Polymer, curable resin composition, cured product, solid-state imaging device, and image display device

Abstract

The present invention provides a new polymer from which a cured object having a high refractive index can be produced. The polymer according to the present invention is represented by general formula (1). (In the formula, X1 represents an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group including a heterocycle in which a portion of carbon atoms forming any one of said hydrocarbon groups is substituted with a heteroatom, or an organic group in which two or more of those are bound, the four R1s each independently represent hydrogen, a specific organic group A, a specific organic group B, or an organic group C having a specific repeating structural unit, and at least one of the four R1s is an organic group C.)

Description

[Technical field]

[0001] The present invention relates to a novel polymer, a curable resin composition containing the polymer, a cured product obtained from the curable resin composition, and a solid-state imaging device and an image display device each including the cured product. [Background technology]

[0002] 2. Description of the Related Art Transparent members are used as structural members of many devices such as various display devices, image pickup devices, and solar cells, as insulating films, protective films, light extraction layers, spacers, microlenses, and the like.

[0003] Furthermore, transparent members are used as members for adjusting the refractive index in order to improve the performance of devices, and transparent members with a high refractive index are in demand.

[0004] Transparent members with a high refractive index are used in solid-state imaging elements mounted in digital cameras, camera-equipped mobile phones, and the like. Representative solid-state imaging elements include charge coupled device (CCD) image sensors and complementary metal-oxide semiconductor (CMOS) image sensors. These image sensors are provided with microlenses or microlens arrays in which a large number of microlenses are regularly arranged on a substrate for the purpose of improving sensitivity, etc. These microlenses are required to have a high refractive index and high transparency.

[0005] For example, Patent Document 1 proposes a method for producing a microlens array, which includes a photosensitive layer forming step of providing a photosensitive layer made of a specific photosensitive resin composition on a substrate or a display element, an exposure step of irradiating a predetermined portion of the photosensitive layer with active light rays to photocure the exposed portion, a development step of removing the portion other than the exposed portion to form a pattern, and a heating step of heating the pattern. It also discloses that the refractive index of the microlenses obtained by this production method is 1.58 to 1.59.

[0006] Patent Document 2 proposes a method for producing a microlens, which includes the steps of: coating a support with a photosensitive composition containing a polymer (A) having a structural unit of a specific structure, a polymerizable compound (B), a photopolymerization initiator (C), and a solvent (D), removing the solvent (D), exposing the coating obtained by coating through a mask pattern corresponding to a target pattern, developing, irradiating the obtained pattern with ultraviolet light, and heating the pattern. It also discloses that the refractive index of the microlens obtained by this method is 1.58. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2011-002655 A [Patent Document 2] JP 2009-251537 A Summary of the Invention [Problem to be solved by the invention]

[0008] The microlenses described in Patent Document 1 and Patent Document 2 are manufactured using a negative photoresist, and have a relatively high refractive index for a microlens manufactured using a negative photoresist. However, there is an increasing demand for further improvement in sensor sensitivity, etc., and a cured product having an even higher refractive index is required. In addition, in the manufacturing methods of microlenses described in Patent Document 1 and Patent Document 2, a TMAH (tetramethylammonium hydroxide) aqueous solution, which has a relatively high development speed among alkaline developers, is used in the development process. However, in the manufacture of semiconductors, LCDs (Liquid Crystal Displays), and the like, dilute alkaline developers, such as potassium hydroxide and sodium carbonate, which have a relatively slow development speed, are often used. Therefore, when a cured product such as a microlens is mounted on these products or when a cured product such as a microlens is manufactured integrally with these products, the development time is extended if a dilute alkaline developer is used instead of TMAH, which may reduce productivity.

[0009] An object of the present invention is to provide a novel polymer capable of producing a cured product having a high refractive index. Another object of the present invention is to provide a novel polymer that can be developed in a short time even when a dilute alkaline developer is used, and can produce a cured film having a high refractive index. Another object of the present invention is to provide a curable resin composition containing the polymer, a cured product obtained from the curable resin composition, and a solid-state imaging device and an image display device containing the cured product. [Means for solving the problem]

[0010] As a result of intensive research aimed at solving the above problems, the present inventors have found that the above object can be achieved by using the following polymer and a curable resin composition containing the polymer, and have thus completed the present invention.

[0011] The present invention relates to a polymer represented by the following general formula (1). [ka] (In the formula, X 1 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group is substituted with a hetero atom, or an organic group in which two or more of these are bonded together, and four R 1 are each independently hydrogen, an organic group A represented by the following general formula (2-1) or (2-2), an organic group B represented by the following general formula (3), or an organic group C having one or more repeating structural units selected from the group consisting of repeating structural units represented by the following general formulas (4-1) and / or (4-2), repeating structural units represented by the following general formulas (5-1) and / or (5-2), repeating structural units represented by the following general formulas (6-1) and / or (6-2), repeating structural units represented by the following general formulas (7-1) and / or (7-2), repeating structural units represented by the following general formulas (8-1) and / or (8-2), and repeating structural units represented by the following general formulas (9-1) and / or (9-2), 1 At least one of the groups is the organic group C. [ka] (In the formula, R 2 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the hydroxyl group is bonded and the adjacent carbon atom. [ka] (In the formula, R 3 is an organic group having 15 or less carbon atoms. [ka] (In the formula, R 4 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom; X 2 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group are substituted with a hetero atom, or an organic group in which two or more of these are combined. [ka] (In the formula, R 5 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom; X 3 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group are substituted with a hetero atom, or an organic group in which two or more of these are combined. [ka] (In the formula, R 6 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom; R 7 is an organic group having 15 or less carbon atoms, and X 4 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group are substituted with a hetero atom, or an organic group in which two or more of these are combined. [ka] (In the formula, R 8 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom; X 5 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group are substituted with a hetero atom, or an organic group in which two or more of these are combined. [ka] (In the formula, R 9 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom; R 10 is an organic group having 15 or less carbon atoms, and X 6is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group are substituted with a hetero atom, or an organic group in which two or more of these are combined. [ka] (In the formula, R 11 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom; R 12 and R 13 are each independently an organic group having 15 or less carbon atoms, 7 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group are substituted with a hetero atom, or an organic group in which two or more of these are combined.

[0012] The organic group C preferably has one or more repeating structural units selected from the group consisting of repeating structural units represented by general formulae (4-1) and / or (4-2), repeating structural units represented by general formulae (5-1) and / or (5-2), and repeating structural units represented by general formulae (6-1) and / or (6-2).

[0013] The polymer preferably has a carboxy group.

[0014] R 2 , R 4 , R 5 , R 6 , R 8 , R 9 and the R 11 are preferably each independently an organic group containing a (meth)acryloyloxy group, an organic group containing an aromatic hydrocarbon group, an organic group containing an allyl group, an organic group containing a silyl group, or an organic group containing a cyclic ether group.

[0015] R 3 , R 7 , R 10 , R12 and the R 13 are preferably each independently an organic group containing a cyclic ether group, an organic group containing a (meth)acryloyloxy group, or an organic group containing an aromatic hydrocarbon group.

[0016] X 1 , the X 2 , the X 3 , the X 4 , the X 5 , the X 6 and the X 7 are preferably each independently an aromatic hydrocarbon group.

[0017] The polymer preferably contains, in one molecule, a total of 3 to 300 repeating structural units selected from the group consisting of repeating structural units represented by general formulas (4-1) and / or (4-2), repeating structural units represented by general formulas (5-1) and / or (5-2), repeating structural units represented by general formulas (6-1) and / or (6-2), repeating structural units represented by general formulas (7-1) and / or (7-2), repeating structural units represented by general formulas (8-1) and / or (8-2), and repeating structural units represented by general formulas (9-1) and / or (9-2).

[0018] The polymer preferably has an acid value of 20 to 120 mgKOH / g.

[0019] The polymer preferably has a double bond equivalent of 200 to 5,000.

[0020] The polymer preferably has a weight average molecular weight of 1,500 to 100,000.

[0021] The raw materials for the polymer preferably contain a tetracarboxylic acid and / or a tetracarboxylic dianhydride, a hydroxy group-containing compound, and an epoxy group-containing compound.

[0022] The present invention also relates to a curable resin composition containing at least the polymer, a polymerizable monomer, and a polymerization initiator.

[0023] The curable resin composition is preferably a negative photoresist material.

[0024] The present invention also relates to a cured product obtained from the curable resin composition.

[0025] The cured product is preferably a lens, a photospacer, a partition material, an interlayer insulating film material, a protective film material, an optical waveguide material, or a planarizing film material.

[0026] Furthermore, the present invention relates to a solid-state imaging device or an image display device comprising the cured product. Effect of the Invention

[0027] By using the polymer of the present invention, a cured product with a high refractive index can be produced due to its characteristic structure, and even if a dilute alkaline developer is used, a cured film with a high refractive index (for example, a microlens) that can be developed in a short time can be produced. In addition, the cured product obtained by using the polymer of the present invention has high transparency and good transparency even if it is thick. In addition, since the polymer of the present invention can be used as a negative resist polymer contained in a negative photoresist material, the resist material using the polymer of the present invention can easily be made thick and can form a pattern with good transparency.

[0028] When the polymer of the present invention has the organic group C having one or more repeating structural units selected from the group consisting of repeating structural units represented by the general formulae (4-1) and / or (4-2), repeating structural units represented by the general formulae (5-1) and / or (5-2), and repeating structural units represented by the general formulae (6-1) and / or (6-2), that is, when the polymer is a dendritic polymer (hyperbranched polymer) having many branching points in one molecule, the above-mentioned effects can be more excellent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] The polymer of the present invention is represented by the following general formula (1). [ka] (In the formula, X 1 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group is substituted with a hetero atom, or an organic group in which two or more of these are bonded together, and four R 1 are each independently hydrogen, an organic group A represented by the following general formula (2-1) or (2-2), an organic group B represented by the following general formula (3), or an organic group C having one or more repeating structural units selected from the group consisting of repeating structural units represented by the following general formulas (4-1) and / or (4-2), repeating structural units represented by the following general formulas (5-1) and / or (5-2), repeating structural units represented by the following general formulas (6-1) and / or (6-2), repeating structural units represented by the following general formulas (7-1) and / or (7-2), repeating structural units represented by the following general formulas (8-1) and / or (8-2), and repeating structural units represented by the following general formulas (9-1) and / or (9-2), 1 At least one of the groups is the organic group C. [ka] (In the formula, R 2 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the hydroxyl group is bonded and the adjacent carbon atom. [ka] (In the formula, R 3 is an organic group having 15 or less carbon atoms. [ka] (In the formula, R 4 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom; X2 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group are substituted with a hetero atom, or an organic group in which two or more of these are combined. [ka] (In the formula, R 5 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom; X 3 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group are substituted with a hetero atom, or an organic group in which two or more of these are combined. [ka] (In the formula, R 6 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom; R 7 is an organic group having 15 or less carbon atoms, and X 4 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group are substituted with a hetero atom, or an organic group in which two or more of these are combined. [ka] (In the formula, R 8 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom; X 5 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group are substituted with a hetero atom, or an organic group in which two or more of these are combined. [ka] (In the formula, R 9is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom; R 10 is an organic group having 15 or less carbon atoms, and X 6 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group are substituted with a hetero atom, or an organic group in which two or more of these are combined. [ka] (In the formula, R 11 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom; R 12 and R 13 are each independently an organic group having 15 or less carbon atoms, 7 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group are substituted with a hetero atom, or an organic group in which two or more of these are combined.

[0030] In the organic group C, each structure shown as a repeating structural unit has two types of structures. For example, the structures represented by the general formulas (4-1) and (4-2) can be selected depending on the starting material when the ester bond in the repeating structure is generated and the ring-opening direction during the ring-opening reaction of the cyclic compound. Specifically, if the structure is derived from an addition reaction between a carboxylic acid and an epoxy, it will be a structure of general formula (4-1) or formula (4-2) depending on the ring-opening direction. The ratio of general formula (4-1) or formula (4-2) varies depending on the reaction conditions, but generally both coexist. In addition, if it is derived from an addition reaction between an acid anhydride and an alcohol, it will be a structure of general formula (4-1). The same applies to the structures represented by other general formulas as the organic group C and the structures represented by general formulas (2-1) and (2-2) in the organic group A.

[0031] In the present invention, (meth)acrylic means acrylic or methacrylic, (meth)acryloyl means acryloyl or methacryloyl, (meth)acrylic acid means acrylic acid or methacrylic acid, and (meth)acrylate means acrylate or methacrylate, respectively. 2 ~R 13 When the group has a substituent, the number of carbon atoms in the group includes the number of carbon atoms in the substituent.

[0032] In the general formula (1), the X 1 ~X 7 are each independently an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a part of the carbon atoms constituting the hydrocarbon group is replaced with a heteroatom, or an organic group in which two or more of these are bonded. The aromatic hydrocarbon group is not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, a biphenyl ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a fluorene ring, an acenaphthylene ring, an acenaphthene ring, and an aromatic ring in which two or more of these are bonded. The alicyclic saturated hydrocarbon group and the alicyclic unsaturated hydrocarbon group are not particularly limited, and examples thereof include those having 6 to 20 carbon atoms constituting the ring, preferably those having 6 to 12 carbon atoms constituting the ring, and may be a bridged ring or a condensed ring. Examples of the heteroatom of the heterocycle include an oxygen atom, a nitrogen atom, and a sulfur atom, and may include one or more of these heteroatoms. The hydrocarbon group or the organic group may have various substituents (e.g., a halogen group, a hydroxy group, an amino group, an alkyl group, an alkenyl group, an alkoxy group, a silyl group, etc.) within the range that does not impair the effects of the present invention. 1 ~X 7 From the viewpoint of obtaining a cured film having a high refractive index, and from the viewpoint of obtaining a curable resin composition that can be developed in a short time even when a dilute alkaline developer is used, each of them is preferably an aromatic hydrocarbon group, and more preferably each independently is any of the following aromatic hydrocarbon groups: [ka]

[0033] In the general formula (1), the R 2 ~R 13 are each independently an organic group having 15 or less carbon atoms, preferably an organic group having 2 to 12 carbon atoms, and more preferably an organic group having 4 to 10 carbon atoms. 2 may form a ring together with the carbon atom to which the hydroxy group is bonded and the adjacent carbon atom. 4 , R 5 , R 6 , R 8 , R 9 and the R 11 may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom. Examples of the organic group include linear or branched aliphatic saturated or unsaturated hydrocarbon groups, alicyclic saturated or unsaturated hydrocarbon groups (including bridged rings and condensed rings), aromatic hydrocarbon groups (e.g., benzene ring, naphthalene ring, biphenyl ring, anthracene ring, and phenanthrene ring), organic groups in which a part of the carbon atoms constituting the hydrocarbon group is substituted with a heteroatom (e.g., oxygen atom, nitrogen atom, and sulfur atom), and organic groups in which two or more of these are bonded. The hydrocarbon group or the organic group may have various substituents (e.g., halogen group, hydroxy group, carboxy group, amino group, alkyl group, alkenyl group, alkoxy group, aryl group, acryloyloxy group, methacryloyloxy group, oxetanyl group, and silyl group) or functional groups (e.g., ester bond, amide bond, ether bond, thioether bond, urethane bond, and siloxane bond).

[0034] R 2 , R 4 , R 5 , R 6 , R 8 , R 9 and the R 11From the viewpoint of obtaining a cured film having a high refractive index, each of them is preferably an organic group containing a (meth)acryloyloxy group, an organic group containing an aromatic hydrocarbon group, an organic group containing an allyl group, an organic group containing a silyl group, or an organic group containing a cyclic ether group, more preferably an organic group containing a (meth)acryloyloxy group, or an organic group containing an aromatic hydrocarbon group, and even more preferably a (meth)acryloyloxymethyl group, or a phenoxymethyl group.

[0035] In addition, the organic group A represented by the general formula (2-1) or (2-2) is preferably any one of the following organic groups from the viewpoint of obtaining a cured film having a high refractive index and from the viewpoint of the hardness of the obtained cured film. In particular, from the viewpoint of increasing the hardness of the obtained cured film, the organic group A is preferably one having a crosslinkable group. From the viewpoint of increasing the refractive index of the obtained cured film, the organic group A is preferably one having an aromatic hydrocarbon group. [ka]

[0036] In addition, the R 4 , R 5 , R 6 , R 8 , R 9 and the R 11 From the viewpoint of obtaining a cured film having a high refractive index and from the viewpoint of the hardness of the obtained cured film, it is preferable that R is each independently any one of the following organic groups (note that in each of the general formulas above, 4 , R 5 , R 6 , R 8 , R 9 and the R 11 In particular, from the viewpoint of increasing the hardness of the obtained cured film, the above-mentioned R 4 , R 5 , R 6 , R 8 , R 9 and the R 11From the viewpoint of increasing the refractive index of the resulting cured film, the R 4 , R 5 , R 6 , R 8 , R 9 and the R 11 Preferably, the alkyl group has an aromatic hydrocarbon group. [ka]

[0037] R 3 , R 7 , R 10 , R 12 and the R 13 From the viewpoint of obtaining a cured film having a high refractive index, it is preferable that R each independently be an organic group containing a cyclic ether group, an organic group containing a (meth)acryloyloxy group, or an organic group containing an aromatic hydrocarbon group, and more preferably each independently be any of the following organic groups. In particular, from the viewpoint of increasing the hardness of the obtained cured film, 3 , R 7 , R 10 , R 12 and the R 13 From the viewpoint of increasing the refractive index of the resulting cured film, the R 3 , R 7 , R 10 , R 12 and the R 13 Preferably, the alkyl group has an aromatic hydrocarbon group. [ka]

[0038] In the general formula (1), from the viewpoint of obtaining a cured film that can be developed in a short time even when a dilute alkaline developer is used (hereinafter, referred to as the viewpoint of developability), it is preferable that the organic group C has one or more repeating structural units selected from the group consisting of repeating structural units represented by the general formulas (4-1) and / or (4-2), repeating structural units represented by the general formulas (5-1) and / or (5-2), and repeating structural units represented by the general formulas (6-1) and / or (6-2). In other words, it is preferable that the polymer represented by the general formula (1) is a dendritic polymer (hyperbranched polymer) having many branching points in one molecule.

[0039] In the general formula (1), four R 1 At least one of the R 1 Of these, preferably two or more R 1 is the organic group C, and more preferably, three or more R 1 is the organic group C, and more preferably all four R 1 is the organic group C.

[0040] From the viewpoint of developability, the polymer preferably contains 3 to 300 repeating structural units selected from the group consisting of the repeating structural units represented by the general formula (4-1) and / or (4-2), the repeating structural units represented by the general formula (5-1) and / or (5-2), the repeating structural units represented by the general formula (6-1) and / or (6-2), the repeating structural units represented by the general formula (7-1) and / or (7-2), the repeating structural units represented by the general formula (8-1) and / or (8-2), and the repeating structural units represented by the general formula (9-1) and / or (9-2) in total, more preferably 3 to 150, and even more preferably 3 to 100. The number of repeating structural units can be adjusted by the amount (ratio) of the raw materials used and the reaction conditions. The number of repeating structural units can be determined by the molecular weight of the raw materials used in the production of the polymer, the expected polymer structure, and the molecular weight of the polymer. A specific method for determining the number of repeating structural units will be described in the Examples below.

[0041] The polymer preferably has at least one carboxy group in its structure. Specifically, in the general formula (1), at least one R 1 is hydrogen, at least one of the organic groups A has a carboxy group, at least one of the organic groups B has a carboxy group, at least one of the organic groups C has a carboxy group, and combinations of these embodiments.

[0042] The terminal functional group of the organic group C is not particularly limited, and examples thereof include an organic group having a carboxy group at the terminal, an organic group having an ethylenically unsaturated group such as a (meth)acryloyloxy group at the terminal, an organic group having an aromatic hydrocarbon group at the terminal, and an organic group having a cyclic ether group at the terminal.

[0043] The method for producing the polymer is not particularly limited, and the polymer can be synthesized, for example, by polymerizing a monomer composition containing one or more epoxy group-containing compounds such as glycidyl (meth)acrylate and glycidyl phenyl ether, one or more hydroxy group-containing compounds, and tetracarboxylic acid and / or tetracarboxylic dianhydride. In detail, the hydroxy group of the hydroxy group-containing compound, which is a reaction initiator, reacts with the acid anhydride group of the tetracarboxylic dianhydride to generate an ester and a carboxy group, and the generated carboxy group and / or the carboxy group of the tetracarboxylic acid reacts with the epoxy group of the epoxy group-containing compound to further generate an ester, and a hydroxy group is generated at the same time, and the generated hydroxy group reacts with another acid anhydride group or carboxy group. The polymer is obtained by a successive reaction in which these reactions occur in sequence. In addition, the ring-opened free dibasic acid present in the tetracarboxylic dianhydride may react with the epoxy group. In the polymerization reaction, a catalyst such as an alkali metal compound, an organic phosphorus compound, a tertiary amine, a quaternary ammonium salt, a cyclic amine, or an imidazole may be used.

[0044] The weight average molecular weight of the polymer is not particularly limited, but from the viewpoint of developability, it is preferably 1500 to 100000, and more preferably 1500 to 50000. The weight average molecular weight is a value measured using gel permeation chromatography (GPC) in terms of polystyrene, and is a value measured in accordance with JIS 7252-4. The weight average molecular weights described in the examples below are also values ​​determined according to the description in this section.

[0045] The acid value of the polymer is not particularly limited, but from the viewpoint of developability, it is preferably from 20 to 120 mgKOH / g, and more preferably from 40 to 100 mgKOH / g.

[0046] The double bond equivalent of the polymer is not particularly limited, but can be, for example, 200 to 5000. In particular, when used for a microlens, the double bond equivalent of the polymer is preferably 500 to 4000, and more preferably 1000 to 3000, from the viewpoint of forming a good lens shape.

[0047] The curable resin composition of the present invention contains at least the polymer of the present invention, a polymerizable monomer, and a polymerization initiator. The polymerization initiator may be a photopolymerization initiator or a thermal polymerization initiator, and may be appropriately selected depending on the curing method.

[0048] The curable resin composition may contain a known alkali-soluble resin other than the polymer of the present invention. When the curable resin composition contains the polymer of the present invention and an alkali-soluble resin, the content of the polymer of the present invention is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, based on the total of the polymer and the alkali-soluble resin, from the viewpoint of developability.

[0049] The content ratio of the polymer of the present invention relative to the total solid content in the curable resin composition is not particularly limited, but from the viewpoint of developability, it is usually about 30 to 90 mass %, preferably 35 to 85 mass %, and more preferably 40 to 80 mass %.

[0050] The polymerizable monomer is not particularly limited, and examples thereof include monofunctional monomers such as nonylphenylcarbitol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-ethylhexylcarbitol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-vinylpyrrolidone, and ethoxylated-o-phenylphenol (meth)acrylate; polyfunctional aromatic vinyl monomers such as divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; (di)ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, and bisphenol A ethylene oxide adduct di(meth)acrylate. Polyfunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tris(hydroxyethyl)isocyanurate tri(meth)acrylate; and polyfunctional epoxy monomers such as bisphenol diglycidyl ether, phthalic acid diglycidyl ester, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, and triglycidyl isocyanurate. These polymerizable monomers may be used alone or in combination of two or more.

[0051] The content of the polymerizable monomer is not particularly limited, but from the viewpoint of fully obtaining the effects of the present invention, it is preferably 10 to 200 parts by mass, more preferably 20 to 150 parts by mass, and even more preferably 40 to 120 parts by mass relative to 100 parts by mass of the polymer of the present invention.

[0052] The photopolymerization initiator is not particularly limited, and examples thereof include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1,1-dichloroacetophenone; anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloro anthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; acylphosphine oxides, and xanthones. These photopolymerization initiators may be used alone or in combination of two or more kinds.

[0053] The content of the photopolymerization initiator is not particularly limited, but is preferably 0.3 to 8 parts by mass, more preferably 0.5 to 7 parts by mass, and even more preferably 1 to 6 parts by mass, relative to 100 parts by mass of the polymer of the present invention.

[0054] A photopolymerization initiator aid may be added to the curable resin composition. Examples of the photopolymerization initiator aid include trifunctional thiol compounds such as 1,3,5-tris(3-mercaptopropionyloxyethyl)-isocyanurate, 1,3,5-tris(3-mercaptobutyloxyethyl)-isocyanurate (manufactured by Showa Denko K.K., Karenz MT (registered trademark) NR1), and trimethylolpropane tris(3-mercaptopropionate); tetrafunctional thiol compounds such as pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko K.K., Karenz MT (registered trademark) PEI); and polyfunctional thiols such as hexafunctional thiol compounds such as dipentaerythritol hexakis(3-propionate). These photopolymerization initiator aids may be used alone or in combination of two or more.

[0055] Examples of the thermal polymerization initiator include organic peroxides such as cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexanoate, and t-amylperoxy-2-ethylhexanoate; and azo compounds such as 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl 2,2'-azobis(2-methylpropionate). These thermal polymerization initiators may be used alone or in combination of two or more.

[0056] The curable resin composition may contain a curable resin such as a radical polymerizable oligomer, such as an unsaturated polyester, an epoxy acrylate, a urethane acrylate, or a polyester acrylate; or an epoxy resin.

[0057] The curable resin composition may contain a solvent. Examples of the solvent include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform, dimethyl sulfoxide, and the like. These solvents may be used alone or in combination of two or more. The content of the solvent may be appropriately set according to the optimal viscosity when the composition is used.

[0058] The curable resin composition may contain known additives, such as fillers (e.g., aluminum hydroxide, talc, clay, barium sulfate, etc.), crosslinking agents, dyes, pigments, defoamers, coupling agents, leveling agents, sensitizers, release agents, lubricants, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, polymerization inhibitors, thickeners, and dispersants, within a range that does not impair the effects of the present invention.

[0059] The cured product of the present invention is obtained by curing the curable resin composition. Examples of the method for producing the cured product include a method in which the curable resin composition is injected into a molding die (resin die), or the curable resin composition is coated onto a base material (substrate) or various functional layers to form a desired shape, and then the curable resin composition is cured by heating or irradiating with light (e.g., ultraviolet light). The curing conditions are appropriately adjusted depending on the curable resin composition used.

[0060] The refractive index (wavelength 594 nm) of the cured product is 1.60 or more, and preferably 1.61 or more.

[0061] The cured product is suitably used as a lens (microlens), a photospacer, a partition material, an interlayer insulating film material, a protective film material, an optical waveguide material, or a planarizing film material, and is particularly suitably used as a microlens.

[0062] The method for producing a microlens is not particularly limited, and examples thereof include a method in which the curable resin composition is used to form a dot pattern consisting of rectangular dots and lattice-like spaces on a substrate, and then the dot pattern is heated to cause thermal flow to form a microlens pattern (such as a microlens array).

[0063] The substrate is not particularly limited as long as it is a substrate used as a target for forming a microlens pattern. An example of a suitable substrate is a substrate on which a solid-state imaging element, a first planarization film, a color filter, and a second planarization film are formed on a silicon substrate. In such a substrate, a first planarization film having a flat surface is formed so as to cover the solid-state imaging elements scattered at predetermined positions on the silicon substrate. A color filter is formed on the first planarization film at a position above the position of each solid-state imaging element. Then, a second planarization film having a flat surface is formed so as to cover the color filter. In the substrate, the direction from the silicon substrate to the second planarization film side is defined as an upward direction, and the direction from the second planarization film to the silicon substrate side is defined as a downward direction.

[0064] In order to form a microlens pattern on a substrate, first, a dot pattern is formed on the substrate using the curable resin composition. The method for forming the dot pattern is not particularly limited, and the dot pattern may be formed by a printing method such as an inkjet printing method, or may be formed by a photolithography method including patterning by exposure and development.

[0065] In the photolithography method, for example, a negative photolithography method can be suitably used in which a photomask is placed on the coating film of the curable resin composition, the coating film is photocured by irradiating it with ultraviolet light, an alkaline aqueous solution is sprayed onto the coating film after ultraviolet light irradiation, the unexposed parts are dissolved and removed, and the remaining exposed parts are washed with water and developed to form a dot pattern. Note that the polymer etc. of the present invention is not limited to use in the negative photolithography method, and can also be used in the positive photolithography method.

[0066] In the present invention, a cured product having a high refractive index (e.g., a microlens) can be produced by using the curable resin composition containing the polymer. In addition, the curable resin composition of the present invention can be developed in a short time even when a dilute alkaline developer (e.g., a developer having a pH of 11 or less) is used, so that a cured film having a high refractive index (e.g., a microlens) can be produced with good productivity. EXAMPLES

[0067] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples in any way.

[0068] Example 1 [Synthesis of polymer 1] In the general formula (1), X 1 is an organic group represented by the following formula (x), and has four R 1represents an organic group A represented by the following formula (2-1a) and (2-2a), an organic group B represented by the following formula (3a), or a repeating structural unit represented by the following formula (4-1a) and (4-2a), a repeating structural unit represented by the following formula (5-1a), (5-1b), (5-1c), (5-2a), (5-2b), and (5-2c), a repeating structural unit represented by the following formula (6-1a), (6-1b), (6-1c), (6-2a), (6-2b), and (6-2c), a repeating structural unit represented by the following formula (7-1a), (7-1b), ( and an organic group C having one or more repeating structural units selected from the group consisting of repeating structural units represented by the following formulae (8-1a), (8-1b), (8-1c), (8-1d), (8-1e), (8-1f), (8-2a), (8-2b), (8-2c), (8-2d), (8-2e) and (8-2f), and repeating structural units represented by the following formulae (9-1a), (9-1b), (9-2a) and (9-2b), 1 In the synthesis, polymer 1 was synthesized, in which at least one of the organic groups was the organic group C. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] JPEG0007689201000031.jpg186157 [ka]

[0069] 50.0 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 36.5 g of glycidyl phenyl ether, 22.6 g of 3-ethyl-3-oxetanemethanol, 1.6 g of tetrabutylammonium chloride, and 165.9 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube, and reacted at 80°C for 26 hours under a nitrogen atmosphere to obtain a solution containing polymer 1. The weight average molecular weight was measured by GPC, and the weight average molecular weight (Mw) of polymer 1 was 11,500. The molecular weight was measured by gel permeation chromatography (Tosoh Corporation, product number: HLC-8120, column: G-5000HXL and G-3000HXL in two connections, detector: RI, mobile phase: N,N-dimethylformamide). The weight average molecular weight was measured in the following manner. The acid value of Polymer 1 was 70 mgKOH / g.

[0070] From the weight average molecular weight thus obtained, the repeating structural units represented by the formulae (4-1a) and (4-2a), the repeating structural units represented by the formulae (5-1a), (5-1b), (5-1c), (5-2a), (5-2b), and (5-2c), the repeating structural units represented by the formulae (6-1a), (6-1b), (6-1c), (6-2a), (6-2b), and (6-2c), the repeating structural units represented by the formulae (7-1a), (7-2b), and (7-2c), contained in the molecule of polymer 1, were determined to be 0.01 to 0.01% by weight. The total number of repeating structural units represented by the formulae (7-1a), (8-1b), (8-1c), (8-1d), (8-1e), (8-1f), (8-2a), (8-2b), (8-2c), (8-2d), (8-2e), and (8-2f), and the repeating structural units represented by the formulae (9-1a), (9-1b), (9-2a), and (9-2b) were calculated. Polymer 1 is an assembly of hyperbranched polymers. This hyperbranched polymer includes repeating structural units represented by the formulae (4-1a) and (4-2a), repeating structural units represented by the formulae (5-1a), (5-1b), (5-1c), (5-2a), (5-2b) and (5-2c), repeating structural units represented by the formulae (6-1a), (6-1b), (6-1c), (6-2a), (6-2b) and (6-2c), repeating structural units represented by the formulae (7-1a) and (7-1b), , (7-2a) and (7-2b), repeating structural units represented by the formulae (8-1a), (8-1b), (8-1c), (8-1d), (8-1e), (8-1f), (8-2a), (8-2b), (8-2c), (8-2d), (8-2e) and (8-2f), and repeating structural units represented by the formulae (9-1a), (9-1b), (9-2a) and (9-2b).

[0071] The molecular weight of the 3,3',4,4'-biphenyltetracarboxylic dianhydride is 294.22 g / mol, the molecular weight of the glycidyl phenyl ether is 150.18 g / mol, and the molecular weight of the 3-ethyl-3-oxetanemethanol is 116.16 g / mol. Assuming that all of the raw materials used have reacted, the molecular weight of the hyperbranched polymer is the weight average molecular weight. Assuming that one hyperbranched polymer contains A structures derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride, B structures derived from glycidyl phenyl ether, and C structures derived from 3-ethyl-3-oxetanemethanol, then: A piece x 294.22g / mol + B piece x 150.18g / mol + C piece x 116.16g / mol = 11,500 From the molar ratio of 3,3',4,4'-biphenyltetracarboxylic dianhydride, glycidyl phenyl ether, and 3-ethyl-3-oxetanemethanol used, A:B:C=70:100:80 Since the above equation holds, solving these gives us A = 17.93, B = 25.61, and C = 20.49.

[0072] From the above, since the molecular weight is an average value and one repeating structural unit necessarily has one structure derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride, the average number of repeating structural units of the hyperbranched polymer is calculated by multiplying the value of A by the value of X in the general formula (1) which is the core of the hyperbranched polymer. 1 This is the total number of repeating structural units of polymer 1.

[0073] [Preparation of Photosensitive Resin Composition 1] A solution containing 100 parts by mass of the polymer 1, 50 parts by mass of ethoxylated-o-phenylphenol acrylate (A-LEN-10, manufactured by Shin-Nakamura Chemical Co., Ltd.), 5 parts by mass of EO 3.8 mole adduct diacrylate of bisphenol A (V#700HV, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1.60 parts by mass of a photopolymerization initiator (Irgacure OXE01, manufactured by BASF Japan Ltd.), 3.20 parts by mass of a photopolymerization initiator (SPEEDCURE TPO, manufactured by Lambson Corporation), and 0.16 parts by mass of a surfactant (FZ-2122, manufactured by Dow Corning Toray Co., Ltd.) were mixed to prepare a photosensitive resin composition 1 having a solid content of 40% by mass.

[0074] Example 2 [Synthesis of polymer 2] In a glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube, 50.0 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 29.2 g of glycidyl phenyl ether, 6.9 g of glycidyl methacrylate, 22.6 g of 3-ethyl-3-oxetanemethanol, 1.6 g of tetrabutylammonium chloride, 0.01 g of hydroquinone, and 165.3 g of propylene glycol monomethyl ether acetate were placed and reacted for 26 hours at 80°C under a nitrogen atmosphere to obtain a solution containing polymer 2. The weight average molecular weight was measured by GPC, and the weight average molecular weight (Mw) of polymer 2 was 15,200. The acid value of polymer 2 was 57 mgKOH / g, and the double bond equivalent was 2240.

[0075] From the obtained weight average molecular weight, the total number of repeating structural units (specific repeating structural units are omitted) corresponding to the repeating structural units represented by the general formulae (4-1) to (9-2) contained in the molecules of polymer 2 was calculated. Polymer 2 is an assembly of hyperbranched polymers. This hyperbranched polymer may contain repeating structural units corresponding to the repeating structural units represented by the general formulae (4-1) to (9-2).

[0076] The molecular weight of the 3,3',4,4'-biphenyltetracarboxylic dianhydride is 294.22 g / mol, the molecular weight of the glycidyl phenyl ether is 150.18 g / mol, the molecular weight of the glycidyl methacrylate is 142.15 g / mol, and the molecular weight of the 3-ethyl-3-oxetanemethanol is 116.16 g / mol. Therefore, assuming that all of the raw materials used have reacted, the molecular weight of the hyperbranched polymer is the above-mentioned weight average molecular weight. If one hyperbranched polymer contains A structures derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride, B structures derived from glycidyl phenyl ether, C structures derived from glycidyl methacrylate, and D structures derived from 3-ethyl-3-oxetanemethanol, then: A piece x 294.22g / mol + B piece x 150.18g / mol + C piece x 142.15g / mol + D piece x 116.16g / mol = 15,200 From the molar ratio of 3,3',4,4'-biphenyltetracarboxylic dianhydride, glycidyl phenyl ether, glycidyl methacrylate, and 3-ethyl-3-oxetanemethanol used, A:B:C:D=70:80:20:80 Therefore, solving these gives us A = 23.78, B = 27.18, C = 6.79, and D = 27.18.

[0077] From the above, since the molecular weight is an average value and one repeating structural unit necessarily has one structure derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride, the average number of repeating structural units of the hyperbranched polymer is calculated by multiplying the value of A by the value of X in the general formula (1) which is the core of the hyperbranched polymer. 1 This is the total number of repeating structural units of polymer 2.

[0078] [Preparation of Photosensitive Resin Composition 2] A solution containing 100 parts by mass of the polymer 2, 50 parts by mass of ethoxylated-o-phenylphenol acrylate (A-LEN-10, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1.55 parts by mass of a photopolymerization initiator (Irgacure OXE01, manufactured by BASF Japan Ltd.), 3.10 parts by mass of a photopolymerization initiator (SPEEDCURE TPO, manufactured by Lambson Corporation), and 0.15 parts by mass of a surfactant (FZ-2122, manufactured by Dow Corning Toray Co., Ltd.) were mixed to prepare a photosensitive resin composition 2 having a solid content of 40% by mass.

[0079] Example 3 [Synthesis of polymer 3] In a glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube, 50.0 g of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 15.3 g of glycidyl phenyl ether, 6.2 g of glycidyl methacrylate, 14.4 g of 3-ethyl-3-oxetane methanol, 0.9 g of tetrabutylammonium chloride, 0.01 g of hydroquinone, and 130.2 g of propylene glycol monomethyl ether acetate were placed and reacted for 26 hours at 80°C under a nitrogen atmosphere to obtain a solution containing polymer 3. The weight average molecular weight was measured by GPC, and the weight average molecular weight (Mw) of polymer 3 was 7,400. The acid value of polymer 3 was 63 mgKOH / g, and the double bond equivalent was 1970.

[0080] From the obtained weight average molecular weight, the total number of repeating structural units (specific repeating structural units are omitted) corresponding to the repeating structural units represented by the general formulae (4-1) to (9-2) contained in the molecules of polymer 3 was calculated. Polymer 3 is an aggregate of hyperbranched polymers. This hyperbranched polymer may contain repeating structural units corresponding to the repeating structural units represented by the general formulae (4-1) to (9-2).

[0081] The molecular weight of the 9,9-bis(3,4-dicarboxyphenyl)fluorene diacid anhydride is 458.43 g / mol, the molecular weight of the glycidyl phenyl ether is 150.18 g / mol, the molecular weight of the glycidyl methacrylate is 142.15 g / mol, and the molecular weight of the 3-ethyl-3-oxetane methanol is 116.16 g / mol. Therefore, assuming that all of the raw materials used have reacted, the molecular weight of the hyperbranched polymer is the weight average molecular weight. If one hyperbranched polymer contains A structures derived from 9,9-bis(3,4-dicarboxyphenyl)fluorene diacid anhydride, B structures derived from glycidyl phenyl ether, C structures derived from glycidyl methacrylate, and D structures derived from 3-ethyl-3-oxetane methanol, then: A piece x 458.43g / mol + B piece x 150.18g / mol + C piece x 142.15g / mol + D piece x 116.16g / mol = 7,400 From the molar ratio of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, glycidyl phenyl ether, glycidyl methacrylate, and 3-ethyl-3-oxetane methanol used, A:B:C:D=75:70:30:85 Therefore, solving these we get A = 9.40, B = 8.77, C = 3.76, and D = 10.65.

[0082] From the above, since the molecular weight is an average value and one repeating structural unit necessarily has one structure derived from 9,9-bis(3,4-dicarboxyphenyl)fluorene diacid anhydride, the average number of repeating structural units of the hyperbranched polymer is calculated by multiplying the value of A by the value of X in the general formula (1) which is the core of the hyperbranched polymer. 1 This is the total number of repeating structural units of polymer 3.

[0083] [Preparation of Photosensitive Resin Composition 3] A solution containing 100 parts by mass of the polymer 3, 50 parts by mass of ethoxylated-o-phenylphenol acrylate (A-LEN-10, manufactured by Shin-Nakamura Chemical Co., Ltd.), 5 parts by mass of EO 3.8 mol adduct diacrylate of bisphenol A (V#700HV, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 1.60 parts by mass of a photopolymerization initiator (Irgacure OXE01, manufactured by BASF Japan Ltd.), 3.20 parts by mass of a photopolymerization initiator (SPEEDCURE TPO, manufactured by Lambson), and 0.16 parts by mass of a surfactant (FZ-2122, manufactured by Dow Corning Toray Co., Ltd.) were mixed to prepare a photosensitive resin composition 3 having a solid content of 40% by mass.

[0084] Example 4 [Synthesis of polymer 4] 50.0 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 31.9 g of glycidyl phenyl ether, 20.7 g of benzyl alcohol, 1.4 g of tetrabutylammonium chloride, and 155.9 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube, and reacted at 100°C for 9 hours under a nitrogen atmosphere to obtain a solution containing polymer 4. The weight average molecular weight was measured by GPC, and the weight average molecular weight (Mw) of polymer 4 was 3,500. The acid value of polymer 4 was 78 mgKOH / g.

[0085] From the obtained weight average molecular weight, the total number of repeating structural units (specific repeating structural units are omitted) corresponding to the repeating structural units represented by the general formulas (4-1) to (9-2) contained in the molecules of polymer 4 was calculated. Polymer 4 is an aggregate of hyperbranched polymers. This hyperbranched polymer may contain repeating structural units corresponding to the repeating structural units represented by the general formulas (4-1) to (9-2).

[0086] The molecular weight of the 3,3',4,4'-biphenyltetracarboxylic dianhydride is 294.22 g / mol, the molecular weight of the glycidyl phenyl ether is 150.18 g / mol, and the molecular weight of the benzyl alcohol is 108.14 g / mol. Assuming that all of the raw materials used react, the molecular weight of the hyperbranched polymer is the weight average molecular weight. Assuming that one hyperbranched polymer contains A structures derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride, B structures derived from glycidyl phenyl ether, and C structures derived from benzyl alcohol, then: A piece x 294.22g / mol + B piece x 150.18g / mol + C piece x 108.14g / mol = 3,500 From the molar ratio of 3,3',4,4'-biphenyltetracarboxylic dianhydride, glycidyl phenyl ether, and benzyl alcohol used, A:B:C=80:100:90 Therefore, solving these gives us A = 5.78, B = 7.25, and C = 6.52.

[0087] From the above, since the molecular weight is an average value and one repeating structural unit necessarily has one structure derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride, the average number of repeating structural units of the hyperbranched polymer is calculated by multiplying the value of A by the value of X in the general formula (1) which is the core of the hyperbranched polymer. 1 This is the total number of repeating structural units of polymer 4.

[0088] [Preparation of Photosensitive Resin Composition 4] A solution containing 100 parts by mass of the polymer 4, 50 parts by mass of ethoxylated-o-phenylphenol acrylate (A-LEN-10, manufactured by Shin-Nakamura Chemical Co., Ltd.), 5 parts by mass of EO 3.8 mole adduct diacrylate of bisphenol A (V#700HV, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 25 parts by mass of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (Celloxide 2021P, manufactured by Daicel Corporation), 1.86 parts by mass of a photopolymerization initiator (Irgacure OXE01, manufactured by BASF Japan Co., Ltd.), 3.72 parts by mass of a photopolymerization initiator (SPEEDCURE TPO, manufactured by LAMBSON Co., Ltd.), and 0.19 parts by mass of a surfactant (FZ-2122, manufactured by Dow Corning Toray Co., Ltd.) were mixed to prepare a photosensitive resin composition 4 having a solid content of 40% by mass in the composition.

[0089] Example 5 [Synthesis of polymer 5] 50.0 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 31.9 g of glycidyl phenyl ether, 15.4 g of benzyl alcohol, 5.7 g of 2-hydroxyethyl acrylate, 1.4 g of tetrabutylammonium chloride, 0.01 g of hydroquinone, and 156.5 g of propylene glycol monomethyl ether acetate were placed in a glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube, and reacted at 100°C for 9 hours under a nitrogen atmosphere to obtain a solution containing polymer 5. The weight average molecular weight was measured by GPC, and the weight average molecular weight (Mw) of polymer 5 was 3,900. The acid value of polymer 5 was 78 mgKOH / g, and the double bond equivalent was 2110.

[0090] From the obtained weight average molecular weight, the total number of repeating structural units (specific repeating structural units are omitted) corresponding to the repeating structural units represented by the general formulas (4-1) to (9-2) contained in the molecules of polymer 5 was calculated. Polymer 5 is an assembly of hyperbranched polymers. This hyperbranched polymer may contain repeating structural units corresponding to the repeating structural units represented by the general formulas (4-1) to (9-2).

[0091] The molecular weight of the 3,3',4,4'-biphenyltetracarboxylic dianhydride is 294.22 g / mol, the molecular weight of the glycidyl phenyl ether is 150.18 g / mol, the molecular weight of the benzyl alcohol is 108.14 g / mol, and the molecular weight of the 2-hydroxyethyl acrylate is 116.12 g / mol. Assuming that all of the raw materials used have reacted, the molecular weight of the hyperbranched polymer is the weight average molecular weight. Assuming that one hyperbranched polymer contains A structures derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride, B structures derived from glycidyl phenyl ether, C structures derived from benzyl alcohol, and D structures derived from 2-hydroxyethyl acrylate, then: A piece x 294.22g / mol + B piece x 150.18g / mol + C piece x 108.14g / mol + D piece x 116.12g / mol = 3,900 In addition, the molar ratio of 3,3',4,4'-biphenyltetracarboxylic dianhydride, glycidyl phenyl ether, benzyl alcohol, and 2-hydroxyethyl acrylate used was A:B:C:D=80:100:67:23. Therefore, solving these gives us A = 6.44, B = 8.05, C = 5.39, and D = 1.85.

[0092] From the above, since the molecular weight is an average value and one repeating structural unit necessarily has one structure derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride, the average number of repeating structural units of the hyperbranched polymer is calculated by multiplying the value of A by the value of X in the general formula (1) which is the core of the hyperbranched polymer. 1 This is the total number of repeating structural units of polymer 5.

[0093] [Preparation of Photosensitive Resin Composition 5] A solution containing 100 parts by mass of the polymer 5, 50 parts by mass of ethoxylated-o-phenylphenol acrylate (A-LEN-10, manufactured by Shin-Nakamura Chemical Co., Ltd.), 25 parts by mass of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (Celloxide 2021P, manufactured by Daicel Corporation), 1.81 parts by mass of a photopolymerization initiator (Irgacure OXE01, manufactured by BASF Japan Ltd.), 3.61 parts by mass of a photopolymerization initiator (SPEEDCURE TPO, manufactured by LAMBSON), and 0.18 parts by mass of a surfactant (FZ-2122, manufactured by Dow Corning Toray Co., Ltd.) were mixed to prepare a photosensitive resin composition 5 having a solid content of 40% by mass in the composition.

[0094] Example 6 [Synthesis of polymer 6] In a glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube, 50.0 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 24.9 g of glycidyl phenyl ether, 6.8 g of glycidyl methacrylate, 20.7 g of benzyl alcohol, 1.4 g of tetrabutylammonium chloride, 0.01 g of hydroquinone, and 155.6 g of propylene glycol monomethyl ether acetate were placed and reacted at 100°C for 9 hours under a nitrogen atmosphere to obtain a solution containing polymer 6. The weight average molecular weight was measured by GPC, and the weight average molecular weight (Mw) of polymer 6 was 10,000. The acid value of polymer 6 was 78 mgKOH / g, and the double bond equivalent was 2150.

[0095] From the obtained weight average molecular weight, the total number of repeating structural units (specific repeating structural units are omitted) corresponding to the repeating structural units represented by the general formulas (4-1) to (9-2) contained in the molecules of polymer 6 was calculated. Polymer 6 is an aggregate of hyperbranched polymers. This hyperbranched polymer may contain repeating structural units corresponding to the repeating structural units represented by the general formulas (4-1) to (9-2).

[0096] The molecular weight of the 3,3',4,4'-biphenyltetracarboxylic dianhydride is 294.22 g / mol, the molecular weight of the glycidyl phenyl ether is 150.18 g / mol, the molecular weight of the glycidyl methacrylate is 142.15 g / mol, and the molecular weight of the benzyl alcohol is 108.14 g / mol. Assuming that all of the raw materials used have reacted, the molecular weight of the hyperbranched polymer is the weight average molecular weight. Assuming that one hyperbranched polymer contains A structures derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride, B structures derived from glycidyl phenyl ether, C structures derived from glycidyl methacrylate, and D structures derived from benzyl alcohol, then: A piece x 294.22g / mol + B piece x 150.18g / mol + C piece x 142.15g / mol + D piece x 108.14g / mol = 10,000 From the molar ratio of 3,3',4,4'-biphenyltetracarboxylic dianhydride, glycidyl phenyl ether, glycidyl methacrylate, and benzyl alcohol used, A:B:C:D=80:100:67:23 Therefore, solving these gives us A = 6.64, B = 6.48, C = 7.47, and D = 1.86.

[0097] From the above, since the molecular weight is an average value and one repeating structural unit necessarily has one structure derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride, the average number of repeating structural units of the hyperbranched polymer is calculated by multiplying the value of A by the value of X in the general formula (1) which is the core of the hyperbranched polymer. 1 This is the total number of repeating structural units of polymer 6.

[0098] [Preparation of Photosensitive Resin Composition 6] A solution containing 100 parts by mass of the polymer 6, 50 parts by mass of ethoxylated-o-phenylphenol acrylate (A-LEN-10, manufactured by Shin-Nakamura Chemical Co., Ltd.), 25 parts by mass of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (Celloxide 2021P, manufactured by Daicel Corporation), 1.81 parts by mass of a photopolymerization initiator (Irgacure OXE01, manufactured by BASF Japan Ltd.), 3.61 parts by mass of a photopolymerization initiator (SPEEDCURE TPO, manufactured by LAMBSON), and 0.18 parts by mass of a surfactant (FZ-2122, manufactured by Dow Corning Toray Co., Ltd.) were mixed to prepare a photosensitive resin composition 6 having a solid content of 40% by mass in the composition.

[0099] Comparative Example 1 [Synthesis of polymer 7] In a glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube, 50.0 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 22.3 g of benzene dimethanol, 1.1 g of tetrabutylammonium chloride, and 73.41 g of propylene glycol monomethyl ether acetate were added and reacted at 100°C for 4 hours under a nitrogen atmosphere, and then 1.84 g of benzyl alcohol and 1.84 g of propylene glycol monomethyl ether acetate were added and reacted at 100°C for 8 hours under a nitrogen atmosphere. 25.52 g of glycidyl phenyl ether, 7.25 g of glycidyl methacrylate, and 32.77 g of propylene glycol monomethyl ether acetate were further added to the obtained solution and reacted at 100°C for 12 hours under a nitrogen atmosphere to obtain a solution containing polymer 7. The weight average molecular weight was measured by GPC, and the weight average molecular weight (Mw) of polymer 7 was 5,800. The acid value of Polymer 7 was 76 mgKOH / g, and the double bond equivalent was 2,100.

[0100] [Preparation of Photosensitive Resin Composition 7] A solution containing 100 parts by mass of the polymer 7, 50 parts by mass of ethoxylated-o-phenylphenol acrylate (A-LEN-10, manufactured by Shin-Nakamura Chemical Co., Ltd.), 25 parts by mass of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (Celloxide 2021P, manufactured by Daicel Corporation), 1.81 parts by mass of a photopolymerization initiator (Irgacure OXE01, manufactured by BASF Japan Ltd.), 3.61 parts by mass of a photopolymerization initiator (SPEEDCURE TPO, manufactured by Lambson Corporation), and 0.18 parts by mass of a surfactant (FZ-2122, manufactured by Dow Corning Toray Co., Ltd.) were mixed to prepare a photosensitive resin composition 7 having a solid content of 40% by mass.

[0101] [Evaluation of developability] On each of the 10 cm x 10 cm square glass substrates, the photosensitive resin compositions 1 to 7 were applied to the thicknesses shown in Table 1 using a spin coater to form coating films, and the coating films were heated on a hot plate at 90°C for 2 minutes to completely remove the solvent. 2 CO 3 Alkaline development was carried out using an aqueous solution, and the time required for the coating film to be dissolved and removed was defined as the minimum development time, and the developability was evaluated according to the following criteria. ◯: The minimum development time is less than 90 seconds. △: The minimum development time is 90 seconds or more and 180 seconds or less. ×: The minimum development time is more than 180 seconds.

[0102] [Fabrication of microlens patterns] On each of the 10 cm x 10 cm square glass substrates, the photosensitive resin compositions 2, 3, 5, 6, and 7 were applied to the thicknesses shown in Table 1 using a spin coater to form coatings, and the coatings were heated on a hot plate at 90°C for 2 minutes to completely remove the solvent. 2 Light from an ultra-high pressure mercury lamp was irradiated at 100 mJ / cm through a pattern mask with 100 holes per square centimeter, each hole having a diameter of 20 μm. 2 Irradiated (illuminance of 21 mW / cm in i-line equivalent) 2The exposure was performed with the mask and substrate gap (exposure gap) set at 100 μm. 2 CO 3 Alkaline development was performed using an aqueous solution. The development time was 1.5 times the minimum development time measured by the above method. After that, the substrate was washed with water and post-baked at 230°C for 30 minutes to produce a microlens pattern.

[0103] [Refractive index measurement] The photosensitive resin compositions 1 to 7 were applied to each of 10 cm x 10 cm square glass substrates using a spin coater to form a coating film, and the coating film was heated on a hot plate at 90°C for 2 minutes to completely remove the solvent. Thereafter, the obtained coating film was irradiated with light from an ultra-high pressure mercury lamp at 100 mJ / cm. 2 The entire surface was irradiated (illuminance of 21 mW / cm in i-line equivalent). 2 ). Then, 0.3% Na 2 CO 3 Alkaline development was performed using an aqueous solution. The development time was 1.5 times the minimum development time measured by the above-mentioned method. After that, the film was washed with water and post-baked at 230°C for 30 minutes to form a cured film. The refractive index of the obtained cured film was measured at 594 nm using a refractive index measuring device Model 2010 Prism Coupler (manufactured by Metricon).

[0104] [Evaluation of microlens shape] The prepared microlenses were observed with a scanning electron microscope (SEM) and the microlens shapes were evaluated according to the following criteria. ◯: The lens shape is hemispherical and good. ×: The lens shape could not be formed due to excess melt.

[0105] [Table 1]

[0106] Photosensitive resin compositions 1 to 6 of the present invention (Examples 1 to 6) could be developed in a short time even when a dilute alkaline developer was used, and a cured product with a high refractive index of 1.60 or more could be produced. In addition, the cured product produced using the polymer of the present invention had high transparency and little coloring. [Industrial Applicability]

[0107] The polymer of the present invention and a curable resin composition containing the polymer are suitably used as raw materials for lenses (microlenses), photospacers, partition materials, interlayer insulating film materials, protective film materials, optical waveguide materials, or planarizing film materials.

Claims

1. A polymer represented by the following general formula (1): 【Chemistry 1】 (In the formula, X 1 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a part of the carbon atoms constituting the hydrocarbon group is substituted with a hetero atom, or an organic group in which two or more of these are bonded together; 1 are each independently hydrogen, an organic group A represented by the following general formula (2-1) or (2-2), an organic group B represented by the following general formula (3), or an organic group C having one or more repeating structural units selected from the group consisting of repeating structural units represented by the following general formulas (4-1) and / or (4-2), repeating structural units represented by the following general formulas (5-1) and / or (5-2), and repeating structural units represented by the following general formulas (6-1) and / or (6-2), 1 At least one of the groups is the organic group C. 【Chemistry 2】 (In the formula, R 2 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the hydroxy group is bonded and the adjacent carbon atom. 【Chemistry 3】 (In the formula, R 3 is an organic group having 15 or less carbon atoms. 【Chemistry 4】 (In the formula, R 4 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom; X 2 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group is substituted with a hetero atom, or an organic group in which two or more of these are bonded together. 【Chemistry 5】 (In the formula, R 5 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom; X 3 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group is substituted with a hetero atom, or an organic group in which two or more of these are bonded together. 【Chemistry 6】 (In the formula, R 6 is an organic group having 15 or less carbon atoms, which may form a ring together with the carbon atom to which the oxygen atom is bonded and the adjacent carbon atom; R 7 is an organic group having 15 or less carbon atoms, 4 is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocycle in which a portion of the carbon atoms constituting the hydrocarbon group is substituted with a hetero atom, or an organic group in which two or more of these are bonded together.

2. The polymer of claim 1 , wherein the polymer comprises a carboxy group.

3. The R 2 , the R 4 , the R 5 and R6 are each independently an organic group containing a (meth)acryloyloxy group, an organic group containing an aromatic hydrocarbon group, an organic group containing an allyl group, an organic group containing a silyl group, or an organic group containing a cyclic ether group.

4. The R 3 2. The polymer according to claim 1, wherein R7 is an organic group containing a cyclic ether group, an organic group containing a (meth)acryloyloxy group, or an organic group containing an aromatic hydrocarbon group.

5. The X 1 , the X 2 , the X 3 2. The polymer according to claim 1, wherein X4 is an aromatic hydrocarbon group.

6. The polymer according to claim 1, comprising, in one molecule, a total of 3 to 300 repeating structural units selected from the group consisting of repeating structural units represented by general formula (4-1) and / or (4-2), repeating structural units represented by general formula (5-1) and / or (5-2), and repeating structural units represented by general formula (6-1) and / or (6-2).

7. The polymer according to claim 1, wherein the polymer has an acid value of 20 to 120 mg KOH / g.

8. The polymer according to claim 1, wherein the polymer has a double bond equivalent weight of 200 to 5,000.

9. The polymer according to claim 1, wherein the polymer has a weight average molecular weight of 1,500 to 100,000.

10. The polymer according to claim 1 , wherein raw materials of the polymer include a tetracarboxylic acid and / or a tetracarboxylic dianhydride, a hydroxy group-containing compound, and an epoxy group-containing compound.

11. A curable resin composition comprising at least the polymer according to any one of claims 1 to 10, a polymerizable monomer, and a polymerization initiator.

12. The curable resin composition according to claim 11, which is a negative photoresist material.

13. A cured product obtained from the curable resin composition according to claim 12.

14. The cured product according to claim 13, which is a lens, a photospacer, a partition material, an interlayer insulating film material, a protective film material, an optical waveguide material, or a planarizing film material.

15. A solid-state imaging device comprising the cured product according to claim 13.

16. An image display device comprising the cured product according to claim 13.

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