] ·Synthesis of BHXFGA Charge 23.8 g (0.05 mol) of BHXFG, 7.2 g (0.1 mol) of acrylic acid, 3.6 g, 0.06 g of 4-methoxyphenol, 0.10 g of tetraethylammonium bromide, and 19.8 g of CPN into a flask, react at 120 °C for 7 hours, and leave it to cool to room temperature to obtain a cyclopentanone solution of BHXFGA with a solid content concentration of 61%.

[0123] <Synthesis of [A] Compound> [Synthesis Example 1] Synthesis of (A-1) Add 7.07 g (10 mmol) of BNFGA, PGMEA (in an amount such that the ratio of the total mass of BNFGA and (3-1) to the total mass of BNFGA, (3-1), and PGMEA is 68%), 3.08 g (20 mmol) of (3-1), 10 mg (0.1% based on the total mass of BNFGA and (3-1)) of 4-methoxyphenol, and 0.52 g (0.1 mmol) of TPP to a 100 mL three-necked flask equipped with a reflux condenser and a thermometer, and react at 120 °C for 2 hours and at 70 °C for 6 hours. As a result, a light brown solution containing a compound with Mw of 1,200 (designated as (A-1)) was obtained.

[0124] [Synthesis Examples 2 to 20] Synthesis of (A-2) to (A-20) Synthesis was carried out in the same manner as in Synthesis Example 1 with the composition shown in Table 1 to obtain solutions each containing a compound with Mw shown in Table 1 (each compound is designated as (A-2) to (A-20)). Note that Mw is a value expressed by rounding the tens digit in consideration of the accuracy of GPC (the same applies to the Mw of the compounds obtained in Synthesis Examples 21 to 25). The amount of the solvent in Table 1 represents the ratio (%) of the total mass of the precursor and the acid anhydride to the total mass of the precursor, the acid anhydride, and the solvent.

[0125] [Synthesis Example 21] Synthesis of (A-21) To a 100 mL three-necked flask equipped with a reflux condenser and a thermometer, 10.2 g (10 mmol) of the cyclohexanone solution of BHXFGA obtained above, CPN (in an amount such that the ratio of the total mass of BHXFGA and (3-1) to the total mass of BHXFGA, (3-1), and CPN is 50%), 3.08 g (20 mmol) of (3-1), 10 mg (0.1% based on the total mass of BHXFGA and (3-1)) of 4-methoxyphenol, and 0.52 g (0.1 mmol) of TPP were added, and the reaction was carried out at 120 °C for 2 hours and at 70 °C for 6 hours. As a result, a light brown solution of a compound with Mw of 1,000 (this is designated as (A-21)) was obtained.

[0126] [Synthesis Example 22] Synthesis of (A-22) In Synthesis Example 21, the modification reaction was carried out in the same manner except that 20 mmol of (3-8) was used instead of (3-1). As a result, a light brown solution of a compound with Mw of 1,000 (this is designated as (A-22)) was obtained.

[0127]

Table 1

[0128] [Synthesis Example 23] Synthesis of (D-1) Into a flask equipped with a cooling tube and a stirrer, 4 parts by mass of 2,2'-azobisisobutyronitrile and 190 parts by mass of propylene glycol monomethyl ether acetate were charged, and subsequently, 55 parts by mass of methacrylic acid, 45 parts by mass of benzyl methacrylate, and 2 parts by mass of α-methylstyrene dimer as a molecular weight regulator were charged. While gently stirring, the temperature of the solution was raised to 80 °C, and after maintaining the temperature after the temperature rise for 4 hours, it was raised to 100 °C, and the temperature after the temperature rise was maintained for 1 hour to effect polymerization, thereby obtaining a solution containing a copolymer. Next, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing this copolymer, and after stirring at 90 °C for 30 minutes under an air atmosphere, 74 parts by mass of glycidyl methacrylate was added and reacted at 90 °C for 10 hours to obtain a methacrylic acid-modified acrylic resin (designated as (D-1)) (solid content concentration = 35.0%). The Mw measured by GPC of (D-1) was 9,000.

[0129] [Synthesis Example 24] Synthesis of (A-24) Into a 100 mL three-necked flask equipped with a thermometer and a dropping funnel, 7.07 g (10 mmol) of BNFGA, 9.4 g of tetrahydrofuran, PGMEA (an amount such that the ratio of the total mass of BNFGA and (3-16) to the total mass of BNFGA, (3-16), and PGMEA is 50%), 10 mg of 4-methoxyphenol (0.1% based on the total mass of BNFGA and (3-16)), and 2.46 g (15 mmol) of (3-16) were added. Then, 1.67 g (16.5 mmol) of triethylamine was added dropwise through the dropping funnel, and the mixture was stirred at 50 °C for 1 hour. After completion of the reaction, 50 mL of tetrahydrofuran and 50 mL of ethyl acetate were added, 50 mL of a saturated aqueous sodium bisulfate solution was added for liquid separation, and then the mixture was separated and washed three times with water. Next, 9.5 g of PGMEA was added, and the mixture was concentrated to about 19 g. This operation was repeated twice to obtain a colorless and transparent PGMEA solution of (A-24) with a solid content concentration of 50% and an Mw of 1,100.

[0130] [Synthesis Example 25] Synthesis of (A-25) Synthesis was carried out in the same manner as in Synthesis Example 24 except that the amount of the acid anhydride was changed to the amount shown in Table 2, and a PGMEA solution containing a compound with Mw of 1,000 ((A-25)) was obtained.

[0131]

Table 2

[0132] 2. Preparation of Radiation-Sensitive Resin Composition The [B] photoinitiator, [C] compound, [D] additive, and [E] solvent used in the preparation of the radiation-sensitive resin composition are shown below.

[0133] [B] Photoinitiator B-1: 1,2-Octanedione-1-[4-(phenylthio)-2-(O-benzoyloxime)] (Irgacure OXE01, manufactured by BASF) B-2: 2-Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (Irgacure 907, manufactured by BASF) B-3: Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide B-4: 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone

[0134] [C] Compound C-1: Benzyl acrylate C-2: Divinylbenzene C-3: Phenoxybenzyl acrylate C-4: Pentaerythritol tetraacrylate C-5: Dipentaerythritol hexaacrylate C-6: Tris(2-acryloyloxyethyl) isocyanurate

[0135] [D] Additive (polymer additive) D-1: Methacrylic-modified acrylic resin (polymer obtained by Synthesis Example 23) D-2: Fluorene resin (photosensitive resin described in Example 2 (paragraph 0071) of International Publication No. 2009 / 119622) [Chemical formula] D-3: Cresol novolak type epoxy acrylate resin "CCR-1235" (manufactured by Nippon Kayaku Co., Ltd.)

[0136] [E] Solvent E-1: Propylene glycol monomethyl ether acetate (PGMEA) E-2: Cyclopentanone (CPN)

[0137] [Example 1] [A] A solution containing 100 parts by mass (solid content) of (A-1) as a compound, [B] 5 parts by mass of (B-1) as a photopolymerization initiator, and [C] 20 parts by mass of (C-1) and 10 parts by mass of (C-4), 0.5 parts by mass of an adhesion aid (3-glycidyloxypropyltrimethoxysilane), and 0.2 parts by mass of a surfactant ("FTX-218" manufactured by Neos Co., Ltd.) were mixed, and then [E] (E-1) as a solvent was added so that the solid content concentration became 35% by mass, followed by stirring and dissolving. Next, the mixture was filtered through a membrane filter with a pore size of 0.2 μm to prepare the radiation-sensitive resin composition of Example 1.

[0138] [Examples 2 to 24 and Comparative Examples 1 and 2] [A] The types of the compound and [E] the solvent, and the types and compounding amounts (parts by mass) of [B] the photopolymerization initiator, [C] the compound, and [D] the additive were made the same as those shown in Table 3, respectively, and the radiation-sensitive resin compositions of Examples 2 to 24 and Comparative Examples 1 and 2 were prepared in the same manner as in Example 1. In Table 3, the compounding amount of [A] the compound is 100 parts by mass. The numerical values of [B] the photopolymerization initiator, [C] the compound, and [D] the additive indicate the compounding ratio (parts by mass) of each compound with respect to 100 parts by mass of [A] the compound used in the preparation of each radiation-sensitive resin composition.

[0139] [Table 3]

[0140] 3. Evaluation of Radiation-Sensitive Resin Composition The characteristics of the radiation-sensitive resin compositions prepared in Examples 1 to 24 and Comparative Examples 1 and 2 were evaluated as follows. The evaluation results are shown in Table 4.

[0141] [Evaluation of Refractive Index] The radiation-sensitive resin composition was applied onto a soda-lime glass substrate using a spinner, and then pre-baked on a hot plate at 85°C for 2 minutes to form a coating film with a film thickness of 5.0 μm. Next, the obtained coating film was irradiated with radiation using a high-pressure mercury lamp (SUSS) at an exposure dose of 200 mJ / cm 2 . Then, a cured film was formed by post-baking in an oven at 100°C for 40 minutes. The refractive index of the obtained cured film at 589 nm was measured using a prism coupler and evaluated according to the following evaluation criteria. Good (◎): Refractive index ≧ 1.64 Fair (○): 1.64 > Refractive index ≧ 1.60 Poor (×): 1.60 > Refractive index

[0142] [Evaluation of Patterning Characteristics] Each radiation-sensitive resin composition was applied onto a soda-lime glass substrate using a spinner, and then pre-baked on a hot plate at 85°C for 2 minutes to form a coating film with a film thickness of 5.0 μm. Next, the obtained coating film was irradiated with radiation through a photomask having a plurality of circular remaining patterns with different sizes (in 1-μm increments) in the range of 8 to 25 μm in diameter, using a high-pressure mercury lamp, with the exposure dose varied in the range of 200 to 1,000 mJ / cm 2 in 100 mJ / cm 2 increments. Thereafter, development was carried out for 60 seconds at 25°C by the liquid puddle method using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23°C as the developer, followed by pure water washing for 60 seconds. Then, it was dried to form a pattern composed of a plurality of fine bodies formed from the radiation-sensitive resin composition on the glass substrate (see Fig. 1(a)). After development, the substrate was observed with an optical microscope, and the patterning characteristics were evaluated according to the following evaluation criteria. When there is no residue on the substrate and almost no pattern peeling is observed: "○" When a small amount of residue or pattern peeling is observed on the substrate: "△" When residue is observed on most of the substrate or the pattern is peeled off and almost no pattern remains on the substrate: "×"

[0143] [Evaluation of lens shape] On a non-alkali glass substrate, after each radiation-sensitive resin composition was applied by a spinner, pre-baking was performed on a hot plate at 85 °C for 2 minutes to form a coating film with a film thickness of 5.0 μm. Next, the obtained coating film was irradiated with radiation through a photomask having a plurality of circular remaining patterns with a diameter of 25 μm using a high-pressure mercury lamp with an exposure amount of 200 mJ / cm 2 ². Then, using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide at 23 °C as a developer, development was carried out for 60 seconds at 25 °C by the puddle method, followed by pure water washing for 60 seconds. Then, it was dried to form a pattern composed of a large number of minute cured products formed from the radiation-sensitive resin composition on the glass substrate (see Fig. 1(a)). Further, post-baking was performed in an oven at 85 °C for 40 minutes, and a lens pattern in which a large number of microlenses were regularly arranged was formed on the substrate due to the thermal flow of each minute cured product. Then, the substrate before and after post-baking was observed by SEM. As shown in Fig. 1(b), if a hemispherical lens can be formed by the thermal flow due to post-baking, it is evaluated as "○", if partial thermal flow occurs but the lens shape is trapezoidal when viewed from the side, it is evaluated as "△", and if the thermal flow is insufficient and the shape does not change (that is, when it remains rectangular when viewed from the side as shown in Fig. 1(a)), it is evaluated as "×". For the examples evaluated as "×" in [Evaluation of patterning characteristics], since lenses could not be formed, they were denoted as "-" in Table 4.

[0144] [Evaluation of heat resistance] The substrate having the lens pattern obtained in the above [Evaluation of lens shape] was heated on a hot plate at 120 °C for 30 minutes. If there was no change in the shape of the lens after heating, it was evaluated as "○". If the thermal flow further progressed by additional heating and the lens shape changed although the hemispherical shape was maintained, it was evaluated as "△". If the thermal flow further progressed by additional heating and the lens did not form a hemispherical shape, it was evaluated as "×". In addition, for the examples evaluated as "×" in the [Evaluation of patterning properties], since the lens could not be formed, it was denoted as "-" in Table 4.

[0145]

Table 4

[0146] As shown in Table 4, according to the radiation-sensitive resin compositions of Examples 1 to 24, the evaluations of refractive index, patterning property, lens shape, and heat resistance were "◎", "○", or "△", and the balance of various properties was achieved even when the lens was formed by thermal flow at a low temperature. Among these, when comparing Example 1 and Example 24 using the same type of [A] compound, Example 1 with a sufficiently large content of [C] compound had improved patterning property and heat resistance. Further, when comparing Example 1 using a compound (C1) having 1 or 2 functional groups and a compound having 3 or more functional groups as the [C] compound with Example 23 using only a compound having 3 or more functional groups, Example 1 containing compound (C1) had improved refractive index, patterning property, and lens shape. On the other hand, in Comparative Examples 1 and 2 using a fluorene compound (BNFGA, BHXFGA) not modified with a carboxylic anhydride instead of the compound (Compound (A)) represented by the above formula (1), although the evaluation of refractive index was good, the patterning property was evaluated as "×".

[0147] [Example 25] By performing the same treatment as the above [Evaluation of lens shape] using the radiation-sensitive resin composition of Example 24, a substrate having a lens pattern was obtained. To this lens pattern, further 300 mJ / cm 2Post-exposure was carried out with the exposure amount described above. Subsequently, when the same evaluation as the above [Evaluation of heat resistance] was carried out, the evaluation of heat resistance was "○". From this result, it was found that the heat resistance of the film can be further improved by performing post-exposure.

[0148] [Examples 26, 27] [A] The type of the compound and [E] the type of the solvent, and the types and blending amounts (parts by mass) of [B] the photopolymerization initiator, [C] the compound, and [D] the additive were the same as those shown in Table 5, respectively, and each radiation-sensitive resin composition of Examples 26 and 27 was prepared in the same manner as in Example 1. In Table 5, the blending amount of [A] the compound is 100 parts by mass. The numerical values of [B] the photopolymerization initiator, [C] the compound, and [D] the additive indicate the blending ratio (parts by mass) of each compound with respect to 100 parts by mass of [A] the compound used for the preparation of each radiation-sensitive resin composition.

[0149]

Table 5

[0150] In addition, the evaluation of the characteristics of each radiation-sensitive resin composition of Examples 26 and 27 was carried out in the same manner as in Examples 1 to 24 and Comparative Examples 1 and 2. The evaluation results are shown in Table 6.

[0151]

Table 6

[0152] As shown in Table 6, according to the radiation-sensitive resin compositions of Examples 26 and 27, the evaluations of the refractive index, patterning property, lens shape, and heat resistance were "◎" or "○", and the balance of various properties was achieved even when the lens was formed by thermal flow at a low temperature.

[0153] From the above results, it has become clear that according to the radiation-sensitive composition containing the compound (A) represented by the above formula (1), a photopolymerization initiator, and a compound (C) having a polymerizable carbon-carbon unsaturated bond, the pattern after exposure and development can be fluidized by heating at 100 ° C or lower, and a cured product having high heat resistance and a high refractive index can be obtained.

Claims

1. A step of applying a radiation-sensitive composition onto a substrate to form a coating film; exposing a portion of the coating to radiation; developing the irradiated coating to form a pattern on the substrate; heating the pattern at 100° C. or less to form lenses; A radiation-sensitive composition for use in a lens manufacturing method by a thermal flow system, comprising: Component (A): a compound represented by the following formula (1): Component (B): a photopolymerization initiator, and Component (C): A compound having a polymerizable carbon-carbon unsaturated bond and including a trifunctional or higher functional (meth)acrylic acid ester (excluding the component (A)). A radiation-sensitive composition for use in producing lenses by a thermal flow system, comprising: 【Chemistry 1】 (In formula (1), Ar １ and Ar ２ are each independently an aromatic ring group. １ and R ２ are each independently a monovalent substituent, or R １ and R ２ and are combined together to form Ar １ and Ar ２ The fused ring structure is a fused ring structure in which two aromatic rings are bonded together with a single bond, —O—, —S—, —NR ８ -, methylene group or ethylene group. ８ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ３ and R ４ are each independently a monovalent substituent. １ and X ２ are each independently a group represented by the following formula (1x): m1 and m2 are each independently an integer of 0 to 6; k1 and k2 are each independently an integer of 0 to 4; n1 and n2 are each independently an integer of 1 to 6. In the formula, R １ ~R ４ , X １ , X ２ When there are multiple R １ ~R ４ , X １ , X ２ are the same or different.) 【Chemistry 2】 (In formula (1x), R ５ is an alkanediyl group having 2 to 4 carbon atoms. ６ is a hydrogen atom or a methyl group. １ is a hydrogen atom or "-C(=O)-R ７ -COOH" group. ７ is a divalent organic group having 1 or more carbon atoms. １ At least one of the groups is "-C(=O)-R ７ -COOH". p is an integer of 0 to 4. When p is 2 or more, multiple R ５ are the same or different.)

2. 2 . The radiation-sensitive composition for producing a lens according to claim 1 , wherein an amount of the component (C) is 5 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the component (A).

3. 2. The radiation-sensitive composition for producing a lens according to claim 1, wherein the component (C) contains 50 mass% or more of a compound (C1) having 1 or 2 polymerizable carbon-carbon unsaturated bonds in one molecule, based on the total amount of the component (C).

4. The above R ７ is a group having one or more heteroatoms selected from the group consisting of a sulfur atom, a nitrogen atom, and a phosphorus atom, or is a group having a monocyclic aromatic hydrocarbon ring, a condensed polycyclic aromatic hydrocarbon ring, or an aliphatic hydrocarbon ring.

5. The above R ７ is represented by the following formula (y-1), formula (y-2), formula (y-3) or formula (y-4): 【Chemistry 3】 (In formula (y-1), Ar ３ R is a (r+2)-valent monocyclic aromatic hydrocarbon ring group, a condensed polycyclic aromatic hydrocarbon ring group, a nitrogen-containing heterocyclic group, a sulfur-containing heterocyclic group, or an aliphatic hydrocarbon ring group. １０ is a monovalent substituent. r is an integer of 0 to 5. When r is 2 or more, multiple R １０ In formula (y-2), Ar ４ and Ar ５ are each independently a nitrogen-containing heterocyclic group or a sulfur-containing heterocyclic group. ９ is a monovalent hydrocarbon group. ９ In formula (y-4), R １１ and R １２ are each independently an alkanediyl group. t is an integer from 1 to 3. When t is 2 or 3, multiple R １１ are the same or different. "*" represents a bond.)

6. The radiation-sensitive composition for producing a lens according to claim 1 , wherein the component (C) is a compound having a molecular weight of less than 600.

7. The component (A) is Ar in the above formula (1). １ and Ar ２ has a condensed polycyclic aromatic hydrocarbon ring, or R １ and R ２ and are combined together to form Ar １ and Ar ２ The radiation-sensitive composition for producing a lens according to claim 1 , which has a condensed ring structure constituted by the following formula:

8. Component (D): a polymer having a molecular weight of 2,000 or more and 100,000 or less The radiation-sensitive composition for producing a lens according to claim 1 , further comprising:

9. 9. The radiation-sensitive composition for producing a lens according to claim 8, wherein the content of the component (D) is 50 parts by mass or less per 100 parts by mass of the component (A).

10. A display element comprising a lens produced using the radiation-sensitive composition for producing a lens according to any one of claims 1 to 9.

11. A display device comprising the display element according to claim 10.

12. A solid-state imaging device comprising a lens produced using the radiation-sensitive composition for producing a lens according to any one of claims 1 to 9.

13. An imaging device comprising the solid-state imaging device according to claim 12.

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