Polymer, polymer solution, photosensitive resin composition, and cured product

Abstract

To provide a polymer having excellent sensitivity and also having excellent alkali solubility.SOLUTION: A polymer contains a constitutional unit represented by formula (IN) and a specific constitutional unit containing a (meth)acryloyl group. (In the formula (IN), R1-R8 independently represent a hydrogen atom or a C1-30 organic group).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polymer, a polymer solution containing the polymer, a photosensitive resin composition containing the polymer solution, and a cured product of the photosensitive resin composition. [Background technology]

[0002] Liquid crystal display devices and solid-state imaging devices are usually equipped with color filters and black matrices. The color filters and black matrices are configured by forming structures such as colored patterns and protective films on a substrate. As a method for forming the colored patterns and protective films among these structures, a method of forming them by photolithography using a photosensitive resin composition is mainstream. Regarding photosensitive resin compositions, various studies have been conducted in the past, and for example, Patent Document 1 describes a photosensitive resin composition containing an alkali-soluble resin having at least a group having an acidic group and two or more different polymerizable unsaturated groups in the side chain, a polymerizable compound, and a photopolymerization initiator. In addition, an example of Patent Document 1 describes that a methacrylic acid / allyl methacrylate / glycidyl adduct was synthesized as an alkali-soluble resin, and a photosensitive resin composition was prepared using this. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2012 / 147706 Summary of the Invention [Problem to be solved by the invention]

[0004] Photosensitive resin compositions for forming color filters and black matrices use resins that undergo polymerization reactions and harden when exposed to light. Color filters and black matrices are produced by patterning a photosensitive resin composition through exposure and development, and then hardening the composition. Although "high sensitivity" is considered a common issue for photosensitive resin compositions, higher levels of sensitivity are required as display devices and imaging devices become more complex and widespread. The higher the sensitivity of the photosensitive resin composition, the shorter the time required for exposure, which can improve productivity. In addition, photosensitive resin compositions are required to have excellent processability in photolithography using an alkaline developer. [Means for solving the problem]

[0005] The present inventors have discovered that by improving the polymer used in the photosensitive resin composition, a photosensitive resin composition having good sensitivity and high alkali solubility, and therefore excellent developability, can be obtained, and have arrived at the present invention.

[0006] According to the present invention, the structural unit represented by the formula (IN) ,formula Structural unit represented by (1) and a structural unit represented by formula (3) A polymer comprising: [ka] (In formula (IN), R 1 ~R 8 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. [ka] (In formula (1), R p is a group having two or more (meth)acryloyl groups. [ka]

[0007] The present invention also provides a polymer solution containing the above polymer.

[0008] According to the present invention, there is also provided a photosensitive resin composition comprising the above polymer solution and a photoradical polymerization initiator.

[0009] According to the present invention, there is also provided a cured product of the above photosensitive resin composition. Effect of the Invention

[0010] According to the present invention, there is provided a resin composition which has good sensitivity and high alkali solubility, and therefore excellent developability, as a resin material for use in a photosensitive resin composition. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a diagram (cross-sectional view) illustrating a schematic example of the structure of a liquid crystal display device and / or a solid-state imaging device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. In all drawings, similar components are given similar reference numerals, and the description will be omitted as appropriate. In addition, all drawings are for explanatory purposes only. The shape and dimensional ratio of each member in the drawings do not necessarily correspond to the actual article. In this specification, the expression "a to b" in the description of a numerical range means "a or more and b or less" unless otherwise specified. For example, "5 to 90% by mass" means "5% by mass or more and 90% by mass or less".

[0013] In the description of groups (atomic groups) in this specification, when a description is made without specifying whether the group is substituted or unsubstituted, the description includes both groups having no substituents and groups having a substituent. For example, the term "alkyl group" includes not only alkyl groups having no substituents (unsubstituted alkyl groups) but also alkyl groups having a substituent (substituted alkyl groups).

[0014] In this specification, the term "(meth)acrylic" refers to a concept that includes both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In particular, the term "(meth)acryloyl group" in this specification refers to a -C(=O)-CH=CH 2 and an acryloyl group represented by -C(=O)-C(CH 3 )=CH 2 This concept includes a methacryloyl group represented by the formula:

[0015] [Polymer P] The polymer of this embodiment (herein referred to as "polymer P") contains a structural unit represented by formula (IN) and a structural unit represented by formula (1).

[0016] [ka]

[0017] In formula (IN), R 1 ~R 8 are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms.

[0018] [ka]

[0019] In formula (1), R p represents a group containing two or more (meth)acryloyl groups.

[0020] The polymer P of this embodiment contains a structural unit derived from indene represented by the general formula (IN). This structural unit (IN) is chemically robust. Therefore, the polymer P containing this structural unit has a small weight loss when subjected to heat treatment and is stable. Therefore, the photosensitive resin composition containing the polymer P can be suitably used for producing a film or a filter for use in a liquid crystal display device or a solid-state imaging device that requires heat resistance.

[0021] In the structural unit represented by the general formula (IN) constituting the polymer P, R 1 ~R 8 Examples of the organic group having 1 to 30 carbon atoms that can constitute the above group include substituted or unsubstituted, linear or branched alkyl groups having 1 to 30 carbon atoms, and more specific examples thereof include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkaryl groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxyl groups.

[0022] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

[0023] Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group. The alkynyl group includes, for example, an ethynyl group. Examples of the alkylidene group include a methylidene group and an ethylidene group. Examples of the aryl group include a tolyl group, a xylyl group, a phenyl group, a naphthyl group, and an anthracenyl group.

[0024] Examples of the aralkyl group include a benzyl group and a phenethyl group. Examples of the alkaryl group include a tolyl group and a xylyl group. Examples of the cycloalkyl group include an adamantyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentyloxy group, a neopentyloxy group, and an n-hexyloxy group. Examples of the heterocyclic group include an epoxy group and an oxetanyl group.

[0025] In the structural unit represented by the general formula (IN), R 1 ~R 8 is preferably hydrogen or an alkyl group, and more preferably hydrogen. In addition, R 1 ~R 8 The hydrogen atoms in the organic group having 1 to 30 carbon atoms may be substituted with any atomic group. For example, they may be substituted with a fluorine atom, a hydroxyl group, a carboxyl group, or the like. More specifically, R 1 ~R 8 As the organic group having 1 to 30 carbon atoms, a fluorinated alkyl group or the like may be selected.

[0026] The proportion of the structural units represented by formula (IN) in all structural units of the polymer P is preferably from 10 to 90 mol %, more preferably from 30 to 70 mol %, and further preferably from 40 to 60 mol %.

[0027] The polymer P of the present embodiment contains a structural unit represented by general formula (1). In the structural unit represented by general formula (1) which can constitute the polymer P, R p R is a group containing two or more (meth)acryloyl groups, preferably a group containing 2 to 6 (meth)acryloyl groups, and more preferably a group containing 3 to 5 (meth)acryloyl groups. p By optimizing the number of (meth)acryloyl groups contained in, the sensitivity of the polymer P containing the same can be further increased in exposure treatment. In addition, it becomes easier to achieve a high degree of compatibility between the sensitivity and alkali solubility of the polymer P. Furthermore, the heat resistance of the polymer P can be improved.

[0028] R in general formula (1) p is preferably a group represented by general formula (1b), a group represented by general formula (1c), or a group represented by general formula (1d), and includes at least one selected from these. By being such a group, it tends to be easy to obtain the various effects described above.

[0029] [ka]

[0030] In formula (1b), k is 2 or 3; R is a hydrogen atom or a methyl group, and multiple R may be the same or different. X 1 is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are multiple X 1 may be the same or different, X 1 ' is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X 2 is a k+1 valent organic group having 1 to 12 carbon atoms. R is preferably a hydrogen atom in view of further improving sensitivity (ease of polymerization) and the like. Although k may be 2 or 3, it is preferably 3 from the viewpoints of availability of raw materials and further improvement of sensitivity.

[0031] X 1 When is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched. X 1 When X is an alkylene group having 1 to 6 carbon atoms, 1 is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably -CH 2 -(methylene group).

[0032] X 1 When is a group represented by -ZX- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), the alkylene group having 1 to 6 carbon atoms of X may be linear or branched. The alkylene group having 1 to 6 carbon atoms for X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and further preferably -CH 2 -CH 2 -(ethylene group) or -CH 2 -CH(CH 3 )-.

[0033] X 1 When X′ is an alkylene group having 1 to 6 carbon atoms, specific embodiments thereof are 1 is the same as: X 1 When X′ is a group represented by —X′-Z′-, specific embodiments of X′ are the same as those of X described above.

[0034] X 2 The k+1 valent organic group having 1 to 12 carbon atoms can be any group obtained by removing k+1 hydrogen atoms from any organic compound. The "any organic compound" here is, for example, an organic compound having a molecular weight of 300 or less, preferably 200 or less, and more preferably 100 or less. X 2 is, for example, a group in which k+1 hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). More preferably, it is a group in which k+1 hydrogen atoms have been removed from a linear hydrocarbon having 1 to 3 carbon atoms. The hydrocarbon here may contain an oxygen atom (for example, an ether bond or a hydroxyl group). In addition, the hydrocarbon is preferably a saturated hydrocarbon. In another embodiment, X 2 may be a group containing a cyclic structure. Examples of the group containing a cyclic structure include a group containing an alicyclic structure and a group containing a heterocyclic structure (for example, an isocyanuric acid structure).

[0035] [ka]

[0036] In formula (1c), k, R, X 1 and X2 are R, k, and X in formula (1b), respectively. 1 and X 2 and R may be the same or different from each other, and X 1 may be the same or different, X 3 is a divalent organic group having 1 to 6 carbon atoms, X 4 and X 5 each independently represents a single bond or a divalent organic group having 1 to 6 carbon atoms, X 6 is a divalent organic group having 1 to 6 carbon atoms.

[0037] R, k, X 1 and X 2 Specific embodiments, preferred embodiments, etc. of are the same as those explained for general formula (1b). X 3 and X 6 Examples of the divalent organic group having 1 to 6 carbon atoms include a group in which two hydrogen atoms have been removed from a linear or branched hydrocarbon having 1 to 6 carbon atoms. The hydrocarbon may contain an oxygen atom (for example, an ether bond or a hydroxyl group). The hydrocarbon is preferably a saturated hydrocarbon. X 4 and X 5 The divalent organic group having 1 to 6 carbon atoms may be a linear or branched alkylene group. The linear or branched alkylene group preferably has 1 to 3 carbon atoms.

[0038] [ka]

[0039] In formula (1d), n is an integer of 2 to 5, and preferably 2 or 3. Specific embodiments and preferred embodiments of R are the same as those explained in relation to general formula (1b).

[0040] The proportion of the structural units represented by formula (1) in all structural units of the polymer P is preferably from 3 to 40 mol %, more preferably from 3 to 30 mol %.

[0041] In one embodiment, the polymer P may contain a structural unit represented by general formula (2) in addition to the structural units described above. By containing the structural unit represented by general formula (2), the polymer P may have high sensitivity and high alkali solubility. As a result, the photosensitive resin composition containing the polymer P may have excellent developability when subjected to photolithography processing using an alkaline aqueous solution as a developer.

[0042] [ka]

[0043] In formula (2), R s is a group having one (meth)acryloyl group.

[0044] R S is, for example, a group represented by the following formula (2a).

[0045] [ka]

[0046] In formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group. X 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 10. In formula (2a), X 10 is a divalent organic group, and R is a hydrogen atom or a methyl group. X 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 10. X 10As the divalent organic group, for example, an alkylene group is preferable. 2 The - may be an ether group (-O-). The alkylene group may be linear or branched, but is more preferably linear.

[0047] X 10 The divalent organic group X is more preferably a linear alkylene group having a total of 3 to 6 carbon atoms. 10 The number of carbon atoms (X 10 By appropriately selecting the chain length of the structural unit represented by formula (2), the structural unit represented by formula (2) can be more easily involved in the crosslinking reaction, thereby increasing the sensitivity.

[0048] X 10 The divalent organic group (for example, an alkylene group) may be substituted with any substituent, such as an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. Also, X 10 The divalent organic group may be any group other than an alkylene group, for example, a divalent group formed by linking one or more groups selected from an alkylene group, a cycloalkylene group, an arylene group, an ether group, a carbonyl group, a carboxy group, and the like.

[0049] When polymer P contains a structural unit represented by general formula (2), the proportion of the structural unit represented by general formula (2) in all structural units of polymer P is preferably 5 to 40 mol %, more preferably 10 to 30 mol %.

[0050] When polymer P contains both structural units represented by general formula (1) and structural units represented by general formula (2), the total content of structural units represented by general formula (1) and structural units represented by general formula (2) in polymer P is preferably 5 to 60 mol %, more preferably 10 to 50 mol %, and even more preferably 10 to 40 mol %, based on all structural units constituting polymer P.

[0051] In one embodiment, the polymer P may contain a structural unit represented by formula (3) in addition to the structural units described above. By containing the structural unit represented by formula (3), the polymer P has high alkali solubility. As a result, the photosensitive resin composition containing the polymer P has excellent developability when subjected to a photolithography process using an alkaline aqueous solution as a developer.

[0052] [ka]

[0053] When polymer P contains a structural unit represented by general formula (3), the proportion of the structural unit represented by general formula (3) in all structural units of polymer P is preferably 1 to 15 mol %, more preferably 2 to 10 mol %.

[0054] In one embodiment, the polymer P may contain a structural unit represented by formula (MA) in addition to the above structural units. The structural unit represented by formula (MA) is ring-opened by an alkaline developer to generate two carboxyl groups. Therefore, the polymer P containing this structural unit has excellent developability. When the polymer P contains the structural unit represented by formula (MA), the proportion of the structural unit represented by formula (MA) in all structural units of the polymer P is preferably 1 to 10 mol %, more preferably 2 to 7 mol %.

[0055] [ka]

[0056] The content (ratio) of each structural unit contained in polymer P can be determined by the amount (molar amount) of the raw materials used in synthesizing the polymer, the amount of the raw materials remaining after synthesis, and various spectra (e.g., IR spectrum, 1 H-NMR spectrum, 13 It can be estimated / calculated from the presence and peak area of ​​the C-NMR spectrum.

[0057] The weight average molecular weight Mw of the polymer P is, for example, 1000 to 80000, preferably 2000 to 70000, more preferably 3000 to 60000, and further preferably 3000 to 55000. By appropriately adjusting the weight average molecular weight, it is possible to adjust the sensitivity and the solubility in an alkaline developer.

[0058] The dispersity of the polymer P (weight average molecular weight Mw / number average molecular weight Mn) is preferably 1.0 to 10.0, more preferably 1.0 to 8.0, and even more preferably 1.0 to 7.0. By appropriately adjusting the dispersity, the physical properties of the polymer P can be made uniform, which is preferable. These values ​​can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

[0059] The glass transition temperature of the polymer P is preferably 150 to 250° C., more preferably 170 to 230° C. The polymer P has a relatively high glass transition temperature due to the inclusion of a structural unit represented by the formula (IN). This is preferable in that a pattern formed on a substrate can be stably present when producing a liquid crystal display device or a solid-state imaging device. The glass transition temperature can be determined, for example, by differential thermal analysis (DTA).

[0060] The acid value of the polymer P is, for example, 105 mgKOH / g or more and 150 mgKOH / g or less, preferably 110 mgKOH / g or more and 150 mgKOH / g or less, more preferably 120 mgKOH / g or more and 150 mgKOH / g or less. The double bond equivalent of the polymer P is, for example, 300 g / mol or more and 500 g / mol or less, preferably 320 g / mol or more and 500 g / mol or less, more preferably 350 g / mol or more and 500 g / mol or less. When the acid value of the polymer P is 100 mgKOH / g or more, good developability can be obtained. Also, when the double bond equivalent is 500 g / mol or less, the sensitivity of the photosensitive resin composition containing the polymer P can be increased.

[0061] If the acid value of the polymer P is higher than the upper limit, the exposed portion may be easily dissolved during development with an alkaline developer, which may increase the amount of exposure required for photocuring or result in an insufficient pattern shape. Therefore, in this embodiment, the upper limit of the acid value is set to 150 mgKOH / g. In addition, if the double bond equivalent of the polymer P is lower than the lower limit (i.e., if the density of double bonds in the polymer is too high), the unexposed or low-exposed areas tend to be difficult to dissolve during development with an alkaline developer, and a residual film tends to be generated during development. In addition, if the double bond equivalent is too small, crosslinking causes an excessive increase in molecular weight, which may result in an excessive decrease in solubility. Therefore, in this embodiment, the lower limit of the double bond equivalent is set to 300 g / mol.

[0062] By adjusting the acid value and / or double bond equivalent of the polymer P, it is possible to achieve both sensitivity and developability at a higher level.

[0063] The acid value and double bond equivalent of the polymer P can be determined by spectrum measurement or the like. For example, they can be determined by the following procedure. For more details, see the examples. (1) Polymer 1 From the H-NMR chart, the areas (integral values) of the peaks corresponding to the hydrogen atoms of the carboxyl group and the hydrogen atoms in the vicinity of the polymerizable carbon-carbon double bond are determined. (2) From the area determined in (1) and the area of ​​the peak derived from the standard substance, the amount of carboxyl groups and the amount of carbon-carbon double bonds are calculated. (3) Convert the amount of carboxyl groups obtained in (2) into an acid value (mgKOH / g). Also, convert the amount of polymerizable carbon-carbon double bonds obtained in (2) into a double bond equivalent (g / mol).

[0064] The acid value and double bond equivalent of polymer P can be adjusted to desired values ​​by appropriately designing the ratio of structural units introduced into polymer P, in particular the number of polymerizable carbon-carbon double bonds possessed by the (meth)acryloyl groups contained in the structural units represented by formulas (1) and (2).

[0065] [Method of manufacturing polymer P] Here, a method for producing the above-mentioned polymer P will be described. The polymer P can be produced (synthesized) by any method. The polymer P can be, for example, Step (I): preparing a raw material polymer containing a structural unit represented by formula (IN) and a structural unit represented by formula (MA); Step (II): A step of reacting the raw polymer obtained in step (I) with a compound having a hydroxyl group and two or more (meth)acryloyl groups (hereinafter referred to as a "polyfunctional (meth)acrylic monomer") and / or a compound having a hydroxyl group and one (meth)acryloyl group (hereinafter referred to as a "monofunctional (meth)acrylic monomer") in the presence of a basic catalyst to prepare a polymer P containing a structural unit represented by formula (IN), as well as a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further containing a structural unit represented by formula (MA).

[0066] In the step (II), when both a polyfunctional (meth)acrylic monomer and a monofunctional (meth)acrylic monomer are used, it is preferable to first react the polyfunctional (meth)acrylic monomer with the raw material polymer, and then react the monofunctional (meth)acrylic monomer with the resulting reaction mixture.

[0067] When the polymer P further contains a structural unit represented by formula (3), in step (II), a polymer containing a structural unit represented by formula (IN), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (MA) is prepared, and then the polymer is treated with water in the presence of a base catalyst (step (III)).

[0068] (Process (I)) In step (I), the step of preparing a raw polymer containing a structural unit represented by formula (IN) and a structural unit represented by formula (MA) includes a step of polymerizing (addition polymerization) a monomer represented by formula (INm) with maleic anhydride. 1 ~R 8 The definition of is the same as that of formula (IN). The same also applies to preferred embodiments.

[0069] [ka]

[0070] Although there is no limitation on the polymerization method, radical polymerization using a radical polymerization initiator is preferable. As the polymerization initiator, for example, an azo compound, an organic peroxide, etc. can be used. Specific examples of the azo compound include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), and 1,1'-azobis(cyclohexanecarbonitrile) (ABCN). Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). The polymerization initiator may be used alone or in combination of two or more kinds.

[0071] The solvent used in the polymerization reaction may be, for example, an organic solvent such as diethyl ether, tetrahydrofuran, toluene, methyl ethyl ketone, etc. The polymerization solvent may be a single solvent or a mixed solvent.

[0072] The synthesis of the raw material polymer is carried out by dissolving the monomer represented by formula (INm), maleic anhydride and a polymerization initiator in a solvent and charging the solution into a reaction vessel, then heating the mixture and allowing addition polymerization to proceed while dropping the bifunctional or higher thiol group-containing compound. The heating temperature is, for example, 50 to 80°C, and the heating time is, for example, 5 to 20 hours. The molar ratio of the monomer represented by formula (INm) to maleic anhydride when charged into a reaction vessel is preferably 0.5:1 to 1:0.5. From the viewpoint of controlling the molecular structure, the molar ratio is preferably 1:1. By such a process, a "raw polymer" can be obtained. The raw polymer may be any of random copolymers, alternating copolymers, block copolymers, and periodic copolymers. Typically, it is a random copolymer or an alternating copolymer. Maleic anhydride is generally known as a monomer with strong alternating copolymerizability.

[0073] After synthesis of the raw polymer, a step of removing low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators may be carried out. Specifically, the organic phase containing the synthesized raw polymer and low molecular weight components is concentrated and then mixed with an organic solvent such as tetrahydrofuran (THF) to obtain a solution. This solution is then mixed with a poor solvent such as methanol to precipitate the monomer. The precipitate is filtered and dried to increase the purity of the raw polymer.

[0074] (Step (II)) The raw polymer obtained in step (I) is reacted with a polyfunctional (meth)acrylic monomer and / or a monofunctional (meth)acrylic monomer in the presence of a basic catalyst, whereby a portion of the structural units represented by formula (MA) contained in the raw polymer undergoes ring-opening to form structural units represented by formula (1) and / or structural units represented by formula (2), thereby obtaining a polymer P containing a structural unit represented by formula (IN), and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally containing a structural unit represented by formula (MA).

[0075] More specifically, first, a solution is prepared by dissolving the raw polymer in an appropriate organic solvent. As the organic solvent, a single solvent or a mixed solvent such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), tetrahydrofuran (THF), etc. can be used, but it is not limited to these, and various organic solvents used in the synthesis of organic compounds and polymers can be used.

[0076] Next, a polyfunctional (meth)acrylic monomer is added to the above solution. A basic catalyst is further added. The solution is then mixed appropriately to obtain a homogeneous solution, thereby obtaining a polymer containing at least the structural unit of formula (IN) and the structural unit of formula (1) (step (II-i)).

[0077] Examples of the polyfunctional (meth)acrylic compound that can be used herein include a compound represented by formula (1b-m), a compound represented by formula (1c-m), and a compound represented by formula (1d-m). 2 The definitions and specific embodiments of are the same as those in the above formula (1b). In addition, k, R, and X in formula (1c-m) 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific embodiment of are the same as those in the above formula (1c). n and R in formula (1d-m) are the same as those in the above formula (1d).

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] Next, the polymer obtained in step (II-i) is reacted with a monofunctional (meth)acrylic monomer in the presence of a basic catalyst to obtain a polymer containing at least the structural unit of formula (IN), the structural unit of formula (1), and the structural unit of formula (2) (step (II-ii).

[0082] Examples of the monofunctional (meth)acrylic compound that can be used include compounds represented by the following general formula (2a-m). In the general formula (2a-m), X 10 The definition of R is the same as that in general formula (2a).

[0083] [ka]

[0084] Specific examples of the compound represented by general formula (2a-m) include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and 2-(meth)acryloyloxyethyl-2-hydroxyethyl-phthalic acid.

[0085] Although only step (II-i) may be carried out, it is preferable to carry out both step (ii-i) and step (II-i).When carrying out both step (II-i) and step (II-ii), it is preferable to carry out step (II-ii) following step (II-i).

[0086] (Process (III)) When carrying out step (III), a process of treating the polymer obtained in step (II) with water in the presence of a basic catalyst is used. Step (III) causes ring-opening of the structural unit represented by formula (MA) contained in the polymer obtained in step (II), forming a structural unit represented by formula (3), and a polymer P containing a structural unit represented by formula (IN), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (3) can be produced. When a part of the structural unit represented by formula (MA) is ring-opened and a part of the structural unit of formula (MA) remains without being ring-opened, the polymer P contains a structural unit represented by formula (MA) in addition to the structural units of formula (IN), formula (1) and / or formula (2), and formula (3).

[0087] The basic catalyst used in step (III) includes amine compounds such as triethylamine, pyridine and dimethylaminopyridine, and nitrogen-containing heterocyclic compounds.

[0088] In step (III), water is added to the reaction system containing the polymer obtained in step (II), and the resulting reaction solution is heated, preferably at 60 to 80° C. for about 0.25 to 6 hours, to open the structural unit of formula (MA) contained in the polymer, and generate a structural unit represented by formula (3). The basic catalyst remaining in the reaction system obtained in step (II) can be used as it is. Therefore, step (III) is preferably carried out in situ by adding water to the reaction mixture obtained in step (II) without performing any post-treatment on the reaction mixture.

[0089] The polymer P of the present embodiment can be obtained by the above steps. From the viewpoint of the effects of the present invention, however, the following steps may be further appropriately carried out in order to remove unnecessary components other than the desired polymer.

[0090] First, the reaction product containing the polymer P obtained above is diluted with an organic solvent, and the reaction solution to which an acid (e.g., formic acid, etc.) is added is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more, separated into an organic phase and an aqueous phase, and the aqueous phase is removed. In this way, an organic solution of the polymer P is obtained. The obtained organic solution containing the polymer P is purified using a reprecipitation method or a liquid-liquid extraction method. In the reprecipitation method, the obtained organic solution of the polymer P is added to an excess amount of toluene or water to reprecipitate the polymer. In addition, the polymer powder obtained by reprecipitation is washed several times with toluene or water. Furthermore, in order to remove formic acid and basic catalyst, the obtained polymer powder is washed with ion-exchanged water several times (about 1 to 3 times). The polymer powder after washing with ion-exchanged water is dried, for example, at 30 to 60 ° C for 16 hours or more to obtain a high-purity polymer.

[0091] In the liquid-liquid extraction method, water is added to the obtained organic solution of polymer P, and the solution is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more, and the organic phase and aqueous phase are separated, and the aqueous phase is removed. Further, water is added to the organic solution of the polymer after the aqueous phase has been removed, and the solution is vigorously stirred in a separatory funnel for at least 3 minutes. This is left to stand for 30 minutes or more, and the organic phase and aqueous phase are separated, and the aqueous phase is removed. In this way, an organic solution of the polymer is obtained. If necessary, the steps of adding water and removing the aqueous phase may be further carried out. The obtained organic solution of polymer P can be concentrated by heating under reduced pressure using a rotary evaporator, and then the final solvent (PGMEA, etc.) is added to dilute the solution, and this process can be repeated to obtain a solution of polymer P dissolved in the final solvent.

[0092] The polymer solution may contain a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound used in synthesizing the polymer P. When the polymer solution contains these (meth)acrylic compounds, the peak area derived from the polyfunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart is preferably 5 to 50%, particularly 10 to 35%, of the peak area of ​​the polymer P, and the peak area derived from the monofunctional (meth)acrylic compound is preferably 5 to 50%, particularly 10 to 35%, of the peak area of ​​the polymer P. This allows the photosensitive resin composition containing this polymer solution to have good alkali solubility and good sensitivity in photolithography.

[0093] [Polymer solution] The polymer solution of this embodiment contains the polymer P described above. The polymer solution of the present embodiment may contain, together with the polymer (A), at least one selected from a polyfunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and a compound having a thiol group and an alkoxy group or an oligomer thereof.

[0094] (Polyfunctional (meth)acrylic compound) The polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound that can be contained in the polymer solution of this embodiment may be an unreacted (meth)acrylic compound used in the production of polymer P, or may be one that has been added separately.

[0095] Examples of polyfunctional (meth)acrylic compounds that can be incorporated into the polymer solution include, but are not limited to, compounds represented by the following general formula (1b-p), compounds represented by general formula (1c-p), and compounds represented by general formula (1d-p).

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] k, R, and X in general formula (1b-p) 1 , X 1 ' and X 2 The definitions and specific embodiments of are the same as those in the above general formula (1b). 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific embodiments of are the same as those in the above general formula (1c).

[0100] In general formulae (1b-p), (1c-p) and (1d-p), Y is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[0101] The compounds in which Y is a hydrogen atom in general formula (1b-p), general formula (1c-p) and general formula (1d-p) may be unreacted monomers (i.e., compounds represented by general formula (1b-p), general formula (1c-p) and general formula (1d-p)) or may be added separately. In the general formula (1d-p), n is an integer of 2 or more, preferably an integer of 2 to 5, and more preferably an integer of 2 to 3.

[0102] When a polyfunctional (meth)acrylic compound is blended into the polymer solution of this embodiment in addition to the unreacted polyfunctional (meth)acrylic compound used in the production of polymer P, the blending amount can be such that the peak area attributable to the polyfunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less of the peak area of ​​polymer P.

[0103] (Monofunctional (meth)acrylic compound) The monofunctional (meth)acrylic compound to be blended in the polymer solution of the present embodiment includes a compound represented by the following formula (2a-m). In formula (2a-m), X 10 and R is defined as in formula (2a).

[0104] [ka]

[0105] When a monofunctional (meth)acrylic compound is blended into the polymer solution of this embodiment in addition to the unreacted monofunctional (meth)acrylic compound used in the production of polymer P, the blending amount can be such that the peak area attributable to the monofunctional (meth)acrylic compound in a gel permeation chromatography (GPC) chart of the polymer solution is preferably 10% or less, more preferably 5% or less, and even more preferably 2% or less of the peak area of ​​polymer P.

[0106] (Compound having a thiol group and an alkoxy group or an oligomer thereof (compound (B))) The compound having a thiol group and an alkoxy group or its oligomer (referred to as "compound (B)" in this specification) that can be blended into the polymer solution of this embodiment can be any known compound as long as it has a thiol group and an alkoxy group and can achieve the effects of the present invention.

[0107] The polymer solution of the present embodiment contains the compound (B) or its oligomer, and thus can provide a resin cured product having excellent adhesion to a substrate, etc. The substrate is not particularly limited, but examples thereof include a glass substrate, a silicon wafer, a ceramic substrate, an aluminum substrate, a SiC wafer, a GaN wafer, and a copper-clad laminate, as described below.

[0108] In the present embodiment, from the viewpoint of the effects of the present invention, the alkoxy group contained in compound (B) is preferably an alkoxy group having 1 to 3 carbon atoms, and also preferably has a structure in which a thiol group and an alkoxy group are bonded to an organic chain which may contain one or more atoms selected from O, N, S, P, and Si. Specifically, the compound (B) preferably includes a compound represented by the following general formula (a).

[0109] [ka]

[0110] In general formula (a), R each independently represents an alkoxy group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms, and at least two R are alkoxy groups having 1 to 3 carbon atoms. L represents an m+n valent organic chain which may contain one or more atoms selected from O, N, S, P and Si.

[0111] In this embodiment, examples of the m+n valent organic chain of L include a linear or branched alkylene group (m+n:2) having 1 to 10 carbon atoms, an m+n valent group derived from a linear or branched alkane having 1 to 20 carbon atoms, and an m+n valent group derived from a substituted or unsubstituted siloxane.

[0112] X represents a single bond, or a divalent organic group which may contain a carbonyl group, a (thio)ester group or a (thio)amide group. In this embodiment, X is preferably a single bond or an alkylene ester group having 1 to 10 carbon atoms. Q represents a single bond, or a divalent organic group which may contain a carbonyl group, a (thio)ester group, or a (thio)amide group. In this embodiment, Q is preferably a single bond or an alkylene ester group having 1 to 10 carbon atoms. The molar ratio of m:n is 1:1 to 1:8, and m+n is 2 to 20. The weight average molecular weight of the compound is 100-2,000.

[0113] Examples of compound (B) include 3-mercaptopropylmethyldimethoxysilane (KBM-802, manufactured by Shin-Etsu Silicones), 3-mercaptopropyltrimethoxysilane (KBM-803, manufactured by Shin-Etsu Silicones), (3-mercaptopropyl)triethoxysilane, a siloxane chain-containing multifunctional silane coupling agent (KR-519, manufactured by Shin-Etsu Silicones), and an organic chain-containing multifunctional silane coupling agent having the following structural unit:

[0114] [ka]

[0115] In the above general formula, a:b (molar ratio) is 2:1 to 4:1. The weight average molecular weight is 1000 to 1500. * is a bond. Examples of the compound include X-12-1154 (manufactured by Shin-Etsu Silicones). The compound (B) or its oligomer may be used alone or in combination of two or more kinds.

[0116] In the polymer solution of this embodiment, the compound (B) is blended in an amount of 0.25 to 20 mass %, preferably 1.0 to 15 mass %, and more preferably 2.0 to 12 mass %, relative to the polymer P, from the viewpoint of the effects of the present invention.

[0117] The polymer solution of the present embodiment typically contains an organic solvent and is provided in the form of a liquid or varnish. The organic solvent may be one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, etc.

[0118] Specific examples of the organic solvent include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyrolactone, N-methylpyrrolidone, cyclohexanone, etc. These may be used alone or in combination of two or more. The amount of the organic solvent used is not particularly limited, but is used in such an amount that the concentration of the non-volatile components becomes, for example, 10 to 70% by mass, and preferably 15 to 60% by mass.

[0119] [Preparation of polymer solution] The polymer solution of the present embodiment can be prepared by mixing the above components by a known method. The polymer solution of the present embodiment is used as a resin material for the photosensitive resin composition described below.

[0120] [Photosensitive resin composition] The photosensitive resin composition of the present embodiment includes the above-mentioned polymer P and a photoradical polymerization initiator. That is, the photosensitive resin composition of the present embodiment includes the above-mentioned polymer solution and a photoradical polymerization initiator. Each component will be described below.

[0121] (Photoradical polymerization initiator) As the photoradical polymerization initiator used in the photosensitive resin composition of the present embodiment, a known compound can be used, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-hydroxy-2-methylpropionyl}benzyl]phenyl. alkylphenone compounds such as 2-methyl-1-(4-morpholinophenyl)-2-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzophenone compounds such as benzoin methyl ether, 4,4'-bis(dimethylamino)benzophenone, and 2-carboxybenzophenone; benzoin compounds such as benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, and 2,4-diethylthioxanthone; 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl ... halomethylated triazine compounds such as 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine; halomethylated oxadiazole compounds such as 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole;Biimidazole compounds such as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole; 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzoyloxime)], ethanone, Examples of the photoradical polymerization initiator include oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium; benzoic acid ester compounds such as p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid; and acridine compounds such as 9-phenylacridine. The photoradical polymerization initiator may be used alone or in combination of two or more kinds. The photoradical polymerization initiator is used in an amount of, for example, 1 to 20 parts by mass, preferably 3 to 10 parts by mass, relative to 100 parts by mass of the polymer.

[0122] The photosensitive resin composition of the present embodiment contains the above components, and thus has high sensitivity in photolithography processing and excellent alkali solubility, and therefore has excellent developability and processability in photolithography.

[0123] (Coloring agent) In one embodiment, the photosensitive resin composition may contain a colorant. By containing a colorant, the composition can be preferably used as a material for forming a color filter of a liquid crystal display device or a solid-state image sensor. As the colorant, various pigments or dyes can be used. As the pigment, an organic pigment or an inorganic pigment can be used.

[0124] Examples of organic pigments that can be used include azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, perinone pigments, isoindolinone pigments, isoindoline pigments, dioxazine pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, metal complex pigments, diketopyrrolopyrrole pigments, xanthene pigments, pyrromethene pigments, and dye lake pigments.

[0125] Examples of inorganic pigments that can be used include white pigments and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), chromatic pigments (yellow lead, cadmium-based pigments, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine, Prussian blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), luster pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.).

[0126] As the dye, for example, known dyes described in JP-A-2003-270428, JP-A-9-171108, JP-A-2008-50599, etc. can be used. When the photosensitive resin composition contains a colorant, the photosensitive resin composition may contain only one type of colorant, or may contain two or more types of colorants.

[0127] Colorants (particularly pigments) having an appropriate average particle size can be used depending on the purpose and application. When transparency is required, such as in color filters, a small average particle size of 0.1 μm or less is preferred, while when hiding properties are required, such as in paints, a large average particle size of 0.5 μm or more is preferred.

[0128] Depending on the purpose and use, the colorant may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating, etc.

[0129] When the photosensitive resin composition contains a colorant, the amount of the colorant may be appropriately set depending on the purpose and use. In order to achieve a balance between the coloring concentration and the dispersion stability of the colorant, the amount of the colorant is preferably 3 to 70 mass %, more preferably 5 to 60 mass %, and even more preferably 10 to 50 mass % based on the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

[0130] (Surfactant) The photosensitive resin composition of the present embodiment may contain a surfactant, and the surfactant is preferably a nonionic surfactant.

[0131] The inclusion of a nonionic surfactant improves the coatability of the photosensitive resin composition when it is applied onto a substrate to obtain a resin film, making it possible to obtain a coating film of uniform thickness, and also makes it possible to prevent residues and pattern lifting during development of the coating film.

[0132] The nonionic surfactant is, for example, a compound containing a fluorine group (e.g., a fluorinated alkyl group) or a silanol group, or a compound having a siloxane bond as the main skeleton. In this embodiment, it is more preferable to use a nonionic surfactant containing a fluorine-based surfactant or a silicone-based surfactant, and it is particularly preferable to use a fluorine-based surfactant. Examples of fluorine-based surfactants include, but are not limited to, Megafac F-171, F-173, F-444, F-470, F-471, F-475, F-482, F-477, F-554, F-556, and F-557 manufactured by DIC Corporation, and Novec FC4430 and FC4432 manufactured by Sumitomo 3M Limited. When a surfactant is used, the amount of the surfactant added is preferably 0.01 to 10% by weight based on 100 parts by weight of the resin.

[0133] (solvent) The photosensitive resin composition may typically contain a solvent. As the solvent, an organic solvent is preferably used. Specifically, one or more of ketone-based solvents, ester-based solvents, ether-based solvents, alcohol-based solvents, lactone-based solvents, carbonate-based solvents, etc. may be used.

[0134] Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutyl carbinol (MIBC), gamma butyrolactone (GBL), N-methylpyrrolidone (NMP), methyl-n-amyl ketone (MAK), diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, or mixtures thereof. The amount of the solvent used is not particularly limited, but is used in an amount such that the concentration of non-volatile components becomes, for example, 10 to 70% by mass, and preferably 15 to 60% by mass.

[0135] (Light blocking agent) The resin composition of the present embodiment may contain a light-shielding agent. The photosensitive resin composition may contain only one type of light-shielding agent, or may contain two or more types of light-shielding agents.

[0136] When the photosensitive resin composition contains a light-shielding agent, the amount of the light-shielding agent may be appropriately set depending on the purpose and use. In order to achieve a balance between the light-shielding performance and the dispersion stability of the light-shielding agent, the amount of the light-shielding agent is preferably 3 to 70 mass %, more preferably 5 to 60 mass %, and even more preferably 10 to 50 mass % based on the total non-volatile components (components excluding the solvent) of the photosensitive resin composition.

[0137] (Crosslinking agent) The photosensitive resin composition of the present embodiment may contain a crosslinking agent. The crosslinking agent is not particularly limited as long as it is capable of crosslinking a polymer (capable of chemically bonding with a polymer) by the action of an active chemical species generated from a photoradical polymerization initiator. The crosslinking agent may form a bond by reacting with itself instead of only chemically bonding with the polymer.

[0138] The crosslinking agent is preferably, for example, a polyfunctional compound having two or more polymerizable double bonds in one molecule, and more preferably a polyfunctional (meth)acrylic compound having two or more (meth)acryloyl groups in one molecule (however, the crosslinking agent does not fall under the above-mentioned polymer). It is preferable to use a crosslinking agent having the same type of crosslinking group as the crosslinking group (polymerizable double bond) of the polymer in terms of uniform curing property, further improvement of sensitivity, etc. There is no particular upper limit to the number of functions (the number of polymerizable double bonds) per molecule of the crosslinking agent, but it is, for example, 8 or less, and preferably 6 or less.

[0139] Specific examples of crosslinking agents include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, bisphenol F alkylene oxide di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene polyfunctional (meth)acrylates such as ethylene oxide-added ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added ditrimethylolpropane tetra(meth)acrylate, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate, and ε-caprolactone-added dipentaerythritol hexa(meth)acrylate; polyfunctional vinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexavinyl ether; vinyl ether group-containing (meth)acrylic acid esters, such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate; polyfunctional allyl ethers such as ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether; Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate; Polyfunctional (meth)acryloyl group-containing isocyanurates such as tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide-added tri(acryloyloxyethyl)isocyanurate, and alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate; Polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; Polyfunctional urethane (meth)acrylates obtained by reacting polyfunctional isocyanates, such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, with hydroxyl group-containing (meth)acrylic acid esters, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Polyfunctional aromatic vinyls such as divinylbenzene; etc. can be mentioned.

[0140] Of these, trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate, tetrafunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate and ditrimethylolpropane tetra(meth)acrylate, and hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate are preferred.

[0141] When the photosensitive resin composition contains a crosslinking agent, the photosensitive resin composition may contain only one type of crosslinking agent, or may contain two or more types of crosslinking agents. When the photosensitive resin composition contains a crosslinking agent, the amount of the crosslinking agent may be appropriately set according to the purpose and use. As an example, the amount of the crosslinking agent may be usually 30 to 70 parts by mass, preferably about 40 to 60 parts by mass, relative to 100 parts by mass of the photosensitive resin.

[0142] (Other additives) The photosensitive resin composition may contain components such as a filler, a binder resin other than the above-mentioned polymer, an acid generator, a heat resistance improver, a developing aid, a plasticizer, a polymerization inhibitor, an ultraviolet absorber, an antioxidant, a matting agent, an antifoaming agent, a leveling agent, an antistatic agent, a dispersant, a slip agent, a surface modifier, a thixotropic agent, a thixotropic aid, a silane coupling agent, and a polyhydric phenol compound depending on various purposes and required properties.

[0143] [Application] A patterned film can be obtained by forming a film using the above-mentioned photosensitive resin composition, and then exposing and developing the film to form a pattern. This film is applied to color filters, black matrices, and the like. That is, a color filter can be obtained by forming a pattern using a photosensitive resin composition containing a colorant. Also, a black matrix can be obtained by forming a pattern using a photosensitive resin composition containing a light-shielding agent. Then, a liquid crystal display device or a solid-state imaging device equipped with a color filter or a black matrix can be manufactured. A typical procedure for forming a pattern will now be described.

[0144] (Photosensitive resin film formation) For example, the above-mentioned photosensitive resin composition is applied onto any substrate and dried as necessary to obtain a photosensitive resin film.

[0145] The substrate to which the composition is applied is not particularly limited, and examples thereof include glass substrates, silicon wafers, ceramic substrates, aluminum substrates, SiC wafers, GaN wafers, and copper-clad laminates. The substrate may be an unprocessed substrate or a substrate having electrodes or elements formed on its surface, and may be surface-treated to improve adhesion.

[0146] The method for applying the photosensitive resin composition is not particularly limited, and may be spin coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, an inkjet method, or the like.

[0147] The photosensitive resin composition applied onto the substrate is typically dried by heating using a hot plate, hot air, an oven, etc. The heating temperature is usually 80 to 140° C., and preferably 90 to 120° C. The heating time is usually 30 to 600 seconds, and preferably about 30 to 300 seconds.

[0148] The thickness of the photosensitive resin film is not particularly limited and may be adjusted appropriately depending on the pattern to be finally obtained, but is usually 0.5 to 10 μm, preferably 1 to 5 μm. The thickness can be adjusted by the content of the solvent in the photosensitive resin composition, the coating method, etc.

[0149] (exposure) Exposure is typically carried out by applying actinic rays to the photosensitive resin film through an appropriate photomask.

[0150] Examples of actinic rays include X-rays, electron beams, ultraviolet rays, and visible rays. In terms of wavelength, light of 200 to 500 nm is preferred. In terms of pattern resolution and ease of handling, the light source is preferably g-ray, h-ray, or i-ray from a mercury lamp, and particularly preferably i-ray. Two or more light rays may be mixed and used. As the exposure device, a contact aligner, a mirror projection aligner, or a stepper is preferred. The amount of light for exposure may be appropriately adjusted depending on the amount of photosensitizer in the photosensitive resin film, but is, for example, 100 to 500 mJ / cm 2 That's about it.

[0151] After exposure, the photosensitive resin film may be heated again (post-exposure bake) if necessary. The temperature is, for example, 70 to 150° C., and preferably 90 to 120° C. The time is, for example, 30 to 600 seconds, and preferably 30 to 300 seconds. Post-exposure bake promotes the reaction caused by the radicals generated from the photoradical polymerization initiator, and further accelerates the curing reaction.

[0152] (developing) The exposed photosensitive resin film can be developed with an appropriate developer to obtain a pattern, and a substrate having a pattern can be produced. A photosensitive resin film made of a photosensitive resin composition containing the polymer solution of this embodiment has excellent adhesion to a substrate, and therefore peeling of the pattern is suppressed during the development process.

[0153] In the development step, development can be carried out using an appropriate developer, for example, by a dipping method, a paddle method, a rotary spray method, etc. By development, the exposed area (in the case of a positive type) or the unexposed area (in the case of a negative type) of the photosensitive resin film is dissolved and removed, thereby obtaining a pattern. There is no particular limitation on the type of developer that can be used, and for example, an alkaline aqueous solution or an organic solvent can be used.

[0154] Specific examples of the alkaline aqueous solution include: (i) aqueous inorganic alkaline solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia; (ii) aqueous organic amine solutions such as ethylamine, diethylamine, triethylamine, and triethanolamine; and (iii) aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide. The polymer of the present embodiment has adjusted alkali solubility and excellent sensitivity, and therefore, when a strongly basic developer such as a TMAH (tetramethylammonium hydroxide) solution is used, a pattern after exposure and development can be formed into a designed shape.

[0155] Specific examples of the organic solvent include ketone-based solvents such as cyclopentanone, ester-based solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether-based solvents such as propylene glycol monomethyl ether. The developer may contain, for example, a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like.

[0156] In this embodiment, it is preferable to use an alkaline aqueous solution as the developer, and it is more preferable to use tetramethylammonium hydroxide, an aqueous sodium carbonate solution, or an aqueous potassium hydroxide solution. The concentration of the aqueous alkaline solution is preferably 0.01 to 10% by mass, and more preferably 0.5 to 5% by mass. Through the above steps, a pattern can be obtained / a substrate having a pattern can be manufactured, but various treatments may be carried out after development.

[0157] For example, after development, the pattern and the substrate may be washed with a rinse solution. Examples of the rinse solution include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether. These may be used alone or in combination of two or more.

[0158] The pattern thus obtained may be heated to be sufficiently cured. The heating temperature is typically 150 to 400°C, preferably 160 to 300°C, and more preferably 200 to 250°C. The heating time is not particularly limited, but is, for example, within the range of 15 to 300 minutes. This heat treatment can be performed using a hot plate, an oven, a temperature-programmable heating oven, or the like. The atmospheric gas used in the heat treatment may be air or an inert gas such as nitrogen or argon. Heating may also be performed under reduced pressure. FIG. 1 shows a schematic diagram of an example of the structure of a liquid crystal display device and / or a solid-state imaging device that includes a color filter and / or a black matrix.

[0159] A black matrix 11 and a color filter 12 are formed on a substrate 10. In addition, a protective film 13 and a transparent electrode layer 14 are provided on the black matrix 11 and the color filter 12.

[0160] The substrate 10 is usually made of a material that transmits light, such as glass, polyester, polycarbonate, polyolefin, polysulfone, a polymer of a cyclic olefin, etc. The substrate 10 may be subjected to a corona discharge treatment, an ozone treatment, a chemical treatment, etc., as necessary. The substrate 10 is preferably made of glass. The black matrix 11 is made of, for example, a cured product of a photosensitive resin composition containing a light-shielding agent.

[0161] There are usually three colors, red, green, and blue, for the color filter 12. The color filter 12 is made of a cured product of a photosensitive resin composition containing a coloring agent corresponding to each color.

[0162] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can also be adopted. Examples of embodiments are given below. 1. A polymer comprising a structural unit represented by formula (IN) and a structural unit represented by formula (1).

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[0163] EXAMPLES Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited to these.

[0164] The compounds used in the examples may be indicated by the following abbreviations or trade names. ·MA: Maleic anhydride ·IN: Inden ·NB: 2-Norbornene ST: Styrene MEK: Methyl ethyl ketone ·PGMEA: Propylene glycol monomethyl ether acetate KBM-803: 3-mercaptopropyltrimethoxysilane (Shin-Etsu Silicone Co., Ltd.) 4-HBA: 4-Hydroxybutyl acrylate A-TMM-3LM-N: A mixture of the following two compounds. The amount of the compound on the left in the mixture based on gas chromatography is approximately 57% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0165] [ka]

[0166] A-TMM-3L: A mixture of the following two compounds. The amount of the compound on the left in the mixture based on gas chromatography is approximately 55% (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0167] [ka]

[0168] <Synthesis of raw polymer> (Synthesis of raw polymer 1) In a reaction vessel of suitable size equipped with a stirrer and a cooling tube, 122.4g (1.05 mol) of indene, 1376.7g of methyl ethyl ketone, and 9.70g (0.042 mol) of dimethyl 2,2'-azobis(2-methylpropionate) were weighed and placed in the vessel, and stirred and dissolved. Next, the dissolved oxygen in the system was removed by nitrogen bubbling, and the vessel was heated. When the internal temperature reached 80°C, 103.2g (1.05 mol) of maleic anhydride was dissolved in 741.30g of MEK, and the solution in which the dissolved oxygen in the system was removed by nitrogen bubbling was added over 3 hours. After that, the vessel was heated at 80°C for 4 hours to polymerize maleic anhydride and indene, and a polymerized solution was produced. The polymerization solution obtained above was dropped into 2047.94 g of methanol to precipitate a white solid. The obtained white solid was washed with 2047.94 g of methanol and then vacuum dried at a temperature of 120° C. to obtain 320.1 g of a polymer (raw polymer 1) having a structural unit derived from indene and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 9248 and a polydispersity index (weight average molecular weight Mw) / (number average molecular weight Mn) of 2.31.

[0169] (Synthesis of raw polymer 2) 353.02g (3.6 mol) of maleic anhydride, 338.94g (3.6 mol) of 2-norbornene, and 33.16g (0.144 mol) of dimethyl 2,2'-azobis(2-methylpropionate) were weighed into a suitable sized reaction vessel equipped with a stirrer and a condenser, and dissolved in a mixed solvent of 1030.1g of methyl ethyl ketone and 113.0g of toluene to prepare a solution. Nitrogen was bubbled through this solution for 30 minutes to remove oxygen, and then the solution was heated at 65°C for 1.5 hours with stirring, and then further heated at 80°C for 6 hours to polymerize the maleic anhydride and 2-norbornene, producing a polymerized solution. The polymerization solution obtained above was dropped into 8519.9 g of methanol to precipitate a white solid. The obtained white solid was vacuum dried at a temperature of 120° C. to obtain 607.5 g of a polymer (raw polymer 2) having a structural unit derived from 2-norbornene and a structural unit derived from maleic anhydride. The resulting polymer was measured by gel permeation chromatography (GPC) to find that it had a weight average molecular weight Mw of 7,000 and a polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) of 1.82.

[0170] (Synthesis of raw polymer 3) XIRAN (registered trademark) 1000 (styrene-maleic anhydride copolymer, (styrene:maleic acid ratio = 1:1), manufactured by Tomoe Engineering Co., Ltd.), which is a copolymer consisting of structural units derived from styrene and structural units derived from maleic anhydride, was prepared and used as raw polymer 3. The weight average molecular weight Mw of the raw material polymer 3 was 6,478, and the polydispersity (weight average molecular weight Mw) / (number average molecular weight Mn) was 2.51.

[0171] <Preparation of Polymer P> In each preparation example, polymer P was prepared. Table 1 shows the components used in the preparation examples, the amount of each component charged in terms of maleic anhydride (MA), and the amount of each structural unit (mol fraction, mol%). 1 The values ​​were calculated by 1 H-NMR integral analysis and expressed in terms of maleic anhydride (MA).

[0172] (Preparation Example 1) Polymer P1 was prepared by ring-opening the MA units of raw material polymer 1 with a trifunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound, as described in detail below. First, 99.71g of MEK was added to 60g of raw polymer 1 (0.312 moles of MA) to prepare a solution. Next, 38.75g of A-TMM-3LM-N was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. After that, 56.27g (0.390 moles) of 4-HBA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. The reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase. The polymer was then purified as follows: The polymer was reprecipitated with an excess amount of toluene. The polymer powder obtained by reprecipitation was washed twice with an excess amount of toluene. After washing twice, the polymer powder was washed with an excess amount of water three times. The resulting reaction product was dried at 40°C for 16 hours. As a result of the above, 48.12 g of polymer P1 was obtained in which the structural units derived from maleic anhydride in raw polymer 1 were ring-opened with A-TMM-3LM-N and 4-HBA. By GPC measurement of the polymer P1, it was confirmed that the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used disappeared. This confirmed that the obtained polymer P1 did not contain any unreacted (meth)acrylic compound or any (meth)acrylic compound without a hydroxyl group. The weight average molecular weight (Mw) and polydispersity (Mw / Mn) of the polymer P1 measured by GPC measurement are shown in Table 1. Polymer P1 has a structure in which the ring is opened with A-TMM-3LM-N and 4-HBA. 1 This was confirmed by H-NMR.

[0173] (Preparation Example 2) The MA units of the raw material polymer 1 were ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water to prepare a polymer P2, as described in detail below. 99.71g of MEK was added to 60g of raw polymer 1 (0.312 moles of MA) to prepare a solution. Next, 38.75g of A-TMM-3LM-N was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. After that, 56.27g (0.390 moles) of 4-HBA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. Next, 3.00 g (0.167 mol) of water was added to the resulting reaction solution without post-treatment, and the mixture was reacted at 70° C. for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. The polymer was then purified by the following procedure. The polymer was reprecipitated with an excess amount of toluene. The polymer powder obtained by reprecipitation was washed twice with an excess amount of toluene. After washing twice, the polymer powder was washed with an excess amount of water three times. The reaction product was dried at 40°C for 12 hours. As a result of the above, 45.12 g of polymer P2 was obtained by ring-opening the structural units derived from maleic anhydride in raw polymer 1 with A-TMM-3LM-N, 4-HBA and water. By GPC measurement of polymer P2, it was confirmed that the peaks of the polyfunctional (meth)acrylic compound and monofunctional (meth)acrylic compound used disappeared. This confirmed that the obtained polymer P7 did not contain any unreacted (meth)acrylic compound or (meth)acrylic compound without a hydroxyl group. The weight average molecular weight (Mw) and polydispersity (Mw / Mn) of polymer P2 measured by GPC measurement are shown in Table 1. The polymer P2 has a structure in which the ring is opened with A-TMM-3LM-N, 4-HBA and water. 13 Confirmed by C-NMR.

[0174] (Preparation Example 3) The MA unit of the raw material polymer 1 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water to prepare a resin mixture containing the polymer P3. The details are described below. First, 99.71g of MEK was added to 60.00g of raw polymer 1 (0.312 moles of MA) to prepare a solution. Next, 38.75g of A-TMM-3LM-N was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. After that, 56.27g (0.390 moles) of 4-HBA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. Next, 3.00 g (0.167 mol) of water was added to the resulting reaction solution without post-treatment, and the reaction was allowed to proceed at 70° C. for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. Liquid-liquid extraction and subsequent solvent replacement were then carried out according to the following procedure. Liquid-liquid extraction: The reaction solution was diluted with MEK, then water was added and treated to remove the aqueous phase from the reaction solution, and the same procedure was repeated once more. Solvent replacement: The resulting reaction mixture was subjected to solvent removal at 50°C under reduced pressure using a rotary evaporator. When it was confirmed that the solid content of the polymer solution was 27±2% by mass as measured by a heat-drying moisture meter, the solvent removal operation was discontinued. After that, PGMEA was added so that the solid content was 18% by mass, and mixed until uniform. The same operation was performed to remove the solvent at 50°C under reduced pressure, and the solid content was adjusted to 27±2% by mass as measured by a heat-drying moisture meter. Then, PGMEA was added so that the solid content was 18% by mass, and the operation of mixing until uniform was repeated two more times. After that, the solvent was removed or PGMEA was added so that the solid content was 30±3% by mass, and the mixture was stirred until uniform. The above operation removed the solvent used in the reaction, and the solvent was replaced with PGMEA. Next, 5% by mass of KBM-803 was added to the solid content of the obtained polymer solution. As a result of the above, polymer P3 was obtained by ring-opening the structural units derived from maleic anhydride in raw polymer 1 with A-TMM-3LM-N, 4-HBA, and water, and polymer solution 3 containing remaining (free) A-TMM-3LM-N, remaining (free) 4-HBA, and KBM-803 was obtained. The obtained polymer solution 3 was analyzed by gel permeation chromatography to measure the amounts of polymer P3, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the composition, as well as the weight average molecular weight and polydispersity of polymer P3. The results are shown in Table 1. The amount of free (meth)acrylic compounds is shown as the ratio (%) of the peak area of ​​the free (meth)acrylic compounds to the peak area of ​​polymer P3 in a gel permeation chromatography (GPC) chart of the resin mixture. The measurement conditions for gel permeation chromatography are as follows. The GPC measurement device used was a Tosoh HLC-8320GPC EcoSEC. The column temperature was set to 40.0°C, and the pump flow rate was set to 0.350 mL / min. Peak position (retention time) - Polymer P3: Peak detected before 20 minutes (peak with shorter retention time and larger molecular weight than A-TMM-3LM-N and 4-HBA) -A-TMM-3LM-N: Sum of two peaks, 20.0-20.6 minutes and 20.6-21.5 minutes -4-HBA: 21.7 to 22.4 minutes Measurement conditions: Analysis was performed using a differential refractive index detector (RI detector).

[0175] (Preparation Example 4) Polymer P4 was prepared by ring-opening the MA units of raw polymer 2 with a hydroxyl group-containing trifunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound, as described in detail below. First, 49.86g of MEK was added to 30g of raw polymer 2 (0.156 moles of MA) to prepare a solution. Next, 19.37g of A-TMM-3L was added to this solution, and then 9.00g (0.089 moles) of triethylamine was added and reacted at 70°C for 2 hours. After that, 28.13g (0.195 moles) of 4-HBA was added and reacted at 70°C for 4 hours to prepare a reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution.The polymer was then purified by the reprecipitation method described below. Reprecipitation method: The polymer was reprecipitated with an excess amount of water. The polymer powder obtained by reprecipitation was washed with an excess amount of water twice. The reaction product obtained was dried at 40°C for 12 hours. As a result, 24.64 g of polymer P4 was obtained by ring-opening the structural units derived from maleic anhydride in raw polymer 2 with A-TMM-3L and 4-HBA. The weight average molecular weight (Mw) and polydispersity (Mw / Mn) of polymer P4 measured by GPC are shown in Table 1. By GPC measurement of the polymer P4, it was confirmed that the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used disappeared, and it was confirmed that the obtained polymer P4 did not contain any unreacted (meth)acrylic compound or any (meth)acrylic compound not having a hydroxyl group. 1 1 H-NMR measurement confirmed that polymer P4 had a structure ring-opened with A-TMM-3L and 4-HBA.

[0176] (Preparation Example 5) The same procedure as in Preparation Example 4 was followed except that A-TMM-3L was replaced with A-TMM-3LM-N, and the structural units derived from maleic anhydride in the raw material polymer 2 were ring-opened with A-TMM-3LM-N and 4-HBA to obtain 23.41 g of polymer P5. The weight average molecular weight (Mw) and polydispersity (Mw / Mn) of polymer P5 measured by GPC are shown in Table 1. GPC measurement of polymer P5 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and monofunctional (meth)acrylic compound used, which confirmed that the obtained polymer P4 did not contain any unreacted (meth)acrylic compound or any (meth)acrylic compound without a hydroxyl group. 1 H-NMR measurement confirmed that polymer P5 had a structure ring-opened with A-TMM-3LM-N and 4-HBA.

[0177] (Preparation Example 6) The MA units of the raw material polymer 2 were ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water to prepare a polymer P6, as described in detail below. 99.71g of MEK was added to 60g of raw polymer 2 (0.312 moles of MA) to prepare a solution. Next, 38.75g of A-TMM-3LM-N was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. Further, 56.27g (0.390 moles) of 4-HBA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. Next, 3.00g (0.167 moles) of water was added to the reaction solution obtained without post-treatment, and the reaction was carried out at 70°C for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution.The polymer was then purified by the reprecipitation method described below. Reprecipitation method: The polymer was reprecipitated with an excess amount of water. The polymer powder obtained by reprecipitation was washed with an excess amount of water twice. The reaction product obtained was dried at 40°C for 12 hours. As a result, 25.77 g of polymer P6 was obtained by ring-opening the structural units derived from maleic anhydride in raw polymer 2 with A-TMM-3LM-N, 4-HBA, and water. The weight average molecular weight (Mw) and polydispersity (Mw / Mn) of polymer P6 measured by GPC are shown in Table 1. GPC measurement of polymer P6 confirmed the disappearance of the peaks of the polyfunctional (meth)acrylic compound and monofunctional (meth)acrylic compound used, which confirmed that the obtained polymer P6 did not contain any unreacted (meth)acrylic compound or any (meth)acrylic compound without a hydroxyl group. Polymer P6 has a structure in which the ring is opened with A-TMM-3LM-N, 4-HBA and water. 13 Confirmed by C-NMR.

[0178] (Preparation Example 7) The MA unit of the raw material polymer 3 was ring-opened with a monofunctional (meth)acrylic compound to prepare a polymer P7, as described in detail below. First, 18.44 g of MEK was added to 10.00 g of raw polymer 3 (0.052 mol in terms of MA) to prepare a solution. Next, 9.38 g (0.065 mol) of 4-HBA was added to this solution, and then 3.00 g (0.030 mol) of triethylamine was added. The mixture was reacted at a temperature of 70° C. for 6 hours to prepare a reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution.The polymer was then purified by the following reprecipitation method. Reprecipitation method: The polymer was reprecipitated with an excess amount of water. The polymer powder obtained by reprecipitation was washed with an excess amount of water twice. The reaction product obtained was dried at 40°C for 12 hours. As a result of the above, 8.0 g of polymer P7 was obtained in which the structural units derived from maleic anhydride in raw polymer 3 were ring-opened with 4-HBA. The weight average molecular weight and polydispersity of the obtained polymer P7 were measured by GPC measurement. The results are shown in Table 1. Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P7, which confirmed that the obtained polymer P7 did not contain any unreacted monofunctional (meth)acrylic compound. 11 H-NMR measurement confirmed that polymer P7 had a structure ring-opened with 4-HBA.

[0179] (Preparation Example 8) The MA unit of the raw material polymer 3 was ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water to prepare a resin mixture containing the polymer P8. The details are described below. First, 99.71g of MEK was added to 60.00g of raw polymer 3 (0.312 moles of MA) to prepare a solution. Next, 38.75g of A-TMM-3LM-N was added to this solution, and then 18.00g (0.178 moles) of triethylamine was added and reacted at a temperature of 70°C for 2 hours. After that, 56.27g (0.390 moles) of 4-HBA was added and reacted at a temperature of 70°C for 4 hours to prepare a reaction solution. Next, 3.00 g (0.167 mol) of water was added to the resulting reaction solution without post-treatment, and the reaction was carried out at 70° C. for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous formic acid solution to remove the aqueous phase from the reaction solution. The polymer was then purified by the following reprecipitation method. Reprecipitation method: The polymer was reprecipitated with an excess amount of water. The polymer powder obtained by reprecipitation was washed with an excess amount of water twice. The reaction product obtained was dried at 40°C for 12 hours. As a result of the above, 45.20 g of polymer P8 was obtained by ring-opening the structural units derived from maleic anhydride in raw polymer 3 with A-TMM-3LM-N, 4-HBA and water. The weight average molecular weight and polydispersity of the obtained polymer P8 were measured by GPC measurement. The results are shown in Table 1. By GPC measurement of the polymer P8, it was confirmed that the peaks of the polyfunctional (meth)acrylic compound and the monofunctional (meth)acrylic compound used disappeared, and it was confirmed that the obtained polymer P8 did not contain any unreacted (meth)acrylic compound or any (meth)acrylic compound not having a hydroxyl group. Polymer P8 has a structure that has been ring-opened with A-TMM-3LM-N, 4-HBA, and water. 13 Confirmed by C-NMR.

[0180] (Preparation Example 9) Polymer P9 was prepared by ring-opening the MA unit of raw material polymer 1 with a monofunctional (meth)acrylic compound, as described in detail below. First, 18.44 g of MEK was added to 10.00 g of raw polymer 1 (0.052 mol in terms of MA) to prepare a solution. Next, 9.38 g (0.065 mol) of 4-HBA was added to this solution, and then 3.00 g (0.030 mol) of triethylamine was added. The mixture was reacted at a temperature of 70° C. for 6 hours to prepare a reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase from the reaction solution.The polymer was then purified by the following reprecipitation method. Reprecipitation method: The polymer was reprecipitated with an excess amount of water. The polymer powder obtained by reprecipitation was washed with an excess amount of water twice. The reaction product obtained was dried at 40°C for 12 hours. As a result of the above, 9.1 g of polymer P9 was obtained in which the structural units derived from maleic anhydride in raw polymer 1 were ring-opened with 4-HBA. The weight average molecular weight and polydispersity of the obtained polymer P9 were measured by GPC measurement. The results are shown in Table 1. Furthermore, the disappearance of the peak of the monofunctional (meth)acrylic compound used was confirmed by GPC measurement of the polymer P9, which confirmed that the obtained polymer P9 did not contain any unreacted monofunctional (meth)acrylic compound. 1 H-NMR measurement confirmed that polymer P9 had a structure ring-opened with 4-HBA.

[0181] (Physical property evaluation) The acid value and double bond equivalent of each of the polymers P prepared in the above Preparation Examples were measured by the following methods.

[0182] (Acid value) The acid value of the polymer was measured by the following method. Approximately 50 mg of the polymer and approximately 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in DMSO-d6. The solution was analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 1 H-NMR measurements were performed. 1 The amount of carboxyl groups is calculated from the integral value of the H peak (around 12.4 ppm) of the polymer's carboxyl group (-COOH) using the integral value of the 4H peak (around 8.1 ppm) of the phenyl group of dimethyl terephthalate, the internal standard for H-NMR measurement, as the standard. The acid value (mgKOH / g) can then be calculated from this amount. The higher the acid value, the greater the amount of carboxyl groups per unit mass of polymer. The results are shown in Table 1. When the acid value is 105 gKOH / g or more, it can be considered that the polymer has a carboxy group necessary for the polymer to have sufficient developability.

[0183] (double bond equivalent) The double bond equivalent of the polymer was measured by the following method. As with the above method for measuring acid value, 1 H-NMR was measured. The amount of acryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal (5.6-5.8 ppm, 3H) derived from the acryloyl group in the obtained spectrum chart to the signal (8.1 ppm, 4H) derived from the phenyl group of the internal standard substance, and the amount of methacryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal (5.6-5.8 ppm, 2H) derived from the phenyl group of the internal standard substance to the signal (8.1 ppm, 4H). Here, the signal derived from the methacryloyl group at 6.0-6.1 ppm was small and overlapped with the signal of the acryloyl group, so it was calculated as the signal of the acryloyl group. The amount of double bonds (mol / g) was calculated from the sum of the amount of acryloyl groups (mol / g) and the amount of methacryloyl groups (mol / g) in the calculated polymer, and the double bond equivalent (g / mol) was calculated from the amount of double bonds. The results are shown in Table 1. A smaller double bond equivalent value indicates a larger amount of C=C double bonds per unit mass of the polymer.

[0184] [Table 1]

[0185] ( Reference example 1, Working Example 2 ~3, Comparative Examples 1~6) Each Example , reference example In the comparative examples, the following items were evaluated.

[0186] <Evaluation> [Alkaline dissolution rate of polymer P (dissolution rate of polymer P in alkaline developer)] The polymers P1, P2, and P4 to P9 obtained in Preparation Examples 1, 2, and 4 to 9 were each dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution having a solid concentration of 30 mass %. Next, the above solution and polymer solution 3 were spin-coated onto a wafer, the PGMEA was dried, and the wafer was pre-baked at a temperature of 100° C. for 2 minutes to prepare a resin film having a thickness of 2 μm±0.2 μm. This resin film was immersed together with the wafer in a 2.0 mass % aqueous sodium carbonate solution at 23° C., and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer, measuring the time it took for the resin film to dissolve and the interference pattern to disappear, and dividing that time by the film thickness. The results are shown in Table 2. If the alkali dissolution rate is 300 nm / s or higher, the developability can be considered to be good, and if it is 400 nm / s or higher, the developability can be considered to be even better.

[0187] [Sensitivity evaluation of photosensitive resin composition (2.0 mass% sodium carbonate aqueous solution)] First, a photosensitive resin composition was obtained by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solid content concentration was 30% by mass. Polymer P (polymers P1, P2, P4 to P9 obtained in Preparation Examples 1, 2, and 4 to 9): 100 parts by mass (Polymer solution 3 was weighed so that the solid content (the total amount of polymer P3, polyfunctional (meth)acrylic compound, and KBM-803) was 100 parts by mass.) Polyfunctional acrylate (dipentaerythritol hexaacrylate, A-DPH): 50 parts by weight Photopolymerization initiator (BASF, Irgacure OXE01): 5 parts by weight Adhesion aid (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.): 1 part by weight Surfactant (DIC Corporation, F-556): 0.5 parts by weight The obtained photosensitive resin composition was filtered, if necessary, through a PTFE membrane filter Millex-LS (manufactured by Merck Millipore) to remove insoluble matters.

[0188] The obtained resin composition was spin-coated on a 3-inch silicon wafer treated with HMDS (hexamethyldisilazane) and baked on a hot plate at 100° C. for 120 seconds to obtain a thin film A having a thickness of about 3.0 μm (±0.3 μm). This thin film A was irradiated with 100 mJ / cm 2 using a Canon g+h+i line mask aligner (PLA-501F) through a photomask having a gradation of light shielding rate of 1 to 100%. 2 The sample was exposed to g+h+i rays at an exposure dose of 1000 x 1000. After exposure, the thin film is developed in a 2.0 mass% sodium carbonate aqueous solution at 23°C for 60 seconds (immersion with the wafer), resulting in a light exposure of 1 to 100 mJ / cm. 2 Thin film B was obtained by exposure and development at each exposure dose. From the film thicknesses of Thin Film A and Thin Film B obtained by the above method, the remaining film rate was calculated according to the following formula. Remaining film rate (%) = (film thickness of thin film B at each exposure dose / film thickness of thin film A) x 100 The exposure dose at which the residual film ratio was 95% or more was regarded as the sensitivity of each photosensitive resin composition and evaluated according to the following criteria. The results are shown in Table 2. The smaller the value of the exposure dose at which the residual film ratio was 95% or more, the higher the sensitivity. 2 If the intensity is less than 15 mJ / cm, it can be used as a photosensitive material without any problems. 2 If it is below this, the sensitivity can be considered to be good.

[0189] [Alkaline dissolution rate of photosensitive resin composition (2.0 mass% sodium carbonate aqueous solution)] The photosensitive resin composition prepared in the above-mentioned sensitivity evaluation was spin-coated onto a wafer, the PGMEA was dried, and the wafer was pre-baked at a temperature of 100° C. for 2 minutes to produce a resin film with a thickness of about 2 μm. This resin film was immersed together with the wafer in a 2% aqueous sodium carbonate solution at 23° C., and the dissolution rate of the resin film was measured. The dissolution rate was calculated by visually observing the immersed wafer, measuring the time it took for the resin film to dissolve and the interference pattern to disappear, and dividing that time by the film thickness. The results are shown in Table 1. If the alkali dissolution rate is 350 nm / s or higher, it can be used as a photosensitive material without any problems, if it is 380 nm / s or higher, the developability can be considered good, and if it is 500 nm / s or higher, the developability can be considered particularly good.

[0190] The results of the alkaline dissolution rate and sensitivity evaluation are shown in Table 2.

[0191] [Table 2]

[0192] The photosensitive resin compositions of the examples had a good alkali dissolution rate and therefore excellent developability. The photosensitive resin compositions of the examples had an exposure dose of 20 mJ / cm2 at which the residual film ratio was 95% or more. 2In other words, it can be said that the photosensitive resin composition of the examples is cured with a low exposure dose and has high sensitivity. Therefore, the photosensitive resin composition of the examples had a good balance between high developability and high sensitivity.

[0193] <Production of color filters> Reference Example 1 and Working Example 2 A suitable amount of pigment dispersion NX-061 (green, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) was further added to the photosensitive resin composition prepared in ~3 to prepare a colored photosensitive resin composition. This was formed into a film on a substrate, and then exposed to light and developed with an alkali to form a green color filter. In addition, by using the same company's NX-053 (blue) or NX-032 (red) as the pigment dispersion liquid instead of NX-061, it was possible to form blue or red color filters.

[0194] <Preparation of black matrix> Reference Example 1 and Working Example 2 A black photosensitive resin composition was prepared by further adding an appropriate amount of carbon black dispersion liquid NX-595 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) to the photosensitive resin composition prepared in ~3. This was applied to a substrate as a film, and then exposed to light and developed with an alkaline solution to form a black matrix. [Explanation of symbols]

[0195] 10 Substrate 11 Black Matrix 12 Color Filters 13 Protective film 14 Transparent electrode layer

Claims

1. A polymer comprising a structural unit represented by formula (IN), a structural unit represented by formula (1), and a structural unit represented by formula (3). 【Chemistry 1】 (In formula (IN), R １ ~R ８ are each independently a hydrogen atom or an organic group having 1 to 30 carbon atoms. 【Chemistry 2】 (In formula (1), R ｐ is a group having two or more (meth)acryloyl groups. 【Chemistry 3】

2. The polymer according to claim 1 , further comprising a structural unit represented by formula (2): 【Chemistry 4】 (In formula (2), R ｓ is a group having one (meth)acryloyl group.

3. The polymer according to claim 1 or 2, further comprising a structural unit represented by the formula (MA). 【Chemistry 5】

4. R in the structural unit represented by the formula (1) ｐ is at least one selected from a group represented by formula (1b), a group represented by formula (1c), and a group represented by formula (1d): 【Chemistry 6】 (In formula (1b), k is 2 or 3; R is a hydrogen atom or a methyl group, and multiple R may be the same or different. X １ is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -Z-X- (Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are a plurality of X １ may be the same or different, X １ ' represents a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented by -X'-Z'- (X' represents an alkylene group having 1 to 6 carbon atoms, and Z' represents -O- or -COO-), X ２ is a k+1 valent organic group having 1 to 12 carbon atoms. 【Chemistry 7】 (In formula (1c), k, R, X １ and X ２ respectively represent R, k, and X in formula (1b). １ and X ２ Each R may be the same or different; each X may be the same or different. １ may be the same or different, X ３ is a divalent organic group having 1 to 6 carbon atoms, X ４ and X ５ each independently represents a single bond or a divalent organic group having 1 to 6 carbon atoms, X ６ is a divalent organic group having 1 to 6 carbon atoms. 【Chemistry 8】 (In formula (1d), n is an integer from 2 to 5, R is a hydrogen atom or a methyl group, and multiple R may be the same or different.

5. R in the structural unit represented by the formula (2) ｓ The polymer according to claim 2 , wherein is a group represented by formula (2a): 【Chemistry 9】 (In formula (2a), X １０ is a divalent organic group, and R is a hydrogen atom or a methyl group.

6. 6. The polymer according to claim 1, having an acid value of 105 mg OKH / g or more and 150 mg OKH / g or less, and a double bond equivalent of 300 g / mol or more and 500 g / mol or less.

7. A polymer solution comprising the polymer according to any one of claims 1 to 6.

8. The polymer solution according to claim 7 , further comprising at least one selected from a polyfunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and a compound having a thiol group and an alkoxy group or an oligomer thereof.

9. The polymer solution according to claim 7 or 8, which is used for forming a color filter or a black matrix.

10. A polymer according to any one of claims 1 to 6; A photoradical polymerization initiator, Photosensitive resin composition.

11. A cured product formed from the photosensitive resin composition according to claim 10.

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