TW202336171A - Polymer, curable resin composition, cured object, solid state imaging element, and image display apparatus - Google Patents

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

Polymers, curable resin compositions, cured materials, solid-state imaging elements, and image display devices

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 element and an image display device containing the cured product.

Transparent components are in the form of insulating films, protective films, light capture layers, spacers, and microlenses, and are used as structural components of various devices such as display devices, photography devices, and solar cells.

In addition, in order to improve device performance, transparent members are used as members for adjusting the refractive index, and transparent members with high refractive index are currently being sought.

Transparent members with a high refractive index are used, for example, in solid-state photographic components mounted on digital cameras, mobile phones with cameras, etc. Representative solid-state imaging elements include CCD (charge coupled device) image sensors, CMOS (complementaly metal-oxide semiconductor) image sensors, and the like. These image sensors are provided with microlenses or a microlens array in which multiple microlenses are regularly arranged on a substrate for the purpose of improving sensitivity. At present, high refractive index and high transparency of this microlens are being sought.

For example, Patent Document 1 proposes a method for manufacturing a microlens array. The manufacturing method includes the following steps: a photosensitive layer forming step of installing a photosensitive layer composed of a specific photosensitive resin composition on a substrate or a display element; and exposure. The step is to irradiate active light to a predetermined portion of the photosensitive layer to photoharden the exposed portion; the developing step is to remove the portion other than the exposed portion to form a pattern; and the heating step is to heat the pattern. It is also revealed that the refractive index of the microlens produced by this manufacturing method is 1.58~1.59.

Furthermore, Patent Document 2 proposes a method for manufacturing a microlens, which method has the following steps: combining a polymer (A) containing a structural unit with a specific structure, a polymerizable compound (B), and a photopolymerization initiator (C). ), and a photosensitive composition of solvent (D) on the support; a step of removing the solvent (D); and a step of exposing the coated film through a mask pattern corresponding to the target pattern. ; Development step; step of irradiating the obtained pattern with ultraviolet rays; step of heating the pattern. It is also revealed that the refractive index of the microlens produced by this manufacturing method is 1.58.

[Advanced technical documents] [Patent Document] [Patent Document 1] Japanese Patent Application Publication No. 2011-002655 [Patent Document 2] Japanese Patent Application Publication No. 2009-251537

Summary of the invention [Problem to be solved by the invention] The microlenses described in Patent Document 1 and Patent Document 2 are manufactured using a negative photoresist, and have a certain high refractive index as microlenses manufactured using a negative photoresist. However, requirements for further improving sensor sensitivity are gradually increasing, and hardened materials with higher refractive index are now being sought. In addition, in the manufacturing methods of microlenses described in Patent Document 1 and Patent Document 2, a TMAH (tetramethylammonium hydroxide) aqueous solution with a relatively fast development speed in an alkaline developer is used in the development step. However, when manufacturing semiconductors, LCD (Liquid crystal display), etc., weakly alkaline developers such as potassium hydroxide and sodium carbonate, which develop relatively slowly, are mostly used. Therefore, when these products are equipped with hardened materials such as microlenses, or when hardened materials such as microlenses are manufactured integrally with these products, if a weak alkali developer is used instead of TMAH, the development time may become longer. , concerns about productivity decline.

One of the objects of the present invention is to provide a new polymer that can produce hardened materials with high refractive index. Furthermore, one of the objects of the present invention is to provide a novel polymer that can be developed in a short time even when using a weakly alkaline developer and can produce a cured film with a high refractive index. Furthermore, one object of the present invention is to provide a curable resin composition containing the aforementioned polymer, a cured product obtained from the aforementioned curable resin composition, and a solid-state imaging element and an image display device containing the aforementioned cured product. .

As a result of intensive research to solve the above-mentioned problems, the inventors of the present invention found that the above-mentioned object can be achieved by using the following polymer and a curable resin composition containing the polymer, and completed the present invention.

The present invention relates to a polymer represented by the following general formula (1): [Chemical Formula 1] (In the ^formula , A part of the carbon atoms constituting the aforementioned hydrocarbon group are substituted by heteroatoms; each of the four R ^1s is independently hydrogen, the organic group A represented by the following general formula (2-1) or (2-2), the following general formula (3 ) represented by the organic group B, or the organic group C having a repeating structural unit, the repeating structural unit is selected from the repeating structural units represented by the following general formulas (4-1) and/or (4-2), the following The repeating structural unit represented by the following general formula (5-1) and/or (5-2), the repeating structural unit represented by the following general formula (6-1) and/or (6-2), the following general formula ( Repeating structural units represented by 7-1) and/or (7-2), repeating structural units represented by the following general formula (8-1) and/or (8-2), and the following general formula (9-1 ) and/or (9-2), at least one of the groups of repeating structural units represented by (9-2), at least one of the four R ^1s is the aforementioned organic group C); [Chemical Formula 2] (In the formula, R ² is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom to which the hydroxyl group is bonded and its adjacent carbon atoms); [Chemical Formula 3] (In the formula, R ³ is an organic group with less than 15 carbon atoms); [Chemical Formula 4] (In the formula, R ⁴ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bonded to the oxygen atom and its adjacent carbon atoms; X ² is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an aliphatic A cyclic unsaturated hydrocarbon group, an organic group containing a heterocyclic ring, or an organic group in which two or more of these are bonded, and a part of the carbon atoms constituting the aforementioned hydrocarbon group in the aforementioned heterocyclic ring is replaced by a heteroatom); [Chemical Formula 5 ] (In the formula, R ⁵ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bound to the oxygen atom and its adjacent carbon atoms; X ³ is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an aliphatic A cyclic unsaturated hydrocarbon group, an organic group containing a heterocyclic ring, or an organic group in which two or more of these are bonded, and a part of the carbon atoms constituting the aforementioned hydrocarbon group in the aforementioned heterocyclic ring is replaced by a heteroatom); [Chemical Formula 6 ] (In the formula, R ⁶ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bound to the oxygen atom and its adjacent carbon atoms; R ⁷ is an organic group with less than 15 carbon atoms; X ⁴ is An aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocyclic ring, or an organic group formed by bonding two or more of these, the carbon atoms in the aforementioned heterocyclic ring constituting the aforementioned hydrocarbon group Part of is replaced by heteroatoms); [Chemical Formula 7] (In the formula, R ⁸ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bound to the oxygen atom and its adjacent carbon atoms; X ⁵ is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an aliphatic A cyclic unsaturated hydrocarbon group, an organic group containing a heterocyclic ring, or an organic group in which two or more of these are bonded, and a part of the carbon atoms constituting the aforementioned hydrocarbon group in the aforementioned heterocyclic ring is replaced by a heteroatom); [Chemical Formula 8 ] (In the formula, R ⁹ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bound to the oxygen atom and its adjacent carbon atoms; R ¹⁰ is an organic group with less than 15 carbon atoms; X ⁶ is An aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocyclic ring, or an organic group formed by bonding two or more of these, the carbon atoms in the aforementioned heterocyclic ring constituting the aforementioned hydrocarbon group Part of is replaced by heteroatoms); [Chemical Formula 9] (In the formula, R ¹¹ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bound to the oxygen atom and its adjacent carbon atoms; R ¹² and R ¹³ are independently an organic group with less than 15 carbon atoms. ^group ; A part of the carbon atoms of the aforementioned hydrocarbon group is replaced by a heteroatom).

The aforementioned organic group C preferably has a repeating structural unit selected from the group consisting of repeating structural units represented by the aforementioned general formulas (4-1) and/or (4-2) and represented by the aforementioned general formulas (5-1) and/or (5-2). Repeating structural units, and one or more repeating structural units in the group consisting of the repeating structural units represented by the aforementioned general formulas (6-1) and/or (6-2).

The aforementioned polymer preferably has a carboxyl group.

The aforementioned R ² , the aforementioned R ⁴ , the aforementioned R ⁵ , the aforementioned R ⁶ , the aforementioned R ⁸ , the aforementioned R ⁹ , and the aforementioned R ¹¹ are preferably each independently an organic group containing a (meth)acryloxy group or an aromatic hydrocarbon group. Organic group, organic group containing allyl group, organic group containing silicon group, or organic group containing cyclic ether group.

The aforementioned R ³ , the aforementioned R ⁷ , the aforementioned R ¹⁰ , the aforementioned R ¹² , and the aforementioned R ¹³ are preferably each independently an organic group containing a cyclic ether group, an organic group containing a (meth)acryloxy group, or an aromatic group. Organic radical of hydrocarbon group.

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

The aforementioned polymer preferably contains a total of 3 to 300 repeating structural units per molecule, and the repeating structural units are selected from the group consisting of repeating structural units represented by the aforementioned general formulas (4-1) and/or (4-2), the aforementioned general formulas The repeating structural unit represented by formula (5-1) and/or (5-2), the repeating structural unit represented by the aforementioned general formula (6-1) and/or (6-2), the aforementioned general formula (7-1) and/or the repeating structural unit represented by (7-2), the repeating structural unit represented by the aforementioned general formula (8-1) and/or (8-2), and the aforementioned general formula (9-1) and/or (9 -2) More than one type in the group consisting of the repeating structural units shown.

The acid value of the aforementioned polymer is preferably 20 to 120 mgKOH/g.

The double bond equivalent of the aforementioned polymer is preferably 200 to 5000.

The weight average molecular weight of the aforementioned polymer is preferably 1,500 to 100,000.

The raw materials of the aforementioned polymer preferably include tetracarboxylic acid and/or tetracarboxylic dianhydride, hydroxyl-containing compounds, and epoxy group-containing compounds.

Furthermore, the present invention relates to a curable resin composition containing at least the aforementioned polymer, a polymerizable monomer, and a polymerization initiator.

The aforementioned curable resin composition is preferably a negative photoresist material.

Furthermore, the present invention relates to a cured product obtained from the aforementioned curable resin composition.

The aforementioned hardened material is preferably a lens, an optical spacer, a partition wall material, an interlayer insulating film material, a protective film material, an optical waveguide material, or a planarizing film material.

Furthermore, the present invention relates to a solid-state imaging element or an image display device including the aforementioned hardened material.

[Effects of the invention] If the polymer of the present invention is used, a cured product with a high refractive index can be produced due to its characteristic structure, and a cured film with a high refractive index that can be developed in a short time even when using a weakly alkaline developer can be produced (for example, microlens). In addition, the cured product obtained by using the polymer of the present invention has high transparency, and the transparency is good even if the thickness is thick. In addition, the polymer of the present invention can be used as a negative resist polymer contained in a negative photoresist material. Therefore, the resist material using the polymer of the present invention can be easily thickened and can form a film with good transparency. graphics.

The polymer of the present invention has the aforementioned organic group C, and the organic group C has a repeating structural unit selected from the aforementioned general formula (4-1) and/or (4-2), the aforementioned general formula (5-1 ) and/or (5-2), and more than one type of repeating structural unit in the group consisting of the repeating structural units represented by the aforementioned general formula (6-1) and/or (6-2) , that is, when it is a dendritic polymer (hyperbranched polymer) having many branch points in one molecule, the above-mentioned effect can be obtained even more excellently.

The polymer of the present invention is represented by the following general formula (1): [Chemical Formula 10] (In the ^formula , A part of the carbon atoms constituting the aforementioned hydrocarbon group are substituted by heteroatoms; each of the four R ^1s is independently hydrogen, the organic group A represented by the following general formula (2-1) or (2-2), the following general formula (3 ) represented by the organic group B, or the organic group C having a repeating structural unit, the repeating structural unit is selected from the repeating structural units represented by the following general formulas (4-1) and/or (4-2), the following The repeating structural unit represented by the following general formula (5-1) and/or (5-2), the repeating structural unit represented by the following general formula (6-1) and/or (6-2), the following general formula ( Repeating structural units represented by 7-1) and/or (7-2), repeating structural units represented by the following general formula (8-1) and/or (8-2), and the following general formula (9-1 ) and/or (9-2), at least one of the group of repeating structural units represented by (9-2), at least one of the four R ¹ is the aforementioned organic group C); [Chemical Formula 11] (In the formula, R ² is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom to which the hydroxyl group is bonded and its adjacent carbon atoms); [Chemical Formula 12] (In the formula, R ³ is an organic group with less than 15 carbon atoms); [Chemical Formula 13] (In the formula, R ⁴ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bonded to the oxygen atom and its adjacent carbon atoms; X ² is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an aliphatic A cyclic unsaturated hydrocarbon group, an organic group containing a heterocyclic ring, or an organic group in which two or more of these are bonded, and a part of the carbon atoms constituting the aforementioned hydrocarbon group in the aforementioned heterocyclic ring is replaced by a heteroatom); [Chemical Formula 14 ] (In the formula, R ⁵ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bound to the oxygen atom and its adjacent carbon atoms; X ³ is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an aliphatic A cyclic unsaturated hydrocarbon group, an organic group containing a heterocyclic ring, or an organic group in which two or more of these are bonded, and a part of the carbon atoms constituting the aforementioned hydrocarbon group in the aforementioned heterocyclic ring is replaced by a heteroatom); [Chemical Formula 15 ] (In the formula, R ⁶ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bound to the oxygen atom and its adjacent carbon atoms; R ⁷ is an organic group with less than 15 carbon atoms; X ⁴ is An aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocyclic ring, or an organic group formed by bonding two or more of these, the carbon atoms in the aforementioned heterocyclic ring constituting the aforementioned hydrocarbon group Part of is replaced by heteroatoms); [Chemical Formula 16] (In the formula, R ⁸ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bound to the oxygen atom and its adjacent carbon atoms; X ⁵ is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an aliphatic A cyclic unsaturated hydrocarbon group, an organic group containing a heterocyclic ring, or an organic group in which two or more of these are bonded, and a part of the carbon atoms constituting the aforementioned hydrocarbon group in the aforementioned heterocyclic ring is replaced by a heteroatom); [Chemical Formula 17 ] (In the formula, R ⁹ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bound to the oxygen atom and its adjacent carbon atoms; R ¹⁰ is an organic group with less than 15 carbon atoms; X ⁶ is An aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocyclic ring, or an organic group formed by bonding two or more of these, the carbon atoms in the aforementioned heterocyclic ring constituting the aforementioned hydrocarbon group Part of is replaced by heteroatoms); [Chemical Formula 18] (In the formula, R ¹¹ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bound to the oxygen atom and its adjacent carbon atoms; R ¹² and R ¹³ are independently an organic group with less than 15 carbon atoms. ^group ; A part of the carbon atoms of the aforementioned hydrocarbon group is replaced by a heteroatom).

In the organic group C, each structure shown as a repeating structural unit exists in two structures. For example, the structures represented by the general formulas (4-1) and (4-2) can be selected based on the starting material when generating the ester bond in the repeating structure, the ring-opening direction during the ring-opening reaction of the cyclic compound, and the like. Specifically, if it is a structure derived from the addition reaction of carboxylic acid and epoxy, it will have a structure of general formula (4-1) or formula (4-2) depending on its ring-opening direction. The ratio of the general formula (4-1) or the formula (4-2) changes depending on the reaction conditions, etc., but generally both of them coexist in many cases. Moreover, if it is derived from the addition reaction of an acid anhydride and an alcohol, it will become the 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 the general formulas (2-1) and (2-2) of the organic group A.

In the present invention, (meth)acrylic ((meth)acrylic) means acrylic or methacrylic; (meth)acryloyl ((meth)acryloyl) means acryloyl. Or methacryloyl; (meth)acrylic acid means acrylic acid or methacrylic acid; (meth)acrylate Means acrylate or methacrylate. In addition, the carbon number of the aforementioned R ² to R ¹³ also includes the carbon number of the substituent when it has a substituent.

In the aforementioned general formula (1), the aforementioned X ^{1 ~} In the organic group formed by the bond, part of the carbon atoms constituting the hydrocarbon group in the heterocyclic ring are replaced by heteroatoms. The aforementioned aromatic hydrocarbon group is not particularly limited, and examples thereof include benzene ring, naphthalene ring, biphenyl ring, anthracene ring, phenanthrene ring, pyrene ring, fentanyl ring, acenaphthylene ring, ethane naphthalene ring, and two of these. Aromatic rings formed by the above bonds, etc. The aforesaid alicyclic saturated hydrocarbon group and alicyclic unsaturated hydrocarbon group are not particularly limited. For example, the number of carbon atoms constituting the ring is 6 to 20. Preferably, the number of carbon atoms constituting the ring is 6 to 12. They may also be bridged. ring or condensed ring. Examples of the heteroatoms of the heterocyclic ring include oxygen atoms, nitrogen atoms, and sulfur atoms, and these heteroatoms may include one type or two or more types. The above-mentioned hydrocarbon group or the above-mentioned organic group may also have various substituents (for example, halogen group, hydroxyl group, amino group, alkyl group, alkenyl group, alkoxy group, and silicon group, etc.) within the scope that does not impair the effects of the present invention. 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 using a weakly alkaline developer, the above X ¹ to X ⁷ are preferably The aromatic hydrocarbon group is preferably any one of the following aromatic hydrocarbon groups independently. [Chemical formula 19]

In the aforementioned general formula (1), the aforementioned R ² to R ¹³ are each independently an organic group having a carbon number of 15 or less, preferably an organic group having a carbon number of 2 to 12, and more preferably an organic group having a carbon number of 4 to 10. The aforementioned R ² may also form a ring together with the carbon atom to which the hydroxyl group is bonded and its adjacent carbon atoms. Furthermore, the aforementioned R ⁴ , the aforementioned R ⁵ , the aforementioned R ⁶ , the aforementioned R ⁸ , the aforementioned R ⁹ , and the aforementioned R ¹¹ may respectively form a ring together with the carbon atom to which the oxygen atom is bonded and its adjacent carbon atoms. 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 (for example, benzene ring, naphthalene ring, biphenyl ring, anthracene ring, and phenanthrene ring, etc.), an organic group in which part of the carbon atoms constituting the aforementioned hydrocarbon group is substituted by a heteroatom (such as an oxygen atom, a nitrogen atom, a sulfur atom, etc.), and this An organic radical formed by the bonding of two or more kinds of them. In addition, the aforementioned hydrocarbon group or the aforementioned organic group may have various substituents (for example, halogen group, hydroxyl group, carboxyl group, amino group, alkyl group, alkenyl group, alkoxy group, aryl group, acryloxy group, methacryloxy group group, oxetanyl group, and silicon group, etc.), functional groups (for example, ester bond, amide bond, ether bond, thioether bond, urethane bond, and siloxane bond, etc.).

From the viewpoint of obtaining a cured film having a high refractive index, it is preferred that the above R ² , the above R ⁴ , the above R ⁵ , the above R ⁶ , the above R ⁸ , the above R ⁹ , and the above R ¹¹ each independently include (methyl ) Organic groups containing acryloyloxy groups, organic groups containing aromatic hydrocarbon groups, organic groups containing allyl groups, organic groups containing silicon groups, and organic groups containing cyclic ether groups, preferably containing (methyl) The organic group of acryloxy group or the organic group containing aromatic hydrocarbon group is more preferably (meth)acryloxymethyl group or phenoxymethyl group.

Furthermore, from the viewpoint of obtaining a cured film having a high refractive index and the hardness of the obtained cured film, the organic group A represented by the general formula (2-1) or (2-2) is preferably any of the following: Organic based. In particular, from the viewpoint of increasing the hardness of the obtained cured film, the organic group A preferably has a crosslinking group. From the viewpoint of making the refractive index of the obtained cured film high, the organic group A preferably has an aromatic hydrocarbon group. [Chemical formula 20]

Moreover, from the viewpoint of obtaining a cured film having a high refractive index and the hardness of the obtained cured film, the above R ⁴ , the above R ⁵ , the above R ⁶ , the above R ⁸ , the above R ⁹ , and the above R ¹¹ are suitable. Each independently represents any of the following organic groups (in addition, in each of the aforementioned general formulas, the aforementioned R ⁴ , the aforementioned R ⁵ , the aforementioned R ⁶ , the aforementioned R ⁸ , the aforementioned R ⁹ , and the aforementioned R ¹¹ are bonded to the carbon atoms of oxygen atoms. When an atom and its adjacent carbon atoms together form a ring, it is recorded as including the ring structure). In particular, from the viewpoint of improving the hardness of the obtained cured film, it is preferable that the above R ⁴ , the above R ⁵ , the above R ⁶ , the above R ⁸ , the above R ⁹ , and the above R ¹¹ have a crosslinking group. From the viewpoint of improving the refractive index of the obtained cured film, it is preferable that the aforementioned R ⁴ , the aforementioned R ⁵ , the aforementioned R ⁶ , the aforementioned R ⁸ , the aforementioned R ⁹ , and the aforementioned R ¹¹ have an aromatic hydrocarbon group. [Chemical formula 21]

From the viewpoint of obtaining a cured film having a high refractive index, it is preferred that the aforementioned R ³ , the aforementioned R ⁷ , the aforementioned R ¹⁰ , the aforementioned R ¹² , and the aforementioned R ¹³ are each independently an organic group containing a cyclic ether group, including (methane (yl) acryloxy group, or an organic group containing an aromatic hydrocarbon group, preferably each independently is any one of the following organic groups. In particular, from the viewpoint of improving the hardness of the obtained cured film, it is preferable that the above R ³ , the above R ⁷ , the above R ¹⁰ , the above R ¹² , and the above R ¹³ have a crosslinking group. From the viewpoint of improving the refractive index of the obtained cured film, it is preferable that the above R ³ , the above R ⁷ , the above R ¹⁰ , the above R ¹² , and the above R ¹³ have an aromatic hydrocarbon group. [Chemical formula 22]

In the general formula (1), from the viewpoint of obtaining a cured film that can be developed in a short time even when a weakly alkaline developer is used (hereinafter referred to as the viewpoint of developability), the organic group C preferably has a compound selected from the group consisting of: The repeating structural unit represented by the aforementioned general formula (4-1) and/or (4-2), the repeating structural unit represented by the aforementioned general formula (5-1) and/or (5-2), and the aforementioned general formula ( One or more repeating structural units in the group consisting of the repeating structural units shown in 6-1) and/or (6-2). That is, the polymer represented by the general formula (1) is preferably a dendritic polymer (hyperbranched polymer) having a plurality of branch points in one molecule.

In the aforementioned general formula (1), at least one of the four R ^1s is the aforementioned organic group C. From the viewpoint of developability ^{, it is preferable that at least 2 or more of the four R 1s are} the aforementioned organic group C. Preferably, three or more R ¹ are the aforementioned organic groups C, and more preferably, all four R ¹ are the aforementioned organic groups C.

From the viewpoint of developability, the polymer preferably contains a total of 3 to 300 repeating structural units per molecule, and the repeating structural units are selected from the group consisting of the aforementioned general formulas (4-1) and/or (4-2). The repeating structural unit shown, the repeating structural unit represented by the aforementioned general formula (5-1) and/or (5-2), the repeating structural unit represented by the aforementioned general formula (6-1) and/or (6-2), The repeating structural unit represented by the aforementioned general formula (7-1) and/or (7-2), the repeating structural unit represented by the aforementioned general formula (8-1) and/or (8-2), and the aforementioned general formula (9 -1) and/or (9-2) contains at least one type of the group of repeating structural units, preferably a total of 3 to 150 units per molecule, more preferably a total of 3 to 100 units. The number of repeating structural units can be adjusted according to the amount (ratio) of raw materials used and reaction conditions. In addition, the number of repeating structural units can be determined by the molecular weight of the raw materials used when producing the polymer, the predicted structure of the polymer, and the molecular weight of the polymer. Specific methods for determining the number of repeating structural units are described in the Examples described below.

The aforementioned polymer preferably has at least one carboxyl group in its structure. Specifically, in the general formula (1), at least one R ¹ is hydrogen, at least one organic group A has a carboxyl group, and at least one organic group B has a carboxyl group. , an aspect in which at least one of the aforementioned organic groups C has a carboxyl group, and an aspect in which these aspects are combined.

The terminal functional group of the aforementioned organic group C is not particularly limited, and examples thereof include: an organic group having a carboxyl group at the terminal; an organic group having an ethylenically unsaturated group such as a (meth)acryloxy group at the terminal; Organic groups such as aromatic hydrocarbon groups, organic groups having a cyclic ether group at the end, etc.

The method for producing the aforementioned polymer is not particularly limited. For example, it can be synthesized by polymerizing a monomer composition containing one or more types of glycidyl (meth)acrylate, epoxy Epoxy group-containing compounds such as propyl phenyl ether; one or more hydroxyl-containing compounds; tetracarboxylic acid and/or tetracarboxylic dianhydride. Specifically, the hydroxyl group of the hydroxyl-containing compound that is the reaction initiator will react with the acid anhydride group of tetracarboxylic dianhydride, and generate a carboxyl group while generating an ester. Next, the generated carboxyl group and/or the carboxyl group of the tetracarboxylic acid It will react with the epoxy group of the epoxy-containing compound to further generate ester, and at the same time generate a hydroxyl group, which will react with other anhydride groups or carboxyl groups. The aforementioned polymer can be obtained by sequential reactions in which these reactions occur sequentially. In addition, the ring-opened free diprotic acid present in the tetracarboxylic dianhydride may react with the epoxy group. The following catalysts can also be used in the polymerization reaction: alkali metal compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, and imidazoles.

The weight average molecular weight of the aforementioned polymer is not particularly limited, but from the viewpoint of developability, it is preferably 1,500 to 100,000, more preferably 1,500 to 50,000. The weight average molecular weight mentioned above is a value measured using gel permeation chromatography (GPC) and converted to polystyrene, and is a value measured in accordance with JIS 7252-4. The weight average molecular weights described in the examples described below are also values obtained in accordance with this description.

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

The double bond equivalent of the aforementioned polymer is not particularly limited, but as an example, it can be set to 200 to 5,000. Especially when used in microlenses, from the viewpoint of forming a good lens shape, the double bond equivalent of the polymer is preferably 500 to 4000, and more preferably 1000 to 3000.

The curable resin composition of the present invention contains at least the aforementioned polymer of the present invention, a polymerizable monomer, and a polymerization initiator. The polymerization initiator can be a photopolymerization initiator or a thermal polymerization initiator, which can be appropriately selected according to the hardening method.

The curable resin composition may contain known alkali-soluble resins other than the polymers described above in the present invention. When the aforementioned curable resin composition contains the aforementioned polymer of the present invention and an alkali-soluble resin, from the viewpoint of developability, the content of the aforementioned polymer of the present invention is preferably 70 mass based on the total of the aforementioned polymer and alkali-soluble resin. % or more, preferably 80 mass% or more, more preferably 90 mass% or more.

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

The polymerizable monomer is not particularly limited, and examples thereof include nonylphenylcarbitol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-ethylhexyl Carbitol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-vinylpyrrolidone, and ethoxylated-o-phenylphenol (meth)acrylate and other monofunctional monoacrylates Polyfunctional aromatic vinyl monomers such as divinylbenzene, diallyl phthalate, and diallyl phenylphosphate; (di) ethylene glycol di(meth)acrylate, propylene glycol Di(meth)acrylate, trimethylolpropane di(meth)acrylate, bisphenol A ethylene oxide addition di(meth)acrylate, trimethylolpropane tri(meth)acrylate ,Neopenterythritol di(meth)acrylate,Neopenterythritol tri(meth)acrylate,Neopenterythritol tetra(meth)acrylate,DiNeopenterythritol di(meth)acrylate, Dineopenterythritol tri(meth)acrylate, dipenterythritol tetra(meth)acrylate, dipenterythritol penta(meth)acrylate, dineopenterythritol hexa(meth)acrylate esters, and polyfunctional (meth)acrylates such as tri(meth)acrylate of (hydroxyethyl)tripolyisocyanate; bisphenol diepoxypropyl ether, diepoxypropyl phthalate, 3' , 4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, and triepoxypropyltriisocyanate and other multifunctional epoxy monomers. These polymerizable monomers may be used alone, or two or more types may be used in combination.

The content of the aforementioned 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, preferably 20 to 150 parts by mass based on 100 parts by mass of the aforementioned polymer. , more preferably 40 to 120 parts by mass.

The aforementioned photopolymerization initiator is not particularly limited, and examples thereof include benzoin, benzoin alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenone, 2 , 2-Dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone and other acetophenones; 2-methylanthraquinone, 2-pentylanthraquinone, 2-t-butanone Anthraquinones such as 1-chloroanthraquinone and 1-chloroanthraquinone; 2,4-dimethyl 9-oxysulfide𠮿 , 2,4-diisopropyl 9-oxosulfide𠮿 , 2-chloro-9-oxosulfide𠮿 Etc. 9-oxysulfur𠮿 Class; ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal; diphenyl ketones such as diphenyl ketone; 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholinyl-propan-1-one, 2-phenylmethyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1; acylphosphine Oxides and ketones, etc. These photopolymerization initiators may be used alone, or two or more types may be used in combination.

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

A photopolymerization initiating assistant may also be added to the aforementioned curable resin composition. Examples of photopolymerization starting aids include: 1,3,5-tris(3-mercaptopropyloxyethyl)-triisocyanate, 1,3,5-tris(3-mercaptobutyloxyethyl) trifunctional thiol compounds such as triisocyanate (manufactured by Showa Denko Co., Ltd., Karenz MT (registered trademark) NR1), trimethylolpropane tris(3-mercaptopropionate); neopentylerythritol tetrakis(3- Tetrafunctional thiol compounds such as mercaptopropionate), neopentyltetrakis (3-mercaptobutyrate) (manufactured by Showa Denko Co., Ltd., Karenz MT (registered trademark) PEI); dineopenterythritol hexa(3-propane) Hexafunctional thiol compounds such as acid esters) and other polyfunctional thiols. These photopolymerization starting aids may be used alone, or two or more types may be used in combination.

Examples of the thermal polymerization initiator include hydrocumene peroxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, and benzyl peroxide. Peroxides, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-caproic acid ethyl ester, t-pentylperoxy-2-caproic acid ethyl ester and other organic peroxides ; 2,2'-Azobis(isobutyronitrile), 1,1'-Azobis(cyclohexanenitrile), 2,2'-Azobis(2,4-dimethylvalonitrile), Azo compounds such as methyl 2,2'-azobis(2-methylpropionate), etc. These thermal polymerization initiators may be used alone or in combination of two or more types.

Radically polymerizable oligomers such as unsaturated polyester, epoxy acrylate, polyurethane acrylate, and polyester acrylate; and curable resins such as epoxy resin may also be added to the aforementioned curable resin composition.

The curable resin composition may contain a solvent. Examples of the solvent include ethers such as tetrahydrofuran, dihexane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Ketones; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and other esters; methanol, ethanol, isopropyl alcohol, n-butanol, ethylene glycol Alcohols such as alcohol monomethyl ether and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform, dimethyl sulfoxide, etc. These solvents can be used alone, or two or more types can be used in combination. In addition, the solvent content can be appropriately set according to the most suitable viscosity when using the composition.

The aforementioned curable resin composition may also contain: filling materials such as aluminum hydroxide, talc, clay, and barium sulfate; cross-linking agents, dyes, pigments, defoaming agents, coupling agents, modifiers, etc., within the scope that does not impair the effect of the present invention. Well-known additives such as flattening agents, sensitizers, release agents, lubricants, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, polymerization inhibitors, tackifiers, and dispersants.

The cured product of the present invention is obtained by curing the aforementioned curable resin composition. Examples of methods for producing the cured product include injecting the curable resin composition into a mold (resin mold), or applying the curable resin composition to a base material (substrate), various functions, etc. After the curable resin composition is formed into a desired shape, it is heated or irradiated with light (for example, ultraviolet rays) to harden the curable resin composition. The curing conditions are appropriately adjusted according to the aforementioned curable resin composition used.

The refractive index (wavelength 594 nm) of the hardened material is 1.60 or more, preferably 1.61 or more.

The aforementioned hardened product is suitable for use as a lens (microlens), an optical spacer, a partition wall material, an interlayer insulating film material, a protective film material, an optical waveguide material, or a planarizing film material, and is particularly suitable for use as a microlens.

The manufacturing method of the microlens is not particularly limited, and the following method can be cited as an example: using the aforementioned curable resin composition, a dot pattern composed of rectangular dots and grid-like spaces is formed on the substrate, and then the dot pattern is formed by Heating causes heat flow to form a microlens pattern (microlens array, etc.).

The substrate is not particularly limited as long as it is used as a target for forming the microlens pattern. An example of a suitable substrate includes a substrate in which a solid-state imaging element, a first planarizing film, a color filter, and a second planarizing film are formed on a polysilicone substrate. In this substrate, a first planarization film having a flat surface is formed by covering the solid-state imaging elements dispersed at predetermined positions on the polysiloxane substrate. A color filter is formed on the first planarizing film above the position of each solid-state imaging element. Next, a second planarizing film having a flat surface is formed by covering the color filter. In addition, in the substrate, the direction from the polysilicone substrate to the second planarizing film side is set to upward, and the direction from the second planarizing film to the polysilicone substrate side is set to downward.

In order to form a microlens pattern on a substrate, first, the aforementioned curable resin composition is used to form a dot pattern on the substrate. The method of forming a dot pattern is not particularly limited. For example, it can be formed by a printing method such as inkjet printing, or by photolithography, which includes patterns formed by exposure and development. change.

In photolithography, for example, negative photolithography can be suitably used. In this method, a mask is placed on the coating film of the curable resin composition, and the coating film is photohardened by irradiating ultraviolet rays. The coating film is sprayed with an alkaline aqueous solution to dissolve and remove the unexposed parts, and then the remaining exposed parts are washed and developed to form a dot pattern. In addition, the polymers of the present invention are not limited to negative photolithography, but can also be used in positive photolithography.

In the present invention, by using the curable resin composition containing the polymer, a cured product (for example, a microlens) with a high refractive index can be produced. In addition, the curable resin composition of the present invention can be developed in a short time even when using a weakly alkaline developer (for example, a developer with a pH of 11 or less), and therefore can produce a high refractive index cured film (for example, a high refractive index film) with good productivity. , microlens).

[Example] Although Examples and Comparative Examples will be given below to illustrate the present invention, the present invention is not limited to these Examples in any way.

Example 1 [Synthesis of Polymer 1] Polymer 1 was synthesized by the following production method. The polymer 1 is as follows: In the aforementioned general formula (1), X ¹ is an organic group represented by the following formula (x) , 4 R ¹ are organic groups A represented by the following formulas (2-1a) and (2-2a), organic groups B represented by the following formula (3a), or organic groups C having repeating structural units, the aforementioned repeating The structural unit is selected from the group consisting of repeating structural units represented by the following formulas (4-1a) and (4-2a), the following formulas (5-1a), (5-1b), (5-1c), (5 Repeating structural units represented by -2a), (5-2b) and (5-2c), the following formulas (6-1a), (6-1b), (6-1c), (6-2a), (6 Repeating structural units represented by -2b) and (6-2c), repeating structural units represented by the following formulas (7-1a), (7-1b), (7-2a) and (7-2b), the following formulas (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 the following formulas (9-1a), (9-1b), (9-2a) and ( 9-2b) More than one type of the group consisting of the repeating structural units, and at least one of the four R ^1's is the aforementioned organic group C. [Chemical formula 23] [Chemical formula 24] [Chemical formula 25] [Chemical formula 26] [Chemical formula 27] [Chemical formula 28] [Chemical formula 29] [Chemical formula 30] [Chemical Formula 31]

In a glass flask equipped with a heating, cooling and stirring device, a reflux cooling tube, and a nitrogen introduction tube, add 50.0g of 3,3',4,4'-biphenyltetracarboxylic dianhydride and glycidyl phenyl ether. 36.5g, 22.6g of 3-ethyl-3-oxetanemethanol, 1.6g of tetrabutylammonium chloride, and 165.9g of propylene glycol monomethyl ether acetate, in a nitrogen atmosphere, react at 80°C for 26 hours, a solution containing polymer 1 was obtained. As a result of measuring the weight average molecular weight by GPC, the weight average molecular weight (Mw) of polymer 1 was 11,500. In addition, the molecular weight was measured using gel permeation chromatography (manufactured by Tosoh Corporation, product number: HLC-8120, column: G-5000HXL and G-3000HXL 2-link, detector: RI, mobile phase: N, N -dimethylformamide). The weight average molecular weight is measured using the same method below. In addition, the acid value of polymer 1 is 70 mgKOH/g.

From the obtained weight average molecular weight, calculate the total number of the following repeating structural units contained in the molecules of polymer 1: repeating structural units represented by the aforementioned formulas (4-1a) and (4-2a), the aforementioned formula (5 -Repeating structural units represented by -1a), (5-1b), (5-1c), (5-2a), (5-2b) and (5-2c), the aforementioned formulas (6-1a), (6- Repeating structural units shown in 1b), (6-1c), (6-2a), (6-2b) and (6-2c), the aforementioned formulas (7-1a), (7-1b), (7-2a ) and the repeating structural unit represented by (7-2b), the aforementioned formulas (8-1a), (8-1b), (8-1c), (8-1d), (8-1e), (8-1f) , the repeating structural units shown in (8-2a), (8-2b), (8-2c), (8-2d), (8-2e) and (8-2f), and the aforementioned formula (9-1a) , (9-1b), (9-2a) and (9-2b) as the repeating structural units. Polymer 1 is an aggregate of hyperbranched polymers. This hyperbranched polymer may include the following repeating structural units: repeating structural units represented by the aforementioned formulas (4-1a) and (4-2a), the aforementioned formulas (5-1a), (5-1b), (5-1c) ), (5-2a), (5-2b) and (5-2c), the aforementioned formulas (6-1a), (6-1b), (6-1c), (6-2a) , the repeating structural units represented by (6-2b) and (6-2c), the repeating structural units represented by the aforementioned formulas (7-1a), (7-1b), (7-2a) and (7-2b), the aforementioned Formula (8-1a), (8-1b), (8-1c), (8-1d), (8-1e), (8-1f), (8-2a), (8-2b), ( Repeating structural units shown in 8-2c), (8-2d), (8-2e) and (8-2f), and the aforementioned formulas (9-1a), (9-1b), (9-2a) and ( The repeating structural unit shown in 9-2b).

The molecular weight of the aforementioned 3,3',4,4'-biphenyltetracarboxylic dianhydride is 294.22g/mol, the molecular weight of glycidyl phenyl ether is 150.18g/mol, and the 3-ethyl-3-oxo ring The molecular weight of butanemethanol is 116.16g/mol. Therefore, it is assumed that all the raw materials used have reacted, and the molecular weight of the hyperbranched polymer is set to the aforementioned weight average molecular weight, and 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 3-ethyl-3-oxetane The structure of alkanemethanol, at this time, A × 294.22g/mol + B × 150.18g/mol + C × 116.16g/mol = 11,500, and the 3,3',4,4'-biphenyltetracarboxylic acid used The molar ratio of dianhydride, glycidyl phenyl ether, and 3-ethyl-3-oxetanemethanol is A: B: C = 70: 100: 80. Therefore, when solving this equation, A = 17.93 , B=25.61, C=20.49.

According to the above content, from the perspective that the aforementioned molecular weight is an average value, and from the fact that there must be a structure derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride in a repeating structural unit, the hyperbranched polymer is The average number of repeating structural units is calculated by subtracting the ^value of quantity.

[Preparation of photosensitive resin composition 1] Mix 100 parts by mass of a solution containing the aforementioned polymer 1, 50 parts by mass of ethoxylated-o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-LEN-10), and EO 3.8 Mo of bisphenol A. 5 parts by mass of ear addition diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., V#700HV), 1.60 parts by mass of photopolymerization initiator (manufactured by BASF JAPAN Co., Ltd., Irgacure OXE01), and 1.60 parts by mass of photopolymerization initiator (manufactured by LAMBSON Co., Ltd. SPEEDCURE TPO) 3.20 parts by mass and surfactant (FZ-2122 manufactured by Dow Corning Toray Co., Ltd.) 0.16 parts by mass to prepare a photosensitive resin composition 1 with a solid content of 40% by mass.

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

Based on the obtained weight average molecular weight, calculate the repeating structural units contained in the molecules of polymer 2 corresponding to the repeating structural units represented by the aforementioned general formulas (4-1) to (9-2) (the details are omitted here). the total number of repeating structural units.). Polymer 2 is an aggregate of hyperbranched polymers. The hyperbranched polymer may include repeating structural units corresponding to the repeating structural units represented by the aforementioned general formulas (4-1) to (9-2).

The molecular weight of the aforementioned 3,3',4,4'-biphenyltetracarboxylic dianhydride is 294.22g/mol, the molecular weight of glycidyl phenyl ether is 150.18g/mol, and the molecular weight of glycidyl methacrylate is 294.22g/mol. The molecular weight is 142.15g/mol, and the molecular weight of 3-ethyl-3-oxetanemethanol is 116.16g/mol. Therefore, it is assumed that all the raw materials used have been reacted, and the molecular weight of the hyperbranched polymer is assumed to be the aforementioned The weight average molecular weight is assumed to be 1. A hyperbranched polymer contains A structures derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride and B structures derived from glycidyl phenyl ether. structure, C structures derived from glycidyl methacrylate, and D structures derived from 3-ethyl-3-oxetanemethanol, at this time, A × 294.22g/mol + B × 150.18g /mol＋C pieces The molar ratio of glycidyl acrylate and 3-ethyl-3-oxetanemethanol is A: B: C: D = 70: 80: 20: 80. Therefore, when solving this equation, A = 23.78 , B=27.18, C=6.79, D=27.18.

According to the above content, from the perspective that the aforementioned molecular weight is an average value, and from the fact that there must be a structure derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride in a repeating structural unit, the hyperbranched polymer is The average number of repeating structural units is calculated by subtracting the ^value of quantity.

[Preparation of photosensitive resin composition 2] Mix 100 parts by mass of a solution containing the aforementioned polymer 2, 50 parts by mass of ethoxylated-o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-LEN-10), and a photopolymerization initiator (BASF JAPAN The prepared composition contains 1.55 parts by mass of Irgacure OXE01, manufactured by the company, 3.10 parts by mass of a photopolymerization initiator (SPEEDCURE TPO, manufactured by LAMBSON), and 0.15 parts by mass of a surfactant (FZ-2122, manufactured by Dow Corning Toray). Photosensitive resin composition 2 with a solid content of 40% by mass.

Example 3 [Synthesis of Polymer 3] In a glass flask equipped with a heating, cooling and stirring device, a reflux cooling tube, and a nitrogen introduction tube, add 50.0g of 9,9-bis(3,4-dicarboxyphenyl)bazidic anhydride and glycidyl phenyl 15.3g ether, 6.2g glycidyl methacrylate, 14.4g 3-ethyl-3-oxetanemethanol, 0.9g tetrabutylammonium chloride, 0.01g hydroquinone, and propylene glycol monomethyl ether 130.2 g of acetate was reacted at 80° C. for 26 hours in a nitrogen atmosphere to obtain a solution containing polymer 3. As a result of measuring the weight average molecular weight by GPC, the weight average molecular weight (Mw) of polymer 3 was 7,400. In addition, the acid value of polymer 3 is 63 mgKOH/g, and the double bond equivalent is 1970.

Based on the obtained weight average molecular weight, calculate the repeating structural units contained in the molecules of polymer 3 corresponding to the repeating structural units represented by the aforementioned general formulas (4-1) to (9-2) (specific details are omitted here). The total number of repeating structural units.). Polymer 3 is an aggregate of hyperbranched polymers. The hyperbranched polymer may include repeating structural units corresponding to the repeating structural units represented by the aforementioned general formulas (4-1) to (9-2).

The molecular weight of the aforementioned 9,9-bis(3,4-dicarboxyphenyl)azidic anhydride is 458.43g/mol, the molecular weight of glycidyl phenyl ether is 150.18g/mol, and the molecular weight of glycidyl methacrylate is 458.43g/mol. The molecular weight of 3-ethyl-3-oxetanemethanol is 142.15g/mol, and the molecular weight of 3-ethyl-3-oxetanemethanol is 116.16g/mol. Therefore, it is assumed that all the raw materials used have been reacted, and the molecular weight of the hyperbranched polymer is set to The aforementioned weight average molecular weight is assumed to mean that one hyperbranched polymer contains A structures derived from 9,9-bis(3,4-dicarboxyphenyl)azidic anhydride and B structures derived from epoxypropylphenyl groups. The structure of ether, C structures derived from glycidyl methacrylate, and D structures derived from 3-ethyl-3-oxetanemethanol, at this time, A × 458.43g/mol + B × 150.18g/mol + C pieces The molar ratio of glycidyl methacrylate and 3-ethyl-3-oxetanemethanol is A: B: C: D = 75: 70: 30: 85. Therefore, solving this equation is A=9.40, B=8.77, C=3.76, D=10.65.

According to the above content, from the perspective that the aforementioned molecular weight is an average value, and from the fact that there must be a structure derived from 9,9-bis(3,4-dicarboxyphenyl)bazidic anhydride in a repeating structural unit, the hyperbranched polymer The average number of repeating structural units is calculated by subtracting from the ^A value the value of Total quantity.

[Preparation of photosensitive resin composition 3] Mix 100 parts by mass of a solution containing the aforementioned polymer 3, 50 parts by mass of ethoxylated-o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-LEN-10), and EO 3.8 Mo of bisphenol A. 5 parts by mass of ear addition diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., V#700HV), 1.60 parts by mass of photopolymerization initiator (manufactured by BASF JAPAN Co., Ltd., Irgacure OXE01), and 1.60 parts by mass of photopolymerization initiator (manufactured by LAMBSON Co., Ltd. SPEEDCURE TPO) 3.20 parts by mass, and surfactant (FZ-2122 manufactured by Dow Corning Toray Co., Ltd.) 0.16 parts by mass to prepare a photosensitive resin composition 3 with a solid content of 40% by mass.

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

Based on the obtained weight average molecular weight, the repeating structural units contained in the molecules of the polymer 4 corresponding to the repeating structural units represented by the aforementioned general formulas (4-1) to (9-2) are calculated (the details are omitted here). the total number of repeating structural units.). Polymer 4 is an aggregate of hyperbranched polymers. The hyperbranched polymer may include repeating structural units corresponding to the repeating structural units represented by the aforementioned general formulas (4-1) to (9-2).

The molecular weight of the aforementioned 3,3',4,4'-biphenyltetracarboxylic dianhydride is 294.22g/mol, the molecular weight of glycidyl phenyl ether is 150.18g/mol, and the molecular weight of benzyl alcohol is 108.14g. /mol, therefore, it is assumed that all the raw materials used have reacted, and the molecular weight of the hyperbranched polymer is set to the aforementioned weight average molecular weight, and 1 hyperbranched polymer contains A derived from 3,3',4, The structure of 4'-biphenyltetracarboxylic dianhydride, B structures derived from glycidyl phenyl ether, and C structures derived from benzyl alcohol, at this time, A × 294.22g/mol + B × 150.18g/mol + C pieces The ear ratio is A: B: C = 80: 100: 90. Therefore, solving this equation means A = 5.78, B = 7.25, and C = 6.52.

According to the above content, from the perspective that the aforementioned molecular weight is an average value, and from the fact that there must be a structure derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride in a repeating structural unit, the hyperbranched polymer is The average number of repeating structural units is calculated by subtracting the ^value of quantity.

[Preparation of photosensitive resin composition 4] Mix 100 parts by mass of a solution containing the aforementioned polymer 4, 50 parts by mass of ethoxylated-o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-LEN-10), and EO 3.8 Mo of bisphenol A. 5 parts by mass of ear-addition diacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., V#700HV), 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by DAICEL) , CELLOXIDE 2021P) 25 parts by mass, photopolymerization initiator (Irgacure OXE01 manufactured by BASF JAPAN) 1.86 parts by mass, photopolymerization initiator (SPEEDCURE TPO manufactured by LAMBSON) 3.72 parts by mass, and surfactant (Dow Corning Photosensitive resin composition 4 (manufactured by Toray Co., Ltd., FZ-2122) 0.19 parts by mass, and the solid content in the prepared composition is 40% by mass.

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

Based on the obtained weight average molecular weight, the repeating structural units contained in the molecules of polymer 5 corresponding to the repeating structural units represented by the aforementioned general formulas (4-1) to (9-2) are calculated (the details are omitted here). the total number of repeating structural units.). Polymer 5 is an aggregate of hyperbranched polymers. The hyperbranched polymer may include repeating structural units corresponding to the repeating structural units represented by the aforementioned general formulas (4-1) to (9-2).

The molecular weight of the aforementioned 3,3',4,4'-biphenyltetracarboxylic dianhydride is 294.22g/mol, the molecular weight of glycidyl phenyl ether is 150.18g/mol, and the molecular weight of benzyl alcohol is 108.14g. /mol, the molecular weight of 2-hydroxyethyl acrylate is 116.12g/mol, therefore, it is assumed that all the raw materials used have reacted, and the molecular weight of the hyperbranched polymer is set to the aforementioned weight average molecular weight, and is set to 1 The 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 The structure of the alcohol, D structures derived from 2-hydroxyethyl acrylate, at this time, A × 294.22g/mol + B × 150.18g/mol + C × 108.14g/mol + D × 116.12g/mol = 3,900, and , the molar ratio of the used 3,3',4,4'-biphenyltetracarboxylic dianhydride, glycidyl phenyl ether, benzyl alcohol, and 2-hydroxyethyl acrylate is A:B :C:D=80:100:67:23, so solving this equation means A=6.44, B=8.05, C=5.39, D=1.85.

According to the above content, from the perspective that the aforementioned molecular weight is an average value, and from the fact that there must be a structure derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride in a repeating structural unit, the hyperbranched polymer is The average number of repeating structural units is calculated by subtracting the ^value of quantity.

[Preparation of photosensitive resin composition 5] Mix 100 parts by mass of a solution containing the aforementioned polymer 5, 50 parts by mass of ethoxylated-o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-LEN-10), and 3',4'-epoxy 25 parts by mass of cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (CELLOXIDE 2021P manufactured by DAICEL), 1.81 parts by mass of photopolymerization initiator (Irgacure OXE01 manufactured by BASF JAPAN), photopolymerization starter Photosensitive resin composition 5 with a solid content of 40% by mass was prepared using 3.61 parts by mass of agent (SPEEDCURE TPO manufactured by LAMBSON Co., Ltd.) and 0.18 parts by mass of surfactant (FZ-2122 manufactured by Dow Corning Toray Co., Ltd.).

Example 6 [Synthesis of Polymer 6] In a glass flask equipped with a heating, cooling and stirring device, a reflux cooling tube, and a nitrogen introduction tube, add 50.0g of 3,3',4,4'-biphenyltetracarboxylic dianhydride and glycidyl phenyl ether. 24.9g, glycidyl methacrylate 6.8g, benzyl alcohol 20.7g, tetrabutylammonium chloride 1.4g, hydroquinone 0.01g, and propylene glycol monomethyl ether acetate 155.6g, in nitrogen gas The reaction was carried out at 100°C for 9 hours under ambient conditions to obtain a solution containing polymer 6. As a result of measuring the weight average molecular weight by GPC, the weight average molecular weight (Mw) of polymer 6 was 10,000. In addition, the acid value of polymer 6 is 78 mgKOH/g, and the double bond equivalent is 2150.

From the obtained weight average molecular weight, the repeating structural units contained in the molecules of polymer 6 corresponding to the repeating structural units represented by the aforementioned general formulas (4-1) to (9-2) are calculated (the details are omitted here). the total number of repeating structural units.). Polymer 6 is an aggregate of hyperbranched polymers. The hyperbranched polymer may include repeating structural units corresponding to the repeating structural units represented by the aforementioned general formulas (4-1) to (9-2).

The molecular weight of the aforementioned 3,3',4,4'-biphenyltetracarboxylic dianhydride is 294.22g/mol, the molecular weight of glycidyl phenyl ether is 150.18g/mol, and the molecular weight of glycidyl methacrylate is 294.22g/mol. The molecular weight is 142.15g/mol, and the molecular weight of benzyl alcohol is 108.14g/mol. Therefore, it is assumed that all the raw materials used have reacted, and the molecular weight of the hyperbranched polymer is set to the aforementioned weight average molecular weight, and is set to 1 The 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 methyl The structure of glycidyl acrylate and D structures derived from benzyl alcohol. At this time, A × 294.22g/mol + B × 150.18g/mol + C × 142.15g/mol + D × 108.14g/mol = 10,000 , and the molar ratio of 3,3',4,4'-biphenyltetracarboxylic dianhydride, glycidyl phenyl ether, glycidyl methacrylate, and benzyl alcohol used is established A:B:C:D=80:100:67:23, so solving this equation means A=6.64, B=6.48, C=7.47, D=1.86.

According to the above content, from the perspective that the aforementioned molecular weight is an average value, and from the fact that there must be a structure derived from 3,3',4,4'-biphenyltetracarboxylic dianhydride in a repeating structural unit, the hyperbranched polymer is The average number of repeating structural units is calculated by subtracting the ^value of quantity.

[Preparation of photosensitive resin composition 6] Mix 100 parts by mass of a solution containing the aforementioned polymer 6, 50 parts by mass of ethoxylated-o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-LEN-10), and 3',4'-epoxy 25 parts by mass of cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (CELLOXIDE 2021P manufactured by DAICEL), 1.81 parts by mass of photopolymerization initiator (Irgacure OXE01 manufactured by BASF JAPAN), photopolymerization starter Photosensitive resin composition 6, which contains 3.61 parts by mass of agent (SPEEDCURE TPO manufactured by LAMBSON Co., Ltd.) and 0.18 parts by mass of surfactant (FZ-2122 manufactured by Dow Corning Toray Co., Ltd.), has a solid content of 40 mass % in the composition.

Comparative example 1 [Synthesis of Polymer 7] In a glass flask equipped with a heating, cooling and stirring device, a reflux cooling tube, and a nitrogen introduction tube, add 50.0g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, 22.3g of benzenedimethanol, and tetracarboxylic acid dianhydride. 1.1g butylammonium chloride and 73.41g propylene glycol monomethyl ether acetate were reacted at 100°C for 4 hours in a nitrogen atmosphere, and then 1.84g benzyl alcohol and propylene glycol monomethyl ether acetate were added. 1.84g of ester was reacted at 100°C for 8 hours in a nitrogen atmosphere. To the obtained solution, 25.52g of glycidyl phenyl ether, 7.25g of glycidyl methacrylate, and 32.77g of propylene glycol monomethyl ether acetate were further added, and the reaction was carried out at 100°C for 12 seconds in a nitrogen atmosphere. hours, a solution containing polymer 7 was obtained. As a result of measuring the weight average molecular weight by GPC, the weight average molecular weight (Mw) of polymer 7 was 5,800. In addition, the acid value of polymer 7 is 76 mgKOH/g, and the double bond equivalent is 2100.

[Preparation of photosensitive resin composition 7] Mix 100 parts by mass of a solution containing the aforementioned polymer 7, 50 parts by mass of ethoxylated-o-phenylphenol acrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-LEN-10), and 3',4'-epoxy 25 parts by mass of cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (CELLOXIDE 2021P manufactured by DAICEL), 1.81 parts by mass of photopolymerization initiator (Irgacure OXE01 manufactured by BASF JAPAN), photopolymerization starter 3.61 parts by mass of agent (SPEEDCURE TPO manufactured by LAMBSON Co., Ltd.) and 0.18 parts by mass of surfactant (FZ-2122 manufactured by Dow Corning Toray Co., Ltd.), and the solid content in the prepared composition was 40 mass % of the photosensitive resin composition 7 .

[Evaluation of developability] The aforementioned photosensitive resin compositions 1 to 7 were each coated with a film thickness listed in Table 1 using a spin coater on each 10 cm × 10 cm square glass substrate to form a coating film, and heated at 90°C. The coating film was heated on the plate for 2 minutes to completely remove the solvent. Thereafter, the obtained coating film was subjected to alkaline development using a 0.3% Na ₂ CO ₃ aqueous solution, and the time required for the coating film to be dissolved and removed was regarded as the minimum development time, and the developability was evaluated based on the following criteria. 〇: 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 greater than 180 seconds.

[Preparation of Microlens Patterns] Use a spin coater to apply the aforementioned photosensitive resin compositions 2, 3, 5, 6, and 7 on each of the 10 cm × 10 cm square glass substrates at the film thicknesses listed in Table 1. A coating film was formed, 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 an ultra-high-pressure mercury lamp at 100 mJ/cm ² (illuminance converted to i-line: 21 mW/cm ² ) through a pattern mask having 100 openings of 20 μm diameter holes per 1 cm ² . In addition, exposure was performed with the distance (exposure gap) between the mask and the substrate being 100 μm. After that, alkaline development was performed using 0.3% Na ₂ CO ₃ aqueous solution. The development time is set to 1.5 times the minimum development time measured by the aforementioned method. After that, it is washed with water and post-baked at 230°C for 30 minutes to produce a microlens pattern.

[Measurement of refractive index] Use a spin coater to apply the aforementioned photosensitive resin compositions 1 to 7 on each glass substrate measuring 10 cm x 10 cm to form a coating film, and heat the coating film on a 90°C hot plate for 2 minutes. Remove solvent completely. Thereafter, the entire coating film obtained was irradiated with an ultrahigh-pressure mercury lamp at 100 mJ/cm ² (illuminance converted to i-line: 21 mW/cm ² ). After that, alkaline development was performed using 0.3% Na ₂ CO ₃ aqueous solution. The development time is set to 1.5 times the minimum development time measured by the aforementioned method. Thereafter, it 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 2010 Model 2010 Prism Coupler (manufactured by Metricon Corporation, Model 2010 Prism Coupler).

[Evaluation of microlens shape] The microlenses produced as described above were observed with a scanning electron microscope (SEM), and the shape of the microlenses was evaluated based on the following criteria. 〇: It is hemispherical and the lens shape is good. ×: Unable to form a lens shape due to excessive melting.

[Table 1]

The photosensitive resin compositions 1 to 6 (Examples 1 to 6) of the present invention can be developed in a short time even when using a weak alkaline developer, and can produce hardened products with a high refractive index of 1.60 or more. things. In addition, the cured product produced using the polymer of the present invention has high transparency and little coloration.

[Industrial availability] The polymer of the present invention and the curable resin composition containing the polymer can be suitably used as lenses (microlenses), optical spacers, barrier rib materials, interlayer insulating film materials, protective film materials, optical waveguide materials, or planarization Raw materials for membrane materials.

(without)

Claims (17)

A polymer represented by the following general formula (1): [Chemical Formula 1] (In the ^formula , A part of the carbon atoms constituting the aforementioned hydrocarbon group are substituted by heteroatoms; each of the four R ^1s is independently hydrogen, the organic group A represented by the following general formula (2-1) or (2-2), the following general formula (3 ) represented by the organic group B, or the organic group C having a repeating structural unit, the repeating structural unit is selected from the repeating structural units represented by the following general formulas (4-1) and/or (4-2), the following The repeating structural unit represented by the following general formula (5-1) and/or (5-2), the repeating structural unit represented by the following general formula (6-1) and/or (6-2), the following general formula ( Repeating structural units represented by 7-1) and/or (7-2), repeating structural units represented by the following general formula (8-1) and/or (8-2), and the following general formula (9-1 ) and/or (9-2), at least one of the groups of repeating structural units represented by (9-2), at least one of the four R ^1s is the aforementioned organic group C); [Chemical Formula 2] (In the formula, R ² is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom to which the hydroxyl group is bonded and its adjacent carbon atoms); [Chemical Formula 3] (In the formula, R ³ is an organic group with less than 15 carbon atoms); [Chemical Formula 4] (In the formula, R ⁴ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bonded to the oxygen atom and its adjacent carbon atoms; X ² is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an aliphatic A cyclic unsaturated hydrocarbon group, an organic group containing a heterocyclic ring, or an organic group in which two or more of these are bonded, and a part of the carbon atoms constituting the aforementioned hydrocarbon group in the aforementioned heterocyclic ring is replaced by a heteroatom); [Chemical Formula 5 ] (In the formula, R ⁵ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bound to the oxygen atom and its adjacent carbon atoms; X ³ is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an aliphatic A cyclic unsaturated hydrocarbon group, an organic group containing a heterocyclic ring, or an organic group in which two or more of these are bonded, and a part of the carbon atoms constituting the aforementioned hydrocarbon group in the aforementioned heterocyclic ring is replaced by a heteroatom); [Chemical Formula 6 ] (In the formula, R ⁶ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bound to the oxygen atom and its adjacent carbon atoms; R ⁷ is an organic group with less than 15 carbon atoms; X ⁴ is An aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocyclic ring, or an organic group formed by bonding two or more of these, the carbon atoms in the aforementioned heterocyclic ring constituting the aforementioned hydrocarbon group Part of is replaced by heteroatoms); [Chemical Formula 7] (In the formula, R ⁸ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bound to the oxygen atom and its adjacent carbon atoms; X ⁵ is an aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an aliphatic A cyclic unsaturated hydrocarbon group, an organic group containing a heterocyclic ring, or an organic group in which two or more of these are bonded, and a part of the carbon atoms constituting the aforementioned hydrocarbon group in the aforementioned heterocyclic ring is replaced by a heteroatom); [Chemical Formula 8 ] (In the formula, R ⁹ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bound to the oxygen atom and its adjacent carbon atoms; R ¹⁰ is an organic group with less than 15 carbon atoms; X ⁶ is An aromatic hydrocarbon group, an alicyclic saturated hydrocarbon group, an alicyclic unsaturated hydrocarbon group, an organic group containing a heterocyclic ring, or an organic group formed by bonding two or more of these, the carbon atoms in the aforementioned heterocyclic ring constituting the aforementioned hydrocarbon group Part of is replaced by heteroatoms); [Chemical Formula 9] (In the formula, R ¹¹ is an organic group with less than 15 carbon atoms, and can also form a ring with the carbon atom bound to the oxygen atom and its adjacent carbon atoms; R ¹² and R ¹³ are independently an organic group with less than 15 carbon atoms. ^group ; A part of the carbon atoms of the aforementioned hydrocarbon group is replaced by a heteroatom). The polymer of claim 1, wherein the aforementioned organic group C has a repeating structural unit selected from the group consisting of repeating structural units represented by the aforementioned general formulas (4-1) and/or (4-2), the aforementioned general formulas (5-1) and/ Or one or more repeating structural units in the group consisting of the repeating structural unit represented by (5-2) and the repeating structural unit represented by the aforementioned general formula (6-1) and/or (6-2). The polymer of claim 1, wherein the aforementioned polymer has a carboxyl group. The polymer of claim 1, wherein the aforementioned R ² , the aforementioned R ⁴ , the aforementioned R ⁵ , the aforementioned R ⁶ , the aforementioned R ⁸ , the aforementioned R ⁹ , and the aforementioned R ¹¹ are each independently a group containing a (meth)acryloxy group. Organic group, an organic group containing an aromatic hydrocarbon group, an organic group containing an allyl group, an organic group containing a silicon group, or an organic group containing a cyclic ether group. The polymer of claim 1, wherein the aforementioned R ³ , the aforementioned R ⁷ , the aforementioned R ¹⁰ , the aforementioned R ¹² , and the aforementioned R ¹³ are each independently an organic group containing a cyclic ether group and a (meth)acryloxy group. organic groups, or organic groups containing aromatic hydrocarbon groups. The polymer of claim 1, wherein the aforementioned X ¹ , the aforementioned X ² , the aforementioned X ³ , the aforementioned X ⁴ , the aforementioned X ⁵ , the aforementioned X ⁶ , and the aforementioned X ⁷ are each independently an aromatic hydrocarbon group. The polymer of claim 1, wherein the aforementioned polymer contains a total of 3 to 300 repeating structural units in one molecule, and the repeating structural units are selected from the group consisting of the aforementioned general formulas (4-1) and/or (4-2) The repeating structural unit shown, the repeating structural unit represented by the aforementioned general formula (5-1) and/or (5-2), the repeating structural unit represented by the aforementioned general formula (6-1) and/or (6-2), The repeating structural unit represented by the aforementioned general formula (7-1) and/or (7-2), the repeating structural unit represented by the aforementioned general formula (8-1) and/or (8-2), and the aforementioned general formula (9 -1) and/or (9-2) more than one type in the group consisting of the repeating structural units. Such as the polymer of claim 1, wherein the acid value of the aforementioned polymer is 20~120mgKOH/g. Such as the polymer of claim 1, wherein the double bond equivalent of the aforementioned polymer is 200~5000. The polymer of claim 1, wherein the weight average molecular weight of the aforementioned polymer is 1,500~100,000. The polymer of claim 1, wherein the raw materials of the aforementioned polymer include tetracarboxylic acid and/or tetracarboxylic dianhydride, hydroxyl-containing compounds, and epoxy-containing compounds. A curable resin composition containing at least the polymer according to any one of claims 1 to 11, a polymerizable monomer, and a polymerization initiator. The curable resin composition of claim 12 is a negative photoresist material. A cured product obtained from the curable resin composition of claim 13. The cured article of claim 14, wherein the cured article is a lens, an optical spacer, a partition wall material, an interlayer insulating film material, a protective film material, an optical waveguide material, or a planarizing film material. A solid-state photographic element including a hardened object according to claim 14 or 15. An image display device comprising the hardened object of claim 14 or 15.