Polymers, polymer solutions, photosensitive resin compositions, and cured products

Abstract

To provide a polymer that has improved heat properties, resulting in excellent processability and patternability in photolithography, well-balanced sensitivity, alkali solubility and thermal yellowing resistance, as well as superior cured resin sensitivity.SOLUTION: A polymer comprises structural units represented by a predetermined formula (NB) and a predetermined formula (AK), and structural units represented by a predetermined formula (1), illustrated below, or a predetermined formula (2). In the formula (1), Rp is a group having two or more (meth)acryloyl groups, and R21 and R22 independently represent a hydrogen atom or a C1-3 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 image sensors typically include color filters and black matrices. Color filters and black matrices are constructed by forming structures such as colored patterns and protective films on a substrate. Among these structures, the most common method for forming colored patterns and protective films is by photolithography using a photosensitive resin composition. Various studies have been conducted on photosensitive resin compositions. For example, Patent Document 1 describes a photosensitive resin composition comprising an alkali-soluble resin having at least one acidic group and two or more different polymerizable unsaturated groups in its side chain, a polymerizable compound, and a photopolymerization initiator. Furthermore, the examples in Patent Document 1 describe the synthesis of a methacrylic acid / allyl methacrylate / glycidyl adduct as the alkali-soluble resin, and the preparation of a photosensitive resin composition using this adduct. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2012 / 147706 [Overview of the project] [Problems that the invention aims to solve]

[0004] Photosensitive resin compositions used to form color filters and black matrices utilize resins that undergo polymerization reactions and harden upon exposure to light. Color filters and black matrices are produced by patterning the photosensitive resin composition through exposure and development, and then curing it. While "increasing sensitivity" may seem like a common challenge for photosensitive resin compositions, the increasing complexity and widespread use of display and imaging devices necessitates even higher levels of sensitivity. The higher the sensitivity of the photosensitive resin composition, the shorter the exposure time required, thereby improving productivity. Furthermore, photosensitive resin compositions are required to have excellent processability in development processes using alkaline developers. In addition, the cured product of the photosensitive resin composition is required to have high transparency. Moreover, especially when dyes and pigments are included in the photosensitive resin composition, light does not reach the bottom surface of the pattern as easily as the top surface during exposure, resulting in insufficient curing by exposure, which can cause the sides of the bottom surface of the pattern to dissolve during development. During the curing process after development, if the pattern melts due to heat, it can fill in the melted portion on the sides of the bottom surface of the pattern. Therefore, the cured product of the photosensitive resin composition requires a low softening point and melting point. [Means for solving the problem]

[0005] The present inventors have discovered that by improving the polymer used in the photosensitive resin composition and the formulation of the composition, it is possible to obtain a cured resin product that has a low softening point and melting point, and therefore excellent processability and pattern formation in photolithography, as well as a good balance of sensitivity, alkali solubility and resistance to heat yellowing, leading to the present invention.

[0006] According to the present invention, A polymer having a structure represented by formula (P'), [ka] In equation (P'), n is an integer between 2 and 6. p, q, and r each represent the molar content of A, B, and C, respectively, where p + q + r = 1, p > 0, q > 0, and r ≥ 0 Larger , and p, q, or r may be the same or different for each structural unit within the n [ ]. A represents a structural unit represented by formula (NB). B contains at least one structural unit selected from the structural unit represented by formula (1) and the structural unit represented by formula (2). C represents a structural unit represented by formula (AK). Multiple As, Bs, and Cs may be the same or different from each other. X is a hydrogen atom. Y is ,blood an organic group having a thioether group, which is a divalent to hexavalent organic group derived from at least one selected from the bifunctional or higher thiol group-containing compounds represented by formulas (s-1) to (s-21). The organic group having the thioether group is bonded to any one of A, B, and C via a thioether group (-S-* (* is a bond)) derived from the thiol group-containing compound. The structural units A, B, and C are arranged randomly or alternately.

Chemical formula

Chemical formula

Chemical formula

[0008] Furthermore, according to the present invention, a polymer solution containing the above-mentioned polymer is provided.

[0009] Furthermore, the present invention provides a photosensitive resin composition comprising the above-mentioned polymer solution and a photopolymerization initiator.

[0010] Furthermore, the present invention provides a cured product formed from the above-mentioned photosensitive resin composition. [Effects of the Invention]

[0013] The present invention provides a polymer for use in a photosensitive resin composition that has a low softening point and melting point, thus exhibiting excellent pattern formation after curing, high alkali solubility, thus exhibiting excellent developability, reduced yellowing, thus exhibiting high heat discoloration resistance, and good sensitivity. [Brief explanation of the drawing]

[0014] [Figure 1] This is a schematic diagram (cross-sectional view) illustrating an example of the structure of a liquid crystal display device and / or a solid-state image sensor. [Figure 2]This is the 13C-NMR chart of raw material polymer 5. [Figure 3] This is the TMA chart for raw material polymer 5. [Modes for carrying out the invention]

[0015] Embodiments of the present invention will be described below. In all drawings, similar components are denoted by the same reference numerals, and their descriptions are omitted as appropriate. Furthermore, all drawings are for illustrative purposes only. The shapes and dimensional ratios of each component in the drawings do not necessarily correspond to actual articles. In this specification, the notation "a~b" in the description of numerical ranges means "a or more and b or less" unless otherwise specified. For example, "5~90%" means "5% or more and 90% or less".

[0016] In this specification, when a group (atomic group) is not specified as substituted or unsubstituted, it includes both unsubstituted and substituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups.

[0017] In this specification, the term "(meth)acrylic" refers to a concept that encompasses both acrylic and methacrylic. The same applies to similar terms such as "(meth)acrylate." In particular, the term "(meth)acryloyl group" as used herein refers to a concept that encompasses both the acryloyl group represented by -C(=O)-CH=CH2 and the methacryloyl group represented by -C(=O)-C(CH3)=CH2.

[0018] [Polymer P] The polymer of the present invention (hereinafter referred to as "polymer P") will now be described. Unless otherwise specified, structural units or compounds represented by the same structural formula have the same definitions across all embodiments, and the same applies to preferred embodiments.

[0019] [First Embodiment] (Polymer P(I)) The polymer in the first embodiment of the present invention (hereinafter referred to as "polymer P(I)") includes a structural unit represented by (NB), a structural unit represented by formula (AK), a structural unit represented by formula (1), and a structural unit represented by formula (2), at least one structural unit selected from these.

[0020] [ka] In equation (NB), R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2.

[0021] [ka] In formula (AK), R 11 , R 12 , R 13 and R 14 At least one of them is a linear or branched alkyl group having 3 or more carbon atoms, R 11 , R 12 , R 13 and R 14 The remaining elements are, independently, hydrogen atoms or linear or branched alkyl groups having 1 to 30 carbon atoms.

[0022] [ka] In formula (1), R p R is a group having two or more (meth)acryloyl groups, 21 and R 22 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0023] [ka] In formula (2), R sR is a group having one (meth)acryloyl group, 21 and R 22 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0024] The polymer P(I) of this embodiment has structural units derived from norbornene represented by formula (NB). Structural units derived from norbornene monomer are chemically robust. Therefore, polymer P(I) containing these structural units exhibits little weight loss and is stable when subjected to heat treatment.

[0025] Furthermore, the polymer P(I) of this embodiment has structural units derived from long-chain alkenes represented by formula (AK). By introducing structural units (AK) derived from long-chain alkenes into polymer P(I), the softening point and melting point of polymer P(I) can be lowered without altering sensitivity, alkali solubility, or heat resistance to yellowing. As a result, polymer P(I) having structural units (AK) derived from long-chain alkenes is easily melted by heat during curing, and exhibits excellent processability and pattern formation properties in photolithography. Therefore, photosensitive resin compositions containing polymer P(I) can be suitably used to manufacture films and filters for use in liquid crystal display devices and solid-state image sensors that require heat resistance.

[0026] Furthermore, the polymer P(I) of this embodiment includes structural units represented by formula (1) and / or formula (2). In other words, polymer P(I) includes either one or both of the structural units represented by formula (1) and formula (2). As a result, the photosensitive resin composition containing polymer P(I) has excellent sensitivity when subjected to photolithography. This is thought to be because the (meth)acryloyl group contained in the structural unit represented by formula (1) or formula (2) promotes the curing reaction (polymerization reaction).

[0027] In a preferred embodiment, polymer P(I) includes a structural unit represented by general formula (1) as an essential component. Since the structural unit represented by formula (1) has at least one (meth)acryloyl group, polymer P(I) containing it has high sensitivity in photolithography.

[0028] In the structural unit represented by the above formula (NB) that constitutes polymer P(I), R 1 ~R 4 Organic groups having 1 to 30 carbon atoms that can constitute these include substituted or unsubstituted, linear or branched alkyl groups having 1 to 30 carbon atoms. More specifically, these include alkyl groups, alkenyl groups, alkynyl groups, alkylidene groups, aryl groups, aralkyl groups, alkalil groups, cycloalkyl groups, alkoxy groups, heterocyclic groups, and carboxyl groups.

[0029] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl groups.

[0030] Examples of alkenyl groups include allyl groups, pentenyl groups, and vinyl groups. Examples of alkynyl groups include the ethynyl group. Examples of alkylidene groups include methylidene groups and ethylidene groups. Examples of aryl groups include tolyl, xylyl, phenyl, naphthyl, and anthracenyl groups.

[0031] Examples of aralkyl groups include the benzyl group and the phenethyl group. Examples of alkalyl groups include tolyl groups and xylyl groups. Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentyloxy, neopentyloxy, and n-hexyloxy groups. Examples of heterocyclic groups include epoxy groups and oxetanyl groups.

[0032] In the structural unit represented by formula (NB), R 1 , R 2 , R 3 and R 4 Hydrogen or alkyl groups are preferred, with hydrogen being more preferred. Note, R 1 , R 2 , R 3 and R 4 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 fluorine atoms, hydroxyl groups, carboxyl groups, etc. More specifically, R 1 , R 2 , R 3 and R 4 As the organic group having 1 to 30 carbon atoms, alkyl groups such as fluoride may be selected. In the structural unit represented by formula (NB), a1 is preferably 0 or 1, more preferably 0.

[0033] The proportion of the structural unit represented by formula (NB) among all structural units constituting polymer P(I) is preferably 25 to 75 mol%, more preferably 30 to 65 mol%, and even more preferably 35 to 60 mol%.

[0034] In the structural unit represented by formula (AK), R 11 , R 12 , R 13 and R 14 At least one of them is a linear or branched alkyl group having 3 or more carbon atoms, preferably 4 or more carbon atoms, more preferably 5 or more carbon atoms, and even more preferably 6 or more carbon atoms. 11, R 12 , R 13 and R 14 The remaining elements are, independently, hydrogen atoms or linear or branched alkyl groups having 1 to 30 carbon atoms. R 11 , R 12 , R 13 and R 14 The upper limit of the number of carbon atoms in a linear or branched alkyl group having 3 or more carbon atoms that constitutes at least one of the elements is, for example, 30 carbon atoms or less, preferably 25 carbon atoms or less, and more preferably 20 carbon atoms or less. In particular, the structural unit represented by formula (AK) is easily introduced into polymer P(I), thus simplifying molecular design, and the resulting polymer P(I) has a low softening point and a low melting point without impairing heat resistance to yellowing, therefore, in the structural unit represented by formula (AK), R 11 , R 12 , R 13 and R 14 One of them is a linear or branched alkyl group having 3 or more carbon atoms, R 11 , R 12 , R 13 and R 14 The remaining three are preferably hydrogen atoms. More preferably, in the structural unit represented by formula (AK), R 11 , R 12 , R 13 and R 14 One of them is a linear alkyl group having 3 or more carbon atoms, R 11 , R 12 , R 13 and R 14 The remaining three are hydrogen atoms. R 11 , R 12 , R 13 and R 14 The more carbon atoms a linear or branched alkyl group with 3 or more carbon atoms makes up at least one of the polymers, the lower the softening point and melting point of the resulting polymer P(I) tend to be. Therefore, the number of carbon atoms in the structural unit of formula (AK) can be selected according to the desired softening point or melting point for the application of polymer P(I).

[0035] The proportion of structural units represented by formula (AK) in the total structural units constituting polymer P(I) is preferably 2 to 30 mol%, more preferably 3 to 28 mol%, and even more preferably 5 to 25 mol%. By setting the proportion of structural units represented by formula (AK) in polymer P(I) within the above range, it is possible to obtain polymer P(I) that has a low softening point and a low melting point, as well as a highly improved balance of sensitivity, alkali solubility, and heat discoloration resistance.

[0036] Polymer P(I) contains structural units comprising two or more (meth)acryloyl groups (-C(=O)-CH=CH2) represented by formula (1), or structural units comprising one (meth)acryloyl group represented by formula (2), or a combination thereof. By comprising such structural units, polymer P(I) has superior sensitivity in exposure processing.

[0037] In equation (1) or equation (2), R 21 and R 22 Organic groups having 1 to 3 carbon atoms that can constitute this include methyl, ethyl, n-propyl, and isopropyl groups. 21 and R 22 Preferably, both are hydrogen atoms.

[0038] In the structural unit represented by formula (1), 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 polymer, the sensitivity of polymer P(I) containing it during exposure treatment can be further increased. Furthermore, it becomes easier to achieve a higher level of compatibility between the sensitivity and alkali solubility of polymer P(I). Additionally, the heat resistance of polymer P(I) can be improved.

[0039] R in equation (1) pis preferably a group represented by formula (1b), a group represented by formula (1c), or a group represented by formula (1d), and contains at least one selected from these. By being such a group, there is a tendency to easily obtain the above various effects.

[0040]

Chemical formula

[0041] In formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and a plurality of Rs 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 a plurality of Xs 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 terms of further improving sensitivity (ease of polymerization). k may be 2 or 3, but is preferably 3 from the viewpoints of availability of raw materials and further improvement of sensitivity.

[0042] X 1 When is an alkylene group having 1 to 6 carbon atoms, the alkylene group may be linear or branched. X 1 When is an alkylene group having 1 to 6 carbon atoms, X 1 is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and even more preferably -CH2- (methylene group).

[0043] X 1When the group is represented by -Z-X- (where 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 of X is preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 3 carbon atoms, and still more preferably -CH2-CH2- (ethylene group) or -CH2-CH(CH3)-.

[0044] X 1 When X' is an alkylene group having 1 to 6 carbon atoms, the specific embodiments thereof are the same as those of X. 1 are the same. X 1 When X' is a group represented by -X'-Z', the specific embodiments of X' are the same as those of X above.

[0045] X 2 As the k + 1-valent organic group having 1 to 12 carbon atoms of X, any group obtained by removing k + 1 hydrogen atoms from any organic compound can be mentioned. Here, the "any organic compound" 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 obtained by removing k + 1 hydrogen atoms from a linear or branched hydrocarbon having 1 to 12 (preferably 1 to 6) carbon atoms. More preferably, it is a group obtained by removing k + 1 hydrogen atoms from a linear hydrocarbon having 1 to 3 carbon atoms. Here, the hydrocarbon may contain an oxygen atom (such as an ether bond or a hydroxy group). Further, 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 (such as an isocyanuric acid structure).

[0046]

Chemical formula

[0047] In formula (1c), k, R, X 1 and X 2 These are R, k, and X in equation (1b), respectively. 1 and X 2 This is synonymous with multiple Rs, which may be the same or different from each other, and multiple X 1 They may be the same or different from each other. X 3 It is a divalent organic group having 1 to 6 carbon atoms. X 4 and X 5 Each of these is independently a single bond or a divalent organic group having 1 to 6 carbon atoms. X 6 It is a divalent organic group having 1 to 6 carbon atoms.

[0048] R, k, X 1 and X 2 The specific embodiments and preferred embodiments are the same as those described in formula (1b). X 3 and X 6 Examples of divalent organic groups having 1 to 6 carbon atoms include groups obtained by removing two hydrogen atoms from a linear or branched hydrocarbon having 1 to 6 carbon atoms. The hydrocarbon here may also contain oxygen atoms (e.g., ether bonds or hydroxyl groups). Furthermore, the hydrocarbon is preferably a saturated hydrocarbon. X 4 and X 5 Examples of divalent organic groups having 1 to 6 carbon atoms include linear or branched alkylene groups. The linear or branched alkylene group preferably has 1 to 3 carbon atoms.

[0049] [ka]

[0050] In equation (1d), n is an integer between 2 and 5, preferably 2 or 3. The specific and preferred embodiments of R are the same as those described in equation (1b).

[0051] When polymer P(I) contains structural units represented by formula (1), the proportion of structural units represented by formula (1) in the total structural units of polymer P(I) is preferably 3 to 40 mol%, more preferably 3 to 30 mol%.

[0052] In the structural unit represented by formula (2) that can constitute polymer P(I), R S This group contains only one (meth)acryloyl group. In particular, in the design of typical photosensitive resin compositions, when curability is increased to increase sensitivity, curing tends to progress too much, resulting in poor developability. On the other hand, when developability is improved, curing tends to be insufficient. Therefore, it is preferable that polymer P(I) contains either or both of the structural units represented by formula (1) and the structural units represented by formula (2), thereby achieving a good balance between sensitivity and developability.

[0053] R S This is a group represented, for example, by the following formula (2a).

[0054] [ka]

[0055] In equation (2a), X 10 X is a divalent organic group, and R is either a hydrogen atom or a methyl group. 10 The total number of carbon atoms is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. X 10 A preferred divalent organic group is, for example, an alkylene group. Some of the -CH2- groups in this alkylene group may be ether groups (-O-). The alkylene group may be linear or branched, but linear is more preferred.

[0056] X 10 The divalent organic group is more preferably a linear alkylene group having a total of 3 to 6 carbon atoms. 10Number of carbon atoms (X 10 By appropriately selecting the chain length, the structural unit represented by formula (2) becomes more readily involved in the crosslinking reaction, thereby increasing sensitivity.

[0057] X 10 The divalent organic group (e.g., alkylene group) may be substituted with any substituent. Examples of substituents include alkyl groups, aryl groups, alkoxy groups, and aryloxy groups. Also, X 10 The divalent organic group may be any group other than an alkylene group. For example, it may be a divalent group formed by linking one or more groups selected from alkylene groups, cycloalkylene groups, arylene groups, ether groups, carbonyl groups, carboxyl groups, etc.

[0058] When polymer P(I) contains structural units represented by formula (2), the proportion of structural units represented by formula (2) in the total structural units of polymer P is preferably 5 to 30 mol%, more preferably 10 to 20 mol%.

[0059] Furthermore, if polymer P(I) contains both structural units represented by formula (1) and structural units represented by formula (2), the total proportion of structural units represented by formula (1) and structural units represented by formula (2) in polymer P(I) is preferably 5 to 40 mol%, more preferably 10 to 35 mol%, and even more preferably 15 to 30 mol%, based on the total structural units constituting polymer P(I).

[0060] The polymer P(I) of this embodiment may contain structural units represented by formula (3) in addition to the structural units described above. By containing structural units represented by formula (3), polymer P(I) has high alkali solubility. As a result, the photosensitive resin composition containing polymer P(I) has excellent developability when subjected to a photolithography method using an alkaline aqueous solution as a developer. The proportion of structural units represented by formula (3) in the total structural units of polymer P(I) is preferably 1 to 10 mol%, more preferably 2 to 7 mol%. [ka]

[0061] The polymer P(I) of this embodiment may contain structural units represented by formula (MA) in addition to the above-mentioned structural units. The structural units represented by formula (MA) undergo ring-opening with an alkaline developer to produce two carboxyl groups. Therefore, polymer P(I) has excellent developability. When polymer P(I) contains structural units represented by formula (MA), the amount of structural units represented by formula (MA) in the total structural units of polymer P(I) is preferably 3 to 40 mol%, more preferably 10 to 30 mol%. [ka]

[0062] The content (ratio) of each structural unit contained in polymer P(I) depends on the amount (moles) of raw materials used in the synthesis of the polymer, the amount of 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 of peaks in the 1C-NMR spectrum and their peak areas.

[0063] The weight-average molecular weight Mw of polymer P(I) is, for example, 2,000 to 30,000. Preferably, the weight-average molecular weight Mw of polymer P(I) is 2,500 to 25,000, and more preferably 3,000 to 20,000. By appropriately adjusting the weight-average molecular weight, the sensitivity and solubility in alkaline developers can be adjusted. Furthermore, the degree of dispersion (weight-average molecular weight Mw / number-average molecular weight Mn) of polymer P(I) in this embodiment is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0. By appropriately adjusting the degree of dispersion, the physical properties of polymer P can be made homogenized, which is preferable. These values ​​can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance.

[0064] The glass transition temperature of polymer P(I) is preferably 100 to 250°C, more preferably 120 to 230°C. When it mainly contains structural units of formula (NB), the glass transition temperature tends to be higher, while when it contains structural units represented by formula (AK), the glass transition temperature tends to be lower. Polymer P in this embodiment has a favorable glass transition temperature because it contains structural units of formula (NB) and structural units represented by formula (AK). This is advantageous in that the patterns formed on the substrate can exist stably when manufacturing liquid crystal display devices and solid-state image sensors. The glass transition temperature can be determined, for example, by differential thermal analysis (DTA).

[0065] The acid value of polymer P(I) is, for example, 70 mg KOH / g or more and 150 mg KOH / g or less, preferably 80 mg KOH / g or more and 140 mg KOH / g or less. The double bond equivalent of polymer P1 is, for example, 100 g / mol or more and 900 g / mol or less, preferably 200 g / mol or more and 850 g / mol or less, more preferably 200 g / mol or more and 800 g / mol or less. By having an acid value of 70 mgKOH / g or higher for polymer P(I), good developability can be obtained. Furthermore, by having a double bond equivalent of 900 g / mol or less, the sensitivity of the photosensitive resin composition containing polymer P(I) can be increased.

[0066] Furthermore, if the acid value of polymer P(I) is too high, there is a concern that the exposed areas may dissolve easily during development with an alkaline developer, leading to an increased exposure amount required for photocuring or an insufficient pattern shape. Therefore, in this embodiment, the upper limit of the acid value is set to 150 mg KOH / g. Furthermore, if the double bond equivalent of polymer P(I) is too small (i.e., if the density of double bonds in the polymer is too high), unexposed or underexposed areas tend to be difficult to dissolve during development with an alkaline developer, and residual film tends to form during development. Also, if the double bond equivalent is too small, the molecular weight may increase excessively due to crosslinking, raising concerns about an excessive decrease in solubility. Therefore, in this embodiment, the lower limit of the double bond equivalent is set to 100 g / mol.

[0067] The polymer P(I) of this embodiment, by having the above configuration, can have an alkali dissolution rate of 120 nm / s or more, preferably 150 nm / s or more, more preferably 200 nm / s or more, and particularly more preferably 300 nm / s or more. The upper limit is not particularly limited, but for example it may be 2000 nm / s or less. In this specification, the alkali dissolution rate is the value obtained when measured under the following conditions. (Method for measuring alkali dissolution rate) Polymer P(I) is dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution with a solid content concentration of 30% by mass. Next, the obtained polymer solution is spin-coated onto a wafer, the PGMEA is dried, and a resin film with a thickness of 2 μm ± 0.2 is prepared by pre-baking at a temperature of 100°C for 2 minutes. This resin film, along with the wafer, is immersed in a 2.0% by mass sodium carbonate aqueous solution at a temperature of 23°C. The immersed wafer is visually observed, and the time until the resin film dissolves and the interference pattern disappears is measured. The alkali dissolution rate (μm / sec) is calculated by dividing the film thickness before immersion (2 μm ± 0.2) by that time.

[0068] By adjusting the acid value and / or double bond equivalent of polymer P(I), it is possible to achieve an even higher level of balance between sensitivity and developability.

[0069] The acid value and double bond equivalent of polymer P(I) can be determined by spectral measurement or other methods. For example, they can be determined by the following procedure (see the examples for more details). (1) Polymer 1From the 1H-NMR chart, the area (integral value) of the peaks corresponding to hydrogen atoms of the carboxyl group and hydrogen atoms near polymerizable carbon-carbon double bonds is determined. (2) The area obtained in (1) is used to determine the amount of carboxyl groups and carbon-carbon double bonds from the area of ​​the peaks originating from the standard substance. (3) Convert the amount of carboxyl groups obtained in (2) to the acid value (mgKOH / g). Also, convert the amount of polymerizable carbon-carbon double bonds obtained in (2) to the double bond equivalent (g / mol).

[0070] The acid value and double bond equivalent of polymer P(I) can be adjusted to desired values ​​by appropriately designing the ratio of structural units introduced into polymer P(I), particularly the number of polymerizable carbon-carbon double bonds in the (meth)acryloyl groups contained in the structural units represented by formula (1) or formula (2).

[0071] The content (ratio) of each structural unit contained in polymer P(I) of this embodiment depends on the amount (moles) of raw materials charged during polymer synthesis, the amount of raw materials remaining after synthesis, and the peak areas of various spectra (for example, 1 It can be estimated / calculated from the peak area of ​​the 1H-NMR spectrum, etc.

[0072] The polymer P(I) of this embodiment has a low softening point of 110°C or less due to the inclusion of structural units represented by formula (AK). The softening point of polymer P(I) is preferably 100°C or less, and more preferably 90°C or less. Furthermore, the polymer P(I) of this embodiment has a low melting point of 140°C or less due to the inclusion of structural units represented by formula (AK). The melting point of polymer P(I) is preferably 130°C or less, and more preferably 120°C or less. In this specification, the softening point and melting point of the polymer are values ​​obtained under the following conditions. (Method for measuring the softening point) 0.1–1.0 mg of the polymer to be measured was placed in an aluminum sample pan, and the softening point was measured under a nitrogen atmosphere using a differential thermal analyzer (Hitachi High-Tech Science Corporation, "EXSTAR TMA / SS6100"). The measurement mode was compression, the load was 30 mN, and the temperature was increased from 30°C to 200°C at a heating rate of 3°C / min. When the sample softened due to heating, the sample deformed, and the displacement (μm) was detected. The softening point was defined as the extension of the straight section with no displacement on the low-temperature side, or the intersection of the tangent to the section with the minimum displacement velocity and the tangent to the section with the maximum displacement velocity. (Method for measuring the melting point) 1-2 mg of the polymer to be measured was placed in an aluminum sample pan and heated under a nitrogen atmosphere using a differential thermal analyzer (Hitachi High-Technologies Corporation, "STA7200RV") while observing the image, starting from 30°C and increasing at a heating rate of 10°C / min. The temperature at which the sample began to melt was visually confirmed and defined as the melting point.

[0073] (Method for producing polymer P(I)) Polymer P(I) can be manufactured (synthesized) by any method. Typically, polymer P(I) can be manufactured by the following steps aI, aII, and aIII. Step aI: A step of preparing a raw material polymer containing structural units represented by formula (NB), formula (AK), and formula (MA); Step aII: This step involves reacting the raw material polymer obtained in Step aI with a compound having a hydroxyl group and two or more (meth)acryloyl groups (a polyfunctional (meth)acrylic compound), and / or a compound having a hydroxyl group and one (meth)acryloyl group (a monofunctional (meth)acrylic compound), in the presence of a basic catalyst, to prepare a polymer P(I) that includes a structural unit represented by formula (NB), a structural unit represented by formula (AK), and a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and optionally further including a structural unit represented by formula (MA).

[0074] If polymer P(I) further contains structural units represented by formula (3), the following step aIII is performed. Step aIII: A polymer precursor (corresponding to polymer P(I) in step aII) is prepared in step aII, comprising a structural unit represented by formula (NB), a structural unit represented by formula (AK), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (MA), and then the polymer precursor is treated with water in the presence of a base catalyst to obtain polymer P(I).

[0075] In step aII, if both a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound are used, it is preferable to first react the polyfunctional (meth)acrylic compound with the raw material polymer obtained in step aI, and then react the resulting reaction mixture with the monofunctional (meth)acrylic compound.

[0076] The following describes each step. (Process aI) The step in step aI, which involves preparing a raw material polymer containing structural units represented by formula (NB), formula (AK), and formula (MA), can be carried out by polymerizing (addition polymerization) a monomer composition containing monomers represented by formula (NBm), monomers represented by formula (AKm), and monomers represented by formula (MAm). Here, in formula (NBm), R 1 , R 2 , R 3 and R 4 Furthermore, the definition of a1 is the same as that in equation (NB). Also, R in equation (AKm) 11 , R 12 , R 13 and R 14 The definition of is the same as in equation (AK). Also, R in equation (MAm) 21 and R 22 The definition is the same as that in equation (MA).

[0077] [ka]

[0078] Examples of monomers represented by formula (NBm) include norbornene, bicyclo[2.2.1]-hepto-2-ene (common name: 2-norbornene), 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-allyl-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(1-methyl-4-pentenyl)-2-norbornene, 5-ethynyl-2-norbornene, 5-benzyl-2-norbornene, 5-phenethyl-2-norbornene, 2-acetyl-5-norbornene, methyl 5-norbornene-2-carboxylate, and 5-norbornene-2,3-dicarboxylic acid anhydride. During polymerization, the monomer represented by formula (NBm) may be used alone or in combination of two or more types.

[0079] [ka]

[0080] In long-chain alkenes represented by formula (AKm) as monomers, the stereochemistry with respect to the double bond may be either cis or trans. Examples of long-chain alkenes represented by formula (AKm) include linear 1-alkenes such as 1-hexene, 1-heptadecene, 1-octene, 1-decene, 1-undecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-trichocene; branched 1-alkenes such as 3,5,5-trimethyl-1-hexene; and linear or branched alkenes such as 4-octene, 3-octene, 2-decene, 5-methyl-2-heptene, 5-methyl-3-heptene, 2,4,4-trimethyl-2-pentene, 3-methyl-2-heptene, and cis-9-trichocene.

[0081] [ka]

[0082] While the polymerization method is not limited, radical polymerization using a radical polymerization initiator is preferred. Examples of polymerization initiators include azo compounds and organic peroxides. Specific examples of azo compounds include azobisisobutyronitrile (AIBN), dimethyl 2,2'-azobis(2-methylpropionate), and 1,1'-azobis(cyclohexanecarbonile) (ABCN). Examples of organic peroxides include hydrogen peroxide, di-tert-butyl peroxide (DTBP), benzoyl peroxide (benzoyl peroxide, BPO), and methyl ethyl ketone peroxide (MEKP). Regarding polymerization initiators, one type may be used, or two or more types may be used in combination.

[0083] For the polymerization reaction, organic solvents such as diethyl ether, tetrahydrofuran, toluene, and methyl ethyl ketone can be used as solvents. The polymerization solvent may be a single solvent or a mixture of solvents.

[0084] The raw material polymer is synthesized by dissolving monomers represented by formula (NBm), (AKm), and (MAm), along with a polymerization initiator, in a solvent, charging the mixture into a reaction vessel, and then heating it to allow addition polymerization to proceed. The heating temperature is, for example, 50-80°C, and the heating time is, for example, 5-20 hours. When charging the reaction vessel, the molar ratio of the total amount of monomer represented by formula (NBm) and monomer represented by formula (AKm) (NBm + AKm) to the monomer represented by formula (MAm) is preferably (NBm + AKm):(MAm) = 0.5:1 to 1:0.5. From the viewpoint of molecular structure control, a molar ratio of 1:1 is preferable. The molar ratio of monomer represented by formula (AKm) and monomer represented by formula (NBm) is preferably (AKm):(NBm) = 0.5:9.5 to 5:5, and more preferably 1:9 to 4:6. Through this process, "raw material polymers" can be obtained. The raw material polymer may be any of the following: random copolymer, alternating copolymer, block copolymer, or periodic copolymer. Typically, it is a random copolymer or alternating copolymer. Maleic anhydride is generally known as a monomer with strong alternating copolymerizability.

[0085] Furthermore, after the synthesis of the raw material polymer, a step may be taken to remove low molecular weight components such as unreacted monomers, oligomers, and residual polymerization initiators. Specifically, the organic phase containing the synthesized raw material 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 monomers. By filtering and drying this precipitate, the purity of the raw material polymer can be increased.

[0086] (Step aII) In step aII, the raw material polymer obtained in step aI is reacted with a polyfunctional (meth)acrylic compound and / or a monofunctional (meth)acrylic compound in the presence of a basic catalyst. This causes some of the structural units represented by formula (MA) in the raw material polymer to open rings, forming structural units represented by formula (1) and / or formula (2). A polymer precursor is obtained that contains structural units represented by formula (NB), structural units represented by formula (AK), and structural units represented by formula (1) and / or formula (2), and optionally contains structural units represented by formula (MA). The polymer precursor obtained here can be used as polymer P(I) in this embodiment, but for the sake of explanation, it is referred to as a polymer precursor.

[0087] More specifically, first, a solution is prepared by dissolving the raw material polymer in a suitable organic solvent. As the organic solvent, single or mixed solvents such as methyl ethyl ketone (MEK), propylene glycol monomethyl ether acetate (PGMEA), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and tetrahydrofuran (THF) can be used, but are not limited to these; various organic solvents used in the synthesis of organic compounds and polymers can be used.

[0088] To obtain a polymer precursor containing structural units represented by formula (NB), structural units represented by formula (AK), and both structural units represented by formula (1) and formula (2), a polyfunctional (meth)acrylic compound is added to the above solution. A basic catalyst is then added. The solution is then properly mixed to obtain a homogeneous solution containing at least the structural units of formula (NB), the structural units of formula (AK), and the structural units of formula (1) (step aII-i).

[0089] Examples of polyfunctional (meth)acrylic compounds that can be used here include the compound represented by formula (1b-m), the compound represented by formula (1c-m), and the compound represented by formula (1d-m). k, R, and X in formula (1b-m) 1 , X 1 'and X 2 The definition and specific form of are the same as in equation (1b) above. Also, k, R, and X in equation (1c-m) 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific form of are the same as those in equation (1c) above. n and R in equation (1d-m) are the same as those in equation (1d) above.

[0090] [ka]

[0091] [ka]

[0092] [ka]

[0093] Next, the polymer obtained in step aII-i is reacted with a monofunctional (meth)acrylic compound in the presence of a basic catalyst to obtain a polymer precursor containing the structural units of formula (NB), formula (AK), formula (1), and formula (2) (step aII-ii).

[0094] As a basic catalyst, amine compounds and nitrogen-containing heterocyclic compounds known in the field of organic synthesis can be used as appropriate. For example, amine compounds such as triethylamine, pyridine, and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds can be used as catalysts. The amount of basic catalyst used can be, for example, about 10 to 60 parts by mass per 100 parts by mass of raw material polymer. Note that using an excess of basic catalyst may increase the amount of acid required for neutralization, potentially complicating the purification process.

[0095] By heating the above solution at a temperature of preferably 60-80°C for about 3-9 hours, ring-opening of the structural unit of formula (MA) and formation of the structural unit of formula (1) contained in the raw material polymer are achieved.

[0096] For example, by adding a monofunctional (meth)acrylic compound having a hydroxyl group to the reaction system during the heating process described above, ring-opening of the structural unit of formula (MA) contained in the raw material polymer and formation of the structural unit of formula (2) occur, and polymer P(I) having the structural unit represented by formula (2) is produced.

[0097] Due to steric hindrance and other factors, monofunctional (meth)acrylic compounds containing hydroxyl groups tend to react more readily with the starting polymer than polyfunctional (meth)acrylic compounds containing hydroxyl groups. Therefore, when preparing a polymer precursor having the structural unit of formula (2), it is preferable not to add the monofunctional (meth)acrylic compound containing hydroxyl groups to the reaction system from the beginning, but rather to add it to the reaction system later. Examples of monofunctional (meth)acrylic compounds having a hydroxyl group include compounds represented by the following formulas (2a-m). In equation (2a-m), X 10 The definition of R is the same as that in equation (2a).

[0098] [ka]

[0099] Specific examples of compounds represented by 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.

[0100] When obtaining a polymer precursor containing a structural unit represented by formula (NB), a structural unit represented by formula (AK), or either a structural unit represented by formula (1) or a structural unit represented by formula (2), only one of steps aII-i or aII-ii needs to be carried out after step (I).

[0101] (Step aIII) When step aIII is carried out, the polymer precursor obtained in step aII is treated with water in the presence of a basic catalyst. Step aIII causes the structural unit represented by formula (MA) contained in the polymer precursor obtained in step aII to undergo ring opening, forming the structural unit represented by formula (3), thereby producing polymer P(I) containing the structural unit represented by formula (NB), the structural unit represented by formula (AK), the structural unit represented by formula (1) and / or the structural unit represented by formula (2), and the structural unit represented by formula (3). If some of the structural unit represented by formula (MA) undergoes ring opening and some of the structural unit of formula (MA) remains unringed, polymer P(I) further contains the structural unit represented by formula (MA).

[0102] Examples of basic catalysts used in step aIII include amine compounds such as triethylamine, pyridine, and dimethylaminopyridine, or nitrogen-containing heterocyclic compounds.

[0103] In step aIII, water is added to the reaction system containing the polymer precursor obtained in step aII, and the resulting reaction solution is heated, preferably at 60-80°C for about 0.25-6 hours, causing the structural unit of formula (MA) contained in the polymer to open its ring and generate the structural unit represented by formula (3). The basic catalyst can be the catalyst remaining in the reaction system obtained in step aII. Therefore, it is preferable to carry out step aIII by adding water to the reaction mixture obtained in step aII in situ without any post-treatment of the reaction mixture.

[0104] The polymer P(I) of this embodiment can be obtained by the above steps, but from the viewpoint of the effects of the present invention, the following steps may be performed as appropriate to remove unwanted components other than the desired polymer.

[0105] First, the reaction solution, which has been diluted with an organic solvent and to which an acid (such as formic acid) has been added, is vigorously stirred in a separatory funnel for at least 3 minutes. This is then left to stand for at least 30 minutes to separate the organic phase from the aqueous phase, and the aqueous phase is removed. In this way, an organic solution of the polymer is obtained.

[0106] The obtained organic solution of polymer P(I) is purified using either a reprecipitation method or a liquid-liquid extraction method. In the reprecipitation method, the obtained organic solution of polymer P(I) is added to an excess amount of toluene or water to reprecipitation the polymer. The polymer powder obtained by reprecipitation is then washed several more times with toluene or water. Furthermore, in order to remove formic acid and basic catalysts, the obtained polymer powder is washed with deionized water several times (approximately 1 to 3 times). High-purity polymers can be obtained by drying the polymer powder, after washing it with deionized water, at a temperature of, for example, 30-60°C for 16 hours or more. In the liquid-liquid extraction method, water is added to the obtained organic solution of polymer P(I), and the mixture is vigorously stirred in a separatory funnel for at least 3 minutes. This mixture is then allowed to stand for at least 30 minutes to separate the organic phase from the aqueous phase, and the aqueous phase is removed. Water is then added to the organic solution of the polymer after the removal of the aqueous phase, and the mixture is vigorously stirred in a separatory funnel for at least 3 minutes. This mixture is then allowed to stand for at least 30 minutes to separate the organic phase from the aqueous phase, 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 repeated. The obtained organic solution of polymer P(I) can be concentrated by heating under reduced pressure using a rotary evaporator, and then diluted by repeating the process of adding a final solvent (such as PGMEA) to obtain a polymer solution dissolved in the final solvent. In addition, further purification by reprecipitation after solvent replacement may be performed.

[0107] Furthermore, the polymer solution may also contain the polyfunctional (meth)acrylic compound and / or monofunctional (meth)acrylic compound used in the synthesis of polymer P(I). When the polymer solution contains these (meth)acrylic compounds, the peak area derived from the polyfunctional (meth)acrylic compound in the gel permeation chromatography (GPC) chart is preferably 3 to 50%, particularly 4 to 30%, and more preferably 5 to 20%, relative to the peak area of ​​polymer P, and the peak area derived from the monofunctional (meth)acrylic compound is preferably 0.2 to 30%, particularly 0.5 to 20%, and more preferably 0.7 to 10%, relative to the peak area of ​​polymer P. As a result, the photosensitive resin composition containing this polymer solution has good alkali solubility and good sensitivity in photolithography.

[0108] [Second Embodiment] (Polymer P(II)) The polymer in the second embodiment of the present invention (hereinafter referred to as "polymer P(II)") has a structure represented by formula (P2). Polymer P(II) has a structure in which a polymer chain, typically composed of structural units A, B, and C, is bonded to a 2- to 6-valent organic group having 1 to 30 carbon atoms, which is derived from a thiol group-containing compound with two or more functions, represented as "Y" in formula (P2).

[0109] [ka]

[0110] In equation (P2), m is an integer between 0 and 5, preferably 0 or 1, and more preferably 0. n is an integer between 1 and 6, preferably between 3 and 6. m+n is between 2 and 6, preferably between 3 and 6. p, q, and r represent the molar content of A, B, and C, respectively, and p + q + r = 1. p is greater than 0, preferably 0.25 to 0.75, more preferably 0.3 to 0.65, and more preferably 0.35 to 0.60. q is greater than 0, preferably 0.10 to 0.6, more preferably 0.2 to 0.50, and more preferably 0.25 to 0.45. r is greater than 0, preferably 0.03 to 0.3, more preferably 0.04 to 0.28, and particularly preferably 0.05 to 0.25. p, q, or r may be the same or different for each of the n structural units within the [ ] brackets. X is either hydrogen or an organic group having between 1 and 30 carbon atoms. Y is a 2- to 6-valent organic group having 1 to 30 carbon atoms derived from a thiol group-containing compound with two or more functionalities. A is a structural unit represented by formula (NB). B represents at least one structural unit selected from the structural units represented by formula (1) and the structural units represented by formula (2). C represents a structural unit expressed by formula (AK). Multiple instances of A, B, or C may be identical or different. D is any structure different from the structure in [ ]n, for example, one or two of A, B, and C mentioned above.

[0111] [ka]

[0112] In equation (NB), R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2.

[0113] [ka]

[0114] In formula (1), R p is a group having two or more (meth)acryloyl groups, and R 21 and R 22 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0115] [Chemical formula]

[0116] In formula (2), R s is a group having one (meth)acryloyl group, and R 21 and R 22 are each independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0117] [Chemical formula]

[0118] <了 In formula (AK), at least one of R 11 , R 12 , R 13 and R 14 is a linear or branched alkyl group having 3 or more carbon atoms, and the rest of R 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 30 carbon atoms. <)

[0119] The polymer P(II) having the structure represented by formula (P2) may contain a structural unit represented by formula (3) as the structural unit B.

[0120] [Chemical formula]

[0121] In formula (3), R 21 and R 22 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0122] A polymer P(II) having the structure represented by formula (P2) may include a structural unit represented by formula (MA) as structural unit B. [ka]

[0123] In formula (MA), R 21 and R 22 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0124] In one embodiment, polymer P(II) may have a structure represented by formula (P'). Here, formula (P') corresponds to the form in formula (P2) above where m is 0.

[0125] [ka]

[0126] In equation (P'), n, as well as p, q, and r, are the same as defined in equation (P2), and X, Y, A, B, and C are the same as defined in equation (P2).

[0127] In formula (P2), Y is a divalent to hexavalent organic group (i) having 1 to 30 carbon atoms derived from a polyfunctional thiol group-containing compound (hereinafter referred to as "organic group (i)" in this specification). In the present embodiment, the valence number is the number of functional groups (the number of thiol groups). That is, the polyfunctional thiol group-containing compound contains two or more thiol groups, and the organic group (i) is bonded to the structural unit within [ ]n and the structural unit within [ ]m through 2 to 6 thioether groups derived from the thiol groups. The organic group (i) may have a thiol group that does not participate in the bonding with the structural unit within [ ]n and the structural unit within [ ]m, and the polymer P(II) can be obtained as a mixture of resins in which the number (number of bonds) of n + m is 2 to 6 respectively. The organic group (i) having 1 to 30 carbon atoms is polyfunctional, preferably trifunctional or more. The upper limit is not particularly limited, but it is hexavalent or less. From the viewpoint of the effects of the present invention, the valence number of the organic group (i) having 1 to 30 carbon atoms is divalent to hexavalent, preferably trivalent to hexavalent.

[0128] The divalent to hexavalent organic group (i) having 1 to 30 carbon atoms may contain one or more atoms selected from O, N, S, P, and Si. Examples of the divalent to hexavalent organic group (i) having 1 to 30 carbon atoms include an alkyl group, an alkenyl group, an alkynyl group, an alkylidene group, an aryl group, an aralkyl group, an alkaryl group, a cycloalkyl group, an alkoxy group, and a heterocyclic group having 2 to 6 thioether groups (-S-* (* is a bond)).

[0129] 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. Examples of the alkenyl group include an allyl group, a pentenyl group, and a vinyl group.

[0130] Examples of the alkynyl group include an ethynyl group. Examples of alkylidene groups include methylidene and ethylidene. Examples of aryl groups include tolyl, xylyl, phenyl, naphthyl, and anthracenyl groups. Examples of aralkyl groups include the benzyl group and the phenethyl group. Examples of alkalyl groups include tolyl groups and xylyl groups.

[0131] Examples of cycloalkyl groups include adamantyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, s-butoxy, isobutoxy, t-butoxy, n-pentyloxy, neopentyloxy, and n-hexyloxy groups. Examples of heterocyclic groups include epoxy groups and oxetanyl groups.

[0132] Examples of thiol group-containing compounds with two or more functionalities that can derive Y in formula (P2) include compounds represented by the following chemical formulas (s-1) to (s-21). That is, polymer P(II) contains a divalent to hexavalent organic group (i) with 1 to 30 carbon atoms derived from the difunctional to thiol group-containing compounds represented below.

[0133] [ka]

[0134] [ka]

[0135] [ka]

[0136] [ka]

[0137]

change

[0138]

change

[0139]

change

[0140]

change

[0141]

change

[0142]

change

[0143]

change

[0144]

change

[0145]

change

[0146]

change

[0147] [ka]

[0148] [ka]

[0149] [ka]

[0150] [ka]

[0151] [ka]

[0152] [ka]

[0153] [ka]

[0154] A thiol group-containing compound with two or more functions may be used alone or in a mixture of two or more. In particular, it is preferable to use a thiol group-containing compound with three to six functions (three to six valents) having three to six thiol groups in one molecule, as it exhibits excellent reactivity with other monomers. In this embodiment, the thiol group-containing compound with two or more functions more preferably includes compounds represented by chemical formulas (s-1) to (s-3), (s-5), and (s-8) to (s-10) among the compounds represented by chemical formulas (s-1) to (s-21), and is particularly preferably includes compounds represented by chemical formulas (s-1) to (s-3), (s-5), and (s-9). The 1-6 valent organic group (i) having 1 to 30 carbon atoms has a thioether group (-S-* (* is a bonding hand)) derived from the thiol group of these thiol group-containing compounds at its terminus, and bonds to the structural units in [ ]n and [ ]m via the thioether group. The organic group (i) may also have a thiol group that does not participate in bonding to the structural units in [ ]n and [ ]m.

[0155] When a tetrafunctional (tetravalent) thiol group-containing compound represented by the above formula (s-2) is used as the thiol group-containing compound of the polymer P(II) of this embodiment, it can have a structure such as that represented by the following formula (I).

[0156] [ka]

[0157] In formula (I), A, B, C, X, p, q, and r are equivalent to those in formula (P2). The A, B, C, X, p, q, and r contained in the four structural units within the brackets [ ] may be the same or different.

[0158] In formula (I), the bonding order of A, B, and C is not particularly limited, and any of A, B, or C may be bonded to the thioether group. Furthermore, although formula (I) is shown as an example in which the four structural units in [ ] are bonded via thioether groups derived from the four mercapto groups of the compound represented by chemical formula (s-2), it is also possible that 1 to 3 structural units in [ ] are bonded to the thioether groups derived from the four mercapto groups, and the remaining thioether groups are bonded to organic groups different from the structural units in [ ]. In this embodiment, polymer P can be obtained as a mixture containing at least one compound in which 1 to 4 of the structures in [ ] are bonded.

[0159] The weight-average molecular weight Mw of polymer P(II) is, for example, 2,000 to 20,000. The weight-average molecular weight Mw of polymer P(I) is preferably 2,500 to 17,500, more preferably 3,000 to 15,000. By appropriately adjusting the weight-average molecular weight, the sensitivity and solubility in alkaline developers can be adjusted. Furthermore, the degree of dispersion (weight-average molecular weight Mw / number-average molecular weight Mn) of polymer P(I) in this embodiment is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0. By appropriately adjusting the degree of dispersion, the physical properties of polymer P can be made homogenized, which is preferable. These values ​​can be determined by gel permeation chromatography (GPC) measurement using polystyrene as a standard substance. The physical properties of polymer P(II), such as glass transition temperature, softening point, melting point, acid value, double bond equivalent, and alkali dissolution rate, are the same as those of polymer P(I) described above.

[0160] (Method for manufacturing polymer P(II)) A method for producing polymer P(II) will be described. Polymer P(II) can be manufactured (synthesized) by any method. Typically, polymer P(II) can be manufactured by the following steps: process bII and process bIII. Step bI: A step of preparing a raw material polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (AK), a structural unit represented by formula (MA), and an organic group (i) having 1 to 30 carbon atoms with a valency of 2 to 6; Step bII: This step involves reacting the raw material polymer obtained in Step bI with a compound having a hydroxyl group and two or more (meth)acryloyl groups (a polyfunctional (meth)acrylic compound), and / or a compound having a hydroxyl group and one (meth)acryloyl group (a monofunctional (meth)acrylic compound), in the presence of a basic catalyst, to prepare polymer P(II) which contains a structural unit represented by formula (NB), a structural unit represented by formula (AK), a 2-6 valent organic group (i) having 1 to 30 carbon atoms, and 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).

[0161] If polymer P(II) further contains structural units represented by formula (3), the following step bIII is performed. Step bIII: A polymer precursor (corresponding to polymer P(II) in step bII) is prepared in step bII, comprising a structural unit represented by formula (NB), a structural unit represented by formula (AK), a structural unit represented by formula (1) and / or a structural unit represented by formula (2), and a structural unit represented by formula (MA), and then the polymer precursor is treated with water in the presence of a base catalyst to obtain polymer P(II).

[0162] In step bII, when both a polyfunctional (meth)acrylic compound and a monofunctional (meth)acrylic compound are used, it is preferable to first react the polyfunctional (meth)acrylic compound with the raw material polymer obtained in step bI, and then react the resulting reaction mixture with the monofunctional (meth)acrylic compound.

[0163] The following describes each step. (Process bI) The step in step bI of preparing a raw material polymer containing a structural unit represented by formula (NB), a structural unit represented by formula (AK), a structural unit represented by formula (MA), and a 2-6 valent organic group (i) having 1 to 30 carbon atoms can be carried out by polymerizing (addition polymerization) a monomer composition containing a monomer represented by formula (NBm), a monomer represented by formula (AKm), and a monomer represented by formula (MAm) in the presence of a compound containing a thiol group with two or more functionalities.

[0164] Examples of thiol group-containing compounds with two or more functions include, but are not limited to, the compounds represented by the chemical formulas (s-1) to (s-21) above. A single thiol group-containing compound with two or more functions may be used, or two or more may be used in combination. The specific conditions for step bI are the same as those for step aI in the method for producing polymer P(I) of the first embodiment.

[0165] (Step bII) Step bII can be performed under the same conditions as step aII in the method for producing polymer P(I) of the first embodiment.

[0166] (Step bIII) Step bIII can be performed under the same conditions as step aIII in the method for producing polymer P(I) of the first embodiment.

[0167] [Third Embodiment] (Polymer P(III)) The polymer in the fifth embodiment of the present invention (hereinafter referred to as "polymer P(III)") is a polymer comprising a structural unit represented by formula (NB), a structural unit represented by formula (AK), and a structural unit represented by formula (MA).

[0168] [ka]

[0169] In equation (NB), R 1 , R 2 , R3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2.

[0170] [ka]

[0171] In formula (MA), R 21 and R 22 Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0172] [ka]

[0173] In formula (AK), R 11 , R 12 , R 13 and R 14 At least one of them is a linear or branched alkyl group having 3 or more carbon atoms, R 11 , R 12 , R 13 and R 14 The remaining elements are, independently, hydrogen atoms or linear or branched alkyl groups having 1 to 30 carbon atoms.

[0174] Polymer P(III) is a raw material polymer used in the production of polymer P(I) in the first embodiment, and is the polymer obtained in step aI described above.

[0175] Polymer P(III) has a low softening point of 160°C or less due to the inclusion of structural units represented by formula (AK). The softening point of polymer P(III) is preferably 140°C or less, and more preferably 130°C or less. Polymer P(III) also has a low melting point of 180°C or less due to the inclusion of structural units represented by formula (AK). The melting point of polymer P(III) is preferably 160°C or less, and more preferably 140°C or less.

[0176] The weight-average molecular weight Mw of polymer P(III) is, for example, 1,000 to 10,000. Preferably, the weight-average molecular weight Mw of polymer P(III) is 1,000 to 7,500, and more preferably 1,000 to 5,000. By appropriately adjusting the weight-average molecular weight, it is possible to adjust the weight-average molecular weight of polymer P(I) obtained from polymer P(III), and as a result, the sensitivity and solubility of polymer P(I) in alkaline developers can be adjusted to a desired degree. Furthermore, the degree of dispersion of polymer P(III) (weight-average molecular weight Mw / number-average molecular weight Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and even more preferably 1.0 to 3.0.

[0177] [Fourth Embodiment] (Polymer P(IV)) The polymer in the fourth embodiment of the present invention (hereinafter referred to as "polymer P(IV)") has a structure represented by formula (P4). Polymer P(IV) has a structure in which a polymer chain, typically composed of structural units A, B', and C, is bonded to a 2- to 6-valent organic group having 1 to 30 carbon atoms, which is derived from a thiol group-containing compound with two or more functionalities, represented as "Y" in formula (P4).

[0178] [ka]

[0179] In equation (P4), m is an integer between 0 and 5, preferably 0 or 1, and more preferably 0. n is an integer between 1 and 6, preferably between 3 and 6. m+n is between 2 and 6, preferably between 3 and 6. p, q, and r represent the molar content of A, B, and C, respectively, and p + q + r = 1. p is greater than 0, preferably 0.25 to 0.75, more preferably 0.3 to 0.65, and more preferably 0.35 to 0.60. q is greater than 0, preferably 0.10 to 0.6, more preferably 0.2 to 0.50, and more preferably 0.25 to 0.45. r is greater than 0, preferably 0.03 to 0.3, more preferably 0.04 to 0.28, and particularly preferably 0.05 to 0.25. p, q, or r may be the same or different for each of the n structural units within the [ ] brackets. X is either hydrogen or an organic group having between 1 and 30 carbon atoms. Y is a 2- to 6-valent organic group having 1 to 30 carbon atoms derived from a thiol group-containing compound with two or more functionalities. A is a structural unit represented by formula (NB). B' is a structural unit represented by formula (MA). C represents a structural unit expressed by formula (AK). Multiple instances of A, B', or C may be identical or different. D is any structure different from the structure in [ ]n, for example, one or two of A, B', and C mentioned above.

[0180] [ka]

[0181] In equation (NB), R 1 , R 2 , R 3 and R 4 Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a1 is 0, 1, or 2.

[0182] [ka] In formula (MA), R 21 and R 22Each of these is independently a hydrogen atom or an organic group having 1 to 3 carbon atoms.

[0183] [ka] In formula (AK), R 11 , R 12 , R 13 and R 14 At least one of them is a linear or branched alkyl group having 3 or more carbon atoms, R 11 , R 12 , R 13 and R 14 The remaining elements are, independently, hydrogen atoms or linear or branched alkyl groups having 1 to 30 carbon atoms.

[0184] Polymer P(IV) is a raw material polymer used in the production of polymer P(II) described above, and is the polymer obtained in step bI described above.

[0185] The weight-average molecular weight Mw, dispersion (weight-average molecular weight Mw / number-average molecular weight Mn), softening point, and melting point of polymer P(IV) are the same as those of polymer P(III) described above.

[0186] [Polymer solution] The polymer solution of this embodiment comprises the polymer P(I) or polymer P(II) described above. The polymer solution of this embodiment may also contain, along with polymer P(I) or polymer P(II), at least one selected from polyfunctional (meth)acrylic compounds and monofunctional (meth)acrylic compounds.

[0187] (Polyfunctional (meth)acrylic compounds) The polyfunctional (meth)acrylic compound or monofunctional (meth)acrylic compound that may be contained in the polymer solution of this embodiment may be unreacted (meth)acrylic compounds used in step aII or step bII of the production of polymer P, or may be added separately.

[0188] Examples of polyfunctional (meth)acrylic compounds that can be incorporated into polymer solutions include, but are not limited to, the compounds represented by the following formulas (1b-p), (1c-p), and (1d-p).

[0189] [ka]

[0190] [ka]

[0191] [ka]

[0192] k, R, X in equation (1b-p) 1 , X 1 'and X 2 The definition and specific form of are the same as in equation (1b) above. Also, k, R, and X in equation (1c-p) 1 , X 2 , X 3 , X 4 , X 5 and X 6 The definition and specific form of are the same as those in formula (1c) above.

[0193] In formulas (1b-p), (1c-p), and (1d-p), Y is a hydrogen atom, a (meth)acryloyl group, or a combination thereof.

[0194] Compounds in formulas (1b-p), (1c-p), and (1d-p) where Y is a hydrogen atom may be unreacted monomers (i.e., compounds represented by formulas (1b-p), (1c-p), and (1d-p)) and may be added separately. In equation (1d-p), n is an integer greater than or equal to 2, preferably an integer between 2 and 5, and more preferably an integer between 2 and 3.

[0195] When a polyfunctional (meth)acrylic compound is added to the polymer solution of this embodiment separately from the unreacted polyfunctional (meth)acrylic compound used in the production of polymer P(I), polymer P(II), polymer P(III), or P(IV), the amount added may be such that the peak area derived from the polyfunctional (meth)acrylic compound in the 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, relative to the peak area of ​​polymer P(I), polymer P(II), polymer P(III), or P(IV).

[0196] (Monofunctional (meth)acrylic compounds) Examples of monofunctional (meth)acrylic compounds incorporated into the polymer solution of this embodiment include compounds represented by the following formula (2a-m). In formula (2a-m), X 10 The definition of R is the same as that in equation (2a).

[0197] [ka]

[0198] When a monofunctional (meth)acrylic compound is added to the polymer solution of this embodiment separately from the unreacted monofunctional (meth)acrylic compound used in the production of polymer P(I), polymer P(II), polymer P(III), or P(IV), the amount added may be such that the peak area derived from the monofunctional (meth)acrylic compound in the 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, relative to the peak area of ​​polymer P(I), polymer P(II), polymer P(III), or P(IV).

[0199] The polymer solution of this embodiment typically contains an organic solvent and is provided in the form of a liquid or varnish. As the organic solvent, one or more of the following can be used: ketone solvents, ester solvents, ether solvents, alcohol solvents, lactone solvents, carbonate solvents, etc.

[0200] Specific examples of organic solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, γ-butyl lactone, N-methylpyrrolidone, and cyclohexanone. These may be used individually or in combination of two or more. The amount of organic solvent used is not particularly limited, but it is used in such an amount that the concentration of nonvolatile components is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0201] [Production of polymer solutions] The polymer solution of this embodiment can be prepared by mixing the above components by a known method. The polymer solution of this embodiment is used as a resin material in the photosensitive resin composition described below.

[0202] [Photosensitive resin composition] The photosensitive resin composition of this embodiment comprises the above-mentioned polymer P(I), polymer P(II), polymer P(III), or polymer P(IV), and a photopolymerization initiator. That is, the photosensitive resin composition of this embodiment comprises the polymer solution of this embodiment described above and a photopolymerization initiator. Each component is described below.

[0203] (Photopolymerization initiator) Examples of photopolymerization initiators used in the photosensitive resin composition of this embodiment include photoradical polymerization initiators. Known compounds can be used as photoradical polymerization initiators, such as 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1 Alkylphenone compounds such as -one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-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 benzophenone, 4,4'-bis(dimethylamino)benzophenone, 2-carboxybenzophenone; benzoin methyl ether, benzoin ethyl Benzoin compounds such as benzoin 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, and 2-(4-ethoxynaphthyl)- Halomethylated triazine compounds such as 4,6-bis(trichloromethyl)-s-triazine and 2-(4-ethoxycarbokynylnaphthyl)-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)], etanone, Examples include oxime ester compounds such as 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyloxime); titanocene compounds such as bis(η5-2,4-cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-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. 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, per 100 parts by mass of polymer P.

[0204] The photosensitive resin composition of this embodiment, by containing the above-mentioned components, has high sensitivity in photolithography processing and excellent alkali solubility. Therefore, the photosensitive resin composition has excellent developability and excellent processability in the photolithography method.

[0205] (Coloring agent) In one embodiment, the photosensitive resin composition may contain a coloring agent. The inclusion of a coloring agent makes it suitable for use as a material for forming color filters in liquid crystal displays and solid-state image sensors. Various pigments or dyes can be used as the coloring agent. Organic pigments and inorganic pigments can be used as pigments.

[0206] 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, pyromethene pigments, and dye lake pigments.

[0207] Inorganic pigments that can be used include white and extender pigments (titanium dioxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), chromatic pigments (lead yellow, cadmium-based pigments, chrome vermilion, nickel titanium, chromium titanium, yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine, Prussian blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), luminescent pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), and fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.).

[0208] As dyes, for example, known dyes described in Japanese Patent Publication No. 2003-270428, Japanese Patent Publication No. Hei 9-171108, Japanese Patent Publication No. 2008-50599, etc., can be used. If the photosensitive resin composition contains a coloring agent, the photosensitive resin composition may contain only one type of coloring agent or two or more types.

[0209] Colorants (especially pigments) can be of an appropriate average particle size depending on the purpose and application. In particular, when transparency is required, such as in color filters, a small average particle size of 0.1 μm or less is preferred, while in other cases, such as in paints where opacity is required, a larger average particle size of 0.5 μm or more is preferred.

[0210] Depending on the purpose and application, the colorants may undergo surface treatments such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, or wax coating.

[0211] If the photosensitive resin composition contains a colorant, the amount can be set appropriately depending on the purpose and application, but in order to balance the color concentration and the dispersion stability of the colorant, it is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 50% by mass, relative to the total nonvolatile components (components excluding solvents) of the photosensitive resin composition.

[0212] (Surfactants) The photosensitive resin composition of this embodiment may contain a surfactant, and a nonionic surfactant is preferred as the surfactant.

[0213] The inclusion of a nonionic surfactant improves the coatability of the photosensitive resin composition when applying it to a substrate to obtain a resin film, allowing for the creation of a coating film of uniform thickness. Furthermore, it prevents residue and pattern lifting during the development of the coating film.

[0214] Nonionic surfactants are, for example, compounds containing a fluorine group (e.g., a fluorinated alkyl group) or a silanol group, or compounds with a siloxane bond as the main skeleton. In this embodiment, it is more preferable to use a nonionic surfactant that includes 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 from DIC Corporation, and Novec FC4430 and FC4432 from Sumitomo 3M Co., Ltd. When using a surfactant, the amount of surfactant added is preferably 0.01 to 10% by weight per 100 parts by weight of resin.

[0215] (solvent) Photosensitive resin compositions typically contain a solvent. Organic solvents are preferred as the solvent. Specifically, one or more of the following can be used: ketone solvents, ester solvents, ether solvents, alcohol solvents, lactone solvents, carbonate solvents, etc.

[0216] Examples of solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl isobutylcarbinol (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 solvent used is not particularly limited, but it is used in such an amount that the concentration of nonvolatile components is, for example, 10 to 70% by mass, preferably 15 to 60% by mass.

[0217] (Light-blocking agent) The resin composition of this embodiment may contain a light-shielding agent. The photosensitive resin composition may contain only one type of light-shielding agent, or it may contain two or more types.

[0218] When a photosensitive resin composition contains a light-shielding agent, the amount can be set appropriately depending on the purpose and application, but in order to balance light-shielding performance and dispersion stability of the light-shielding agent, the amount is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 50% by mass, relative to the total non-volatile components (components excluding solvents) of the photosensitive resin composition.

[0219] (Crosslinking agent) The photosensitive resin composition of this embodiment may contain a crosslinking agent. The crosslinking agent is not particularly limited as long as it is capable of crosslinking polymer P (i.e., chemically bonding with polymer P) through the action of activated chemical species generated from the photopolymerization initiator. The crosslinking agent may not only chemically bond with the polymer, but may also react with other crosslinking agents to form bonds.

[0220] The crosslinking agent is preferably 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 polymers mentioned above). Using a crosslinking agent having the same type of crosslinkable group (polymerizable double bond) as the polymer is preferable in terms of uniform curability and further improvement of sensitivity. There is no particular upper limit to the number of functionalities (number of polymerizable double bonds) per molecule of the crosslinking agent, but it is, for example, 8 or less, preferably 6 or less.

[0221] Specifically, the 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 oxide-added ditrimethylolpropanetetra(meth)acrylate, ethylene oxide-added pentaerythritoltetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropanetri(meth)acrylate, propylene oxide-added ditrimethylolpropanetetra(meth)acrylate, propylene oxide-added pentaerythritoltetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropanetri(meth)acrylate, ε-caprolactone-added ditrimethylolpropanetetra(meth)acrylate, ε-caprolactone-added pentaerythritoltetra(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 hexanyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexanyl ether; Vinyl ether group-containing (meth)acrylic acid esters such as (meth)acrylate 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 2-(vinyloxyethoxyethoxyethoxy)ethyl; 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 (meth)acrylic acid allyl; 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 the reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxyl-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; Polyfunctional aromatic vinyls such as divinylbenzene; Examples include:

[0222] Among 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.

[0223] When a photosensitive resin composition contains a crosslinking agent, the composition may contain only one type of crosslinking agent or two or more types. When a photosensitive resin composition contains a crosslinking agent, the amount can be appropriately set according to the purpose and application. As an example, the amount of crosslinking agent can usually be about 30 to 70 parts by mass, preferably about 40 to 60 parts by mass, per 100 parts by mass of photosensitive resin.

[0224] (Other additives) Depending on the purpose and required properties, the photosensitive resin composition may also contain components such as fillers, binder resins other than the polymers mentioned above, acid generators, heat resistance improvers, developing aids, plasticizers, polymerization inhibitors, ultraviolet absorbers, antioxidants, matting agents, defoamers, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers, oscillating agents, oscillating aids, silane coupling agents, and polyvalent phenol compounds.

[0225] [Application] A patterned film can be obtained by forming a film using the above-described photosensitive resin composition and then exposing and developing the film to form a pattern. This film can be applied to color filters, black matrices, and the like. In other words, a color filter can be obtained by forming a pattern using a photosensitive resin composition containing a coloring agent. A black matrix can also be obtained by forming a pattern using a photosensitive resin composition containing a light-shielding agent. Then, liquid crystal display devices and solid-state image sensors equipped with color filters and black matrices can be manufactured. This section describes a typical procedure for forming a pattern.

[0226] (Formation of a photosensitive resin film) For example, the above photosensitive resin composition is applied to any substrate and dried as necessary to first obtain a photosensitive resin film.

[0227] The substrate to which the composition is applied is not particularly limited. Examples 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 with electrodes or elements formed on its surface. It may also be surface-treated to improve adhesion.

[0228] The method of coating the photosensitive resin composition is not particularly limited. It can be done by rotary coating using a spinner, spray coating using a spray coater, dipping, printing, roll coating, inkjet method, etc.

[0229] The photosensitive resin composition applied to the substrate is typically dried by heat treatment using a hot plate, hot air, oven, etc. The heating temperature is usually 80 to 140°C, preferably 90 to 120°C. The heating time is usually 30 to 600 seconds, preferably 30 to 300 seconds.

[0230] The thickness of the photosensitive resin film is not particularly limited and can be adjusted as appropriate depending on the pattern to be ultimately obtained, but is usually 0.5 to 10 μm, preferably 1 to 5 μm. The film thickness can be adjusted by the solvent content in the photosensitive resin composition and the application method.

[0231] (exposure) Exposure is typically performed by irradiating a photosensitive resin film with active light through a suitable photomask.

[0232] Examples of active light include X-rays, electron beams, ultraviolet light, and visible light. In terms of wavelength, light in the range of 200 to 500 nm is preferred. In terms of pattern resolution and handling ease, the light source is preferably the g-line, h-line, or i-line of a mercury lamp, with the i-line being particularly preferred. Alternatively, two or more light rays may be mixed and used. As the exposure apparatus, a contact aligner, mirror projection, or stepper is preferred. The amount of light used for exposure can be adjusted as appropriate depending on the amount of photosensitive agent in the photosensitive resin film, for example, 100-500 mJ / cm². 2 It is to that extent.

[0233] Furthermore, if necessary, the photosensitive resin film may be heated again after exposure (post-exposure baking). The temperature is, for example, 70 to 150°C, preferably 90 to 120°C. The time is, for example, 30 to 600 seconds, preferably 30 to 300 seconds. Post-exposure baking promotes the reaction by radicals generated from the photoradical polymerization initiator, further accelerating the curing reaction.

[0234] (developing) A pattern can be obtained by developing an exposed photosensitive resin film with a suitable developer, and a substrate with the pattern can be manufactured. The photosensitive resin film made from the photosensitive resin composition containing the polymer solution of this embodiment exhibits excellent adhesion to the substrate, thereby suppressing pattern peeling during the development process.

[0235] In the development process, development can be carried out using a suitable developer solution and methods such as immersion, paddle, or rotary spray. Development removes the exposed areas (in the case of positive film) or unexposed areas (in the case of negative film) of the photosensitive resin film, thereby obtaining a pattern. The type of developer that can be used is not particularly limited. For example, alkaline aqueous solutions and organic solvents can be used.

[0236] Examples of specific alkaline aqueous solutions include (i) inorganic alkaline aqueous solutions such as sodium hydroxide, sodium carbonate, sodium silicate, and ammonia; (ii) organic amine aqueous 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 this embodiment has adjusted alkali solubility and excellent sensitivity, so when using a strongly basic developer such as TMAH (tetramethylammonium hydroxide) solution, the pattern after exposure and development can be made into the shape as designed.

[0237] Examples of organic solvents include ketone solvents such as cyclopentanone, ester solvents such as propylene glycol monomethyl ether acetate (PGMEA) and butyl acetate, and ether solvents such as propylene glycol monomethyl ether. The developing solution may contain, for example, water-soluble organic solvents such as methanol or ethanol, or surfactants.

[0238] In this embodiment, it is preferable to use an alkaline aqueous solution as the developer, and more preferable to use tetramethylammonium hydroxide, an aqueous sodium carbonate solution, or an aqueous potassium hydroxide solution. The concentration of the alkaline aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.5 to 5% by mass. Through the above process, a pattern can be obtained and a substrate with the pattern can be manufactured, but various processing steps may be performed after development.

[0239] For example, after development, the pattern and substrate may be washed with a rinsing solution. Examples of rinsing solutions include distilled water, methanol, ethanol, isopropanol, and propylene glycol monomethyl ether. These may be used individually or in combination of two or more.

[0240] The resulting pattern may also be heated to ensure sufficient curing. The heating temperature is typically 150-400°C, preferably 160-300°C, and more preferably 200-250°C. The heating time is not particularly limited, but is, for example, in the range of 15-300 minutes. This heat treatment can be carried out using a hot plate, an oven, or a heating oven with a temperature programmable. The atmospheric gas used during the heat treatment may be air, or an inert gas such as nitrogen or argon. Heating may also be carried out under reduced pressure. Figure 1 schematically shows an example of the structure of a liquid crystal display device and / or solid-state image sensor, which includes a color filter and / or black matrix.

[0241] A black matrix 11 and a color filter 12 are formed on the substrate 10. A protective film 13 and a transparent electrode layer 14 are provided above the black matrix 11 and color filter 12.

[0242] The substrate 10 is typically made of a light-transmitting material, such as glass, polyester, polycarbonate, polyolefin, polysulfone, or polymers of cyclic olefins. The substrate 10 may also be subjected to corona discharge treatment, ozone treatment, chemical treatment, etc., as needed. The substrate 10 is preferably made of glass. The black matrix 11 is composed, for example, of a cured product of a photosensitive resin composition containing a light-shielding agent.

[0243] Typically, there are three colors for the color filter 12: red, green, and blue. The color filter 12 is composed of a cured product of a photosensitive resin composition containing a coloring agent corresponding to each color.

[0244] The embodiments of the present invention have been described above, but these are merely examples, and various other configurations can also be adopted. [Examples]

[0245] The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0246] The compounds used in the examples may be indicated by the following abbreviations or trade names. MAN: Maleic anhydride NB:2-Norbornen • FADB: Dibutyl fumarate BVE: Butyl vinyl ether VBR: Vinyl butyrate · HXE:1-Hexene • OTE:1-Octene ·DCE:1-Desen ·DDCE:1-Dodesen • ODCE:1-Octadecene • MEK: Methyl ethyl ketone • PEMP: Pentaerythritol tetrakis(3-mercaptopropionate), a thiol group-containing compound of the above formula (s-2) (manufactured by SC Organic Chemicals Co., Ltd.) 4-HBA: 4-hydroxybutyl acrylate • A-TMM-3LM-N: A mixture of the following two compounds. Based on gas chromatography measurements, the amount of the compound on the left in the mixture is approximately 57% (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

[0247] [ka]

[0248] <Synthesis of raw material polymers> (Synthesis of raw material polymer 1) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 602.56 g of a 75% toluene solution of 2-norbornene (equivalent to 451.92 g of 2-norbornene, 4.8 mol), maleic anhydride (MAN, 470.69 g, 4.8 mol), and 2281.74 g of methyl ethyl ketone (MEK) were added and stirred until dissolved. Next, dissolved oxygen was removed from the system by nitrogen bubbling, and the mixture was heated. When the internal temperature reached 80°C, a solution of 2,2'-dimethyl azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 44.21 g, 0.19 mol) and PEMP (93.82 g, 0.19 mol) dissolved in 193.4 g of MEK was added over 1 hour. The reaction was then continued at 80°C for 7 hours. Finally, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 3686.4 g of methanol to precipitate a white solid. The obtained white solid was then washed with another 3686.4 g of methanol and vacuum-dried at 120°C to obtain 910.1 g of a polymer (raw material polymer 1) comprising structural units derived from 2-norbornene and structural units derived from maleic anhydride. The obtained raw material polymer 1 was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 3,500, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.62.

[0249] (Confirmation of the thioether structure contained in raw material polymer 1) The elemental PEMP is represented by the following chemical formula. 13 1C-NMR measurements revealed a peak a originating from carbon a at approximately 19.0 ppm and a peak b originating from carbon b at approximately 62.0 ppm.

[0250] [ka]

[0251] Raw material polymer 1 synthesized using PEMP 13In 1C-NMR measurements, a peak b originating from carbon b was observed at approximately 62.0 ppm. GPC measurements of the reaction solution showed no peak for PEMP alone, indicating that no unreacted PEMP remained, thus confirming that PEMP was incorporated into the raw material polymer 1.

[0252] Also, raw material polymer 1 13 In 1C-NMR measurements, peak a, originating from carbon a, was not observed. Instead, peak c, corresponding to a thioether (RS-R'), appeared around 28 ppm. Since the integral value of peak c is approximately twice that of peak b, it was determined that the raw material polymer 1 has a skeleton containing a thioether group as described below, and the thiol group has disappeared.

[0253] [ka]

[0254] 13 The conditions for 1C-NMR measurement are as follows: (Test conditions) The measurement sample was prepared by adding the measurement solvent to the weighed sample to adjust the concentration, and then pouring the specified amount into an NMR measurement sample tube. • Measurement equipment: JEOL JNM-ECA400 superconducting FT-NMR spectrometer ·Resonance frequency: 100.53MHz • Measurement nucleus: 13 C • Measurement method: NNE measurement (inverse gate decoupling method) • Pulse width: 3.83 μsec • Pulse repetition waiting time: 30s • Total number of times: 4096 ·Measurement temperature: room temperature • Measurement solvent: DMSO-d6 (deuterated dimethyl sulfoxide) • Sample concentration: 20% (w / v) The amount of sulfur in the obtained polymer was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in the polymer. Furthermore, GPC analysis of the reaction solution before methanol addition showed the disappearance of the PEMP-derived peak, confirming that PEMP was incorporated into the starting polymer 1.

[0255] Elemental analysis revealed that the sulfur content in raw polymer 1 was 2.4 wt%.

[0256] (Synthesis of raw material polymer 2) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 112.98 g of a 75% toluene solution of 2-norbornene (equivalent to 84.75 g of 2-norbornene, 0.900 mol), maleic anhydride (MAN, 88.25 g, 0.900 mol), 102.73 g of dibutyl fumarate (0.450 mol), and 179.12 g of methyl ethyl ketone (MEK) were added and stirred until dissolved. Next, dissolved oxygen in the system was removed by nitrogen bubbling, and the system was heated. When the internal temperature reached 70°C, a solution of dimethyl 2,2'-azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 10.36 g, 0.045 mol) and PEMP (32.98 g, 0.0675 mol) dissolved in 76.77 g of MEK was added over 1 hour. The temperature was further increased to 80°C, and the reaction was carried out at 80°C for 7 hours. The reaction mixture was then cooled to room temperature. The polymerization solution obtained above was added dropwise to 3016.2 g of methanol to precipitate a white solid. The obtained white solid was then washed with 754.1 g of methanol and vacuum-dried at 120°C to obtain 154.2 g of polymer (raw material polymer 2) comprising structural units derived from 2-norbornene, structural units derived from dibutyl fumarate, and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 2,800, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.54.

[0257] [Structural analysis of raw material polymer 2] The synthesis of raw material polymer 2 begins with the monomer and PEMP dissolved in the solvent at the start of the reaction, after which the reaction proceeds to produce the polymer. Analysis of the reaction solution and the resulting polymer yielded the following results.

[0258] (a) Analysis of the reaction solution GPC analysis of the reaction solution before reprecipitation and purification showed no peak for PEMP alone. This confirmed that no PEMP remained in the reaction solution. Furthermore, GC (gas chromatography) analysis of the reaction solution before reprecipitation and purification showed a decrease in the peaks for norbornene alone, dibutyl fumarate alone, and maleic anhydride alone in the reaction solution after the reaction compared to before the reaction. This confirmed that norbornene alone, dibutyl fumarate, and maleic anhydride reacted to form polymers.

[0259] (b) Analysis of polymers GPC analysis of the polymer after reprecipitation and purification did not reveal peaks for PEMP, norbornene, dibutyl fumarate, or maleic anhydride. This confirmed that no PEMP, norbornene, dibutyl fumarate, or maleic anhydride remained in the polymer.

[0260] (Synthesis of raw material polymer 3) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 112.98 g of a 75% toluene solution of 2-norbornene (equivalent to 84.75 g of 2-norbornene, 0.900 mol), maleic anhydride (MAN, 1110.32 g, 1.125 mol), butyl vinyl ether (BVE) 22.54 g (0.225 mol), and methyl ethyl ketone (MEK) 206.89 g were added and stirred until dissolved. Next, dissolved oxygen in the system was removed by nitrogen bubbling, and the system was heated until the internal temperature reached 80°C. Then, a solution of 2,2'-dimethyl azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 10.36 g, 0.045 mol) and PEMP (21.99 g, 0.045 mol) dissolved in 109.99 g of MEK was added over 1 hour. The reaction was then continued at 80°C for 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 3016.2 g of methanol to precipitate a white solid. The obtained white solid was further washed with 754.1 g of methanol and then vacuum-dried at 120°C to obtain 181.5 g of polymer (raw material polymer 3) comprising structural units derived from 2-norbornene, structural units derived from butyl vinyl ether, and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 4,500, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 2.33.

[0261] The amount of sulfur in the obtained raw material polymer 3 was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in raw material polymer 3. Furthermore, GPC measurement of the reaction solution before methanol addition showed the disappearance of the peak derived from PEMP, confirming that PEMP was incorporated into the polymer.

[0262] (Synthesis of raw material polymer 4) Except for using 25.68 g (0.225 mol) of vinyl butyrate (VBR) instead of butyl vinyl ether (BVE), the process was the same as for raw material polymer 3, and 195.1 g of polymer (raw material polymer 4) was obtained, which contained structural units derived from 2-norbornene, structural units derived from butyl vinyl ether, and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 3,700, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.89.

[0263] The amount of sulfur in the obtained raw material polymer 4 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur was confirmed in the raw material polymer 4. In addition, GPC measurement of the reaction solution before methanol addition showed that the peak derived from PEMP had disappeared, confirming that PEMP had been incorporated into the polymer.

[0264] (Synthesis of raw material polymer 5) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 112.98 g of a 75% toluene solution of 2-norbornene (equivalent to 84.75 g of 2-norbornene, 0.900 mol), maleic anhydride (MAN, 110.32 g, 1.125 mol), 1-decene (DCE), 31.56 g (0.225 mol), and methyl ethyl ketone (MEK) were added and stirred until dissolved. Next, dissolved oxygen in the system was removed by nitrogen bubbling, and the system was heated until the internal temperature reached 80°C. Then, a solution of 2,2'-dimethyl azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 10.36 g, 0.045 mol) and PEMP (21.99 g, 0.045 mol) dissolved in 48.20 g of MEK was added over 1 hour. The reaction was then continued at 80°C for 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 3621.5 g of methanol to precipitate a white solid. The obtained white solid was further washed with 905.4 g of methanol and then vacuum-dried at 120°C to obtain 180.1 g of polymer (raw material polymer 5) comprising structural units derived from 2-norbornene, structural units derived from 1-decene, and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 2,700, and the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.77. Regarding raw material polymer 5, 13 The ratio of structures derived from each monomer actually introduced into the raw material polymer, as calculated by 13C-NMR, was norbornene:maleic anhydride:1-decene = 42.0%:51.0%:7.0%, and the amount of PEMP actually introduced into the raw material polymer was 2.9 mol% of the total amount of each monomer.

[0265] (Confirmation of the structure of raw material polymer 5) The amounts (mole fraction, mol%) of structural units derived from PEMP, 1-decene (structural units of formula (AK)), maleic anhydride (structural units of formula (MA)), and norbornene (structural units of formula (NB)) in raw material polymer 5 are as follows: 13The values ​​were calculated by integral analysis of 1C-NMR. 13 The 1C-NMR chart is shown in Figure 2. 13 The chemical shifts in the 1C-NMR chart were assigned to each structural unit as follows, and the corresponding integral values ​​were measured. PEMP k(4C): 62.0~64.0 ppm • 1-Decene terminus (1C): 13.0~15.0 ppm • Maleic anhydride ester (2C) + PEMP g(4C): 170.0~174.7 ppm • Maleic acid ester (2C) (a structure in which maleic anhydride has been ring-opened): 174.7~178.0 ppm Alkyl chain: 20-60 ppm • DMSO: around 40 ppm Norbornene(7C)=alkyl chain-DMSO-PEMP(9C, h+i+j)-maleic anhydride(2C)-maleic acid(2C)-decene(9C) Here, the structural ratio derived from maleic anhydride that was actually introduced into the raw material polymer was calculated by including not only the structural unit of formula (MA) but also the structure of maleic acid obtained by ring-opening maleic anhydride.

[0266] The synthesis of raw material polymer 5 begins with the monomer and PEMP dissolved in the solvent at the start of the reaction, after which the reaction proceeds to produce the polymer. Analysis of the reaction solution and the resulting polymer yielded the following results.

[0267] (a) Analysis of the reaction solution GPC analysis of the reaction solution before reprecipitation and purification showed no peak for PEMP alone. This confirmed that no PEMP remained in the reaction solution. Furthermore, GC (gas chromatography) analysis of the reaction solution before reprecipitation and purification showed a decrease in the peaks for norbornene, 1-decene, and maleic anhydride in the reaction solution after the reaction compared to before the reaction. This confirmed that norbornene, 1-decene, and maleic anhydride reacted to form polymers. The measurement conditions for gas chromatography were as follows: ·GC device: GC-2030 (Shimadzu Corporation) • Carrier gas: N2 • Detector: Flame ionization (FID) detector, FID temperature: 300℃ • Column: SH-RXi-1HT, inner diameter 0.25, length 30m, film thickness 0.25μm (Shimadzu GLC Co., Ltd.) • Evaporation chamber temperature: 210℃ Column flow rate: 0.64 mL / min • Column heating conditions: Hold at 50°C for 5 minutes, heat at 20°C / min up to 300°C, hold at 300°C for 10 minutes.

[0268] (b) Analysis of polymers GPC analysis of the polymer after reprecipitation and purification did not reveal peaks for PEMP, norbornene, 1-decene, or maleic anhydride. This confirmed that no PEMP, norbornene, 1-decene, or maleic anhydride remained in the polymer.

[0269] The amount of sulfur in the obtained raw material polymer 5 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur was confirmed in the raw material polymer 5. Furthermore, GPC measurement of the reaction solution before methanol addition showed that the peak derived from PEMP had disappeared, confirming that PEMP had been incorporated into the polymer.

[0270] (Synthesis of raw material polymer 6) In a reaction vessel equipped with a stirrer, condenser, and dropping funnel, 112.98 g of a 75% toluene solution of 2-norbornene (equivalent to 84.75 g of 2-norbornene, 0.900 mol), maleic anhydride (MAN, 110.32 g, 1.125 mol), 1-decene (DCE), 31.56 g (0.225 mol), and methyl ethyl ketone (MEK) were added and stirred until dissolved. Next, dissolved oxygen in the system was removed by nitrogen bubbling, and the system was heated until the internal temperature reached 80°C. Then, a solution of 2,2'-dimethyl azobisisobutyrate (Wako Pure Chemical Industries, Ltd., trade name: V-601, 10.36 g, 0.045 mol) and PEMP (21.99 g, 0.045 mol) dissolved in 115.43 g of MEK was added over 1 hour. The reaction was then continued at 80°C for 7 hours. Next, the reaction mixture was cooled to room temperature. The polymerization solution obtained above was added dropwise to 3621.5 g of methanol to precipitate a white solid. The obtained white solid was further washed with 905.4 g of methanol and then vacuum-dried at 120°C to obtain 190.1 g of a polymer (raw material polymer 6) comprising structural units derived from 2-norbornene, structural units derived from 1-decene, and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 3,600, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.90.

[0271] The amount of sulfur in the obtained raw material polymer 6 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur was confirmed in the raw material polymer 6. Furthermore, GPC measurement of the reaction solution before methanol addition showed that the peak derived from PEMP had disappeared, confirming that PEMP had been incorporated into the polymer.

[0272] (Synthesis of raw material polymer 7) Except for using 84.74 g of a 75% toluene solution of 2-norbornene (equivalent to 63.55 g of 2-norbornene, 0.675 mol) and 63.12 g (0.450 mol) of 1-decene, 205.1 g of polymer (raw material polymer 7) was obtained in the same manner as raw material polymer 5, with the exception of using 84.74 g of a 75% toluene solution of 2-norbornene (equivalent to 63.55 g of 2-norbornene, 0.675 mol) and 63.12 g (0.450 mol) of 1-decene. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 3,000, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.58. The amount of sulfur in the obtained raw material polymer 7 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur was confirmed in the raw material polymer 7. Furthermore, GPC measurement of the reaction solution before methanol addition showed that the peak derived from PEMP had disappeared, confirming that PEMP had been incorporated into the polymer.

[0273] (Synthesis of raw material polymer 8) Except for using 18.94 g (0.225 mol) of 1-hexene instead of 1-decene, the process was the same as for raw material polymer 5, and 179.2 g of polymer (raw material polymer 8) was obtained, which contained structural units derived from 2-norbornene, structural units derived from 1-hexene, and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 2,900, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.73. The amount of sulfur in the obtained raw material polymer 8 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur was confirmed in the raw material polymer 8. Furthermore, GPC measurement of the reaction solution before methanol addition showed that the peak derived from PEMP had disappeared, confirming that PEMP had been incorporated into the polymer.

[0274] (Synthesis of raw material polymer 9) Except for using 25.25 g (0.225 mol) of 1-octene instead of 1-decene, the process was the same as for raw material polymer 5, and 185.1 g of polymer (raw material polymer 9) was obtained, which contained structural units derived from 2-norbornene, structural units derived from 1-octene, and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 2,900, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.74. The amount of sulfur in the obtained raw material polymer 9 was confirmed by elemental analysis using flask combustion and ion chromatography, confirming the presence of sulfur in the raw material polymer 9. Furthermore, GPC measurement of the reaction solution before methanol addition showed the disappearance of the peak derived from PEMP, confirming that PEMP was incorporated into the polymer.

[0275] (Synthesis of raw material polymer 10) Except for using 37.87 g (0.225 mol) of 1-dodecene instead of 1-decene, the process was the same as for raw material polymer 5, and 192.7 g of polymer (raw material polymer 10) was obtained, which contained structural units derived from 2-norbornene, structural units derived from 1-dodecene, and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 2,900, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.98. The amount of sulfur in the obtained raw material polymer 10 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur was confirmed in the raw material polymer 10. Furthermore, GPC measurement of the reaction solution before methanol addition showed that the peak derived from PEMP had disappeared, confirming that PEMP had been incorporated into the polymer.

[0276] (Synthesis of raw material polymer 11) Except for using 56.81 g (0.225 mol) of 1-octadecene instead of 1-decene, the process was the same as for raw material polymer 6, and 205.7 g of polymer (raw material polymer 11) was obtained, which contained structural units derived from 2-norbornene, structural units derived from 1-octadecene, and structural units derived from maleic anhydride. The obtained polymer was measured using gel permeation chromatography (GPC), and the weight-average molecular weight Mw was 2,900, while the polydispersity (weight-average molecular weight Mw) / (number-average molecular weight Mn) was 1.79. The amount of sulfur in the obtained raw material polymer 11 was confirmed by elemental analysis using flask combustion and ion chromatography, and the presence of sulfur was confirmed in the raw material polymer 11. In addition, GPC measurement of the reaction solution before methanol addition showed that the peak derived from PEMP had disappeared, confirming that PEMP had been incorporated into the polymer.

[0277] For raw material polymers 2-11, the amount of each monomer in the reaction solution before and after the reaction was measured by gas chromatography (GC), and the consumption of each monomer was calculated to determine the ratio of each monomer introduced into the raw material polymer. Table 1 below shows the charge ratio of monomers used in the synthesis of the raw material polymer, the ratio of monomers introduced into the raw material polymer, the weight-average molecular weight (Mw) and heterodispersity (Mw / Mn) of the raw material polymer. The measurement conditions for gas chromatography are as follows: ·GC device: GC-2030 (Shimadzu Corporation) • Carrier gas: N2 • Detector: Flame ionization (FID) detector, FID temperature: 300℃ • Column: SH-RXi-1HT, inner diameter 0.25, length 30m, film thickness 0.25μm (Shimadzu GLC Co., Ltd.) • Evaporation chamber temperature: 210℃ Column flow rate: 0.64 mL / min • Column heating conditions: Hold at 50°C for 5 minutes, heat at 20°C / min up to 300°C, hold at 300°C for 10 minutes.

[0278] [Table 1]

[0279] <Synthesis of Polymer P> Polymer P was prepared using the following method.

[0280] (Preparation Example 1) Polymer P1 was prepared by ring-opening the MA units of raw material polymer 1 with a monofunctional (meth)acrylic compound. Details are described below. First, 18.44 g of MEK was added to 10.00 g of raw material polymer 1 (calculated from the amount of raw material polymer 1 used, equivalent to 0.052 moles of MA) to prepare a solution. Next, 9.38 g (0.065 moles) of 4-HBA was added to this solution, followed by 3.00 g (0.030 moles) of triethylamine. The mixture was reacted at 70°C for 6 hours to prepare the reaction solution. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase. The polymer was then purified by the reprecipitation method described below. • Reprecipitation method: The polymer was reprecipitation with an excess amount of water. The polymer powder obtained by reprecipitation was washed with an excess amount of water, and this process was repeated twice. The resulting reaction product was dried at 40°C for 12 hours. Based on the above, 8.7 g of polymer P1 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 1 with 4-HBA. The obtained polymer P1 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P1 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the obtained polymer P1 did not contain any unreacted monofunctional (meth)acrylic compound.

[0281] (Preparation Example 2) Polymer P2 was prepared by ring-opening the MA units of raw material polymer 1 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. Details are described below. First, a solution was prepared by adding 99.93g of MEK to 60.00g of raw material polymer 1 (calculated from the amount of raw material polymer 1 used, equivalent to 0.312 moles of MA). Next, 77.49g of A-TMM-3LM-N was added to this solution, followed by 18.00g (0.178 moles) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Subsequently, 56.27g (0.390 moles) of 4-HBA was added, and the mixture was reacted at 70°C for 4 hours to prepare the reaction solution. Next, without any post-treatment of the resulting reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70°C for 2 hours. The resulting reaction solution was diluted with MEK and treated with an aqueous citric acid solution to remove the aqueous phase. Further liquid-liquid extraction and subsequent solvent replacement were performed 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 under reduced pressure at 50°C using a rotary evaporator. The solvent removal process was stopped when the solid content of the polymer solution was confirmed to be 27±2% by mass, as measured by a heat-drying moisture meter. Then, PGMEA was added to bring the solid content to 18% by mass and mixed until homogeneous. The same procedure was repeated two more times: solvent removal under reduced pressure at 50°C, adjusting the solid content to 27±2% by mass as measured by a heat-drying moisture meter, then adding PGMEA to bring the solid content to 18% by mass and mixing until homogeneous. Subsequently, solvent removal or the addition of PGMEA was performed, and the mixture was stirred until homogeneous, to bring the solid content to 30±3% by mass. Through these operations, the solvent used in the reaction was removed and replaced with PGMEA. Further purification was then carried out according to 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. The polymer powder, after being washed twice as described above, was washed three times with an excess amount of water. The resulting reaction product was dried at 40°C for 12 hours. Based on the above, polymer P2 was prepared by ring-opening the MA units of raw material polymer 1 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The obtained polymer P2 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P2 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P2 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 13 1C-NMR measurements confirmed that polymer P2 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0282] (Preparation Example 3) Polymer P3 was prepared in the same manner as in Preparation Example 1, except that 10.00 g of raw material polymer 2 (0.034 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 2) was used instead of raw material polymer 1, by ring-opening the MA units of raw material polymer 2 with a monofunctional (meth)acrylic compound. The obtained polymer P3 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P3 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P3 did not contain any unreacted monofunctional (meth)acrylic compound. Also 131C-NMR measurements confirmed that polymer P3 has a structure in which a structural unit derived from maleic anhydride is ring-opened with 4-HBA.

[0283] (Preparation Example 4) Except for using 60.00 g of raw material polymer 2 (0.204 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 2) instead of raw material polymer 1, polymer P4 was prepared in the same manner as in Preparation Example 2 by ring-opening the MA units of raw material polymer 2 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The obtained polymer P4 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P4 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P4 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 13 1C-NMR measurements confirmed that polymer P4 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0284] (Preparation Example 5) Except for using 60.00 g of raw material polymer 3 (0.304 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 3) instead of raw material polymer 1, polymer P5 was prepared in the same manner as in Preparation Example 2 by ring-opening the MA units of raw material polymer 3 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The obtained polymer P5 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P5 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P5 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 13 1C-NMR measurements confirmed that polymer P5 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0285] (Preparation Example 6) Polymer P6 was prepared in the same manner as in Preparation Example 2, except that 60.00 g of raw material polymer 4 (0.300 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 4) was used instead of raw material polymer 1, and the MA units of raw material polymer 4 were ring-opened with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The obtained polymer P6 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P6 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P6 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 13 1C-NMR measurements confirmed that polymer P6 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0286] (Preparation Example 7) Polymer P7 was prepared in the same manner as in Preparation Example 1, except that 10.00 g of raw material polymer 5 (0.048 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 5) was used instead of raw material polymer 1, by ring-opening the MA units of raw material polymer 5 with a monofunctional (meth)acrylic compound. The obtained polymer P7 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P7 confirmed the disappearance of the peak of the monofunctional (meth)acrylic compound used. This confirmed that the resulting polymer P7 did not contain any unreacted monofunctional (meth)acrylic compound. Also 13 1C-NMR measurements confirmed that polymer P7 has a structure in which a structural unit derived from maleic anhydride is ring-opened with 4-HBA. Polymer P7 1 The molar ratio of the compound reacted with the starting polymer in the overall structure was calculated using 1H-NMR measurement. The results are shown in Table 2.

[0287] (Preparation Example 8) A resin mixture (polymer solution P8) containing polymer P8, obtained by ring-opening the MA units of raw material polymer 5 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared. Details are described below. First, a solution was prepared by adding 99.93 g of MEK to 60.00 g of raw material polymer 5 (calculated as 0.290 mol in MA equivalent based on the composition ratio calculated from the GC measurement of raw material polymer 5). Next, 77.49 g of A-TMM-3LM-N was added to this solution, followed by 18.00 g (0.178 mol) of triethylamine, and the mixture was reacted at 70°C for 2 hours. Subsequently, 56.27 g (0.390 mol) of 4-HBA was added, and the mixture was reacted at 70°C for 4 hours to prepare the reaction solution. Next, without any post-treatment of the resulting reaction solution, 3.00 g (0.167 mol) of water was added to the reaction solution, and the mixture was reacted at 70°C for 2 hours. The resulting reaction solution was diluted with MEK, and the aqueous phase was removed from the reaction solution by treating it with aqueous formic acid and aqueous citric acid solutions. Further liquid-liquid extraction and subsequent solvent replacement were performed according to the following procedure. • Liquid-liquid extraction: The reaction solution was diluted with MEK, then a water / methanol mixed solvent was added and treated to remove the aqueous phase from the reaction solution. This procedure was then repeated once more. • Solvent Replacement: The solvent was removed from the resulting reaction mixture under reduced pressure at 50°C using a rotary evaporator. The solvent removal operation was stopped when the solid content concentration of the polymer solution was confirmed to be 27±2 mass% by measurement using a heat-drying type moisture meter. Then, PGMEA was added to bring the solid content concentration to 18 mass% and mixed until homogeneous. The same procedure was repeated two more times, removing the solvent under reduced pressure at 50°C, adjusting the solid content concentration to 27±2 mass% by measurement using a heat-drying type moisture meter, and then adding PGMEA to bring the solid content concentration to 18 mass% and mixing until homogeneous. After that, the solvent was removed or PGMEA was added and stirred until homogeneous to bring the solid content concentration to 30±3 mass%. Through these operations, the solvent used in the reaction was removed and replaced with PGMEA.

[0288] Based on the above, polymer P8 was obtained by ring-opening the structural units derived from maleic anhydride in raw material polymer 5 with A-TMM-3LM-N, 4-HBA, and water, and a resin mixture (polymer solution P8) containing residual (free) A-TMM-3LM-N and residual (free) 4-HBA was obtained. The obtained polymer solution P8 was analyzed by gel permeation chromatography to determine the amounts of polymer P8, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds in the solution, as well as the weight-average molecular weight and polydispersity of polymer P8. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P8 in the 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 the HLC-8320GPC EcoSEC from Tosoh Corporation. The column temperature was set to 40.0°C and the pump flow rate to 0.350 mL / min. • Peak position (holding time) Polymer P8: Peak detected before 20 minutes (a peak with a shorter retention time and higher molecular weight than A-TMM-3LM-N and 4-HBA) A-TMM-3LM-N: Total of two peaks at 20.0-20.6 minutes and 20.6-21.5 minutes. 4-HBA: 21.7~22.4 minutes • Measurement conditions: Analysis was performed using a differential refractive index detector (RI detector).

[0289] (Preparation Example 9) A resin mixture (polymer solution P9) containing polymer P9, obtained by ring-opening the MA units of raw material polymer 6 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 8, except that 60.00 g of raw material polymer 6 (0.296 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 6) was used instead of raw material polymer 5.

[0290] The obtained polymer solution P9 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 8 to determine the amounts of polymer P9, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P9. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P9 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0291] (Preparation Example 10) A resin mixture (polymer solution P10) containing polymer P10, obtained by ring-opening the MA units of raw material polymer 7 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 8, except that 60.00 g of raw material polymer 7 (0.291 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 7) was used instead of raw material polymer 5.

[0292] The obtained polymer solution P10 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 8 to determine the amounts of polymer P10, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P10. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P10 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0293] (Preparation Example 11) A resin mixture (polymer solution P11) containing polymer P11, obtained by ring-opening the MA units of raw material polymer 8 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 8, except that 60.00 g of raw material polymer 8 (0.302 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 8) was used instead of raw material polymer 5.

[0294] The obtained polymer solution P11 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 8 to determine the amounts of polymer P11, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P11. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P11 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0295] (Preparation Example 12) A resin mixture (polymer solution P12) containing polymer P12, obtained by ring-opening the MA units of raw material polymer 9 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 8, except that 60.00 g of raw material polymer 9 (0.298 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 9) was used instead of raw material polymer 5.

[0296] The obtained polymer solution P12 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 8 to determine the amounts of polymer P12, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P12. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P2 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0297] (Preparation Example 13) A resin mixture (polymer solution P13) containing polymer P13, obtained by ring-opening the MA units of raw material polymer 10 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 8, except that 60.00 g of raw material polymer 10 (0.290 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 10) was used instead of raw material polymer 5.

[0298] The obtained polymer solution P13 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 8 to determine the amounts of polymer P13, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P13. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P13 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0299] (Preparation Example 14) A resin mixture (polymer solution P14) containing polymer P14, obtained by ring-opening the MA units of raw material polymer 11 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water, was prepared in the same manner as in Preparation Example 8, except that 60.00 g of raw material polymer 11 (0.298 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 11) was used instead of raw material polymer 5.

[0300] The obtained polymer solution P14 was analyzed by gel permeation chromatography under the same conditions as in Preparation Example 8 to determine the amounts of polymer P14, free polyfunctional (meth)acrylic compounds, and free monofunctional (meth)acrylic compounds contained in the solution, as well as the weight-average molecular weight and polydispersity of polymer P14. The results are shown in Table 2. The amount of free (meth)acrylic compounds is expressed as the percentage (%) of the peak area of ​​the free (meth)acrylic compounds relative to the peak area of ​​polymer P14 in the gel permeation chromatography (GPC) chart of the resin mixture.

[0301] (Preparation Example 15) Except for using 60.00 g of raw material polymer 5 (0.290 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 5) instead of raw material polymer 1, polymer P15 was prepared in the same manner as in Preparation Example 2 by ring-opening the MA units of raw material polymer 5 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The obtained polymer P15 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P15 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P15 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 131C-NMR measurements confirmed that polymer P15 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0302] (Preparation Example 16) Except for using 60.00 g of raw material polymer 8 (0.302 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 8) instead of raw material polymer 1, polymer P16 was prepared in the same manner as in Preparation Example 2 by ring-opening the MA units of raw material polymer 8 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The obtained polymer P16 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P16 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P16 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 13 1C-NMR measurements confirmed that polymer P16 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0303] (Preparation Example 17) Except for using 60.00 g of raw material polymer 9 (0.298 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 9) instead of raw material polymer 1, polymer P17 was prepared in the same manner as in Preparation Example 2 by ring-opening the MA units of raw material polymer 9 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The obtained polymer P17 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P17 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P17 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 13 1C-NMR measurements confirmed that polymer P17 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0304] (Preparation Example 18) Except for using 60.00g of raw material polymer 10 (0.290 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 10) instead of raw material polymer 1, polymer P18 was prepared in the same manner as in Preparation Example 2, by ring-opening the MA units of raw material polymer 10 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The obtained polymer P18 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine its weight-average molecular weight and polydispersity. The results are shown in Table 2. Furthermore, GPC analysis of polymer P18 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P18 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 13 1C-NMR measurements confirmed that polymer P18 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0305] (Preparation Example 19) Except for using 60.00g of raw material polymer 11 (0.298 moles in MA equivalent, calculated from the composition ratio calculated from GC measurement of raw material polymer 11) instead of raw material polymer 1, polymer P15 was prepared in the same manner as in Preparation Example 2, by ring-opening the MA units of raw material polymer 11 with a trifunctional (meth)acrylic compound, a monofunctional (meth)acrylic compound, and water. The obtained polymer P19 was subjected to GPC (Geomorphic Spectroscopy) measurements to determine the weight-average molecular weight and polydispersity of polymer P195. The results are shown in Table 2. Furthermore, GPC analysis of polymer P19 confirmed the disappearance of peaks for both the polyfunctional (meth)acrylic and monofunctional (meth)acrylic compounds used. This confirmed that the obtained polymer P19 did not contain any unreacted polyfunctional (meth)acrylic or monofunctional (meth)acrylic compounds. Also 13 1C-NMR measurements confirmed that polymer P19 has a structure in which structural units derived from maleic anhydride are ring-opened with A-TMM-3LM-N, 4-HBA, and water.

[0306] (Evaluation of physical properties) The acid value and double bond equivalent of each polymer P prepared in Preparation Examples 3, 4, 7, and 15-19 were measured by the method described below.

[0307] (Acid value) The acid value of the polymer was measured by the following method. Approximately 50 mg of polymer and approximately 5 mg of dimethyl terephthalate as an internal standard were weighed and dissolved in DMSO-d6. This solution was then analyzed using a nuclear magnetic resonance spectrometer JNM-AL300 (manufactured by JEOL). 1 1H-NMR measurements were performed. 1 The amount of carboxyl groups is determined by using the integral value of the 4H peak (around 8.1 ppm) of the phenyl group of the dimethyl terephthalate, an internal standard in 1H-NMR measurements, as a reference, and then using the integral value of the H peak (around 12.4 ppm) of the carboxyl group (-COOH) of the polymer. From this amount, the acid value (mgKOH / g) can be calculated. A higher acid value indicates a greater amount of carboxyl groups per unit mass of polymer. The results are shown in Table 2. An acid value of 50 gKOH / g or higher indicates that the polymer contains sufficient carboxyl groups necessary for adequate development.

[0308] (double bond equivalent) The double bond equivalents of the polymer were measured by the following method. Similar to the above method for measuring acid value, 1 ¹H-NMR measurements were performed. The amount of acryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal originating from acryloyl groups (5.6-5.8 ppm, 3H) and the signal of the phenyl group of the internal standard (8.1 ppm, 4H) in the obtained spectral chart. The amount of methacryloyl groups (mol / g) in the polymer was calculated from the integral ratio of the signal originating from methacryloyl groups (5.6-5.8 ppm, 2H) and the signal of the phenyl group of the internal standard (8.1 ppm, 4H). Here, the signal originating from methacryloyl groups at 6.0-6.1 ppm was negligible and overlapped with the signal of acryloyl groups, so it was calculated as the signal of acryloyl groups. The amount of double bonds (mol / g) was calculated from the sum of the calculated amount of acryloyl groups (mol / g) and methacryloyl groups (mol / g) in the polymer, and the double bond equivalent (g / mol) was calculated from the double bond amount. The results are shown in Table 2. A smaller double bond equivalent value indicates a larger amount of C=C double bonds per unit mass of polymer.

[0309] [Table 2]

[0310] (Examples 1-13, Comparative Examples 1-6) In each example and comparative example, a resin composition was prepared and evaluated for the following items. <Rating> [Alkali dissolution rate of resin compositions] Polymers P1-P6 and P15-P19 obtained in Preparation Examples 1-6 and 15-19 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare resin compositions 1-7 and 15-19 with a solid content concentration of 30% by mass. Next, resin compositions 8 to 14, consisting of the above resin compositions 1 to 7, 15 to 19, or polymer solutions P8 to P14 obtained in preparation examples 8 to 14, were spin-coated onto the wafer, the PGMEA was dried, and then the film was pre-baked at 100°C for 2 minutes to produce a resin film with a thickness of approximately 2 μm. The resin film, along with the wafer, was immersed in a 2% sodium carbonate aqueous 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 then dividing the film thickness by that time. The results are shown in Table 3. If the alkali dissolution rate is 120 nm / s or higher, it can be used without problems as a photosensitive material; if it is 200 nm / s or higher, it can be considered to have good developability; and if it is 300 nm / s or higher, it can be considered to have even better developability.

[0311] [Softening point of raw polymer] The softening points of raw polymers 1 to 11 were measured using the following method. First, 0.1 to 1.0 mg of the target polymers (raw material polymers 1 to 11) were placed in an aluminum sample pan, and the softening point was measured under a nitrogen atmosphere using a differential thermal analyzer (Hitachi High-Tech Science Corporation, "EXSTAR TMA / SS6100"). The measurement mode was compression, the load was 30 mN, and the temperature was increased from 30°C to 200°C at a heating rate of 3°C / min. When the sample softened due to heating, the sample deformed, and the displacement (μm) was detected. The softening point was defined as the extension of the straight section with no displacement on the low-temperature side, or the intersection of the tangent to the minimum displacement velocity and the tangent to the maximum displacement velocity. As an example, the TMA chart for raw material polymer 5 is shown in Figure 3. The measurement results for the softening point are shown in Table 1. A raw polymer can be said to have a low softening point if it is 160°C or below, even lower if it is 140°C or below, and particularly low if it is 130°C or below.

[0312] [Melting point of raw material polymer] The melting points of raw material polymers 1 to 11 were measured using the following method. First, 1-2 mg of the polymer to be measured (raw material polymers 1-11) was placed in an aluminum sample pan and heated from 30°C at a heating rate of 10°C / min under a nitrogen atmosphere using a differential thermal analyzer (Hitachi High-Tech Science Corporation, "STA7200RV") while observing the image. The temperature at which the sample began to melt was visually confirmed and defined as the melting point. A raw polymer can be said to have a low melting point if it is 180°C or below, even lower if it is 160°C or below, and particularly low if it is 140°C or below. The results are shown in Table 1.

[0313] [Softening point of polymer P] The softening points of polymers P1-P6 and P15-P19 obtained in Preparation Examples 1-6 and 15-19 were measured by the following method. First, 0.1 to 1.0 mg of the target polymers (polymers P1 to P6, P15 to P19) were placed in an aluminum sample pan, and the softening point was measured under a nitrogen atmosphere using a differential thermal analyzer (Hitachi High-Tech Science Corporation, "EXSTAR TMA / SS6100"). The measurement mode was compression, the load was 30 mN, and the temperature was increased from 30°C to 200°C at a heating rate of 3°C / min. When the sample softened due to heating, the sample deformed, and the displacement (μm) was detected. The softening point was defined as the extension of the straight section with no displacement on the low-temperature side, or the intersection of the tangent to the section with the minimum displacement velocity and the tangent to the section with the maximum displacement velocity. The results are shown in Table 2. A polymer P can be said to have a low softening point if it is 110°C or below, an even lower softening point if it is 100°C or below, and an especially low softening point if it is 90°C or below.

[0314] [Melting point of polymer P] The melting points of polymers P1-P6 and P15-P19 obtained in Preparation Examples 1-6 and 15-19 were measured by the following method. First, 1-2 mg of the target polymers (polymers P1-P6, P15-P19) were placed in an aluminum sample pan and heated from 30°C at a heating rate of 10°C / min under a nitrogen atmosphere using a differential thermal analyzer (Hitachi High-Technologies Corporation, "STA7200RV") while observing the image. The temperature at which the sample began to melt was visually confirmed and defined as the melting point. The results are shown in Table 2. A polymer P can be said to have a low melting point if it is 140°C or below, an even lower melting point if it is 130°C or below, and an especially low melting point if it is 120°C or below.

[0315] [Softening point of cured photosensitive resin composition] The softening points of the photosensitive resin compositions prepared from polymers P1-P6 and P15-P19 obtained in Preparation Examples 1-6 and 15-19, or from polymer solutions P8-P14 obtained in Preparation Examples 8-14, were measured by the following method. First, a photosensitive resin composition was obtained by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solids content concentration was 30% by mass. Polymers P1-P6, P15-P19 (polymers P1-P6 and P15-P19 from Preparation Examples 1-6 and 15-19, respectively) or resin mixtures 8-14 (polymer solutions P8-P14 from Preparation Examples 8-14, respectively): 100 parts by mass (Here, resin mixtures 8-14 were weighed so that the total amount of solids (polymers P8-P14) and polyfunctional (meth)acrylic compounds was 100 parts by mass.) • Photopolymerization initiator (BASF, Irgacure OXE01): 5 parts by mass The obtained photosensitive resin composition was poured into a 2cm x 2cm, 5mm high container lined without gaps with Teflon adhesive tape (Nitoflon adhesive tape, No. 903UL (thickness 0.08mm, width 25mm, length 10mm), Nitto Denko Corporation), and then vacuum-dried at 40°C for 16 hours to remove the solvent. Subsequently, a 100mJ / cm² test was performed using a Canon g+h+i ray mask aligner (PLA-600F). 2The g+h+i line was exposed with the specified exposure dose. After exposure, the cured product was peeled off the Teflon adhesive tape to obtain a cured product of the photosensitive resin composition. 0.1 to 1.0 mg of the cured photosensitive resin composition to be measured was placed in an aluminum sample pan, and the softening point was measured under a nitrogen atmosphere using a differential thermal analyzer (Hitachi High-Tech Science Corporation, "EXSTAR TMA / SS6100"). The measurement mode was compression, the load was 30 mN, and the temperature was increased from 30°C to 200°C at a heating rate of 1°C / min. When the sample softened due to heating, the sample deformed, and the displacement (μm) was detected. The softening point was defined as the extension of the straight section with no displacement on the low-temperature side, or the intersection of the tangent to the section with the minimum displacement velocity and the tangent to the section with the maximum displacement velocity. Table 3 shows the evaluation results of the softening point of the cured products of the photosensitive resin compositions, evaluated according to the following criteria. ○: Softening point is below 100°C ×: Softening point is above 100°C If the softening point of the cured photosensitive resin composition is 100°C or lower, it can be said that the softening point is low and the pattern-forming properties are good.

[0316] [Sensitivity evaluation of photosensitive resin composition 1 (exposure amount at which the residual film rate is 90% or more / exposure amount at which the residual film rate is 95% or more)] First, a photosensitive resin composition was obtained by dissolving the following components in propylene glycol monomethyl ether acetate (PGMEA) so that the total solids content concentration was 30% by mass. Polymers P1-P6, P15-P19 (polymers P from Preparation Examples 1-6 and 15-19, respectively) or resin compositions 8-14 (polymer solutions P8-P14 from Preparation Examples 8-14, respectively): 100 parts by mass (Here, for resin compositions P8-P14, the total amount of solids (polymers P8-P14) and polyfunctional (meth)acrylic compounds was weighed to 100 parts by mass.) • Polyfunctional acrylate (dipentaerythritol hexaacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., A-DPH): 50 parts by mass • Photopolymerization initiator (BASF, Irgacure OXE01): 5 parts by mass • Adhesion enhancer (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403): 1 part by mass • Surfactant (manufactured by DIC Corporation, F-556): 0.5 parts by mass

[0317] The obtained photosensitive resin composition was rotary coated onto 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 with a thickness of approximately 3.0 μm (±0.3 μm). This thin film A is subjected to a 100 mJ / cm² radiation dose using a Canon g+h+i-ray mask aligner (PLA-501F) via a photomask with a light-shielding rate of 1-100%. 2 The g+h+i line was exposed with the specified exposure dose. After exposure, the thin film is developed in a 2.0% by mass sodium carbonate aqueous solution at 23°C for 60 seconds (wafer immersion) to achieve a radiation level of 1-100 mJ / cm². 2 Thin films B were obtained by exposing and developing them at each exposure level. The residual film percentage was calculated from the film thicknesses of thin films A and B obtained by the above method using the following formula. Residual film percentage (%) = (Film thickness of thin film B at each exposure dose / Film thickness of thin film A) × 100 The exposure dose at which a residual film rate of 90% or more was achieved was measured as the sensitivity of each photosensitive resin composition. The results are shown in Table 3. The exposure dose at which a residual film rate of 90% or more was 35 mJ / cm². 2 If the following conditions are met, it can be used without problems as a photosensitive composition, up to 20 mJ / cm². 2 The sensitivity can be considered good if it is below 15 mJ / cm². 2 The following can be considered better, and an additional 10 mJ / cm² is also acceptable. 2 The following can be considered particularly good. Furthermore, the exposure dose at which a residual film rate of 95% or more was achieved was measured as the sensitivity of each photosensitive resin composition. The results are shown in Table 3. The exposure dose at which a residual film rate of 95% or more was 50 mJ / cm² 2 If the following conditions are met, it can be used without problems as a photosensitive composition, and the concentration is 30 mJ / cm². 2 If the following is achieved, the sensitivity can be considered good: 20 mJ / cm² 2The following can be considered better, and an additional 15 mJ / cm² is also acceptable. 2 The following can be considered particularly good.

[0318] [Sensitivity evaluation of photosensitive resin composition 2 (residual film rate after exposure at low exposure)] (5mJ / cm 2 (Percentage of residual film at the exposure level) The photosensitive resin composition prepared in Sensitivity Evaluation 1 described above was rotary coated onto 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 with a thickness of 3.0 μm (±0.3 μm). This thin film A is subjected to a photomask with a light-shielding rate of 1-100% using a Canon g+h+i-ray mask aligner (PLA-501F) at a rate of 5 mJ / cm². 2 The g+h+i line was exposed with the specified exposure dose. After exposure, the thin film was developed in a 2.0% by mass sodium carbonate aqueous solution at 23°C for 60 seconds (immersed together with the wafer) to obtain thin film B. The residual film percentage was calculated from the film thicknesses of thin films A and B obtained by the above method using the following formula. Residual film percentage (%) = (Film thickness of thin film B at each exposure dose / Film thickness of thin film A) × 100 The results are shown in Table 3. 5 mJ / cm 2 The higher the residual film ratio at a given exposure level, the more easily the film hardens at lower exposure levels, and the better the sensitivity can be considered to be.

[0319] (10mJ / cm 2 (Percentage of residual film at the exposure level) The photosensitive resin composition prepared in Sensitivity Evaluation 1 described above was rotary coated onto 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 with a thickness of 3.0 μm (±0.3 μm). This thin film A is subjected to a 10 mJ / cm² radiation dose using a Canon g+h+i-ray mask aligner (PLA-501F) via a photomask with a light-shielding rate of 1-100%. 2The g+h+i line was exposed with the specified exposure dose. After exposure, the thin film was developed in a 2.0% by mass sodium carbonate aqueous solution at 23°C for 60 seconds (immersed together with the wafer) to obtain thin film B. The residual film percentage was calculated from the film thicknesses of thin films A and B obtained by the above method using the following formula. Residual film percentage (%) = (Film thickness of thin film B at each exposure dose / Film thickness of thin film A) × 100 The results are shown in Table 3. 10 mJ / cm 2 The higher the residual film ratio at a given exposure level, the more easily the film hardens at lower exposure levels, and the better the sensitivity can be considered to be.

[0320] [Alkaline dissolution rate of photosensitive resin composition (2.0% by mass sodium carbonate aqueous solution)] The photosensitive resin composition prepared in Sensitivity Evaluation 1 described above was spin-coated onto a wafer, the PGMEA was dried, and then a resin film with a thickness of approximately 2 μm was fabricated by pre-baking at a temperature of 100°C for 2 minutes. The resin film, along with the wafer, was immersed in a 2% sodium carbonate aqueous 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 then dividing the film thickness by that time. The results are shown in Table 3. If the alkali dissolution rate is 480 nm / s or higher, it can be used without problems as a photosensitive material; if it is 700 nm / s or higher, it can be considered to have good developability; and if it is 900 nm / s or higher, it can be considered to have particularly good developability.

[0321] [Yellow Index] The photosensitive resin composition prepared in Sensitivity Evaluation 1 described above was rotary coated onto Eagle XG glass (Corning, 0.5 mm thick) and baked on a hot plate at 100°C for 120 seconds to obtain a thin film with a thickness of approximately 3.0 μm (±0.1 μm). This thin film was subjected to a 100 mJ / cm² radiation dose using a Canon g+h+i-line mask aligner (PLA-600F). 2 The g+h+i line was exposed with the specified exposure dose. After exposure, the thin film is developed in a 2.0% by mass sodium carbonate aqueous solution at 23°C for 60 seconds (wafer immersion) to achieve a radiation level of 100 mJ / cm². 2 A thin film was obtained by exposing and developing it with the specified exposure level. The thin film was heat-treated at 230°C for 30 minutes under air conditions. After the thin film was cooled under air conditions at room temperature, it was heat-treated again at 230°C for 30 minutes under air conditions. The same procedure was repeated, and the heat treatment under air for 30 minutes was performed a total of three times. The yellow index (YI) of the thin film obtained by the above method was measured three times at different measurement points using a colorimeter CR-5 (manufactured by Konica Minolta), and the average value was taken as the YI value. The measurement type was transmission measurement, and 100% calibration was performed using uncoated Eagle XG glass (manufactured by Corning, thickness 0.5 mm). The results are shown in Table 3. A yellow index of 1.40 or less can be considered to indicate good heat discoloration resistance, 1.20 or less can be considered to indicate better heat discoloration resistance, 1.10 or less can be considered to indicate even better heat discoloration resistance, and 1.00 or less can be considered to indicate particularly good heat discoloration resistance.

[0322] The results of the developability and sensitivity evaluations are shown in Table 3.

[0323] [Table 3]

[0324] A comparison of raw material polymers 5-11 with raw material polymer 1 revealed that raw material polymers 5-11, which contain structural units derived from long-chain alkenes, had significantly lower softening and melting points compared to raw material polymer 1. In a comparison of raw material polymers 5 and 8-11, the softening and melting points decreased as the chain length of the long-chain alkene-derived structure introduced into the polymer increased. Furthermore, polymers P7, P15-P19, which contain structural units derived from long-chain alkenes, had a softening point of 110°C or lower and a melting point of 140°C or lower, exhibiting both low softening and melting points. The photosensitive resin compositions containing the polymers of Examples 1 to 13 had a good balance of alkali solubility, sensitivity, and heat discoloration resistance, and the cured photosensitive resin compositions made from the polymers of Examples 1 to 13 had a softening point lower than 100°C. The polymer of Comparative Example 1 had a low softening point and melting point, and the cured photosensitive resin composition made from the polymer of Comparative Example 1 had a softening point lower than 100°C, but the sensitivity of the photosensitive resin composition was insufficient. The polymer of Comparative Example 2 had a high softening point and melting point, and the cured photosensitive resin composition made from the polymer of Comparative Example 2 had a softening point of 100°C or higher. The polymers of Comparative Examples 3 and 4, and their raw material polymers, had low softening points and melting points, and the cured photosensitive resin compositions made from the polymers of Comparative Examples 3 and 4 had a softening point lower than 100°C, but the alkali solubility of the polymers and photosensitive resin compositions was insufficient. The polymers of Comparative Examples 5 and 6, and their raw material polymers, had low softening and melting points. Although the softening point of the cured photosensitive resin compositions made from the polymers of Comparative Examples 5 and 6 was lower than 100°C, the heat discoloration resistance of the photosensitive resin compositions was insufficient. The photosensitive resin compositions made from Examples 2 to 13, which included polymers containing structural units derived from long-chain alkenes and having a ring-opened structure with a polyfunctional (meth)acrylic compound, showed particularly excellent sensitivity. The photosensitive resin compositions made from Examples 2 to 8, which contained free polyfunctional / monofunctional (meth)acrylic compounds in the polymer solution, showed a sensitivity of 5 mJ / cm³. 2 The residual film ratio was high at the exposure level, and the sensitivity was particularly superior.

[0325] <Creating a color filter> To the photosensitive resin compositions prepared in Examples 1 to 13, an appropriate amount of pigment dispersion NX-061 (manufactured by Dainichi Seika Kogyo Co., Ltd., green) was added to prepare a colored photosensitive resin composition. By forming this film on a substrate and then performing exposure and alkaline development processes, we were able to create a green color filter. Furthermore, instead of NX-061, the company's own NX-053 (blue) and NX-032 (red) pigment dispersions were used to form blue or red color filters.

[0326] <Creation of a Black Matrix> To the photosensitive resin compositions prepared in Examples 1 to 13, an appropriate amount of carbon black dispersion NX-595 (manufactured by Dainichi Seika Kogyo Co., Ltd.) was added to prepare a black photosensitive resin composition. By depositing this onto a substrate and performing processes such as exposure and alkaline development, a black matrix could be formed. [Explanation of Symbols]

[0327] 10 circuit boards 11 Black Matrix 12 Color Filters 13 Protective film 14 Transparent electrode layer

Claims

1. A polymer having a structure represented by formula (P'), 【Chemistry 1】 In equation (P'), n is an integer between 2 and 6. p, q, and r represent the molar content of A, B, and C, respectively, where p + q + r = 1, p is greater than 0, q is greater than 0, and r is greater than 0. p, q, or r may be the same or different for each of the n structural units within the brackets. A represents a structural unit represented by formula (NB), B includes at least one structural unit selected from the structural units represented by formula (1) and the structural units represented by formula (2), C represents a structural unit represented by formula (AK), Multiple A's, B's, and C's may be the same or different. X is a hydrogen atom, Y is an organic group having a thioether group, which is a divalent to hexavalent organic group derived from at least one selected from two or more thiol group-containing compounds represented by formulas (s-1) to (s-21), and the organic group having the thioether group is bonded to any of A, B, or C via a thioether group (-S-* (* is a bond)) derived from the thiol group-containing compound. The structural units A, B, and C are arranged randomly or alternately. 【Chemistry 2】 In equation (NB), R １ , R ２ , R ３ and R ４ Each of these is independently a hydrogen atom or an organic group having 1 to 30 carbon atoms, and a １ is 0, 1, or 2, 【Transformation 3】 In formula (AK), R １１ , R １２ , R １３ and R １４ one of which is a linear alkyl group having 3 or more carbon atoms, and the remaining three are hydrogen atoms, 【Chemistry 4】 In formula (1), R ｐ R is a group having two or more (meth)acryloyl groups, ２１ and R ２２ It is a hydrogen atom, 【Transformation 5】 In formula (2), R ｓ R is a group having one (meth)acryloyl group. ２１ and R ２２ is a hydrogen atom, 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 【Chemistry 23】 【Chemistry 24】 【Chemistry 25】 【Chemistry 26】 polymer.

2. The polymer according to claim 1, The aforementioned B further includes a structural unit represented by formula (3), 【Chemistry 27】 In formula (3), R ２１ and R ２２ It is a polymer, which is composed of hydrogen atoms.

3. A polymer according to claim 1 or 2, The aforementioned B further includes a structural unit represented by formula (MA), 【Chemistry 28】 In formula (MA), R ２１ and R ２２ It is a polymer, which is composed of hydrogen atoms.

4. A polymer according to any one of claims 1 to 3, The aforementioned B includes a structural unit represented by formula (1), R in formula (1) ｐ is at least one selected from the group represented by formula (1b), the group represented by formula (1c), and the group represented by formula (1d), 【Chemistry 29】 In formula (1b), k is 2 or 3, R is a hydrogen atom or a methyl group, and multiple Rs may be the same or different. X １ X is a single bond, an alkylene group having 1 to 6 carbon atoms, or a group represented as -Z-X- (where Z is -O- or -OCO-, and X is an alkylene group having 1 to 6 carbon atoms), and there are multiple X groups. １ They 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'- (where X' is an alkylene group having 1 to 6 carbon atoms, and Z' is -O- or -COO-), X ２ This is a k+1 valent organic group having 1 to 12 carbon atoms. 【Transformation 30】 In formula (1c), k, R, X １ and X ２ These are R, k, and X in equation (1b), respectively. １ and X ２ This is synonymous with multiple Rs, which may be the same or different from each other, and multiple X １ They may be the same or different from each other. X ３ This is a single bond or a divalent organic group having 1 to 6 carbon atoms. X ４ and X ５ Each of these is independently a single bond or a divalent organic group having 1 to 6 carbon atoms. X ６ It is a divalent organic group having 1 to 6 carbon atoms. 【Chemistry 31】 In formula (1d), n is an integer between 2 and 5. R is independently either a hydrogen atom or a methyl group. polymer.

5. A polymer according to any one of claims 1 to 4, The aforementioned B includes a structural unit represented by formula (2), R in formula (2) ｓ This is a base represented by formula (2a), 【Chemistry 32】 In formula (2a), X １０ R is a divalent organic group, and R is either a hydrogen atom or a methyl group. polymer.

6. A polymer according to any one of claims 1 to 5, A polymer having a weight-average molecular weight of 2,000 or more and 30,000 or less.

7. A polymer according to any one of claims 1 to 6, A polymer whose softening point is 110°C or lower.

8. A polymer solution comprising the polymer described in any one of claims 1 to 7.

9. A polymer solution according to claim 8, A polymer solution further comprising a polyfunctional (meth)acrylic compound or a monofunctional (meth)acrylic compound, or a combination thereof.

10. A polymer solution according to claim 8 or 9, A polymer solution used to form a color filter or black matrix.

11. A polymer according to any one of claims 1 to 7, A photoradical polymerization initiator, Photosensitive resin composition.

12. A cured product formed from the photosensitive resin composition described in claim 11.

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